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By O. C. Blade

Sales of diesel fuel in the United States during the post year and a half have increased greatly. In 1955 over 174 million barrels were sold of which 80 million (or 46 percent), were used by the railroads, and over 44 million barrels (25 ½ percent) of the fuel were used in trucks, busses, tractors, and heavy moving equipment. Vessels (12 percent), industry (9 ½ ), the military forces (4 ½ ), power plants (2), and oil companies (1/2 percent) account for the remainder. 2/ Dally deliveries of diesel type fuel from refineries averaged over 16,750 barrels during the first six months of 1956 in comparison with 15, 250 barrels during the corresponding period of 1955. 3/ Information on the properties of diesel fuel is very important to the petroleum industry, engine manufacturers, and consumers. To supply such information the American Petroleum Institute and the Bureau of Mines, United States Department of the Interior, under cooperative agreement, are conducting annual surveys of diesel fuel oil produced in refineries in this country.

Jan 1, 1957

By J. W. McCammon

CRANGES in construction ideas and the continually rising costs of labour and conventional building materials, particularly since World War II, have prompted widespread investigations into the development and adaptation of new materials to meet the new requirements and to help reduce costs. Lightweight aggregates have been prominent in these investigations. The lightweight aggregates most commonly used today are foamed slag, cinders, pumice, diatomite, exfoliated vermiculite, expanded perlite, and bloated clay or shah. Lightweight aggregates contribute to the building industry in several ways: ( 1) in large structures the reduction in deadweight effected by the use of lightweight materials reduces the amount of reinforcing and structural steel necessary to support the structure; ( 2) the decrease in weight of lightweight blocks makes handling easier and faster; (3) pre-fabricated floor and roof slabs and tilt-up walls of lightweight concrete have become feasible and popular; ( 4) lightweight aggregate concrete has good nailability and is easily channelled; (5) concrete and plaster made with lightweight aggregate have good heat and sound insulation properties.

Jan 1, 1957

By Richard N. Appling

This compilation presents information obtained through investigation of manganese deposits and a reconnaissance of potential manganese-bearing areas of southwestern Oregon and Del Norte County, Calif., from October 1952 to September 1955. The report includes maps, assays, and preliminary examination data on 39 manganese deposits distributed throughout Curry, Coos, Douglas, Josephine, and Jackson Counties, Oreg., and 1 deposit in Del Norte County, Calif. On the basis of mineral content the deposits can be divided into three groups: 1 Manganese silicate deposits, manganese oxide deposits, and manganiferous iron de-posits. Generally the oxides occur along the coast in the Curry-Coos County area, the manganiferous iron deposits are in the Josephine-Douglas area, and the manganese silicates are found in both the Josephine-Douglas and Jackson County areas. The deposits are characteristically irregular in form and usually small. Most silicate and manganiferous iron deposits are in metasediments of Triassic (?) age; oxide deposits are in sediments varying in age from Jurassic to Eocene.

Jan 1, 1957

By S. K. Nowak

The lithium solubility limit in solid aluminum was determined by the use of micro-graphic techniques. The solubility limit thus established was shown to be a true equilibrium by checking the reversibility of AlLi phase precipitation and dissolution around the equilibrium temperature. The experimental results fit a straight line by plotting log N(LI) against 1/T. The metallurgical reasons explaining the lack of agreement among previous investigations are discussed. THE solubility limit of lithium in solid aluminum was determined by Shamray and Saldau1 by micrography and by Grube et al.' and also Voss-Kiihler- by measurement of electrical resistivity. Since the addition of lithium induces extremely small changes in the aluminum lattice, X-ray techniques could not be employed for this purpose; in fact, the addition of lithium does not cause an expansion of the lattice as might be expected from a consideration of atomic radii, but causes a small contraction from 4.040 to 4.037A3, 4 when the solvent aluminum is saturated with this element. An analysis of the results from previous investiga-tions'" shows that with improvement of investigation techniques the solubility limit tends toward a lower lithium content. Again, some of the author's own experimental results on the action of atomic hydrogen on A1-Li alloys seemed to indicate that the solubility of lithium should be much lower, i.e., about 0.3 pet at 300°C: instead of 1.15 pet, the lowest published value.4 For the foregoing reasons it was decided to investigate this problem. The aluminum and the lithium used for this purpose were of the highest purity. The lithium solubility limit was determined by metallographic techniques, in particular by the use of a reagent especially developed for the purpose of revealing the AlLi phase. The solubility limit thus determined was shown to be a true equilibrium by checking the reversibility of AlLi phase dissolution and precipitation around the equilibrium temperature. All of the experimental work was carried out in 1951 at the Centre d'Etudes de Chimie Metallur-gique at Vitry, France, under the direction of Georges Chaudron.

Jan 1, 1957

By Harold R. Bradford

EXPANSION initiated during and after the war has placed industrial plants in new areas and increased reduction and manufacturing facilities in communities already established. With added expansion interest has grown in possible area contamination from waste products. Evolved flue waste contains many chemical contaminants that may or may not cause concern; however, atmospheric pollution has always been a problem to industrial communities. For some time effects attributed to small quantities of compounds of fluorine in various waste gases have been studied by industrial, medical, agricultural, and associated interests.1,2 Aside from an article by Churchill, Rowley, and Martin in 1948,3 little has been published on the subject of fluorine in coal except by foreign investigators.

Jan 1, 1957

By J. D. Milburn, H. J. Hill

In quantitative interpretation of electrical logs the presence of clay minerals introduces an additional variable which further complicates an already complex problern. Although recognizing the difficulties introduced as a result of the heterogeneity of natural sediments and despite the present incomplete state of knowledge regarding electrochemical behavior of shales, dissemirzated clay minerals and concentrated electrolytes, it was felt that useful empirical correlations might be obtained from experimental investigation. Six typical sandstone formations, having a wide variety of petrophysical properties, were selected for the study. Approximately 45 samples from each formation were selected to satisfactorily represent the range of pore size distribution within the particular formation, As a matter of general interest, four limestone formations were also included in the investigation. Previously proposed equations relating to resistivity, SP and interrelationship of the two phenomena have, where possible, been tested with data obtained in this investigation. These equations do not satisfactorily describe experimental behavior of samples through all degrees of shaliness or throughout the range of brine solution resistivities normally encountered in logging practice. An empirical equation has been developed which quantitatively relates formation resistivity factor to satirrnting solution resistivity, porosity, and "effective clay content." This relation is indicated to be uniformly applicable to clean or shaly reservoir rocks. It is shown that both the SP and resistivity phenomena of shaly samples are related to the sample cation exchange capacity per unit pore volume. The independent chemical determination of this parameter is thus a means of determining the "effective clay content" of samples. Some implications regarding theory and electric log interpretation of shaly sands are discussed. INTRODUCTION The use of electrical resistivity logs as a means for estimating formation porosity is based upon the original work of Archie1. It was shown by empirical methods that the resistivity of a rock, when 100 per cent saturated with brine solution, could be related to rock porosity through the equation, F = Ro/ RW = f-m.......(1) where F, the formation resistivity factor, is defined as the ratio of the resistivity of the 100 per cent water saturated rock, Ro, to the saturating solution resistivity, Rw; f is the ratio of pore volume to bulk volume; and m is the slope of the average line when the data are plotted on log-log paper. This relation was established for relatively shale-free formations containing water having high salt concentrations, and under these conditions F may be considered constant for a given rock sample. Applications of Eq. 1 to interpretation of logs of shale-free formations has been quite successful when satisfactory formation water resistivity data could be obtained. The most readily available means of estimating formation water resistivity is the self-potential log. Conventional methods of SP log interpretation involve correct.

Jan 1, 1957

With the sinking of the new No. 3 Shaft and the increasing depth and northward movement of the mining operations, improved ventilation of the mine workings became necessary and it was decided to sink a new upcast ventilation shaft midway between No. 2 Shaft and No. 3 Shaft.The shaft is finished to 16 ft. internal diameter and connects with the mine workings at the 2,600-ft. level. It is lined with unreinforced Concrete approximately 12 in. thick. The shaft sinking routine was drilling, blasting and mucking by hand using a 27-cub. ft. capacity bucket. The concrete lining was poured in conjunction with the sinking and was normally finished within 30 to 50 ft. of the shaft bottom.

Jan 1, 1957

By N. A. Eilertsen

Among the numerous Low-grade manganese deposits in eastern Aroostook County, Maine, the Dudley deposit near Mapleton in the northern district is one of the few known to contain an appreciable tonnage averaging above 10 percent manganese. The ore body, consisting of stratified manganiferous hematitic shale, is over 5,000 feet long and ranges in width from 30 to 175 feet. The deposit was extensively explored during 1942-44 by the Manganese Ore Co., a subsidiary of M. A. Hanna Co. of Cleveland, Ohio. Data obtained from this work were made available to the State and Federal Geological Surveys for estimating ore reserves. An estimate by the Maine Geological Survey, using a 10-percent manganese cutoff and to a depth of 200 feet, shows 609,000 long tons of manganese metal in material averaging 12.6 percent manganese. By lowering the cutoff limit to 5 percent manganese, the estimate was increased to 919,000 long tons of metallic manga¬nese in material averaging, 10.4 percent manganese,

Jan 1, 1957

By Wallace E. Anable

This investigation by the Bureau of Mines was conducted chiefly on Cuban serpentine nickeliferous ores to determine whether these materials would be amenable to direct carbothermic reduction in an electric furnace to produce a low-carbon ferro-nickel. The project was carried out as one of several under a Memorandum of Agreement between the Bureau of Mines and the General Services Administration (Contract GS-OO-B (D)-152l). Two ore samples were received for this investigation. One was a mixture of nickeliferous serpentine from the North Ocujal, South Ocujal, and San Juan claims of the Nicaro Nickel Co. The other sample was a mixture of material from the Ramona and the Lorna Mulo claims of the Cuban Nickel Co. Most of the ore from the Ocujal-San Juan deposits and about 40 percent of the sample from the Ramona-Lorna Mulo deposits were calcined before smelting. The remainder of the sample from the Ramona-Loma Mulo deposits was smelted after drying to about 8 percent moisture. An arc-resistance, selective-reduction smelting technique was employed in these tests. Either bagasse alone or a mixture of bagasse and coke was used for reductants. No flux was used in the furnace charges.

Jan 1, 1957

President-Mrs John R C Mann, 90 Edgemont Road, Scarsdale, N Y First Vice-President-Mrs C P Pollock, 27 Dante Street, Larchmont, N Y. Second Vice-President-Mrs Mendum B Littlefield, 40 Lincoln Street, Larchmont, N Y Third Vice-President-Mrs J B Cunningham, 236 East 2nd St , Tucson, Ariz Fourth Vice-President-Mrs Theodore Loftus, 410 Cowles St, Fairbanks, Alaska Fifth Vice-President-Mrs George L Craig, 109 Calumet Avenue, Calu¬met, Mich Recording Secretary-Mrs Arnold H Miller, 601 West 115th St, New York 25, N Y Assistant Recording Secretary-Mrs R J Mechin, 66 East 79th St, New York 21, N Y Corresponding Secretary-Mrs John A Poulin, 4 East 70th St , New York 21, N Y Treasurer-Mrs Robert W Rowen, 29 West 39th Street, Room 914, New York 18, N Y Assistant Treasurer-Mrs Samuel H Dolbear, 1000 Park Avenue, New York 28, N Y Assistant Treasurer-Mrs Roger H Sherman, 8 Roman Avenue, Forest Hills Gardens 75, N Y.

Jan 1, 1957

By Bruce I. Thomas

As a part of the United States Department of the Interior program for developing natural resources in Alaska, the Bureau of Mines studied the tin-bearing gold-placer deposits in the Tofty area of the Hot Springs district in central Alaska. The principal objective of the Bureau's work was to obtain facts about the extent and character of the placer deposits (including tailing) to indicate the economic or strategic tin-production potential of the Tofty "tin belt." A secondary objective was to determine (if possible) the bedrock Source of the cassiterite and other minerals found in the placer deposits. The placer phase of the work was begun in July 1954 and was continued during the 1955 and 1956 field seasons. Extensions to, and connections between, known placer channels were sought by 82 churn-drill holes. The Bureau drilling did not expand the placer deposits beyond the limits established by drift-mining operations and by previous drilling done by private concerns.

Jan 1, 1957

By H. W. Mead, C. E. Birchenall

SELF-DIFFUSION of iron in austenite is a process which may play a significant role in some of the practically important reactions which occur in solid irons and steels. It also provides a system in which the interaction of vacancies on substitutional sites and atoms in interstitial positions may be investigated. For both purposes, accurate values of the diffusivities are required. Two sets of previous measurements exist, each containing features which require checking. In the course of an investigation to determine the rate of diffusion of iron in certain steels, Garwick and Rosenqvist' measured the self-diffusion coefficient of iron in a 0.10 pct* C steel and obtained a dicated that while at lower temperatures D increased with increasing carbon content, at the higher temperatures it first increased and then decreased. At the same time the activation energy decreased linearly from a value of 69,000 cal per g-atom for pure iron to 33,000 cal per g-atom at 1.06 pct C. This rapid decrease in activation energy implies that iron at higher temperatures within the austenite range would diffuse more slowly in high carbon steels than in steels of lower carbon content. Experimental Procedure The radioactive iron used in this work was obtained from Oak Ridge National Laboratory. The unit consisted of about 1 microcurie each of Fe7 and Fe It was allowed to decay for two years. At the end of this time most of the Fe with a half-life of 46.3 days, had decayed, while most of the original Fe(half-life 2.91 years) still remained. The iron as chloride was extracted into an ether layer, using the method of Ashley and M~rray. After evaporation of the ether the iron chloride was dissolved in 250 ml of aqueous solution containing 2.4 gpl Fe. The compositions of the steels used are listed in Table I. Disks of ¾ in. diam and about ¼ in. thick were machined from these steels for use in diffusion couples. The disks were surface ground on both sides to ensure parallel opposite faces. One face of each disk was polished through 000 emery paper. Half of the prepared disks were plated with radioactive iron. For this, 1 ml of the radioactive iron

Jan 1, 1957

Jan 1, 1957

By Murray F. Hawkins

Horner1 and van Everdingen8 ave shown that the pressure drop within the wellbore, as a result of having produced the well at a constant rate q for time t, where t is sufficiently large, is: van Everdingen observed that better agreement between theory and well performance can be obtained if, instead of assuming the permeability is kc everywhere about the well, it is assumed the permeability near the well-bore is substantially reduced as a result of drilling, completion and/or production practices. In order to account for the additional pressure drop he introduced the dimensionless quantity S, the skin effect factor, so that Eq. 1 becomes: Eq. 2 might have also been obtained as follows. Assume a zone of altered permeability k, exists about the well out to a radius r and beyond that the unaltered, external permeability k. The additional pressure drop required to overcome this skin of reduced permeability may be calculated with sufficient accuracy using the incompressible flow equation; for Browns-combe and Collins1 have shown almost no difference between compressible and incompressible steady-state flow, in the vicinity of the wellbore, and the small volume of fluid in the vicinity of the wellbore makes unsteady-state mechanics unnecessary. Then. The sign of this skin pressure drop will be positive or negative depending upon whether the altered permeability k, is smaller or larger, respectively, than the external permeability k... Adding the pressure drop of Eq. 3 to Eq. 1 to find the total pressure drop: Comparing Eq. 4 with Eq. 3 it is seen that the skin effect may be defined by: be determined from pressure build-up tests1,3,4,5,6,7,8 The average permeability kavg including the altered and external permeabilities, can be determined from PI tests, and may be defined approximately on the basis of steady-state flow, as was done by Thomas' in defining the damage factor, by: The productivity ratio is the ratio of the average to the external permeability, kavg/ke or This equation shows that the productivity ratio and the skin effect are not uniquely related, because of the uncertainty in the drainage radius, and also, in many instances, the wellbore radius. Fortunately, they enter in the logarithm. The curves of Fig. I are plots of Eq. 8 for values from 100 to 50,000. The points represent the skin effects and corresponding productivity ratios from a large number of well tests, taken from Fig. 15 of Ref. 5 or Fig. 13 of Ref. 9. While some of the data

Jan 1, 1957

By B. H. Clemmons

A field method has been devised for rapid determination of heavy minerals occurring in the unconsolidatod beach and dune sands. The method has been proved practical by usage in field evaluations of several hundred beach- and dune-sand samples in the Florida area. The simple equipment required and the techniques involved are described. Other data show that the method is relatively insensitive to variations in the mineralogical content or size distribution of the mixed heavy minerals contained in the samples tested. A modification of this procedure, found to be suitable for plant use in determining the relative purity of heavy-mineral flotation concentrates, is also described. A specific application is determination of the amount of feldspar-quartz in spodumene flotation concentrates. The results of the rapid evaluation techniques closely approximate those obtained by more precise laboratory procedures.

Jan 1, 1957

By O. C. Blade

This report on the properties of motor fuels sold through service stations in the United States was made in accordance with a cooperative agreement between the American Petroleum Institute and the Bureau of Mines of the United States Department of the Interior. By agreement with the American Petroleum Institute, identification of the items is confidential. .It presents analytical data for 4, 457 samples, representing the products of 92 companies. The samples were collected by companies during June, July, and August 1956, As in previous surveys, the gasolines covered by this survey include those from both large and small suppliers. The data were obtained by laboratories of various refiners, motor manufacturers, and chemical companies and submitted to the Bureau of Mines for compilation. A list of the National Motor Gasoline Survey reports published during the past 10 years is on page 5.

Jan 1, 1957

By Nicholas J. Grant, H. C. Chang

Microscopic observations during creep tests were made on AI-20 pet Zn, 80 pet Ni-20 pet Cr, and 25 and 3S aluminum specimens. All these materials failed in an inter-crystalline manner under certain stress and temperature conditions. Particular atten-tion was given to the initiation and propagation of intercrystalline cracks in coarsegrained AI-20 pct Zn specimens. The geometry of the grains and grain boundaries in these specimens was known before the tests. On the basis of the observations and a knowledge of the interaction between grains and grain boundaries, a mechanism of intercrystalline fracture and propagation of the fracture has been proposed. METAL, and alloy fracture occurs essentially in two ways: transcrystalline and intemrystalline. In the past most of the work done in this field was centered on the determination of stress criteria for fracture. The specimens used for these studies were tested under varying conditions of stress state, temperature, and strain rate. Unfortunately, very little attention was given to the initiation and propagation of the fracture, whereas the nature of fracture was examined closely only after failure. Several extensive reviews of these studies have been published by Orowan, Smith, Barrett, and Petch.1, 4 It is well known that a material which exhibits a ductile and transcrystalline fracture can be made to exhibit a brittle and intercrystalline fracture by modifying its composition and by heat treatment. This modification may or may not result in microscopically observable precipitation in the grain boundaries." In the creep of any one alloy the transition of transcrystalline to intercrystalline fracture is a function of stress, strain rate, and temperature." The tendency for intercrystalline fracture to occur increases as the strain rate decreases and the testing temperature increases. Extensive work on high purity aluminum (99.995 pet) under creep conditions showed the importance of the interaction between grains and grain boundaries, and the different responses of grain and grain boundaries to the variables: stress, strain rate, and temperature.7, 8 It was also shown that grain boundary deformation necessarily has to be accommodated in the grains by various deformation means as. for example, fold formation. The type of fracture resulting from the creep of high purity aluminum was invariably found to be transcrystalline. On the other hand, 2S and 3s aluminum were, under certain conditions, found to fracture in an intercrystalline manner." One reason given for this was that the grains could accommodate to a lesser extent the deformation of the grain boundaries.19 It was decided to examine this line of reasoning in greater detail and to investigate the particular interactions between grains and grain boundaries that result in the incidence and progression of inter-ct,ystalline fracture. It is also the purpose of this paper to show where and how intercrystalline cracks start and how they propagate to result in fracture. Several alloys—Al-20 pct Zn, 80 pet Ni-20 pet Cr, 2S and 3s aluminum-— were used for this study, but attention was paid mainly to the behavior of an A1-20 pet Zn alloy, since its general creep behavior has been established." From the results of this study a mechanism of intercrystalline fracture is proposed. Experimental Procedure The experimental procedure was similar to that used in previous work and has been detailed elsewhere.' Two parallel flat surfaces were milled from an originally round specimen, giving a gage portion which was 1x0.09X0.17 in. Some round specimens, 1/4 in. round by 1 in., were also tested. The A1-20 pet Zn specimens. which were annealed at 1030°F for 24 hr, showed two to four grains across the width of the test bar, and most of the grains occupied the whole thickness of the specimenu. Before some of the specimens were subjected to creep, the grain arrangement was mapped out in a development drawing, Fig. 1. The initiation and

Jan 1, 1957

By J. A. Morgan

IN the art of roasting sulfides it is well known that the lower the temperature and the higher the pressure of SO, the larger will be the amount of sulfate present in the product. However, the mechanism of sulfate formation is not generally understood. The following experiment" demonstrates in a direct way that, in the roasting of Cu2S, the sulfate forms from the reaction of Cu2O, formed by the oxidation of Cu2s, with gaseous SO, (or SO3) and 0,. Thus, the sulfate does not form at the sulfide surface. The reaction at the sulfide surface is the same whether or not sulfate is formed. Using an indirect method, Ong, Fassell, and Wadsworth' infer that sulfate forms after oxidation, during the roasting of sphalerite, agreeing with the observations of this paper. The method presented here of demonstrating that sulfate forms after formation of Cu2O is to roast a sample of Cu2S and then to locate and identify the phases formed.' A solid cube of cuprous sulfide, made by melting Fisher reagent grade Cu2S powder and measuring about 1.5 cm on edge, was placed on a Nichrome wire grid suspended over the top of an Alundum combustion boat. The assembly was placed in a tube furnace at 600°C and oxygen gas, flowing at 0.60 liters per min, was passed around the specimen for 24 hr. The furnace tube diameter was 1.5 in. The partially roasted sample was removed from the furnace and impregnated with resin No. BR 0014, obtained from the Palmer Products Co., and the impregnated sample was then mounted in Lucite. A cross section was obtained by grinding and the surface was prepared by the following steps: 1) grinding—60 grit, 3M disk, dry; 2) preliminary polishing —60 through 600 grit, 3M disk, dry; 3) polishing— 8 µ diamond putty, silk cloth; and 4) final polishing —1evigated magnesia in isopropyl alcohol, Selvyt cloth. The color micrograph of the polished surface is shown in Fig. 1. The layers present in the micrograph are given along the side. The comwositions of the various layers were established by Debye-Scherrer patterns. From this evidence the following sequence of reactions which occur in the roasting of Cu2S is inferred: 1) The oxidation of Cu2S occurs with oxygen which has been transported through the oxide-sulfate layer by either gaseous or solid state diffu- sion. The products of this reaction at the Cu2S surface are Cu2O and SO,. 2) The SO, diffuses out through the pores in the Cu2O and finally reaches a position in the Cu2O where the oxygen pressure and the SO, pressure have values such that the thermodynamic conditions for the formation of CuSO4 are fulfilled. Then, the mixture of SO2, SO3, and oxygen reacts with the Cu2O to form CuSO1. 3) The CuSO, decomposes by the evolution of SO,, or SO, and O2, to form the basic sulfate. This is reasonable, since the SO, gradient will decrease toward the oxygen gas phase from the CuSO4 layer. 4) For this same reason the basic sulfate will decompose to form CuO. The above sequence of events is based on the assumption that diffusion through the oxide and sulfate layers, rather than the reaction at the sulfide-oxide interface, is rate-determining. This assumption is supported by the observation that these oxide and sulfate layers combined are almost nonperme-able to the flow of gases through them. Acknowledgments This research was supported by the U. S. Air Force, through the Office of Scientific Research of the Air Research and Development Command. The authors wish to acknowledge the helpful suggestions of Ralph Wells of the Applied Research and Developmeit Laboratory, U. S. Steel Corp. References E. A. Peretti: A New Method for Studying the Mechanism of Roasting Reactions. Discussions Faraday Soc. (1948) 4, p. 174. - J. N. Ong, Jr., M. E. Wadsworth, and W. M. Fassell. Jr.: Kinetic Study of the Oxidation of Sphalerite. Trans. AIME (1956) '206, pp. 257-263; Journal OF Metals (February 1956).

Jan 1, 1957

By L. L. Seigle

Free energies, heats, and entropies of mixing of solid Fe-Au alloys have been measured by the galvanic cell method between 800° and 900°C. A positive deviation from Raoult's law and a large excess entropy of mixing were observed, both attributable to lattice distortion caused by the disparity in component atom sizes. Since the terminal solid solutortiontions are not regular, thermodynamic properties computed from the location of the mis-cibility gap do not agree well with measured quantities. The electromotive force data suggest some changes in the existing Fe-Au phase diagram. ALTHOUGH a considerable amount of information has been accumulated about the thermodynamic properties of metal solid solutions which exhibit negative deviation from Raoult's law, particularly those in which ordering occurs, relatively few experimental measurements have been made on solutions with positive deviation. This is due to the infrequency of broad homogeneous regions suitable for experimental measurement in solutions of this type, since any marked positive deviations from ideality lead to restricted solubility and the formation of miscibility gaps. Thermodynamic data reported in the literature for such systems have usually been calculated from the location of the miscibility gap boundaries under the assumption that the entropies of mixing are ideal, i.e., the terminal solutions are regular.' One of the few binary systems with both positive deviation and a wide homogeneous range in the solid is the Ni-Au system. A recent investigation of solid Ni-Au alloys' revealed that the entropies of mixing were much larger than ideal and consequently thermal data computed from the phase boundaries assuming regular solutions were seriously in error. Theoretical considerations put forward by Zener indicated that high entropy values should generally be associated with systems possessing a miscibility gap in the solid, when this is due to differences in the size of component atoms. These facts suggest that the regular solution assumption is a poor approximation for many solid solutions with positive deviation and that reliable thermodynamic data generally cannot be obtained by conventional methods from the location of miscibility gap boundaries. The Fe-Au system, Fig. 1, resembles the Ni-Au system in certain respects. The presence of a miscibility gap in the solid indicates a large positive deviation from ideality, but there is nevertheless an extensive single phase region suitable for experimental measurement. The following investigation of solid Fe-Au alloys was carried out in order to obtain additional data on the thermodynamic properties of metal solid solutions with positive deviation from Raoult's law and to further compare thermodynamic data computed from miscibility gap boundaries with those measured experimentally. Experimental Method The thermodynamic properties were derived from measurements of the potential developed between pure solid iron and Fe-Au alloys in a high temperature galvanic cell. The experimental apparatus and technique were the same as those used for the Ni-Au alloys and described in a previous report.' Cell electrodes were 1/16 in. diam rods swaged from chill-cast ingots and annealed for one week at 850°C. The alloys were prepared by melting fine gold granules under argon with pure iron obtained from the National Research Co. The cell electrolyte was

Jan 1, 1957

By J. P. Zannaras

If we assume that testing of the model started at time t1, that time t2 was the instant at which the elastic limit of the material was passed at the points of the maximum stress, and that at time t3 the failure of the model was completed as shown in the typical photograph (Fig. I), then actually the photograph shows the final results of what took place between time t2 and t3. By the principle of similitude all conclusions drawn from the behavior of the model were applicable and valid for actual mine roofs up to the time t2 after time t2 motions and friction came into play during the destruction of the model. The events between t2 and t3 and the photograph itself are not representative of the events expected in an actual mine roof unless corrections imposed by the principle of similitude are made. It can therefore be stated that all conclusions and observations of the author from the photographs are applicable only to his small-scale experiments and not to actual mine roofs. Without investigation of the true stresses or the combined maximum stress induced in the beds it has been assumed by the author that failure occurred solely due to bending stress caused by loading of the beds. (The author states that D was taken to be the theoretical strain given by elementary beam theory.) Fig. 1 shows that the beds were clamped together. This clamping was necessary to prevent slipping of the beds due to the horizontal shear. However, this clamping caused an uncontrolled and undertermined com-pressive stress S at the end of the beds, and this com-pressive stress caused a true tensile stress ?S (? PoiS-son ratio). This true tensile stress combined with the tensile stress produced at the end of the beds due to loading (fixed beam uniformly loaded), and the horizontal shear which is maximum at the end appears to be the most probable maximum stress produced in the beds. It is therefore evident that the author in performing this experiment has introduced stresses in the model not existing or dissimilar to actual mine roofs, and therefore his conclusions may be applicable to his small-scale experiments but inapplicable to actual mine roofs. Louis A. Panek (author's reply)—The discusser's difficulty is related to mechanics of materials rather than similitude. The effect of time did not enter into the tests in any way, being simply excluded from consideration in this study, because all quantitative results entering into the design equations are based on measured (between time t1 and time t2) bending strains that are well below the breaking strain (i.e., in the elastic range) for the model material. Time does not become a significant factor until the rock stress reaches 80 to 90 pct of the breaking stress." The objective of this investigation was not to predict that bolted roof will fail after time t, but was instead to develop a safe roof, that is, roof in which the bending strain is much less than (say less than 50 pct of) the breaking strain. The models tested to failure had no direct bearing on the design equations. Although for some rocks time may influence the magnitude of stress or strain at which fracture occurs, breaking stress or breaking strain values were not employed for any purpose in this investigation. Tests to failure were made only to obtain additional evidence regarding the behavior of the bolted laminae' as evinced by the locations of the cracks. As stated in the last paragraph of the paper, if one wishes to predict the time or stress conditions for which the roof will fail, additional information is required. The reason for clamping the laminae is to make them behave liked clamped beams, which closely approximate the clamped-plate condition of the actual mine roof beds (Ref. 5, p. 1; Ref. 6). The writer has previously demonstrated that the bending stresses induced by centrifugal loading in a clamped model beam are in agreement with those predicted by theory;' hence clamping has no significant effect on the bending ,trains measured during a test. Moreover, actual ,in, roof beds are likewise subject to a clamping effect due to weight of superincumbent strata carried by the pillars or ribs on each side of the opening. It is emphasized that this study was restricted to evaluating only the reinforcing effect produced by the bolts. Procedures employed in the experiments and in the data analysis were such as to deliberately exclude the effects of other factors. The objections offered are therefore invalid,

Jan 1, 1957