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By R. G. Bentsen, D. A. T. Donohue

The cyclic steam injection process has become the most widely applied and most successful thermal recovery technique in use today.1-4 Normally, steam stimulation is repeated several times during the life of a project. The problem is to select the optimum number and size of steam treatments so that the profits realized over the entire life of the project are maximum. Obviously, operating costs rise directly with the frequency and amount of steam injection. Operating efficiency, on the other hand, can be adversely affected if the amount and frequency of stimulation are insufficient. Thus arises a multistage decision problem; that is, a decision must be made at each sub-period (day, for example), as to whether steam should be injected, and, if so, how much. It is desirable that these decisions be made in such a way as to secure maximum net profit before taxes. This can be achieved by dynamic programming. To use dynamic programming, we must be able to predict not only the production rate-time curve resulting from a given stimulation, but also how changes in stimulation policy will affect this curve. In this study, the effect of steam injection on well performance is estimated on the basis of a simple model that takes into account both steady-state and transient flow. Oil production rate is calculated for both types of flow, and the larger of the two values is used. This allows the calculation to change to radial steady-state flow at such time as this mechanism becomes more effective than the transient mechanism. We propose to show how dynamic programming can be used to optimize the steam soak process with respect to net profit. For this, a mathematical representation of the steam soak technique is necessary. A further objective, therefore, is the formulation of a mathematical model capable of realistically simulating the physical process. Oil Production Response Model The advantage of using a mathematical model is its generality and ease of manipulation. However, the model must be an accurate representation of the physical process, for a solution derived from a model can be no better than the model itself. The question now arises as to how well the model should be expected to simulate reality. In general, the simplest model should be tried first, for additional accuracy is apt to require additional cost and time. Also, the search for a high degree of accuracy may yield only greater complexity and difficulty without yielding significantly better results. With this in mind, we kept our model as simple as possible, yet generally representative of the actual physical process. The number of state variables is limited to three, and stochastic variations in the parameters are ignored. As a consequence, use of this model should be restricted to cases in which the underlying assumptions are not severely violated. In

Jan 1, 1970

By L. W. Strock

Metallurgists handling lead and zinc ores have long been familiar with the spectrograph as a routine analytical tool, as its earliest regular use by American industry was in controlling impurities of zinc metal and its alloys. This application has been extended to other metal industries on an extensive scale, accompanied by refinements of procedure to such an extent that a large part of some metals produced, especially magnesium, aluminum and steel, are checked only by spectrographic methods for conformity to specifications. The spectrographic analysis of ores and other poorly conducting powdered solids presents difficulties not encountered with metallic samples, which can be arced or sparked as self-electrodes or can be readily dissolved, so that their solutions can be analyzed, as in the American Society for Testing Materials standard methods for zinc and zinc-base alloys. Spectra of powdered solid samples can be prepared by using carbon electrodes provided with a crater of suitable size, into which the sample is packed. Ore samples and many other powdered solid materials usually analyzed in the chemical and metallurgical laboratory are more complex and varied in composition than samples of metals produced in large tonnages. 'lore preliminary work therefore is usually necessary in devising a spectrographic method for analyzing a given type of powdered sample than for analyzing metal samples, in order to use that method with confidence. The howledge that the standard samples and unknowns produce equivalent line intensities at equal concentration is the fundamental basis of any quantitative spectrographic method. On the other hand, powdered samples have an advantage over metals in that any desired number of chemical compounds can be mixed dry in any desired ratio to produce a synthetic standard. Expcrience has shown, however, that spectra of elements in finely divided compounds introduced into a standard in preparing a synthetic ore sample do not always behave in the electric arc in a manner that produces spectral line intensities similar to those observed at the same concentration in a natural mineral. In ore samples minor elements frequently are contained in the crystal lattice of larger particles of an abundant ore mineral. Their dissociation and volatilization from the sample into the arc then proceeds differently in the standard and sample, with resultant differences in intensity. During the past 10 years I have devised and applied several quantitative spectrographic methods for determining various elements in rocks and minerals in connection with studies on their geochemistry,' but the incentive has gradually changed since the summer 0. 1940 to the specific practical problem of searching for domestic sources of rare and stratcgic metals. The

Jan 1, 1949

By Lester W. Strock

METALLURGISTS handling lead and zinc ores have long been familiar with the spectrograph as a routine analytical tool, as its earliest regular use by American industry was in controlling impurities of zinc metal and its alloys. This application has been extended to other metal industries on an extensive scale, accompanied by refinements of procedure to such an extent that a large part of some metals produced, especially magnesium, aluminum and steel, are checked only by spectrographic methods for conformity to specifications. The spectrographic analysis of ores and other poorly conducting powdered solids presents difficulties not encountered with metallic samples, which can be arced or sparked as self-electrodes or can be readily dissolved, so that their solutions can be analyzed, as in the American Society for Testing Materials standard methods for zinc and zinc-base alloys. Spectra of powdered solid samples can be prepared by using carbon electrodes provided with a crater of suitable size, into which the sample is packed. Ore samples and many other powdered solid materials usually analyzed in the chemical and metallurgical laboratory are more complex and varied in composition than samples of metals produced in large tonnages. More preliminary work therefore is usually necessary in devising a spectrographic method for analyzing a given type of powdered sample than for analyzing metal samples, in order to use that method with confidence. The knowledge that the standard samples and unknowns produce equivalent line intensities at equal concentration is the fundamental basis of any quantitative spectrographic method. On the other hand, powdered samples have an advantage over metals in that any desired number of chemical compounds can be mixed dry in any desired ratio to produce a synthetic standard. Experience has shown, however, that spectra of elements in finely divided compounds introduced into a standard in preparing a synthetic ore sample do not always behave in the electric arc in a manner that produces spectral line intensities similar to those observed at the same concentration in a natural mineral. In ore samples minor elements frequently are contained in the crystal lattice of larger particles of an abundant ore mineral. Their dissociation and volatilization from the sample into the arc then proceeds differently in the standard and sample, with resultant differences in intensity. During the past 10 years I have devised and applied several quantitative spectrographic methods for determining various elements in rocks and minerals in connection with studies on their geochemistry,1 but the incentive has gradually changed since the summer of 1940 to the specific practical problem of searching for domestic sources of rare and strategic metals. The

Jan 1, 1945

By Earl Oliver

IN times like these, the A. I. M. E. and similar societies have their greatest usefulness. . . . Individuals and companies acting alone in the development of public opinion are merely voices crying in the wilderness. United and organized they make a great force that can and does influence public action. . . . What part, if any, then, shall the A. I. M. E. take in these great stabilization processes of civilization? Shall it help to give direction and force to scientific knowledge which comes within its field of activity or shall it merely develop more of it? . . . Is it the A. I. M. E.'s function to help bring system, order and direction out of this situation so that the world can again have forward economic movement, or should it rest on its oars until other agenciess develop that public understanding and direction so necessary for economic progress? As we understand the functions of the A. I. M. E. Petro¬leum Division, they are to discover and promote knowl¬edge for the benefit of society on the mining of oil and gas. To the individual member of the Petroleum Division, there are certain advantages of social and professional contacts, but the collective purpose is that described. And the individual is benefited by membership only as the Division measures up to the purposes of its existence. Consequently, the welfare of this Division and that of its members depends on the extent to which it keeps pace with the needs of society on matters relating to the mining of oil and gas.

Jan 1, 1932

By Leo Behr

RECENT years have seen important practical advances in the construction of recording instruments for use with thermocouples. The difficulties of the problem will be appreciated when it is remembered that a 10° F. change in temperature of a base-metal couple at 1500° means a change in the electromotive force of about 0.00035 volt. In a circuit having a resistance of 350 ohms, this means a change in the current of 0.00000,1 amp.; and despite this requirement of great sensitivity the instruments must be sufficiently robust to withstand the rough usage which is so often their lot. Two methods are in common use for the measurement of the electromotive force produced by a thermocouple: 1. The milliammeter method, in which the current produced by the thermocouple in a circuit of known resistance is measured and from. this the electromotive force is deduced by Ohm's law. 2. The potentiometer method in which a known potential difference is opposed to the thermocouple electromotive force. The use of thermocouple and milliammeter for measuring temperature introduces some possible sources of error, for the reading depends on a number of factors, including the following: (1) Electromotive force set up at the hot junction, (2) electromotive force set up at the cold junction, (3) resistance of the circuit including thermocouple, lead wires, and meter, (4) field strength of magnets, (5) strength of controlling springs in meter, (6) friction at pivots, of pointer on paper, etc. It is obviously necessary to so design and maintain the installation that the reading is independent of all the factors except the first. The electromotive force set up at the cold junction can easily be taken care of provided it is constant. This has been approximately accomplished by burying the cold junction in the ground or actually secured by locating it in a container, the temperature of which is kept constant by means of a thermostat.

Jan 9, 1919

By George W. Doffing

Numerous contradictory statements have been made in the past regarding the importance of the seasonal influence of demand for motor fuel on prices of oil securities. It has often been said that the time to buy oil securities is in the spring, or just prior to the heavy consuming season for gasoline. The fallacy of this argument is brought out in the following paragraphs. Seasonality of Oil-security Prices The indexes used in this paper as indicators of prices of oil securities and general industrials are those compiled by Standard Statistics Co. The oil producing and refining stock index includes 14 representative petroleum companies, while the all-industrials index is made up of 347 issues. All figures are stated as relatives, with 1926 = 100. The primary basis of the index, and one that gives a good weighting of the relative importance of the company within the industry, is the total market value of the stock issue outstanding; i.e., the market price times the number of shares outstanding. Adjustments are made for the addition or elimination of issues from the group index, for stock dividends, split-ups, stock rights, et cetera. At the present time the oil producing and refining index includes the following companies: Atlantic Refining Co., Consolidated Oil Corporation, Continental Oil Co., Gulf Oil Corporation, Humble Oil & Refining Co., Ohio Oil Co., Royal Dutch Co., Shell Union Oil Corporation, Socony-Vacuum Oil Co., Standard Oil Company of California, Standard Oil Co. (Indiana), Standard Oil Co. (New Jersey), Texas Corporation, Union Oil Company of California. In calculating the seasonal for oil-security prices several periods have been selected as indicat,ive of major changes in the industry, as follows: 1. 1918 through 1936. This gives an over-all picture of the industry during the motor-vehicle, motor-fuel era. 2. 1927 through 1936. This period includes the control stages, both voluntary and coercive. 3. 1927 to September, 1933. This is the pre-code period of control.

Jan 1, 1937

By A. L. Holley

THERE are regularly manufactured in the eleven Bessemer steel rail mills of the United States, 119 patterns* of steel rails, of 27 different weights per yard. This list does not include patterns which, although still largely inn use, are regarded by experts as obsolete, and which would swell the number to nearly 300; nor does it include all, the patterns for which rolls are kept on hand to fill a possible demand; nor does it include extra pattern,- rolled in one finishing groove by opening or closing the rolls so as to get different weights with the same contours. The list embraces only those separate patterns which are subject to current orders. How thoroughly modern these patterns are, is shown by the fact that of the whole 119, there are but five patterns of conspicuously bad shape; all the rest more or less completely illustrate the standard features,-a heavy bead,. light web and flanges, and a good angle :to hold the fish-plate. Sixty-two per cent. of the patterns have the "Chanute" head, which was not designed until 1874.† Sixty-four per cent. of the 119 patterns are embraced under five weights per yard,; three only of these vary from standard type; there am thus 76 patterns, all of them modern and standard, to represent five different weights, for which five patterns would perfectly answer. Of the 60-lb. rails, there is only one of the pear-head type, while a dozen of the bevelled head templets cannot be distinguished from each other * From all the works 188 patterns were sent to me as standard. Of these I found 119 different shapes and 69 duplicates. † Since this paper was read I have seen at the Bethlehem Iron. Works the templet of a 68-pound Lehigh Valley rail, with the bevelled head, usually called the "Chanute" head, and marked "Templet of 1872." This is shown on Plate II. I learn that iron rails, with bevelled heads, were rolled at Bethlehem prior to 1870.

Jan 1, 1881

By Alexander Gakner

Since the end of World War II the Soviet Union has made great strides toward economic development of the country. Today it is firmly established as the world's second largest industrial power after the United States and it has committed itself before the people on both sides of the Iron Curtain to catch up with and to overtake us within a few decades. No nation could achieve such a degree of industrialization or aspire to become the world's industrial leader without a large supply of many basic mineral raw materials or at least easy access to such resources. In addition, it requires technical competence, a large skilled labor force, and a high rate of capital investment. Why should we concern ourselves with these Soviet aspirations? The Free World's yardstick of measuring a nation's well-being is the standard of living of the people in that country. Presumably even Communist governments are committed to some, however gradual, improvement in the standard of living of their people. The population of the USSR is 20 pct greater than that of the United States. Hence, if they ever achieve a standard of living equal to ours, they must by all logic reach a greater overall industrial output. However, in the U.S.S.R. the standard of living of the masses has not kept pace with the expanding industrial production and is still far behind that of the United States. Our concern, therefore, is with what the USSR intends to accomplish with its expanding industrial power: Will they produce large mineral raw-material surpluses and manufacture products to compete with us for world markets and attempt to put us out of business if not use it directly to wage war; or will they use their resources merely to produce more consumer goods for the Soviet people; or will they, along with other Communist nations in the not-too-distant future, compete with us for the world's sources of mineral raw-materials to maintain a high level of mass consumption?

Jan 6, 1960

By Lewis Reeve

As part of a program of investigation of the properties of electric arc welds carried out in the laboratories of the A. 0. Smith Corporation, considerable work has been done on the determination of the oxygen, nitrogen and hydrogen content of different types of weld metal, employing for this purpose the so-called "vacuum fusion method." It is the purpose of this paper to describe certain improvements that have been introduced in this method of determining the gas content of metals, with particular references to the steel specimens examined in this investigation. The method and apparatus used at the beginning of the investigation were essentially those of the Bureau of Standards as described by Vacher and Jordan.' Later a number of changes were introduced which resulted in more rapid evacuation of the graphite crucibles employed and which enabled larger volumes of gas to be dealt with than could be handled conveniently in the Bureau of Standards equipment. In addition, the analyzing of the gases evolved from a melt in the same apparatus as collected was abandoned in favor of analysis outside the equipment using standard methods of gas analysis. The time required for gas analysis in the apparatus itself, as described by the Bureau of Standards, was found to be considerable, and during this time the rest of the equipment was tied up, preventing its use for the analysis of further steel samples. As a result of the modifications introduced, the time required for the analysis of a steel sample for gas content was reduced from about 8 hours to less than 3 hours. Subsequently, the whole procedure of melting the sample and collecting the gases evolved was modified so as to enable a distinction to be drawn between the easily reducible oxides such as iron oxide and the more stable oxides such as silica and alumina. At the same time evidence was obtained indicating the probable existence in the steels of other nitrides than those of iron alone and making possible their quantitative etermination.

Jan 1, 1934

By M. R. Pickus, I. W. Pickus

ORDINARILY age-hardening is thought of as being associated with a limited solubility of one metal in another. Much less has been written about the type of age-hardening that attends the formation of superstructures. Solid solutions generally have a disordered or random arrangement of atoms; that is to say, in a unit cell, such as that of the face-centered cubic lattice, there is no distinction between atomic sites. Atoms of a given metal may occupy cube corners or face centers. Under certain conditions, however, some alloys develop what is known as an ordered structure. In this case, cube corners would be occupied by only one type of atom and face centers by another type, Associated with this ordering process are many interesting changes in physical and electrical properties. Moreover, in many instances the alloys become susceptible to age-hardening. From the evidence now to be described, it appears that age-hardening in 14-carat gold alloys is due to the formation of both a super-structure and a precipitate. Alloys of the metals gold, silver and copper were known in antiquity. The available knowledge regarding their constitution has been ably summarized and extended by Sterner-Rainer,1 Janecke,2 Carter,3 Wise,4 and Coleman.5 Despite the long familiarity with these alloys and the numerous investigations of their properties that have been made, there is still much that remains unexplained. It has been known for a long time that the hardness of these alloys is closely related to the rate of cooling, Similar changes have been observed in the binary gold-copper system,6 one alloy of which corresponding to the formula Cu3Au, has been the subject of a careful and competent report by the English investigators, Sykes and Evans.7 They have established the fact that the shift of atoms from the ordered to the disordered condition takes place in some critical temperature range. At temperatures above the critical range the structure is random, and at temperatures below it the structure is ordered. No difference between these two structures is revealed by the microscope. Both have a face-centered cubic lattice and complete solubility, so that there is no evidence to suggest that the changes in properties are associated with a phase change, The more slowly the alloy is cooled, the higher is the degree to which the ordering process proceeds and the more marked is the increase in hardness. As experimental data were accumulated on 14-carat gold alloys, several contradictions arose. Certain observations tended to confirm the existence of a superstructure, while other observations seemed to be inconsistent with such a transformation. PRESENT INVESTIGATION As a focal point about which to develop this subject, it is expedient to consider first

Jan 1, 1943

By R. E., Head

THE use of lime in flotation has become so general in recent years that its functions are familiar to plant operators. The conditions and phenomena described in this paper are of interest because they are directly associated with the use of lime as a reagent and the resulting formation of lime scale worth nearly $1 per pound for its gold content. It is not known to what extent lime scale is common in flotation plants where lime is used, but as several occurrences have been re- ported, its existence is not limited to one particular plant. In November, 1927, the author's attention was drawn to a lime scale that formed on the sides of Callow flotation cells in the Walker Mining Co. mill at Spring Gar- den, Cal. The scale was described as an accumulation of hard material that built up on the sides of both the rougher and cleaner cells and in some instances attained a thickness of 2 in. The lime scale builds up in the cleaner cell at the rate of about 1/10 in. per month, or slightly more than ?12 in. during six months' operation. The rate of growth in the rougher cells is slower, and about 3/s in. of scale forms in six months. Analyses' of typical lime scale samples are as follows:

Jan 1, 1928

By C. E. BOCKUSD

WHEN Mr. Bain asked me to lunch with you he requested that I say a few words as to how the Institute could be helpful to the bituminous coal industry. I feel like saying, "Thank you, what have you?" I do not want to trace in detail the story that is old already to many of you. On the other hand it does take some little stage-setting to illustrate what is the matter in the bituminous coal industry, a trouble that must some day be cured. There has been something over a century of bituminous coal production as a real business in this country. True, Joliet and Marquette discovered coal in Illinois in 1673, according to published accounts of their travels, and shortly thereafter Father Hennepin also found Illinois coal in 1689. Coal was mined near Richmond in 1750, and Richmond shipped coal to New York and Philadelphia in 1789. But it was not until 1838 that the production of bituminous coal in this country totaled a yearly output equal to the minimum for one class A mine today, for that was the first year that production exceeded 200,000 tons.

Jan 1, 1930

By Werner Joseph, Richard R. Knobler

When the first batch of refined copper ingots was cast at Mantos Blancos in January 1961, eight years of exploration, development and metallurgical pioneering by Mauricio Hochschild & Co. had come to a successful conclusion. This Chilean copper deposit, located in the Atacama Desert 30 miles from Antofagasta, is now producing approximately 20,000 tons of copper per year. The Mantos Blancos deposit has been known since 1912 and various attempts had been made to work the high-grade zones before the present operation was started. The major drawback of the ore to any previous development was its chloride content which varies between 0.4% and 1.5% C1. Although the chloride ruled out the conventional leaching-electrolysis scheme, it did lend itself to the process of precipitating the copper as cuprous chloride.

Jan 1, 1962

By Paul Rhedey

Various commercial pelroleum cokes were heat-1,reated at temperatures between 500° and 1500°C, in a nitrogen atmosphere, in laboratovy induction furnaces. The rate of tenlperature rise was varied betzveen 10" and 300°C per min, or the green cokes were flash-calcined, orv a combination of heating rates was used. Changes in the rate of heating had only negligible effects on the degree of' calcination as characterized by mean crystallite thickness and the chemical properties of the calcined coke. The physical structure of the cake was however significantly affected when rate of heating during calcination exceeded 50°C per min over the temperature range of 600° to 900°C. Surface-accessible porosily increased with the .rate of temperature rise, and this was accompanied by a change in pore size distribution. Source and properties of the green coke also had an influence on the structure of the calcined coke. The evidence presented suggests a similar mechanism of porosity development in petroleuiiz coke during calcination in industvial equiplnenl, such as rotary kilns. An increase in surface accessible povosity incveased the pitch binder requirement when the coke was used as aggregate in Soderberg paste. A correlation was established between calcined coke porosity and paste binder requiremenl. ManY results have been published on the changes of properties of petroleum coke during calcination, such as chemical composition, real density, electrical resistivity, crystallite and pore structure. The correlation of these properties with temperature of calcination and time at maximum temperature has been rather well established in both laboratory and pilot plant experiments. Surprisingly little attention has been given however to the effect of calcination conditions, such as rate of temperature rise or furnace atmosphere, on the chemical and structural properties of the calcined coke. It has been observed that petroleum coke, when calcined in industrial equipment, acquires higher porosity and lower real density than those attainable in laboratory furnaces at apparently identical calcina- tion temperature and soaking time. This paper describes a study of the effect of rate of heating during calcination on calcined coke properties using green petroleum cokes of different volatile matter, hydrogen, and sulfur content. An attempt was made to correlate the changes in coke structure with the flowability of anode paste of the type normally used in aluminum reduction cells. EXPERIMENTAL Petroleum Cokes Used. In the study of release of volatile matter and sulfur during calcination and the effect of rate of heating on calcined coke properties two delayed cokes of different sulfur contents were used. The results of analysis of the green cokes are given in Table I. In the study of the effect of flash calcination thirty-six commercial petroleum cokes from twelve different refineries were used with a range of properties shown in Table 11. Calcination Conditions. Calcination experiments were carried out in a laboratory induction furnace. In each run a 200-g sample of dry green coke sized to 10 by 65 Tyler mesh was calcined in a graphite crucible. The crucible containing the sample was placed in the middle of a stack of eight others filled with metallurgical coke to reduce temperature gradients within the sample. Temperature was measured by two Pt, Pt-10 pct Rh thermocouples and controlled by a Celectray instrument. The two couples generally agreed within 5°C. In the study of volatile matter and sulfur release the samples were heated to temperatures in the range of 500" to 1500°C at a rate of 10°C per min in a nitrogen atmosphere and held at the final temperatures for 30 min. In the study of the effect of heating rate on calcined coke properties the desired rates between 10' and 300°C per min were obtained by manually adjusting the power input. Flash calcination was carried out by dropping 100 g of the green coke into the graphite dish preheated to the calcination temperature. Because of the small heat capacity of the furnace the coke was introduced in 20-g portions at a time. For this purpose a 2-in.-long nipple between two 1-in. gate valves installed on the top flange of the furnace served to provide a gas seal while feeding coke to the furnace. It was estimated that the temperature of the coke reached that of the furnace at a rate of approximately 1000°C per min. Holding time at final temperature was also 30 min. Calcined Coke Proper- Determined. Porosity was determined on 20 by 35 Tyler mesh samples using an Aminco-Winslow mercury pressure porosimeter with an operating range of 1.8 to 3000 psi absolute pressure (100 to 0.05 p pore diameter range).' Apparent density was obtained by the mercury poro-simeter. It represents a particle density of the 20 by

Jan 1, 1968

By W. H. Class

The embrittling effects of oxygen, ozone, nitrogen, air, and surface residues, on NaCl has been investigated. The embrittlement by ozone and oxygen was found to be associated with the formation of a NaClO3 surface compound. In these cases the initial crack that was responsible for fracture (in a bend test) always nucleated at the corners between the tension and side faces. The behavior of air was very erratic and on certain days did not produce enzbrittlement. During these periods, crystals that had become embrittled by the ozone treatment completely recovered their ductility after a short exposure to the ambient atmosphere, It was established many years ago1 that considerable ductility could be obtained in NaCl single-crystal specimens if the crystal surfaces were dissolved in water either during or immediately prior to the test. The original interpretation of this effect by Joffe attributed the enhanced ductility to the removal of surface microcracks by dissolution. Later investigations2'3 have suggested that the exclusion of air from the specimen surface is the criterion for extensive plastic flow prior to fracture. The air em-brittlement in this later work was attributed to the diffusion of gaseous atoms into the surface layers of the crystal, thereby impeding the movement of dislocations. This model satisfactorily accounts for the reembrittlement observed after further air exposure subsequent to the water dissolution treatment. However, the situation has recently become more complex by the observations in several laboratories4-t that under certain conditions air exposure does not impair the ductility of NaC1. It has also been recognized5 that improper drying operations after water dissolution can leave surface precipitates that lead to embrittlement. Cleavage defects on as-cleaved crystals can often be another source of embrittlement. In the present work the effect of the gaseous atmospheres nitrogen, argon, air, oxygen, and ozone, on the ductility of rock salt was studied extensively. The embrittlement resulting from oxygen and ozone exposures was found to be associated with the formation of a NaC1O3 surface film. It is suggested that certain atmospheres, one of which often can be ambient air, which inhibit the formation or favor the decomposition of this compound, can promote ductility. Thus one aspect of the Joffe effect is certainly related to the removal of surface compounds or complexes by water dissolution. The effect of surface precipitates that remain after drying operations and of cleavage defects were also studied. In neither of the latter cases was the embrittlement as severe as that found with a NaClO3 surface layer. PROCEDURE AND SPECIMEN PREPARATION The nature of the embrittlement produced by the agents mentioned above was studied by means of microscopy, mechanical testing, and X-ray diffraction. Specimens were cleaved from large crystals of optical quality sodium chloride obtained from the Harshaw Chemical Co., and, except for those tested in the as-cleaved condition, were given a 15- to 20-sec immersion in distilled water followed by a rinse in absolute methyl alcohol. The specimens were then blotted on a soft, absorbent paper, and dried by a few seconds exposure to a stream of warm, dry air. Such a procedure was found to give a control surface which was microscopically free of residues. (A few crystals were intentionally painted with a concentrated NaCl solution in order to investigate the effect of surface residues). All specimens were of 0.140 sq in. cross-section. Crystals prepared in the above manner were immediately placed in a gas train where they could be exposed to the desired gases for preselected periods of time. For the oxygen and nitrogen exposures, pure reagent-grade gases were employed. The ozone was provided in the form of an ozone-oxygen mixture (approximately 10 pct ozone) prepared by passing commercial grade oxygen over a strong ultraviolet light source. All gases were dried prior to their introduction into the train. Since argon was found to be completely inert in its behavior (i.e., residue-free specimens that were exposed to argon were not embrittled), it was periodically utilized to check the control specimen surfaces as well as the condition of the gas train used for aging the specimens. After exposure to the gaseous media in question, the crystals to be used for the measurement of the strain to fracture were transferred from the gas train to a protective oil bath (without further exposure to the atmosphere) where the tests were conducted in three-point bending. The apparatus was so adjusted that the load could be applied at a constant, continuous rate. Other Snecimens from the gas train were deformed

Jan 1, 1962

By Cyril Smith

THE method of thermal analysis, so important in the development of metallographic science, has of recent years been falling into disuse owing to the development of other physical methods which give results easier of interpretation and which can be used for the study of either equilibrium or transitional conditions because they do not require a continuously changing temperature. Nevertheless thermal analysis remains useful in the study of reactions that take place rapidly, and the simplicity of the experimental technique and the general availability of the apparatus involved are points in its favor. Theoretically, thermal analysis is capable of giving specific and latent heat measurements and therefore should permit the study of reactions on a more fundamental basis than any other method. It is, however, difficult or impossible to obtain quantitative heat measurements from cooling curves obtained in the usual way. Even if the furnace containing the sample is cooled or heated at a linear rate, or if a gradient furnace is employed to maintain a constant rate over a large range of tempera-ture, the heat flow from or to the specimen depends on its previous his-tory, for the difference of temperature between the specimen and its surroundings varies. The emissivity of the specimen surface, moreover, is unlikely to be constant. The able mathematical analysis by Russell,1 although it prevents misinterpretation of data, has an effect rather the reverse of that intended, and leaves the reader doubtful of the possibility of ever obtaining quantitative results from thermal curves. Nothing can be done to apply thermal analysis to the study of equilib-rium conditions of reactions that are not completed at rates of tempera-ture change below about 1° C. per minute, and this unfortunately excludes most solid transformations in alloys. ? For the determination of liquidus

Jan 1, 1939

By Halbert Powers Gillette

In every chemical reaction heat is either developed or absorbed, and this plus or minus heat of formation is as definite in quantity as the weights of the reacting elements. In this paper I shall show that each chemical element and each chemical radical has its own definite heat-valency,—a fact which, so far as I know, has hitherto escaped the attention of investigators, but, I feel sure, will be admitted after the demonstration here given, and may lead to some practical conclusions of value. When Berthelotys " law of maximum work " was found to have so many inexplicable exceptions, the pendulum of a scientific theory swung away from a recognition of the truth underlying that proposition; and this reaction went so far that not only has thermal chemistry been relatively neglected by recent investigators, but it is not uncommon now to find textbooks on physical chemistry which practically ignore all that Thomsen, Berthelot and others have done. To this temporary tendency of thought I attribute the failure to recognize the principles herein announced and explained. Not long ago, while studying tables of the formation-heat of various salts, I noticed that in this respect all potassium salts in solution differ from the corresponding sodium salts by 9.3 cal.1 I found also that similar differences exist between other salts, not only when the basic radical is varied, while the acid radical remains constant, but also when the acid radical is the variable. Thus chlorine salts in solution differ from bromine salts in this respect by 10.9 cal. Upon further study, I found that Thomsen had noted similar constant differences, but, so far as I can ascertain, he appears to have attached no great significance thereto.

Jan 1, 1904

By Robert Williams

A description is given of a double heat treatment of 60-40 brass. Photomicrographs are included to show the changes that take place in the microstructure on reheating the water-quenched specimens. A wide variation in the mechanical properties may be obtained by the described heat-treatment method. ON SEVERAL occasions, when 60-40 brass is first obtained in the beta condition by quenching at about 825° C. and is then reheated, the writers have noticed that recrystallization will take place in the form of twin crystals at the grain boundaries of the original beta crystals. It was, therefore, thought that interesting results would be obtained if this twinning process was studied further, especially as to the temperature at which it first occurs. The material used in the investigation was a bar of extruded muntz metal, 1/2 in. in diameter, and of the following composition: Copper, 60.21 per cent.; zinc, 39.73 per cent.; lead, trace; iron, trace; tin, nil. Specimens I in. in length were sawed from this bar and a hole was drilled into the side of each specimen until it reached the center, and the tip of a platinum-platinum rhodium thermocouple was inserted. A small Hoskins' resistance-type electric furnace was used for heating the specimens. The specimens were first heated at 840°C. for 2 hr. and then quenched in cold water, in order to get the material entirely in the beta state. In every case, in the reheating process, the furnace was brought to the desired temperature before the specimen was introduced. The time occupied in preheating was from 20 to 30 min. By sawing back 1/4 in. on each side of the hole, two parts were obtained from each specimen

Jan 3, 1924