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By H. G. Doll

A new electrical logging method called Laterolog is described which provides for better recording of formation resistivity. In this method a current, preferably of constant intensity, is forced into the formation perpendicularly to the wall of the hole as a sheet of predetermined thickness by means of a special electrode arrangement and of an autonlatic control system. The essential advantages of the Laterolog over the regular resistivity logs are explained. With the Laterolog, the mud column has much less influence than with conventional methods. The Laterolog is, therefore. particularly useful in wells drilled with highly conductive mud. Moreover. when the electrode system is located opposite a bed of moderate or small thickness, the disturbing effect of the adjacent formations becomes practically eliminated, provided the bed is thicker than the sheet of current. which itself is usually a few inches to a few feet thick. The sequences of beds are. therefore, much more sharply differentiated, and, in many cases, it is possible to read directly from the logs values close to the true resistivities of the formations without further corrections. Field examples are shown to illustrate the results of the method in various types of formations. INTRODUCTION As soon as it was introduced into the petroleum industry, electrical logging roved to be a powerful instrument for the delineation of the strata traversed by bore holes and for correlation of such strata." Research and engineering efforts were mostly devoted at this early time to the design of the techniqurs which could provide the best data for these purpoes. Later, attention was directed toward the quantitative analy5i.s of electrical logs, in order to obtain information on. reservoir characteristics, and, in particular, on oil and water saturation.3,4 Efforts have been made, accordingly, with a view to improving the already existing methods, or to finding new methods which could satisfy these new requirements." Quantitative analysis implies a determination as accurate as possible of the true resistivity of the formations. In fact, however; the "apparent resistivity" recorded in front of a given bed by a conventional electrical logging method is frequently quite different from the true resistivity of this bed. This is due to the combined influence of the mud column, of the adjacent formations both above and below the bed, and of the invaded zone, in which the original fluid has been more or less replaced by mud filtrate. When the beds are thick enough, and, as is frequently the case in sand and shale formations, when their resistivity is not much greater than that of the mud, it is generally possible to obtain their true resistivity directly on the electric log, or at least to obtain an approximate value which can be corrected without undue difficulty by means of recently published charts known as "departure curves."" When the beds are thin, and particularly when, in addition. their resistivity is substantially greater than that of the mud column, the apparent resistivities recorded on conventional logs are seriously affected, and it is generally very difficult, if at all possible, to estimate their true resistivity with a good enough accuracy. In the most severe cases, such as are encountered in holes drilled through hard formations with muds of high salinity, the conventional logs are so distorted and rounded that they do not even show clearly the houndaries of the different beds. In order to overcome the effect of the mud column and of the adjacent formations, it is possible to make use of appro. priate systems whereby the measurements involve a comp3ratjvelv thin slice of space at the level of the measuring device. A mention is due, in this respect, to a measuring system. called the "guarded electrode;" invented by C. Schlumberger over 20 years ago. The system, schematically represented in

Jan 1, 1951

By H. G. Doll

A new electrical logging method called Laterolog is described which provides for better recording of formation resistivity. In this method a current, preferably of constant intensity, is forced into the formation perpendicularly to the wall of the hole as a sheet of predetermined thickness by means of a special electrode arrangement and of an autonlatic control system. The essential advantages of the Laterolog over the regular resistivity logs are explained. With the Laterolog, the mud column has much less influence than with conventional methods. The Laterolog is, therefore. particularly useful in wells drilled with highly conductive mud. Moreover. when the electrode system is located opposite a bed of moderate or small thickness, the disturbing effect of the adjacent formations becomes practically eliminated, provided the bed is thicker than the sheet of current. which itself is usually a few inches to a few feet thick. The sequences of beds are. therefore, much more sharply differentiated, and, in many cases, it is possible to read directly from the logs values close to the true resistivities of the formations without further corrections. Field examples are shown to illustrate the results of the method in various types of formations. INTRODUCTION As soon as it was introduced into the petroleum industry, electrical logging roved to be a powerful instrument for the delineation of the strata traversed by bore holes and for correlation of such strata." Research and engineering efforts were mostly devoted at this early time to the design of the techniqurs which could provide the best data for these purpoes. Later, attention was directed toward the quantitative analy5i.s of electrical logs, in order to obtain information on. reservoir characteristics, and, in particular, on oil and water saturation.3,4 Efforts have been made, accordingly, with a view to improving the already existing methods, or to finding new methods which could satisfy these new requirements." Quantitative analysis implies a determination as accurate as possible of the true resistivity of the formations. In fact, however; the "apparent resistivity" recorded in front of a given bed by a conventional electrical logging method is frequently quite different from the true resistivity of this bed. This is due to the combined influence of the mud column, of the adjacent formations both above and below the bed, and of the invaded zone, in which the original fluid has been more or less replaced by mud filtrate. When the beds are thick enough, and, as is frequently the case in sand and shale formations, when their resistivity is not much greater than that of the mud, it is generally possible to obtain their true resistivity directly on the electric log, or at least to obtain an approximate value which can be corrected without undue difficulty by means of recently published charts known as "departure curves."" When the beds are thin, and particularly when, in addition. their resistivity is substantially greater than that of the mud column, the apparent resistivities recorded on conventional logs are seriously affected, and it is generally very difficult, if at all possible, to estimate their true resistivity with a good enough accuracy. In the most severe cases, such as are encountered in holes drilled through hard formations with muds of high salinity, the conventional logs are so distorted and rounded that they do not even show clearly the houndaries of the different beds. In order to overcome the effect of the mud column and of the adjacent formations, it is possible to make use of appro. priate systems whereby the measurements involve a comp3ratjvelv thin slice of space at the level of the measuring device. A mention is due, in this respect, to a measuring system. called the "guarded electrode;" invented by C. Schlumberger over 20 years ago. The system, schematically represented in

Jan 1, 1951

By Nicholas J. Grant, Robert H. Kane, Bill C. Geissen

The platinum-rich section of the Ta-Pt Phase diagram was worked out by metallographic and X-ray techniques, using twenty alloys; solidus temperatures and solid solubilities were determined. Besides s phase, four intermediate stoi-chiometric phases were found: TaPt (high-temperatzrre phase, structure unknown); TaPt2 (ortho-rhomhic, new type); a TaPt3 (orthorhombic, TiCu3 type); ß TaPf3 (monoclinic, new type). TaPt2 and TaPt3 melt congmentlv; two eutectic, two beritec-tic, and one eutectoid reactions occur in the inuestigated range. THE Ta-Pt system was examined as part of a study of the phase diagrams and the intermediate phases of niobium and tantalum with Group VIII transition metals. Since the main scope of this work was the relation among the ordered close-packed phases occurring in the concentration range from AB to AB3 (A = Nb, Ta; B = Pd, Pt, and so forth), only the platinum-rich side of the diagram was worked out thoroughly, while spot checks were made to determine the approximate outline of the tantalum-rich portion. The system has not been thoroughly treated in the literature; Greenfield and Beck1 in their survey of refractory metal intermediate phases found a o phase between -18 and 37 at. pct Pt which coexists at higher platinum concentrations with an unidentified intermediate phase. Browning2 worked on the range between 55 and 100 at. pct Pt; however, this preliminary study did not cover temperatures >1500°C, and included no conclusive crystallo-graphic data. More recently, a study of the platinum-rich section of the Ta-Pt system has been carried out by Ray,3 while Hartley, Parsons, and steedly4 have studied the tantalum-rich section. The crystal structures of TaPt2, a TaPt3, ß TaPt3, and others have been reported in abstracted form by Giessen and Grant.5 EXPERIMENTAL METHODS The methods of alloy preparation and processing and of the metallographic and X-ray procedures follow very closely those described by Ritter, Giessen, and rant' for other refractory metal-noble metal systems, and will not be repeated except where significant differences exist. Starting materials were: tantalum rod of 99.95 pct purity, supplied by National Research Corp., and platinum sponge 99.9 pct, supplied by The International Nickel Co. An oxygen analysis of the tantalum rod showed 30 ppm O; other impurities were C, N, Si, Nb, Mo, none of these exceeding 50 ppm, and 100 ppm W. Homogeneous buttons were readily prepared as follows: ingots of 5 g were weighed and arc-melted under welding grade argon, followed by two remelts after inverting the button. Between 40 and 100 at. pct Pt, weight losses during the first melt rarely exceeded 0.1 pct, in which case the alloy was rejected, and were nil on subsequent remelts. Since the vapor pressure of platinum far exceeds that of tantalum, the small evaporation loss could be assumed to consist of platinum; therefore, a corresponding amount of platinum was added on the second melt. Since it was confirmed on pure tantalum samples that no weight gain through oxygen or impurity pickup occurs (see Ref. 71, it could be assumed that the uncertainty in the composition did not exceed ±0.1 at. pct for the range 40 to 100 at. pct Pt. For the four control melts from 0 to 40 at. pct Pt, an error of ±0.5 at. pct was calculated. Microscopic examination of the whole buttons after melting showed no inhomogeneity other than local coring. This was eliminated by a homogenization heat treatment. A total of twenty-three alloys were prepared. Heat treatments were carried out in a tantalum

Jan 1, 1965

By James H. Boettcher, W. Durand Eppler

INTRODUCTION In the second quarter of 1979, Rapid Mining Co., Inc. ("Rapid") inquired whether Crocker National Bank ("CNB") would provide $4 million in term loan financing to help ("Dry Creek") acquire the outstanding shares of the Dry Creek Coal Company ("Dry Creek") in West Virginia. Prior to approaching CNB, Rapid had sought financing with the assistance of a financial advisor from a number of commercial banks without success. A summary of the initial terms requested by Rapid is shown in Table 1 compared with the actual terms on which the transaction closed. It is not difficult to note that the two sets of terms differ significantly. This is often the case when financing requests based on the expectations and vision of a mine developer are juxtaposed with more pragmatic requirements of a commercial bank. The "art" and fund of structuring financing plans for mining ventures (highly leveraged acquisitions or grass roots) comes in working with mine developers to arrive at a final financial structure that meets their objectives and constraints as well as those of the bank or other financial institutions providing much of the financing. Beginning with the terms requested by Rapid and ending with the terms that closed the transaction, this article briefly describes the process we went through with Rapid Mining. The Seller and Buyer The Dry Creek Coal Company was established in 1961, after its owner acquired the coal leases from Republic Steel. Republic has mined the primary coal seam from 1948-1961. Dry Creek was owned as a subchapter S corporation (i.e., for federal income tax purposes, income is taxed at the shareholder level) and had been run on a low key basis. Since the company had virtually no debt and limited cash needs, the owner produced primarily when rail cars were available and income was required. Output was therefore erratic as is shown in the top of Table II, but the result was a profitable little company with an attractive free cash position. Because the owner wished to retire and enjoy his wealth in a more readily spendable form, he had put the mine, with stated recoverable reserves of approximately 13 million tons, up for sale. In contrast, Rapid Coal's investors consisted of a number of investors of disparate financial situations. They had agreed upon a primary objective of income maximization and planned an annual production rate of 120,000 TPA which they and the current owner believed realizable. The Formulation of a Financing Structure Figure 1 presents a simplified overview of the sequence of steps taken in the financing process which lasted approximately three months from start to finish. Since banks see many requests for funding and considerble time is required to follow up on each, an important step was determining, after a brief review of the materials provided to us, whether the basic "eonomic entity" was viable. In this case, the size and quality of the reserves, the inherent operating cost characteristics, the sales arrangements, the management/labor situation and Rapid's principles all appeared to be sound enough to warrant investing the time necessary to do a thorough analysis of the project. Once this decision was made, the evaluation and analytic process shown in Figure 2 was initiated. The first and most fundamental concern of any banker is whether the loan will be paid back as scheduled from the cash flow generated by the project. The amount of debt relative to the owner's equity is of course crucial in such a determination. Before the debt/equity issue was addressed, however, a number of more qualitative factors had to be studied and if

Jan 1, 1985

By I. S. Levy, J. L. Brimhall, B. Mastel

Specimens of' Hastelloy X-280, a low-cobalt version of the solid-solution- hardened nickel-base alloy Hastelloy X, were given a series of thermomechanical treatttzents. They were then Lensile-tested at room temperature and 1350°F. The Microstructures of the specimens tested at 1350°F were studied by electron Microscopy. Microscopy showed that dislocation tangling, caused by the cold working, mas still in evidence after aging-for 24 hr to temperatures as high as 1550oF. (Cr, Mo)23 C6, (Fe, Mo)6 C'. as well us an unidentifiable phase precipitale due to the combination of the thermomechanical treatments and subsequent tensile strain. The room -temperature and 1350°F tensile properties show a general increase ill strength and decreccse in ductility with increusing cold-work level. This is due to the dislocation taangling-. PerLurbatiot~s to this general trend occur- due to solid-solution weakening at the higher cold-work levels as a direct result of the preciplitation reactions. THE requirements for corrosion resistance and high-temperature strength place nickel-base alloys among the more promising materials for advanced nuclear reactor applications. However, when these alloys are irradiated at service temperatures, they generally suffer severe embrittlement'" and reduction in rupture life.3 Certain experimental treatments resulted in improvements in the tensile and stress-rupture properties of Hastelloy X-280, a solution-hardened nickel-base alloy.' To provide a basis for understanding these improvements, unirradiated tensile specimens were examined by electron microscopy. The results are reported in this paper. EXPERIMENTAL DETAILS Material. Hastelloy X-280, a low-cobalt version of Hastelloy X, is a member of the solution-hardened class of nickel-base alloys. The Hastelloy X-280 was obtained from 4- and 1-in: thick plates in the mill -annealed condition. Table I gives the chemical composition of the material as reported by the National Spectrographic Laboratories. ~x~erimental Treatments. Plates of suitable size, 12 by 3 by 1 in., or by + in., were cut under a water jet from the stock material and examined ultrasonic -ally for homogeneity of grain size and absence of voids. The acceptable plates were solution-treated at 2150°Ffor 1 hr and air-cooled. These plates were then reduced in thickness by cold rolling 0, 10, 15: or 20 pct along the original rolling direction. The plates were machined into buttonhead tensile specimens with a gage diameter of 0.125 in., with a gage length of 1.125 in., and with their tensile axes parallel to the rolling direction. The specimens were examined for quality of finish with a penetrant dye, ultra son ically checked for voids, and finally given a dimensional tolerance check with an optical comparator. The acceptable specimens were aged for 24 hr at either 1000" or 1500 F and air-cooled. These specimens were then held at 540°F in a water loop for approximately 18 days to qualify as controls for similar specimens irradiated under the same conditions of time, temperature, water chemistry, and flow rate. Table U summarizes the treatments. These treatments were investigated to establish whether prior precipitation and stabilization of carbide phases at strain sites within the matrix could reduce the amount of carbides available for precipitation at grain boundaries during service. Tensile-Test Conditions. Specimens were tested to fracture at room temperature or 1350 F in air on an Instron tensile-testing machine at a crosshead speed of 0.05 in. per min. The time for the furnace to reach equilibrium at 1350°F was approximately 30 min; soak time prior to testing was 15 min; and test duration was approximately 5 min.

Jan 1, 1968

By E. C. Tveter, L. A. Roe

The authors present a general outline of the theory and development of heavy-liquid application to mineral processing. Patent literature and processes are reviewed with special emphasis on liquid recovery systems which have been employed or proposed. Advantages and disadvantages of the process are discussed together with the recent developments which have revived interest in this old concentration method. The most important single factor in this resurgence of interest is concluded to be the narrowing gulf between chemical engineering and mineral dressing which has opened the field for new concepts of mineral plant design. A partial summary of patents on heavy liquid separations is included. In spite of the fact that heavy-liquid separation with organic liquids has been used in the laboratory for over 50 years, this process has never graduated to large scale commercial use for any extended period. However, a variation of this process, the sink-float or heavy-media separation process has found wide acceptance and is used to separate minerals from diamonds to gravel. Materials used to increase the specific gravity of the pulps used as heavy media include sand, clay, barite, magnetite, galena, hematite, atomized lead and ferrosilicon. Because of the greater ease of recovery, the magnetic materials, magnetite and ferrosilicon, are the preferred media today. In the U. S. alone, heavy-media iron ore plants with a capacity of over 10 million tons of concentrate per year are in existence. Heavy-media separation involving use of solid, inorganic particles suspended in water rapidly found a wide range of commercial use with the introduction of magnetic media. The minerals engineer is experienced in working with suspensions and quickly learned to develop and control such media at a cost compatible to the type of separation desired. The natural superiority of a heavy liquid with uniform chemical and physical properties has never been questioned since its first use in laboratory mineral separatory procedures. It offers the only method for gravity separation of fine particles of relatively close specific gravity. The most important early attempt to make heavy liquid separations commercial were made by the DuPont Co. which began experimental work on Virginia limonite in 1904. The appended "Partial Summary of Patents" compiled by W.L. O'Connell of The Dow Chemical Co. demonstrates the quantity and sequence of this work. Both inorganic and organic parting liquids were investigated and numerous patents were issued on the use and recovery of these liquids. The work culminated in the heavy liquid plant of the Weston Coal Co. at Shenandoah, Pa. Chemical engineering design of this plant was the responsibility of Francis I. and Hubert I. DuPont. Heavy-liquid separation of coal almost achieved commercial status at this plant which actually processed over 20,000 tons of coal. The liquids used were tetrabromethane, pentachloroethane and trichlo-roethylene, with liquid losses ranging from 8.9 to 12.4 oz per ton of cleaned coal. The reasons for failure of this plant are not clear but probably involved toxicity problems as well as other problems in chemical engineering. Excellent economics were reported. A more recent pilot plant was built in 1954-55 by Norris Goodwin for the Inerto Co. to treat hectorite clay. This plant employed carbon tetrachloride in jigs with liquid recovery by evaporation. Although good separation was achieved, incomplete removal of the CCl, from the clay prevented commercial operation. The only present operations known to the authors employing heavy liquids for gravity separations are limited to the use of calcium chloride in certain coal washers and bromochloromethane in a small batch operation (one ton solids per day) for the separation of beryllium metal particles from slag materials. This is not strictly a minerals beneficiation problem but it has demonstrated the feasibility of such separations. PROBLEMS Critics of early attempts to commercialize heavy-liquid separation of minerals summarize the draw-

Jan 1, 1963

By W. A. Riggs

In a single year the total transportation cost equals nearly 30 pct of the value of mineral commodities, the largest single cost from the deposit to consumer. The magnitude of this economic factor calls for more complete understanding of cost and operational problems between producer and carrier than now exists. Details are given of the costs of providing transportation as well as freight rates for selling transportation. In 1958, transportation of mineral commodities in the United States required 600 billion ton-miles to move 1 3/4 billion tons of products of mines comprising solid fuels, crude oil, industrial minerals and rocks, and ores. Possibly 17 pct was handled by more than one mode of transport, since combinations of several modes of transport may, at times, achieve better service/cost results than any single mode. Total transportation cost of nearly $5 billion equaled roughly 30 pct of the value of the mineral commodities, the largest single cost from the mineral deposit to the consumer. The tremendous magnitude of this transportation undertaking demands much more complete understanding than now exists between mineral producers and carriers about the economic and operational problems of each other. A substantial portion of the daily work of the writer is spent in trying to act as a combination interpreter and catalyst between potential shippers and carriers, hoping to direct both to points of mutual understanding and advantage. For the purpose of this paper, it is necessary to ask mining people to accept some terminology and to try to appreciate the mental approach of the freight rate making people of the carriers. This paper will consider costs of providing transportation as well as freight rates for selling transportation—although these are fields of limited certainty. There are no accurate statistical breakdowns for all modes of transport and types of carriers indicating commodities, volume of traffic, distances, costs, and rates. Much information is available for railroads, and some for the regulated portions of air, motor, pipeline, and water transportation. Unregulated carriers, handling about half of the transportation of products of mines, are not required to report, and very little is known of their activities. Figures used herein are national in scope, unless otherwise indicated, and have generally been derived from Interstate Commerce Commission reports and files. Tonnage figures have been reduced to net tons of 2000 lb. The very generalized comparison of average mileage freight rate levels for various modes of transport provided by Fig. 1 affords advantageous perspective for the entire field of transportation costs. Dashed guide lines show cents per ton-mile, and dotted guide lines show percentage of first class railroad freight rate. While costs of other than railroad transportation more nearly follow constant cents per ton-mile functions, costs of railroad transportation show characteristic taper, or decrease in cents per-ton mile with increasing length of haul. This fundamental difference in cost is due largely to the fact that railroads and pipelines provide their own fully taxed roadway facilities while highway, waterway, and air carriers use government-provided tax-free roadway at no cost other than fuel, license, and certain excise taxes. Thus railroad and pipeline transportation might be said to carry heavy threshold costs in addition to those transportation costs which are directly variable with ton miles of transportation produced. The original basis of railroad freight rate structures lies in the classification of all articles of commerce into railroad class ralings ranging from 7 to 40 pct of first class (100 pct) rate level, dependent on value, hazard, loading characteristics, service requirements, and whether carload or less than carload. Classification tables and mileage-based (but arbitrarily grouped), rate scales are published as tariffs subject to approval by regulatory bodies. Used together, these determine class rates in cents per 100 lb between points in the U. S. Where local commercial or operating conditions render it advantageous for carriers to depart from

Jan 1, 1961

By R. A. Salathiel, A. D. Kaiser, P. H. Monaghan, B. E. Morgan

The productivities of many hydrocarbon-bearing for-rnntions appear to be reduced during drilling, completing and repairing operations. The reason for these othcarwise unexplainable low productivities may be a drastic reduction of formation permeability immediately surrounding the borehole. A possible cause of the reduced permeability is swelling and dispersion of clays present in porous media when contacted by fresh water or mud filtrates. Hence, the invasion of fresh water or mud filtrate into hydrocarbon-bearing formations that contain clays may cause low productivities as a result of formation damage. Present laboratory investigations have yielded results which supplement existing literature on formation damage. An expanded-type clay, montmorillonite, way found in hydrocarbon-bearing formations not previously analyzed. When sand columns and formation cores containing montmorillonite were contacted by fresh water, their oil permeabilities were reduced. This reduction in oil permeability way restored partially but not completely by a repair procedure, i.e., flooding with kerosene containing organic agents or flooding with water containing electrolytes. Hence, where montmorillonite is present in formations, prevention of formation danzage was indicated to be the only complete solution to the problem. To prevernt formation damage, results suggested use of an approximately 1 per cent solution of calcium chloride or stronger solutions of sodium or potassium chloride. In conventional rotary drilling operations the wall of the hole is exposed to drilling mud for days, weeks, and in some instances for as long as several months. During this time, drilling mud filtrate seeps slowly into formations surrounding the hole. The permeability and stability of many formations, especially those containing clayey materials, are impaired by the mud filtrate. Often interaction between the mud filtrate and the formation causes drilling and production difficulties. Serious reduction in productivity of oil and gas formations during drilling, completing and repairing wells has been noted often in recent years. Cases are known of development wells which produced only small volumes of fluid upon completion. However, after a period had elapsed, they began to produce oil or gas in commercial quantities. In other cases, results of drill-stem tests taken during the drilling of deep wells have indicated good production should be obtained from shallow formations. Later difficulty has been experienced in obtaining production from these shallow formations which had remained in contact with drilling muds for an extended time. In yet other cases wells have failed to attain the productivities expected from previous performance after the use of drilling mud as a circulating fluid during workover operations. It is evident from the field behavior cited that the productivities of certain oil- and gas-bearing formations have been damaged by exposure to drilling muds. This reduction in well productivity, called "formation damage", causes serious consequences. In development wells, expensive remedial operations are incurred. In wildcat wells, good formations may appear to be marginal or even non-productive. The importance of formation damage has been recognized by a number of investigators1-s who have considered the effects of fresh water, saline solutions and aqueous mud filtrates on the permeabilities of formations. A general conclusion from such studies is that interaction between water and formation clays reduces permeability of reservoir rock and that the permeability decreases as salinity of the water decreases. Data in these references, however, concern the permeability change with only a single fluid present. A more pertinent and direct consideration in the production of oil and gas from wells is the permeability change when two fluids, oil and water, are present. Recognizing this, Nowak and Kreuger2 and Bertness1" considered several ways in which mud filtrates and saline solutions caused reductions in the oil permeability of formation cores. Investigations discussed here were designed to supplement information in the literature on changes in oil

By C. Cronquist

Since April, 1962, Shell Oil Co. has operated a peripheral line-drive waterflood of the 10.750-ft lower Tuscaloosa (Cretaceous) Denkman sand in the Little Creek field. Located in southwestern Mississippi in the lower Tuscaloosa trend, the field was discovered by Shell in Jan., 1958. Among the largest in the trend, the accumulation is controlled stratigraphically and occurs in an extensive series of alluvial-point bar deposits across a nose that dips gently to the south. The crude oil is 39" API gravity and was highly undersaturated at initial conditions. Early production behavior indicated a depletion drive with slight water influx; primary recovery wm estimated to be 25 million bbl, or 24.5 percent of stock-tank oil originally in place. A.s a result of a favorable mobility ratio and remarkably uniform rock properties, the volumetric sweep eficiency in the waterflood has exceeded 90 percent. Despite the high connate water saturation (56 percent), the displacement efficiency by water injection has been quite efficient, contrary to traditional concepts. Based on observed field flood-out performance, ultimate recovery is calculated to be 46 million bbl. As anticipated, the production rate began declining during 1964 due to a continu ing reducrion in the number of producing wells as flood fronts advanced across the field. Cumulative recovery as of Jan., 1968, was 44.8 million bbl; waterflood operations ~hould be complete by 1970. Introduction Most waterfloods described in reservoir engineering literature involve pattern operations, the most common of which is the five-spot pattern. Only occasiona'lly are linear drives described, even though there probably are increasing numbers being put into operation. Increasing use of linear floods may reflect the accelerating trend towards early application of fluid-injection programs when linear drives are more efficient, as was the case at Little Creek. However. the Little Creek operation is unusual in several respects. It is one of a few successful waterfloods conducted in sands with connate water saturations approaching 60 percent, and it is among the deepest successful water-floods being operated anywhere. Development The Little Creek field was discovered in Jan., 1958, in the lower Tuscaloosa trend in southwestern Mississippi (Fig. 1). The discovery well, Shell-Lemann No. 1, was drilled on a seismic closure about 2 miles southeast of lower Tuscaloosa production at Sweetwater. The well was completed in the Denkman sand at 10,752 ft, and on initial potential it flowed 588 BOPD of 39" API crude on a %+-in. choke; psi was 730 and GOR was 442:l. Development proceeded rapidly on 40-acre spacing, and by the end of 1958 the field was producing approximately 9,100 B/D from 56 wells. Almost all this production came from the northern half of the field. The southern part was discovered in Nov., 1958, at a location almost 2 miles from previously established production. Subsequent drilling established an apparent conneotion about half a mile wide between the twd areas. Development of the field was practically complete by 1961 with the drilling of 155 producers and 35 dry holes. Some early wells were completed open hole but moslt are completed with casing cemented through the productive interval and perforated for production. Geology The lower Tuscaloosa structure in this area is a north-south nose with maximum dips of about 2" on the flanks. There is no discernible faulting at the producing horizon. Productive limits of the field are shown in Fig. 2, which is contoured on a marker just above the main productive zone. A common water level at 10,415 ft subsea was logged at both the northwest and southeast ends of the field. There is a gross oil column of nearly 100 ft (Fig. 2). Since there is less than 40 ft of closure, it is apparent that bhe accumubtion is controlled stratigraphically, being limited by a sand pinch-out across the creslt of the nose. The total produc-

Jan 1, 1969

By B. R. Berger

The Getchell area in the northern Osgood Range, Humboldt County, Nevada, was first prospected in the late 1800s for silver, copper, and gold; the first recorded mention of mining activity concerned a silver discovery. The September 17, 1874 edition of the Winnemucca Silver State notes that the Crystal Mining District was newly organized in the Fremont Range (as the Osgood Range was then called) to include discoveries of silver, lead, and antimony made on the Louisa claim. The name Crystal was derived from the plentiful quartz crystals found in-cavities near the prospects. This same area, occurring on the northwestern margin of the Osgood granodiorite stock, was later mined as the Richmond tungsten property, and crystals may still be found there in cavities in a massive garnet tactite. By 1878, how-ever, the name Crystal had been abandoned in favor of Potosi. The next flurry of activity in the Osgood Range was reported in 1899 when a copper strike on Granite Creek in the southern portion of the range received attention. The copper occukences were in a granite contact zone on the southeastern edge of the Osgood stock and, in 1916, the first tungsten in the district was discovered in the same deposit. During the last part of the nineteenth century, cattle and sheep were brought into the Kelly Creek Valley east of the Osgood Mountains by various ranchers. Alphonso and Adrian Bernard were among these ranchers, and in the first decade of the twentieth century, one of them recognized the altered rock where the Getchell Center it is now located. A 3-m (10-ft) deep prospect pit was dug on the outcrop, but the highest assay ran about $11/t ($10 per st). No further work was done on the gold-bearing rock. In 1934, Emmet Chase of Battle Mountain and Ed Knight of Golconda prospected in the area of the Bernard prospect pit and located several lode claims. At this time, Noble H. Getchell, a state senator, was looking for new mining opportunities to develop. He held interests in the Gold Circle Consolidated at Midas, which was becoming a losing venture. Chase and Knight brought their discovery to his attention, and he grubstaked them to prospect further in the area. In need of financial backing, Getchell solicited the help of George Wingfield, Sr., who held a minor interest in the Gold Circle. Wingfield was a successful banker and mine operator during the heyday of Tonopah and Goldfield, and he had become good friends with Henry C. Frick and Bernard Baruch. Wingfield let Baruch in on several very successful mining ventures in Goldfield, and Baruch returned the favor by underwriting the financing of the Getchell mine. Eleanor Roosevelt and Jack Dempsey were early stockholders in the Getchell operation. George Wingfield brought his brother-in-law, Roy A. Hardy, a consulting engineer who had constructed the American Flat mill near Virginia City, to look at the property. Upon inspecting the Chase-Knight claims, Hardy declared the whole area to be mineralized. A crosscut was driven to check the extent of the ore, and the results were better than anticipated. The locators were reportedly given $50,000 for the claims. The Getchell Mine, Inc., was organized on November 5, 1936. A small railroad that ran from Battle Mountain to Austin was purchased, and the ties and rails were moved to Getchell to be used in underground exploration. Enough reserves were found in the Center and South pit areas to construct a 40 t/d (44 stpd) mill. The financial and engineering help for the mill was provided by the Newmont Mining Co. for a 17 1/2% interest in the corporation. Newmont set about trying to solve the metallurgical problems with the sulfide ore, and also directed the early development work. Newmont wanted to grind the sulfide ore underground and oxidize it in the atmosphere by spreading salt on it. Detrital Flat in Arizona was purchased to provide salt for

Jan 1, 1985

By F. P. Bullen

Empirical relationships between fracture stress, orientation angle, and diameter of crystal have been determined at 77°K. Orientation ranges of markedly different behavior were found—a law of constant normal stress&apos; of value a (diameter)-1/2 for the fracture of ductile crystals, and a condition of shear stress (or strain) for more brittle crystals. The observations are not consistent with current theories. An interpretation is advanced which is also applicable to observations on the effect of prestrain at room temperature on the subsequent fracture stress at 77°K and to the effect of cyclic stressing on the cleavage strength.&apos;&apos; The law of constunt normal stress&apos; and the brittle ductile transition are also explained. The interpretation is more consistent with the initiation of cracks by intersecting dislocations than with theories based on stress -concentration by dislocation arrays. ZINC single crystals are particularly suited to the study of cleavage because fracture occurs on the basal plane over a wide range of crystal orientations. Analysis of the conditions of stress and strain at fracture in crystals of different orientations should indicate which parameters control the cleavage process. Unfortunately, controversy has arisen over the correct empirical relationship between tensile fracture stress and orientation. Schmid&apos;s observations1,2 favored a &apos;law of constant normal stress&apos;, as observed in other materials.2 For zinc, however, the observed values are far below the theoretical strength and cannot represent the true limit of cohesion between neighboring atomic planes. Hence, the interpretation of such a &apos;law&apos; is not straightforward. Deruyttere and Greenough3,4 found a complex variation between tensile fracture stress and orientation; this variation did not agree with a &apos;law of constant normal stress&apos;. Two theories have been advanced to account for their observations: a) the propagation of cracks from low-angle boundaries,5 and b) the release of energy from piled-up dislocations during crack-propagation.4 The present work resolves the apparent discrepancy between the observations and shows that neither of the above theories are applicable to the tensile fracture of zinc single crystals. A phenomenological explanation, along the lines suggested by Gilman,&apos; is advanced and successfully applied to previously unexplained effects. EXPERIMENTAL DETAILS &apos;Crown Special&apos; redistilled zinc was used, except for one comparison series op tests using &apos;Tadanac&apos; electrolytic zinc. Crystals of 1 mm diam, subsequently called &apos;1 mm crystals&apos;, were grown from the melt in vacuo in precision-bore Pyrex tubes internally coated with graphite. Several specimens 1 in. long were cut from each crystal and chemically polished. Jigs were used to minimize handling strains, and crystals were mounted in the Polanyi machine the day prior to testing to allow recovery from any such strains. One-mm crystals were chemically polished for long periods to obtain 0.1 mm (approx) crystals. One-mm crystals were cemented into miniature gimbals by &apos;Araldite&apos; casting resin. The Appendix gives the reasons for using gimbals and the results obtained by other methods. More complete details of all techniques are given elsewhere.7 The symbols and terminology used are as follows: X = orientation angle (angle between tensile axis and line of greatest slope in the basal plane). T = tensile stress (on true cross-section) S,N = shear and normal stress (components of T with respect to the basal plane) ? = shear strain D = crystal diameter. The subscript &apos;f&apos; will be used to denote values at fracture. PART I-ANNEALED CRYSTALS EXPERIMENTAL OBSERVATIONS One-mm crystals were used to establish the variation of fracture stress at 77°K with orientation at fracture (Xf), Fig. 1. For 18 deg = Xf = 55 deg, a &apos;law of constant normal stress&apos; was observed. For Xf > 55 deg, the fracture condition approximated to a constant shear stress. At Xf< 18 deg, twinning occurred before fracture so that the results were not typical of homogeneous single crystals,4,8— such specimens will not be considered herein. The dependences of fracture stress upon Xf were of similar type for 6 mm,* 1 mm, and 0.1 mm crystals,

Jan 1, 1963

By H. M. Strong

Nickel and carbon form a metastable nickel-nickel carbide eutectic system which was ohsen)able by freezing latent-heat arvests at pressures 210 khars. The eutectic freezing temperature Is pressure had a slope of -0.9°Cper kbar. At 50 khars, the nickel-nickel carbide eutectic was at 1297° * 5°C and 0.34 mole fraction Ni3C. The composition of the eutectic increased at an initial rate of 0.004 mol fraction per kbar. The carbon content of the a phase also increased with pressure. Seveval illustrations of nickel carbide microstruc-tures are given and data on the lattice expansion of nickel in terms of carbon content are included. IRON, cobalt, and nickel form a variety of carbides with compositions varying between MeC and MC. Of the three, the carbides of iron are most easily recovered. The nickel carbides are so unstable at temperatures above 900°C that their occurrence in Ni-C alloys is unusual. Under sufficient pressure, however, the temperature range for the stability of the ferrous metal carbides is likely to be increased, or their decomposition suppressed (e.g., see Hilliard&apos; on FesC), providing an opportunity to study the unstable carbides more closely. This was found to be true for nickel carbide which, under pressure, formed a eutectic with nickel. This paper describes the conditions of formation of nickel-nickel carbide eutectic compositions and their subsequent recovery. Despite the comparative instability of the nickel carbides, something is already known about them through various chemical reactions at temperatures not exceeding a few hundred degrees, and from their recovery by the very rapid quenching of molten Ni-C alloys from temperatures of about 1450°C or above. At least four carbides of nickel have been reported: A discussion of the state of knowledge about Ni3C is given by ansen.&apos; The studies of Morrogh and williams7 who obtained Widmanstatten nickel carbide structures and of sidorenko8 who first obtained nickel carbide eutectic structures are also of interest. Sidorenko used short heating times for molten nickel in a graphite crucible followed by very rapid quenching to obtain the eutectic structures. Long heating times produced only the nickel-graphite eutectic probably due to the presence of graphite crystals in the melt which nucleated graphite crystallization. According to the early work summarized by anssen,&apos; nickel carbide may form at temperatures far above the melting point and may be recovered by very rapid quenching. More recently, Giardini and Tydings, working on diamond synthesis, found evidence for "free nickel carbide&apos;&apos; in high-pressure reactions carried to temperatures far in excess of the limit for diamond growth, followed by rapid thermal quench. They stated that nickel carbide was not found in association with diamond growth. In the present work, observations were made on the melting and solidification temperatures of Ni-C alloys as a function of composition, temperature, and pressure. The nickel-nickel carbide eutectic was found at pressures above 10 kbar and its variation with pressure followed up to 60 kbar. Nickel-nickel carbide microstructures were recovered by quenching under pressure from temperatures of about 1400°C and higher. The formation of nickel carbide structures under ordinary diamond-growing conditions was usually observed but the role of carbide formation as an intermediate step in diamond growth needs more study. EXPERIMENTAL METHODS The melting and solidification temperatures of various nickel-graphite compositions were observed by latent-heat arrests in the sample holder illustrated in Fig. 1. The samples were composed of mixtures of carbonyl nickel powder and National Carbon Co.&apos;s SP-1 graphite packed to densities of about 6.4 g per cu cm. They were contained within

Jan 1, 1965

By L. S. Birks

The bainite transformation in a 3.5 pct Ni-1.25 pct Cr steel was studied under various conditions of cooling and stress. Several characteristics may be specified: 1) transformation in the bainite region (925° to 575°F) is very little affected by the manner of cooling from the austenitizing temperature at 1600°F to 575°F)tothe upper limit of bainite transformation at 925°F; 2) starting time for the bainite transformation is the same order of magnitude for either isothermal transformation or continuous cooling, but the rate of transformation is somewhat greater for isothermal transformation; 3) tensile stress accelerates both isothermal and continuous cooling transformation, and 32,000 psi stress changes the form of the isothermal transformation diagram to correspond in appearance to the continuous cooling diagram; 4) transformation for nonlinear, continuous cooling may not be determined directly from the linear, continuous cooling transformation diagram, but may be predicted by assuming first that the fractional amount of austenite transformed in a given small temperature interval depends on the approximate linear cooling rate during that temperature interval and then by summing stepwise over the whole temperature range. IN a previous publication&apos; an X-ray spectrometer was described with which the X-ray diffraction from a specimen could be observed continuously under controlled temperature and tensile stress. This instrument has now been applied to a study of the austenite-bainite transformation in a Ni-Cr steel for both isothermal and continuous cooling conditions, with and without stress. Certain characteristics of the transformation lead to a method of predicting the amount of transformation to be expected at a given temperature for any type of cooling curve. Material and Specimen Preparation The steel chosen for the investigation was a Ni-Cr steel having the composition in the following percentages: 0.30 C, 0.27 Mn, 0.019 P and S, 3.50 Ni, and 1.25 Cr. In order to fabricate specimens suitable for the X-ray spectrometer, a 1/4 in. plate was ground down to 0.060 in. and then cold rolled to about 0.035 in. Next it was heat treated by quenching in oil from 1650°F and tempering at 1200°F for 1 hr. Then it was etched in dilute nitric acid to reduce its thickness to 0.014 in. and cut into blanks in the shape of flat tensile specimens 3 1/4 Vi in. long, 7/16 in. wide, with a notch % in. long and 7/32 in. wide; see Fig. 1. X-Ray Technique Since the X-ray spectrometer has been described in detail elsewhere,&apos; only a brief outline of the principles will be repeated here. A focusing, pow- der-diffraction arrangement&apos; was used, as shown schematically in Fig. 1, and the specimen was mounted vertically in a vacuum furnace (not shown in the figure). The X-rays, moving in a horizontal plane, enter and leave the furnace through beryllium windows. As shown in the figure, X-rays diverging from the line source A are diffracted by the specimen B and converge at the detector slit C. The detector D and the slit C may be set at the proper angle in the horizontal plane to receive X-rays diffracted by either the face-centered phase (austenite) or the body-centered form (ferrite, bainite, martensite). The specimen is heated by electrical conduction between connectors E, and E,, and a Pt—Pt-10 pct Rh thermocouple spot-welded to the center of the notched region on the side away from the X-ray beam indicates the temperature continuously on a Brown recorder. Temperature control is exercised manually with a variable transformer on the input to E,-E,. Any desired time-temperature relationship is easily obtained by first drawing the desired curve on the temperature recorder chart and then adjusting the variable transformer during the run so that the thermocouple

Jan 1, 1957

By Robert Maes, Robert de Strycker

The Fe-Ni-As phase diagram has been established by the study of about a hundred alloys, by microscopic observation, and by thermal analysis, with arsenic contents up to 50 pct. The iron and nickel arsenides present extensive solid-solution fields, owing to the substitution of nickel by iron and vice versa; the extent of the solubility field of each compound has been determined with an accuracy of ±1 pct. In the investigated range of compositions, the solidification reactions were established, and the temperatures of the invariant reaclions detevmined with a preciston of iZ°C in the most favorable and ±5°C in the least favorable cases. The isothermal lines of the liquidus surface have also been drazum, with an accuracy estimated at i5°C. Reactions in the solid state, which take place for the formation or the decomposition of certain phases , were investigated in detail. ThE constitution diagram of the Fe-Ni-As system is fundamental for the understanding of the properties of nickel speiss; these by-products of the extraction of certain nonferrous metals indeed often contain the three elements iron, nickel, and arsenic as main constituents. The Fe-Ni-As system has already been the object of earlier investigations. In 1932, Guertler and Savels-berg&apos; have presented some elements of the ternary phase diagram, for arsenic contents up to 55 pct (all percentages in this paper are given in weight percent), including the vertical section FezAs-Ni&s2. This investigation is, however, incomplete and certain anomalies suggested the necessity to verify the results published by these authors: the section Fe2As-Ni5AsZ, for example, is presented as quasi-binary, with a field of complete miscibility in the solid state, even though these compounds do not have the same structure. Recently, ~useck&apos; established an isothermal section at 800°C in the Fe-Ni-As system by X-ray diffraction and microscopic examination of water-quenched alloys. These techniques are sometimes inaccurate for the determination of the fields where alloys are liquid at the investigated temperature, and they may lead to erroneous conclusions when a compound exists at the investigated temperature but is not stable at room temperature and cannot be maintained by quenching. LIMITING BINARY PHASE DIAGRAMS The Fe-As constitution diagram has been the object of several investigations which have been reviewed by Hansen and Anderko.3 For the Ni-As phase diagram, a recent study has been effected by Yund.4 In this system, Heyding and calvert5 have determined the existence of a compound of unidentified structure at arsenic contents slightly higher than those corresponding to Ni5As2 and at temperatures lower than about 200°C; by analogy with iron and cobalt arsenides, this compound could correspond to the formula Ni2As, as suggested by Kulle-rud; although this is not definitely established. In the region of arsenic contents from 35 to 55 pct, Fried-rich7 detected anomalies in the solidification reactions; an interpretation of these anomalies was given by Hansen ,8 which assumed that the solidification reactions in practice are not in equilibrium, but are meta-stable. The main features of the Fe-Ni constitution diagram are the existence of a complete miscibility field, at least at high temperatures, for the fcc phase (which will be designated by My in the remainder of this work) and of a limited solubility field for the bcc phase (designated by Ma). EXPERIMENTAL METHODS The fundamental technique used in this investigation was microscopic observation, which allowed the determination of the reactions occurring during solidification of the alloys, and possible reactions in the solid state.

Jan 1, 1968

By D. L. Albright, G. A. Colligan

An investigation has been conducted to determine the nature of the crystallographic substructure of nickel and a 1.0 wt pct Ag-Ni alloy which had been undercooled 105°C prior to solidification. A rotating back-reflection X-ray technique and modified Weissmann diffractometer were used to orient single-crystal sections from these poly-crystalline ingots and to determine the substruc-tural features of these single crystals, The sub-grain size in the pure nickel ingot is 0.5 mm diam while the silver-doped nickel subgrain size is only 0.1 mm diam. The misorientation between adjacent subgrains is approximately 1 deg of arc in both ingots, and the spread of orientation of sub-grains about the mean orientation of the crystal is 5 deg of arc in both ingots. The addition of silver results in a stable impurity substructure which is preserved during isothermal solidification and subsequent cooling to room temperature. In the absence of silver the initial impurity substructure is destroyed by dislocation interactions which produce a secondary substructure which grows to a size five times larger than the initial substructure. THE process of undercooling a metal entails cooling of the molten sample below the equilibrium freezing point without the occurrence of solidification, i.e., by exercising proper constraint over the experimental variables contributing to nucleation in the melt. The current work of walker1 and Colligan Metal reports undercooling large continuous samples of nickel by imposing appropriate restrictions upon the parameters of solidification. The silver-nickel equilibrium diagram3 reveals the presence of a monotectic reaction at 1435°C. At this temperature the maximum solid solubility of silver in nickel is approximately 3 wt pct, but this solubility decreases with decreasing temperature and the solute is rejected as a silver-rich liquid phase at temperatures below 1435°C. Thus, the 1.0 wt pct solute should be held in solution during undercooling and solidification and subsequently precipitate as a silver-rich liquid phase at grain and subgrain boundaries following solidification during cooling below 1435. This assumes no solute segregation sufficient to cause the monotectic reaction. One would expect this second phase to inhibit grain and subgrain growth by retarding dislocation motion after solidification is complete. The effectiveness of silver addition in growth retardation of high-angle grain boundaries has been demonstrated by Colligan and suprenantS4 The principal [l00] dendrite growth directions in a 2 wt pct Ag-Ni alloy undercooled 53 all radiated from the nucleation site. A similar pure nickel ingot undercooled 59°C exhibited a random orientation of [l00] dendrite directions with respect to the nucleation site. Since undoped nickel ingots do not retain any evidence of the casting or solidification texture and silver-doped ingots do retain this texture, it is reasonable to assume that considerable grain growth has taken place in the pure nickel. These particular experiments were performed in order to reveal the differences, if any, in the features of the crystallographic substructure of undoped undercooled nickel and silver-doped undercooled nickel. 1) EXPERIMENTAL PROCEDURE Data are reported on selected specimens from two massive (approximately 260 g) undercooled ingots of nickel. One ingot consisted of electrolytic nickel and the other of this same material with 1.0 wt pct addition of high-purity silver. Powder patterns were taken of both the as-received and as-solidified materials; in all cases the reflections recorded were attributable to the individual elements nickel and/or silver. Fig. 1 is a. schematic diagram of the apparatus employed for the undercooling experiments. The equipment consists in part of a fused silica crucible for containing the charge. A fused silica tube encloses the system, which is covered by a brass cap to permit partial sealing of the inert atmosphere. This cap contains a hole through which a Pt-Pt 13 pct Rh thermocouple is inserted for temperature measurement. The charge is inductively heated under a purified argon atmosphere.

Jan 1, 1963

By K. Takahashi, I. Iwasaki

The methyl stretching vibrations for a series of normal xanthates, isoxanthates and normal amines were determined with the aid of an infrared spectro-photometer, and the results were compared with published information on the corresponding alcohols. The frequency shifts of methyl stretching vibrations may be attributed to the inductive effect of polar groups. The hydrogens in the shorter chain alkyl groups are somewhat polar and can be expected to interact with water molecules by hydrogen bonding. Contact angle, surface tension lowering, solubility, and critical micelle concentration appear to be related to the induced polarity of the alkyl groups. Traube&apos;s rule states that in homologous series of compounds solubility decreases and surface activity increases regularly with the size of the hydrocarbon group. Analyzing the work of transfer of a solute from solution to surface, Langmuir&apos; interpreted this rule to mean that each CH2 group added to a molecule produced its effect independently of the others. It is also well known2 that the maximum equilibrium contact angle with sulfhydryl collectors is independent of the polar groups and of the sulfide minerals, and that it increases to a certain limit with the number of carbon atoms in the alkyl group. This observation is thought to demonstrate the orientation of the collector molecules at the sulfide surfaces. The dependence on the hydrocarbon chain length is usually explained as due to the screening of the force field of polar mineral surfaces.3-5 Here again, Langmuir&apos;s principle of independent surface action appears to be implied. Heteropolar compounds consist of nonpolar and polar groups, the former being the hydrocarbon group and the latter containing such electronegative atoms as O, N, S, P, or halogens. According to Palit6 the hydrogens in the alkyl groups are more electroposi- tive than in the paraffins owing to the negative inductive effect of the polar groups and a possibility that a hydrogen bond with water molecules ensues. Goto and Takenaka7 provided direct evidence of the inductive effect by measuring the shift of the C-H stretching vibrations of alcohols, acids, and alkyl bromides with an infrared spectrophotometer. Their approach appeared to be directly applicable to the studies of surface activity both at air-water and water-mineral interfaces encountered in flotation systems. The present article attempts to relate the C-H stretching vibrations of alkyl xanthates, alcohols, and amines with such flotation chemistry parameters as contact angle, surface tension lowering, solubility, and critical micelle concentration. MATERIALS AND METHODS Normal xanthates from methyl to octyl inclusive and the isopropyl, isobutyl, and isoamyl xanthates used in this investigation were prepared in the usual manner.8 Normal amine hydrochlorides with carbon chain lengths of 1, 2, 4, and 6 were from Distillation Products Industries, of 8 from Archer-Daniels-Midland Co., and of 10, 12, 14 and 16 from Armour and Co. Normal propylamines, pentylamines and heptylamines from Distillation Products Industries were used both as received and as hydrochloride formed by converting the amines according to the procedure described by Li9 Perkin-Elmer Model 521 and 621 infrared spectro-photometers were used to investigate the spectra in the frequency region of 3050 to 2800 cm-&apos; with frequency scale expansion. The accuracy of the frequency readings was within + 1 cm-1. The KBr micropellet technique was used to prepare the xan-thate samples for measurements, and the halocarbon mull technique was used for amines and amine hydrochlorides. EXPERIMENTAL RESULTS Fig. 1 shows the CH3 asymmetric stretching vibrations as a function of the number of carbons in the alkyl group for normal xanthates, isoxanthates and amines. Also included in the figure are data for normal alcohols and isoalcohols taken from the article

Jan 1, 1970

By O. K. Miniato, L. Massé, K. Nobe, J. S. Aronofsky, W. F. 213-000-000-016 Seyer

MUCH work has been done dealing with the effect of mechanical stress on electrode potential in an electrochemical system. The contradictory nature of the experimental results indicates the complexity of the problem although thermodynamic considerations show that a simple relationshir, should exist. In those systems where a gas was the electromotive active substance satisfactory agreement between theory and practice has been found. Des Coudres&apos; found this to be so even when the active substance of the electrode, in this case mercury, was in the liquid state. In contrast, attempts to correlate theory and experiment for the solid state have met with a very limited success. The early workers in this field, Andrews,2 Walker and Dill3 used iron, certainly one of the most reactive of metals. Others have made use of less active metals such as copper and nickel. Recently Fryxell and Nachtrieb4 investigated the electrochemical behavior of gold and silver under both tensile and compressive stresses and concluded that it was doubtful whether true stress potentials could ever be measured. Much of the lack of success to measure the thermodynamic stress potential can be ascribed to the presence or formation of a complex film on the metal surface in contact with the electrolyte. Further, the theoretical stress potential is very small and therefore difficult to measure directly. Thus the calculated emf between a 24 B & S gage cold-drawn copper wire stressed with a weight of 1 kg and an unstressed portion of the same wire is only 2.60 X 10"7 volts. This is very small compared to that which can be produced by chemical reactions at the metal electrolyte interface which in turn can be so large as to mask completely the stress potential. Hence in this type of measurement all chemical side effects must be eliminated or reduced as much as possible. It was for this reason that the system copper-sodium chloride solution was selected for study. INSTRUMENTATION In the many preliminary experiments conducted, two major difficulties were encountered. The first was to measure the small electro-potentials to be expected and the second to obtain a suitable electrode surface. The conventional potentiometric method was found to be unsatisfactory for measuring the small emf expected. However, by using an L & N No. 2290 galvanometer having a resistance of 915 ohms consistent measurements were possible. The reference electrode was always the unstressed one made from the same sample of wire. The steady current flow was approximately 10-8 amp. Lewis and Randell5 have stated that for currents of the order of 10-8, if there is no sensible polarization, the measured emf may be taken as a reversible one. To check the galvanomenter readings an alternative method was devised to measure the potential difference between the wires. This involved a Liston-Falb d-c breaker amplifier model 10, an L & N k-2 potentiometer and a moving-coil galvanometer having a sensitivity greater than 0.1 µv (microvolt) per mm. To increase further the output voltage of the amplifier a d-c amplifier, model B. L.-932 was introduced into the circuit. This amplifier was in turn connected to a Brush recorder which had been calibrated previously by the test signals from the Liston-Falb instrument. These test voltages employed took into account the impedance of the input current. Unfortunately, this method had too low a sensitivity for measurement below 10 µv. Above this value the voltage agreed reasonably well with those obtained directly by the simple galvanometer method. The main advantage of the amplifier setup was that one did not have to wait until no deflection occurred on the galvanometer in the circuit when first exposing the wires to the solu-

Jan 1, 1959

By N. Jaffee, J. E. Dorn

An activation energy of 27,400 5 1000 cal per mole was obtained for the creep of poly crystaLline aluminum over the temperature range of 273° to 350°K, at strains varying from 0.003 to 0.230. Stresses varied fronz 2250 to 6000 psi, strain rates from 0.1145 x 10-5 to 29.5 x 10~s min.-1. A strain temperature-compensated time correlatzon was oblained indicating that the structure was depedent solely upon the strain at a given stress; X-ray diffraction analyses and tensile tests on precrept specimens verified this. PREVIOUS investigations1 have revealed that the apparent activation energies for creep of high-purity polycrystalline aluminum are insensitive to the applied stress, strain, and strain rate. On the other hand, the apparent activation energy is dependent on the temperature1,2 as shown by the data reproduced in Fig. 1. Each plateau of this curve is associated with a unique rate-controlling dislocation mechanism for thermally activated creep. It is now very well-established that over the high-temperature range, where the activation energy is about 35,500 cal per mole, the creep rate is controlled by the dislocation climb mechanism. 3 Over the intermediate range of temperatures, from about 260° to 370°K, another unique activation energy, namely 28,000 cal per mole, is obtained. Current evidence strongly supports the contention that cross slip is the rate controlling mechanism for creep in this case: 1) Crystal recovery can occur by a number of mechanisms prominent among which are climb and cross slip. Astrom,4 using the Borelius micro-calorimeter, reported rapid crystal recovery of cold-worked polycrystalline A1 at 340° to 370°K giving an activation energy of 28,000 cal per mole and additional recovery at 455° to 478°K giving an activation energy of 3 6,000 cal per mole. Whereas the latter recovery process was clearly associated with the dislocation climb mechanism, the former, 28,000 cal per mole process could have arisen as a result of the cross-slip mechanism. 2) Single crystals of high-purity A1 favorably oriented for octahedral glide exhibit an activation energy for creep of about 3400 cal per mole over the range from 0° to 400°K and that of about 28,O:O cal per mole over the range from 600° to 775°K . Whereas the lower activation energy process is accompanied by the development of sharp slip-band traces, the 28,000 cal per mole process was uniquely characterized by extensive cross slip. 3) Theoretical calculations by Seeger and schoeck6 suggest an apparent activation energy for cross slip in A1 of about 24,000 cal per mole and another theoretical estimate by Friedel 7 gives the observed 28,000 cal per mole as the theoretical activation energy. It is therefore consistent with this evidence to, at least tentatively, ascribe the 28,000 cal per mole creep process in A1 to the operation of cross slip as the rate controlling mechanism. Although creep has been rather well-explored in the dislocation climb range, very little, excepting perhaps the activation energy, is known about creep in the cross slip range. This investigation was undertaken, therefore, to reconfirm the activation energy for creep in polycrystalline A1 in the intermediate temperature range and to study the strain-time relationship for creep at a constant stress in the cross slip region. EXPERIMENTAL PROCEDURE AND TECHNIQUE The three types of high-purity A1 alloy specimens described in Table I were used in this investigation. Specimens were milled from 0.100 in. thick cold-rolled sheets with their tensile axes in the rolling direction following which they were given a recrys-tallization and grain growth heat treatment at temperatures well above those which were subsequently employed in the creep tests.

Jan 1, 1962

By F. A. Schaufelberger

METAL can be recovered from a leach solution either indirectly by precipitation as a compound that is later reduced or directly by electrolysis, cementation, or chemical reduction, for example, with hydrogen. The widely used electrowinning processes suffer from the inefficiency of converting fuel to low voltage dc and from low current efficiency when complete recovery is attempted. With the batch hydrogen reduction methods outlined here, a unit of fuel converted to hydrogen in modern gas reform plants will make two to three times as much metal as can be obtained with electrolysis. With continuous hydrogen reduction, four to six times as much metal is obtained. Precipitation by reducing a metal salt solution with H, has been known for almost 100 years.&apos; Commercial use of the process, however, awaited the research and development program initiated by Chemical Construction Corp. Within the last few years this program has brought about construction of commercial plants, listed on page 545. Ideal hydrogen reduction will precipitate a pure metal from a solution obtained by commercial leaching methods at a rapid rate without excessive temperatures and pressures. The metal precipitate will be of desired size and density, less than a percent left in the vessel being deposited on the wetted parts. The present discussion will outline Chemical Construction Corp.&apos;s early development program and will discuss the chemistry and mechanics of reducing copper, nickel, cobalt, and cadmium from solution by H2. Work on selective reduction of nickel from cobalt has been described earlier.&apos; The article is not concerned with precipitation of copper by disproportionation of cuprous solutions where yield is limited3 to 50 pet.* It does not discuss use of gaseous reducing agents other than hydrogen, such as SO2,4 which may lead to contamination with sulfur, or C0,5 which is considerably more expensive than hydrogen and produces a gaseous reaction product, CO2.† The article does not include use of other nongaseous reducing agents,7 which are far more expensive than CO. Also, notes on the history, engineering design, and performance of commercial plants have been given elsewhere.&apos; It will be shown that a pure metal can be precipitated by reduction with hydrogen from solutions obtained by commercial leaching methods when the solution composition is controlled and proper acidity, proper metal ion concentration through controlled complex formation and hydrolysis, and adequate agitation for suspension of metal and for transfer of reducing gas are maintained. Reasonable temperatures and pressures are used which are less excessive than those used by previous workers, although they are maintained at above equilibrium values because of process kinetics.&apos; It has also been found necessary to induce nuclea-tion and to control growth and agglomeration in order to get a powder product of suitable physical properties. Review of the Literature Muller, Schlecht, and Schubardt of I. G. Farben10 claimed a successive reduction of silver, copper, nickel, cobalt, and zinc from ammoniacal solution by applying progressively higher temperatures and hydrogen pressures. Metals produced by this technique were not pure, since no attempt was made to adjust the solution composition between the different reductions. It is doubtful that the zinc product contained any metallic zinc. The major contribution to the literature" was made by the Ipatiews,12 who prepared platinum, iridium, copper, nickel, cobalt, lead, tin, arsenic, antimony, and bismuth at often extreme conditions, up to the critical temperature of water (373ºC), at 1500 to 7500 psi, for as long as several days. Even cadmium and zinc were claimed to have been observed in trace quantities precipitated together with basic salts. In the early experiments solutions were not stirred. Extensive formation of oxides and basic salts occurred, probably long before sufficient hydrogen could be supplied in the unstirred liquid to decrease the metal concentration in solution by reduction. The importance of hydrogen pressure was

Jan 1, 1957

By L. A. Weitzenkamp, N. M. Bashara

A study of the electrical conductivity of gold films less than 200 in thickness indicates a negative temperature coefficient of resistance and a thermal actiuatlon energy of less than 0.25 ev. The films consist of discrete metal islands of linear dimensions from a few angstroms to 1000A. Films were able to withstand applied fields up to 60,000 v per cm before breakdown occurred. A model for the conduction mechanism is proposed which involtes a Potential barrier due to work junction, irriage forces , and an electrostatic potential arising from separating an electron from a neutral island leaving behind a positively charged metal island. Activation energies of less than 0.25 ev ave consistent with this model, which includes a tunneling andor Thermal mechanism for conduction between the separate metal islands. An apparent satuvation effect in conductivity at high fields is observed experimentally. The saturation effect may be explained by the influence of the electrostatic contribution to the potential barriers for the transition through several islands adjacent to the original island which was activated to give up an electron. The proposed model gives Poor quantitative agyeement for the intermal electrical field between islands. ThIS paper will relate the structure of discontinuous metal films to the electrical properties and will emphasize the following topics: 1) the relation of the conduction mechanism to particle size and a comparison of particle size from electrical measurements with electron-microscope studies; 2) the saturation of the conductivity at high electric fields; and finally, 3) a comparison between the external field applied and the apparent field between particles. che- latter comparison points to a need for a modification in the model for the conduction mechanism first proposed by orter&apos; and expanded by Neugebauer and webb2 which will be dealt with in the discussion. The paper is based on results on gold films on glass microscope slides. The clms were vacuum-evaporated and were about lOOA thick, thickness being measured by interferometry. It has been observed that metal films of this thickness do not exhibit bulk metallic conduction. Films thinner than some critical thiclmess, depending upon substrate temperature and other factors, have conductivities which increase with increasing temperature with thermal activation energies of less than 0.25 ev. Electron-microscope studies3 have shown that these films consist of discrete metal islands having linear dimnsions from a few angstroms to approximately 1000A. When the metal is being vacuum-deposited on the substrate, islands on the order of a few angstroms appear first. As the deposition continues the islands may tend to agglomerate into larger particles and may eventually grow together into a continuous film,3&apos;&apos;&apos; In our tests the conductivity of the gold films was found to be about ten orders of magnitude less than the bulk conductivity of gold. When oxygen was introduced into the test chamber the conductivity decreased by a factor of about one-third. This can be related to an increase in work function for gold caused by adsorption of oxygen, as reported by Oullet and Rideal.s Exposure to an atmosphere of water vapor caused an increase in conductivity by a factor of 2 or 3 when a low field was applied. When the films were exposed to water vapor under a high field the conductivity increased by as much as two orders of magnitude. The activation energies measured were much less than the work function for gold, 0.25 ev or less, with the smaller activation energies observed for thicker films. It will be shown that the activation energy is a function of particle size and spacing. In general the model for the potential between metal islands would include the effective work function, the image force, the applied field, and an electrostatic term. The electrostatic contribution arises from the potential required to separate an electron from a conducting sphere. According to Neugebauer and webb2 the maximum potential due to the field and the electrostatic term only is

Jan 1, 1967