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By Alexander L. Field

IN a previous paper,' the experimental methods used and some of the results obtained in an extensive investigation of steels containing zirconium were described. The present paper considers in greater detail one of the most interesting of these effects, namely, the elimination of " red shortness" and the occurrence in steel of a compound of zirconium and sulfur. A consideration of the actual percentages of zirconium, manganese, and sulfur in numerous steels in the light of behavior during rolling has led to new conclusions of the most practical import regarding the reciprocal relationships of these elements. The microscopic examination of high-sulfur steels containing zirconium has also been productive of interesting results. Before discussing the experimental data in question, it may be stated, briefly, that the rettetion between zirconium and sulfur in molten steel may be represented by the simple equation, Zr + 25 = ZrS², and that the zirconium sulfide thus formed occurs in the finished steel in the form of gray-colored inclusions, closely resembling manganese sulfide and, like the latter, exhibiting plasticity at rolling temperatures. Molten steel containing zirconium retains such a negligibly small amount of oxygen in solution that the foregoing reaction goes to completion. Hot-rolling Properties of High-sulfur Steels with and without Zirconium The chemical composition of twenty-eight steel ingots embracing eleven heats made in a basic-lined electric furnace is shown in Table 1. The practice followed in the manufacture of these high-sulfur steels was described in the previous paper. Table 1 also gives the behavior of the

Jan 1, 1924

By Albert R. Ledoux

I am indebted to The Kaolin Co. of West Cornwall, Conn., and particularly to its engineer, Mr. M. Wanner, for permission to make public, through the Transactions of the American Institute of Mining Engineers, the interesting results of his experiments, having in view the winning of kaolin from deep deposits without shaft-sinking or removing of the overburden. So far as I am aware, nothing like it has been accomplished heretofore, although it reminds one of the methods successfully employed in Louisiana for the winning of sulphur from deep beds by the sinking of pipes one within another, injecting superheated steam under pressure through one pipe, the heat of the steam liquefying the sulphur and the pressure forcing it up through the other pipe to bins at the surface. The kaolin-deposit at West Cornwall is an alteration in situ— that is, it is not sedimentary. A series of clay-veins, dipping about 50" from the vertical, lie between a foot-wall of' limonite and a hanging-wall of gneiss and hornblende schist. The clay-veins alternate with veins or seams of more or less broken quartz, and unaltered feldspar. The deposit, which occurs at a point about 600 ft. above the Housatonic river, was opened five years ago, and about 5,000 tons of a superior grade of washed kaolin have been extracted from open pits, and sold. It soon became evident that this mode of extracting the product would prove unremunerative, by reason of the dip of the vein and the intercalary strata and lenses of quartz, and a more satisfactory method of working the deposit was sought. It is well understood that, in the preparation of all clays for market, especially residuary kaolin, the most important as well as the most difficult step is the washing of the crude product. The dificulties increaee with the percentage of foreign matter, especially quartz and mica, contained in the product. Hence, a system

Jan 1, 1907

By Andrew Hyslop

In our never ending search for new and better ways of underground mining, we find that transportation has had its share of new ideas in the past few years. The old and still effective method of track haulage has had some competition from rubber-tired cars and belt conveyors, each of which has its own safety hazards which demand close scrutiny in any safety study. The use of shuttle cars, in particular, has introduced clearance hazards caused by the absence of the more or less positive guides formed by the rails of a track sys- tem; likewise the requirement of greater clearance tends to increase roof hazards which we all know to be great enough with the best of methods. However, the subject of transportation hazards is too broad to be covered entirely in one paper, so I will confine myself to track methods which carry the preponderance of underground tonnage. I am quite sure that to this group it is an evident fact that haulage accidents are of major importance. However, to stress the point, it may be well to look at a few figures. Safety statistics can be quite boring and often are subject to question as to mathematical accuracy because of different

Jan 1, 1949

By Andrew Hyslop

IN our never ending search for new and better ways of underground mining, we find that transportation has had its share of new ideas in the past few years. The old and still effective method of track haulage has had some competition from rubber tired cars and belt conveyors, each of which has its own safety hazards which demand close scrutiny in any safety study. The use of shuttle cars, in particular, has introduced clearance hazards caused by the absence of the more or less positive guides formed by the rails of a track sys¬tem; likewise the requirement of greater clearance tends to increase roof hazards which we all know to be great enough with the best of methods. However, the subject of transportation hazards is too broad to be covered entirely in one paper, so I will confine myself to track methods which carry the preponderance of underground tonnage. I am quite sure that to this group it is an evident fact that haulage accidents are of major importance. However, to stress the point, it may be well to look at a few figures. Safety statistics can be quite boring and often are subject to question as to mathematical accuracy because of different

Jan 1, 1948

By E. Miller, R. Geffken, K. L. Komarek

The thermodynamzc properties oJ liquid Cd-Sb alloys were investigated using the cell arrangement measurments were obtained every 2°C at a heating and cooling rate of 12°C per hr and at equilibrium every 2O0C frorn 500°C down through the stable liquidus. The S-shaped asCd US composition curve was used in the cotnposition regzon near Cd,Sb, to calculate a tempeerture-dependent inleraction coefficient from quasichemical theory. Rapid changes in a scd were observed at a transition temperature varying from 400" to 465°C depending on con/kosition. It could not be determined if the changes in aScd were discontinuous, but tlze composition dependeke of the magnitude of the change is indicative of a second-order phase transformation in the liquid. The values of the experimental changes in ASCd are in agreement with calculations from the slope of the transition temperature, using the concept that a second-ovdev phase transition occurs in liquid Cd-Sb alloys. II is suggested that the transformalion is associated with the formation of Cd4Sb3 molecules in the liquid. ThE structure of liquid alloys is the subject of many investigations. X-ray, resistivity, and thermody-namic data have been interpreted as indicating varying degrees of short-range order in the liquid in alloy systems forming inter metallic compounds. In general, the melting process is not a transition from an ordered to a completely disordered state, but some degree of order is retained in the liquid. Maximum ordering in the liquid state occurs close to the melting temperature of the compound and the arrangement of atoms becomes more random at higher temperatures. Of special interest in this respect is the Cd-Sb system. It is one of the few metallic systems which form both stable and metastable compounds when liquid alloys are cooled at normal rates. The stable system exhibits an intermetallic compound, CdSb, melting at 459"c.l A second compound, CdrSbs, has also been reported,' melting close to this temperature. The metastable system has one compound, CdsSbz, melting at 420"c.I Resistivity measurements on liquid Cd-Sb alloys close to the liquidus temperatures have been interpreted in terms of a complex ordering behavior which changes rapidly with increasing temperature.3 The resistivity-composition curve is characterized by two maxima corresponding in composition to CdSb and CdsSbz. The resistivity-temperature plots show sharp breaks for alloys in the composition range of 45 to 70 at. pct Cd on cooling through a transition temperature close to the stable liquidus. Fisher and phillips4 investigated the influence of temperature and composition on the viscosity of liquid CdSb alloys. The viscosity of some alloys increases sharply on supercooling below the stable liquidus. A maximum in the viscosity-composition curve occurs at the composition CdSb. The thermodynamic properties of liquid Cd-Sb alloys have been investigated by Seltz and ~e~itt' and Elliott and chipmane by the electromotive-force method and their results are in good agreement. However, these investigations were carried out at temperatures well above the liquidus temperatures of the alloys, and the temperature coefficients of the electromotive force, dE/dT, were obtained from experimental points for each alloy at a few temperatures considerably above the liquidus temperature. Scheil and ~aach' investigated the thermodynamic properties of this system by the dew point method in the temperature range from about 100°C above the stable liquidus down into the supercooled liquid region. They reported several anomalies, i.e., the activity of a melt on heating differed from that on cooling, and the activity increased sharply in the limited temperature interval immediately above the liquidus temperature of the stable alloy, followed by a sudden decrease below the liquidus. Values obtained on heating and cooling were not in agreement. A reinvesti-gation of a few alloys by Scheil and Kalkuhl' by the electromotive-force method failed to confirm these observations. The authors concluded that the anomalies were due to inhomogeneities in the starting alloys and they discarded their previous results. The present investigation was undertaken in order to obtain thermodynamic data close to the liquidus temperature and in the supercooled region where the anomalies were originally reported, employing the electro motive-force method. This method is quite precise and will most easily permit observations of small changes in activity and partial molar entropy with temperature. Measurements were taken every few degrees so that the dE/dT values could be calculated over the entire temperature range and small changes in the thermodynamic properties close to the liquidus temperature could be observed. I) EXPERIMENTAL PROCEDURE Specimens were prepared from 99.999+ pct Cd and Sb (Cominco). Surface oxide was removed by scraping and then melting the metals under vacuum and filtering through Pyrex wool. Appropriate amounts of the metals were weighed on an analytical balance to k0.1 mg, sealed in double Pyrex capsules under vacuum,

Jan 1, 1968

By Hsun Hu, R. S. Cline

The annealing behavior and the mechanism of re-orientation during recrystallization of iodide titanium cold-rolled 94 pct have been studied in detail. Results indicate that recrystallization occurs by the nucleation and growth of new grains, as in other common metals. Recrystallization nuclei form by the coalescence of subgraim, and the change in texture as a result of recrystallization is largely due to selective growth among the nuclei formed. The annealing of titanium is characterized by a wide range of overlap of the various stages of the annealing process, which may be responsible for a range of activation energies observed, and for the apparently gradual change in the annealing texture as a function of time or temperature. The deformation and recrystallization characteristics of titanium and zirconium are very similar. In cold-rolled strip, the deformation texture consists of two symmetrically oriented components, each having the basal plane laterally tilted at about 30 deg from the rolling plane and the [1010] direction parallel to the rolling direction. Upon annealing for recrystallization, the change in texture can be described, for simplicity,* as rotations around [0001].2'6'8 According to McGeary and Lustman,' recrystallization occurs in zirconium through normal growth of the subgrains, which they called "domains", without the nucleation of new grains; and the magnitude of rotation around the [0001] axis increases gradually during the progress of recrystallization. If these conclusions were true, the mechanism of recrystallization in zirconium would be basically different from that in most metals, since it is commonly known that recrystallization with reori-entation always involves the migration of high-angle boundaries. In an attempt to clarify the situation, the mechanism of reorientation during recrystallization in iodide titanium cold-rolled 94 pct was studied in detail. The structural and textural changes upon annealing at various temperatures were examined by optical and transmission-electron microscopy, X-ray pole figures, pole density distribution measurements, and micro-beam techniques. EXPERIMENTAL PROCEDURE Material and Specimen Preparation. An iodide titanium crystal bar was are-melted and solidified in a cold-hearth crucible under a purified argon atmosphere. The solidified ingot had dimensions of approximately 3 by 1/2 by 3 in. One face of the ingot was somewhat uneven, but was as clean and shiny as the remaining parts of the ingot. Large grains with a Widmanstatten internal structure were clearly shown on the shiny surfaces, indicating the occurrence of P — a transformation upon rapid cooling from the melt. Analysis of the are-melted ingot indicated C 0.033, N 0.010, H 0.013, 0 0.002 in weight percent, and traces of iron, copper, and silicon as detectable impurities. The ingot was cold-rolled -40 pct to 0.300 in. thick with a reduction of 0.005 in. per pass. The defects on the uneven side of the ingot were then removed by machining. This reduced the thickness to 0.285 in. The piece was then recrystallized by annealing at 800°C for 1 hr in a fused silica boat charged into a fused silica tube furnace under a vacuum of 10~5 mm Hg. To refine the grain size, the recrystallized metal was again cold-rolled 40 pct to 0.170 in., then annealed at 700°C for 1 hr. These treatments yielded a strip with a uniform equiaxed grain structure, having a penultimate average grain diameter of 0.04 mm and a hardness of approximately 90 Dph. Final rolling reduced the thickness from 0.170 to 0.010 in., corresponding to a reduction of 94 pct. The strip was rolled in both directions by reversing end for end between passes. Surface lubrication was provided by oil-soaked pads attached to both rolls. Specimens of 1 in. length (for X-ray examinations) and +in. length (for hardness and microstructure examinations) were cut from the rolled strip, and a width of & in. was cut from the edges of each specimen by a jeweler's saw. These specimens were then etched in a solution of 10 cu cm HN03, 5 cu cm HF, and 50 cu cm H,O to 0.008 in. thick to remove the surface metal, as well as the distorted metal at the saw cuts, prior to annealing or measurements. To minimize any surface reaction with the atmosphere, all specimens were kept in an evacuated desiccator. Isothermal Anneals. All annealing treatments were conducted in vacuum in a fused silica tube furnace as described earlier. The temperature of the furnace was controlled to within *2"C. The specimen was placed in a fused silica boat, then pushed into the hot zone of the furnace. It took about 5 to 6 min for the specimen to reach the furnace temperature. After the specimen was held at temperature for a desired length of time the boat was pulled to the cold zone of the furnace; the heating-up period was excluded from the isothermal annealing time. Thus, the uncertainty in annealing time is higher for very short anneals, but negligible for long anneals.

Jan 1, 1969

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Jan 1, 1913

By Marvin Lee

Kansas retained, for the eighth consecutive year, the fourth position in the list of oil-producing states. The total crude-oil production during 1934, as reported by purchasers to the State Corporation Commission, was 45,538,564 bbl. on 97 per cent tank table calculations of the purchasers, or 46,946,973 bbl. as carried on 100 per cent measurement in U.S. Government reports. The corresponding figures for 1933 are 40,008,940 and 41,236,021, respectively. The increase of production over 1933 was due to the rising demand for oil from Kansas, caused principally by three factors: the continued regulation of the producing branch of the industry by Federal and State authorities, which had the effect of reducing illegal production that has been so destructively competitive with Kansas crude and refined products; the normal decline of production in other areas; and, last and best, general increased demand of the public for petroleum products. The price level remained unchanged for the first time in oil history for so long a period. Kansas 36" gravity crude remained at $1 per barrel from September, 1933, and throughout 1934. Price stability and the confidence in the regulation of production to meet the consumer demand, which is increasing, brought greatly renewed interest in Kansas fields. Drilling activity has been largely in the western part of the state where expiration of leases, on large blocks of acreage, assembled before the depression, is forcing either action or loss of the lease investment carried for a long period. The drilling of these many blocks of acreage, previously assembled on geologic information, has caused the opening of more fields than during any previous year of Kansas oil history and is proceeding faster than anticipated a year ago. Interest grows within a successful enterprise, and the momentum caused by the successes of 1934 will continue in 1935 unless unusual conditions arise and end the apparently good opportunity for financial return. Geological exploration methods used in new field discoveries are shown in the tabulation of new discoveries (Table 3).

Jan 1, 1935

By J. H. Hollomon, L. D. Jaffe, M. R. Norton

In the practical heat-treatment of steel the decomposition of austenite usually occurs during cooling rather than at constant temperature. Nevertheless, the course of this decomposition has generally been studied only isothermally. Isothermal studies are not only simpler experimentally, but have the great theoretical advantage that one of the variables, temperature, is constant. It is the purpose of this paper to outline the principles that govern the relations between isothermal and anisothermalt‡ decomposition of austenite, to present and systematize the available experimental information, and to indicate the gaps in the existing knowledge. Some of the experimental information is the result of new work.§ Most of it is derived from scattered data in the literature. Many of these data were obtained incidentally in the course of research on other subjects and their significance has not been pointed out and perhaps not understood. It is hoped that this paper will aid future planning of more extensive research on anisothermal decomposition. Method In order to study the relations between isothermal and anisothermal decomposition, it appears fruitful to view anisothermal decomposition as taking place at a series of constant temperatures1 (except for the martensite reaction, which does not occur isothermally to an appreciable extent). When the time the steel is at each temperature is finite, the over-all amount of the reaction is considered to be the sum of the amounts occurring at each of the successive temperatures. During continuous cooling or heating, the time the steel is at each temperature and the difference between successive temperatures can be considered to approach zero. The over-all amount of transformation will then be given by integration over the range of temperatures involved. This point of view is advantageous in that it considers anisothermal transformation to be a series of isothermal transformations. The problem thus becomes one of determining the effect of partial decomposition at any given temperature upon subsequent decomposition at another temperature. Single Anisothermal Reaction Consider a phase brought to a temperature at which it is unstable, held there until it has partially transformed, and then brought to another temperature at

Jan 1, 1947

By L. D. Jaffe, M. R. Norton, J. H. Hollomon

In the practical heat-treatment of steel the decomposition of austenite usually occurs during cooling rather than at constant temperature. Nevertheless, the course of this decomposition has generally been studied only isothermally. Isothermal studies are not only simpler experimentally, but have the great theoretical advantage that one of the variables, temperature, is constant. It is the purpose of this paper to outline the principles that govern the relations between isothermal and anisothermalt‡ decomposition of austenite, to present and systematize the available experimental information, and to indicate the gaps in the existing knowledge. Some of the experimental information is the result of new work.§ Most of it is derived from scattered data in the literature. Many of these data were obtained incidentally in the course of research on other subjects and their significance has not been pointed out and perhaps not understood. It is hoped that this paper will aid future planning of more extensive research on anisothermal decomposition. Method In order to study the relations between isothermal and anisothermal decomposition, it appears fruitful to view anisothermal decomposition as taking place at a series of constant temperatures1 (except for the martensite reaction, which does not occur isothermally to an appreciable extent). When the time the steel is at each temperature is finite, the over-all amount of the reaction is considered to be the sum of the amounts occurring at each of the successive temperatures. During continuous cooling or heating, the time the steel is at each temperature and the difference between successive temperatures can be considered to approach zero. The over-all amount of transformation will then be given by integration over the range of temperatures involved. This point of view is advantageous in that it considers anisothermal transformation to be a series of isothermal transformations. The problem thus becomes one of determining the effect of partial decomposition at any given temperature upon subsequent decomposition at another temperature. Single Anisothermal Reaction Consider a phase brought to a temperature at which it is unstable, held there until it has partially transformed, and then brought to another temperature at

Jan 1, 1947

By John G. Reid

Subsequent to extensive laboratory testing, a pilot plant was constructed to further evaluate the process for high temperature copper cementation on iron in continuous operation. The plant was designed to produce 1 to 10 tons of copper a day depending on the copper concentration of the pregnant solution. The energy required to operate the plant was very low as virtually all the solution heating requirements were supplied by the exothermic cementation reaction. The results demonstrated that this, process has potential for commercial application with respect to operating considerations, and yields a copper product in excess of 95% copper at high reaction rates, low iron consumption, and at least 98% copper recovery from solution.

Jan 1, 1976

By P. L. De Bruyn, R. J. Charles

THE transfer of kinetic energy of translation into other forms of energy by impact is a fundamental process in most crushing and grinding operations. During and after the impact process the original source energy may be accounted for in any of the following possible forms: 1) Kinetic energy of translation of both the impacted and impacting objects. 2) Kinetic energy of vibration of the components of the impact system. 3) Potential energy as strain energy of the components of the system or in the form of residual stresses. 4) Heat generated by internal friction during plastic deformation or during damping of elastic waves. 5) New surface energy of fractured materials. At any instant during the impact process only the strain energy of the components of the system can contribute directly to the brittle fracture process. If fracture is the desired result, as in comminution, it would seem advantageous to choose or arrange the conditions of impact so that a maximum amount of the original kinetic energy could be converted to strain energy at some moment during a single impact. The present work deals with determination of these desirable conditions for a simple case of impact and application of the principles involved to general cases of impact. Experimental Method: Longitudinal impact of a rod with a fixed end was chosen as the impact system for investigation. The rod was mounted horizontally and the fixed end was formed by butting one end of the rod against a rigidly mounted steel anvil. The rod, of pyrex glass, was 10 in. long by 1 in. diam with both ends rounded to a 6 in. radius. The rounded ends permitted reproducible impacts on the free end of the rod and assured a symmetrical fixed end. Pyrex was selected as the rod material because of the marked elastic properties of such glass and the similarity of fracture between pyrex and many materials encountered in crushing and grinding operations. The frequency of natural longitudinal oscillation of the rod was 10 kc, and thus simple electronic equipment could be used for observation of strain changes occurring in the rod at this frequency. As shown in Fig. 1, impacts on the free end of the rod were obtained either by a pendulum device or by a spring-loaded gun. Relatively heavy hammers (100 to 600 g) of mild steel were used in the pendu- lum impacts, while fairly light projectiles (20 to 80 g) were fired from the spring-loaded gun. One of the main objects of the experimental work was to obtain the strain-time history of the rod as a function of the mass and kinetic energy of the impacting hammers. For this purpose a technique involving wire resistance strain gages and a recording oscilloscope was employed. Five gages were applied at equidistant sections along the rod, and by means of a switching arrangement the strain-time history at any section, and for any impact, could be obtained in the form of an oscillograph with a time base. The equation relating strain and voltage change across a strain gage through which a constant current is flowing is as follows: e = ?v/iRF [1] ? = strain, ?v = voltage change, i = gage current, R = gage resistance, and F = gage factor (from manufacturer's data — SRA type, Baldwin Lima Corp.). With the above equation an oscillograph depicting voltage change vs time on a single trace can be converted directly to a strain-time diagram if a calibration of the vertical response on the oscilloscope screen for specific voltage inputs is available. In the present case the calibration was obtained by photographing precisely known audio frequency voltages on the same oscillograph as that on which a voltage-time trace from a strain gage had been made. Synchronization of the beginning of the single trace with the beginning of the impact was accomplished by permitting contact of the impacting objects to close an electrical circuit from which a voltage pulse, sufficient to initiate the trace, was obtained. The struck end of the rod was lightly silvered for purposes of electrical conduction so that it would form one of the electrical contacts. Markers every 100 micro-seconds on the traces served for a time base calibration. Determinations of the kinetic energies of translation prior to impact were made in the case of the pendulum hammers by measuring the height of fall of the hammer and in the case of the projectiles by measuring the exit velocity from the gun barrel by means of an electrical circuit employing light sources, slits, and phototubes.' During the experimental work it became evident that the time of contact between the impacting object and the rod was an important variable in the impact process. Measurements of the times of contact were made, therefore, for every impact for which a strain-time record was obtained. The time of contact was determined by permitting the impacting components, when in contact, to act as a closed switch and discharge a condenser at relatively constant voltage. The discharge was observed and photographed with a time base on the oscilloscope screen.

Jan 1, 1957

By E. M. Porbansky

DURING the investigation of the electrical transport properties of copper, it became necessary to prepare large single crystals of the highest obtainable purity. In an effort to meet these demands, single crystals of copper have been grown by the conventional pulling technique—as has been used for the growth of germanium and silicon crystals.' Low-temperature resistance measurements made on these crystals show that, as far as their electrical properties are concerned, they are generally of significantly higher purity than the original high-purity material. The use of these pure single crystals with very high resistance ratios has made possible the acquisition of detailed information regarding the electron energy band structure of copper2-' and has stimulated widespread effort on Fermi surface studies of a number of other pure metals. It is the purpose of this note to describe our method of preparing very pure copper crystals by the Czochralski technique. Precautions were taken to prevent contamination of the melt from the crystal growing apparatus. A new fused silica growing chamber was used to prevent possible contamination from previous groqths of other materials such as germanium, silicon, and so forth. A new high-purity graphite crucible was used to contain the melt. This crucible was baked out in a hydrogen atmosphere at -1200°C for an hour, prior to its use in crystal growth. Commercial tank helium, containing uncontrolled traces of oxygen, was used as the protective atmosphere. A trace of oxygen in the atmosphere appears to be necessary for obtaining high-purity copper single crystals. A 3/8-in-diam polycrystalline copper rod of the same purity as the melt was used as a seed. The copper rod was allowed to come in contact with the melt while rotating at 57 rpm. When an equilibrium was observed between the melt and the seed (that is, the seed neither grew nor melted), the seed was pulled away from the melt at a rate of 0.5 mils per sec. As the seed was raised, the melt temperature was slowly increased, so that the grown material diminished in diameter with increasing length. When this portion of the grown crystal was -1 in. long and the diameter reduced to less than 1/8 in., the melt was slowly cooled and the crystal was allowed to increase to - 1-1/4 in. diam as it was grown. By reducing the diameter of the crystal in this manner, the number of crystals at the liquid-solid interface was decreased until only one crystal remained. Fig. 1 shows a typical pulled copper single crystal. The purity of the starting material and the crystals was determined by the resistance ratio method: where the ratio is taken as R273ok/R4.2ok. The starting material, obtained from American Smelting and Refining Co., was the purest copper available. Most of the pulled copper crystals had much higher resistance ratios than the starting material. The highest ratio obtained to data is 8000. Table I is an example of the data obtained from some of the copper crystals. Note that Crystal No. 126 had a lower resistance ratio than its starting material and this might be due to carbon in the melt. The melt of this crystal was heated 250" to 300°C above the melting point of copper. At this temperature it was observed that copper dissolved appreciable amounts of carbon. The possible presence of carbon at the interface between the liquid and the crystal will result in reducing conditions and negate the slight oxidizing condition required for high purity as discussed below. The possible explanations of the improvement in the copper purity compared to the starting material are: improvement in crystal perfection, segregation, and oxidation of impurities. Of these, the latter seems to be most probable. A study of the etch pits in the pulled crystals showed them to have between 107 and 108 pits per sq cm. The etch procedure used was developed by Love11 and Wernick.10 The resistivity of the purest copper crystal grown was 2 x 10-10 ohm-cm at 4.2oK; from the work of H. G. vanBuren,11 the resistivity due to the dislocations would be approximately 10-l3 ohm-cm, which indicates that. the dislocations in the copper crystals would contribute relatively little to the resistivity of the crystals at this purity level. Segregation does not seem likely as the reason for purification of the material, since the resistivity of the first-to-freeze and the last-to-freeze portions are approximately the same, as was observed on Crystal No. 124. On most of the crystals that were examined, the entire melt was grown into a single crystal. If the

Jan 1, 1964

By T. E. Leontis, F. N. Rhines

THE oxide scale that forms upon magnesium at elevated temperatures is nonprotective in the sense that the rate of oxidation is constant and thus does not decrease with the growth of the scale as it does with other common metals. This generality was first stated by Pilling and Bedworth1 and has been verified by Suzuki2 and by Scheil.3 Pilling and Bedworth argued that the nonprotective characteristic could be predicted from the fact that magnesium oxide occupies less space than does the metal from which it springs, wherefore the scale is not expected to cover the metal so completely as to exclude all direct access to the atmosphere. Linear oxidation is thought by Scheil to be common to all cases where the reaction occurs at the oxide-metal interface. According to Suzuki,2 the product of high-temperature oxidation in the air is MgO contaminated with no more than traces of a nitride. When the metal is allowed to burn freely a fume composed of cubic crystals of Mg04 is given off. Delavault5 observed that excrescences form upon liquid magnesium and alloys in the course of oxidation. Beyond this it is known that the use of atmospheres containing small quantities of sulphur dioxide6 or carbon dioxide serve to retard the oxidation of solid magnesium and that beryllium7and calcium8 minimize the oxidation of molten magnesium exposed to the air. Many studies have been devoted to the nature and rates of "protective" oxidation, as exemplified by the cases of copper and iron, wherein the rate is characteristically parabolic. The theory of parabolic oxidation is well developed.9 Linear oxidation, on the other hand, has received but little attention and the theories proposed by Pilling and Bedworth and by Scheil have yet to withstand careful examination. There exists no comprehensive survey of the high-temperature oxidation of magnesium (or of any other metal that exhibits linear oxidation) over a broad range of temperature, under a variety of atmospheric conditions and covering a large group of alloys. It has been the purpose of the present investigation to provide such a survey, with the object of gaining a fuller understanding of linear oxidation, especially as applied to magnesium. EXPERIMENTAL PROCEDURE AND RESULTS The experimental studies undertaken were of two kinds: (I) measurement of the rate of oxidation as influenced by the

Jan 1, 1946