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By A. Simkovich, R. W. Lindsay

The possibility of using sodium sulfide slags to remove copper from ferrous alloys has been investigated by Jordan1 and by Langenberg.2, 3 In these studies, such slags were determined to be capable of removing copper and sulfur from the melt. The present work represents additional effort to clarify the effects of temperature on copper removal. The experiments were performed in a 17-lb induction furnace. Graphite crucibles contained the melts and kept the baths saturated with carbon. Temperatures were measured with a calibrated optical pyrometer and were controlled by manipulation of power input to the furnace. Estimated accuracy of temperatures in this investigation is ± 10°C (18°F) for measurements prior to slag additions, and + 20°C (36°F) after slag formation. The procedure consisted of melting 800 g of electrolytic iron. During this step, powdered graphite covered the exposed iron surface. After a predetermined temperature was reached, copper shot was added. A sample of the molten alloy for chemical analysis was then aspirated into a silica sheath. Next, a slag-forming mixture of sodium sulfite and graphite was added instantaneously to the melt. The sodium sulfite amounted to one-tenth the charge weight of iron; sufficient graphite was added to combine with oxygen in the sodium sulfite, assuming formation of carbon monoxide and reduction of the sulfite to sulfide. Subsequent to the slag addition, the molten alloy was sampled periodically, with the exception of heat A in which no intervening samples were taken between the slag addition and the end of the run. The iron was poured into a graphite mold, and the ingots sectioned and drilled for samples. Results of selected heats are presented in Table I. Analyses of samples drawn from the iron prior to slag addition are listed under zero time. Two samples from heat D were reported with copper contents greater than the initial concentration in the bath. Owing to the gradual but complete disappearance of slag during this heat, it is believed copper momentarily became more concentrated in the upper portion of the bath while reverting from the slag. This is the region from which samples were drawn. It should be noted that analysis of the ingot was equal to the copper content at the time of slag addition. The terminal temperatures of heats D and E, and the initial sulfur content of heat A are also to be noted. Because of the large temperature drop which occurred when slag was formed in heat D, power input to the furnace was increased in heat E after the slag addition, causing a higher terminal temperature. In heat A, the initial sulfur concentration was relatively high as compared to heats B through E owing to contamination by some slag remaining in the crucible from a previous heat. It is evident from Table I that copper was removed at the onset of slag formation. Roughly 30 pct of the copper was taken into the slag, with the exception of heat D, which had approximately 50 pct removed. For a comparatively short time of slag-metal contact, it appears that no gain is to be made in copper removal through use of high or low temperatures. If the slag initially formed remains in contact with the iron for an extended period, temperature has a marked effect upon copper removal, as can be seen by studying results for the two extremes in temperature. At about 1425°C, the copper level remained relatively constant after the initial removal by the slag. However, in the region of 1670°C, a definite reversion of copper occurred. Reversion was incomplete in heat D, and complete in heat E. The final temperatures of heats D and E differed by about 75°C. This temperature difference is thought to be the reason for only partial copper reversion in heat D. It is believed the effects of temperature noted above are related to the evolution of a white fume, which appeared in every run except heat A. (In the case of heat A, the fume was practically indiscernible.) After each slag addition, a yellow flame formed for about 5 sec. When the flame subsided, a white fume appeared. Upon contact with surrounding cooler surfaces, this fume deposited as a white solid. In the experiments made at 1425°C, evolution of fume continued unchanged to the end of the runs. However, heats D and E exhibited a different behavior. A very noticeable decrease in fume evolution from heat D was observed. Furthermore, this heat had much less slag remaining than did runs A through C when the experiments were terminated. No slag remained at the end of heat E; evolution of fume from this heat ceased prior to pouring. Spec-trographic analysis of the white deposit indicated sodium to be the major metallic element, with the maximum concentration of iron and copper as 0.1 and 0.01 pct, respectively. It is supposed the white fume observed in these experiments is principally sodium oxide (Na2O), formed by oxidation of sodium in the slag and subsequent sublimation. (Sodium oxide is a white to gray substance in the solid state; at 1275oC, it sublimes.4) According to this mechanism, elevated temperatures would accelerate removal of sodium from the slag, sulfur pickup by the

Jan 1, 1961

By C. W. Chen

MARTENSITE transformations in ß Cu-Al alloys have been studied by Greninger1 and other investigators. According to Greninger, the parent phase ß1 an ordered body-centered-cubic structure obtained from ß phase by suppressing the eutectoid decomposition, transforms into an ordered hexagonal-close-packed phase in composition containing 12.9 to 14.7 pct Al. The M, temperature decreases with increasing aluminum content; for the alloy containing 14.5 pct Al, for example, the ß1??' transformation occurs below room temperature. More recently, Kurjumow2 studied the transformation in ß Cu-Al alloys with the addition of nickel. His report stimulated new interest in the subject due to the observation of completely reversible transformation without hysteresis in the transformation temperature ranging from 10° to —10°C. In the present paper some characteristics are described of the transformation of Cu-Al-Ni alloys that were partly studied by Kurjumow. Experimental Procedure High purity copper (99.999 pct) and aluminum (99.99 pct) and electrolytic nickel were used in the preparation, by the Bridgman technique, of single crystal specimens which contained aluminum and nickel of 14.5 and 0.5 to 3.0 pct, respectively. Polished surfaces were prepared mechanically. Specimens were then chemically etched to remove distorted material, homogenized at 1000°C for several hours, and quenched drastically to room temperature in a 10 pct NaOH bath to produce the parent phase ß1. The transformation was studied under a microscope and, in some cases, recorded by means of motion pictures. A device similar to that designed by Greninger and Mooradian3 was used to cool and reheat the specimens. Results and Discussion When the specimens were cooled below room temperature, the ß1 to ?' transformation began at 10°C with the appearance of ?' crystals In relief, Fig. la. As the specimen temperature dropped further, the transformation continued, either by the growth of the ?' crystals, with the ß1 — ?' interface moving into the ß1 phase, Fig. 1c and 1d, or by the formation of new ?' crystals, Fig. 1b. As a consequence of the former process, banded structure is observed as a common feature of the low temperature phase. According to the theory of the formation of martensite by Wechsler, Lieberman, and Read,' the bands of ?' phase are probably twin-related, as is the case in the diffusionless phase change of In-T1 alloys,5 but this was not revealed by X-ray tech- niques. New ?' crystals, in needle form, often emerged suddenly across the ?' bands during the transformation. These acicular crystals then grew, both in length and in width, see Fig. 2a through 2d. The transformation on cooling is completed at about -35°C. Upon heating, the reverse transformation started at —10° C, in a manner nearly opposite to the transformation on cooling, and completed at 35°C. There was no noticeable change in the transformation temperature when the nickel content was varied within the limits previously mentioned. Through control of the specimen temperature, the transformation can be started, stopped, or reversed at will. This phenomenon has frequently been observed in the martensite transformation of many nonferrous alloy systems. Other systems are Au-Cd6 and In-Tl.5 ow-- ever, in the latter systems, the transformation is accomplished by single interface motion if the specimen composition is homogeneous and the temperature gradient in the specimen is uniform and sharp, whereas in the Cu-Al-Ni specimens, only multiple interface transformation is observed. The speed of the interface motion appears to be a functionof the rate of temperature change and the temperature gradient across the specimen length. In one case, in which the temperature increased at the rate of 10°C per min and there was no temperature gradient along the specimen axis, the speed of the disappearance of a ?' plate was determined, by the study of the motion pictures made, to be 26 µ per sec. Quench markings were observed on the polished surfaces of specimens. The markings were grouped into one or more sets of different orientations, and were parallel in each set. The ?' plates formed in subsequent transformation were parallel to the markings, indicating that the ?' plates and the quench markings had the same geometric relation-ship to the ß1 matrix. The quench markings on two intersecting surfaces of a specimen were therefore used in the determination of the habit plane of transformation, by the trace method suggested by Barrett.' Results obtained from five sets of markings in three specimens indicate that the habit plane is an irrational plane about 2" from one of the {221} planes. This is very close to the habit plane (3" from 221 planes) of ß Cu-Al alloys containing more than 13.0 pct Al.1 The martensite transformation of Cu-Al-Ni alloys is reproducible. No sluggishness was found between consecutive transformation cycles, although a slight difference in the distribution pattern of the ?' plates was observed, compare Figs. Id and 2d. The transformation can be strain-induced. This characteristic has been tested by a simple method. When a specimen was elastically strained slowly in a vise, ?' plates were gradually produced in the same fashion as during transformation on cooling, This test was done at room temperature, and thus above the M,

Jan 1, 1958

By N. Van Wingen, Norris Johnston

Laboratory flood pot testing of California sands has progressed to a considerable extent in the past 18 months. Flood evaluations have been carried out on over 200 large core samples. Many of these were heavy oil sands of high permeability and completely unconsolidated in nature. The oil frequently formed a bank, though some of the oil was recovered in the subordinate phase of the flood, by viscous drag. Flood pot recoveries as high as 1400 bbl/acre ft have been recorded. Reservoir analysis suggests a conformance factor of 0.4 to reduce laboratory recovery to probable field practice. Oils with viscosities up to 1800 cp have been successfully handled in flood pot evaluations. The shallow, loose sands are not well adapted to the application of- high pressures to offset the high viscosities. INTRODUCTION Secondary recovery may be said to have started 60 years ago when accidental floods occurred in the Bradford sand in Pennsylvania. About 1921 artificially conducted water drives came into extensive use and since that time the great Bradford field has been almost completely subjected to water flooding. During the last 30 years, most of the known medium and deeper production in California has been discovered and is being exploited by primary recovery methods supplemented in some instances by high pressure gas injection. The California area is just beginning to feel the need for secondary recovery in view of an unprecedented market demand and the rapidly rising cost of new pool discoveries. With the presently recognized desirability of secondary recovery in California, there must also be appreciated a number of serious differences between the water flooding problems here as compared to the territory east of the Rockies. California sands are generally thicker, and are frequently soft and argillaceous. The oils are often heavier and asphaltic. Much of the oil is below 15°API, occurs at shallow depth, is cool and free from appreciable dissolved gas, which results in relatively high reservoir oil viscosity. Secondary recovery is particularly beneficial where primary recovery has been poor and where no natural water drive exists. These conditions apply particularly to the heavy, shallow, clean production from soft, often argillaceous California sands so abundantly found at depths less than 1500 feet. Often, too, there is a totally insufficient supply of water of satisfactory quality to inject at a reasonable cost. Also, the crude oils are priced far below the premium Bradford crude. Although these and a number of minor problems beset the operator desirous of starting secondary recovery, great progress has been made in the past few years in finding how to adapt previous Mid-Continent and Eastern experience to water flooding in California. There are about nine projects for subsurface injection of water which can be said to classify as secondary recovery operations. Subsurface water disposal would so classify when the sand receiving the water is a nearby oil producer, as is often the case. When water is injected subsurface into a barren sand, the operation does not classify as secondary recovery. Several of the most active operators avail themselves extensively of preliminary engineering and laboratory work to guide their decisions, while others enter small scale flooding operations directly in the field. It is the laboratory work pertinent to several of the California secondary recovery projects that this paper discusses. PURPOSES OF LABORATORY FLOODING TESTS Experience in areas where water flood operations have been carried out has indicated that careful engineering planning is an important requisite for subsequent economically successful field operation. Floods that fail are more frequently those where operations were instigated without a prior engineering investigation to determine the effectiveness of the injection fluid as an oil displacing medium. Laboratory data are essential in the evaluation of an oil property for secondary recovery possibilities. Success or failure of secondary operations can under certain special circumstances be determined directly by cores and their subsequent routine analysis. This is particularly the case where flushing of the cores in the course of coring is negligible and where the results of the analysis can be compared with existing secondary recovery operations. Where these conditions cannot be' fulfilled, the application of core analysis is more limited. In such event, the results obtained by water flooding core samples in the laboratory have been found to be of prime importance. Cores may be flooded "raw" as taken from the well or in the event flushing and depletion of the cores in the process of drilling are major factors the fluid content may be artificially restored prior to the flooding. Laboratory studies should also be made to determine the suitability of the water selected for injection. Thus interaction between injected and formation water may cause precipitates to be formed which may plug the sand. Even more important, especially to California operations, is the possibility of the hydration of formation clays by the injection water. The aims of flood pot and associated tests are basically to determine the residual oil saturation after flood, the water-oil throughput ratio and to establish whether an oil bank is formed. Additional information which can be obtained from flood pot tests pertains to the pressure differential required to effect displacement, the relative permeability to oil in the oil bank and the relative permeability to water in the watered out region behind the bank.

Jan 1, 1953

By Cuppam Dasarathy

The incidence of liquid inzmiscibility in binar)) indium alloys has been theoretically analyzed on the basis of the Hildebrand-Alott equation. Bedictions of miscibility or otherwise Imve in general been found to agree with those phase diagrams that are already publislzed in the literature. Out of a total of 27 systems, where either the complete phase diagrams are published or liquid immiscible behavior is reported, the Predictions agree with the experimental data in 25 systems, the exceptions being the Te-In and Ni-In systems. According to the equation, liquid immiscibility is also indicated in the binary alloys of indium with K, Rb, Cs, Na, Sr, Ba, Ti, Zr, V. Nb(Cb), Ta, W, U, Re, Ru, Rh, Os, and Ir. RECENT investigations by the author have shown that indium when alloyed with iron, chromium, and cobalt shows liquid immiscible behavior.1"3 The Fe-In phase diagram shows a wide range of compositions where the liquids are immiscible.4,5 No intermediate phases are present in this system. No precise information is available about the extent of liquid immiscibility in the Co-In system. However, it is certain that there is a range of compositions where the liquids are immiscible and that there are two or three intermediate phases,376 in the system. Liquid immiscibility is also strongly indicated in the Cr-In system and no evidence was obtained in the brief investigation to indicate the presence of intermediate Cr-In phases.2 The present paper deals with a theoretical analysis of binary alloys of indium with certain elements of the periodic table and indicates the systems where liquid immiscibility may be expected. The incidence of liquid immiscibility in binary systems has been theoretically examined by many workers and many excellent papers are available on the subject. In this paper, the alloy systems are examined on the basis of the more recent ideas proposed by Mott.7,8 It has been claimed8 that the Mott parameter predicts the incidence of miscibility or otherwise with reasonable accuracy and consistency. BACKGROUND TO MOTT&apos;S APPROACH Hildebrand applied his immiscibility rule for non-polar liquids to various alloy systems.9 The basis of this rule is that the equation for the excess free energy of formation of a liquid solution is rather similar to the theoretical expression for the energy of mixing of a regular solution. He postulated that when the heat of mixing is sufficiently high, separation into liquid phases will occur and the condition for complete CUPPAM DASARATHY is at the Research Centre, British Steel Corporation, (South Wales Group), Port Talbot, Glamorgan, Great Britain. Manuscript submitted March 12, 1969. IMD miscibility was shown as where VA and VB were the atomic volumes of the components A and B, and ?EV the energy of vaporization of the component. The term (?EVA/VA)1/2 was regarded as a measure of the binding energy of the component A and was called the L&apos;solubility parameter" 8A. On this basis immiscibility occurs when 1/2(VA+VB)(bA-bBf > 2RT [2] Apparently, however, there were several inconsistencies in that according to Eq. [2] several systems known to be miscible in the liquid state were predicted as immiscible. MOTT&apos;S ANALYSIS ~ott&apos;" regards that the reason for the inconsistencies arising out of Hildebrand&apos;s equation was largely due to the electrochemical attraction between the two elements, not being considered. Hence, Eqs. [I] and [2] were modified by taking into account the electro-negativities of the two elements XA and XB, and Mott arrived at an equation for immiscibility, i(VA + VB)(6A - aB)2 - 23,Q60n(XA - XBf > 2RT [3j which can be written as i **&£*&* >&apos;*°™- &apos;• HI T being the melting point of the more refractory component of the system. In Eq. [4], the numerator was called the Hildebrand term, the denominator, the electronegativity term, and their ratio, the Mott number. Mott observed that if the Mott number of a given binary system was greater than the maximum number of Pauling bonds which the two metals could form, then liquid immiscibility could be expected. The maximum number of bonds formed by a given metal was considered to be directly related to the number of bonding electrons available, i.e., to its maximum valency. Since the valencies of the elements considered vary from 1 to 6, Mott assumed that if the ratio of the Hildebrand term to the electronegativity term was >6, then immiscibility could be expected. On the contrary, if the ratio is <1, the metals should be miscible. Further, the alloying behavior is not only influenced by the valencies of the two elements but also by the relative atomic sizes that influence the types of packing and hence the coordination number. Mott considers that on average the maximum number of near neighbors of unlike atoms is 6. Thus, on both valency and size factor considerations, Mott concludes that the maximum number of bonds&apos; possible in any system was 6, this being the upper limit of the Mott number for miscibility. In considering the alloying behavior of systems with Mott numbers between 1 and 6, Mott plotted the num-

Jan 1, 1970

By F. C. Turin, K. M. Cornelius

1. INTRODUCTION Underground mining in the USA has undergone significant change in the past 20 years. Two key elements have been increased mechanization and a more educated work force in spite of these changes, many jobs continue to be labor-intensive and repetitive in nature. They entail tasks that, performed over time, can take a toll on the soft tissues and joints. The problem may be compounded by an aging mining workforce. In 1996 the mean age of the coal mining work force was 45 years and the median total years of experience was 20 (NMA 1998). As a person ages, the body resilience to chronic wear and. tear is reduced, which may cause a worker to pay an increasingly higher health price for performing the same task. Mining companies, like many others, are becoming more aware of cumulative effects to the worker as reports of these types of injuries rise. . Conducting a job analysis is an important step when considering a job redesign or modification to reduce worker cumulative trauma exposure. A basic approach to job analysis is to examine the types of aches and pains reported, the tasks performed, and work site conditions. The US Bureau of Mines (USBM) conducted an evaluation of roof-bolting tasks performed at an underground coal mine concerned about early warning signs of cumulative trauma. This evaluation will comprise the primary focus of this chapter. The approach used for the roof-bolting race study may be applicable to other work environments. 2. FUNDAMENTALS OF CUMULATIVE TRAUMA EXPOSURE Musculoskeletal injury is a term used to describe a wide range of soft tissue disorders that affect the nerves, tendons and muscles. Common examples include lower back pain, tendinitis and carpal tunnel syndrome. The majority of these injuries are not the result of sudden mishaps, but usually develop gradually from repeated wear and tear. Symptoms may not appear immediately, but can take weeks, months or even years. Symptoms may result from many types of activities, performed at work or at home, and it is often difficult to attribute there to a single event. In fact, it is more common to identify factors that may have contributed to the development of the condition. The terms repetitive strain injuries or cumulative trauma disorders (CTD) have been commonly used to refer to disorders that have occurred due to work-related activities. Three main risk factors contribute to CTD: force, repetition and awkward postures. Any one or combination of these may contribute to the development of CTD. Therefore, the design of equipment in conjunction with the required tasks should be evaluated when attempting to reduce these risk factors. Examining the layout of the work area to help identify tasks which may contribute to cumulative trauma is necessary. The following list (Putz-Anderson 1988), describes ergonomics concerns that, overall, should be minimized at the work area: • Crowding or cramping the worker: a work area layout may unnecessarily constrain movements of the worker. • Twisting or turning: placement of tools and materials may require the worker to twist the spine to fulfill the requirements of the job. • Repeated reaching motions: the layout of the work area may require the worker to lean to reach and grasp the necessary tools and controls. • Misalignment of body parts: the arrangement of the work area may require the worker to frequently have one shoulder higher than the other or have the neck or spine bent to one side. While many of these concerns are a function of equipment design and environmental conditions, making workers aware of these issues may help them to adapt their work habits to reduce risk of injury. Additionally, this information is useful when conducting an ergonomic evaluation of a work area and associated tasks. 3. UNDERGROUND MINING ENVIRONMENT The underground mining environment is a unique challenge. It is more difficult to develop controls for an underground mine site as compared with a factory setting where equipment and facilities can be more easily designed to reduce worker force, posture and repetitive exposures. In an underground mine, workers are required to perform labor-intensive tasks that often cannot be avoided due to environment constraints. The dynamic nature of the environment does not allow easy implementation of mechanical assists to reduce force exposure. Many of the tasks performed by workers are repetitive. Restrictive work areas due to low ceiling height, low lighting levels and large pieces of equipment cause workers to perform these tasks in postures that are not desirable. Designers of underground mining equipment can control how a machine will function, but not the environment in which it will be used, Hazards in an underground mine cannot be completely removed by redesigning the system. There are many hazards and information sources that must be continually monitored by workers including their position in relation to large pieces of mobile equipment and unpredictable geological anomalies. Thus, immediate dangers may take priority over awareness of ergonomic considerations while performing a job. 4. CASE STUDY OF UNDERGROUND ROOF BOLTING 4.1. Roof Bolting and Cumulative Trauma Exposure In an underground coalmine, after an area is mined it is necessary to support the roof to keep it from collapsing. Since 1950, the primary method for supporting the mine roof has been installation of roof bolts. Long bolts installed into the roof compress the layers of strata achieving a uniformly distributed support anchorage. Roof bolts, typically 6-8 feet long, are installed by workers using large roof-bolting machines. There are different types of machines

By Arnt Solbu, Jomar Thonstad

The reaction between CO, and aluminum in cryolite-alumina melts in contact with aluminum has been studied by passing CO2 over the melt. In unstirred melts a homogeneous reaction between dissolved metal and dissolved CO2 was observed. In stirred melts in which convection was induced by bubbling argon through the melt, the dissolved metal apparently reacted mainly with gaseous CO2. The rate of formation of CO increased slightly with increasing depth of the melt, and it did not depend on whether CO2 was passed over or bubbled through the melt. The rate of formation of CO increased with increasing area of the metal/melt interface and with the application of anodic current to the metal. It is concluded that the dissolution of metal into the melt is the rate-determining reaction. THE current efficiency in aluminum electrolysis is determined by the rate of the recombination reaction between the anode gas and the metal: 2A1 + 3CO2—A12O3 + 3CO [1] as originally stated by Pearson and waddington.1 The occurrence of this reaction in cryolite-alumina melts in contact with aluminum was first verified experimentally by Schadinger.2 Thonstad3 has shown that the reaction may proceed further to give free carbon: 2A1 + 3CO— A12O3 + 3C [2] Normally only a few percent of the CO formed undergoes such reduction. The mechanism of these reactions has not yet been clarified. Aluminum, as well as CO,, is soluble in the melt. The solubility of aluminum in cryolite-alumina melts at around 1000°C corresponds to 75 x 10- 6 mole A1 per cu cm,4 while that of CO2 is only 3 x 10-6 mole CO, per cu cm.5 Taking into account the stoichiometry of Reaction [I], the ratio between dissolved aluminum and dissolved CO2 available for the reaction in a saturated melt is about 40. Therefore, as will be shown in the following, the reaction probably mainly occurs between gaseous COa and dissolved aluminum. The dissolved aluminum presumably consists of subvalent ions of aluminum and sodium.4&apos;6 Since the interpretation of the present results is not dependent upon the nature of this solution, the dissolved metal will be designated solely as Al+ in the following. The reaction can then be divided into four steps: A) dissolution of metal, e.g., 2A1 + Al3 — 3A1+ [3] B) diffusion of dissolved metal through a boundary layer; C) transport of dissolved metal through the bulk of the melt; D) Reaction [1]. If dissolved CO, takes part in the reaction, three additional steps embodying the dissolution and transport of CO2 must be added. schadinger2 observed, when bubbling CO2 through the melt, that the rate of formation of CO (in the following designated rfco) did not depend on the distance from the metal surface. The results also indicate that the rate of bubbling did not affect the rfco. When passing CO, over the melt, Revazyan7 found that the loss of metal did not depend on the depth of the melt above the metal or on the flow rate of CO2, and concluded that Step A is rate-determining. In an unstirred melt, however, Gjerstad and welch8 found that the rfCo decreased with increasing depth of the melt, indicating that step C was rate-determining. It thus appears that the rate control of the process depends on the experimental conditions, particularly on the convection. In the present measurements the reaction has been studied in unstirred as well as in stirred melts. EXPERIMENTAL AND RESULTS The experiments were carried out at 1000°C in a Kanthal furnace with a 10-cm uniform temperature zone (±0.l°C). The melts were made up of "super purity" aluminum (99.998 pct), hand-picked natural cryolite, and reagent-grade alumina. In experiments where alumina crucibles were used, the alumina content in the melt was close to saturation (13.5 wt pct9); otherwise it was 4 wt pct. Pure Co2 (99.85 pct) was passed over the melt, and the exit gas was analyzed for CO2 and CO by the conventional absorption method.3 From the weighed amount of CO (as CO2) the rfco was calculated as the number of moles of CO formed per min per sq cm of the surface area of the melt. The amount of carbon formed by Reaction [2] was not determined. As already indicated the rfco is much higher than the rfC, by Reaction [2]. Since the rfC probably is proportional to the rfco, the measured rfco should then the proportional to, but slightly lower than, the total rate of Reactions [I] and 121. In general the scatter of results obtained in duplicate measurements was ±5 to 10 pct, while within a given run a precision of ±3 to 5 pct was obtained. The various crucible assemblies that were used will be described below. Measurements in Unstirred Melts. When carrying out aluminum electrolysis in small alumina crucibles. Tuset10 observed that after solidification the lower part of the electrolyte was gray and contained free metal, while the upper part near the anode was white and contained no metal. One may test for the presence of free metal by treating with dilute hydrochlorid acid.

Jan 1, 1969

By George W. Mitchell

THE property of Eureka Corp. Ltd. is located in the approximate geographic center of Nevada, 2 miles from Eureka, the county seat. The great sources of power, the Colorado, Snake, and Salmon Rivers and the rivers of northern California, are 300 to 500 miles distant, and no lines serve areas closer than 150 miles. Fuel for diesel and steam generation is available in Utah, 300 to 400 miles to the east. Eureka&apos;s railhead is 80 miles north where two trunk lines cross the county. A spur line serves Ely, 77 miles east. Good highways connect Eureka to the railheads. Activity in the Eureka mining district began in the early 1870&apos;s. The oxidized high grade lead-sil-ver-gold ore terminated against the footwall of the Ruby Hill fault, and in 1890 the main operations ceased. In 1938 Eureka Corp. Ltd. discovered ore in the hanging wall of the fault by diamond drilling. The history of Eureka in the late 1800&apos;s indicates that there was some water at 600 to 800 ft in the old workings, probably accumulations above the water table which did not seriously interfere with mining operations. Both the Locan and Richmond shafts were sunk to a level below the table, but apparently the only serious difficulty with water occurred in the Locan. The steam pump used when the last work was done on the 1200 level in 1923, many years after exhaustion of the main orebodies, is still installed on the Locan 900 level. The capacity was about 500 gpm, lifting 750 ft to the 100 level, which connected with the surface. In addition to this. bailers were used to keep the 1200 level free of water. It is said that pumping in 1923 lowered the water in the Holly shaft, about a mile and a half away, but this seems doubtful. The pumping was of short duration because no ore was found. When work at the new Fad shaft was started in 1941 Eureka Corp. Ltd. engineers were fully aware of the probability of encountering water in large volume. Their primary exploration and development had to be carried on at the 2250 level. The first water was encountered at 300 ft. This was undoubtedly surface drainage in the bedding of the Pogonip limestone and was less than 100 gpm. The fractured, loose Hamburg dolomite at the water table was not well cemented, and relatively little water, 300 gpm, percolated through it with difficulty. At 1350 ft well-cemented dolomite containing some open fractures was encountered. These fractures produced the first water of consequence, 750 gpm. At 1700 ft the volume was 1000 gpm increasing to the maximum during shaft sinking, 1600 gpm, at the 2000 level. Secret Canyon shale, a dry formation, was entered at 2100 ft, where a concrete water ring was placed to catch all of the water. The volume decreased rapidly to a constant flow of 1200 gpm. Below 2100 ft the shaft and stations remained in the shale and water was not a problem. Several faults of moderate displacement, including the reverse Martin fault, had been intersected during the traversing of 1000 ft of wet Hamburg, but no undue quantities of water were encountered. Observations in the diamond drill holes in the ore zone area showed a rapid lowering of the water table. The shaft was flooded when it left the dry shale and entered the water-bearing Eldorado dolomite on the 2250 level, crossing a fissure which paralleled the Martin fault. High pressure water doubled the volume then being pumped. Pipe failure through a water door bulkhead was a contributing factor. Immediately following this flooding in March 1948 preparations were made to recover the shaft as rapidly as possible by increasing power and pump capacities as needed. Measurements before flooding indicated the water could be lowered at a fast rate. However, the water table did not recede as rapidly as expected and volumes required to lower the water in the shaft were higher. Obviously the size of the main water channel on the 2250 level was increasing because of erosion, allowing greater volumes to enter the workings and draining beyond the cone originally being drained during shaft sinking. Eroded material was being deposited in the shaft below the 2250 level in serious proportions. In December 1948 a second flooding of the Fad shaft was allowed for the purpose of reassessing existing conditions and studying alternate methods of attack. The detailed geology of the Eureka mining district, see Fig. 1, has been described during the past 75 years by many geologists.&apos; Only the general features and those which seem to affect the drainage problem will be discussed. The old ore zone, mined between 1870 and 1890, is located in a wedge-shaped block of Eldorado dolomite between the footwall of the Ruby Hill fault and the underlying Prospect Mountain quartzite, see Fig. 2. Production of high grade oxidized lead ore containing high values in gold and silver has been variously estimated at $50 to $90 million. The tonnage mined was probably close to 1,500,000, nearly all of which was found above the water table. The new ore, discovered by diamond drilling in the hanging wall of the Ruby Hill fault, is a flat-

Jan 1, 1954

By A. F. van Everdingen

The pressure drop in a well per unit rate of flow is conrolled by the resistance of the formation, the viscosity of the fluid. and the additional resistance concentrated around the well bore resulting from the drilling and completion technique employed and, perhaps, from the production practices used. The pressure drop caused by this additional resistance is defined in this paper as the skin effect. denoted by the symbol S. This skin effect considerably detracts from a well&apos;s capacity to produce. Methods are given to determine quantitatively (a) the value of S, (b) the final build-up pressure, and (c) the product of average permeability times the thickness of the producing formation. INTRODUCTION Equations which relate the pressure in a well producing from a homogeneous formation with pressures existing at various distances around the well are generally used within the industry. The relation ii quite simple when the fluid flowing is assumed to be incompressible. It becomes somewhat more complicated when the flowing fluid is considered compressible so that the duration of the flow can he considered. In each case the major portion of the pressure drop occurs close to the well bore. However analyses of pressure build-up curves indicate that the pressure drop in the vicinity of the well bore is greater than that computed from these equations using the known, physical characteristics of the formation and the fluids. In order to explain there excessive drops it is necessary to assume that permeability of the formation at and near the well bore is substantially reduced as a result of drilling. completion and, perhaps. production practice. This possibility has been recognized in the literature. A method to compute the pressure drop due to a reduction of the permeability of the formation near the well bore. which is designated as the skin effect. S, is given in the following paragraphs. To start, equations normally used to describe flow in the vicinity of a well are given without considering this effect. These equations then are modified to include the effect of a skin on the pressure behavior. Finally a method is given to estimate the effect of the skin on the pressure and production behavior of a well. PRESSURE EQUATIONS Incompressible Fluid Flow If p is defined as the flowing pressure in a well of radius the pressure at distance r from the well has been shown to be:" The total pressure drop between the drainage boundary, and the well bore is given by These equations are valid only if the flow towards the well occurs in a horizontal homogeneous medium and the fluids are incompressible. The assumptions imply that all fluid taken from the well enters the system at r a condition rarely encountered in practice. Compressible Fluid Flow, Steady State A more realistic equation is obtained if it is assumed that the compressibility, c, of the flowing fluids is small and has a constant value over the pressure range encountered. After the well has been producing for some time so that its rate has become constant and steady state is reached, the pressures throughout the drainage area are falling by the same amount per unit of time, and the pressure differences between a point in the drainage area and the well are constant. When these conditions are met. the rate of production, q, from a well is equal to where dp/dt is the pressure drop per unit time. The fluid flowing at a distance from the center of the well is equal to From the last equation and from Darcy&apos;s law it can be shown that The equation holds for a depletion-type reservoir of radius drained by a well located in its center, provided the compressibility of the fluid per unit pressure drop is small and constant, and no fluid moves across the boundary Compressible Fluid Flow — Nonsteady State Table 111 of reference (5) shows the relationship between the pressure at the well bore and the reduced time, The pressure-drop function, p represents the drop below the original reservoir pressure, p caused by unit rate of production for several values of R, the ratio of drainage boundary radius to well radius, r In most reservoirs the values of approach infinity. and under these conditions the values of p shown in Table I of reference (5) can be used where p then signifies the difference between the pressure in the well and the prevailing reservoir pressure per unit rate of flow. The total pressure drop below prevailing reservoir pressure amounts to where the factor converts the cumulative pressure drop per unit rate of production to cumulative pressure drop for actual rate. q. For values of T > 100 the P function may be written (equation VI-15 of reference 5) as Using the time conversion the difference in pressure between reservoir and well becomes If values for the physical constants of the formation and the fluids are inserted, it is found that T exceeds 100 after a few seconds of production (or closed-in time), so that the approximation becomes valid almost at once. A simple relation between the pressure in the well and in the reservoir can also be derived by considering the well as a point source"" &apos;" instead of a unit circle source, that is, by using Lord Kelvin&apos;s solution instead of the unit circle source

Jan 1, 1953

By N. F. Dyson, T. R. Scott

The iilzfluence of catalytic agents on the oxidation of ZnS has been studied under pressure leaching conditions, using a chemically prepared sample of ZnS which was substantially unreactive on heating at 113°C with dilute sulfuric acid and 250 psi oxygen. Nurnerous prospective catalysts were added at the ratio of 0.024 mole per mole ZnS in the above reaction but pvonounced catalytic activity was confined to copper, bismuth, rutheniuwl, molybdenum, and iron in order of. decreasing effectiveness. In the absence of acid, where sulfate was the sole product of oxidation, catalysis was exhibited by copper and ruthenium only. Parameters affecting the oxidation rate were catalyst concentration, temperature, time, oxygen pressure, and a7riount of acid, the first two being most important. The main product of oxidation in the acid reaction was sulfur, with trinor amounts of sulfate. An electrochemical (galvanic) mechanism has been suggested for the sulfuv-forming reaction, whereby the relatively inert ZnS is "activated" by incorporation of catalyst ions in the lattice and the same catalysts subsequently accelerate the reduction of dissolved oxygen at cathodic sites on the ZnS surface. Insufficient data was obtained to Provide a detailed mechanism for sulfate fornzation, which is favored at low acidities and probably proceeds th&apos;rough intermediate transient species not identified in the preseni work. THE oxidation of zinc sulfide at elevated temperatures and pressures takes place according to the following simplified reactions: ZnS + io2 + H2SO4 — ZnSO4 + SG + HsO [i] ZnS + 20,-ZSO [21 In dilute acid both reactions occur but Reaction [I] is usually predominant, whereas in the absence of acid only Reaction [2] can be observed. Both proceed very slowly with chemically pure zinc sulfide but can be greatly accelerated by the addition of suitable catalysts, as suggested by jorling&apos; in 1954. Nevertheless, an initial success in the pressure leaching of zinc concentrates was achieved by Forward and veltman2 without any deliberate addition of catalytic agents and it was only later that the catalytic role of iron, present in concentrates both as (ZnFe)S and as impurities, was recognized and eventually patented.3 It is now apparent that another catalyst, uiz., copper, may have also played a part in the successful extraction of zinc, since copper sulfate is almost universally used as an activator in the flotation of sphalerite and can be adsorbed on the mineral surface in sufficient amount The importance of catalysis in oxidation-reduction reactions such as those cited above has been emphasized by various writers and Halpern4 sums up the situation when he writes that "there is good reason to believe that such ions (e.g., Cu) may exert an important catalytic influence on the various homogeneous and heterogeneous reactions which occur during leaching, particularly of sulfides, thus affecting not only the leaching rates but also the nature of the final products." Nevertheless relatively little work has appeared on this topic, one of the main reasons being that sufficiently pure samples of sulfide minerals are difficult to prepare or obtain. When it is realized that 1 part Cu in 2000 parts of ZnS is sufficient to exert a pronounced catalytic effect, the magnitude of the purity problem is evident. An incentive to undertake the present work was that an adequate supply of "pure" zinc sulfide became available. When preliminary tests established that the material, despite its large surface area, was substantially unreactive under pressure leaching conditions, the inference was made that it was sufficiently free from catalytic impurities to be suitable for studies in which known amounts of potential catalytic agents could be added. The first objective in the following work was to identify those ions or compounds which accelerate the reaction rate and, for practical reasons, to determine the effects of parameters such as amgunt of catalyst, temperature, time, acid concentration, and oxygen pressure. The second and ultimately the more important objective was to make use of the experimental results to further our knowledge of the reaction mechanisms occurring under pressure leaching conditions. The fact that catalysts can dramatically increase the reaction rate suggests that physical factors such as absorption of gaseous oxygen, transport of reactants and products, and so forth, are not of major importance under the experimental conditions employed and an opportunity is thereby provided to concentrate on the heterogeneous reaction on the surface of the sulfide particles. As will appear in the sequel, the first of these objectives has been achieved in a semiquantitative fashion but a great deal still remains to be clarified in the field of reaction mechanisms. EXPERIMENTAL a) Materials. The white zinc sulfide used was a chemically prepared "Laboratory Reagent" material (B.D.H.) and X-ray diffraction tests showed it to contain both sphalerite and wurtzite. The specific surface area, measured by argon absorption at 77"K, varied between 3.9 and 4.6 sq m per g. Analysis gave 65.0 pct Zn (67.1 pct theory) and 31.9 pct S (32.9 pct theory). Other metallic sulfides (CdS, FeS, and so forth) used in the experiments were also chemical preparations of "Laboratory Reagent" grade. Samples of mar ma-

Jan 1, 1969

By Harold A. Krueger

FACILITIES and mining operations of the National Lead Co., St. Louis Smelting and Refining Division, near Fredericktown, Mo., are situated in a famous mining area. Copper, lead, nickel, and cobalt have been mined here for more than 100 years, work having been started on a high sulphide copper outcrop in 1847. Lamotte sandstone is characterized by differential compaction on a rigorously eroded pre-Cambrian surface. The Bonneterre formation was therefore a good host for minerals not generally found in mineable quantities in these midwestern areas. Unusually complex minerals, however, make beneficiation difficult, and because of irregular ore thicknesses and elevations many engineers and operators have not attempted to mine the property. Others have tried who failed. This paper deals with economic, efficient, and competitive methods of mining these highly irregular orebodies, as compared to the open-stope, room-and-pillar methods normally used for horizontal-bedded lead deposits. For the purpose of this study it should be understood that the ore is found in two distinctly different types of occurrences, one to be designated as basin ore and the other as contact ore. Mining of basin ore is complicated by many faults, fractures, cross faults, and breaks. Contact ore is complex because it is found on flanks or slopes of pre-Cambrian knobs or highs. The dip of the mining floor for the latter type varies between 18" and 45". Occurrences of both types of ore are complicated by water courses or solution channels which carry unconsolidated shale, lime, sand, and dolomite. This material is also found between the bedding planes of the members of the Bonneterre formation. The water found where there are fractures, faults, and channels makes it very fluid and tacky, see Fig. 1, particularly after it has been blasted and handled by loading and hauling machines. Much of the ore can be wadded and thrown without dispersing. During early operations by the Buckeye Copper Co. in 1861 and the North American Lead Co. from 1900 to 1910, conventional narrow-gage railroad and side dump mine cars were used with hand shoveling. The complications of mining the contact ore, the only type attempted at this time, can be appreciated when it is realized that operators were obliged to use mules for haulage. Haulageways constructed on these slopes were of necessity similar to wagon trails or goat trails up the side of a mountain. In other words, it was merely a matter of going from side to side of the strike length of the slope, gaining a little in elevation on each shuttle trip. Production totaled only one to two tons per manshift. A few years later, about 1913, the property was purchased by combined Canadian interests known as the Missouri Cobalt Co., and the use of trolley locomotives was initiated. Between 1900 and 1928 a land agent using churn and diamond drilling methods prospected scattered sections of the area. In 1928 the first property was purchased by the present company, then operating as the St. Louis Smelting and Refining Co. Check drilling and prospecting was carried out by the company at various times between 1928 and 1939 to correlate the erratic mineralization. Much information about both types of orebodies was accumulated, but it was still questionable as to whether money should be invested to work these occurrences. In anticipation of high lead and copper prices, about the time World War II started, it was decided to develop and bring into production some of this ore. In 1942 No. 1 shaft was put down on the largest basin-type orebody and in 1943 No. 2 shaft was put down on contact-type ore. Operations were expanded when No. 3 shaft was completed in 1943, and progressed further in 1948, when National Lead Co. dewatered and opened No. 5 and 6 mines, old workings of the North American Lead Co. and the Missouri Cobalt Co. Because of the differential compaction of Lamotte sandstone over the pre-Cambrian porphyry, in some instances mineable thicknesses of basin-type ore occurred 20 to 30 ft above the sand. This is the exception rather than the rule, since most of the mineralization starts at the sand and is variable in thickness. The ore was attacked, therefore, by development drifts and crosscuts at the lowest possible elevation, where the ore immediately overlying the Lamotte sandstone could be drained and made accessible for mining. It was planned to connect to the drifts and crosscuts with raises to mine ore deposited 20 to 30 ft higher. The higher orebodies were thus mined as slusher levels. Slusher hoists were used to drag the ore into the raises, which were made into hoppers. The ore was then loaded into 32x32-in. ore cans, hauled to the shaft by battery locomotives, and hoisted by the conventional Tri-State method. The rate of efficiency was 5 to 6 tons per manshift underground. The contact-type ore was attacked in a similar way, except that the orebodies were not nearly so wide, so that they were more flexible for slusher loading into cans. This advantage was offset, however, by haulage complexities, since the railroad was constructed on steep slopes. Through experience and ingenuity, many improvements were made in mining both types of ores. The two levels, so-called, in the basin-type ore-bodies were connected as previously planned, more efficient locomotives replaced the older ones, and a

Jan 1, 1954

By Ming-Kao Yen

A considerable amount of work has been reported in the literature in regard to the texture and earing behavior of copper strip. The rolling texture of copper has been confirmed as (110) [112] and (112) [111], which yields ears of a drawn cup at the position 45" from the rolling direction.1-3 The recrystallization texture has been established as the cubic or (100) [001] texture, where the earing positions are at 0" and 90" to the rolling direction.4-8 It has also been reported that in the development of cubically aligned grains of copper strips, the percentage of this cubic texture increased with an increase of final reduction and final annealing temperature.8,9 A comprehensive study on H.C. copper (British commercial copper of high-conductivity quality = Cu 99.95 pct, O2 0.03 pct, Ag 0.003 pct, Fe 0.005 pct and Pb < 0.001 pct) was made by Cook and Richards.6 They concluded that the recrystallization textures could be described as one or more of the following textures: (1) a single texture (100) 10011, (2) a twin texture (110) [112] and (3) a random orientation, depending upon the previous history of the specimen concerned. The effect of various alloying additions in copper was reported by Dahl and Pawlek.10 They found that certain alloying additions, such as 5 pct Zn, 1 pct Sn, 4 pct Al, 0.5 pct Be, 0.5 pct Cd, or 0.05 pct P suppressed the formation of cubic texture. Brick, Martin and Angierll reported that the cold rolled textures due to various additions fitted a rather simple pattern. However, the recrystallization textures were subject to very considerable variations. In the discussion of this paper, Baldwin stated that deoxidized copper containing 0.02 pct P gave a complicated recrystallization texture at lower temperature. When this copper was annealed at high temperature, a single texture appeared which was described as (110) [ill] but. according to a pri- vate communication from Baldwin, this orientation reported was in error and should have been reported as (110)[112]. He also reported that the earing positions of drawn cups were at 60" to the rolling direction.12 Recently, Howald, in his discussion on the paper by Hibbard and Yen,13 reported that the rolling texture of phosphorus deoxidized copper, containing from 0.006 to 0.020 pct phosphorus, was of the pure copper type. When these coppers were annealed at lower temperatures, they exhibited a random orientation, and when they were annealed at higher temperatures they had a mixed (111)[110] and (100)[001] texture, depending on the severity of the final reduction and annealing temperature. However, the specific influence of phosphorus and other impurities on the recrystallization textures and the deep drawing properties of copper strip has not been thoroughly reported. Therefore, an attempt has been made in the present work to determine the rolling and recrystallization textures and also the earing behavior of five types of commercial copper and thereby to evaluate the effect of phosphorus and some other significant impurities on the development of texture for cold reductions of about 87 to 89 pct. Materials Used The five types of copper employed in the present investigation were two phosphorus deoxidized coppers of different phosphorus content (0.007 and 0.013 pct P), an oxygen-free copper (OFHC), an electrolytic tough-pitch copper, and a fire-refined tough-pitch copper. These materials were subjected to a thorough spectroscopic and chemical analysis. The designations and the chemical compositions were as shown in Table 1. The coppers, FA1, FA2 and FA3. were hot-forged from 3-in. billets into a ½ X 6-in. plate and cold rolled to the ready-to-finish gauge indicated below. FA4 and FA5 were hot rolled and scalped to ready-to-finish gauge. The grain size of all the materials in the ready-to-finish condition was about 0.030 to 0.045 mm. Table 2 shows the last stage of the production schedule for each copper strip used. Experimental Procedure ANNEALING, GRAIN SIZE AND HARDNESS DETERMINATIONS Specimens of each type of copper were finally annealed in air for periods of one hour at temperatures ranging from 300 to 1600°F and were subsequently cooled in air. The average grain diameter of the annealed specimen was estimated by comparing with a standard grain size chart. Hardness was determined on the Rockwell 15 T scale. CUPPING TESTS Cups were made in a blanking and drawing set, in which blanks of 2-in. diam were drawn to a cup of 1.25-in. diam with an average depth of about 0.75 in. The clearance between the punch and die was about 0.032 in. The ears of the cup were measured with a special fixture which read the height of ears to one-thousandth of an inch on every ten-degree interval along the circumference of the cup. POLE FIGURES The usual transmission diffraction method with unfiltered copper radiation was employed to determine the pole-figures of the specimens cold-rolled or annealed at 900°F. All the pole-figures were derived from the positions of intensity maxima on 111 diffraction rings of the X ray photo-grams taken at 10 rotation of a

Jan 1, 1950

By J. J. Jonas, G. Gagnon

SHG zinc was extruded in the temperature range 110" to 350°C and the strain rate range 0.05 to 5 sec-1 The strain rate/flow stress/temperature results were analyzed using a power sinh stress relationship. When temperature changes due to the heat of deformation and to heat losses are neglected, the exponent of the sinh function of the stress is 5.6, and the apparent activation energy of deformation is 28 kcal per mole. When these changes are taken into account, the exponent decreases to 4.7 and the activation energy to 23 + 2 kcal per mole. The corrected stress exponent and activation energy are in very good agreement with published values obtained from creep experiments, and suggest that the hot extrusion of zinc is controlled by a mechanism involving self-diffusion. When the extrusion and creep data are compared using a Zener-Hollomon parameter and either a sinh or an exponential stress term, an appreciable offset is observed, which may be due to the difference in impurity content. For a given set of extrusion conditions the ram speed, maximum pressure, and initial temperature can also be correlated using a Zener-Hollomon parameter and a sinh pressure term. THE deformation of metals at temperatures over about one-half the absolute melting temperature has been extensively studied at creep strain rates. By contrast, relatively little work has been carried out on the behavior of metals at hot working strain rates. Most of the latter investigations have been performed using simulative methods, such as hot torsion and hot compression, in which the friction conditions and temperature rise during deformation may differ appreciably from those existing under industrial conditions. Recently, however, Wong and Jonas1 used a scaled-down industrial process to determine the stress and temperature dependence of the strain rate during the extrusion of aluminum. In such tests, the effects of friction and adiabatic heating are closer to those produced in industrial operations. Also, with regard to the testing of materials of limited ductility such as zinc, hot compression and hot torsion do not permit the attainment of true strains as large as the deformations usually applied commercially. The present study was undertaken to investigate the extrusion behavior of Special High Grade (SHG) zinc. The detailed objectives were: 1) to establish the stress and temperature dependence of the strain rate with and without a consideration of adiabatic heating, 2) to study the pressure and temperature dependence of the ram speed, and 3) to investigate the microstruc- tural changes occurring during the deformation. The last aspect of the investigation will be covered in a separate paper. The treatment described below differs from that of Wong and Jonas in that the adiabatic temperature rise during deformation is taken into account, and the calculation of the mean equivalent strain rate is based on the redundant as well as on the homogeneous work. EXPERIMENTAL PROCEDURE Rods from two shipments of continuously cast SHG zinc* were used in the investigation. The composition *Supplied by courtesy of Cominco Ltd. range of the impurities present, as given by the supplier, was: Pb: 0.0013 to 0.0023 pct, Fe: 0.001 pct max Cd: 0.0001 to 0.0006 pct, Cu: 0.0002 to 0.0005 pct, Ti: 0.0001 pct max; thus, by balance, zinc valued from 99.9963 to 99.9966 pct. The as-received rods were machined into billets having a nominal diameter of 1.56 in. and a nominal length of 1½ in.; longer billets up to 4 in. in length, were also used to investigate special aspects. The as-machined rods were annealed at 400°C for 24 hr and slowly cooled. This treatment produced a columnar grain structure, with a grain size of about $ by 2½ cm which was appreciably larger than the as-cast one. A 150-ton, direct extrusion, vertical press was used. Ram displacement and force were recorded continuously against time. A constant flow control valve permitted the maintenance of a range of preselected ram speeds up to in. per sec. The selected speed was held constant, irrespective of the required force, as long as the load developed was below the maximum available. Strain gages were used to determine the force; the gages were calibrated before and after each testing period with a 200,000-lb capacity load cell. Further details of the experimental equipment can be found in Ref. 2. The billets were preheated for 90 min in the extrusion container, which was well insulated so as to minimize temperature gradients. This period was sufficient for the billet to reach a uniform temperature at all temperatures between 110" and 350°C. A square-shoulder die having a 0.290-in. diam central hole was used. The extrusion ratio was 30 to 1. This is equivalent to a reduction in area of 96.7 pct, an elongation of 2900 pct, and a true strain of 3.4. The ram speed was varied over two orders of magnitude from 0.0027 to 0.26 in. per sec. The ram was water-cooled during most of the tests, although some experiments were conducted with a preheated, uncooled ram. All extrusions were run without lubricant, which resulted in conditions of sticking friction. EXPERIMENTAL RESULTS Stress Dependence of the Strain Rate Neglecting Adiabatic Heating. The maximum force required to extrude is given in Table 1 for each of the five initial

Jan 1, 1970

By J. Leja, J. H. Schulman

FROTH flotation is usually effected by the addition of a collector agent and a frothing agent to an aqueous suspension of suitably comminuted mineral ores. The action of collectors is to adsorb onto the surfaces of minerals to be separated, sensitizing them to bubble adherence. The action of frothers has, in the past, been accepted as that of froth formation only, brought about by a lowering of the air/water interfacial tension. Substances capable of producing froth are classed1a,b according to their relative capacities for production of froth-volume and froth stability in the simple frother-water system. The purpose of this paper is to show that the surface active agents acting as frothers become effective only when there is a suitable degree of molecular interaction taking place between collector molecules and frother molecules at the air/water and solid/ water interfaces. Further, the discussion will demonstrate that the actual mechanism of adherence of an air bubble to a suitably collector-coated particle is due to the molecular interaction collector-frother. This leads to the formation of a continuous interfacial film of associated molecules, anchored to the mineral by polar groups of the collector, and enveloping the whole bubble. The tenacity of adhesion mineral-to-bubble results from the strength and the visco-elasticity of this mixed film. Some 20 years ago Christman2 postulated mutual dependence of collector and frother in effecting flotation. This view was, however, strongly opposed by Wark,3 who pointed out that an addition of frother had no effect on the value of contact angle once this was established in the solution of collector. More recent work by Taggart and Hassialis&apos; indicated that the presence of frother, namely, cresol, leads to the immediate establishment of a contact angle on sphalerite, partially coated with xanthate, whereas an air bubble fails to make contact in potassium ethyl xanthate solution alone, even after 60 min induction time. Wrobel5 raws attention to the selectivity of frothers in flotation. Many instances of antagonistic effects of certain mixtures of frothers (or collectors and frothers) on flotation froth have been known to flotation operators and have been reported in literature. Taggart6 and Cooke7 give several examples of incompatibility of certain ratios of frothers and collectors, e.g., oleate and long-chain sulphates, pine oil and soaps. Monolayer Penetration. Properties of insoluble films produced by molecules of surface active agents orientated at the air/liquid interface are conveniently studied by the Langmuir trough technique, described fully by Adam.&apos; Using the trough technique Schulman and Hughes" and Schulman et al.10a. b, c, d,e established the existence of molecular interactions occur- ring between certain types of surface active agents. Their experiments revealed the phenomenon of penetration of an insoluble monolayer (e.g., a film of a long-chain alcohol) by a soluble agent (e.g., sodium alkyl sulphate) injected into the substrate (water or salt solution). The degree of molecular interaction taking place on penetration is determined by changes in the surface pressure of the resulting film, changes of its surface potential and its mechanical properties (viscosity and rigidity). When the interaction takes place between both polar groups and both hydrophobic groups of the two participating amphipathic molecules a molecular complex is formed. Complexes formed on penetration of the monolayer at interfaces are not necessarily true chemical compounds: they are labile in solution, the activity and reactivity of individual components are greatly different from those of the molecularly associated complex, and on crystallization they usually separate out into components. However, when formed in the orientated state at interfaces they are found to be very stable, although some mixed films spread as monolayers of stoichiometric complexes can show further penetration by subsequent additions of the soluble component injected into the substrate.&apos;" The degree of association between two or more types of surface active agents is very sensitive even to small changes in electric (dipole) moment of the polar groups of the amphipathic molecules as influenced by magnitude and position of neighboring ions or dipoles, their size, concentration, and stereochemistry. In addition, the molecular association is greatly influenced by concentration and type of inorganic salts in the substrate, by its pH, and by temperature. The nonpolar groups of interacting molecules greatly affect the stability of molecular complexes. Progressive shortening of the aliphatic chain of one of the reacting molecules weakens (at an increasing rate) its tendency to form stable complexes. Similarly, introduction of a double bond of cis-form into one of the reacting chains, which changes the straight hydrocarbon chain into a kinked one, or introduction of a branched chain, reduces the stability of the associated complex. Monolayer Adsorption. Using the trough technique and injecting metal ions into the substrate (water or salt solution) underlying insoluble films of fatty acids, alkyl amines, and sulphates, Wolsten-holme and Schulman11a,b,e. &apos; and Thomas and Schulman" have established conditions, namely, pH, concentration. and steric factors, under which molecular interactions take place between the polar groups of the surface active agents and the metal ions. These interactions are marked by great changes in the solubility and mechanical properties of the monolayer of the agent; no surface pressure increases are observed as in monolayer penetration experiments. The results of these adsorption studies, correlated with flotation experiments, indicated that in the case of fatty acids and alkyl sulphates their adsorption onto minerals of base-metals takes place by a similar

Jan 1, 1955

By Donald Warren, J. F. Libsch

HIS investigation originated as a result of a pre-vious experimental study&apos; of the magnetic properties of Fe-Co alloys fabricated by the powder metallurgy technique. Densities of powder compacts prepared for the magnetics investigation varied from 7.45 to 7.70 g per cu cm or from 93 to 95 pct of the experimental value of 8.08 g per cu cm for a fused alloy of the same composition.&apos; While this range of density is considered sufficiently high for most applications, the highest possible density is to be desired for maximum magnetic properties. By applying a technique similar to the one described above to a pure electrolytic iron powder, Rostoker³ was able to achieve a density of 7.895 g per cu cm, which is the highest density ever reported for sintered iron. While Rostoker&apos;s work involved the sintering of an elemental powder rather than a mixture, it was believed that higher densities should also have been obtained for alloys using the above technique because of the recoining operation and the high sintering temperature. Consequently, it was decided to investigate the various factors affecting the density of this alloy with the idea that such a study might lead to higher densities and, as a result, powder alloys having magnetic properties identical with those of the fused alloys. It was believed that the principal reason that near-theoretical densities for the powdered alloy were not obtained was the interference of gases with the normal sintering mechanism. When present during the sintering operation, gases can exert several harmful effects: they can remain on the particle surface and interfere with surface diffusion and plastic flow; they can be released and, under certain conditions, expand the void spaces through gas pressure; or they can remain trapped in the pores and exert a hydrostatic pressure that retards elimination of the pores. Jones,4 Rhines,5 Goetzel," and others have given the effect of gases in the sintering of powder compacts an extensive treatment. Among the more important sources of gases in the sintering process are dissolved gases, adsorbed gases, air entrapped during pressing, and gaseous products of chemical reactions. During sintering adsorbed gases are partly released at a relatively low temperature, while those gases entrapped during pressing cannot escape until their pressure is increased sufficiently through increasing temperature to expand the interpartjcle openings. The remaining adsorbed gases, gaseous reduction products, and dissolved gases produce a similar effect at the higher temperatures. If, in the sintering process, gas evolution occurs after the interpore channels have been sealed, an exaggerated expansion of the void spaces results. This is particularly true if the temperature is high enough for extensive plastic flow. In his fabrication of powder bars from tantalum, Balke7 had to consider the effect of adsorbed hydrogen and provide for its escape during sintering by limiting the compacting pressure to a maximum of 50 tons per sq in. The effect of gases entrapped during pressing was first noted by Trzebiatowski8 when he found that gold and silver powders decrease in density with increasing sintering temperature if pressed at 200 tsi, while they exhibit the usual increase when pressed at 40 tsi. Recent investigators9-11 have also noted that entrapped gases have an effect on the expansion of copper compacts during sintering. Proper provision for the escape of gaseous products of reduction must be made in order to avoid deleterious effects. Myers" states that in the sintering of electrolytic tantalum powder, the temperature was gradually raised to 2600°F with a pause at 2000°F to permit reduction of the oxides. Experimental Details For the present study, 50 pct Co-50 pct Fe compacts in the form of circular disks 1½ in. in diam and 0.15 in. thick were fabricated by the pressing and sintering of a mixture of the elemental powders. It was decided to follow the sintering process by means of liquid permeability measurements, because it was thought that such measurements might serve as a measure of relative pore sizes, as well as a possible indication of the point at which most of the interpore channels become sealed. However, since the permeability as measured by the flow of a liquid, such as ethylene glycol, does not give an absolute indication of the point where the pores have become isolated, a method for determining the percentage of pores connected to the surface was set up. As an additional cross check on the permeability measurements, metallographic methods were used to study the relative pore size. Finally, the property of ultimate interest, the density, was measured. Raw Materials: The powders used consisted of an annealed, 99.9 pct pure, —150 mesh grade of electrolytic iron powder, and a 98 pct pure, —200 mesh grade of reduced and comminuted cobalt powder. The cobalt powder was not further processed either by hydrogen reduction or annealing. The screen analyses for the iron and cobalt powders are given in Table I, while the chemical analyses for each type of powder are listed in Table 11. Table 111 gives the hydrogen loss measurements for the powders according to the M.P.A. Standard Method and for a higher temperature as well. Preparation of Compacts: Equal amounts of the elemental powders were mixed by rotation for 1 hr and then pressed into compacts approximately 0.15

Jan 1, 1952

By Joyce A. Ober

Minerals for electronic and optical uses divide easily into two sections: 1) quartz and 2) minerals other than quartz. QUARTZ The properties of quartz crystal that make it useful for radio communications were discovered in 1918. Since that time, an in¬dustry for the mining and processing of natural quartz crystal has grown, matured, and been almost entirely replaced by new tech¬nology. The new technology still involves quartz crystal, but ma¬terial that is grown rather than mined. An economic summary of the commercial growing of quartz crystals has a place in a handbook directed to the mineral engi¬neering industry because quartz crystals have long been an impor¬tant commercial mineral, and the raw material for cultured quartz - ¬that is to say, quartz crystals grown through the ingenuity of man - is still natural quartz. Nearly all the natural crystals that have been used for elec¬tronics and optics came from Brazil. The larger pieces which met rigorous standards of quality were used for electronic and, to a lesser extent, optical components. Smaller pieces and fragments were used for vitreous silica. The need for high quality material in quantity led to US government sponsored research and exploration programs in the 1940s. No deposits meeting the very rigid requirements for electronic-grade quartz were found, but other projects resulted in the development of a process for the factory growth of beautiful crystals of prescribed shape, size, and quality. Domestic deposits of appropriate quality were identified to use as raw materials for the quartz culturing process. The development of the cultured quartz crystal illustrates the success that technology can have in adapting a product of the mine to increasingly sophisticated uses. A remarkable achievement per¬haps, but foreshadowed by experiments by Giorgio Spezia (1908), an Italian geologist studying the relative effects of temperature and alkaline environment on the solubility of quartz. Modem radio equipment is most often controlled as to fre¬quency by the presence in the circuit of a separately added crystal¬ - the 1918 discovery responsible for the existence and growth of the quartz industry. The crystal is quartz, but this component is a carefully oriented and prepared slice from a crystal, but not a crystal as recognized by a rock hound or seen in a museum. How quartz operates to control frequencies is not a proper subject for a handbook on industrial minerals, and references should be consulted (Cady, 1964, Mason, 1964). Quartz belongs to a class of materials called dielectrics: those that do not conduct an electric current but permit electric fields to exist and act across them. Quartz shows the piezoelectric effect, which means that when a quartz plate is mechanically deformed against its natural stiffness, one of its surfaces becomes negatively charged, the other positively charged. When the plate is released quickly from the stress, the charges disappear as the plate regains its original shape, but because of mechanical momentum the plate deforms in the opposite direction (to a lesser amount) and the surfaces correspondingly become charged in the opposite direction. By thinly coating the two surfaces with metal and attaching flexible wires, these charges can be brought into an electronic circuit. If the surfaces are suddenly electrically charged by movement of current through the wires, the converse piezoelectric effect occurs and the plate deforms. Carry the thought further and it is realized that an alternating current flowing through the wires responds to the mechanical oscillation. By controlling the thickness of the plate, its mechanical vibration frequency can be varied through a wide range. One type of quartz plate, the AT-cut, has a precisely defined orientation with respect to the crystallographic axes of the crystal and vibrates on a microscopic scale much as a book would deform when placed flat on a table and the top cover moved parallel back and forth with the hand. At least 17 other orientations have been studied, some of which have preferred uses in various applications (Cady, 1964). The quartz crystal industry is composed of three main segments (excluding fused quartz and quartz used for optical purposes): 1. Natural electronic-grade quartz crystals. Mined quartz suitable for fabrication into piezoelectric units. Zlobik (1981a) esti¬mated the waste to ore ratio at 1:1000 to 1000 000, depending upon the deposit. 2. Lasca. Mined quartz usable as feedstock in the production of cultured quartz. Approximately 0.63 kg of lasca are required to produce 0.45 kg of cultured quartz. 3. Cultured quartz. Cultured quartz is produced from lasca feed¬stock in a process of crystal growth in an autoclave under conditions of heat, pressure, and time. It is estimated that 0.45 kg of cultured quartz is equivalent to 1.4 to 4.5 kg of natural quartz crystal in yield of commercial quartz suitable for slicing into piezoelectric units. The chronology of the development of the quartz crystal industry both natural and cultured follows: Date Comment 1918 Discovery of the piezoelectric effects of quartz crystal 1921 Application of the piezoelectric effects of quartz crystal in the circuitry of radios 1948 Establishment of a quartz crystal commodity stockpile by the US Government 1952 US consumption of natural quartz crystal at an all time high of 228 t 1958 First commercial production of cultured quartz crystal 1970 Cultured quartz crystal production exceeds imports of nat¬ural quartz crystal 1971 Cultured quartz crystal consumption surpasses natural quartz crystal consumption

Jan 1, 1994

By L. T. Larson, M. L. Picklesimer

The relationship between the apparent angle of rotation of monochromatic plane polarized light and the tilt of the basal pole from the surface normal has been experimentally determined for zirconium over the wavelength range of 500 to 655 mp. This relationship allows the determination of the spatial orientation of the basal pole of an individual grain in a polycvystal-ling zivrconium specimen to within ±3 deg by three simple tneasurements with a polarized-light metallurgical microscope. The method of measurement is discussed in detail. THE optical anisotropy of materials having noncubic crystal structures has long been used to reveal features by polarized-light microscopy. Petrographers have used measurements of certain optical properties to identify and classify transparent or translucent minerals. More recent work (i.e., Cameron1) has extended such measurements to opaque minerals in reflected light. Few attempts have been made to make similar measurements on noncubic metals. Couling and pearsall2 have reported that a sensitive tint plate can be used in a polarized-light metallurgical microscope to determine the position of the basal-plane trace in a grain of polycrystalline magnesium. Reed-Hill3 has reported that the same technique can be used for zirconium. We have found that the precision of measurement can be increased to about ±0.5 deg by using a Nakamura plate4,5 to determine the exact extinction position after the sensitive tint plate has been used to locate approximately the basal-plane trace. This report describes a method for measurement of another optical property, the apparent angle of rotation. This measurement permits determination of the angle between the basal pole of a grain of a hcp metal and the normal to the surface of the specimen. When the two measurements are combined, the orientation of the basal pole in space can be determined from three simple measurements on a single surface. One to two hundred such determinations will permit plotting of a basal-pole figure for the polycrystalline material with reasonable accuracy. When normally incident, monochromatic, plane-polarized light is reflected from the surface of an optically anisotropic material, the light may be converted to elliptically polarized light, the plane of vibration may be rotated, or both may occur. The el- lipticity, the angle of rotation, and the reflectivity can be related to the indices of refraction and the absorption coefficients of the material.6,7 Ellipticity values can be determined with an elliptical compensator, but not with the ease and precision desirable for the present purposes. Measurement of the angle of rotation requires only the determination of the angle from the crossed position (90 deg to the polarizer) that the analyzer must be rotated to obtain extinction when the trace of the optical axis in the surface is at 45 deg to the vibration direction of the polarizer. The angle of rotation of the analyzer is approximately 6/5 that of the true angle of rotation of the light as reflected from the specimen because there is a small amount of additional rotation produced during the passage of the reflected light through the mirror of the microscope. Since we are presently interested only in determining the tilt of the basal pole, the angle of rotation of the analyzer (the apparent angle of rotation of the light, i.e., uncorrected) can be used. Precision of the measurement can be increased substantially by the use of a Nakamura plate4,5 in determining the extinction position. In an optically uniaxial material (hcp or tetragonal crystal structure) the angle of rotation depends only on the optical properties of the material and the orientation of the optical axis of the grain relative to the plane of incidence of the plane-polarized light.7,8 Thus, in a metal such as zirconium, the apparent angle of rotation at the 45-deg position in any given wavelength of light is a direct measure of the tilt of the basal pole from the normal to the surface. If the optical properties vary with wavelength, the apparent angle of rotation for any given tilt of the basal pole will vary. None of the required information exists in the literature for zirconium nor for any other non-cubic metal. MEASUREMENTS ON SINGLE-CRYSTAL ZIRCONIUM A single-crystal sphere of zirconium 9/16 in. in diam was spark-cut from a single-crystal rod grown from iodide bar by an electron-beam zone-melting process.9 The damaged surface was removed by chemical polishing in a 45/45/10 mixture (by vol) of water, concentrated HNO3, and HF (48 pct) and then electropolishing at 50 v in a bath1&apos; of methyl alcohol and perchloric acid (95/5 by vol) at -70-C. The single-crystal sphere was mounted in a five-axis goniometer stage having a removable eucentric X-ray diffraction goniometer head for the two inner orientation axes. The basal pole of the single-crysta sphere was aligned parallel to a third axis of the goniometer stage by using the sensitive tint method to determine the basal-plane trace at several rotational positions of the sphere. The alignment was then checked by removing the sphere and eucentric gonio-

Jan 1, 1967

By R. A. Vandermeer, J. C. Ogle

The preferred crystallographic orientations (texture) developed in randomly oriented, poly crystalline niobium during rolling were studied by means of X-ray diflraction techniques. The evolution of texture at both the surface and center regions of the rolled strip was carefully examined as a function of increasing defamation throughout the range 43 to 99.5 pct reduction in thickness. Certain aspects of the center texture development in niobium are in agreement with the predictions of a theory by Dillamore and Roberts, but others cannot be explained by the theory in its present form. Above 87 pct reduction by rolling, a distinctly different texture appeared in the surface layers which was unlike the center texture. The present results are compared with previous results obtained from other bcc metals and alloys. RANDOMLY oriented, poly crystalline metal aggregates when plastically deformed to a sufficiently large extent develop preferred orientations or textures. In a recent review article, Dillamore and Roberts1 pointed out that the nature of the developed texture may be influenced by a large number of variables. These include both material variables such as crystal structure and composition and treatment variables such as stress system, amount of deformation, deformation temperature, strain rate, prior thermal-mechanical history, and so forth. From a practical point of view, the control of preferred orientation may often be important for the successful fabrication of metals into usable components. During the past few decades many experiments have been devoted to the study of deformation textures. This work, however, has been confined in large part to metals and alloys that have an fcc crystal lattice. By comparison, bcc metals and alloys have received much less attention, and consequently our understanding of preferred orientations in these materials is only shallow. This state of affairs worsens when it is realized that almost all of our present howledge about this class of materials derives from studies on irons and steels.&apos; The bcc refractory metals, which are relative newcomers to the industrial world, have, on the other hand, been given at best only passing glances in the area of texture development. Our understanding of the evolution of preferred orientations in bcc metals can only remain fairly limited until systematic studies of metals and alloys other than the irons and steels have been carried out and the influence of the many variables has been determined. To that end a program was initiated to investigate in detail texture development in niobium. The present paper reports some of the results of this study. Textures were determined at both the center and surface of strips rolled variously to as much as 99.5 pct reduction in thickness at subzero temperatures. Emphasis in this paper is on texture description and on texture evolution during rolling to progressively heavier deformation. EXPERIMENTAL PROCEDURE The niobium was purchased from the Wah Chang Corp. as a 3-in.-diam electron-beam-melted billet. Chemical analysis indicated the impurities to be less than 300 ppm Ta, 40 ppm C, 10 ppm H, 170 ppm 0, and 110 ppm N. All other impurities were below the limits of detection by spectrochemical analysis. This large-grained billet was fabricated into specimen stock so that a fine-grained randomly oriented grain structure resulted. This was accomplished in three deformation steps alternated with recrystalli-zation anneals of 1 hr at 1200°C in a vacuum of low 10"6 Torr range after each deformation step. The first step was to alternately compress the billet 10 to 20 pct in each of three orthogonal directions. The second step was to compress in only two directions 90 deg apart to produce a 2-in.-sq bar. The final step was to roll this bar 50 pct to give a 1-in. by 2-in. cross section. After the final anneal, metallo-graphic examination showed the material to have an average grain size equivalent to ASTM No. 5 at 100 times (i.e., 0.065 in. diam). Specimens cut from the center and edges of this bar gave no indication of detectable preferred orientation when examined by X-ray diffraction. Samples 1.5 in. long, either 0.625 or 0.750 in. wide, and approximately 0.400 in. thick were machined from this fabricated ingot. The surfaces corresponding to the rolling planes were ground so as to be parallel. The samples were chemically polished in a solution of 60 pct nitric acid and 40 pct hydrofluoric acid (48 pct solution) prior to rolling to remove any cold work introduced in the machining operations. Rolling was accomplished with a 2-high hand-operated laboratory rolling mill that had 2.72-in.-diam rolls. Prior to operation, the rolls were polished with 600 grit paper, cleaned with acetone, and then soaked in a container of liquid nitrogen for several hours. The samples were also soaked in liquid nitrogen prior to rolling and were recooled between each pass. While some slight heating of the samples occurred during rolling, this procedure maintained the sample temperature well below 0°C at all times. The samples were rolled unidirectionally, and the rolling plane surfaces were not inverted during any phase of the operation. The draft per pass averaged between 0.010 to 0.012 in. After 96 or 97 pct reduction the draft was reduced to 0.001 to 0.002 in. per pass. Samples were rolled to various reductions in thickness between 43 and 99.5 pct.

Jan 1, 1969

By Mehdi Asgharifar, Rouzbeh Sarrafi, Radovan Kovacevic

"The surface treatment of aluminum alloys using atmospheric-pressure of low intensity DC plasma arc discharge is investigated in terms of surface properties. With respect to the conventional surface treatment processes for aluminum alloys mostly based on chemical etching or sand blasting, this process is very environmentally friendly and cost-effective. The effect of two processing parameters, the current and the plasma torch scanning speed, on the surface morphology is studied by using a scanning electron microscope. The effects of cathode spots within the tested range of process parameters are determined, and the limiting factors of the process (such as surface cracking) are discussed. The topographical studies of the treated surfaces have suggested potential enhancement of surface properties for different applications, such as preparing surface for painting and adhesive bonding.IntroductionIn the last decade the aluminum alloys are finding broad applications in automotive industry. In order to successfully execute the joining process of aluminum alloys such as arc welding, laser welding, and adhesive bonding, there is a need to remove oxides for welding and texture the surface for bonding along the join line. A number of surface treatment techniques such as chemical etching, sand blasting, and plasma treatment have been used by industry. It is shown [1] that plasma surface treatment is characterized as environmentally friendly, lower cost, and easier to control process. Bogaerts et al. [1] mention that when an adequately high potential difference is applied between cathode and anode, electrons are accelerated toward anode by an electric field coming in collision with gas atoms. The gas breaks down into positive ions and electrons, giving rise to gas discharge. The DC electrical discharges used in industrial plasma sources can be related to their location on the voltage-current curve as shown in Figure 1.It is generally believed that dark discharges other than coronas, and arc or torch plasmas are not very good candidates for surface treatment because oflow or high power density and active species flux. However, the glow discharge plasma is used for plasma surface treatment applications because of its proper power density and active-species flux [2]. Our objective is to investigate the feasibility of using low intensity DC plasma arc discharge as a surface treatment method without damaging the cathodic non-thermionic workpiece."

Jan 1, 2011

By Jessica Elzea, Haydn Murray

The term bentonite was first proposed in 1898 by Knight, a year after he had named this clay taylorite, because taylorite had been previously used for another mineral. The name taylorite was after the Taylor ranch, the site of the first mine, near Rock River, WY, and the name bentonite is from the Benton Shale in which the clay was thought at that time to occur. The Benton Shale was, in turn, named after Fort Benton, MT, located more than 640 km miles north of Rock River. Early in the 20th century, several geologists recognized that bentonite, mainly in beds in Cretaceous and Tertiary rocks, originated from transported volcanic materials. This recognition led to definitions based on origin, the one most widely quoted and generally accepted by geologists is the following definition by Ross and Shannon (1926): "Bentonite is a rock composed essentially of a crystalline clay-like mineral formed by devitrification and the accompanying chemical alteration of a glassy igneous material, usually a tuff or volcanic ash; and it often contains variable proportions of accessory crystal grains that were originally phenocrysts in the volcanic glass. These are feldspar (commonly orthoclase and oligoclase), biotite, quartz, pyroxenes, zircon, and various other minerals typical of volcanic rocks. The characteristic clay-like mineral has a micaceous habit and facile cleavage, high birefringence and a texture inherited from volcanic tuff or ash, and it is usually the mineral montmorillonite, but less often beidellite." The difficulty in applying the foregoing definition to bentonite as an industrial mineral commodity is that it is based on origin and is restricted to an ash, tuff, or volcanic glass parent material. Therefore, deposits consisting of the clay minerals required by this definition, but having uncertain origin or parent materials, cannot properly be called bentonite. Furthermore, many deposits in the western United States and in other countries that have formed from rocks other than the types required by the definition are being mined and sold as bentonite. Perhaps the best definition of bentonite as an industrial mineral is one given by R.E. Grim in a plenary lecture at the International Clay Conference (AIPEA) at Madrid, Spain, June 27, 1972. According to this redefinition, which will be used in this chapter, bentonite is a clay consisting essentially of smectite minerals (montmorillonite group of some usages), regardless of origin or occurrence. This definition solves the problem of the difference between the geologic and industrial usages of the term and overcomes the difficulty in assigning a name to smectite clay that formed from igneous rock other than ash, tuff, or glass, or those of sedimentary or uncertain origin. However, bentonite, when used with this meaning is still a rock term (consisting of more than one mineral), and it will not be possible to distinguish it from fuller&apos;s earth in many instances. One way of classifying bentonite is based on its swelling capacities when wet or added to water. Bentonite having sodium (Na+) as either the dominant or as an abundant exchangeable ion typically has very high swelling capacities and forms gel-like masses when added to water. Bentonite in which exchangeable calcium (Ca++) is more abundant than other ions has much lower swelling capacities than sodium varieties. Some calcium types swell little more than common clay, and most crumble into granular masses in water. Intermediate calcium-sodium bentonites, the so called mixed types, tend to swell moderately and to form gels of lesser volumes than equal masses of the sodium type bentonite. Because of the general relationship of swelling and exchangeable ion characteristics bentonite is commonly divided into the high swelling or sodium, low swelling or calcium, and moderate swelling or intermediate types. The term sub-bentonite (Davis et a]., 1940) is used inconsistently in industry for the low or moderate swelling varieties. The authors believe the use of this term should be discouraged because of its implication of low quality or low value and the lack of a mineralogical or use basis for it. In the United States bentonite is also classified by geographic location and the uses for which it is sold. Inasmuch as most of the low swelling calcium type occurs in states bordering the Gulf of Mexico, this variety is commonly called Southern bentonite. The largest high swelling sodium bentonite deposits and the major producing districts are in Wyoming and adjacent states. Therefore, this bentonite is commonly called the Wyoming or Western type. Such terms as drilling mud bentonite, foundry bond bentonite, and taconite bond bentonite relating directly to use are applied in marketing. Other terms including high and low yield bentonite, high and low gel bentonite, and high and low strength bentonite are also used to distinguish different grades. The varied classifications notwithstanding, bentonite occurs in so many different varieties that some cannot logically be classified according to any of the foregoing groupings. One of these types is hectorite, which is a high swelling lithium-bearing variety of smectite occurring mainly in California and adjacent states. It is, therefore, not a Wyoming type, and it occurs even farther west than the so called western bentonites. Others are bentonites having magnesium (Mg++) or hydrogen (H+) as the most abundant or dominant exchangeable ion. These types are neither sodium nor calcium varieties, and apparently some are low swelling, whereas others have rather high swelling capacities. Still another type of bentonite, the so-called potassium type, K-bentonite, or metabentonite, occurs in Ordovician and other Pa-

Jan 1, 1994

By P. L. Hendricks, J. W. Spretnak

The interstitial atom principally responsible for the yield point and strain aging in electron-beam-melted tantalum is identified by analysis of the kinetics of the return of the yield point after an increment of plastic deformation. Two sets of specimens contained two levels of oxygen with very low hydrogen contents and the third set had comparable oxygen and hydrogen contents. The activation energy for the return of the yield point agrees well with that for diffusion of oxygen for the first two sets of specimens. For the third set of specimens, the activation-energy value lies between those for diffusion of hydrogen and for diffusion of oxygen. The advent of the dislocation model of plastic deformation in metals has revitalized interest in the yield point and strain aging in bcc metals containing a certain minimum content of interstitial solute elements. Much theoretical and experimental work has been performed in recent years to elucidate the detailed mechanism of these phenomena. The purpose of this investigation is to attempt to identify the principal interstitial element responsible for the yield-point phenomenon in electron-beam-melted tantalum by analysis of the kinetics of the return of the yield point after an increment of plastic deformation. Some of the earlier theories of the yield-point phenomenon proposed a grain boundary film of iron carbide. Such models could not satisfactorily explain all features of strain aging and the yield-point phenomena. The most widely accepted explanation is that of Cottrell,1 later extended by Cottrell and Bilby.2 Strain aging is ascribed to "locking" of dislocations by interstitial solute "atmospheres". The yield-point phenomenon results when the dislocations are torn away from their atmospheres. The strain-aged condition is re-established after sufficient time to allow the interstitial atoms to diffuse to the dislocation lines and re-establish the locking atmospheres. Clearly, the Cottrell-Bilby model is concerned with the bulk of the grain and does not specifically involve the grain boundary. The recent modification of the Cottrell-Bilby model is a redirection of attention to the role of the grain boundary and the possibility of multiplication of a limited number of free dislocations rather than unlocking all of the dislocations. Theories have been advanced by Hahn3 and conrad4 which are modifications of the Cottrell-Bilby theory. The model proposed by Hahn indicates that, although the possibility of un- locking anchored dislocations is not excluded, it implies that unlocking is not necessarily required to explain yield drop. Locking of dislocations during the aging treatment is a necessary part of the theory; however, it assumes that dislocations once locked remain locked. It is suggested that the yield drop observed is a result of the following factors: 1) the presence of a small number of mobile dislocations initially, 2) rapid dislocation multiplication, 3) the stress dependence of dislocation velocity. In the case of bcc metals, locking is considered to be the means by which dislocations are immobilized. Cold working of the metal results in the generation of larger numbers of new dislocations and the stress dependence of the dislocation velocity accounts for yield drop observed. Conrad&apos; has proposed a model similar to the one just described which applies to strain aging of iron and steel and which logically could be extended to other bcc metals. This model also does not require large-scale unlocking of dislocations. It is proposed that, during initial loading of a specimen below the upper yield stress, a few dislocations are torn free of their Cottrell atmospheres at regions of stress concentrations. With an increasing stress, some multiplication of dislocations occurs by a double cross slip mechanism, thus giving a preyield microstrain. At some critical stress represented by the upper yield stress, sudden profuse multiplication of dislocations occurs, enabling plastic flow to proceed at a lower stress. In this model, microstrain, preyielding, and flow represent the movement of free dislocations. It should be noted that this model also requires the locking of dislocations by interstitial solute atoms for the occurrence of a yield point; however, unlocking of large numbers of dislocations is not required. If it is assumed that the yield point will return when some fraction of free dislocations produced during pre-straining are pinned, the number of solute atoms required to pin unit length of a dislocation line can be calculated when prestrain and reloading are done at the same temperature and strain rate. Since the migration of solute atoms back to the stress fields of dislocation lines is controlled by the diffusion rate of interstitial solute atoms, it is to be expected that the activation energy for strain aging would be identical to the activation energy for diffusion. It would also be expected that the strain aging observed will be controlled by the fastest diffusing species capable of producing locking over the temperature range investigated. The rate of yield-point return has been found to be adequately expressed by an empirical rate equation of the form: rate=Ae-Q/RT [1] where A = constant, Q = activation energy, R = gas constant, and T = absolute temperature. Cottrell and Bilby2 have expressed the number of atoms per unit length of dislocation line which arrive

Jan 1, 1967