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On July 25, the first copper ore From American Smelting & Refining Co.'s Mission open pit nine was sent into the new 15,000-tpd concentrator : three clays later, the first rail cars containing the Mission concentrate were sent north to the smelter at Hayden, Ariz. Thus two y,ears after stripping was started, Asarco's new mine, located south of Tucson. went on stream several months ahead of schedule. The plant, designed and constructed by Western Knapp Engineering Co., is expected to be operating at full capacity about September 1. with present plans calling for the copper concentrate from Mission to be shipped to Asarco's smelters at Hayden and El Paso.

Jan 9, 1961

PRACTICAL PROBLEMS AND BASIC PRINCIPLES ranging from ore testing to cost estimation get a working over from top men in the minerals beneficiation field. The Minerals Beneficiation Division developed this symposium for presentation at the 1953 Los Angeles General Meeting to assist the many people who think that having a new plant necessitates a lot of trouble and dismay. The papers and free discussion from the floor give ways and means of approaching a new plant that will relieve the strain on the organization, if adequate attention is put on the program before work begins - that is if thought is given to the program itself, before tackling the actual mill design.

Jan 9, 1953

By William H. Spice

No devclopment of major importance has been made in the south central fault-line district of Texas during 1939. Four new fields have been discovcred, all of which appear to be of minor importance, with small wells in the Navarro sand, the Taylor marl or the Austin chalk. Drilling along the fault line has not developed any new prospects in the Edwards lime, the most prolific producing horizon of the district. At the close of the year, a few deep tests for lower producing horizons have been projected and should prove to be of interest, and plans are under way for further development of the Pearsall field, which has been under the control of a single company until recently. Production from the 46 producing fields was maintained at 8,460,000 bbl. for the year, a decrease of approximately 400,000 bbl. under 1938. This decrease is due in part to natural decline of production and in part to decreased allowed production. Approximately 55 producing wells were completed on proven acreage in the Darst Creek and Salt Flat fields. No new lease plays were made during the year, although approximately the same amount of land, 600,000 acres, remained under lease during the year. Some geophysical operations of various types were carried on along the fault-line area itself and also in the Edwards plateau and in the area south and southeast of the main fault line.

Jan 1, 1940

By William H. Spice

No devclopment of major importance has been made in the south central fault-line district of Texas during 1939. Four new fields have been discovcred, all of which appear to be of minor importance, with small wells in the Navarro sand, the Taylor marl or the Austin chalk. Drilling along the fault line has not developed any new prospects in the Edwards lime, the most prolific producing horizon of the district. At the close of the year, a few deep tests for lower producing horizons have been projected and should prove to be of interest, and plans are under way for further development of the Pearsall field, which has been under the control of a single company until recently. Production from the 46 producing fields was maintained at 8,460,000 bbl. for the year, a decrease of approximately 400,000 bbl. under 1938. This decrease is due in part to natural decline of production and in part to decreased allowed production. Approximately 55 producing wells were completed on proven acreage in the Darst Creek and Salt Flat fields. No new lease plays were made during the year, although approximately the same amount of land, 600,000 acres, remained under lease during the year. Some geophysical operations of various types were carried on along the fault-line area itself and also in the Edwards plateau and in the area south and southeast of the main fault line.

Jan 1, 1940

By C.H. Lorig, M.C. Udy

Through the years much interest has been centered in attempting to develop a direct method of iron-ore reduction, to replace or supplement the present indirect blast-furnace process. It would not be difficult to produce a list of more than 500 patents dealing with the direct production of iron and steel, but the few of this type of process that have proved successful do not produce in competition with the blast furnace; they produce special products. A survey of the literature reveals that the equilibrium conditions for the reduction reactions (iron oxides with carbon monoxide and with hydrogen) have been fairly well established but that data on the rate of reaction are discordant, although the genera1 effects of the variables are known. This dissertation deals with the rate of reduction of a magnetite concentrate with hydrogen. The following variables have been studied: bed depth, gas velocity, particle size and temperature. The behavior of a single particle was also studied. Literature Two general factors should be considered in a study of reduction of iron oxide: (I) equilibrium relations, and (2) rate of reaction. The first factor, equilibrium, has received the attention of many investigators and the equilibria Fe304-FeO-H2-H2O, Fe3O4-FeO-CO-CO2, FeO-Fe-H2-H2O, FeO-Fe-CO-CO2 are fairly well established. Of the second factor, the rate of reaction, much less is known. Data are comparatively scarce and there is very little concordance. The discordance probably results from the large number of variables influencing the reactions. However, the general effect of the variables is known. Among these variables are temperature, gas velocity, particle size, porosity, gas composition (distance from equilibrium), presence of impurities, greater or less prevalence of side reactions, and even design of the apparatus itself. Wetherill and Furnasl published an excellent paper in 1934. They point out that any one or more of five processes (the chemical reaction, diffusion of the reactant through the gas film, diffusion of the reactant through the solid phase, diffusion of the reaction product through the solid phase, or diffusion of the reaction product through the gas film) may be the slow process, and thus the rate-controlling process. It is regretted that the work of these authors was limited to experiments at One temperature, and that the range of gas compositions was limited. Langmuir2 has shown that heterogeneous reactions take place at phase boundaries.

Jan 1, 1943

By M. C. Udy, C. H. Lorig

Through the years much interest has been centered in attempting to develop a direct method of iron-ore reduction, to replace or supplement the present indirect blast-furnace process. It would not be difficult to produce a list of more than 500 patents dealing with the direct production of iron and steel, but the few of this type of process that have proved successful do not produce in competition with the blast furnace; they produce special products. A survey of the literature reveals that the equilibrium conditions for the reduction reactions (iron oxides with carbon monoxide and with hydrogen) have been fairly well established but that data on the rate of reaction are discordant, although the genera1 effects of the variables are known. This dissertation deals with the rate of reduction of a magnetite concentrate with hydrogen. The following variables have been studied: bed depth, gas velocity, particle size and temperature. The behavior of a single particle was also studied. Literature Two general factors should be considered in a study of reduction of iron oxide: (I) equilibrium relations, and (2) rate of reaction. The first factor, equilibrium, has received the attention of many investigators and the equilibria Fe304-FeO-H2-H2O, Fe3O4-FeO-CO-CO2, FeO-Fe-H2-H2O, FeO-Fe-CO-CO2 are fairly well established. Of the second factor, the rate of reaction, much less is known. Data are comparatively scarce and there is very little concordance. The discordance probably results from the large number of variables influencing the reactions. However, the general effect of the variables is known. Among these variables are temperature, gas velocity, particle size, porosity, gas composition (distance from equilibrium), presence of impurities, greater or less prevalence of side reactions, and even design of the apparatus itself. Wetherill and Furnasl published an excellent paper in 1934. They point out that any one or more of five processes (the chemical reaction, diffusion of the reactant through the gas film, diffusion of the reactant through the solid phase, diffusion of the reaction product through the solid phase, or diffusion of the reaction product through the gas film) may be the slow process, and thus the rate-controlling process. It is regretted that the work of these authors was limited to experiments at One temperature, and that the range of gas compositions was limited. Langmuir2 has shown that heterogeneous reactions take place at phase boundaries.

Jan 1, 1943

Jan 1, 1938

Jan 1, 1938

By J. O. Betterton, W. M. Spicer

The solubilities of antimony in the a and ß-forms of zirconium were determined between 750" and 1300°C. The a-phase forms by a peritectoid reaction, and the a/(a + ß) and ß/(a + ß) phase boundaries rise in temperature with in- ' creasing antimony. Impurities in the 99.95 pct zirconium were sufficient to influence the phase boundaries and the variation reported is approximate. The restricted solid solubility of the terminal zirconium phases, which is especially characteristic of this system, is thought to result from the low free energy of the Zr2Sb phase. ZIRCONIUM-antimony alloys are important in zirconium alloying studies since antimony is one of the highest valent elements which can be used to make zirconium alloys. The dilute alloys are of further interest as they have somewhat better corrosion resistance' than pure zirconium. The first investigation of the phase diagram was made by Russi and wilhelm2 who found a eutectic reaction, liquid (- 17.5 at. pct Sb) = ß zirconium (- 11 at. pct Sb) + Zr2Sb, at 1430°C'. The Zr2Sb phase was of complicated hexagonal structure, and by thermal analyses of the relatively impure alloys then available, Russi and Wilhelm found evidence for the peritectoid formation of the a-phase. EXPERIMENTAL In the present work, the phase diagram was re-investigated in the region 0 to 5 at. pct Sb and 750" to 1300°C using iodide-zirconium alloys. Details of the procedure have been described earlier. Essentially the alloys were prepared by arc casting and were then examined by the annealing and quenching method. The times of annealing varied from 1 hr at 1300°C to 30 days at 760°C. As in other zirconium phase-diagram studies1"5 the impurities in the zirconium were still sufficient to affect the results, and the experiments will therefore be described in 3 parts. The results from the first 2 parts of the work are shown in Fig. 1. Here the ß/(ß + Zr2Sb) and a/(a + ZrzSb) phase boundaries were determined with alloys made from 99.9 pct zirconium,* and cast under such conditions that the Vickers hardness of a alloys extrapolated to 95 to 110 VPN at 0 at. pct Sb. Such alloys were not suitable for investigations of the (a + ß) region, and the results shown in Fig. 1 near the (a+ ß) and (a +ß + Zr2Sb) regions were determined with purer alloys. These alloys had an extrapolated hardness range of 75 to 85 VPN and were made from 99.95 pct zirconium. A deviation from binary equilibrium occurs in Fig. 1 as indicated by the (a + ß) region of pure

Jan 1, 1959

By Walter Knox, J. D. Doherty

IN 1939, at the request of The Koppers Coal Co., the Koppers Company Research Department established a Stoker Coal Research Laboratory for the purpose of investigating the performance characteristics of stoker coals in typical domestic stoker installations. Fig. I is a photograph of part of the laboratory. The material in this paper deals with the performance of one coal in a single installation. Presented are details of this installation, mechanical characteristics of the stoker, and the results of a series of burning tests in which adjustments were systematically varied. SUMMARY OF RESULTS Mechanical Features I. A large percentage of the total power consumed by a domestic stoker is used to operate the gear case and motor (Fig. 3). 2. The power consumption per ton goes down with an increase in rate of coal feed (Fig. 4). 3. The automatic air control in this stoker showed advantages over manual control (Fig. 5). 4. The air velocities through the retort tuyeres were uniform around the retort, but varied between the rows of tuyere rings (Fig. 6). 5. The crushing of coal with this stoker increased the minus 1/8-in. from 1 1.6 per cent to 19.2 per cent. There was a noticeable segregation of coal as it came from the retort and distribution was not uniform (Fig. 7). 6. Measurement of air entering over the fire showed that with some not uncommon adjustments this air may he a high percentage of the total air supply (Fig. 8 and Table I). Operating Performance I. The removal of clinker was shown to give a period of poor performance characterized by a high fuel-bed resistance and a high percentage of carbon monoxide in the flue gases (Fig. 10). 2. The fuel-bed resistance was found to decrease as the fuel bed built up in a normal response to heat demand after a prolonged hold-fire (Fig. II). 3. With intermittent operation the burning rate was almost always less than the feeding rate. The wide variations were found to be greatly dependent upon the length of the On period and the length of the intervals between On periods (Fig. 12). 4. The maintenance of a low furnace draft led to less fly ash, better clinker formation, and higher efficiencies (Fig. I3). 5. The maintenance of a minimum of excess air also resulted in less fly ash, better clinker formation, and higher efficiencies (Fig. 14). GUIDING PRINCIPLES In planning the investigations, the following principles were adopted: Selection of Healing Equipment.-Use only standard models of stokers and furnaces representative of those widely used.

Jan 1, 1942

By L. C. Aycock, J. Hunter, P. M. Lyons

In view of the unfavorable discovery trend that has set in during the past few years, it seems permissible to infer that the large, more easily found crude reserves in Louisiana are now known. Without doubt, many new producing areas will be located, but in the light of development during the past few years the majority of new areas probably will be found at greater depths and from relatively poorer sands. f Although sufficient reserves exist in Louisiana to last at the present rate of production for a considerable period, additional reserves must be found in more intensive development of the presently known structures. In order to ensure the greatest ultimate recovery from such structures, the most advanced technical methods must be employed in their exploitation. Wherever possible, cycling and repressuring plants should be installed. 'here are presently in Louisiana, especially in south Louisiana, a great many fields that contain gas-condensate reservoirs. These reservoirs cannot be produced for their liquid hydrocarbon content under present conditions without wasting an enormous quantity of gas and creating underground waste. Although some of these reservoirs are being produced, such production must be considered in the nature of a salvage operation rather than as a sound economic proposition. Such reservoirs, however, can become profitable ven- tures through the use of cycling and repressuring plants. Cycling operations now operating in Louisiana have increased the ultimate recovery from gas-condensate reservoirs anywhere from 10 to 30 per cent. Cycling operations will also provide a considerable reserve of gas, without which Louisiana cannot hope to develop any program of industrialization. During the past year, Louisiana attained the rank of third among the oil-producing states of this country. With a proper program of exploitation and development, and with emphasis on conservation, Louisiana can maintain this position for a great many years. Production On Dec. 31, 1943, oil and/or gas were being. produced in 52 parishes, or 81 per cent of all the parishes in the state. Thirty-three of the parishes produced oil and gas, 14 produced oil, and 5 produced solely gas. Tensas Parish in north Louisiana and Assumption Parish in south Louisiana formerly contained no producing fields but during 1943 joined the ranks of the producing parishes. Twenty-three new fields, including one rediscovery, were found during 1943-—a rate of discovery almost comparable to that of the preceding year. Eleven of these new discoveries were either gas or gas-condensate fields. Thus, the trend of development in finding new reserves was also comparable to that of 1942. Many reasons of considerable merit have been advanced to account for the discouraging lack of crude-oil reserves found during the past year. None are, however, completely satisfactory.

Jan 1, 1944

By J. Hunter, P. M. Lyons, L. C. Aycock

In view of the unfavorable discovery trend that has set in during the past few years, it seems permissible to infer that the large, more easily found crude reserves in Louisiana are now known. Without doubt, many new producing areas will be located, but in the light of development during the past few years the majority of new areas probably will be found at greater depths and from relatively poorer sands. f Although sufficient reserves exist in Louisiana to last at the present rate of production for a considerable period, additional reserves must be found in more intensive development of the presently known structures. In order to ensure the greatest ultimate recovery from such structures, the most advanced technical methods must be employed in their exploitation. Wherever possible, cycling and repressuring plants should be installed. 'here are presently in Louisiana, especially in south Louisiana, a great many fields that contain gas-condensate reservoirs. These reservoirs cannot be produced for their liquid hydrocarbon content under present conditions without wasting an enormous quantity of gas and creating underground waste. Although some of these reservoirs are being produced, such production must be considered in the nature of a salvage operation rather than as a sound economic proposition. Such reservoirs, however, can become profitable ven- tures through the use of cycling and repressuring plants. Cycling operations now operating in Louisiana have increased the ultimate recovery from gas-condensate reservoirs anywhere from 10 to 30 per cent. Cycling operations will also provide a considerable reserve of gas, without which Louisiana cannot hope to develop any program of industrialization. During the past year, Louisiana attained the rank of third among the oil-producing states of this country. With a proper program of exploitation and development, and with emphasis on conservation, Louisiana can maintain this position for a great many years. Production On Dec. 31, 1943, oil and/or gas were being. produced in 52 parishes, or 81 per cent of all the parishes in the state. Thirty-three of the parishes produced oil and gas, 14 produced oil, and 5 produced solely gas. Tensas Parish in north Louisiana and Assumption Parish in south Louisiana formerly contained no producing fields but during 1943 joined the ranks of the producing parishes. Twenty-three new fields, including one rediscovery, were found during 1943-—a rate of discovery almost comparable to that of the preceding year. Eleven of these new discoveries were either gas or gas-condensate fields. Thus, the trend of development in finding new reserves was also comparable to that of 1942. Many reasons of considerable merit have been advanced to account for the discouraging lack of crude-oil reserves found during the past year. None are, however, completely satisfactory.

Jan 1, 1944

The Secretary of the Treasury, in a recent ruling, allows 18 months from date of discharge within which former service men may reinstate their Government insurance policies lapsed f or non-payment of premiums. The point just now confronting the Bureau of War Risk Insurance and all those who are interested in the immediate and the future welfare of the young men who offered their lives for the flag and the country is that they be kept mindful that the provisions of the War Risk Act were not solely war measures, but that the framers of the Act provided insurance protection for all time to come for the boys in uniform and all dear to them. Under this ruling those making application for reinstatement will be required to pay only the premium on the amount of insurance to be reinstated for the month of grace during which they were protected, and for the current month. When the men are mustered out of the service, the insurance continues in force for one month and they are fully protected during that period even if their premium has remained unpaid. In reinstating, that month's premium will be required as well as the premium for the month in which reinstatement is effected. The ruling also stipulates that when applying for reinstatement the man must be in as good health as at the date of discharge, and so state in his application. After complying with these simple requirements, a Government insurance policy may be made as sound as on the day it was written. The Bureau of War Risk Insurance is now searching out its delinquent policy holders and offering them this renewal of Government protection. It needs the assistance of public spirited, patriotic, business and professional men everywhere, for the sake of our former service men, who must be given the information about its privileges to which they are entitled.

Jan 9, 1919

By H. F. Perkins

CORROSION as an economic problem is growing rapidly in importance not only because it entails a replacement of corroded parts, but because it interrupts operation and causes hazards of damage and injury through failures of corroded equipment. Nearly all industries are interested in this subject. This paper, although concerned chiefly with corrosion in a complete refinery on the sea coast, discusses many of the various forms of chemical decomposition, most of which are found universally. The petroleum refining industry, in the writer's opinion, is seriously afflicted by the presence of sulfur in nearly all crude oils. The complete removal of sulfur from the crude as it enters the plant would cause such a relief from corrosion that this problem for research would seem to demand active attention. Next to sulfur the most troublesome corrosive agent is the saltmagnesium chloride, found in the water associated with crude oil, the last traces of which are so difficult to remove. This is much less serious, however, than the sulfur. Refinery corrosion can be tabulated as follows: Causes of Corrosion and Places of Attack in a Refinery CORROSIVE ELEMENTS MATERIAL ATTACKED Air: Pipe lines Moisture Tanks COQ Electric fixtures Sulfur gases Still towers Chlorine Condenser boxes Other acid-forming gases Ladders and stairs Smoke stacks Steel buildings All exposed metal Water: Alkali Fire lines and hydrants Acids Cooling water lines Air Condensers and coolers Other dissolved gases Boiler tubes Steam Steam pipes and valves Turbines Oil Sulfur compounds Tanks, pipes, valves, stills, towers MgCl2-Hydrochloric acid Condensers Air contamination

Jan 12, 1926

By Theron Wasson

The discovery of eight new oil fields, two of which may be of major importance, was the outstanding record in Michigan this year. These new fields have helped to support the declining production from old areas and place the total of 18,559,000 bbl. in line with the past six or seven years. Thus, it appears that Michigan is doing its part in maintaining the production of the country in the third year of the war. The new fields are in the central basin area where oil was first discovered in Michigan, thus tending to focus attention on the deeper part of the lower peninsula of the state. Through 1944 the state of Michigan has produced a total of 222,-641,580 bbl. of crude oil from 100 pools, many of which arc relatively small. Among the previous1y discovered fields Reed City is still the outstanding producer, with Fork, Headquarters, and Adams following in the order named. The Reed City pool produced a little over 5,000,00 bbl., which was more than one third of the state's total for the year. Almost two thirds of the year's total oil production came from fields discovered in the past five years. Maps A map of the oil and gas fields of Michigan in 1943, published in the A.I.M.E. report for 1944,* shows the main producing areas and should be referred to if information in regard to their location is desired. The producing zones are shown in the columnar section in the same publi- cation." The data in Tables I and 2 have been carefully ' checked and every effort has been made to show as complcte information as possible. New Discoveries and New Developments Eight new producing areas were discovered during 1944 which, in order of importance, are: Deep River Field.—The discovery well in the Deep River field was drilled by Don Rayburn and others, and should be listed as a chance discovery, as, from a geological standpoint, it was not considered favorable until oil was found at a depth of 2838 ft. in a dolomitic layer in the top of the Dundee limestone. The first well was completed in January 1944, with an initial production of 2500 bbl. By the end of the year 15 wells had been completed, proying an area 2 1/2 miles long and 1/2 mile wide. Coldttater Field.-The Coldwater field was discovered in August 1944, by the Sohio Oil Co. Production is from secondary dolomite at the top of the Dundee at a depth of 3703 ft. To the end of 1944 nine wells had been drilled on 40-acre spacing. Essexville Field.—Essexville field was discovered by United Drillers and Producers, Inc. Eight wells had been completed to the Dundee lime by the end of 1944, and prospects were good for further development during 1945. Hilliards Field.—Hilliards field was discovered by Cook and Fortney. Production is from the Traverse lime at an average depth of 1588 feet,

Jan 1, 1945

By C. W. Washburne

FORMER studies of sedimentary strata have been based upon the mineralogical and mechanical characters of the solid components, rather than upon the open spaces between them. For present purposes let us take another point of view, and consider not the rock material, but rather its cavities, the pores and the fissures or cleaved joints which connect with them. Let us think of the geologic column not as a series of rocks, but as a mass of irregular connecting capillaries. Different parts of the column may be distinguished by the absolute size and by the relative amount of its open spaces. Porosity Each stratum of the column is characterized by a certain porosity, which would be independent of the size of the rock grains if all were of the same shape. Slichter has shown that the percentage of open space in a pile of equal spheres is practically constant regardless of the diameter of the spheres. This is approximately true of clean, assorted sand or gravel, but it is far from being the case with most natural sediments which have a widely variable porosity, the magnitude of which is determined mainly by the amount of fine and of secondary material between the larger grains. The shape of the grains materially affects porosity, round grains leaving more open space than angular or flat grains. The thin plates of kaolin and the fine plastic matter of clay fit quite perfectly when pressed together, and it is probably this close fit, determined by shape of grain, rather than the small size of a grain, that causes the low porosity of ordinary clay shale.

Jan 9, 1914

By H. B. C. Nitze

A description of some of the magnetic ore-deposits in this region should be of interest to the mining and metallurgical public, inasmuch as very little has been said or written concerning them. I refer to the magnetite deposits of Franklin and Henry counties, Va., and of Stokes county, N. C. These deposits remained comparatively unexplored until recently, when the construction of the Roanoke & Southern R. R. through this territory has called attention to them, by furnishing the means of transportation for the ores. It is true that the ores have long been known, at least locally, and were smelted in catalan forges and old-fashioned, cold-blast charcoal-furnaces long before and during the late war. At the present time, however, the old workings are caved in, filled up and over-grown to such an extent that, as a rule, but little can be learned from them. No prospecting of any consequence has been done, and as my time was too limited and the territory to be examined too extensive to permit additional openings of a more satisfactory nature to be made, the incormpleteness of some of the data I have to offer (notably, those referring to the absolute width of the veins) will be pardoned. It will hardly be necessary to say that this ore-bearing formation belongs to the Archaean, or Eozoic age, the usually occurring rocks being schist, shale, gneiss, granite, sandstone and quartzite. The stratigraphy is, as a rule, quite regular (excepting in the Danbury section, Stokes county, N. C.), the general strike being northeast and southwest, and the dip nearly vertical. The country is gently roll-

Jan 1, 1892

By Barry D. Lichter, Pierre Sommelet

High-temperature heat contents of InSb, GaSb, and AlSb were measured over the temperature range 400" to 1450°K using a diphenyl ether drop calorimeter. Smoothed ualues of the thermal properties, H$ - H:9s, have been derived and are tabulated at even temperature intervals. The heats of fusion of the three compounds were determined as, respectively, 5707 *100, 7780 * 100, and 9800 5 3011 cal per g-atorn at the determined melting points of 797" l°, 985" * , and 1330" * 5°K. The calculated entropies of fusion are, respectively, 7.16 0.12, 7.90 * 0.11, and 7.37 * 0.23 cal per deg per g-atotn. The heat capacities increase substantially on tnelting in contrast to the behauior of structurally related germanium and silicon. Deriations from the Kopp-Neumann rule are negative for solid compounds and positive for the liquid phases. Previously obsevrrd "post melting" in InSb is confirmed. The high-temperature thermal properties of 111-V compounds are presently not well-established, despite the technical importance of these semiconducting cbmpounds. Uncertainties in available heats of fusion and heat contents have seriously hampered thermo-chemical evaluations' and thermodynamic analyses of phase equilibria2"" in these systems. This paper reports results of high-temperature heat content investigations of InSb, GaSb, and AlSb measured in the range 400" to 1450°K employing a diphenyl ether drop calorimeter. Similar measurements for InAs and GaAs will be reported in a following publication.~ EXPERIMENTAL PROCEDURES Samples. High-purity samples of the compounds InSb and GaSb were supplied in the form of crushed crystal fragments by Dr. Carl Thurmond of the Bell Telephone Laboratories and in the form of single crystals by Dr. A. Strauss of the M.I.T. Lincoln Laboratory. Single-crystal samples of semiconductor-grade AlSb were supplied by Dr. W. P. Allred of the Bell and Howell Research Center. Chemical analyses indicated that all compounds were stoichiometric to *0.1 at. pct, which is within the experimental uncertainties of the analyses. Samples were crushed, weighed, and encapsulated in evacuated, thin-walled, fused silica capsules. The capsules were nearly identical in external shape, 2 cm by 2 cm diam, but varied in weight due to differences in wall thickness. One sample of AlSb was contained in a thin-walled, high-purity alumina cup encapsulated in silica and used for heat content determinations of liquid AlSb. The capsule materials showed no visual evidence of reaction with any of the compounds. The sample and capsule weights are given in Table I. Calorimeter. A Bunsen-type calorimeter, similar in design to a previously described instrument6 but employing diphenyl ether (C6H5)'0 as the calorimetric substance, was used for measurements of heat contents above 300.0°K, the melting point of diphenyl ether. Heat input to the calorimeter caused isothermal melting of diphenyl ether, and the resulting increase in volume was measured by displacement of mercury from the calorimeter into a 200 cm horizontal, calibrated capillary, 1.25 * 0.01 mm diam, or into a weighed beaker. The advantages of diphenyl ether over water have been previously pointed out7 and include: i) an increase by a factor of 3.5 in sensitivity as measured by the ratio of the volume change to the enthalpy change on fusion, ii) the smaller required extrapolation from the melting point to the standard temperature of 298.17"K, and iii) the positive volume change on fusion of diphenyl ether in contrast to the contraction which occurs on fusion of ice. Diphenyl ether was purified by fractional crystallization to 99.95 mol pct as determined from the melting point depression with fraction crystallized. During assembly of the calorimeter, the ether was repeatedly outgassed under high vacuum to remove dissolved air. The calorimeter receiving vessel consisted of an 8-in.-long by 1:-in.-diam copper tube with twelve horizontal 3-in.-diam radiator "fins" for dissipating heat to the surrounding mantle of diphenyl ether. Before forming the mantle the chamber surrounding the receiving vessel contained 3300 cu cm of liquid diphenyl ether above 250 cu cm of mercury which was

Jan 1, 1970

THE problem of reaction rates in the open-hearth process is essentially that of trying to form a fairly clear picture of the "chemical mechanisms" in the bath. Quantitative data on reaction rates would perhaps not be of much practical importance even if they were available; however, what few approximate data there are can be used in combination with data given in Chapters 16 and 17 to sketch a picture of the "chemical mechanics" of the open-hearth process that is consistent with essentially all the present available evidence. The result may later be found incorrect in many details but even so it will illustrate certain useful methods for obtaining a clearer understanding of the process. Consistent with the treatment in Chapter 15, but in simpler terms, we may say that chemical reactions in general involve the following elements or steps: 1. The reacting molecules are mixed together in space in such fashion as to favor collisions among them. 2. Units of what is usually an intermediate molecular arrangement called an activated complex are formed at a certain rate, depending on temperature and concentrations. 3. These activated complex units decompose into the reaction products (this step usually assumed to be so rapid as never to limit the over-all process). 4. In any of these steps, heat energy may have to flow into, or away from, the reaction zone to permit the reaction to proceed. 5. The products of reaction will usually have to move out of the way to permit further reaction. The temperature factor enters mainly through step 2, and its effect is very marked. (What is called temperature is really the mean energy content of all the molecules of the substance involved; at any one temperature a certain proportion of the moleculea will have much higher energy content than the mean value.) Various reaction rates measured at around room tem-

Jan 1, 1951

By R. H. Edsal, G. Horvay

The transient one-dimensional heat-conduction equation is solved for two semi-infinite media, at different initial temperatures, brought into (poor) thermal contact. It is shown that the two interface temperatures gradually approach the well-known, instantaneously assumed, common interface temperature of the case of zero contact resistance. The present analysis, with slight modifications, may be used in fair approximation also for the class of problems involving a change of phase. One particular application of the boundary value problem solved in this paper concerns the determination of the temerature distribution in metal castings and molds.P This problem has been treated extensively by analytical methods (see e.g., the literature listed in Refs. 1 to 4) by electrical analogs (see e.g., Refs. 11 to 14) and also by experimental methods (see the literature listed in Refs. 4, 5), but prior to the work of Pellini and Ruddle the experimental results were rather unreliable. Immediate motivation for the work described in this paper was to better understand the results of Pellini,' which are typified by the curves of Fig. 1. Pellini cast 20-in. high, 7-in. sq steel ingots into cast-iron molds of various thicknesses. He measured the temperatures at mid-height, at a number of stations in the casting and the mold, and obtained the cooling curves shown in Fig. 1. The most conspicuous thing about Fig. 1 is the large temperature discontinuity at the interface between casting and mold, due presumably to the shrinking away of the casting from the wall and the attendant creation of an airgap, as the casting cools. Such a contact resistance slows down the anticipated freezing rate; an analytical prediction of this is of much interest in foundry practice. The determination of the effect of contact resistance in the presence of a change of phase will be dealt with, by an approximate method, in a separate paper.' In the present paper the much simpler problem is considered in which there is contact resistance but no change of phase. This problem frequently arises in the analysis of aircraft structures.+ It can initial temperature, and may be regarded as semi-infinite. We suppose the thermal properties in the two media to be time, temperature, and space independent; there are no sources or sinks within the media. In Fig. 2(a) we illustrate, schematically, the case of no contact resistance. The semi-infinite media "0" and "2:' initially at temperatures 8 (- m) and 8(+ -), respectively, are brought into contact at time t =0. A common interface temperature 8,i = is instantaneously established, and thereafter remains constant. Temperature curves are drawn for three instants of time. When there is contact resistance between the two media, the temperature equalization occurs as sketched in Fig. 2(b). Fig. 2(c) illustrates a temperature curve, using the dimension-less notation Barber-Weiner-Boley6 have stated the equations [23a, b] given below, which govern the heat transfer in the two media, and solved them for a rather complicated special case. In their example both media "O" and "2" are finite, are insulated at their far ends, and there is steady heat input into medium 2. In Eq. [27] we give the general solution of the most important special case, where the two media are semi-infinite and there are no sources or sinks. In this case the results may be stated in simple closed form. In Fig. 3, to be discussed in the next section, we illustrate the variation of the interface temperature when steel at 2760" is brought into contact with iron at 100". This example, if we disregard the effect of the heat of fusion, is comparable to Pellini's experimental results, Fig. 1. (Unfortunately, however, experimental determination of the interface temperatures was difficult to carry out, and hence Fig. 1 is not very accurate near the interface.) In Figs. 4 and 5 of the following section, we similarly compare Pellini's sandcasting tests with analytical results for the case where steel at 2760" is brought into contact with sand at 100". It will be pointed out that, insofar as the interface temperatures are concerned, heat of fusion has a minor effect, and so the present approximation, with small modifications, may be

Jan 1, 1961