Search Documents

By D. Turnbull, J. H. Hollomon

THERE is a large body of evidence'" indicating that solidification during the liquid-solid transition is usually induced by heterogeneities present in the liquid. By dispersing liquid metals into small droplets, the impurities responsible for catalyzing solidification are isolated within a small number of these droplets. The effect of the foreign body therefore is restricted to a single drop by this technique. Thus upon cooling below the melting temperature, solidification is initiated by homogeneous nucleation in the majority of the droplets that do not contain impurities. In the case of solidification of liquid metals, the activation energy for nucleation is so great that its rate changes by orders of magnitude for a change in temperature of only several degrees centigrade.' Effectively homogeneous nucleation occurs at a critical temperature upon continuous cooling. Thus by microscopic observation of single particles during cooling, a temperature at which the rate of homogeneous nucleation becomes sensible can be determined.3 since at the temperatures at which nucleation occurs in the absence of impurities the rate of crystal growth is extremely rapid, the temperature at which the entire particle solidifies is very nearly the temperature at which the nucleation of the solidification occurs. Thus for liquids that freeze at high temperatures the onset of nucleation can be established by simply observing the temperature at which the marked heat evolution and increase in brightness of the particle occur. For liquids that freeze at lower temperatures the onset of nucleation can be determined by a rumpling and change in shape of the particle resulting from its solidification. The microscopic technique for observing the solidification of small particles has already been described." In earlier papers the nucleation of solidification of pure metals 5,6 and of alloy systems7 showing complete liquid and solid solubility have been described. In the present paper, the observations are extended to a simple eutectic system (Pb-Sn) where the possibility of the formation of two solid phases exists. Metals for the investigation were obtained from the American Smelting and Refining Co. in the form of pure lead and pure tin, 99.8 and 99.9 pct purity, respectively. An ingot of each of the pure metals was made into shot by heating the metals at a temperature about 50 °C in excess of the melting point and pouring the liquid slowly into a container of water at 15°C. Samples of the shotted pure metals were weighed out to make alloys containing 5, 10, 15, 20, 25, 30, 40, 50, 60, 70, 80, and 90 atomic pct Pb. Samples of each alloy were then melted in separate beakers. Each melt was poured through a pyrex funnel into a cylindrical mold (% in. ID). The casting solidified in 10 to 20 sec. The inside of the mold as well as the funnel through which the metal was poured were coated with graphite to eliminate adherence of the metal. Analyses were performed on some of the compositions and are given in Table I. The compositions also were checked for these samples and for those that were not analyzed by determining the spread between the liquidus and the solidus upon melting the small metal particles. These measurements agreed as well with the nominal compositions as the analyses listed above. Results The results of the supercooling experiments for the several alloys are summarized in Table II and plotted on the constitution diagram in Fig. 1. Data for the pure lead and pure tin were taken from earlier investigations. The values for the maximum supercooling of the several alloys are the average of several determinations on a number of drops of each alloy. The maximum value in any determination was within about 2 pct of the average. For the alloys containing from 20 to 60 atomic pct Sn, inclusive, two marked changes of the surface structure were observed upon cooling. At the higher temperature, after the first appearance of the solid phase it continued to grow slowly at a constant temperature and then stopped. At the lower temperature the alteration of surface structure was abrupt. For the alloys containing from 70 to 95 atomic pct Sn, inclusive, an abrupt change in surface structure was observed at a single critical temperature.

Jan 1, 1952

By G. J. Heuer, J. N. Dew, G. C. Clark

The effect on well behavior of partial permeability barriers, changes in producing rates and well spacings have been calculated through use of a radial, unsteady-state, two-phase-flow mathematical model. This model allows for variations in permeabilities and porosities with distance from the wellbore. The numerical methods necessary to solve the problem require use of a highspeed digital computer, in this case an IBM 704. In each instance, pressure and saturation gradients, gas-oil ratios and recoveries around a well producing by solution-gas drive have been calculated as a function of time and distance from the wellbore. Comparisons are made to show the effect of changes in producing rate and of varying permeability near the wellbore and out in the formation on the production and pressure history of the well. The effect of different well spacings on producing rate and ultimate recovery is considered. Although the mathematical description of the reservoir is simplified in comparison to an actual reservoir, the results do give some insight into the difficult problem of spacing and proration in a heterogeneous solution-gas-drive reservoir. Results show that for the cases considered spacing has little effect on ultimate recovery and that permeability barriers removed from the well decrease producing rate for a period of time but have only a small effect on ultimate production. INTRODUCTION The effect of spacing and producing rate on the production characteristics and ultimate recovery of a well producing by the solution-gas-drive mechanism have been topics of interest to the oil industry for many years and the subject of many hearings before state regulatory bodies. The problem is very complicated because of the difficulty of simulating in the laboratory a reservoir producing by the solution-gas-drive mechanism under anything like normal field conditions. This paper gives the initial results of a study aimed at determining the effect of these factors on production from reservoirs simulated by a mathematical model. Two-phase, unsteady-state equations are used to calculate pressures, saturations, and rates of oil and gas flow as a function of time and distance from the wellbore. The model is radial, and reservoir properties may be varied with distance from the wellbore. A decrease in permeability at a given distance results in a low-permeability ring concentric with the wellbore through which all the fluids from more distant portions of the reservoir must flow. The current mathematical model allows for variation of permeability, porosity and saturations as a function of distance from the well. Any desired drainage radius for the well may be selected. Drainage radii of 745 and 1,053 ft, which correspond to 40- and 80-acre spacing, were chosen for the calculations which follow. A large amount of the input data has been held constant. No investigation was made into the effect of changes in fluid properties and relative permeability characteristics on oil and gas production behavior. Fluid properties and relative permeabilities are essentially those of the White Mesa portion of the Greater Aneth area in southeastern Utah. A recently concluded hearing before the Utah Oil and Gas Conservation Commission to determine spacing for the field aroused interest in the possible effect of permeability constrictions located some distance from the well on production and recovery. This interest stimulated the present study. In this paper, no attempt has been made to simulate any field production characteristics exactly. Only the solution-gas-drive mechanism has been investigated, and production by liquid expansion has not been considered. This investigation is exploratory in nature but does give some insight into the problems of spacing and proration in a solution-gas-drive field having permeability variations. THE MATHEMATICAL MODEL The mathematical model is similar to that proposed by West, Garvin and Sheldon.' Approximately the same techniques have been used in arriving at a solution. The equations are nonlinear, partial differential equations which have been known for some time. The particular equations used for this study neglect the effects of capillary pressure and gravitational forces. The advent of modern digital computing equipment has made their solution practical. Basically, the method solves for pressure, saturations, and oil and gas flow rates as a function of distance and time. In our model, distance to the

By G. Wakefield, A. H. Daane, D. H. Dennison, F. H. Spedding

Preparation of pure scandium metal was accomplished by calcium reduction of the fluoride by two methods; a low-temperatzdre alloy process and direct reduction with subsequent distillation of the product. The following properties were determined: melting point: 1181OK; boiling point (calculated): 3000°K; lattice constants at 298°K (hexagonal lattice): a = 3.308 * 0.001 A, c = 5.267 * 0.003A; calculated density at 298°K, g per cm3: 2,990 + 0.007; electrical resistivity, ohm-cm: 299°K, 66.6 ± 0.2 x 10 -6; 373oK, 77.4 * 0.2 x 10 -6; thermal coefficient at 299°K, ohm-cm per deg: 5.4 X x; heat of sublimation at 298°K, kcal pel- mole: 80.79. The vapor pressure was determined as a function of temperature between 1505o and 1748°K, with the data fitted to a straight line shielding the equation: Log Pmm = -1.718 X 104/ToK + 8.298. SCANDIUM, element number 21, was first discovered by Nilson in 1879 and was recognized as the Ekaboron as predicted by Mendeleff. As it is in group III of the periodic table, the general properties are a little like aluminum and also resemble quite closely the properties of yttrium and the rare-earth metals, in both the metallic and ionic form. Although the earth's crust contains approximately 5 ppm of scandium (the element is as abundant as arsenic and twice as abundant as boron) it generally occurs so widely distributed that it has earned the reputation of being very rare. The one exception to this is the mineral thortveitite, which has been found in Madagascar (20 pct Sc2O3) and in Norway (35 pct Sc2O3). Scandium also occurs in small but distinct amounts in uranium and rare-earth ores; the recent larger scale processing of these materials has made some scandium available from these sources. As with other naturally-occurring monoisotopic elements (except Be), scandium contains an odd number of protons and an even number of neutrons. Scandium metal was first prepared by Fischer and coworkers1 in 1937 by electrolysis of scandium chloride in a molten eutectic mixture of lithium and potassium chlorides, using molten zinc as a cathode and collector of the scandium metal produced. The zinc was removed from the Zn-2 pct Sc alloy by vacuum distillation, leaving a product reported to be 94 to 98 pct Sc, with the main impurities being iron and silicon. They reported a melting point of 1400° C for this material. Scandium has also been prepared by the reduction of scandium chloride with potassium metal in a glass apparatus by Bommer and Hohmann in 1941,' resulting in a mixture of metal and potassium chloride; these workers did not isolate the metal proper, but the X-ray diffraction of the slag-metal mixture showed it to be hexagonal with a = 3.30A, c = 5.45A. petru3, 4 and coworkers have recently reported the preparation of the metal in a compact form by the reduction of either ScF3 or ScC13 with calcium metal and subsequent distillation of the product. This process probably yielded a metal of high purity, but they list no chemical analysis nor do they list any of the properties of their product. Previous related work in this Laboratory has been concerned with the production of yttrium and the rare-earth metals and the determination of their physical properties. Because of its similarity to these metals, scandium is being included in this study. PREPARATION OF SCANDIUM METAL The preparation of yttrium and the rare-earth metals may be accomplished by reduction of their fluorides with calcium metal in tantalum crucibles.5 This process leads to the introduction of tantalum (up to 0.5 pct) as an impurity in the higher melting rare earths, but since the tantalum occurs as dendrites, uncombined with the rare-earth metals, its presence is not objectionable in some cases. The preparation of scandium metal in this manner, however, was found to yield a product containing 2 to 5 pct Ta. To obtain a purer product, the following two methods were developed for the reduction of scandium fluoride with calcium metal: i) a low-temperature process utilizing zinc to form a low

Jan 1, 1961

By Leo Horvitz

Microanalysis of near-surface soils for hydrocarbons is the basis of a method for locating gas and oil deposits. To substantiate this technique, evidence of vertical migration of hydrocarbons from petroleum accumulations is presented. Tabulated data relevant to hydrocarbon surveys conducted in several petroleum provinces are included. PEROLEUM and natural gas are composed principally of the saturated hydrocarbons ranging from methane, the lightest, to nonvolatile liquids and solids containing approximately thirty-five carbon atoms. A technique for locating buried accumulations of these hydrocarbons before drilling obviously requires that some of the hydrocarbons leave the deposit and migrate toward the surface of the earth where they may be detected in their original form. Earliest attempts to link near surface hydrocarbons to petroleum at depth were apparently made by Laubmeyer' in Germany and by Sokolov in Russia. These investigators collected samples of soil air from boreholes one to two meters deep and analyzed them for traces of hydrocarbons. They found that soil air over producing areas is richer in these constituents than is soil air over barren areas. Since 1936 work on petroleum exploration techniques of this type has been going on in this country. However, instead of determining hydrocarbon content of soil air collected in the field, investigators analyze samples of the soil itself for adsorbed and occluded hydrocarbons, which are released by suitable treatment and found in larger amounts than are the quantities reported for soil air. Difficulties often encountered in collecting gas samples in the field, moreover, are eliminated when soil is used as the sampling medium. Field Procedure: Sample locations are first surveyed over the area to be investigated. Care is taken to locate the stations at considerable distances from roads, pipelines, drilling wells, and other sources of contamination. The borehole pay be dug with a bucket-type hand auger or with mechanical drilling equipment. Lubricants are avoided in either case. When the desired depth is reached, a sample is brought to the surface, placed in a pint glass jar or can, and securely sealed. Sample containers are carefully labeled and delivered to the analytical laboratory. Generally a satisfactory sampling depth range is 8 to 12 ft. In some regions, however, satisfactory data are obtained from samples collected at much shallower depths. Such is the case, for example, in areas of west Texas where the limestone and caliche near the surface occlude hydrocarbons and prevent their rapid escape to the atmosphere. In carrying out broad reconnaissance surveys in search of large features, considerable time is saved by first taking samples one-fourth to one-half mile apart along profiles about one mile apart. If the analytical data indicate a hydrocarbon anomaly of interest, additional samples are taken to produce a more dense and uniform sampling pattern within the interesting area. This sampling program is particularly adaptable to areas that are sectionized. In areas covered with a network of roads, sampling along these roads facilitates the reconnaissance survey. Actual sampling density used depends upon areal extent of features expected. When flanks of piercement-type domes where accumulations may be only several hundred feet wide are sampled, stations are often no more than 200 ft apart. Analytical Technique: Of the hydrocarbons composing petroleum, only the more volatile would be expected to reach the surface of the earth. The analytical technique, therefore, was developed to determine only those constituents that exert a vapor pressure at room temperature. Actually, in near-surface soils, only a very small part of the hydrocarbons are heavier than pentane. Details of the analytical technique have previously been reported. Only a brief description of the methods will be presented here. A weighed portion of the sample, about 100 g, is first treated with an aqueous solution of copper sulphate and then with phosphoric acid in a partial vacuum. The copper sulphate prevents the reaction of the acid with carbides that may be present because the sample has been contaminated by auger particles. Such a reaction may produce spurious methane. The role of the acid is to decompose any carbonates present, thereby helping to release the hydrocarbons. The carbon dioxide is removed with potassium hydroxide and the flask containing the

Jan 1, 1955

By E. D. Gardner

FIFTY years ago the Utah Copper enterprise at Bingham was just getting under way. An epic in metal mining was in the making. Throughout the West the bonanza deposits were approaching exhaustion and most ore still went direct to smelter. But concentrators were shortly to be constructed for treating milling grade ores, and most important, the pilot plant for the Utah Copper enterprise was being built that year at the mouth of Bingham Canyon. The same decade was to see development at the Inspiration mine in Arizona of the most important new mining method for 50 years to come—undercut block caving. Although the average grade of ore being mined has been declining for 50 years, and wage rates and prices of supplies have been greatly increased, the mining industry has continued to grow and to prosper. Technology has advanced to a point where minerals can be mined under the most severe conditions. The hardest rock can be drilled and broken and the heaviest ground handled. Large or small, an ore-body can be mined successfully, at any desired rate of production. It is possible to pump great volumes of water and to ventilate the most extensive workings; air conditioning has made practicable the mining of ore where the rock temperatures are beyond those that can be borne by man. Mining today in the U. S. is a huge earth-moving operation. In 1953 nearly 2 billion tons of material were mined for direct use or for processing. Stripping at open-cut mines totaled about 1.7 billion cu yd. Table I gives relative tonnages of the branches of the mineral industry in 1953. In addition to the solid materials moved, 350 million tons of petroleum and 340,000 tons of gas were produced in 1953. Fifteen million tons of salt and 5 million tons of liquid sulphur were pumped from wells. An appreciable amount of copper was recovered by leaching old mine workings and dumps. Total value of minerals produced in 1953 was $14.4 billion: oil and gas $7.6 billion, coal $2.6 billion, nonmetallics $2.4 billion, and metals $1.8 billion. Formidable problems face some branches of the industry today, especially pertaining to increased output tons per manshift. The time has come when these problems should be reappraised. With current wage rates, the industry no longer can afford to pay men to do manual labor. It should be recognized, also, that the miner is a skilled worker; efforts to promote the dignity of his calling and his pride of accomplishment have yielded beneficial results. Mineral deposits occur under widely varying conditions. In most instances the degree of support needed by the roof and walls is the deciding factor in selection of an underground mining method. The degree of support needed, in turn, is governed by natural physical characteristics of the ore and its enclosing rocks. Mine operators, of course, learn to judge ground by observation, and an experienced mine boss generally can anticipate what will happen following any given mining operation. A more scientific approach, however, would be advantageous in most cases. More should be known about the strength of the ore and the enclosing rocks, more about stresses set up in the ground when ore is removed, and more about the mechanics of moving ground. Better understanding would work both ways: first, favorable rock conditions could be fully utilized for more efficient mining, and second, hazards of rock falls could be minimized, loss of ore in mining reduced, and expenses caused by ground pressures and subsidence lowered. In general, mining comprises breaking the ore or rock in place, supporting the mine workings, and transporting the ore to the surface. This latter is a materials handling problem. Ventilation, of course, must be provided, and the mines must be kept free of water. Development work at some places is the most important cost item in extracting ore. Drilling and blasting remain the usual practice for breaking ore or rock from place except, of course, at block-caving mines. The drilling and blasting practice at a mine must fit the mining method. In laying out mining procedures attention is being given to

Jan 1, 1956

THE refining period of an open-hearth heat blends imperceptibly into the finishing period, during which final adjustments are made in slag composition, in bath action and temperature, and in composition of the steel, in order to prepare it for casting into ingots. Operations must be governed by the consideration that alterations in the character of the heat during the finishing period must be held to a minimum. In a broad sense, the finishing and deoxidation period of a heat may be said to begin when the action of the last ore addition has ceased, and to end when the teeming of the ingots is completed. INGOT STRUCTURES A survey of the relative advantages and disadvantages of different types of ingot structure is required because deoxidation treatments during the finishing period control the amount of gas evolved during solidification and consequently determine the type of ingot structure. Four classes of ingots are recognized, depending upon the degree of deoxidation to which the steel has been subjected. These types are killed, semikilled, capped, and rimmed; typical examples of their structures are represented by ingots 1, 2, 5, and 7, respectively, of Fig 9-1. The actual ingots from which these cross sections were sketched were all poured to the same height (indicated by the dotted lines) in the same type and size of bottle-top molds. The eight drawings of the figure represent selected types of ingot structure in a continuous series from "dead killed" to "wild," resulting from variations in the total quantity of gas evolved, from none at all to copious amounts, during solidification of the steel in the mold. Killed and semikilled steels are adjacent at the "quiescent" end of the ingot structure series where only small amounts of gas are evolved. The term "quiescent" describes the action of the molten metal during and subsequent to the teeming of killed and semikilled steels. Capped and rimmed steels are adjacent at the

Jan 1, 1951

By B. E. Morgan, C. K. Dumbauld

The need for a low-strength cementing composition for use in well cementing is reviewed and results are presented of laboratory and experimental field tests of a modified cement having a controlled ultimate tensile strength of approximately 200 psi. The modified cementing composition may he prepared from either high early strength or normal portland cements by the addition of bentonite clay and a suitable agent for dispersing and controlling the set of the slurry. Substitution of the modified cement for conventional slow-set cements may give better completion results in many wells because the modified cementing composition has lower set strength, lower slurry density, and greater slurry stability than conventional cement slurrieh. The lower ultimate strength allows greater penetration with less shattering of the set cement when perforating casing and cement. The lower elurry density allows the placement of longer columns of cement slurry, and the greater slurry stability reduces the possibility of having an uncemented section caused by the settling of cement particles before the cement set.. INTRODUCTION High strength lias always been one of the accepted criteria of a good cement. During the early use of portland cement in well cementing. emphasis was placed upon securing cements with higher strengths. In 1931, Barkis' reported that, "Normal oil well cements have been improved to develop greater strengths and uniformity of product, which has aided in producing successful jobs in cementing the deeper strings." As long as most wells were completed by the open-hole method. the use of cements having high strengths seemed desirable, and there was no objection raised against high-strength cementing compositions. For a number of years. how-ever, the industry has been completing a large numher of wells by setting and cementing casing through productive horizons and then obtaining production by gun-perforating the section of casing opposite the desired interval. Although this method has been generally successful, difficulties have been experienced in some cases in completing or recompleting wells because of apparent lack of adequate penetration by the bullets through the casing and surrounding sheath of cement and into producing formation. In addition to the penetration trouble: there have been indications that fracturing and shattering of the set cement by perforating might he a contributing factor in causing the failure of some jobs to exclude water or gas from oil producing zones. The possibility that cements having high set strengths were contributing to til difficully ill obtaining satihfartory perforating results has re. ceived attention during recent years. Gun perforating tests conducted in 1944 showed that the depth of bullet penetration into set cement varied with the hardness of the cement, the greater the strength of the cement the less being the penetration. In 1946, Farris2 pointed out that high strength cements were not needed in well cementing, and in 1947, data published by Oliphant and Farris3 showed that set cement was perforated without shattering at approximately 150 psi tensile strength. whereas at approximately 300 psi tensile strength severe cracking and shattering occurred. Oliphant and Farris suggested that wells be perforated at the proper time interval after placement of the cement so that the set cement would have the desired strength. Several difficulties may he encountered in trying to perforate a cement job at the correct time to catch the tensile strength near 150 psi. The rate of strength development of different cements varies considerably. This fact is illustrated by results of tensile strength measurements presented in Fig. 1. These data show that at 175°F the tensile strengths of three conventional slow-set cements varied from 75 to 235 psi at the end of 12 hours. After 24 hours, the tensile strengths varied from 200 to 455 psi. The rate of strength development is affected. also. by the temperature of the forniation, and this adds to the uncertainty of perforating at the rorrect time, since accurate well cementing temperatures may not he known in many cases. Furthermore, in the recomple-tion of wells it is sometimes necessary to perforate cement which has set for a long period and has developed maximum or final strength. In view of the apparent need for a cementing composition having a controlled ultimate strength, an investigation was

Jan 1, 1951

By James H. Boettcher

INTRODUCTION A complex interaction of worldwide economic and political forces is increasingly requiring 3 primary participants for the successful development of large natural resource projects in developing countries. They are the host government of the developing country (the "host government"), one or a consortium of international natural resource companies, (the "Resource Company") and one, or more likely, a syndicate of international lenders. The host government typically controls the rights to its country's natural resources and establishes the economic ground rules for their development. However, because of worldwide inflation and the depletion of easily accessible, high-grade resources, the nominal and real capital development and operating costs of projects have been spiraling. Moreover, the depletion of high-grade and mineralogically uncomplicated resources also raises the technical and operating risks associated with resource recovery. Thus, despite increasing political self-consciousness and economic nationalism in developing countries, international resource companies are still often necessary project sponsors since they can provide, among other things, the required technical and management expertise and equity capital. The presence of these factors, and often the addition of worldwide market access in a project, is often critical in determining whether or not the project will be considered creditworthy by international commercial lenders. The international commercial lender is often the critical third party in project development, due in a large part to the ever escalating-costs of project developments relative to the financial resources of many companies and even a growing number of countries. In addition, lenders have other reasons for taking more than a passive interest in all aspects of a project's development. These reasons include the following: 1. Projects are often financially structured such that the primary security for a loan, once completion and performance standards are met, is the cashflow of the project rather than recourse to its sponsors. 2. Lenders, in addition to the "project risk" just described, are frequently asked to assume various elements of "political" risk which nay put them in a sensitive economic position between the host government and international resource firms (This is discussed later). 3. International banks today have large loan portfolios of developing country debt with final maturities ranging from one to fifteen years. The various current projects undertaken are the building blocks of most developing country economies that will hopefully contribute to the long run economic development of a country as well as generate the foreign exchange necessary to repay foreign loans in the future. In this regard it is useful for lenders to realize whether a given project "makes sense" in terms of a country's natural resource endowments and competitive advantages over other countries. The type of framework discussed in this article would help lenders to better make such assessments. In order to facilitate the continued international flow of capital and technology to developing countries and of readily available supplies of raw materials from them, it is important for each of these three parties to increase its awareness of the goals and objectives of the other parties as well as the bargaining process that results in the legal, financial, credit and fiscal structures by which a joint venture project ultimately proceeds. Each of the parties faces increasingly complicated accept/reject decisions when they are faced with difficult choices among. a wide range of alternative structural combinations each of which has different implications for risk and reward to them. Therefore, by increasing the mutual, 3-way awareness of the decision processes of the other parties, it should be possible to: • provide better information and results in the formation of more rational expectations by all parties going into negotiations, • facilitate the project formulation process by allowing parties to focus more clearly on the areas of common interest and conflict, • result more frequently in final structures and agreements that better reflect the economic and political realities associated with a project and thus • result in more creative, innovative agreements that should reduce the need for changes to them and thus promote the kind of long run political stability conducive to attracting capital and further investment.

Jan 1, 1982

By R. J. Wagner, G. H. Gronhovd, A. J. Wittmier

The paper describes the results of a series of full-scale boiler tests run to determine the ash fouling characteristics of a North Dakota lignite as a function of sodium content of the coal. Four levels of sodium were investigated and rate of fouling was determined both by boiler performance and by specially constructed probe equipment. Discussed is information on chemical and physical properties of the ash deposits. The vast lignite deposits in North Dakota are becoming increasingly important as a source of low-cost fuel for power generation. A new 200-megawatt lignite-burning plant located near Stanton, N.D., was placed in operation early in 1966. Another 172-mega-watt unit in the same area is scheduled for operation late in 1966, and plans have recently been announced for a 212-megawatt unit to be in operation by 1970. If these plants show good performance, western North Dakota could become a major power production center for a large geographic area in the upper midwest. One of the problems associated with the use of lignite in power boilers is its tendency to form troublesome ash deposits on boiler tube surfaces. This problem varies considerably from one lignite-fired boiler to another and is dependent upon such factors as source of lignite, boiler design, load factor, tube metal temperatures, and soot-blowing practices. This report presents data on sodium content* variation in a North Dakota mine, describes the results of a series of tests performed to determine the relationship between ash fouling tendencies and the sodium content, and tells how the mining company and electric utility have coordinated their operations to reduce the ash fouling problem. GENERAL BACKGROUND Until recent years it was generally assumed that North Dakota lignite from a given mine had qualities peculiar to that mine, but that within the mine, the lignite was quite uniform. In 1959, the Otter Tail Power Co. installed a 53.5-megawatt lignite-burning unit at its Hoot Lake plant, Fergus Falls, Minn. Shortly after the unit was put into operation, it was noted that at certain times under high load conditions, ash fouling problems were quite severe, but not consistent or predictable. Each time fouling occurred in the unit the position of the loading shovel at the mine was noted. Within two years it became apparent that there were certain areas in the Knife River Coal Mining Co. mine at Beulah, N.D., where the lignite apparently had a high fouling tendency for the Hoot Lake unit. Results from analyses of the coal did not show large differences in moisture percentage, ash percentage, heating value, or ash fusion temperature between the highly troublesome and less troublesome coals. After three years of operation, the troublesome areas had been quite well defined and the mining company started a procedure of bypassing these areas when load conditions at the plant were high and then returning to the troublesome areas to load the lignite during the summer months when peak loads were lower. It was noted that the lignite from the areas which caused severe fouling under high load conditions produced much less fouling at the lower summer loads. However, bypassing certain areas in the strip pit caused the mining company to disrupt their continuous loading schedule, which in turn upset their continuous stripping schedule and made for less efficient mining operation. Meanwhile, at the Hoot Lake plant, the number of soot blowers on No. 2 boiler had been increased from 30 to 55, and a very rigorous blowing schedule had been adopted resulting in soot blowers operating at least some part of 21 hrs per day. Fouling problems continued, with a resulting reduction in plant economy and reliability. During this period the Federal Bureau of Mines Coal Research Laboratory at Grand Forks, N.D., had initiated various research programs relating to the study of lignite ash and ash fouling problems. One project was a survey in which full seam samples were obtained from various locations in all the major

Jan 1, 1968

By J. L. Huitt, J. L. Pekarek, D. K. Lowe

In a theoretical study of hydraulic jetting, the velocity of the abrasive material relative to the velocity of the fluid in the jet stream is analyzed as the jet stream moves through the convergent and straight sections of the nozzle and the region between the nozzle exit and target. The results revealed that the abrasive material exits from the jet nozzle at a lower velocity than the fluid. The exit pmticle velocity can be increased by increasing either the density of the fluid or the length of the nozzle, and/ or decreasing either the particle density or particle diameter. In the divergent jet stream, there exists a point after which the particle velocity exceeds that of the fluid. The relative velocities were considered in the derivation of an equation to predict cutting rate of a circumferential notch and maximum notch depth. Data of a general nature and data which substantiate the theoretical results were obtained experimentally. INTRODUCTION The use of a fluid containing an abrasive material has been an established technique for cleaning and cutting for many years. In the petroleum industry, the early effort to use this technique1 to perforate and/or to overcome wellbore damage met with only limited acceptance because of the short life of the jet nozzle. With the introduction of improved perforating techniques, and later, hydraulic fracturing, the use of hydraulic jetting as a well completion technique became even less appreciated. It was only in recent years that interest in hydraulic jetting was revived. Once this interest was revived, the results of surface tests stimulated the interest of the industry even more than the state of the technology probably warranted because many of the tests were not appropriate for down-hole conditions. However, because of the stimulated interest, the development of the jet nozzle progressed very rapidly to the point where the nozzle life was no longer a prob- lem. With this accomplished, the use of hydraulic jetting in well completion became an accepted practice in a short time. The purpose of this paper is to present a theoretical analysis of the hydraulic jet stream as it passes through the nozzle and travels to its target. With a better understanding of the jet stream and the effects of various parameters, the performance of the process can be predicted more accurately. Equations are presented for cutting rate as applied to circumferential wellbore notching that relate the jet stream make-up, notch configuration and formation material. Also, experimental data are presented on some factors pertinent to hydraulic notching that are not theoretically analyzed. RELATED STUDIES Most of the studiesl-5 reported in the recent literature have pertained to the more practical aspects of hydraulic jetting; i.e., the effects of certain parameters as interpreted from experimental results, and the application of hydraulic jetting in well completion. In reviewing the effects of various parameters, it is interesting to note the reported depths of penetration obtained under various imposed conditions. In general, the depths vary from a few inches to several feet; however, a depth of penetration of less than 6 in., as reported by Thompson,4 seems more realistic for the usual field practice of hydraulic jetting with sand in water for a period of 20 to 30 minutes. In addition to the practical aspects, the study of Brown and Loper5 included a theoretical approach to hydraulic jetting. Their study resulted in the development of a theoretical expression for the maximum depth of penetration if jetting were continued for an infinite time. An analysis of the equations presented reveals that the initial cutting rate is infinite. The equation expressing centerline velocity is that of Forstall and Gaylord,6 which is applicable for a jet stream exiting in a large stationary medium. Since practically all of the fluid pumped into a perforation (or cut) must flow back through the perforation prior to re-entering the wellbore, a description of the medium as finite and non-stationary seems more reasonable. Thus, in this

By P. R. Gage, R. W. Bartlett

At high temperatues and reduced oxygen pressuves, molybdenum silicicles oxidize to form SiO(g) vathev than a passivating SiO2 film. This is a sevious problem for low-pressure applications of sili-cide-coated rejvactory tnetals. As oxiclalion pvoceeds, the higher oxidntion potential of silicon initially suppresses oxidation of molybdenum and silicon is depleted near the surface. Eventually, silicon depletion causes secondary passivation (SiO2) mid an active to passiue transition in oxidntion behavior at moderately low pressures. At very low pressures, silicon depletion continues until steady-state oxidation of both silicon and rnolyhdenum can proceed at rates propovtional to their initial stoicliiorrzetvies. Ohsel-vations of 'oxidatiou-rate belzcriliov at temperatures from 1101° to 1700°C and oxygen pressures from 10-7 to 1 at in were made using thermogravimetn'c, X-ray diffraction, and elect?*on-rtric?ro/,vobe techniqrres. The experimental results are in good agreement with calculated lirnits for the various types of behavior that were based on tlievtnochernicnl atzd dffusion rate data for the Mo-Si system. A protective oxide film normally forms during the oxidation of elemental silicon. However, at elevated temperatures and reduced pressures this film is not present and oxidation is rapid. wagnerl has shown that this behavior occurs because SiO(g) is more stable than SiO2. The behavior of the silicides at high temperatures is similar but more complicated. Molybdenum and several silicide compounds are involved and the chemical activity of silicon, or the equivalent silicon vapor pressure, can vary considerably in these phases. Also, diffusion in the silicides resulting from reactions in which a higher silicide is reduced to a lower silicide, or molybdenum containing dissolved silicon, must be considered. EXPERIMENTAL AND ANALYTICAL METHODS Isothermal oxidation experiments were conducted using hot-pressed MoSi2 and Mo5Si3 wafers. Each experiment was conducted at a fixed oxygen pressure by controlling the flow of oxygen in and out of the furnace chamber. Most of the experiments were conducted in a molybdenum-wound tube furnace. Special construction features, including use of a high-purity dense A12O3 refractory tube, permitted operation in high vacuum to 1500°C. Higher temperatures could be obtained at higher working pressures and with a sacrifice of tube lifetime. Temperature was measured with three Pt 6 pct Rh/Pt 30 pct Rh thermocouples and controlled with a proportional controller. Weight changes were monitored with a quartz spring balance. The few experiments, at higher temperatures and low pressures, were conducted in a cold wall vacuum chamber using induction heating with direct susceptance of the sample. Because of the variable levitation effect of the induction coil on the sample, weight changes could not be monitored continuously in these experiments. All samples representing both experimental methods were weighed before and after oxidiation and examined with a microscope and analyzed by X-ray diffraction. The analytical treatment assumes equilibrium at interfaces and uses existing thermodynamic data. For convenience, equilibria are expressed as chemical potentials or as vapor pressures of the gases involved. The resulting differences in equilibrium vapor pressure between adjacent interfaces and between the surface and external atmosphere drive diffusion processes in the solid and gas boundary film, respectively. These diffusion processes govern the rate of oxidation. A bibliography of the sources of thermochemical data for the reactions pertinent to the Mo-Si-O system is given in Table I. Reactions are listed with the sources of free-energy data referenced. Since all of these reactions involve one or more gas species, usually oxygen, a plot of the product-gas chemical potential, -RT In Pg, vs absolute temperature for each reaction is given in Fig. 1. These curves can be used to determine equilibrium vapor pressures or to compare the stability of different compounds in the various gases: O2, Si, SiO, and Moo3,. The data of Table I and Fig. 1 were used to determine the analytical results presented in this paper. EXPERIMENTAL RESULTS The weight changes for three MoSi, samples oxidized at 1500°C are plotted against time in Fig. 2. The treatments were identical except for the indicated variance of oxygen pressure and each curve represents one of three characteristic types of behavior that were observed. The upper curve is an example of passive oxidation, which is defined as

Jan 1, 1965

By J. F. Pierce, S. M. Enterline

Since January 1959 a zinc refiner of novel design has been in operation at Blackwell, Okla., producing 99.995+ zinc from the output of the Blackwell horizontal retort smelter. The refiner is a continuously operated, pyro-metallurgical unit with principal dimensions horizonhl permitting one floor operation. It is very ruggedly constructed. Furthermore it is not subjected to deterioration from high concentrations of iron in the feed metal because the boiling units are separate from the rectification columns and constructed with silicon carbide brick arches through which the heat is transferred radiantly to the zinc. A zinc refiner of novel design has been in operation since January 1959 at the Blackwell, Okla. plant of the Blackwell Zinc Co., Inc., a wholly owned subsidiary of American Metal Climax, Inc. Developed by the company's technical and operating staffs, the new refiner produces special high-grade zinc (nominally 99.995+ pct Zn) from the prime western1 slab output of the Blackwell horizontal retort smelter. The refiner is a continuously operated, pyromet-allurgical, high-capacity unit employing fractional distillation to separate zinc from its impurities, consisting principally of lead, cadmium, and iron. In prime western slab, these elements may vary in concentration from 0.005 to 1.6 pct. Table I shows the impurities usually encountered in the Blackwell prime western metal fed to the refiner together with their boiling points and vapor pressures at 907oC. The commercial pyrometallurgical smelting processes for extracting zinc from ore include distillation from retorts and a limited degree of refining can be accomplished by redistillation in similar retorts. To achieve special high-grade purity, an impractical number of batch redistillations would be required, however, with an accompanying loss of much metal. A continuously operated and integrated unit is required in which fractional vaporization and condensation can take place in a large number of stages. The first commercial continuously operated unit was developed by the New Jersey Zinc Co.4 In the separation of any two substances the degree of separation is limited if a mixture exists having a constant boiling point. The Zn-cd5 and Zn-pb6 systems contain no constant boiling points and hence these metals may be separated to any degree of purity. Basically, the pyrometallurgical refining of zinc involves three steps: a) iron, copper, and other metals having no appreciable vapor pressures at 907ºC concentrate in the bath when the impure zinc is boiled, b) lead, bismuth, antimony, and other metals having boiling points above but closer to that of zinc are selectively condensed from the vapor boiled from the bath, and c) cadmium and other metals having lower boiling points than zinc are fractionally distilled by reboiling and subsequent condensation of the zinc from the vapor. The boiling and condensation of zinc must be conducted in vessels constructed of materials which are refractory at the temperature involved (907 ºC) and it is highly desirable that they also be resistant to attack by the various metals. This requirement dictates construction from relatively small, simply shaped pieces which limits the pressures which may be employed to avoid leakage through the numerous joints. Stresses induced must be limited essentially to compressive ones and suitable provision must be made to permit thermal expansion of the components in order to minimize these stresses. Where heat is to be added for boiling or removed for condensation, refractory material through which the heat flows must have a high thermal conductivity. Silicon carbide is highly conductive but is subject to attack by iron and is expensive compared to other commonly employed refractories. A hard, dense aluminous fireclay is well suited to contain these metals where high thermal conductivity is not required. Zinc will penetrate the pores of fireclay brick but only to a limited depth in an exterior wall and has little effect other than an increase in weight and conductivity. The design objectives of the Amax refiner were: a) to achieve a long life by heavy, rugged construction and by employing silicon carbide refractories only where required for heat conductivity and not in contact with liquids of high iron concentrations, b) to simplify operation, manning and control by essentially horizontal construction, and c) to obtain high capacity in a single unit. DESCRIPTION Flow of metal through the Amax refiner is shown diagrammatically in Fig. 1 and schematically in Fig. 2.

Jan 1, 1963

By C. K. Dumbauld, B. E. Morgan

The need for a low-strength cementing composition for use in well cementing is reviewed and results are presented of laboratory and experimental field tests of a modified cement having a controlled ultimate tensile strength of approximately 200 psi. The modified cementing composition may he prepared from either high early strength or normal portland cements by the addition of bentonite clay and a suitable agent for dispersing and controlling the set of the slurry. Substitution of the modified cement for conventional slow-set cements may give better completion results in many wells because the modified cementing composition has lower set strength, lower slurry density, and greater slurry stability than conventional cement slurrieh. The lower ultimate strength allows greater penetration with less shattering of the set cement when perforating casing and cement. The lower elurry density allows the placement of longer columns of cement slurry, and the greater slurry stability reduces the possibility of having an uncemented section caused by the settling of cement particles before the cement set.. INTRODUCTION High strength lias always been one of the accepted criteria of a good cement. During the early use of portland cement in well cementing. emphasis was placed upon securing cements with higher strengths. In 1931, Barkis' reported that, "Normal oil well cements have been improved to develop greater strengths and uniformity of product, which has aided in producing successful jobs in cementing the deeper strings." As long as most wells were completed by the open-hole method. the use of cements having high strengths seemed desirable, and there was no objection raised against high-strength cementing compositions. For a number of years. how-ever, the industry has been completing a large numher of wells by setting and cementing casing through productive horizons and then obtaining production by gun-perforating the section of casing opposite the desired interval. Although this method has been generally successful, difficulties have been experienced in some cases in completing or recompleting wells because of apparent lack of adequate penetration by the bullets through the casing and surrounding sheath of cement and into producing formation. In addition to the penetration trouble: there have been indications that fracturing and shattering of the set cement by perforating might he a contributing factor in causing the failure of some jobs to exclude water or gas from oil producing zones. The possibility that cements having high set strengths were contributing to til difficully ill obtaining satihfartory perforating results has re. ceived attention during recent years. Gun perforating tests conducted in 1944 showed that the depth of bullet penetration into set cement varied with the hardness of the cement, the greater the strength of the cement the less being the penetration. In 1946, Farris2 pointed out that high strength cements were not needed in well cementing, and in 1947, data published by Oliphant and Farris3 showed that set cement was perforated without shattering at approximately 150 psi tensile strength. whereas at approximately 300 psi tensile strength severe cracking and shattering occurred. Oliphant and Farris suggested that wells be perforated at the proper time interval after placement of the cement so that the set cement would have the desired strength. Several difficulties may he encountered in trying to perforate a cement job at the correct time to catch the tensile strength near 150 psi. The rate of strength development of different cements varies considerably. This fact is illustrated by results of tensile strength measurements presented in Fig. 1. These data show that at 175°F the tensile strengths of three conventional slow-set cements varied from 75 to 235 psi at the end of 12 hours. After 24 hours, the tensile strengths varied from 200 to 455 psi. The rate of strength development is affected. also. by the temperature of the forniation, and this adds to the uncertainty of perforating at the rorrect time, since accurate well cementing temperatures may not he known in many cases. Furthermore, in the recomple-tion of wells it is sometimes necessary to perforate cement which has set for a long period and has developed maximum or final strength. In view of the apparent need for a cementing composition having a controlled ultimate strength, an investigation was

Jan 1, 1951

By T. K. Perkins, L. R. Kern

A study of fluid mechanics, rupture of brittle materials and the theory of elastic deformation of rocks shows that, for a given formation, crack width is essentially controlled by fluid pressure drop in the fracture. Operating conditions which cause high pressure drop along the crack (such as high injection rate and viscous fluids) will result in relatively wide cracks. Conversely, operating conditions which cause low pressure drop (low injection rates and thin fluids) will result in relatively narrow cracks. Charts and equations have been derived which permit the estimation of fracture widths for a variety of flow conditions and for both horizontal and vertical fractures. INTRODUCTION There has been considerable speculation concerning the geometry of hydraulically created fractures in the earth's crust. One of the questions of practical importance is the width of fractures under dynamic conditions, i.e., while the fracture is being created and extended. Such width information could be used, for instance, to help estimate the area of a fracture generated under various conditions. Also, there has been a recent trend toward the use of large propping partiles.13, 15 Therefore is is desirable to know what factors can be varied in order to assure entry of the large particles into the fracture. There has been some work on fracture widths reported in the literature. In particular, there have been several Russian publications dealing with this sub-jeCt.1.31,3 These papers have dealt principally with the elastic theory and the application of this theory to hydraulic fractures. These studies have not led to an engineering method for estimating fracture widths under dynamic conditions. A recent paper3 has reviewed and summarized the Russian concepts. An earlier paper- from our laboratories also discussed the application of the elastic theory to hydraulic fractures. This first approach, based largely on photoelastic studies, has proved to be too simplified to accurately describe the fracturing process. However, these early thoughts have served as a guide during the development of more exact concepts. We would like to present in this paper our current concepts regarding fracture widths and some estimates of hydraulic fracture widths for several conditions. We believe that it is now possible to predict with fair accuracy the factors influencing fracture widths. Furthermore, the method of prediction has been reduced to a simple and convenient graphical or numerical calculation. CRACKS IN A BRITTLE, ELASTIC MATERIAL Many investigators2, 4, 30 have shown that competent rocks behave elastically over some range of stresses. Of course, if the tensile stress imposed upon a rock exceeds some limiting value, then the rock will fail in tension. In similar manner, there are some limiting shear stresses that can be imposed upon rocks. Hubbert and Willis11 have discussed the shear conditions which will lead to failure. Under moderate stress conditions (such as those likely to be encountered when hydraulically fracturing) and when stresses are rapidly applied, relatively, most rocks will fail in a brittle manner. Hence, for this discussion of hydraulic fractures in the earth's crust, we assume the rocks behave as brittle, elastic materials. Let us develop the discussion in the following way. (The following thoughts are applicable only to brittle materials.) 1. First we consider a brittle, elastic system. An energy balance will show the minimum pressure necessary to fracture rock, and from this pressure we calculate the minimum crack width resulting from extension of a hydraulic fracture. 2. Then we will show that, under ordinary fracturing conditions, fracture widths are appreciably greater than the minimum widths of extending fractures. In fact, we will find that crack width is controlled by fluid pressure drop in the fracture. 3. We will discuss pressure drops in fractures and resulting crack widths for various operating conditions and both vertical and horizontal fractures. 4. Finally, we will discuss the significance of these concepts, their relationship to fracturing pressures, etc. First, consider minimum fracture extension pressures. We can shed some light on this question by considering the theory proposed by Griffith7, 8 Yo explain the rupture of brittle, elastic materials. Griffith recognized that solid materials exhibit a surface energy8 (similar to surface tension in a liquid). The fundamental concept of the Griffith theory is that, when cracks spread without the application of external work (in the interior of an elastic medium which is stressed

By R. F. Mehl, R. F. Bunshah

A fast amplifier technique has been developed for the measurement of the rate of propagation of martensite in an Fe-29.5 pct Ni alloy. The time of formation of one plate of martensite is 3x10 sec and the rate of propagation is 3300 ft per sec approximately. IT has been known for some time that the plate-like structural unit of martensite forms from austenite with great rapidity. Wiester1 and Hane-mann, Hofmann, and Wiester took motion-pictures of the transformation as it occurs in a 1.65 pct C steel; they demonstrated that a single plate formed fully in the time interval between successive frames, viz., 1/20 sec, thus setting an upper limit. Forster and Scheil,3 using an Fe-Ni alloy with 29 pct Ni, recorded the sonic characteristics of the process electrically, upon an oscillograph, setting the upper time limit at 0.002 sec. Forster and Scheil,~ measuring the change in electrical resistance in the same alloy upon a cardiograph, set a limit of 0.02 sec. Forster and Scheil5 later, employing the same alloy, improved their technique, reporting an upper limit of 7.10 sec. In studying signals of such short duration, it is an important question whether the frequency response of the electrical system used is high enough compared to frequency of the pulse measured, or, put differently, whether the system is able to reproduce without distortion the signal arising, in this case, from the formation of a single martensite plate. Forster and Scheil (referring only to their last paper) obtained signals of a frequency of 30 kilocycles (hereinafter kc); this was about the frequency response of the equipment used; thus, if the signal had a frequency higher than 30 kc, it would still appear as a signal of frequency 30 kc. All of these results thus provided upper limits only. Recent developments in electronics have made available equipment with very high frequency response, very high sweep-speeds, high gain, etc. The electrical characteristics of such equipment, used in the present study, are given in Table I. Such equipment offers obvious attraction in the study of the rate of propagation of a martensite structural unit—and perhaps of other structural alterations proceeding at a very high rate. This paper reports an attempt to develop a technique employing such equipment to measure the time of propagation of a martensite structural unit and the variation of this with temperature, with the mode of formation—athermal and isothermal—in both polycrystalline and single-crystal samples; and from such measurements to obtain the rate of propagation. As will be seen, the results obtained are useful theoretically. Materials All data presented here are for an Fe-Ni alloy of the following analysis: 29.5 pct Ni, 0.027 pct C, 0.135 pct Mn, 0.094 pct Si, balance Fe. There were several reasons for choosing this alloy: 1—it is substantially the one used by previous investigators; 2—it exhibits both the athermala and the isothermal' mode of formation of martensite, both studied in detail by Machlin and Cohen; 3—the subzero temperatures of transformation in this alloy are experimentally very convenient; 4—it exhibits the "burst phenomenon";" 5—the change in electrical resistance upon the formation of martensite, a decrease, is great, approximately 50 pct.' The polycrystalline specimens were in the form of wires of 0.025 in. diameter; the single crystals were 1x1/4x1/4 in. Experimental Methods Electrical Apparatus: Fig. 1 is a schematic drawing of the electrical circuit used. The principle used in these measurements is the same as that used by Forster and Scheil." A small direct current, about 1 to 2 amp, is passed through the sample. When a martensite plate forms, the resistance of the sample changes and a high frequency signal is generated. This signal is picked up by the probes attached to the sample, fed into the bank of amplifiers and thence to the vertical deflection plates of a cathode-ray oscilloscope. The signal itself triggers the oscilloscope trace which flashes across the tube face and is photographed by means of a 35 mm movie camera at the end of a light-tight hood. The camera has no shutter. As soon as the signal flashes

Jan 1, 1954

By M. A. Grossmann

THE hardenability of most steels can be predicted within 10 to 15 per cent provided the complete chemical composition is known, including "incidental" elements; and provided the as-quenched grain size is known; and provided, finally, that the composition and heating temperatures for hardening are such as to result in austenite free from carbide particles. In method proposed herein, the steel is considered as having a base hardenability due to its carbon content alone (the hardenability of a ''pure steel" of the given carbon content, without any other elements), and this base hardenability is multiplied by a multiplying factor for each chemical element present. After multiplying all these together, the final product is the hardenability. Grain sue may be taken into account either in the base hardenability or after the multiplication. Hardenability is stated in terms of "ideal critical diameter"; namely, the diameter of bar, in inches, that will just harden all the way through (absence of un- hardened core) in an "ideal" quench, and the calculation may also be related to the Jominy test. The data bring out certain features rather clearly. For example: I. It is quite useless to attempt to predict hardenability unless all elements, including "incidentals," are known; thus an "incidental" chromium content of 0.20 per cent increases the hardenability by about 50 per cent. 2. The relative effectiveness of different alloys is sometimes unexpected; thus molybde- num when calculated in this way appears to be of the same order of effectiveness as manganese, rather than much more powerful as wouldappear to be common experience; observe that an increase from no manganese to 0.20 per cent Mn provides a multiplying factor of 1.67, and an increase from no molybdenum to 0.20 per cent Mo provides a factor of 1.63, an increase of over 60 per cent in each case. However, if to a steel containing 0.50 per cent Mn there is added " 20 points of manganese," the factor is raised from 2.65 (for 0.50 per cent Mn) to 3.35 (for 0.70 per cent Mn), or an increase of only 26 per cent. Thus the first small addition of an element has a much more powerful percentage effect than an equal further addition when some is already present, and in most cases the effect of molybdenum is considered in relation to a steel in which molybdenum is absent. 3. If two elements are equally effective, a greater hardenability will be obtained by using, for example, 0.5 per cent of each than by using 1.0 per cent of either of them alone. 4. A knowledge of the as-quenched grain size is essential for precise work, since a difference of only one grain size number (say No. 7 instead of No. 6) makes a difference of almost lo per cent in hardenability (in these units); this, however, does not apply to certain steels of high hardenability. It should be emphasized that in chromium steels (over 0.30 per cent Cr) and chrome- molybdenum and chrome-vanadium steels, undissolved carbides are likely to be present in the steel as quenched, and that in such cases the charts can indicate only a maximum possible hardenability, whereas the extent of hardening actually obtained may be much less. Thus tests on a number of chrome-molybdenum steels have indicated a degree of hardening amounting to only 50 to 65 per cent of the maximum possible, and in chromium steels from full hardening (100 per cent) down to as low as 70 per cent. On the other hand, when the amount of such elements is small (Cr under 0.30 per cent, Mo up to 0.25 per cent in the absence of Cr, and V up to 0.04 per cent), the charts provide reasonable approximations. The precise figures on the charts are suggested as tentative, subject to some modification as more data accumulate, but the fundamental concept appears to be supported by tests made on a wide variety of steels, a few of the correlations being shown in Fig. I.

Jan 1, 1942

By R. Simon, D. J. Graue

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

Jan 1, 1966

By Alan J. Strauss

The Group IV elements germanium, tin, and lead form nine 1:1 compounds with the Group VI elements sulfur, selenium, and tellurium. This paper reviews the properties of the pseudobinary solid solutions formed by these compounds, including the extent of mutual solid solubility, temperature-composition phase diagrams, transport properties, deviations from stoichiometry, optical properties, and energy band structure. Particular emphasis is placed on the Pbl-xSnxTe and Pb1-xSn,Se alloys with rocksalt structure, because of current interest in these malerials for generating and detecting infrared ,radiation. ThE Group IV elements germanium, tin, and lead form nine 1:1 compounds with the Group VI elements sulfur, selenium, and tellurium. Some of the physical and electronic properties of these compounds, including their melting points1-8 and energy gaps,4'9-12 are listed in Table I. Four compounds (SnTe, PbS, PbSe, and PbTe) have the cubic rocksalt (Bl) structure. At room temperature GeTe has a rhombohedra1 structure closely related to the B1 structure, into which it is transformed at about 400°C. Four compounds (GeS, GeSe, SnS, and SnSe) have the orthorhombic B29 structure. In samples which have not been intentionally doped with impurities, the electrical conductivity is due primarily to electrons or holes produced by the ionization of donor or acceptor lattice defects associated with deviations from stoichiometry. Undoped samples of PbS, PbSe, and PbTe may be either n type or p type, depending on whether they contain excess lead or an excess of the Group VI element, respectively, but only p-type samples of the other compounds have been reported. This paper will review the properties of the pseudo-binary solid solutions formed by the nine 1:l compounds. The topics to be considered include the extent of mutual solid solubility, temperature-composition phase diagrams, transport properties, deviations from stoichiometry, optical properties, and band structure. Particular emphasis will be placed on the Pb]-xSnxTe and Pbl-xSnxSe alloys with B1 structure, which are promising materials for generating and detecting infrared radiation in the 8 to 14 µm atmospheric window and beyond. MUTUAL SOLID SOLUBILITY The extent of mutual solid solubility in the pseudo-binary systems has been investigated for fourteen of the eighteen ternary systems (in which the two terminal compounds have a common element) and for nine of the eighteen quaternary systems. In most cases, X-ray diffraction measurements made at room temperature were used to determine the structure and lattice parameter(s) of the phase(s) present in samples of various compositions prepared by freezing from the melt. In many investigations, including the extensive studies of Krebs and co-workers,13'14 the samples were annealed at elevated temperatures before X-ray measurements were made. In some cases, metallographic examination and thermal analysis have also been employed. The results for the ternary and quaternary systems are summarized in Tables II and III, respectively. (The original references should be consulted for the annealing temperatures.) The solubility of one compound in the other is at least 5 mol pct in all cases, and is often much larger. Complete solid solubility has been observed in all systems so far investigated in which the terminal compounds have the same structure, although in the PbS-PbTe system complete solubility is limited to elevated temperatures. Thus complete solid solubility occurs in five systems where both compounds have the B1 structure (SnTe-PbTe, PbS-PbSe, PbS-PbTe at temperatures above 805°C, PbSe-PbTe, and SnTe-PbSe) and in three where both compounds have the B29 structure (GeS-SnS. GeSe-~n~e-, and SnS-SnSe), as well as in two involving GeTe and a compound with B1 structure (GeTe-SnTe and GeTe-PbTe). On the basis of thermal analysis data, complete solid solubility at sufficiently high temperatures has also been reported for the GeSe-GeTe2 and SnS- pbS22 systems. This seems unlikely, however,

Jan 1, 1969

By Joseph L. Gillson

IT is a somewhat curious circumstance that the newest of the Institute's several awards should be conferred in the oldest of our several professional fields—for there is little question that geology and mining have antedated metallurgy and petroleum. Perhaps so did geophysics. After all, one geophysical instrument, the magnetic compass, has been successfully employed for many centuries. Young in years the Jackling Award may be, but in distinction—whether in terms of the title it bears or in terms of the first three medalists (Reno Sales, E. D. Gardner, and the late Father MaceIwane)—the Jackling Award is already one of the ranking awards of the Institute. The name of the 1957 medalist will bring added luster to an already illustrious roll. J. L. Gillson was born and brought up in Evan-ston, Ill., in an area characterized by singularly flat and uninspiring topography, and devoid of ore deposits and even of bedrock—a most unlikely environment from which to expect a future Jackling medalist to emerge! On graduating from high school he enrolled as a chemistry major at Northwestern University. At the end of his frkshman year his scholastic prowess had won him a prize of two chemistry books. But these went unread, for about this time he came under the spell of U. S. Grant, that distinguished and enthusiastic geologist who for many years was head of Northwestern's geology department. From thence forward Joe was a dedicated geologist. After a Navy interlude in World War I, he went to MIT for graduate work, substituted for the late Professor Palache for one year at Harvard in mineralogy, received his doctorate at MIT and stayed on as a meniber of the MIT faculty, where the geology department was headed by that great dean of all economic geologists, Waldemar Lindgren. In 1926 Joe spent a summer looking into barite deposits for the du Pont Co., and since 1928 he has been du Pont's chief geologist. Do men who lead such active lives in our exploration organizations generally have permission to publish their observations? Do they generally find time to publish, even if they have permission? Alas, no. But in Joe Gillson's case, yes. His bibliography runs to well over two score papers, including one of the very first papers in this country on the applications of petrography to problems of Portland cement. He has written on such topics as the origin of talc and the genesis of ilmenite, fluorspar, and alkaline rocks. Each year for a number of years his annual reviews of industrial minerals in the Mining Congress Journal have been eagerly awaited. - Do men who do so much to advance their science have anything left to give to the advancement of their profession? In Joe Gillson's case, yes. He has been a vice president of the Mineralogical Society of America and has been active in the councils of the Society of Economic Geology, particularly in their research programs. This year he is president of the American Geological Institute, currently perhaps the most challenging post to which a geologist may be elected. His contributions to AIME scarcely need documentation, so I shall mention only three—his chairmanship of the Committee on Democratization of the Institute, a committee whose work and recommendations brought a new and hopeful leaven to AIME at a time when this was sorely needed; his chairmanship, a few years ago, of the Industrial Minerals Division; and his current place on the Board of Directors as Vice President of the Institute. Such' a catalogue of contributions and achievement, even as condensed as I have had to make it, certainly merits the Jackling Award. Yet, implicit although not often expressed in the conferring of most awards is the hope that besides recognizing a distinguished career, it will provide stimulus for further effort. In the present instance, such an expectation is already well on the way to fulfillment. Only recently Joe Gillson has undertaken the editorship of a new and greatly revised edition of the Institute's Seeley Mudd volume, Industrial Minerals and Rocks. And so, Mr. Chairman, it is with pleasure and enthusiasm that I present Dr. J. L. Gillson for the 1957 Jackling Award.

Jan 1, 1958

By W. W. Stephens, W. J. Kroll, H. P. Holmes

THE only two methods for producing commercial quantities of malleable zirconium, up to now, have been using magnesium reduction of the anhydrous chloride under a neutral gas, and using purification of raw zirconium by the iodide dissociation method on a hot filament. The purity of the metal obtained by the latter process is about the same as that resulting from the chloride reduction, with the exception of the oxygen content, which may be about 0.05 pct lower in the iodide metal. Even traces of oxygen have a strong hardening effect on zirconium. Since, in the iodide process, the impurities, Si, Al, Fe, Ni, and Mg in the raw zirconium used, are carried over, it would appear uneconomical to use this method of refining solely to eliminate the traces of oxygen, unless very soft metal is desired. One important step to improve the iodide method, namely, dissociating pure iodide made from carbide and recycling the iodine, which would change this refining process into a method for extracting zirconium from the ore, has not yet been made. The Bureau of Mines, by using the chloride reduction, wanted to produce quantities of a reasonably pure and malleable metal at low cost for large-scale industrial use. This aim has been achieved, and a pilot plant permitting production of 600 lb of malleable zirconium per week will be described (fig. 1). Briefly, the Bureau of Mines process consists of reducing purified gaseous anhydrous zirconium chloride with fused magnesium under a noble-gas atmosphere. The reaction product, magnesium chloride, and any excess magnesium metal present are removed from the sponge zirconium in the next step by fusion and evaporation in a good vacuum at about 925°C. In this process, care is taken to keep air out of contact with the hot metal, which otherwise would contaminate the product with oxygen and nitrogen. Both these impurities embrittle zirconium even when present in an amount as low as 0.1 pct. A number of previous reports1-3 describe the method and the various improvements that finally led to a workable process. The major steps made were the production of large quantities of carbide, which is the raw material for producing the chloride, its chlorination with reasonable efficiencies, and the elimination of iron trichloride contained in the raw chloride, as well as that of the zirconium oxide which is always present in this product. The physical nature of the anhydrous chloride, which sublimes at 331°C at atmospheric pressure and melts at 420°C under a pressure of 25 atm, made it necessary to provide a special safety device on the purification and reduction vessels in the form of a lead-alloy seal, permitting escape of excess gases if pressure tended to build up. The main difficulties encountered in the reduction and in the following step, salt separation in a vacuum at elevated temperature, were caused by the material from which the reaction pot was constructed—iron. This metal reacts with zirconium at about 940°C with formation of a eutectic. The last step, salt separation by evaporation of the magnesium and magnesium chloride in a vacuum, is quite unconventional and has not been used before on such a scale. It is only due to the improved construction of high-vacuum pumps, especially oil-diffusion pumps, that such a method could be used. The various steps of the Bureau of Mines process, as described in the general outline above, may be summarized as follows: (1) production of the carbide, (2) chlorination of the carbide, (3) purification of the raw chloride, (4) reduction of the pure chloride with fused magnesium, (5) separation of excess magnesium and magnesium chloride in vacuum at elevated temperature, and (6) melting of the sponge obtained. Production of Carbide The arc furnace, described in a previous report,' was improved both to reduce the graphite consumption caused by the burning of the bottom plates and to concentrate the heat in order to obtain better power efficiency. This was achieved by providing the bottom with graphite plates entirely embedded in refractory bricks, the contact with the current being made with three water-cooled copper plugs. Figs. 2 and 3 show the arrangement. The crucible, made

Jan 1, 1951