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By M. I. Sherman, J. D. H. Strickland

USE of a hydrometallurgical approach to the oxidation of sulfide ores and extraction of metals therefrom may have advantages over the more common smelting techniques when a low grade deposit is difficult to concentrate or the subsequent separation of metals, coexisting in the ore, is laborious by any known smelting operation. For economic reasons, the most promising oxidants are either atmospheric oxygen or electric power. The use of oxygen, or air under pressure, has recently been revised. Pyrrhotite has been converted to iron oxide and elementary sulfur' and a variety of sulfides have been treated by Forward and co-workers.2-4 Generally sulfate is the end form of the sulfur but with galena in an acid medium, elementary sulfur can be formed." For economic reasons chlorine and ferric iron salts are about the only possible alternatives to the atmosphere as oxidizing agents for base metal sulfides. If aqueous solutions of chlorine or ferric iron are employed, the reduction products can be oxidized electrolytically in situ and used again, thus acting as catalysts for electric power as oxidant. The use of ferric salts for this purpose is established hydrometallurgical practicea but, although chlorine gas has been employed in the dry state at an elevated temperature, its use in aqueous solution at or near room temperature has not found favor. The reaction of chlorine water with the soluble sulfide ion has been studied by several workers,7-9 and both sulfate and elemental sulfur are found as end products, the latter being favored by the presence of a low concentration of oxidant relative to that of sulfide in solutions of about pH 9 to 10. Of direct bearing on the work in hand are an early American patent" and a recent Austrian patent." The former advocates stirring powdered ore with an aqueous solution of ferric chloride chlorine oxides and chlorine. In the latter it is claimed that both metal and sulfur can be obtained by electrolysis, in a diaphragm cell, of a metal ore slurry in brine. Details in these patents are scant and no data or explanation is given for the mechanism of the reaction which, in the Austrian work, is attributed to the (unlikely) action of nascent chlorine at the anode surface. No mention is made of possible differences in behaviour between various ores. Apparatus A complication encountered when working with chlorine water is that a serious loss of chlorine occurs by gas partitioning unless an enclosed system is used and any air space in the apparatus is kept very small and constant. Arrangements were made, therefore, to take out samples for analysis without letting air into the system to replace the liquid removed. For convenience in studying a heterogeneous reaction the apparatus was so designed that a reproducible controlled stirring rate could be maintained and the ratio of surface area of ore to volume of solution was approximately constant throughout any experiment. The apparatus used is shown in Fig. 1. The ground ore was placed in the horizontal cylindrical vessel, A, of about 1 liter capacity, heated by a constant temperature circulating bath pumping water through the concentric jacket, B. By adding chro-mate to this water, an ultraviolet radiation filter effectively surrounded the reaction vessel, greatly reducing any possible photochemical decomposition of chlorine solutions. Stirring was effected by glass paddles, C, attached by an axle to a magnet which was rotated by another powerful Alnico magnet, D, outside the glass end, this magnet being itself rotated by an electric motor electronically controlled to constant speed. Speed could be varied from about 150 to 900 rpm and was measured and held to within 1 pct of a given value. The end of the reaction vessel remote from the stirring magnet was closed by another one-ended glass cylinder, E, connected by thin polyethylene bellows, F, clamped by screw clamps and watertight rubber gaskets to the main vessel. Through E, a glass electrode and calomel electrode projected into the solution and a hypodermic syringe pierced a small bung and allowed acid or alkaline to be added to maintain a constant pH. By pushing the fully extended bellows until the two cylinders touched, from 50 to 100 ml of solution could be forced out through a sintered disk into the three-way tap system, G, either to waste (for flushing purposes) or up into a 10 ml burette where the solution could subsequently be measured out for analysis. The ore samples were introduced at H, the tube being stoppered by a thermometer of —1 to +52ºC range, graduated to 0.1°C intervals. To prevent ore from being ground in the end bearings of the stirrer these bearings were pro-

Jan 1, 1958

By A. R. Troiano, W. J. Barnett

IN recent years the demands of space limitations and increased loads, particularly in the aircraft industry, have accelerated the trend toward utilization of ultra-high strength steels. The increased application of such steels has focused attention on the phenomenon of delayed failure or static fatigue. Parts subjected to a static load, after successfully sustaining the load for an extended period of time, may fail in a brittle manner. Subsequent examination of such failed parts by conventional laboratory tests in many cases reveals no apparent signs of embrittle-ment. That is, the material exhibits good ductility and impact resistance. Furthermore, consideration of the service conditions (environment and temperature) under which this brittle failure occurred eliminates its classification as a stress-corrosion or creep type of failure. Recently this unique time dependent fracture process has been the subject of numerous investigations. The most significant result of these studies was the recognition of hydrogen as the source of embrittlement. While the effect of numerous variables on the occurrence of static fatigue failure has been defined, an adequate explanation of these behaviors is lacking. The occurrence of this phenomenon in steels generally has been limited to strength levels in excess of 180,000 lb per sq in. Although steels at high hardness levels have exhibited delayed failure in the absence of hydrogen introduction after heat treat-ment,'.' this behavior was most prevalent when the material in processing had been subjected to an environment conducive to the absorption of hydrogen. Delayed failures have been produced in high strength steels by the introduction of hydrogen

Jan 1, 1958

By J. L. Huitt, IM. L. Slusser, E. E. Glenn, M. L. Slusser

This paper is concerned with: (1) an analysis and interpretation of the filtration characteristics of drilling muds on filter paper, and (2) an interpretation of early stage "filtration" on consolidated synthetic porous media, herein referred to as the "surge loss" period. It is shown that water-loss data can be plotted so as to disclose the existence of a surge period, a non-uni-form cake thickness period, and a constant pressure filtration period. The same periods occur during exposure of consolidated porous media to muds. The data on consolidated porous media indicate that: (1) mud particles bridge pores inside porous media during the surge period, and (2) "filter cake" build-up inside porous media occurs during subsequent filtration. The data also show that the surge loss increases with sample permeability and with pressure differential. INTRODUCTION The phenomenon of mud filtrate invasion into porous sands of a drilling well has been recognized for many years.1,2,3,4 Part of API Code 29 is concerned with the filtration testing of a drilling mud to yield data on this subject. In a number of investigations "plastering properties" of muds were studied,5,6,7,8 "plastering" apparently meaning cake forming properties. In such studies the characteristics (thickness, permeability, and toughness) of the cake and the rate at which the liquid phase of the mud was separated from the solids (filtration rate through the cake, commonly referred to as water loss) were measured or at least considered. From the standpoint of its effect on well productivity, filtrate invasion into "clean" water-wet pay sands (i.e., those containing no clay minerals) may not necessarily be a serious problem. An increase in water saturation in the zone immediately around the wellbore would cause loss of oil permeability. However, in such a system, much of this water may be removed by oil production. If filtration occurs into "dirty" sands (i.e., those containing appreciable clay minerals), clay swelling or other mechanisms may cause losses in oil permeability which cannot be overcome by oil production.'.' The phenomenon of mud particle invasion into the pay sand of a drilling well was considered to be a possible serious factor in the early days of rotary drilling. Opinions varied as to whether drilling fluids "mudded up" and "sealed" oil sands. In 1932 Rubel,9 Gill,10 and Parsons," in separate papers, presented differences of opinion together with some laboratory and field data concerning loss of oil production caused by drilling fluid invasion into pay zones. These papers, and the discussions, furnish a large background on this subject and indicate the very clear thinking of many men at a time when petroleum production technology was in its infancy. Jones and Babson,6 and Silent,' experimentally found that the depth to which mud particles invaded water-saturated sand packs was small (no greater than 1/16 in). Arn-quist12 in 1937 observed loss of water permeability due to invasion of mud particles into water-saturated, consolidated, sandstone samples. Williams and Cannon5 studied the filtra-tion properties of drilling muds and mentioned "sludge" which penetrated a short distance into the water-saturated filtering medium (sand pack). Byck5 concluded that formation permeability had no effect on the plas-

Jan 1, 1958

By W. W. Eckles

This paper is presented as a suniniary report of the use of well gas composition correlations obtained from mass spectrometer recordings as a means of identification and determination of reservoir continuity. Conventional methods for detecting composition differences are en-pensive, elaborate, and difficult to obtain. This excludes the use of extensive composition data for most applications. During recent years the mass spec-trometer has come into general use as an analytical tool in petroleum refineries. The use of mass spectrometer composition patterns ir~ characterizing or "finger-printing" the produced gas from a reservoir, presents a novel method for correlatitlg gas samples from well to well. The mass spectrometer provides a trace similar to an electric log. having peaks which represent the abuntlnnce of certaitz hydrocarbons in the well gas sample. Without going further into the detailed analysis the idea has been advanced that these traces or patterns could be used as a means of identifying a particular natural gas. This theory has proven to be essentially correct. The mass spectrometer pattern method is simple and cheap as COi?7pared to other standard methods. It greatly facilitates the solution of reservoir and geological problems in which correlation of well gas Com-positions is a factor. Specific field applications have been made. This paper concerns the results obtained in 465 individual gas analyses from 35 fields and 77 res- ervoirs. In a number of cases it has been found that such data have been extremely valuable in the determination of reservoir continuity. In at least one case, the method was a valuable contribution in tracing a reservoir from sand to sand in a coinplex fnulted field involving n11rnerous gas reservoirs. Field applications are presented to illustrate the possibilities of the method at the present stage of developnient and to stimulate the ernployrnent of this new approach by geologists and petroleum engineers in the industry. INTRODUCTION Identification of producing horizons and the determination of reservoir continuity are often a problem in those areas where dome structures and highly faulted sands are encountered. To complicate the picture further, there may be numerous sands, one on top of the other which dip and diverge in different directions. Even though it may be possible to develop some solutions to the preceding problems on the basis of the geological and reservoir data on hand. it is readily recognized that substantiating data based on independent methods would he extremely valuable. It has been found through field studies that correiation of well gas composition can be used to advantage in the geological and engineering study of a complex reservoir identification problem. METHOD FOR COMPARISON AND CORRELATION OF WELL GAS SAMPLES Since a large number of well gas samples are required in a gas identification or reservoir con- tinuity problem, it is necessary that a method of analysis be employed which can detect differences in composition readily and inexpensively. Although detection would be possible by means of low temperature fractional distillation (POD) analpsis, the method requires a relatively large sample and is comparatively slow and expensive to run. The mass spectrometer affords an inexpensive and precise analysis of small well gas samples taken at the surface which are about 1/300 as large as a POD sample. These samples can be obtained by regular field personnei and shipped to the spectrometer for analysis. It is, therefore, a practical approach to the problem. A typical record from the mass spectrometer is illustrated in Fig. I. The peaks on the record represent the abundance of ions produced from the different hydrocarbon molecules making up the gas sam-ple. In well gas comparisons only five peaks are employed, since the other peaks are formed from the same gas molecules and furnish no additional information. The five peaks used represent the abundance of methane, propane, ethane, butane and heavier, and oxygen. They are referred to respectively as the 16, 29, 30, 43, and 32 peaks. The oxygen peak is used to correct for air content in

Jan 1, 1958

By Eugene T. Sheridan

The 24th annual survey of the peat industry by the Bureau of Mines, United States Department of the Interior, revealed that 76 producers in 20 States reported commercial production of peat in 1957. In addition to the States that reported production in 1956, Colorado, Idaho, and Wisconsin produced peat in 1957 Forty-four producers reported humus production; 21, reed-sedge peat; and 22, moss peat production. This total exceeds the number of active plants but several producers recovered more than one type of peat. Fifty percent of the total production was reported as reed-sedge peat, 36 percent as humus, and 14 percent as moss peat. About one-sixth of the total production was raw peat, with no preparation other than being air-dried. The remainder consisted of processed peat prepared for use by cultivation, shredding, and/or kiln drying.

Jan 1, 1958

By L. F. Stutzman, George Thodos

A new graphical method, which is a modification of that proposed by Buckley and Leverett', is presented for the determination of the displacing fluid saturation at breakthrough for frontal drive mechanisms. This method is applicable to all types of fluids, which may be either soluble or insoluble in the oil at reservoir and injection conditions. This adaptation has unique advantages in handling problems in which either liquids or gases are the displacing fluids. INTRODUCTION In the displacement of oil from a reservoir with water or gas injected into the formation or by the expansion of a gas cap, the determination of breakthrough or flood advance is important to define the initial and subordinate phases of the operation. Thus, the determination of the displacing fluid saturation at breakthrough is fundamental to the establishment of over-all reservoir production. Methods for analyzing this saturation and for calculating production rates have been previously reported1,'*".". All of these methods utilize the rate equation for linear flow developed by Buckley and Leverett1. xs = QT - Qn/A? (?fu/?Su) .....(1) Sp where f, represents the volumetric fraction of displacing fluid in the total flowing fluid within the reservoir as is defined by: fo = 1/1+ ku/kd µn/µn .......(2) Since the time, ?, necessary for the flood front to travel distance ?X is unknown, Eq. 1 cannot be solved directly for the determination of the breakthrough point. Therefore, it becomes necessary to solve Eq. 1 simultaneously with an equation representing a fluid bal-ance on the reservoir behind the flood front. To develop such a fluid balance equation, it has been assumed that the fluid composition is uniform in the reservoir behind the flood front. Based upon this assumption, the follow-ing equation can be derived from a material balance on the displacing fluid: x = (?X) s Dx ? x=0 [ Snx - Sn1 ] dx = QT - Qn/A? It is readily observed that the displacing fluid satura-tion behind the flood front, Snx, may be determined through the simultaneous application of Eqs. 1 and 3. Although the approach may vary, this objective re-mains the same for all of the previously mentioned graphical or analytical methods. After Sox is determined, it is then possible to calculate the gas-oil and/or water-oil ratios and the rates during the initial and subordinate phases of production, and thereby define the production history of the reservoir. In this presentation only the de-termination of Snx is considered, and the reader is re-ferred to the several texts in reservoir engineering2,4,5 for a complete discussion on the methods for establish-ing the production history of a reservoir. PROPOSED METHOD FOR DETERMINING Snx Since at any time the quantity, QT - Qn/A? is a constant, Eq. 1 may be expressed in differential form as follows: dxsn = QT - Qn/A? d (? fn/? Sn) sn .....(4) Eq. 4 may be substituted directly into Eq. 3 to obtain: ? fn/? Sn ? [ Snz - Sn] QT - Qn/A? d ( ? fn/? Sn) = QT - Qn/A? ...............(5) Eq. 5 simplifies to the expression: ? fn/? Sn ? [ Snz - Sn] QT - Qn/A? d ( ? fn/? Sn) = 1 ....(6)

Jan 1, 1958

Jan 1, 1958

By M. King Hubbert, David G. Willis

A theoretical examination of the fracturing of rocks by means of pressure applied in boreholes leads to the conclusion that, regardless of whether the fracturing fluid be of the penetrating or non-penetrating type, the fractures produced should be approximately perpendicular to the axis of least stress. The general state of stress underground is that in which the three principal stresses are unequal. For tectonically relaxed areas characterized by normal faulting, the least stress should be horizontal; the fractures produced should be vertical with the injection pressure less than that of the overburden. In areas of active tectonic compression, the least stress should be vertical and equal to the pressure of the overburden; the fractures should be horizontal with injection pressures equal to or greater than the pressure of the overburden. Horizontal fractures cannot be produced by hydraulic pressures less than the total pressure of the overburden. These conclusions are compatible with field experience in fracturing and with the results of laboratory experimentation. INTRODUCTION The hydraulic-fracturing technique of well stimulation is one of the major developments in petroleum engineering of the last decade. The technique was introduced to the petroleum industry in a paper by J. B. Clark,' of the Stanolind Oil and Gas Co. in 1948, and since then its use has progressively expanded so that by the end of 1955 more than 100,000 individual treatments had been performed. The technique itself is mechanically related to three other phenomena concerning which ah extensive literature had previously developed. These are: (1) pressure parting in water injection wells in secondary-recovery operations, (2) lost circulation during drilling, and (3) the breakdown of formations during squeeze-cementing operations, all of which appear to involve the formation of open fractures by pressure applied in a wellbore. The most popular interpretation of this mechanism has been that the pressure had parted the formation along a bedding plane and lifted the overburden, notwithstanding the fact that in the great majority of cases where pressures were known they were significantly less than those due to the total weight of the overburden as determined from its density. Prior to 1948, this prevalent opinion had already been queried by Dickey and Andresen,2 in a study of pressure parting; and by Walker,"' who, in studies of squeeze cementing, pointed out that the pressures required were mostly less than those of the overburden, and inferred that the fractures should be vertical. J. B. Clark,' in his paper introducing hydraulic fracturing, and later Howard and Fast," and Scott, Bearden, and Howard," also of Stanolind, postulated that the entire weight of the overburden need not be lifted in producing horizontal fractures, but that it was only necessary to- lift an "effective overburden," requiring a correspondingly lower pressure. Hubbert,7 in discussing the paper by Scott and associates, pointed out that the normal state of stress underground is one of unequal principal stresses; and in tectonically relaxed areas, characterized by normal faults, the least stress should be horizontal. Therefore, in most cases, fracturing should be possible with pressure less than that of the overburden and, moreover, such fractures should be vertical. Harrison, Kieschnick, and McGuire,8 also on the expectation that the least principal stress should be horizontal, argued strongly in favor of vertical fracturing. Scott, Bearden, and Howard6 observed that, when

Jan 1, 1958

By Robert J. White

Strong's equation for calculating bottom-hole pressure reduction due to gas cutting of drilling mud is corrected, resulting in a simpler equation which is easier to use. Use of the equation is illustrated by examples. It is shown that reduction of weight of a 10 lb/gal mud by 50 per cent at the surface due to gas cutting produces only n 3 per cent decrease in hydrostatic head at the bottom of a 5,000-ft well. It is also shown that at the surface 5 volumes of air per volume of mud are required to reduce the apparent mud weight from 8.5 to 6.5 lh/gal in a 3,000-ft well. Illustrative graphs are included to show the effect of various degrees of gas cutting on apparent mud weight at depths of 2,000, .5,000 and 10,000 ft and to show variation of apparent mud weight, with depth for a 100 lb/cu ft (13.37 lb/gal) mud gas cut to 90 lb/cu ft (12.03 lb/gal) at the surface. INTRODUCTION In 1938, Strong' published the following equation for calculating reduction in bottom-hole pressure due to gas cutting of drilling mud h = 1/D [p + pn/100 In p + p(1-n/100)/p(1- n-100)] where: h = depth in feet P = pressure in atmospheres at depth h due to mud column only D = hydrostatic pressure in atmospheres of a col-umn of uncut mud 1 ft high p = back pressure at well-head (in atmospheres) n/100 = fraction by volume of gas in mud at well-head at back pres-sure p This equation was recently found to contain an error due to an incor-rect expression for variation of vol-ume fraction of gas with pressure. Values calculated by the original equation are close to the correct values for small percentages of gas for which it was derived but become increasingly erroneous as the gas content increases and are completely unusable at the very high gas con-tents employed in aerated mud. DERIVATION The nomenclature used is the same as in Strong's paper. The pres-sure dP exerted by a lamina of thickness dh at a depth h ft is ex-pressed by Eq. 1 where x = volume fraction of gas at depth h dP = D (l - x)dh . . . (1) When we express x in terms of the wellhead per cent gas n, the well-head pressure p and the pressure P at depth h, the result is Eq. 2. x = (np/p+p)/(100-n) + (np/P + p) When this is substituted in Eq. 1 and rearranged to separate the var-iables the result is dh = 1/D [dp + np/100-n dp/(P + p]. Integration between appropriate lim-its results in or if the wellhead is open so that p = 1 atm and we rearrange Eq. 4, the result is loss in head = hD — P = n/100-n In (P + 1) ...(5) Eq. 5 can be solved easily by successive approximation using hD as a first approximation for P on the right-hand side and calculating a first value for loss in head. This can then be used to get a new value of P using the left-hand side of the equation. Values converge very rap-idly even for quite large values of per cent by volume gas n. EXAMPLES The effect on bottom-hole pressure of 50 per cent gas cutting of the mud in a 5,000-ft well using 10 Ib/ gal mud will be calculated, we have: h = 5,000 ft 10 X 7.48 144 X 14.7 = 0.0353 atm/ft hD = 176.5 atm n = 50 Substituting these values in Eq. 5 and using hD as a first approxima-tion of P on the right, we have, approximate loss in head = 50/50 In (176.5 + 1) = 2.30 log 177.5 = 5.17 atm. We calculate a new value of P as follows:

Jan 1, 1958

By W. M. Reilly, Martin E. True, O&apos

A technique, equipment, and a compound have been developed and field tested for sealing tubing joint thread leaks without removing the tubing from the well. This eliminates the necessity of killing the well with possible damage to the producing formation, which could result if it were exposed to drilling mud. A thread sealing compound, developed and tested in the laboratory, is introduced into the tubing and squeezed into the joint to eliminate the leak. A high percentage of successful field applications have eflected an appreciable cost reduction in repairing leaking tubing strings in East Texas and in the Louisiana Gulf Coast area. INTRODUCTION In producing oil and gas wells the industry has been plagued with a never ending problem of tubing connection leakage. This situation is becoming increasingly more significant as more gas wells are placed on production and as higher pressures are encountered at greater depths of current drilling. Substantial progress has been made in minimizing thread leaks by careful handling and cleaning of joints and by the use of improved sealing compounds in combination with controlled makeup. But even with the use of the best known methods and sealing materials during initial makeup, occasional leaks through tubing joint threads appear inevitable. In some instances, tubing joints in high-pressure gas wells have been found to leak gas at relatively less pressure than that at which the tubing had been tested satisfactorily using liquid. Many expedients have been employed to prevent the physical replacement of tubing when leaks have developed. Perhaps the most commonly used is the sodium silicate treatment in which the solution is lubricated into the tubing to form a crystalline plug in the leak. Generally, any benefit realized is of a temporary nature. In addition to field studies on handling and makeup of tubing, extensive laboratory work has been undertaken on the development and testing of thread dopes.' Also, substantial effort has been devoted to testing tubing joints using high-pressure gas as a pressure medium.' The results of this work have emphasized that tubing joints are susceptible to occasional leaks, especially when subjected to relatively high differential pressures. To cope with the problem of leaking connections, an extensive investigation was undertaken to devise means of sealing leaks without removing the tubing from the well and without reducing the inside diameter of the tubing. The purpose of this paper is to present a technique, together with the associated equipment and compound, which have been developed for effecting a seal of leaking tubing in place. DISCUSSION Work was initiated simultaneously on two ventures: (1) to develop a satisfactory leak sealing compound and (2) to develop tools necessary to find the leak and place the compound. Leak Sealing Compound In the development of a sealing compound, tests were conducted on those compounds commercially available which include: (1) conventional thread lubricants, (2) thermo-setting resins and (3) other materials which held promise of effecting a seal. Although none proved completely satisfactory in their available form, two commercial compounds proved nearly equally effective in sealing leaks during laboratory tests after proportioned quantities of graded silica had been added. Field usage has indicated that the preferred compound is one prepared of an aluminum-stearate base thinned to the proper constituency and carrying a mixture of fine mesh graphite and graded silica. The compound developed by Humble Oil & Refining Co. is designated as Tubing Thread Leak Sealant 800. Placement Tools and Technique In developing tools to detect joint leaks and to place the sealing compound, work was done initially on wireline equipment. Preliminary designs were completed of a tool somewhat on the order of a pressure bomb to test individual joints with gas at high pressure to determine if the joint was leaking. An entirely different tool equipped with opposed packers was intended for placement of the sealing compound at high pressures in each leaking joint. The application of these tools

Jan 1, 1958

By T. H. Janes

THE POSSIBILITY of producing pig iron from iron ores of British Columbia for a west coast primary iron and steel industry has been investigated by the provincial government and by commercial interests on sever.al -occasions. The latest study is that currently under way by The Consolidated Mining and Smelting Company of Canada, Limited. The Company is studying the possibility of making pig iron from the oxide calcine resulting from the roasting of pyrrhotite. tailings used in making sulphuric acid for fertilizer production at Kimberley. A comprehensive report on the subject .of establishing a primary iron and steel works in the Province, based on local iron ores, was prepared by Arthur G. Mc-Kee and Company of Cleveland, Ohio, in 1942 for the B.C. Minister of Mines and is available to interested parties. A detailed survey on the subject was also pre-pared in 1954 by Dr. G. P. Con-tractor, then .of the British Columbia Research Council. Considerable information is there-fore available on most aspects of an integrated primary iron and steel industry in British Columbia to supply the needs of the western provinces. To date, however, no basic iron industry has been established despite the .occurrence of high-grade iron ore deposits on the offshore islands and the high freight charges on iron and steel products brought into the area from Eastern Canada and overseas producers. The chief deterrent has always been the relatively small and highly diversified market available to a local steel producer. Other major fact-ors have been the lack of sufficient proven reserves of iron ore, and the difficulty of making pig iron, suit-able for steel manufacture, economically on a small scale. Technical and economic conditions have changed considerably since World War II and the establishment of a primary industry based on electric furnace production of pig iron or on one of the direct reduction processes, coupled with electric furnace steel production, may now be economically feasible.

Jan 1, 1958

By John C. Machisak

Employment and related injury experience of the coking industry in the United States for 1956 contained in this publication is summarized under three general sections: (A) General injury experience: Tables 1 to 9: Current and comparable statistics on operating data, number, frequency, and degree of severity of injuries and major accident agencies involved in the cause of injuries. Data are presented for the industry as a whole, for each type of oven, and for the States in which coke was produced. (B) Selected injury experience: Tables 10 to 15: Comparable injury data covering 5- and 10- year periods on the number and degree of severity of injuries and major accident causes.

Jan 1, 1958

By D. S. Dinsmoor

Boron, estimated to comprise about 0.001 percent of the earth's crust (Fleischer 10), as an element is never found free in nature, although its compounds are found in many localities. the borates are the most important. Sassolite (B(OH)3) and boracite (Mg6C12B1406), non-borates, are-of-minor importance. The crystal structures of most natural borates are still unknown. A classification based solely on the ratio of boron to the total number of cations has been devised (Palache 28). This classification divides the borates into four, sub-groups; anhydrous borates, hydrated borates, borates containing hydroxyl or halogen and compound borates. Only four or five minerals of the hydrated borates group have ever been used commercially. In more recent years, the sodium borates have comprised all but a 'small fraction of all borates used. Borax, the hydrated borate compound, is the most important of all boron compounds. It has been used so long and so often that the layman often confuses borax and boron and, applies the terms synonymously.

Jan 1, 1958

By A. D. Pittuck

Refractory minerals .containing uranium and columbium have been successfully treated at Queen's University, Kingston, to produce high-grade concentrates. Recoveries of over 90 per cent of the uranium and columbium have been obtained when treating concentrates containing euxenite, fergusonite, betafite, and pyrochlore. The processes ?consisted -of leaching the columbium with hydrofluoric acid, and the uranium with nitric acid, sulphuric acid, or sodium carbonate solutions. The leach liquors were extracted with organic solvents from which the values were stripped and precipitated, producing final products assaying 45 to 55 per cent Ob2O5 and 60 to 70 per cent U3Os.

Jan 1, 1958

By J. H. Westbrook

UNTIL very recently the development of high temperature alloys has been strictly empirical. It is, in fact, a great tribute to the intuition, perseverance, and industry of the practicing metallurgists of this country and abroad that the amazing increases in gas turbine service temperature over the past 15 years have been achieved with so little fundamental knowledge. The result of this development has been the realization of successful but highly complex alloys possessing five, six, or more alloying elements and correspondingly complex microstructures. Within the last few years, considerable effort has been devoted to the identification of the secondary phases in these alloys and to the correlation of the presence or absence of such phases with alloy properties. Little attention, however, has been given the problem of identification of the mechanism (s) by which such phases enhance the properties of the alloy and especially to the assessment of the particular properties of the secondary phase (either in- trinsic or relative to the matrix phase) which are basically responsible for the improvement. Conceivable mechanisms which might apply include dispersion hardening and precipitation hardening. In both cases geometrical factors—particle size, dispersion, volume fraction, etc.—and agglomeration re-

Jan 1, 1958

By Lyle L. Marsh, David L. Douglas

CORRELATION was made between the heat treatment and hardness of three U-Ti alloys ranging in composition from 8.5 to 50 atomic pct Ti. The following important observations were made: 1) A direct quench of y U-Ti solid solution resulted in the formation of a hard martensitic phase in low-titanium alloys. 2) Subsequent tempering initially increased the hardness by the precipitation of a fine dispersion of U2Ti; further precipitation of U2Ti with tempering time eventually resulted in softening. 3) High-hardness levels were obtained also by isothermal transformation of an 8.5 atomic pct Ti alloy at 400º and 500°C. 4) The crystal structure of the phases present at the solution-treating temperature (one region in the phase diagram excepted) and the temperature within a given phase region affected the hardness of both quenched and isothermally transformed alloys. Introduction It has been known since 1887 that the mechanical properties of metals were dependent upon their microstructure. Sorby pointed out in that year that annealed gray iron castings were softer than chilled iron castings by virtue of the graphite which had replaced hard cementite in the microstructure. Over the years, interest has increased in the effect of microstructure on the mechanical properties of metals, and now high-strength levels may be achieved by bringing about the dispersion of a second phase or by other microstructural adjustments. The nature of a second phase in an alloy strongly influences the properties. For example, the size, shape, amount, and distribution of a second phase plays a very important role in the ultimate properties of an alloy. Microstructural control is achieved by heat treatments. Hence, any alloy system of potential use should be understood in terms of its response to heat treatment and the resultant effects upon the properties.

Jan 1, 1958

By K. P. Anderko

INVESTIGATIONS of the constitution of the system Mg-Ba were first made by Grube and Dietrich1 between 0 and 47 atomic pct Ba and then by Klemm and Dincke1acker" ver the whole composition range. Klemm and Dinckelacker corroborated intermediate phases of the approximate formulas Mg9Ba and Mg4Ba, and showed a third compound to have the formula Mg2Ba, rather than Mg5Ba, as suggested by Grube and Dietrich. Mg2Ba had been previously recognized by Hellner and Laves3 s a MgZn2 (C14) type structure. The main discrepancies between the results of Grube and Dietrich and those of Klemm and Dinckelacker exist, however, in the liquidus temperatures and solidification equilibria of alloys containing more than about 10 atomic pct Ba. The liquidus temperatures measured by Grube and Dietrich, and the outline of the liquidus of Klemm and Dinckelacker are plotted in Fig. 1 on an enlarged scale. Although there are strong reasons to prefer the results of Klemm and Dinckelacker, it was considered worthwhile to remeasure liquidus temperatures of some alloys in the controversial composition range. The alloys, made up from sublimed magnesium and 99.5 wt pct pure barium, were melted in an Armco-iron crucible in a dynamic argon atmosphere. Thermal analyses were taken using a Speedomax auto- matic recorder. Careful stirring during the solidification process was required in order to avoid segregation. After thermal analysis some of the cast alloys were chemically analyzed. The intended and analyzed compositions of the ten alloys prepared are listed in Table I. Since standard barium determinations cannot differentiate between barium present as element and as oxide, both the barium and magnesium contents of the alloys were analyzed. The fact that the sum of barium and magnesium was close to 100 pct in each case was taken as evidence that no excessive oxidation had occurred. The liquidus temperatures measured are listed in Table I and plotted in Fig. 1. As can be seen, they are in good agreement with the liquidus found by Klemm and Dinckelacker. This leaves no doubt that the thermal results of Grube and Dietrich above 10 atomic pct Ba are incorrect. This work was performed under the sponsorship of the Pitman-Dunn Laboratories of Frankford Arsenal, Philadelphia, Contract No. DA-11-022-ORD-1975. Sponsorship and permission to publish by this organization are gratefully acknowledged.

Jan 1, 1958

By A. Kaufmann, B. Cullity, G. Bitsianes

T0 determine the bulk of the phase diagram, techniques for melting, thermal analysis, heat treatment, metallography, and X-ray diffraction that have already been described were used.' It proved difficult to get definitive results for most of the alloy system because of the large number of compounds, their high melting points, and their extreme brittle-ness which made metallography difficult. The final phase diagram, essentially as shown in Fig. 1, was issued with considerable trepidation.' The phase relationships at the two ends of the system were defined with satisfactory accuracy. In the central region between U,Si, and USi, there was great uncertainty concerning the melting points and even the composition of the compounds. At the uranium end of the system, it is quite clear that a eutectic exists at about 985 °C and approximately 8 or 9 atomic pct Si. The a-to-8 transformation is not appreciably altered by silicon, but the 8-to-y transformation is raised to about 795°C. There is appreciable solid solubility in y-uranium, as demonstrated by the micrographs of Fig. 2. The occurrence of the E phase was not suspected at first, since the alloys as melted and furnace cooled gave no X-ray diffraction or thermal arrest indication of it. However, suitable metallography revealed a rim around each of the compound particles as shown in Fig. 3. Heat treatment above 600°C revealed that the rim was another phase which formed by peritectoid reaction between uranium and U,Si,. This reaction proceeds slowly and it is difficult to get it to go to completion. Consequently, there is some uncertainty concerning the exact composition of P and the exact peritectoid temperature. On the basis of various metallurgical studies, it was decided that the most probable composition for t was about 23 atomic pct Si. Metallographic examination shows the closest approach to a single phase at this composition. Likewise, density and hardness measurements of heat-treated alloys shown in Figs. 9 and 10 show a change in slope at 23 pct Si. This is revealed most clearly by plotting the difference in hardness or density between chill-cast and heat- treated alloys as shown in Fig. 4. Zachariasen2 was able to index the diffraction lines of P and to determine the arrangement of the atoms in the unit cell. He concluded that the composition must be US. However, it is felt that the metallurgical studies are reliable and that Zachariasen's X-ray work does not furnish positive proof that the P phase exists exactly at the stoichiometric composition U3Si. There are many instances in alloy systems where a phase does not occur at the composition dictated by the molecular structure. It is possible that the chemical analyses used in the present work were subject to some systematic error. This seems unlikely, however, since recent work in several laboratories seems to show excess compound at 25 atomic pct Si.

Jan 1, 1958

By F. H. Spedding

CONSIDERABLE confusion exists in the literature concerning the phase transformations exhibited by the lighter rare earth metals; namely, lanthanum,1-8 cerium,1,3,5,8,9-15 praseodymium,8 and neodymium.1,8,16,10 To obtain further information

Jan 1, 1958

By C. S. Roberts, S. L. Couling

PLASTIC strain in polycrystalline metal as a result of bulk movement of one grain with respect to another along grain boundaries is not new. Rosenhain and Humphrey observed such effects shortly after the turn of the century.' Since then, observations of grain boundary deformation have been made on several metals. In recent years, intensive studies of the deformation at grain boundaries have been performed on polycrystalline metal and bicrystals.14-20 Aluminum or its alloys have been used in these latter studies. The subjects of controversy at present appear to be not whether grain boundary deformation exists, but 1) how quantitatively important it can be in polycrystalline metal, and 2) what its detailed mechanism is. Some investigators have concluded that such de- formation is minor in importance while others have concluded that it is a major consideration. Some have concluded that it involves shear of one grain over another at the interface while others have concluded that it operates by crystallographic deformation within the grains near ,the boundary. A categorical statement for electrolytic magnesium cannot be made on either of -these points. When polycrystalline magnesium is deformed in creep under conditions of high strain rate and low temperature, grain boundary deformation is relatively slight." Under these conditions, much deformation occurs within the grains and boundary contours change to a higher-energy jagged form. The result is shown in Fig. 1, where boundary jaggedness is pronounced upon polishing and etching after a plastic strain of approximately 6 .pct at 300°F and 3000 psi. No migration of the boundaries has been detected in this process. When the same metal is deformed the same amount at 600°F and 300 psi, resulting in a much lower strain rate, the boundaries migrate toward a lower energy configuration, where

Jan 1, 1958