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Robert T. Hill, Washington, D. C.: Having studied very minutely the geology of the district referred to by Prof. Branner, I beg to state that his quotation of my classification of the Cretaceous deposits of Arkansas is not the one which I originally gave,* nor is it the one which has since been published and is now generally accepted.? I did not assign ally of the Cretaceous formations of Arkansas to the " middle Cretaceous,"

Jan 1, 1898

By Regis M. N. Pelloux, N. J. Grant

Five or six alloys each in the systems Ni-C.v, Ni-Mo, and NL-W, spaced to cover the single phase areas as well as a part of the adjacent two-phase field, were prepared as uacuum-melted alloys. Tensile tests at room temperature and stress rupture tests at 1200° and 1500°F we.ve run for time periods to give fracture in 0.1 to 500 hr. Observations mere made of solid-solution and second-phase strengthening or uleakening, coupled with studies of ductility and the role of structure on the noted behavior patterns. THE development of stable creep-resistant alloys while broad and systematic is also highly empirical. A number of simple rules have been suggestedL-" but these are based on scant data. Whereas rules for low-temperature alloy strengthening can be applied with some success in more simple systems, the extension to behavior at high temperatures (greater than about 0.4 of the absolute melting temperature) is very poorly understood and has encountered important exceptions and deviations in terms of atom size or valency effects. In particular, the occurrence of both solid-solution weakening4,5 and second-phase weakening2 at high temperatures is of interest. MATERIALS AND PROCEDURE Nickel was chosen as the base material because of its important role in current high-temperature alloy applications, because of its freedom from a phase transformation, and because of wide solubilities for many elements of interest. The selected alloys were single- and two-phase structures in the Ni-Cr,6 Ni-Mo,7 and Ni-w 8 systems. The alloys were vacuum melted and cast, utilizing high-purity raw materials, in the form of 15 lb ingots. They were readily forged into 1/2-in. bar stock (except the two highest chromium alloys). The alloy compositions are shown in Table I. Typical impurity values are: Carbon: Max 0.03 pct (except for 30 and 35 pct Cr alloys which had 0.07) Nitrogen: Max 0.005 pct (except for two of the Cr alloys which had 0.05) Sulfur: Max 0.004 pct Silicon: Max 0.05 pct Each alloy was solution treated (air quenched) to produce comparable grain size. The two-phase alloys were then overaged in an effort to produce a stable structure for testing at 1200° and 1500°F, The results are summarized in Table 11. Following the heat treatments outlined in Table 11, the bars were machined to a gage section of 1.25-in. long by 0.250-in. diam. In addition to room-temperature tensile tests, stress-rupture tests were run at 1200" and 1500°F for time periods from 0.1 to about 500 hr. RESULTS Room-Temperature Mechanical Properties—The ultimate tensile strength, total elongation, and reduction of area values for all the alloys are plotted vs atomic percent of the solute element in Fig. 1. It can be seen that for the same amount of solute element the ultimate tensile strength increases in the order chromium, molybdenum, tungsten. Elongation increases (reduction of area decreases) with increasing amounts of solute for all the solid solution alloys, the values ranging from 50 to 70 pct. The ultimate tensile strength values for the two-

Jan 1, 1961

By R. S. Hoch, Roy A. Bobo

Maintenance of desirable plastic flow properties of weighted drilling muds may be greatly simplified by use of centrifugal classification to control the drilled solids content. The new application of a decanting type centrifuge to separate and reject the low density solids from the weighting material results in a drilling mud of greatly improved quality with lower values of yield and rigidity. Its practicality and economy has been proven in field operation. The degree of separation of light and heavy solids is not limited by the machine, but by the particle size distribution of the solids in the mud. Removal of the low density component of drilling mud that makes chemical treatment necessary permits a marked reduction in chemicals. The main uses of the centrifugal process are the treatment of muds while drilling, the reclaiming of discorded muds, cleaning up of workover muds, and the reduction in lime content of mud for completion. INTRODUCTION Drilling mud in any circulatory system is made viscous and difficult to pump by gradual accumulation of drilled solids which pass through the shale shaker and are continually reground. In a weighted mud containing a large proportion of barite by volume, the amount of drilled solids that may be tolerated is greatly reduced. Much effort has been expended to control by chemical treatment the effects of such solids. Though chemical treatment is quite effective, the time eventually comes at deeper depths after enough drilled solids have entered the system when a portion of the mud must be discarded and replaced with water and more weighting material. Once begun, this process is generally continued at frequent intervals with resultant high maintenance costs. At the termination of drilling, mud highly contaminated with light solids and spent chemicals is poorly suited for completion operations.' It is likewise limited in utility for other drilling operations. This investigation was conducted for the primary purpose of determining an acceptable mechanical means of removing the lightweight solids from weighted drilling muds in order to maintain viscosity at a minimum. A decanting type of centrifuge was selected from the various possible methods of mechanical separation. The centrifugal process has been employed in this country for this purpose in central mud reclamation systems in California in earlier years. It also was used for treatment of weighted muds on the Gulf Coast.' In more recent years only sporadic attempts have been made to employ it in the field on weighted muds. DISCUSSION OF PROCESS Selection of Apparatus Two factors favor mechanical procedure for the separation and removal of drilled solids or clays from the mud circulatory system. First, the greater specific gravity, 4.1 to 4.3, of the barite would promote more rapid settling than the clays whose specific gravity range is from 2.5 to 2.7. Second, the relative coarseness of the barite particles also facilitate faster settling of this phase. A decanting type of centrifuge was preferred for this process over other possible methods for these reasons: 1. Requires no costly additives or excess dilution. 2. Centrifugal force affords greatly accelerated separation as compared to gravity.

Jan 1, 1955

By J. D. Cooner

SINCE my working life of 32 yr has been spent in and about the anthracite mines of the Hudson Coal Co., and the previous 4 yr in a college school of mines, I can write best about the safety program of a coal mining company. However, most of the suggestions, statements and practices mentioned herein are applicable to the members of a safety organization and program of almost any industry. It is realized that industrial officials actually interested in real safety work are fully acquainted with the requirements of a practical safety program. Therefore, for such persons there may be nothing new in this paper. The Hudson Coal Co. of Scranton, Pa., employs 7,000 men and produces 5,000,000 tons of anthracite annually at nine collieries scattered for a distance of 40 miles throughout the Lackawanna and Wyoming valleys of northeastern Pennsylvania. For the past 17 yr of the above mentioned 32, I have been engaged in safety work as a safety inspector, assistant mine superintendent, and at present the safety engineer. I have also had the privilege of visiting coal and metal mines in other parts of the United States and Canada. We Americans are the most careless people in the world. If any one doubts this statement why are 100,000 of our people killed accidentally annually? Or why during the almost four years we were engaged in World War II were more of our people killed accidentally at home than were killed in our army, navy, marine corps, coast guard, and other services during the same period? We are careless everywhere in our homes, on the highway, at work and at play. The purpose of this paper is to outline the requisites of a safety department and its program to stop the accidents occurring to employees at work in mines or industrial plants. The first requisite for a safety program is that the management must be convinced of the need and value of a real safety program. By "management" is meant each department head from the president down. Otherwise a good safety department with a good safety program will not succeed because it will not have the proper personnel and equipment to work with, its rules and regulations will not be enforced, and the members of the safety department will be belittled in the eyes of most of the workmen and supervisors. Next, a safety engineer and his inspectors should have worked in the production end of the mines as workmen and also in an official capacity. They are then in a position to have practical and first hand knowledge of the accident hazards of the industry, how to prevent them, and in general the problems of both the workmen and officials. Some men are appointed as safety inspectors when they are physically unable to carry on as mine officials. Such men may know the safety end of the industry and even be safety-conscious, but if they are physically unable to be mine officials they are also physically unable to be safety inspectors, as a safety inspector in our mines must walk from 2 to 4 miles on each daily inspection-and visit each working

Jan 1, 1948

By D. H. Polonis, J. G. Parr

IN a recent paper on titanium-rich Ti-Fe alloys,' the hardness of quenched powder specimens was given, together with the amounts of martensitic a they contained. The values disagreed in two respects with previous determinations that Worner² made on lump specimens: 1—Some martensitic a' is formed in powder specimens of alloys containing up to 12 atomic pct Fe. On the other hand, Worner reports that, although his results on quenched lumps are not conclusive, alloys containing more than about 4 pct Fe "appear to consist of retained ß'' although they "may not be strictly unaltered solid solutions." 2—According to Worner, quenched lump specimens show a maximum hardness at a composition about 3.5 pct Fe. Earlier -experiments by the authors showed a maximum hardness of martensitic alloys in powder form at 10 pct Fe. Accordingly, more experiments have been conducted in order to confirm these differences and to determine with more accuracy the minimum composition of quenched lump specimens that consist entirely of retained ß. Lump samples?x?x1/20 in. were quenched from 1000°C in helium and, on the whole, showed similar hardness values to the specimens that Worner water-quenched from 950°C. The hardness curve the authors obtained shows a more pronounced peak, but in other respects it is very similar to Worner's curve (Fig. 1). While it was possible to make fairly reliable measurements of the percentage of martensitic a in quenched powders (by Geiger spectrometer), the solid samples allowed only approximate estimates to be made from visual observation of line intensities on film. Retained ? begins to appear in quenched lumps containing 0.2 pct Fe; at 2.2 pct Fe there are approximately equal quantities of ß and a'; in a 4.7 pct Fe alloy only a trace of a' appears. These results are represented as a curve on Fig. 1. The hardness and constitution of powder samples were verified by repeating both types of quenching experiment described in the earlier paper.' Identical results were obtained by the two methods, and they agreed with the figures published previously (Fig. 1). The appearance of the martensitic structure under the microscope is shown in Figs. 2 and 3. The mar-tensite needles are coarser in the lump; otherwise the structures are similar. Three conclusions are made at this juncture: 1— The properties of quenched lumps reported by Worner are confirmed, on the whole. The differences between them and the properties of powders are probably due to an effect of specimen size. Differences of behavior in various sizes of specimen have been observed previously in martensite reactions in Fe-Mn alloys3 and in Cu-A1 alloys. 2—The maximum hardness of both quenched lumps and quenched powders appears at a composition where martensite formation has all but ceased. In this respect, powders and lumps behave similarly. 3—Martensitic a' has essentially the same microscopic appearance both in powders and lumps. Acknowledgment This work is part of a program sponsored by the Defegce Research Board of Canada, Project No. 425.

Jan 1, 1956

By Glenn A. Marsh, George Bernard

It is often assumed that aerated oil field brines which are to be injected underground contain dissolved oxygen in amounts which will cause appreciable corrosion. Through the use of a new portable dissolved oxygen meter, accurate determinations were made at three brine conditioning plants. At two older plants, dissolved oxygen concentration in the final treated brine was found to he almost zero In spite of aeration during the conditioning process. At a new plant, dissolved oxygen was initially present but disappeared soon after the brine was "inoculated" with oxygen-free brine from one of the other plants. Corrosion tests at the two older plants have substantiated predictions that the brines would lint be corrosive. These results show that mechanical deaeration may not always be required in brine treating plants. INTRODUCTION The present work was undertaken to add to our knowledge of aeration and deaeration of oil field brines in brine conditioning plants. It is commonly assumed that brines which are exposed to the air soon become more or less saturated with dissolved oxygen. Since oxygen-containing brines are known to be corrosive, precautions are often taken to keep air out of brine through the use of closed systems or mechanical deaeration. The study of oxygen in brine has been seriously hampered in the past because of the lack of a suitable analytical tool. The standard Winkler method for the determination of dis-solved oxygen is satisfactory for use in fresh water, but not in many oil field brines. Corrections have to be made for a number of reducing substances such as ferrous iron and hydrogen sulfide which are commonly present in natural brines. Very often the correction factors are much greater in magnitude than the amounts of oxygen which are to be determined, and consequently erroneous results are obtained. Also. erratic Winkler data are obtained when appreciable concentrations of calcium and magnesium salts are present. The first step in carrying out a systematic study involved designing a portable dissolved oxygen apparatus which would operate in natural brines. Subsequently, this apparatus was used in three brine conditioning plants. Dissolved oxygen data obtained here, and certain corrosion rate data, illustrate the interesting behavior of oxygen in these oil field brines. APPARATUS A portable dissolved oxygen meter described in detail elsewhere,' was developed specifically for use with oil field brines. It is a polarographic apparatus employing a small rotating platinum electrode (cathode) and calomel reference electrode (anode). A potential of 0.7 volts is applied across the electrodes while they are immersed in the brine to be tested. 4References given at end of paper.

Jan 1, 1952

By R. A. Swalin, B. W. Roberts

ONSIDERABLE controversy has centered about the existence of an order-disorder transformation in alloys in the composition vicinity of 75 atomic pct Ni and 25 atomic pct Cr. All the evidence to date for such a transformation is of a rather indirect nature, since direct X-ray confirmation is difficult to obtain as a result of the small difference in X-ray scattering factors between nickel and chromium. As a result, superlattice lines would be very faint if present. Several investigators1-5 have observed anomalies in the electrical resistivity vs temperature curves of alloys in the vicinity of 25 atomic pct Cr. The observed change is characterized by a rather broad resistivity peak at about 540°C. A discontinuous drop in resistivity is normally associated with ordering. However, Taylor and Hin-ton4 have rationalized that the discrepancy could conceivably be caused by changes in the Brillouin zones upon ordering. The same investigators measured the specific heat as a function of temperature and have also observed anomalies in the vicinity of 540°C. Nordheim and Grant5 have proposed, because of the absence of superlattice lines and the absence of a discontinuity in the resistivity vs temperature curve, that long-range order is improbable and that the results could be better explained by short-range ordering. To date, however, the question has not been resolved satisfactorily. Neutron diffraction techniques provide a method for partially resolving the question since nickel and chromium have considerably different atomic scattering factors in the case of neutrons and, therefore, superlattice peaks, if ordering occurs, should be readily discernable. The results of a neutron diffraction investigation* coupled with a dilatometric in- vestigation are reported here. An alloy containing 28.0 atomic pct Cr was prepared from carbonyl nickel and electrolytic chromium in the form of a 1-in. diam x 10-in. ingot. Melting was done in an alumina crucible and casting in a graphite mold. The ingot was homogenized at 1250°C for seven days, after which a 5-in. long piece was cut into shavings in order to obtain a suitable neutron diffraction sample. Hardness samples and samples suitable for dilatometric analysis (% in. diam x 2 in.) were prepared from the remainlng piece. The neutron diffraction sample, along with a hardness sample, was annealed at 501°C for seven days, at which time the temperature was lowered to 479°C and held at this temperature for twenty-four more days. The hardness was observed to increase from 133 to 147 Vhn during the course of the annealing treatment, in qualitative agreement with Nordheim and Grant." Neutron diffraction traces taken at room temperature and at 42 °K are shown in Fig. 1. The insert shows the trace taken at room temperature with short counting times and thus only fair statistical accuracy. No evidence for superstructure reflections of Cu3Au-type ordering is observed. The statistical accuracy of the 4.2°K trace was improved by using longer counting periods. Several weak intensities are observed at small angles, including an aluminum reflection from the cryostat assembly and a very

Jan 1, 1958

By D. J. Blickwede

PRESENT knowledge of the effects of time and temperature upon stabilization of the austenite-martensite reaction in steel is fairly complete,1-3 but at the time the work described herein was initiated there was no information about the effects of alloy elements on the phenomenon. However, it has been assumed on theoretical grounds that alloy elements, particularly carbide formers, may have a significant effect on stabilization.' The present work was undertaken to provide information about the effect of two common elements, nickel and molybdenum, on stabilization in hypereutectoid and hypoeutectoid steels. Seven induction-furnace melted, 1.2 pct C steels ' with a variation of nickel from 0 to 6 pct and of molybdenum from 0 to 1.0 pct were used for most of the experiments. Along with these a series of 0.4 pct C steels containing 0 to 6 pct Ni were also studied. The chemical compositions of the steels are listed in Table I. Stabilization in these forged, hot-rolled, annealed, and centerless ground steels was measured by aging brine-quenched specimens (aus-tenite temperature, 1800°F) at 95" and 150°F and then determining the change in specific volume produced by subsequent cooling from room temperature to —320°F.³ In presenting the results the decrease in the change in specific volume, ?V, after various stabilization times is used. This is given by ?V -= ?VO - ?V1 where AVO is the change in specific volume on quenching directly to —320°F and aV, is the change in specific volume on quenching to —320°F after stabilizing for time t. In other words, ?V is a direct measure of the amount of martensite that is lost to the subzero quench as a result of stabilization and hence is greater, the longer the aging time or the higher the aging temperature. The results are shown in Fig. 1. The scatter of the data, which are not shown for clarity and brevity, was sufficient to make the relative location of the curves on the ?V axis inaccurate within ±2x10-5 cc per g. However, some generalities appear which are of interest. Effect of Nickel In the 0.4 pct C steels, up to 3 pct Ni has little, if any, effect on the rate or amount of austenite stabilized at 95°F, Fig. la. Increasing nickel from 3 to 6 pct almost doubles the amount of austenite stabilized in a given time. In the 1.2 pct C steels aged at 95°F, increasing the nickel from 1 to 3 pct appears to decrease the amount of stabilization, and a further increase to 6 pct Ni completely eliminates stabilization as shown in Fig. lb (M, of 6 pct Ni steel was below room temperature). The same behavior was exhibited by these steels stabilized at 1500°F, especially after aging for periods longer than 5 hr, Fig. lc. Thus it appears that up to 1 pct Ni has little effect on stabilization at low or high carbon levels. More than 1 pct Ni increases stabilization at low carbon contents and decreases it at high carbon contents. Ward, Jepson, and Rait5 have found that at inter-

Jan 1, 1954

By J. M. Oblak, R. F. Hehemann, R. H. Goodenow

STUDIES of surface relief and growth kinetics have lead to the concept that widmanstatten ferrite along with upper and lower bainite constitute a continuous series of decomposition products.1-4 Current models4 propose that these products form as plates with a coherent or semicoherent leading edge which propagates at a rate controlled by diffusion of carbon into the surrounding austenite. There are, however, important crystallographic and morphological differences between these products—particularly between upper and lower bainite. For example, upper bainite appears to exhibit a (11lIy orientation habit, whereas lower bainite develops with a more irrational habit near {2251y.5-7 Many of the morphological features of these decomposition products are not yet well-documented. Recent studiess have demonstrated that low-carbon martensites form as sheets of closely spaced needles on {lllly planes while higher-carbon martensites form as plates with {225}? or other orientation habits. The similarity in the crystallography of these two modifications of martensite with upper and lower bainite is striking. Therefore, a study of the morphology of bainite in a series of hypoeutec-toid alloy steels has been initiated to explore these relationships further. The question of immediate interest is whether upper and lower bainite form as plates or needles. A two-surface (approximately perpendicular) metallographic method was employed to study the morphology of bainite in a variety of low and medium alloy steels. Compositions of these steels have been reported elewhere. The behavior of 4340 and 4370 was typical and will be described here. Austenitizing treatments involved 20 min at 2350°F for 4340 and at 2000°F for 4370. Isothermal transformation was conducted in molten-salt baths. Upper bainite was produced at 925°F in the 4340 steel and lower bainite at 575°F in 4370 with transformation times adjusted to produce 10 to 15 pct of the decomposition product. Many of the morphological features of upper bainite have been catalogued in the recent literature.'' The two principal variants observed in the present investigation are illustrated in Fig. l(a). One form appears as long, thin plates or needles and the other as small, frequently irregularly shaped particles. Both variants may occur as isolated forms but more frequently appear in groups as demonstrated in Fig. l(a). Two-surface analysis reveals that these two variants constitute different sections through a single morphological form. To demonstrate this, a number of sections perpendicular to the plane of Fig. l(a) were prepared at various positions along the length of the elongated particles. A section taken at position 1 in Fig. l(a) is presented in Fig. l(b). Here, the dark line represents the edge of the sample and the left-hand portion of this photomicrograph is that from the surface perpendicular to the original plane of polish. Since it was necessary to repolish the original surface after each sectioning, the shape of the bainite particles on this surface, right hand side of Fig. l(b), changes with each sectioning. The disappearance of plate A, Fig. l(a), in Fig. l(b) emphasizes the small cross section of these structures. The group of particles in the lower left-hand

Jan 1, 1964

By Roger A. Gregg, Barry J. Piearcey

MANY of the nickel-base superalloys developed recently for use in the as-cast condition exhibit a massive "white-etching" constituent1 in the inter-dendritic regions. Commercial alloys in this category are SM 200,* IN 100, INCO 713, and Nicrotung. The appearance of a similar microconstituent in nickel-rich Ni-A1-B alloys has been reported by Schijbel and Stadelmaier. Their investigation revealed that this constituent was the binary eutectic of the terminal nickel-base solid solution and the inter metallic based on Ni3A1. This binary eutectic is degenerate and NhA1 is the major phase. At lower temperatures the eutectic composition lies within the NkA1 phase field and under equilibrium conditions is single-phase NisAl. Taylor and F&apos;loyd3 have shown that in Ni-Al-Cr alloys containing at least 8 at. pct Cr, liquid compositions which solidify by the eutectic reaction in the nickel-rich portion, precipitate nickel-base solid solution and NiAl rather than nickel-base solid solution and NkA1 in the binary Ni-A1 system. Since the nickel-base alloys contain chromium in excess of 8 at. pct and are further alloyed with one or more of the elements titanium, cobalt, molybdenum, or tungsten, it is possible that the eutectic could contain NiAl rather than NisAl. In addition, Benson4 has reported that in low-nickel austenitic high-temperature alloys, which possess Ni/(Al + Ti) atomic-weight ratios <18.0, the Ni (Al, Ti) phase may precipitate from the melt during solidification. Since SM 200 and similar high-temperature materials were developed from alloys which were designed for solution treatment, the appearance of a eutectic would indicate that the limit of solid solubility has been exceeded. The purpose of this note is to confirm that the massive white constituent in the complex nickel-base alloys investigated is based on the binary eutectic Ni + NbAl and that the limit of solid solubility need not be exceeded to produce it, in common with other observations of cast alloys. Successive polishing of a sample of SM 200 showed that, in agreement with Schobel and Stadelmaier, particles of the constituent were spherulitic and in particular were a) situated between cored dendrite arms, Fig. 1, and b) nucleated at the surface of dendrites, Fig. 2. The Ni/(Al + Ti) atomic-weight ratios for the nickel-base alloys which were observed to contain the massive eutectic constituent in the interdendritic regions are 12.1 (Nicrotung), 9.2 (IN loo), 19.5 (INCO 713), and 14.5 (SM 200). However, the results of X-ray analysis of these alloys in the as-cast condition failed to reveal the presence of the Ni (Al, Ti) phase. An electron microanalyzer was therefore employed to analyze the composition of this constituent in SM 200. The results of analyses of representative particles are as follows5: 8.4 at. pct Ti, 8.8 at. pct Co, 5.5 at. pct Cr, 0.9 at. pct W, 12.8 at. pct Al, and 63.6 at. pct Ni. Assuming that

Jan 1, 1964

By Kendall E. Born

Production of crude oil in Tennessee during 1940 was slightly more than 15,000 bbl., a decrease from 1939 of about 36,000 bbl. This sharp decline has been caused largely by curtailed activities in the shallow pools in Clay County, where approximately 3000 bbl. was marketed off the lease during the year as against more than 37,000 bbl. in 1939. The flashy production found in 1938 in the Celina area has been short-lived and the area is essentially abandoned. Failure to find steady production has been the major factor retarding developments in the northeastern Highland Rim area. The Mississippi lime production in Scott and Morgan Counties continued to show a steady decline. The Tennessee production by counties is shown in Table I. Table i.—Oil Production in Tennessee it1 1940 Production. Bbl. Number of County Wells Pumped 1939 1940 Scott............ 4 4,332 3.596 Morgan.......... I: 6,479 5,751 Fentress.......... 3 I,2XX 1,5xz Pickett........... 1 1.2XX Clay............. 8 37.200 3,XXX Developments There were 32 wells spudded in during 1940, four of which were drilling or only temporarily suspended on Dec. 31, 1940. Twenty-eight wells were completed during the year, four of which were commercial producers. The total footage drilled was 3I,214 ft. The more important wildcats are listed in Table 2; the distribution of 1940 oil and gas tests according to physiographic divisions is given in Table 3. Cumberland Platenu.—Thcre was one completion in the coal area of the state, a test that attempted to extend the Mississippi lime production in the Coon Hollow pool to the southeast in Morgan County. This test encountered only slight shows of oil in the producing horizons of the near-by Coon Hollow and Boone Camp pools. Some surface work was carried on by private interests during the year in Scott and Morgan Counties and two wells were spudded in early in 1941 The revival of interest in the Kentucky portion of the plateau will probably result in increased activity in this part of Tennessee during 1941. Several sizable blocks of acreage, some by major oil companies, are held in Scott, Morgan, and Cumberland Counties. Middle Tennessee.—The northeastern Highland Rim continued to be the most active area in the state with 20 completions, although this figure is about one third of the number drilled in 1939. Four oil wells, none with initial productions of more than I00 bbl., were completed in Clay, Fentress, and Pickett Counties. The producing horizons discovered in Pickett and Fentress Counties were in the "Sunny-brookJ&apos; pays of Trenton age. The Clay County producer was an old test drilled deeper in which oil was found at 671 ft. in the upper part of the Stones River group of limestones, a common pay in this area. All four wells were drilled in or close to old shallow production. Deeper testing into the Knox dolomite group in this area was not particularly encouraging, although one well in Fentress County encountered some saturation at 1860 to 1869 ft. in the upper

Jan 1, 1941

By Kendall E. Born

Production of crude oil in Tennessee during 1940 was slightly more than 15,000 bbl., a decrease from 1939 of about 36,000 bbl. This sharp decline has been caused largely by curtailed activities in the shallow pools in Clay County, where approximately 3000 bbl. was marketed off the lease during the year as against more than 37,000 bbl. in 1939. The flashy production found in 1938 in the Celina area has been short-lived and the area is essentially abandoned. Failure to find steady production has been the major factor retarding developments in the northeastern Highland Rim area. The Mississippi lime production in Scott and Morgan Counties continued to show a steady decline. The Tennessee production by counties is shown in Table I. Table i.—Oil Production in Tennessee it1 1940 Production. Bbl. Number of County Wells Pumped 1939 1940 Scott............ 4 4,332 3.596 Morgan.......... I: 6,479 5,751 Fentress.......... 3 I,2XX 1,5xz Pickett........... 1 1.2XX Clay............. 8 37.200 3,XXX Developments There were 32 wells spudded in during 1940, four of which were drilling or only temporarily suspended on Dec. 31, 1940. Twenty-eight wells were completed during the year, four of which were commercial producers. The total footage drilled was 3I,214 ft. The more important wildcats are listed in Table 2; the distribution of 1940 oil and gas tests according to physiographic divisions is given in Table 3. Cumberland Platenu.—Thcre was one completion in the coal area of the state, a test that attempted to extend the Mississippi lime production in the Coon Hollow pool to the southeast in Morgan County. This test encountered only slight shows of oil in the producing horizons of the near-by Coon Hollow and Boone Camp pools. Some surface work was carried on by private interests during the year in Scott and Morgan Counties and two wells were spudded in early in 1941 The revival of interest in the Kentucky portion of the plateau will probably result in increased activity in this part of Tennessee during 1941. Several sizable blocks of acreage, some by major oil companies, are held in Scott, Morgan, and Cumberland Counties. Middle Tennessee.—The northeastern Highland Rim continued to be the most active area in the state with 20 completions, although this figure is about one third of the number drilled in 1939. Four oil wells, none with initial productions of more than I00 bbl., were completed in Clay, Fentress, and Pickett Counties. The producing horizons discovered in Pickett and Fentress Counties were in the "Sunny-brookJ&apos; pays of Trenton age. The Clay County producer was an old test drilled deeper in which oil was found at 671 ft. in the upper part of the Stones River group of limestones, a common pay in this area. All four wells were drilled in or close to old shallow production. Deeper testing into the Knox dolomite group in this area was not particularly encouraging, although one well in Fentress County encountered some saturation at 1860 to 1869 ft. in the upper

Jan 1, 1941

By R. C. Rumble

To /neet the need for a subsurface flowmeter capable of measuring low rates of flow, a new type flowmeter has been built and tested in the field. This instrument is self-contairzed, can be run on a wire measuritzg line, and may be run through 2-in tubing. It consists of a rotameter flow-measuring assembly used in conjuncfion with a conventional subsurface instrument clock and chart. Integral with the tool is an inflatable packer which, by effecting a seal between casing and tool, diverts all fluid through the metering assembly. Packers of different size adapt the tool to different sizes of casing or liner. The flowmeter is capable of measuring rates of flow as low as 4 BID. The flowmeter has been run experimentally in seven wells. It has yielded satisfactory resrrlts in five of the wells, and in the other two it failed to operate because of loose sand in the hole. INTRODUCTION One of the oldest problems facing the producing branch of the petroleum industry is the location of depths of entry of fluid into a wellbore and the determination of the amount of fluid entering at each depth. This problem is often encountered in oil and gas wells completed in single producing horizons as well as in multiple pays; it is a common problem in oil wells which produce excessive volumes of gas. Several subsurface instruments designed to detect and meter flow in the producing interval of wells have been described in the literature.1,2,3,4 Most of these, however, were apparently intended for use in wells producing at relatively high rates of flow, and consequently lack sensitivity to low flow rates. Because of this and of other possible disadvantages inherent in these instruments, development of the subsurface flowmeter described in this report was undertaken. DESIGN OF FLOWME&apos;I&apos;ER Design Requirements In considering the requirements for a flowmeter that would not be subject to the limitations of devices existing at the time work was started, attention was first given to the size of the tool. Such an instrument should be of sufficiently small diameter that it could be lowered readily in 2-in tubing in a producing well. The flowmeter should contain a recording unit so that it might be run on a wire measuring line with conventional reeling equipment. It should not be too long to be accommodated by a portable lubricator of the type used for running conventional subsurface instruments. The metering mechanism of the flowmeter should not be affected appreciably by the viscosity or density of the flowing fluid. Such an instrument should record flow rates in the range from less than 10 B/D to over 100 B/D. To achieve this, a packer should he provided to divert through the instrument all fluid flow in the wellbore. This packer should be of such nature that in the event of excessive flow the fluid would bypass the instrument instead of forcing it up the wellhore. General Description A flowmeter incorporating most of the desired features outlined above was developed and built. The instrument is an elongated tubular device terminated on

Jan 1, 1956

By A. J. Boyer, T. R. Meadowcroft

An experimental determination has been made of the efject of surface diffusion on the vapor pressure obtained in a Kwudsen cell. The results show that a knife-edge orifice in a molybdenum lid may give erroneous results for the vapor pressure of silver. when a correction suggested by winterbottom and Hirth is made, the results become meaningful. Experimental work with cylindrical orifices in molyhdenz~m lids and knife-edge orifices in ceramic lids shows that good vapor-pressure results may he obtained when the orifice is designed so that ejfusion is the only significant source of weight loss. THE Knudsen effusion cell technique has been used by many investigators to study relative and absolute vapor pressures over metals and alloys at elevated temperatures. As a result of this interest, some theoretical studies have been made of geometric factors affecting effusion from the orifice of a Knudsen cell. A review of these studies has been made by Margrave.1 Recently, Winterbottom and Hirth2 have suggested that a physical effect, that of condensation, surface diffusion, and re-evaporation, may seriously affect Knudsen cell measurements, especially when a knife-edge orifice is used. Inasmuch as many of the present vapor-pressure data have been obtained using knife-edge orifices. it was felt that an experimental evaluation of the effect of surface diffusion on Knudsen cell measurements would be of value both in the design of the cell orifice and in establishing realistic estimates of the limits of error for existing data. The experimental program was in two sections. Firstly, measurements of the vapor pressure of silver were made in cells with cylindrical and conical orifices in which the surface-diffusion contribution to the weight loss should be negligible. These results were correlated with existing data to give a reliable measure of the real vapor pressure of silver. Secondly, measurements made using knife-edge orifices were corrected using the surface-diffusion theory of Winterbottom and Hirth2 and were then compared to the real values. The experimental arrangement is shown in Fig. 1. The balance was an Ainsworth RV-AU-1 automatic recording microbalance capable of measuring weight changes of ±0.02 mg on a total load of up to 100 g. The temperature was measured by an optical pyrometer signted on the bottom of the suspended crucible. The temperature readings were calibrated in a separate experiment in which pyrometer measurements were made while at the same time thermocouple readings were taken of the temperature at the inside top and bottom of the crucible. The range of reproducibility with this technique was ±4°C. A constant voltage source maintained a temperature of ±2°C at 1200°C over 10 hr. Silver of 99.99 pct purity was used in nonporous alumina crucibles. Lids of molybdenum, tantalum, or magnesia were cemented to the crucible using a sodium silicate cement. Table I shows the characteristics of the lids used. The vapor pressure is obtained using the basic Knudsen formula:

Jan 1, 1965

By F. M. d’Heurle

Films of molybdenum have been prepared by sputtering onto oxidized silicon substrates. The resistivity. lattice parameter, orientation, and grain size were studied as a function of substrate temperature and substrate bias. Under normal sputtering conditions, the resistivity of the films was found to be quite high (600 x 10 ohm-crn). However, with the use of the negative substrate bias of 100 v and a substrate temperature of 350°C, films weve produced with a resistivity of ahout twice that of bulk molybdenum. The lattice parameters measured in a direction nornzal to the surface of the films weve found to be gveatev than the bulk value. This was interpreted as being at least partly due to the presence of compressive stresses. The effects of annealing in an Ar-H atmosphere were studied in terms of diffraction line width, lattice parameter, and resistivity. BECAUSE of its relatively low bulk resistivity (5.6 x 106 ohm-cm)&apos; molybdenum is potentially interesting as a thin-film conductor in integrated circuits. An additional feature which makes it attractive for this purpose is its low coefficient of expansion (5.6 x KT6 per "c),&apos; which is fairly well matched to that of silicon (3.2 x 10 per c). It is possible to deposit molybdenum films by evaporation but generally films produced in this manner have a high resistivity. In order to achieve resistivities close to bulk value, Holmwood and Glang found it necessary to operate in a vacuum of about 107 Torr and to maintain the substrates at 600 C during film deposition. Sputtered molybdenum films have been examined by Belser et a1.7 and, recently, by Glang et al.&apos; This paper describes the results of an attempt to extend some of that work and examine the effects of annealing and getter sputtering on the physical and structural properties of the films produced. SPUTTERING APPARATUS AND PROCEDURE The apparatus used for most of the film sputtering work described here consisted of two "fingers" serving as anode and cathode, respectively, which were mounted within an 18-in.-diam glass chamber. A liquid nitrogen-trapped 6-in. diffusion-pump system was used to achieve a vacuum of about 1 x 107 Torr within the chamber prior to sputtering. The essential features of the equipment are shown in Fig. 1. Cathode and anode fingers are stainless-steel tubes isolated from the top and bottom plates by Teflon collars. In order to limit the discharge to the space between anode and cathode, each finger is surrounded by an aluminum hield, at ground potential, having an internal diameter 18 in. larger than the outside diameter of the finger. The cathode and anode fingers are 6 and 4 in. in diam, respectively. A 116-in.-thick sheet of molybdenum is brazed with a 10 pct Pd, 58 pct Ag, 32 pct Cu alloy to a copper disc which is mounted by means of screws and a large 0 ring onto the lower end of the cathode finger. The disc is cooled during sputtering by water circulation inside the finger. The use of several feet of plastic tubing for the water input and outputg reduces leakage to ground to less than 1 ma when the cathode potential is raised to 5 kv. The upper end of the anode finger is terminated by a brazed-on copper block. A variety of specimen holders can be easily mounted on the upper face of this block. Substrate heating or cooling is achieved by use of an appropriate unit attached to the lower face of the same block. Heating is achieved by means of cartridge-type heaters and cooling by copper coils fed with forming gas under pressure. The inner chamber of the specimen finger constitutes a small vacuum chamber of its own which is evacuated by an auxiliary mechanical pump in order to limit heating element oxidation and heat transfer by convection currents. An advantage of the finger arrangement is the absence of cooling and heating coils and wires within the main chamber. The stain less-steel shutter is useful to establish a discharge for cleaning the cathode at the beginning of each sputtering run. Water cooling of the shutter reduces heating and the out-gassing of impurities which might condense on the nearby substrates. Unless otherwise specified, the substrates used in these experiments were 1-in.-diam oxidized silicon wafe:s, 0.007 in. thick, having an oxide thickness of 6000A. The substrate holders were large copper discs onto the surface of which a number of molybdenum discs, 116 in. thick and 78 in. in diam, were brazed. The wafers were clamped to the molybdenum discs

Jan 1, 1967

By Clarence O. Babcock

Model pillars of limestone, marble, sandstone, and granite, with length-to-diameter (LID) ratios of 3, 2, 1, 0.5, and 0.25 (0.286 for granite), were broken in axial compression to determine to what extent an increase in end constraint increased compressive strength. Radial end constraints of 13 to 23% of the average axial stress in the pillar, produced by solid steel rings bonded with epoxy to the ends of dogbone-shaped specimens, increased compressive strength somewhat above that of cylindrical pillars without ring constraint. However, when the results were compared with those obtained by other investigators for straight specimens of several rock types taken collectively, with LID ratios greater than 0.5, the resulting strengths were not significantly different. Thus, the amount of end constraint produced by the solid steel rings was about the same as that produced by the friction from the steel end plates. In other tests, a radial prestress of 3000 or 5000 psi was applied prior to axial loading by adjustable hardened steel rings to increase the constraint above that obtained for the solid rings. The average radial constraint stress, expressed as a percentage of the average axial pillar stress at failure for the 3000 psi prestress, was 54.3% for limestone, 40.3% for marble, 44.7% for sandstone, and 23.4% for granite. The average radial constraint stress, expressed as a percentage of the average axial pillar stress at failure for the 5000 psi prestress, was 74.2% for limestone, 51.2% for marble, 61.6% for sandstone, and 29.7% for granite. These constraints increased the compressive strength significantly above the strength of straight specimens and solid-ring constrained specimens. These results suggest that large horizontal stresses in orebodies mined by the room-and-pillar method should increase the strength of the pillars and allow an increase in ore recovery by a reduction of pillar size when major structural defects are absent. One important objective of the U.S. Bureau of Mines (USBM) mining research program is the rational design of mining systems. In the design of room-and-pillar mining operations, pillar strength is a fundamental variable. It is customary to estimate this strength from uniaxial compression tests of rock samples and to correct this value for the length-to-diameter (LID) ratio of the in-situ pillar. This method of estimating pillar strength corrects for pillar shape but does not consider the effect of a large horizontal in-situ stress field that sometimes exists in underground formations. The purpose of the work covered in this report was to determine to what extent the compressive strengths of model pillars of relatively brittle rock loaded in axial compression were affected by lateral end constraint. In previous work, Obert l used solid steel rings bonded to the ends of dogbone-shaped specimens to study the creep behavior of three quasi-plastic rocks -salt, trona, and potash ore - during a test period of 1000 hr. These rings provided radial constraint during the loading cycle of 20 to 50% of the axial stress for specimens with LID ratios of 2, 0.5, and 0.25. He concluded that (1) "for a quasi-plastic material the end constraint strongly affects the specimen strength, and (2) as D/L increases (length-to-diameter decreases), the specimens lose their brittle characteristics and tend to flow rather than fracture." He also concluded that model pillars constrained by rings were better for use in predicting the strength of mine pillars than either cylindrical or prismatic specimens. This conclusion appears to be valid where mine pillars, roof, and floor are a single structural element. In the present study, 460 specimens of four relatively brittle rocks — limestone, marble, sandstone, and granite - were tested to failure. The study consisted of two parts: (1) the effect on the compressive strength of end constraint produced during the axial loading cycle by solid steel rings bonded with epoxy to the ends of the specimens, and (2) the effect on the compressive strength of increased end constraint produced in part by a prestress applied prior to axial loading and in part by lateral expansion of the specimen during the loading cycle. The first part of this study was reported in some detail earlier.2 EXPERIMENTAL PROCEDURE AND EQUIPMENT Model rock pillars of the sizes and shapes shown in Fig. 1 were broken in axial compression when the ends were constrained as shown in Fig. 2. he straight specimens were broken without ring constraint. The specimens of dogbone shape were broken with (1) solid

Jan 1, 1970

By R. H. Kolb

A long term project at Shell Development Co.&apos;s Exploration and Production Research Laboratory has been the improvement of the accuracy and the ease of BHP measurements. As a result of these efforts, two complete and separate systems have now been built for the automatic logging of BHP variations. The first of these is a small-diameter instrument suitable for running through production tubing on a single-conductor well cable. During the development of this instrument, as much emphasis was placed on providing a high degree of usable sensitivity and repeatable accuracy as on obtaining the advantages of surface recording. The second system combines the benefits of automatic, unattended recording with the convenience of a permanently installed Maihak BHP transmitter.&apos; THE CABLE INSTRUMENT For many years the standard instrument for BHP determination has been the wireline-operated Amerada recording pressure gauge or one of several other similar devices. This gauge records on a small clock-driven chart carried within the instrument, and although relatively precise readings from the chart are possible, they are difficult to ob-tain. a Both the maximum recording time and the resolution of the time measurements are limited by chart size, and when a slow clock is required for long tests, the precision of the time measurement is often inadequate. Since it is impossible to determine the data being recorded until the gauge has been returned to the surface, wasted time often results when a test is protracted beyond the necessary time or when it is terminated too soon and must be re-run. Clock stoppage or other malfunctions which would be immediately apparent with surface recording remains undetected with down-hole recording; the test is continued for its full term with a consequent loss in production time. As new uses for subsurface pressure data evolved, the shortcomings of the wireline instrument became increasingly apparent, and the concurrent development of a surface-recording pressure gauge and the associated high-pressure well cable service unit&apos; was undertaken. Description of the Instrument Because of its ready availability and advanced degree of development, the Amerada bourdon-tube element was chosen as the basic pressure-sensing device. This element converts a given pressure into a proportional angular displacement of its output shaft, and a suitable telemetering system was designed to measure accurately the extent of this displacement and to transmit the measurement to the surface and record it. The telemetering system furnishes a digital record printed on paper tape by an adding machine-type printer. The present arrangement provides a resolution of one part in 42,000 over the angular equivalent of full-scale deflection, giving a usable sensitivity of better than 0.0025 per cent of full scale. An additional refinement simultaneously records on the tape the time or the depth of the measurement, also in digital form. When the instrument is placed in operation, an adjustable programer can be set to initiate a read-out cycle automatically at selected time intervals. When subsurface pressures are changing rapidly, readings may be recorded as frequently as once every 10 seconds; when pressures are more nearly stabilized, the period between readings may be extended to as much as 30 minutes. Because the instrument is surface-powered as well as surface-recording, the maximum period of continuous logging is (for all prac. tical purposes) unlimited. The subsurface instrument is a tubular tool, 1 1/4-in. in diameter and 6.5 ft in length, operating on 12,000 ft of conventional 3/16-in. IHO logging cable. The transmitting section, mounted above the bourdon-tube element in place of the regular recording mechanism, contains no fragile vacuum tubes or temperature-sensitive transistors. This unit has been laboratory-tested to 1 0,000 psi and 300°F and has performed dependably during a number of field operations. The down-hole transmitting arrangement can be fitted to any standard Amerada pressure element, regardless of range and with no modification of the element itself. Calibration To obtain a repeatability commensurate with the sensitivity and resolution of the instrument, it was necessary to develop a special calibrating technique. The manufacturers of the Amerada recording pressure gauge claim an accuracy of only 0.25 per cent of full scale, which is a realistic figure for normal calibrating and operating procedures. An exhaustive investigation was made of the errors inherent in the bourdon-tube element, itself, independent

By A. R. Orban, R. B. Engdahl, J. D. Hummell

The initial phase of a research program on smoke abatement from Bessemer converters is described. In work sponsored by the American Iron and Steel Institute, a 300-lb experimental Bessemer converter was assembled to simulate blowing conditions in a commercial vessel. Measurements of smoke and dust were also made in the field on a 30-ton commercial vessel. During normal blows the dust loading from the laboratory converter averaged 0.51 lb per 1000 lb of exhaust gas. This was similar to the exhaust-gas loading of a commercial vessel. The addition of hydrogen to the blast gas of the laboratory converter caused a decided decrease in smoke density. Smoke was also reduced markedly when methane or ammonia was added instead of hydrogen. The research is continuing on a bench-scale investigation of the mechanism of smoke formation in the converter process. DURING the past 2 years, on behalf of the American Iron and Steel Institute, Battelle has been conducting a research program on the control of emissions from pneumatic steelmaking processes. The objective of the research program is to discover a practical method for reducing to an unobjectionable level the emission of smoke and dust from Bessemer converters. PRELIMINARY INVESTIGATION Although conceivably some new collecting technique may be devised which would be economically practicable for cleaning Bessemer gases, no such system based on presently known principles seems feasible because of the extremely large volume of high-temperature gases involved. Hence, the research is being directed toward prevention of smoke formation at the source. A thorough review was first made of former work to determine the present status of the cleaning of converter gases. No published work was found on work done in the United States on collecting smoke or on preventing its formation in the bottom-blown, acid-Bessemer converter. In Europe, however, a number of investigations have been made on the basic-Bessemer converter. Kosmider, Neuhaus, and Kratzenstein1 conducted tests on a 20-ton converter to obtain characteristic data for dust removal and the utilization of waste heat. They concluded that because of the submicron size of the dust, special equipment would be necessary to clean the exhaust gases. Dehne2 conducted a large number of smoke-abatement experiments at Duisburg-Huckingen in a 36-ton Thomas converter discharging into a stack. A number of wet-scrubbing and dry collectors were tried unsuccessfully. A waste-heat boiler and electrostatic collector with necessary gas precleaners was felt to be the best solution for this particular plant. Meldau and Laufhutte3 determined that the particle size was all below 1 µ in the waste gas of a bottom-blown converter. Sel&apos;kin and zadalya4 describe the use of oxygen-water mixtures injected into a molten bath in refining open-hearth steel. They claim that with use of oxygen-water mixtures the amount of dust formed was reduced between 33.3 and 20 pct of its previous level, and emission of brown smoke almost ceased. Pepperhoff and passov5 attempted unsuccessfully to find some correlation between the optical absorption of the smoke, the flame emission, and the composition of the metal in a Thomas converter in order to determine automatically the metallurgical state in the melt. In a recent U. S. Patent (NO. 2,831,762)&apos; issued to two Austrian inventors, Kemmetmuller and Rinesch, the inventors claim a process for treating the exhaust gases from a converter. By their method the inventors claim that the exhaust gases from the converter are cooled immediately after leaving the converter to a degree that oxidation of the metal vapors and metal particles to form Fe2O3 is inhibited in the presence of surplus oxygen. Gledhill, Carnall, and sargent7 report on cleaning the gases from oxygen lancing of pig iron in the ladle. They claim the Pease-Anthony Venturi scrubber removed 99.5 + pct of the smoke, thereby reducing the concentration to 0.1 to 0.2 grain per cu ft, which resulted in a colorless stack gas after the evaporation of water. Fischer and wahlster8 developed a small basic converter and compared the metallurgical behavior of the blow with that of a large converter. Later work by Kosmider, Neuhaus, and Hardt9 on the use of steam for reduction of smoke from an oxygen-enriched converter confirmed that the cooling effect of steam is detrimental to production. From review of all of the published information on the subject, it was concluded that a practical solution to the smoke-elimination problem had not been found. Accordingly, it was deemed desirable to investigate the feasibility of preventing the initial formation of smoke in the converter.

Jan 1, 1961

By J. H. Swisher

The solubility of graphite in CaO-S2O2-Al,O3 slags was measured by equilibrating slag samples with graphite crucibles and CO gas. Carbon contents as high as 2 ut pct were obtained in CaO-saturated, CaO-A1,O3 slags, and 1.3 wt pct in slags of the composition CaO.Si0,. Although the observed conditions for Sic formation were in agreement with those predicted from thermodynamic data, CaC, was found to form at a lower temperature than predicted frotn thermodynamic data. From measurements of the equilibrium carbon content as a function of CO Partial pressure, it was found that carbide ions dissolve in CaO-A12O3 melts with a valence of minus two. The carbon content increased with CaO concentration in Ca0-Al,O3 melts and increased with SiO, content along the CaO&apos;AlO3-CaOSi0 join in the ternary system. When solid CaC2 was added to CaO-A12O3 and CaO-SiO2-A12O3 slags, it was found that one of the oxides in the slag was reduced by the carbide (Al2O3 in the forrner and SiOz in the latter). In electric furnace steelmaking, a double-slag practice is frequently used to meet alloy specifications. Initially a flush slag, which is oxidizing in nature, is used to remove phosphorus and carbon from the steel bath. Later in the refining period, the flush slag is replaced by a highly reducing carbidic slag. When calcium carbide is formed in or added to a finishing slag, the slag is effective as a desulfurizing agent and also permits alloying elements such as chromium, vanadium, and tungsten to be added to the slag in the form of oxides. The oxides are readily reduced by calcium carbide, thereby minimizing the use of expensive ferroalloys. More work has been done on the thermodynamics of silicon carbide in slags than on calcium carbide. Baird and alor&apos; and Kay and alor&apos; determined the free energy of formation of Sic by measuring the partial pressure of CO in equilibrium with solid silica, silicon carbide, and graphite. Using a similar technique, they determined SiOz activities in CaO-SiOz and Ca0-Si0,-A1203 slags. Rein and chipman3 also determined the free energy of formation of Sic using slag-metal equilibrium measurements. A literature survey has uncovered only one experimental study of the behavior of CaC, in slag systems. Shanahan and cooke4 report the results of some preliminary experiments on the solubility and stability of CaC, in a CaO-A1,03 and a Ca0-Si0-A1,03 slag at a temperature of about 1500". The carbon solubility as CaC, in a slag containing 50 pct CaO and 50 pct A1203 was reported to be 0.6 pct. They also review earlier work on the binary CaO-CaC, system. A eutectic exists in this system, but various investigators disagree on the eutectic temperature and composition. eal has given an explanation for carbide furnace erruptions in terms of the thermodynamic properties of CaC,; his analysis is not based on experimental data, but on compiled data for the free energies of formation of CaC, and CO.&apos; , These data for steel-making temperatures are all extrapolated from the results of low-temperature measurements. In the experiments described in this paper, slag samples were equilibrated with graphite crucibles and with mixtures of CO and argon or with CO gas at 1 atm total pressure for measurement of the carbon solubility. Most of the work was done on Ca0-A1203 binary slags, although in some experiments CaO-SiO, and Ca0-Si0,-A1,03 slags were used. EXPERIMENTAL Slag samples of the desired composition for the solubility measurements were obtained by blending pre-fused master slags. The master slags were prepared by fusing mixtures of reagent-grade CaC03 with either A1,03 or Si0, in a graphite crucible. The master slags were crushed, then decarburized in air in a muffle furnace at 1200O C. A schematic diagram of the apparatus is shown in Fig. 1. The source of carbon for the solubility meas-

Jan 1, 1969

By W. R. Hibbard

THE classical work on the electrical conductivity of alloys was carried out by Matthiessen and his coworkers1 in the early 1860&apos;s. He attempted to correlate the electrical conductivity of alloys with their constitution diagrams, but the information regarding the latter was too meager for success. Guertler2 reworked Matthiessen&apos;s and other conductivity data in 1906 on the basis of volume composition (an application of Le Chatelier&apos;s principle with implications as to temperature and pressure effects), and obtained the following relationships between specific conductivity and phase diagrams (plotted as volume compositions) : 1—For two-phase regions, electrical conductivity can be considered as a linear function of volume composition, following the law of mixtures. 2—For solid solutions, except intermetallic compounds, the electrical conductivity is lowered by solute additions first very extensively and later more gradually, such that a minimum occurs in systems with complete solid solubility. This minimum forms from a catenary type of curve. Intermetallic compound formation with variable compound composition results in a maximum conductivity at the stoi-chiometric composition. Landauer" has recently considered the resistivity of binary metallic two-phase mixtures on the basis of randomly distributed spherical-shaped regions of two phases having different conductivities. His derivation predicts deviations from the law of mixtures which fit measurements on alloys of 6 systems out of 13 considered. Volency (Ionic Charge) Perhaps the first comprehensive discussion of the electrical resistivity of dilute solid-solution alloys was presented by Norbury&apos; in 1921. He collected sufficient data to show that the change in resistance caused by 1 atomic pct binary solute additions is periodic* in character. The difference between the period and/or the group of the solvent and solute elements could be correlated with the increase in resistance. Linde5-7 determined the electrical resistivity (p) of solid solutions containing up to about 4 atomic pct of various solutes in copper, silver, and gold at several temperatures. He reported that the extrapolated"" increase in resistance per atomic percent addition is a function of the square of the difference in group number of the solute and solvent as follows: ?p= a + K(N-Ng)2 where a and K are empirical constants and N and Ng are group numbers of the constituents. This empirical relation was subsequently rationalized theoretically by Mott,8 who showed that the scattering of conduction electrons is proportional to the square of the scattering charge at lattice sites. Thus, the change in resistance of dilute alloys is propor-t,ional to the square of the difference between the ionic charge (or valence) of the solvent and solute when other factors are neglected. Mott&apos;s difficulty in evaluating the volume of the lattice near each atom site where the valency electrons tend to segre-gate: limited his calculations to proportionality relations. Recently, Robinson and Dorn" reconfirmed this relationship for dilute aluminum solid-solution alloys at 20°C, using an effective charge of 2.5 for aluminum. In terms of valence, Linde&apos;s equation becomes ?P= {K2 + K1 (Z8 -Za)2} A where K1 and K2 are coefficients, A is atomic percent solute, Z, is valence of solvent, and Zß, is valence of solute. Plots of these data for copper, silver, gold, and aluminum alloys are shown in Fig. 1. The values of K1 and K2 are constant for a given chemical period (P), but vary from period to period. The value of K, increases irregularly with increasing difference between the period of the solvent and solute element (AP), being zero when AP is zero. The value of K, appears to have no obvious periodic relationship. All factors other than valence that affect resistivity are gathered in these coefficients. Because of the nature of the coefficients, Eq. 1 is of limited use in estimating the effects of solute additions on resistivity unless a large amount of experimental data are already available on the systems involved. It is the purpose of the first part of this report to investigate the factors that may be included in the coefficients of Linde&apos;s equation. On this basis, it is hoped that the relative effects of solute additions on resistivity can be better estimated from basic data, leading to a more convenient alloy design procedure. It is well 10,11 that phenomena that decrease the perfection of the periodic field in an atomic lattice, such as the introduction of a solute atom or strain due to deformation, will also increase the electrical resistivity. Thus, in an effort to relate changes in electrical resistivity to alloy composition, it appears appropriate to consider the atomic characteristics related to solution and strain hardening

Jan 1, 1955