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By Richard J. Borg

The vapor pressure of Cd in equilibrium with CdSb in the presence of excess Sb has been measured using the Knudsen effusion method over the temperature range 276° to 379°C. The free energy of formation of CdSb is given by AF° = -1.58 + 1.53 x l0-4 T, kcal per mole. The enthalpy and entropy are obtained from the temperature coefficient of the .free energy. CADMIUM and antimony have almost imperceptible mutual solid solubility but form a single stable intermediate phase, CdSb. This phase, according to Han-sen,l extends from about 49.5 at. pct to 50 at. pct Cd at 300°C and has the orthorhombic structure. The free energy of formation of CdSb can be calculated from the vapor pressure of Cd for compositions which contain less than 49 at. pct Cd. The appropriate reaction and formulae are given by Eqs. [I] and [2]- CdSb(s, ~ Cd(g)-, +Sb(s) [1] Since Sb is in its standard state, Af - N,,AF'-,, = NcdRT In a,, = NcdRT InP/PO [2] In Eq. [2], P, is the vapor pressure of Cd in equilibrium with the alloy, and Po is the vapor pressure in equilibrium with pure solid Cd. It is implicit in this calculation that the free energy only slightly changes within the narrow limits of the single phase field. Thus, the value obtained from the antimony-rich boundary is truly representative of the stoi-chiometric compound. The results reported herein are obtained from a mixture near the eutectic composition, i.e. 59 at. pct Sb. Only two previous investigations" of the free energy of formation of CdSb have been made. Both relied upon the electromotive force method, and measurements were made over relatively narrow temperature ranges which strongly influences the reliability of the values of AH and aS. EXPERIMENTAL The eutectic composition is prepared by fusing reagent grade Cd and Sb by induction heating in vacuo with the starting materials held in a graphite crucible having a threaded lid. The material obtained from the initial melt is pulverized, sealed under high vacuum in a pyrex capsule, and annealed at 420°C for two weeks. X-ray analysis"gives the following lattize parameters: a = 6.436A, b = 8.230& and c = 8.498A using Cu Ka radiation with A = 1.54056. These values are in fair agreement with the result? previously reported by Al~in:4 i.e. a = 6.471A, b = 8.253A, and c = 8.526A. Vapor pressures are measured using an apparatus which has been described elsewhere,= however, with a single important modification. Knudsen effusion cells are made of pyrex with knife-edged orifices made by grinding the convex surface of the lid on #600 emery paper. Photographs taken at known magnifications using a Leitz metallograph enable the determination of the orifice area. Numerous calibration measurements of the vapor pressure of pure Cd give close agreement with values previously reported5,= thus indicating that no significant error can be ascribed to the substitution of glass cells for metal cells used in previous work. Because the vapor pressure of Cd is reliably established and because it is difficult to obtain Clausing factors for the glass cells, the final values used for the orifice areas are calculated from the calibration measurements of the vapor pressure of pure Cd. Effusion runs are started in an atmosphere of purified helium which is quickly evacuated as soon as the cell attains thermal equilibrium. Less than one minute is necessary to obtain high vacuum after evacuation begins, and the temperature seldom varies by more than 0.5oC from the value obtained prior to pumping out the helium. RESULTS The results of this investigation along with other pertinent data are tabulated in Table I. Fig. 2 is the familiar graph of log P against T-10 K. At least mean squares analysis of the data presented in Table I yields the following equation: log1DJP = 8.790 - 6472 x T"1 [3] The deviations of the individual measurements from the values calculated with Eq. 131 are given in column six of Table I; the average deviation is 4.0% of the calculated value. Although the partial molal properties change significantly with composition within the single phase region, the integral thermodynamic value should remain relatively constant. Hence the results of the following calculations, which use the data obtained for the eutectic composition, are probably representative of the equi-atomic compound. Eq. [4] describes the vapor pressure of pure Cd as a function of temperature and may be combined with Eq. [3] to

Jan 1, 1962

By H. W. Reid

One of the outstanding features of the year was a further marked decline in the footage drilled. This is estimated at 169,000 ft., as against 218,000 ft. for the previous year, and 372,500 ft. in 1930. Owing to repair work and improved production methods, there was an increase of about 4.25 per cent in the amount of oil won, the production being estimated at 10,160,000 bbl., or an increase of 400,000 bbl. over 1931 and nearly 750,000 bbl. more than in 1930. (See Table 1.) At the end of November there were 28 rigs in operation. During the first 11 months of the year 54 new wells were started; the average depth of those completed was 2476 feet. Owing to the continued restriction of drilling programs there has been little of outstanding interest in the way of new plant or technique. The use of the acid bottle, for testing the verticality of wells while drilling, has increased considerably, and this is now in use in practically every well except the very shallowest. During the last six months of the year fairly extensive use has been made of electrical coring. The number of wells started in the Colony up to the end of November, 1932, was 1894. The average number of producing wells during the year was 789, or 41.7 per cent of the total. Of these, 214 were flowing wells, 473 pumping, 80 bailing or swabbing, and 22 were produced by air or gas-lift. Although the last category represents less than 3 per cent of the total, there has been a marked increase in the use of air or gas-lift as compared with 1931. During the year there were 16 companies engaged in producing oil, as compared with 14 in the two previous years. In addition to one small refinery which started to operate at the beginning of the year, the five existing refineries worked continuously. At the latter very little has taken place in the way of extensions, except at one in the Parry Lands—Pitch Lake—Point Fortin area, where extensive alterations and additions are in progress, including the building of a deep-water pipe-line pier. When this is completed there will be five loading terminals, all situated in the sheltered Gulf of Paria, or west, coast, capable of accommodating ocean-going tank steamers. There

Jan 1, 1933

By Alden B. Greninger, Alexander R. Troiano

The crystallographic mechanism for the austenite-to-martensite trensformation has been deduced from the results of the following new experimental determinations: (I) the accurate evaluation of the lattice relationship between austenite and individual crystals of martensite—and thus the relationship between the martensite lattice and the martensite plate, and (2) the measurement and analysis of the change in positions that a volume of austenite unclergoes when it transforms into a crystal of martensite. For the latter study, a new tool was developed, the stereographic analysis of shear. Lattice relationship.—Thirty-five separate 50-gram melts of an alloy containing about 22 per cent nickel and 0.8 per cent carbon were prepared in a high-vacuum furnace. This alloy is all-austenite at room temperature; grain size was about I cm. Specimens of the alloy were cooled to about — 70°C. to form a few martensite crystals, and suitable specimens were ground and polished on a surface parallel to a single martensite plate, exposing the martensite crystal for an area of 1 mm. or more. Four martensite cystals from four diffierent ingots were prepared in this manner; the largest crystal of this group is illuslratecl in Fig. I. Back-reflection Laue patterns were obtained from martensite crystals (and the matrix austenite) both before and after tempering. The locations of the basal-plane pole of martensite was checked by means of oscillating crystal X-ray patterns. All four crystals studied yielded the same solution ( ± 0.5°), and these relationships are expressed in gnomonic projection in Fig. 3.* The narrow dark-etching bands often visible in martensite "needles" were found to be parallel to (112) and thus are undoubtedly twin bands in the martensite crystal.

Jan 1, 1941

By Alden B. Greninger, Alexander R. Troiano

The crystallographic mechanism for the austenite-to-martensite trensformation has been deduced from the results of the following new experimental determinations: (I) the accurate evaluation of the lattice relationship between austenite and individual crystals of martensite—and thus the relationship between the martensite lattice and the martensite plate, and (2) the measurement and analysis of the change in positions that a volume of austenite unclergoes when it transforms into a crystal of martensite. For the latter study, a new tool was developed, the stereographic analysis of shear. Lattice relationship.—Thirty-five separate 50-gram melts of an alloy containing about 22 per cent nickel and 0.8 per cent carbon were prepared in a high-vacuum furnace. This alloy is all-austenite at room temperature; grain size was about I cm. Specimens of the alloy were cooled to about — 70°C. to form a few martensite crystals, and suitable specimens were ground and polished on a surface parallel to a single martensite plate, exposing the martensite crystal for an area of 1 mm. or more. Four martensite cystals from four diffierent ingots were prepared in this manner; the largest crystal of this group is illuslratecl in Fig. I. Back-reflection Laue patterns were obtained from martensite crystals (and the matrix austenite) both before and after tempering. The locations of the basal-plane pole of martensite was checked by means of oscillating crystal X-ray patterns. All four crystals studied yielded the same solution ( ± 0.5°), and these relationships are expressed in gnomonic projection in Fig. 3.* The narrow dark-etching bands often visible in martensite "needles" were found to be parallel to (112) and thus are undoubtedly twin bands in the martensite crystal.

Jan 1, 1941

By R. P. Alger, M. P. Tixier, D. R. Tanguy

In the combination induction-electrical log used at present in the field, the induction logging tool is appropriate for the investigation of moderately invaded formations. A new induction sonde with a radius and investigation about twice as large has been developed recently for the case of deep invasion. It has very nearly the same vertical resolution as the present sonde so that thin beds are defined as accurately as before. The characteristics of the new tool are described, the corresponding interpretation charts are given and field examples are discussed. The design of the sonic logging tool has been modified to improve the calibration and the reliability. The fact that porosity can be accurately recorded by means of the sonic log has prompted new interpretation procedures for saturation estimation, wherein the data concerning the various permeable beds in a given well are correlated. One approach consists of plotting transit time vs true resistivity, with an appropriate scale. With this approach, saturations can be estimated conveniently even in cases where formation water resistivity is not well known. In another approach, a comparison is made of the values of the formation waters computed from the re- sistivity and sonic logs. Using the concept of continuity, this procedure makes possible a quick determination of zones of saturation in shaly sands and/or in case of appreciable variations of formation salinities with depth. It has been found that the comparison of porosity from the sonic log with the apparent porosity computed from a short-investigation resistivity log may reveal, in many cases, the presence of residual oil and thus detect potentially productive formations; this procedure is valuable when the true formation resistivity and the resistivity of the formation water are in doubt. INTRODUCTION During the past year, the efficiency of log interpretation has been vastly improved. The improvements have largely resulted from the introduction of a deep-investigation induction device and from the application of new interpretation techniques that utilize sonic vs resistivity readings. Since the new interpretation techniques depend, in part, upon good values of true formation resistivity, the new induction log will be discussed under Part I. The sonic interpretation techniques will be studied under Part 11. Early in 1959, the 6FF40 induction equipment was introduced in the field. This device was designed for a better approach to true formation resistivities in deeply invaded zones. The greatly improved radial investigation of the 6FF40 equipment has been achieved without sacrificing vertical resolution. The first combination induction-electrical log, the 5FF40, was introduced as a standard tool in 1956 for the logging of wells drilled with fresh muds. The tool has received wide industry acceptance in the United States. 'The 5FF40 induction log has a radial investigation sufficient to overcome average depths of mud filtrate invasion. At 5d invasion, for example, the 5FF40 induction log will read about 1.4 R. in a water sand where R., = 10R,. At 10d invasion, such induction log would read 2.45 R. in the same water sand. In either case, the effects of invasion would not be sufficiently great to cause a water sand to be mistaken for a shale-free oil- or gas-producing zone. Some formations, however, invade deeply — in excess of 10d. Such water zones could be mistaken for oil-or gas-saturated sands unless the porosity balance' can clearly make the distinction. It is for these deeply invaded formations that the 6FF40 was developed. CHARACTERISTICS OF THE 6FF40 Radial Investigation Characteristics To describe the comparative responses of the 5FF40

By T. R. Cass

THE renewed interest in titanium, resulting from its increasing application as a structural material, has stimulated basic deformation studies on this metal. In the course of our work, we have developed a dislocation etchant and applied it to a perfection study of melt-grown single crystals as well as to a preliminary investigation of plastic deformation in titanium. The etchant, Keller's etch (21 cu cm HF, 64 cu cm HC1, 106 cu cm HNO3, and 160 cu cm H20), reveals the emergence of both grown-in and fresh dislocations on pure titanium and a-phase Ti-Al single crystals. Pits are produced only on surfaces within a few degrees of the basal plane; the more exactly parallel to a basal plane the surface is, the more distinct are the pits. The observed pit density, however, does not appear to depend on the surface orientation; the pits simul- taneously become less distinct as the misorientation from a basal plane increases. Etch times are short, a few seconds, for pure titanium; longer times are necessary for alloy crystals.

Jan 1, 1968

C. W. GOODALE, Butte, Mont. (member of the committee)- (communication to the Secretary*).-In the discussion of papers presented at the New York meeting of the Institute in February, 1915, and at the Arizona meeting of September, 1916, I referred to the activities of the Bureau of Safety of the Anaconda Copper Mining Co., and I am now submitting a few thoughts by members of the staff of that Bureau. TORGUS H. OAAS, Safety Engineer, Butte, Mont.-The report of the Committee on Safety and Sanitation has described different organizations and methods of promoting safety work. The effectiveness of these methods would aid the beginner in his campaign for safety in choosing the kind of organization and methods best adapted for his field. This can he obtained only by a discussion by those who have long promoted this kind of work, and have met with successful results. As the field is new, the different organizations promoting safety work have not established a common basis of rating for their fatal, serious and slight accidents, so that it is now difficult to get a comparative basis from which to judge the merits of the different systems. C. W. GOODALE.-The U. S. Bureau of Mines adopted, at the beginning, as a basis for its yearly summaries, the number of accidents. per 1,000 men employed, and it is now (quoting from its report for 1915, Technical Paper 168) making the following "classification of injuries:" "Many of the States now have. compensation laws, and in order to conform with their classifications, the bureau's classification of serious and slight injuries for 1915 is on a 14-day (2-week) basis instead of 20 days, as in previous years. The new classification of injuries includes three types, as follows: 1. Fatal 2. Serious (time lost, more than 14 days) (a) Permanent disability Total Partial

Jan 6, 1917

By T. O. Anderson, E. J. Stahl

Tests to increase knowledge concerning the process of hydraulic fracturing have been performed on three wells in the Allegheny field in western New York. The fracture orientation and its physical appearance at the well-bore was determined by impression packers run at appropriate times throughout the program. Fract~tre azi171uth and its dimensions thus determined were compared to the rock properties and treatment conditions. Logs to provide data concerning rock properties and to improve identification of vertical fractures were run before each step of the fracture treatment. Pressure osc~illu~iot~s were studied after each phase of tile treatments surface pressures during treatment. These measurements show that subsurface pressures exhibit many of the same characteristics as surface pressures during treatment of a well; however, transient pressures are dampened and deelayed in time at the bottom of the well when COmpared with surface pressures. Data obtained from this study provides a means to help locale and determine orientation of vertical fractures made in the open wellbore. Although these rests were performed in only one area, much of the information gained may be applied to fracturing programs in orher areas. INTRODUCTION In this study, various tests were made to provide data to better understand formation fracturing in situ. The reservoir studied is the Richburg oil sand which is a part of a series of predominantly grey sandstones and shales with occasional brown sandstone layers, known as the Caneadea unit of the Canadaway group of Upper Devonian age. Average physical characteristics of 12 cored wells in this area are 13-ft thick gross sand formation, 12-ft thick net sand. 1.7 md permeability, 11 percent porosity, 44 percent oil saturation (before secondary recovery) and 16 percent water saturation (before secondary recovery). This particular area of the Allegheny oil field was originally drilled prior to 1890. The first waterflood secondary recovery attempt was made in 1929. The present sustained waterflood development began in 1951 and is being carried out on a 4.5 to 5-acre spacing. Objectives of these tests were to (I) study fracture azimuth and dimension in relation to rock properties and treating conditions, (2) improve fracture identification techniques, (3) compare surface and subsurface pressure during all phases of treatment and (4) compare the periods of the fluid column oscillations occurring after each phase of treatment. Although the areas of investigation listed appear divergent in purpose, the program was designed primarily to increase knowledge of down-hole conditions leading to rock failure and extension of the fracture thus created. TEST PROCEDURES Wells upon which tests were conducted are designated as Wells 1 through 3. Well 2 was located 440 ft north of Well 1, and Well 3 was located approximately 880 ft west of Well 1. Wells 1 and 2 were completed with cable tools, while the producing interval of Well 3 was rotary cored using fresh water as the drilling fluid to obtain oriented cores. Tests were divided into separate phases on each well as the fracturing program progressed and consisted of measurements performed prior to treatment, during and after the formation breakdown operation. during fracture treatment and after treatment. To verify location and azimuth of the fracture created, and to obtain an impression of wellbore irregularities, a packer was used (Fig. 1). This packer was lowered on tubing into the wellbore opposite the interval under study and inflated in stages to allow the impression material to conform to the wall of the wellbore. A magnetic compass was attached to the tool for orientation reference. Impressions made prior to treatment showed no existing fractures in the wells under study. Impressions made after both formation breakdown and treatment pro-

By Robert H. Hafner, Irvin R. Kramer

In recent years considerable interest has been shown in surface-alloyed metals, particnlarly those of chromium (chromized steels), which have excellent corrosion resistance under a variety of severe conditions, and may undergo bending and flanging operations without spalling. An early method1 employed to produce a high-chromium case on steel was developed by Kelley in 1921. It consisted of heating a low-carbon steel in intimate contact with powdered chromium in the presence of hydrogen at temperatures sufficiently high to permit diffusion of chromium into the steel. The usefulness of this process was limited because the extremely high tem- peratures of 1200º to 1400ºC. (2200° to 2550°F.) caused excessive grain growth and warpage. Louenstein and Ulmer2 packed iron castings in ferrochromium and com- mon salt, and heated for approximately three hours at 930º to 1040°C. (1700º to 1900ºF.). A recent and more practical method of depositing chromium on steel surfaces has been developed in Germany by Daeves, Becker and Steinberg3-8 and in Russia by Izgaryshev and Sarkisov.9 This process consists of passing gaseous chromium chloride over the steel to be chromized at temperatures of 900º to 1000ºC., or packing them in a porous, ceramic material that previously had been saturated with chromium chloride. They reported obtaining a Chromized layer, 0.004 in. thick, on low-carbon steels. Later, Daeves4 established a relationship between the carbon content

Jan 1, 1943

By Robert H. Hafner, Irvin R. Kramer

In recent years considerable interest has been shown in surface-alloyed metals, particnlarly those of chromium (chromized steels), which have excellent corrosion resistance under a variety of severe conditions, and may undergo bending and flanging operations without spalling. An early method1 employed to produce a high-chromium case on steel was developed by Kelley in 1921. It consisted of heating a low-carbon steel in intimate contact with powdered chromium in the presence of hydrogen at temperatures sufficiently high to permit diffusion of chromium into the steel. The usefulness of this process was limited because the extremely high tem- peratures of 1200º to 1400ºC. (2200° to 2550°F.) caused excessive grain growth and warpage. Louenstein and Ulmer2 packed iron castings in ferrochromium and com- mon salt, and heated for approximately three hours at 930º to 1040°C. (1700º to 1900ºF.). A recent and more practical method of depositing chromium on steel surfaces has been developed in Germany by Daeves, Becker and Steinberg3-8 and in Russia by Izgaryshev and Sarkisov.9 This process consists of passing gaseous chromium chloride over the steel to be chromized at temperatures of 900º to 1000ºC., or packing them in a porous, ceramic material that previously had been saturated with chromium chloride. They reported obtaining a Chromized layer, 0.004 in. thick, on low-carbon steels. Later, Daeves4 established a relationship between the carbon content

Jan 1, 1943

By P. G. Sprang, S. Rosen

The Y-Al- C ternary phase diagram for the com -position range from 55 to 100 at. pct Y and for a temperature of 950°C has been constructed from metallographic and X-ray diffraction data. The significant features of the isothermal section which is presented are the small solubility of aluminum in the binary Y3C phase and the presence of a ternary carbide phase with a small homogeneity range around the composition Y3AlC. The similarity in structure and composition between these two carbide phases is discussed in the light of the misci-bility gap which exists between room temperature and 1300°C, which was the temperature range studied. THE occurrence and stability criteria of ternary T3BC, carbide phases having the L'12 structure and the general formula T3BCx have been discussed in detail by stadelmaier1 and more recently by the present authors., Stadelmaier found many representatives of these phases formed between the T metals Mn, Fe, Co, and Ni and the B metals Mg, Al, Zn, Ca, Ge, Cd, In, Sn, Hg, T1, and Pb. The present authors reported on a new series of iso-structural carbide phases formed between the T metals of the Sc group and the B metal, aluminum. These new phases are unique in that many of the Sc group elements form stable binary carbide phases which occur about the composition T3C and which crystallize with a structure similar to that of the T9BCx ternary carbide phases. Furthermore, these binary and ternary phases are found to coexist in equilibrium with each other. The similarity in structure and composition between, for example, Y3C and Y3AlC in the light of the mis-cibility gap which had been found to exist between these two phases indicated a need for a more thorough knowledge of the phase relations which occur in alloys based upon these compositions. Consequently, an investigation of the phase equilibria in the yttrium-rich portion of the Y-A1-C phase diagram was undertaken. The limiting Y-A1 binary diagram determined by Lundin and Klodt3 and the results of Spedding et al.4 governing the Y3C phase were used as guides in , constructing the diagram. EXPERIMENTAL Alloys weighing about 10 g were prepared by arc-melting powder compacts made from the various components on a water-cooled copper hearth using a tungsten electrode in a gettered argon atmosphere. Good homogeneity was obtained by melting the alloys three times. The purity of the yttrium used was 99.9 pct (0.07 pct rare earths). The purity of the aluminum and the carbon was 99.99 pct. The results of chemical analysis on five representative alloys showed that losses during the alloying process were predominantly carbon losses and that in no instance did the measured concentration of this component differ by more than 3 at. pct from the intended composition. For this reason the alloy compositions which are reported are those of the charges prepared for melting. Three alloys which were analyzed for copper, tungsten, nitrogen, and oxygen compositions showed that no contamination had occurred either during casting or during the subsequent annealing treatments. For the major part annealing treatments were carried out on specimens which were placed in

Jan 1, 1965

By George Fowler

THE history of the production of sulfur from salt domes in Louisiana and Texas originated with the operations of the Union Sulphur Co. at Sulphur, La., followed by the Freeport Sulphur Co. at Bryanmound, Tex. Including the present development of Grande Ecaille by the Free-port Sulphur Co., which constitutes the tenth dome to be equipped for the production of sulfur in the Gulf Coast, less than 10 per cent of all the known domes have proved to contain sulfur in commercial quantities. The Grande Ecaille salt dome is in the tidal marsh of the Mississippi River delta in Plaquemines Parish, Louisiana. It is 10 miles southwest of the right descending bank of the river approximately 45 miles below the city of New Orleans and is within 4 miles of the shore line of the Gulf of Mexico.

Jan 1, 1934

By John J. Stokes

Literature on the electrolysis of aluminum from cryolite melts and on the structure of these .melts is surveyed critically. Data on density, freezing point, and other properties are reviewed. Theories of the electrolysis are examined in the light of these data. Two theories are presented which account equally well for the observations. In the early days, the process was thought of as a simple one. The actual mechanisms must be tremendously more complex. This paper is devoted to a rather narrow part of the whole subject, namely, what ions are present in the bath, and by what mechanism the current is carried. Using cryoscopic data, Rolin has determined the following composition for molten cryolite. Na2,AlF 3Na + 3F + AlF [1] He postulates the following equation for the ioniza-tion of alumina at low concentrations Al2O3 Al + AlO2 +O. [2] At concentrations above 0.025M he supposes the ionization of alumina to proceed as follows Al2O3 AlO + AlO2. [3] Rolin's mechanism of electrolysis for the more concentrated solution in Eq. 3 is as follows. The AlO' ion migrates to the cathode. where it is dis- charged, giving metallic aluminum and 0' ions which migrate to the anode. The AlO2- ion migrates to the anode, where it is discharged, giving Al ions and oxygen which reacts with carbon to form CO2 In the case of the extremely dilute solution in Eq. 2 the Al ion migrates to the cathode and the AlO2-and 0 migrate to the anode as before. Another possible mechanism for the electrolysis follows. Ionization of Cryolite Na3AlF4 = 2Na + 2F + NaAlF, Na + AlF-AlF+Na + F [4] Addition of Alumina 2Na2AlF+ 2AL2O4 6Na + 3A12O3F4 [5a] Al2O2F 2AlOF2 [5b] Cathode Process AlF, + 3e+ 4F + Al. [6] Anode Process AlOF2 + 2F AlF1 + 1/20, + 2e or A12O2F + 4F-2A1F; + 0, + 4e. [7] Although both Rolin's and the present mechanism of the Hall process may be qualitatively satisfactory, present data are not adequate for quantitative tests of the theories.

Jan 1, 1959

By R. I. Jaffee, J. G. Dunleavy, H. R. Ogden, Webster Hodge

INTRODUCTION EARLY in 1946, at the instigation of the U. S. Army Signal Corps, the authors made an extensive survey of the available literature covering high-strength, high-conductivity alloys. For the purposes of the Signal Corps, the minimum tensile strength to be considered was 150,000 psi, together with at least 50 pct IACS conductivity. No single alloy was found to be in production, or mentioned in the literature, which had this combination of properties. The constitution diagram for the iron-copper alloys is not well established in the respect to the two-liquid region. Fig I, taken from the 1939 Ed. of the ASM Metals Handbook, shows a two-liquid system existing above the liquidus temperature, but disconnected from it. Although Ruer and Fick1 and Ruer and Goerens2 definitely established the fact that two liquid layers could occur in the system, Ruer3 was not convinced that the line off immiscibility was closed in the center. Maddocks and Claussen4 found no liquid immiscibility at temperatures up to 1570°C in alloys containing almost no carbon. Although the diagram would indicate age hardening of the copper-iron alloys is possible, Hanson and Fords found that little hardening effect could be obtained. However, Gordon and Cohen6 reported that the response is better if the quenching is very efficient. Although iron has a potent effect on the conductivity of copper, Hanson and Ford5 have shown that, when hot-rolled copper iron alloys are aged at 1200°F, the electrical conductivity decreases sharply with iron contents up to 0.2 pct Fe, and then levels off at conductivities between 60 to 70 pct IACS with compositions to 2.1 pct Fe. They also found that aging did not increase the tensile strength, although increasing iron content gave a moderate improvement in strength. High-strength copper-iron alloys, usually containing about 60 pct iron, had been reported by Smith and Palmer.7 They found that an alloy containing 56.4 pct copper, 0.21 pct magnesium, balance iron, would give a maximum tensile strength of 170,000 psi and an electrical conductivity of slightly over 35 pct IACS. The alloy could also be processed to have 150,000 psi tensile strength, and about 41 pct IACS conductivity. Decreasing the iron content increased the electrical conductivity, but the long mushy range during freezing of the alloy containing 10 to 20 pct iron made the production of good castings difficult, In spite of the difficulty encountered by Smith and Palmer with alloys of around 20 pct iron, it was decided to make a rather complete investigation 0f this type of alloy. As a result 0f this investigation, a method of alloying and fabricating copper alloys containing 10 to 15 pct iron was developed

Jan 1, 1948

By Henry M. Otte, Ralph P. I. Adler

The changes of line position and integral line breadth in the X-ray diffraction pattern of a polycvys-talline Cu-30Zn tensile test piece, incrementally loaded (and unloaded) up to fracture, have been an-alyzed in detail. The stacking-fault probahility, cv, increased linearly with increasing strain, E, wheveas the effective domain size, De(hkl), decreased with decreasing E-1 Over the greater part of the stress-strain curve the rate of work hardening was essentially constant (about 86 kg per sq mwz), and could be correlated with the slope of stage II of the single-crystal stress-strain curve. Consequently the theories of work hal-dening (particularly those parts relating to stage 11) as developed by Mott and Hivsch and others could be applied to the observations made on the polycrystalline brass. A relationship of the form Aa = Aao - MhklEhkl between the change, Aa, in the extrapolated lattice pararneter and the rvns strain, Ehkl, was derived and found to fit the results acceptably well. From this and other relationships developed in the papev it was estimated that the equilibrium stacking-fault energy of Cu-30Zn was between 8.4 and 12.5 ergs per sq cm, in fuirly close agreement with the (corvected) value obtained by Howie and Swann (1961)43 using transmission electron microscopy. The theory of work hardening in the jorm developed and recently presented by Hirsch (1964)3 successfully described all the pvesent observations. In order to test certain aspects of the theories of work hardening, as developed by Mott,1 Hirsch,2,3 Seeger et el,4-7 and others (for review see Nabarro, Basinski, and Holt8), several recent investigations have been concerned with relating the dislocation density, p, with the shear stress, 7 (and strain, y), applied to the specimen. The results of these investigations have shown that the square root of the dislocation density appears to be linearly related to the applied shear (or flow) stress for fcc as well as bcc metals and alloys. Furthermore, the relationship appeared to apply not only to the deformation of poly-crystalline specimens, but also to stages I and I1 of the deformation of single crystals. An expression of the form has thus come into wide use. Here b is the Burgers vector for a total dislocation, G is the shear modulus, and 70 and q are constants. A review9 of available values of q shows it to have values (at room temperature) in general between 0.3 and 0.6. Forms of Eq. [1] can be deduced from, or predicted by, the current theories, and the various constants adjusted so that they are compatible with the experimentally found value of q . No unique relationship has yet been found between the dislocation density and the applied shear strain. There are several serious objections to the use of Eq. 11]. In the first place, it relates the shear stress to the density of the dislocations without regard to their arrangement, type, or distribution; the significance of the relation may therefore be justly questioned.5 In the second place, the values of the experimental quantities usually substituted into Eq. [11 are those of the applied shear stress and the total dislocation density measured after unloaditzg. The dislocation density value that should in fact be used is that for the mobile dislocations present in the specimen when under the applied load.* Finally, in cases where the values used for p, the dislocation density, are those obtained by electron microscopy, p is subject to considerable error,' both systematic and random. The corrections to be applied are still controversial. Dislocation densities can also be measured by etch-pit and other techniques,'' each having their specific limitations. An objective of the present investigation has been to obtain information about the dislocation configyration and distribution by analyzing the changes in the position and shape of X-ray diffraction profiles as a function of deformation. The X-ray techniques employed, also open to criticism, have certain advantages, however. Thus, although the X-rays diffract only from the surface layers to an effective depth of about 20 p, the measurements can be made while the specimen is under load. The value of the dislocation density obtained by the X-ray method is also subject to errors, which are different from those of the electron microscope. Though a considerably larger volume of material is sampled by the X-rays, thereby reducing some of the statistical errors inherent in the electron microscope data, the information obtained is less detailed and is dependent on the method of analysis used to obtain a value for the dislocation density. Nevertheless, important observations can be made because the aforementioned advantages outweigh some of the limitations. In the present paper the X-ray method is briefly described and applied to a brass specimens deformed in tension. The results are then discussed in terms of some of the current concepts of work hardening. 1) EXPERIMENTAL PROCEDURE Details have already been extensively published elsewhere11-14 and therefore will only be dealt with briefly here. 1.1) Materials and Specimen Preparation. Commer-

Jan 1, 1968

Under date of Sept. 30, the following open letter was addressed to the Members of the Colorado Section of the American Institute of Min-ing and Metallurgical Engineers by a Colorado Committee: At a meeting of the Colorado Section of the American Institute of Mining and Metallurgical Engineers, held on Friday, Sept. 19, a reso-lution was unanimously passed condemning the Engineers' Licensing Bill passed at the last session of the State Legislature, and requesting the Chairman to appoint a Committee to act in conjunction with the other National Engineering Societies and the Colorado Metal Mining Associa-tion, with a view to securing its repeal at the extra session of the Legis-lature which the Governor has expressed his intention of calling. It may be within your knowledge that the bill in question was passed by the Legislature and signed by the Governor without the knowledge of any of the National Societies, and of few if any of their members. Under its provisions residents of other states cannot even come into this to examine a mine without securing a license, and aliens (among whom are many honored members of, the profession in Colorado) cannot obtain such a license at all. The mining industry in this state needs the coopera-tion of outside engineers, and we should welcome any assistance from them that will tend to develop our resources. To attempt to discourage the activity of visiting engineers will inevitably react on us, and brand the state as being hostile to brains and capital from outside. The difficulty of securing a license will prove a serious handicap to young engineers starting out in the independent practice of their profession. Moreover, a license issued to au engineer qualified in one branch will entitle him to practice in any other: so that the license is apt to mislead the public.

Jan 11, 1919

The entire War Minerals Relief Commission heard the case of the Chas. T. Pyrites & Chemical Company of Georgia on April 15 and 16. The Commission insisted on great detail with regard to the entire enterprise, although the main questions seemed to be of the amount involved. It is considered by the Commission that this claim comes unquestionably under the Act, it is one of the best examples that has been brought to the attention of the Government thus far. Testimony showed that operations were done on the property late in 1916 without request from the Government. Preparations were made to work the pyrites deposit on a comparatively small scale but , following a visit from a representative of the Secretary of Interior and a personal interview of the principal owner of the property and Secretary Lane, operations on a much larger scale were begun. The amounts expended prior to this interview were carefully separated from the expenditures thereafter. Testimony showed that it was the intention of the owners to transport their product by motor truck to the railroad-13 mi. away. This limited shipments to about 50 tons daily. Under the enlarged plan taken against the better business judgment of the owners, a railroad spur at a cost f nearly $200,000 was built to the mine. The operation included a concentrating mill with a capacity f 600 tons daily and an expensive dam to make possible the use of waterpower. With these improvements, the company was just beginning, operation under its enlarged program when the armistice was signed. This resulted in a greatly decreased demand and consequently lower prices, with all prospects indicating that the property could not operate profitably when Spanish pyrites begin to move.

Jan 6, 1919

By F. A. Olson, J. S. Cho, M. E. Wadworth

An infrared study of the states of hydration of MgSO4 revealed a hitherto unreported metustable dehydration state in the temperature range just below that of the stable anhydrous salt. Infrared, thermogvavimetric, and X-ray studies indicated that the state had bisulfate and hydroxide characteristics. A formula fitting all of the experimental evidence is hydrogen-bonded Mg(OH)HSO4, or possibly the chemically equivalent 1/2 Mg(HSO4)2. Mg(OH)2 Infrared spectra of the 7, 6, 1, and OH2O states of hydration are given as well as the spectra of the newly found state which is called the bisulfate state in this paper. Thermogvavimetric studies as a function of water-vapor pressure gave an enthalpy value of 16 cal per mole, and 25 eu for the conversion of the bisulfate state to that of the anhydrous salt. The free energies of the transition varied from 1.76 to 0.18 kcal per mole as the transition temperature varied from 279° to 336°C. The bisulfate state is believed to be of importance in catalytic dehydration phenomena using MgSO4 and may be of interest because of properties in sulfating reactions differing from those of the monohydrate. Also, an analogous state may exist as a hydration state of other sulfates. ANHYDROUS magnesium sulfate is a catalyst with a high degree of specificity for the dehydration of secondary alcohols.1'2 The only product obtained at the usual operating temperature range of 360" to 400°C other than the corresponding olefin is water. Thus, the bonding of water to the anhydrous salt as well as an understanding of the hydration states of MgSO4 became of interest in attempting to understand the catalytic mechanism better. In the process of this study using infrared, X-ray, and thermogravimetric analyses a dehydration state not previously reported was found. Proof of its existence, the nature of the state, and its role, if any, in the catalytic mechanism then became of interest. This paper is concerned principally with the first two aspects of this problem. Magnesium sulfate forms many hydrates, of which the monohydrate and heptahydrate (Epsom salts)3 are most important. Other hydrates4 are known with 1-1/4,5 l-1/2, 5 2, 4, 5, 6, and 12 H2O's. The hydrates with 1-1/4, 1-1/2, 2, 4, and 5 HzO's are unstable. The anhydrous salt is very stable thermally and has a strong affinity for water. It can be heated without additional decomposition to about 800°C.' At 900°C noticeable decomposition takes

Jan 1, 1964

PHILIP D. BLOCK, JR., vice president of Inland Steel Co., visualizes a fine future for the Menominee Range of the Upper Peninsula of Michigan. He sees a future unclouded by threat from foreign ore imports or the development of low grade ore processing in Minnesota. The statement was made during the opening of Inland's new Cayia mine near Crystal Falls. Inland, according to the vice president, is planning to use an increased amount of the high phosphorous ores found on the Menominee Range. He said that other steel companies will probably do the same, because the steel industry has learned how to use ores of high phosphorous content. He said: "I do not mean to imply that we can use an unlimited amount of high phosphorous ores or that we can burden our blast, furnaces with 100 pct high phosphorous ores, but we have reached the point where we can absorb a much larger percentage of these ores without any detrimental effects. Foreign ores and lowgrade Minnesota ores cost too much to offer real competition, Block said. Transportation costs from the Menominee range to steel producing centers in Chicago and on Lake Erie are less than for any other range in this country. In the meantime, the American operators of the Bomi Hills iron ore mine in Liberia, have reportedly signed a new agreement with the Government. Several months ago, President Tubman of Liberia expressed a definite dissatisfaction with the original contract. Informants state that the agreement only needs the approval of the Export-Import Bank, which loaned Liberian Mining Co. $4 million to develop the iron ore properties. Majority stockholder of the Liberian Mining is Republic steel, with 61.57 pct of the stock. Under the new contract, the Liberian Government will start to share in the profits when the indebtedness is liquidated and the return of invested capital accomplished, or April 1, 1957, whichever is earlier. Under the old agreement the Liberian Government received a 5 cent per ton royalty and an additional sum based on the price of pig iron. The royalty rate reached more than 17 cents per ton this year. After debt liquidation the Liberian Government will receive 25 pct of net profits for the first five years; 35 pct for the next ten years; and 50 pct thereafter. Until the Government starts to share in profits it will receive a royalty of $1.50 per ton in U. S. currency, in addition to royalties provided for in the old agreement.

Jan 1, 1952

By Robert M. Dreyer

AGGREGATE With an annual domestic production of over 1.6 billion tons at a value of over $2 billion (see Table 15.1.1), the production of aggregate (crushed rock, sand, and gravel) is a basic industry of utmost economic importance. Because of the role of aggregate materials as essential ingredients of concrete, asphalt surfacing, and plaster, their delivered prices are major factors in determining the cost of construction. The annual domestic production comes from nearly 10,000 plants. About 15% of these plants account for over one-half the production. In a rapidly inflating economy, the average mine sales price of aggregate has remained relatively stable. The actual mine sales prices, however, vary greatly depending on quarrying costs in various parts of the country. Of much more importance in construction costs, however, is the delivered price of aggregate. This varies for each job, depending on the distance from the quarry and resulting transportation costs, as well as the initial cost at the mine. Because of a proliferation of regulations limiting new quarries in the vicinity of the encroaching urban sprawl, the average distance which aggregate must be transported has been increasing rapidly. Although it is impossible to derive an average delivered cost for aggregate, it should be noted that even an increase of only $1 per ton in average delivered cost over the last decade (probably a minimal assumption) would mean an annual cost $1.5 billion higher than ten years ago. In recent years, structural engineering considerations, as well as an increasing use of lightweight concrete blocks, have resulted in a rapidly increasing demand for lightweight concrete and plaster, the essential ingredient of which is lightweight aggregate. Principal lightweight aggregates are: pumice, slag, perlite (thermally expanded hydrous volcanic glass), vermiculite, and expanded shale, formed by the thermal expansion of shale and slate. The United States now has the capacity to expand, annually, over 13 million tons of shale and slate and to expand over 600,000 tons of perlite. In locating a site for aggregate production. the following factors must be considered: (1) tonnage available; (2) quality of aggregate (including local variations); (3) distance from major use areas; (4) transportation costs, including those resulting from present and possible future haulage restrictions; (5) zoning regulations; (6) operating costs, including the cost effects of compliance with local regulations governing blasting, air pollution, water pollution and drainage, noise levels, and operating periods. At one time, locating a suitable site for the production of crushed rock, sand, or gravel, in most areas, was regarded as an extremely simple task. In the past few years, however, finding a site for profitable production of aggregate has assumed ever-increasing com-

Jan 1, 1976