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By Leonard R. Weisberg

The general properties of diffusion in GaAs are reviewed. A total of .fourteen atoms have been studied to date, and activation energies for eleven reported are (in ev): Ga (5.6), As (lo), Zn (2.49), Cd (2.43), Sn (2.5). Mn (2.75). S (4.0). Se (4.2). Ag (0.33), Cu (0.52). and Li (1.0). The dijfusion of the first eight atoms, as measured by Goldstein using radiotracer techniques, established the principle of sub lattice diffusion for both host and impurity atoms, since atoms substituting for gallium have lower activation energies than those substituting for arsenic. The diffusion constant of interstitial copper has been determined for the first time by Hall and Racette using heavily doped p-type samples in which interstitial copper predominates. The anomalous behavior of zinc, which has an abrupt diffusion front and a strong dependence on zinc concentration, has recently been quantitatively explained in terms of an interstitial-substi-tutional equilibrium-diffusion mechanism. Lithium and silver diffuse mainly interstitially, while the diffusion of phosphorus is complicated by the continual formation ofGap. Junction-migration measurements indicate diiferent results than radiotracer techniques, and this is one problem that still remains, together with discrepancies in cadmium-diffusion results, and an unexplained dependence of impurity diffusion on arsenic pressure. BESIDES the usual insights into the behavior of atoms in solids, studies of diffusion in semiconductors have additional importance for device applications. In fact, the amount of diffusion studies performed on a semiconductor might serve as a simple barometer of its technological importance. Thus, the information accumulated for GaAs is not yet quite comparable to that for germanium or silicon, but considerable knowledge is available. The diffusion of at least fourteen atoms has been investigated for GaAs, and the diffusion constants have been determined for eleven of these. Interesting results were found for GaAs that elucidated problems not previously solved for germanium or silicon. For example, the interstitial-diffusion constant for the very fast diffusant, copper, was first measured in GaAs. Also, solutions for interstitial-substitu-tional equilibrium diffusion in extrinsic material were provided first for GaAs, although they are ap- plicable to germanium, silicon, and other semiconductors. Studies in GaAs firmly established the concept of sublattice diffusion, which should have application in many different compound systems. The purpose of this paper is to review briefly the general state of knowledge concerning diffusion in GaAs. First some general aspects of diffusion will be covered, and next attention will be given to the results mentioned above. Diffusion in GaAs has been measured both by radiotracer and junction-penetration techniques, and some discussion will be given of differences in the two sets of results. The comprehensive work of oldsteinl-' has served as the primary reference for the diffusion of well-behaved substitutional atoms in GaAs. Since a review has recently been presented of many of these reults, details of the diffusion data will not be repeated. Neither will any discussion be given of the experimental techniques of diffusion measurements, except to note here, in passing, the simplicity and effectiveness of the precision lapping device employed by Goldstein.' I) EXPERIMENTAL RESULTS AND DISCUSSION A) Summary of Experimental Results. Diffusion constants D = Do exp(E/kT) have been determined for eleven atoms in GaAs: a,' AS,' n,'" Cd,'" n,' n,8 s, e,' Ag,O CU," and i." These results are summarized in Table I. In addition, diffusion was investigated for phosphorus,4'12 germanium,I3 and ilicon,' but Do and E were not determined. Radiotracer techniques were used for most of the studies except for lithium, where a combination of chemical and electrical techniques was employed, and germanium and silicon, where junction-migration techniques were applied. The diffusion of zinc, manganese, sulfur, and tin was also measured using junction migration.13'14 Goldstein demon-

Jan 1, 1964

By O. G. Paasche, Yuan-Shou Shen

THERE is a disagreement among the various authors about the exact manner of transformation of ZrCr2. Rostokerl and others2 stated that ZrCr2 had a C-14 (MgZn2) type of structure below 1000°C and a C-15 (MgCu2) type of structure at temperatures above 1000°C. Alisova3 and others4 reached the opposite conclusion and stated that the transformation temperature is close to the melting point of ZrCr2. A literature survey shows that various investigators3'= who homogenized the specimens at a temperature higher than 1000°C have concluded that ZrCr2 had the C-15 structure at room temperature. Meanwhile, Jordan et al.4 reached similar conclusions without annealing the specimen. Other investigators1,2,6,7 who X-rayed the specimens in the as-cast condition without annealing reached different conclusions. The investigation reported herein was conducted with the aim of exploring the exact manner of transformation of ZrCr2 by various heat treatment tests. The alloys for this examination were prepared from iodide-reduced zirconium crystal bars, 99.9 pct purity, and electrolytic chromium, 99.9 pct purity. They were melted in a nonconsumable electrode arc furnace with water-cooled copper crucible in a helium atmosphere. The melting loss of each alloy was less than 1.5 pct by weight. Chemical analysis of a randomly selected specimen indicated that there was a very close agreement between calculated and analyzed compositions. Before being heat-treated each specimen was encapsulated in a vycor or quartz tube inside which an argon atmosphere was maintained at a pressure of lower than 1 atm. In determining the crystal structure of each specimen with a Debye-Scherrer camera, the standard procedure8 for X-ray quality analysis (Hanawalt method) was followed. The different series of heat treatment tests in this investigation are tabulated in Tables I and 11. The tests in Series I, specimens from 1-1 to 1-9, which were similar to Rostoker's experiment1 indicated that the transformation temperature seemed to fall between 870° and 900°C and that the crystal structure of ZrCr2 at lower temperature seemed to be of the C-14 type. However, once the compound is transformed to C-15 type, it is impossible to reverse the transformation back to the C-14 type by first heating the specimen above 900°C and then annealing it slowly below 900°C as shown in Experiments II-1 to II-3. Thus, it appears that the specimen of ZrCr2 will transform from C-14 to C-15 structure when heated above 900°C but will not transform from C-15 to C-14 when annealed slowly passing 900° C even after the extremely slow cooling process such as indicated in the experiment of Specimen II-3. As a valid transformation temperature is a temperature at which the transformation is reversible, therefore the temperature 900°C (or other temperature close to 900°C) is not the transformation temperature for ZrCr2 and the C-14 structure is not the stable structure of ZrCr2 at lower temperatures. The C-14 structure is retained at room temperature because the transformation to C-15 structure is very sluggish and the fast cooling after melting does not allow enough time for the transformation to take place. Additional energy is required to alter the metastable condition of the C-14 structure. The sluggishness of this transformation was again demonstrated through another series of experiments. Four specimens with C-14 structure were taken. Then they were annealed at 900°C but each specimen was soaked for a different period of time, Table 11. X-ray diffraction patterns of this group indicated that the C-14 structure gradually disappeared as the soaking period was lengthened. The figures listed under the column "C-14 Structure, pct" were estimated from the intensity of the d = 2.330 line of the diffraction pattern corresponding to the structure. Notice that the intensity of this line became weaker for longer soaking periods. To determine the transformation temperature of ZrCr2, specimens with C-14 structure (as-cast condition) were annealed at 1300°, 1400°, 1500°, 1550°, and 1600°C, respectively. A final specimen was first heat-treated to 1500°C in order to transform it to C-15 structure, then heat-treated at 1600°C again. From the X-ray analyses of this series of tests, Specimen Nos. III-1 to III-6, it is evident that a transition from C-15 structure at lower temperatures to the C-14 structure occurs at some temperature between 1550° and 1600°C.

Jan 1, 1969

By C. A. Pierce

STUDIES of roof and floor movement are of interest to those actively engaged in mining. This is especially true in the case of an entirely new area where there is no precedent for guidance. The potash deposit being mined is in the southeast corner of New Mexico, about 20 miles east of Carlsbad. The deposit was formed by the land-locked, shallow, Permian Sea that extended through parts of western Texas, Oklahoma, Kansas, southeastern Colorado, and eastern New Mexico. The saline deposits vary from 500 to 4000 ft. thick. Neither of the companies operating in this area has delimited its com-mercial ore bodies. As all production so far has been from Federal and State leases, the Department of the Interior and the State of New Mexico have a direct interest in the development and extraction of these ore horizons. The ore is composed of an intimate mechanical mixture of sylvite (potassium chloride) and halite (sodium chloride). It lies generally in a horizontal bed varying from 5 to 12 ft. in thickness, and has a cover of approximately 1000 ft., consisting of about 500 ft. of salt beds and 500 ft, of sediments. The immediate mine roof for several feet is principally salt with some potash and clayey material. The next 500 ft. above, from the standpoint of structure, may be considered rock salt with a few inter-bedded potash members. The upper 500 ft. is of sedimentary (Permian and Triassic) origin and contains several water-bearing formations with flows varying from 10 to 500 gal. per minute. This water intensifies the interest in convergence problems as the ore and surrounding for-mations are water soluble. Potash salt (sylvite) and rock salt (halite) are plastic minerals. Plasticity is defined as a "property of solids by virtue of which they hold their shape permanently under the action of small shearing stresses but are readily deformed, worked, or molded under larger stresses."1

Jan 1, 1938

By Joseph T. Singewald

AMONG the genetically interesting iron ores of the United States are those of the St. Francis Mountains near Ironton and Iron Mountain, Missouri. They are specular hematite in porphyry. The Iron Mountain and Shepherd Mountain deposits are generally spoken of as veins and those of Pilot Knob, Cedar Hill, and Russell Mountain as bedded deposits. Iron Mountain has produced nearly 4,000,000 tons of ore and Pilot Knob about 1,500,000 tons. The output of the other three localities has been insignificant. Pilot Knob is no longer worked as an iron mine, but the rock is now being crushed for use as road metal. Iron Mountain has continued as an active producer. In 1927, the property was acquired by the M. A. Hanna Co. and an extensive prospecting and exploration campaign was undertaken, so that the ultimate production of Iron Mountain will doubtless greatly exceed the figures mentioned. Previous Theories of Origin Descriptions of the deposits and theories of their origin have been concerned mainly with Iron Mountain and Pilot Knob, which represent the two contrasting types of occurrence. The Iron Mountain deposits have been considered of close magmatic origin by Whitney' in 18.54, Geijer2 in 1915, and Spurr3 in 1927. Whitney referred to them as of eruptive origin. Geijer considered them fissure fillings at magmatic temperatures. Spurr called them vein dikes formed from ore magma which was essentially fluid iron oxide. Schmidt4 in 1872 ascribed them to fissure filling by thermal chalybeate waters of meteoric origin. Nason5 in 1892 advanced essentially the same explanation. One of the best

Jan 1, 1929

By William Johnson

IT is now recognized that several important types of reactions in metallic systems proceed by the formation of nuclei and the growth of these nuclei. The process of freezing is a simple example of this, as Tammann pointed out years ago.1 Tammann held that ' the rate, of freezing is determined by a rate of nucleation, expressed as the number of nuclei formed per unit volume of unfrozen liquid per second, and a rate of growth of these nuclei, expressed as the linear rate of radial growth in units of length per second. For isothermal freezing the conception is simple; for ordinary freezing, extending over a range of temperature, it is not as simple, for the values of the two constants must change with change in temperature. There is ample evidence that the postulated mechanism is correct even though a quantitative derivation of the rate of isothermal or of ordinary freezing in terms of the two constants has been lacking. In recent years other reactions have been found to proceed in a similar fashion. It has been well established, particularly by Bain,2-8 that. the formation of pearlite from the eutectoid decomposition of the solid solu-tion austenite proceeds in such a way, and Polanyi and Schmid, Tammann and Crone, Karnop and Sachs, and others9-11 have shown that the process of recrystallization proceeds in a similar way. Isothermal reaction rates have been determined for eutectoid decom-position by a number of investigators. Bain's2-8 work on the formation of pearlite from austenite is especially valuable in this respect-the type of isothermal reaction curve obtained, as illustrated in Fig. 13, showed an initial slow rate, accelerating to an intermediate maximum rate which then decelerated to the completion of the reaction; similar curves have been obtained by Wever and his collaborators.12 Other eutectoid decompositions show similar behavior: for example, the decomposition of the beta eutectoid in the copper-aluminum system, studied by Smith

Jan 1, 1939

By Pablo Hadzeriga

Great Salt Lake brine was subjected, in laboratory scale, to conditions simulating solar evaporation. Solid phases and the variation in composition of the liquid phase throughout the potassium salts crystallization zone are presented. These experimental results are discussed and compare with stable equilibrium data of the quinary system Cl-, SO4, Na+, K+, Mg + + and H2O. The Great Salt Lake brine in Utah is a vast reserve of several potential chemicals which has attracted much attention in the recent past. From the standpoint of an ore reserve, it may be said that the lake contains a low grade ore which has to be concentrated by evaporation of water. Because of the fairly favorable weather conditions in the Great Salt Lake area, it seems reasonable to consider solar evaporation as an economical means of concentration. From the view of phase chemistry, the main constituents of Great Salt Lake brine make it belong to the five component system: C1-, SO4=, Na+, K+, Mg++ and H2O. Because of their low concentration, the presence of other elements may be regarded as having little effect on the equilibrium of the five main components. Equilibrium data for the quinary system of our interest has been available for many years. Using these data, it is possible to calculate how the brine of the lake will concentrate when subjected to solar evaporation. In practicing solar evaporation, the weather factor and supersaturation conditions cannot be ignored, but their introduction into calculations using equilibrium diagrams is almost an impossible task. With the experimental work presented in this paper, an attempt is made to compare the stable equilibrium data of the quinary system as applied to the case of the Great Salt Lake brine and the dynamic equilibrium when that brine is subjected to continuous solar evaporation. Sea water brine belongs to this quinary system when only the major constituents are considered. The study of this system has been carried on since the last decades of the nineteenth century. The reason for these intensive studies was to give a geological explanation to the underground potash deposits. AS a result, many theories were presented trying to relate the equilibrium data with the geological formation, paragenesis and metamorphism of these deposits. Two main approaches were followed for the equilibrium studies of this quinary system. One of them, and the best known to us, was the school started in Germany in the last century by J. H. Van't Hoff. The other one, which started about the same time, was the school of N. S. Kurnakov in Russia. Both approaches were different and as a consequence generated opposite theories about the geological formation of potash deposits. The Van't Hoff school studied the quinary system of sea water under careful laboratory control, resulting in stable phase diagrams. During these studies, Van't Hoff recognized the difficulties in crystallizing some double salts.' ". . . . we unexpectedly found that some compounds whose formation in the solutions under investigation was possible at 25°C, nevertheless totally failed to put in an appearance. These, not to mention the calcium salts, were leonite, MgSO4 . K2SO4 4 H2O; kainite, KC1-MgSO4 . 3 H2O; and kieserite, MgSO4 .H2O. Even exceedingly slow crystallization with the addition of the compounds themselves did not remove the condition of supersaturation in the case of these bodies." However, those salts (leonite, kainite, and kieserite) were included in the stable phase diagram at 25°C as shown in Fig. 1 using D'Ans data.3 The figure also shows the sequence of crystallization of the Great Salt Lake brine according to the stable diagram. In later studies by the Van't Hoff school, especially by D'Ans,3 Karsten,4 Autenrieth,5,6 attention

Jan 1, 1968

By I. S. Levy, J. L. Brimhall, B. Mastel

Specimens of' Hastelloy X-280, a low-cobalt version of the solid-solution- hardened nickel-base alloy Hastelloy X, were given a series of thermomechanical treatttzents. They were then Lensile-tested at room temperature and 1350°F. The Microstructures of the specimens tested at 1350°F were studied by electron Microscopy. Microscopy showed that dislocation tangling, caused by the cold working, mas still in evidence after aging-for 24 hr to temperatures as high as 1550oF. (Cr, Mo)23 C6, (Fe, Mo)6 C'. as well us an unidentifiable phase precipitale due to the combination of the thermomechanical treatments and subsequent tensile strain. The room -temperature and 1350°F tensile properties show a general increase ill strength and decreccse in ductility with increusing cold-work level. This is due to the dislocation taangling-. PerLurbatiot~s to this general trend occur- due to solid-solution weakening at the higher cold-work levels as a direct result of the preciplitation reactions. THE requirements for corrosion resistance and high-temperature strength place nickel-base alloys among the more promising materials for advanced nuclear reactor applications. However, when these alloys are irradiated at service temperatures, they generally suffer severe embrittlement'" and reduction in rupture life.3 Certain experimental treatments resulted in improvements in the tensile and stress-rupture properties of Hastelloy X-280, a solution-hardened nickel-base alloy.' To provide a basis for understanding these improvements, unirradiated tensile specimens were examined by electron microscopy. The results are reported in this paper. EXPERIMENTAL DETAILS Material. Hastelloy X-280, a low-cobalt version of Hastelloy X, is a member of the solution-hardened class of nickel-base alloys. The Hastelloy X-280 was obtained from 4- and 1-in: thick plates in the mill -annealed condition. Table I gives the chemical composition of the material as reported by the National Spectrographic Laboratories. ~x~erimental Treatments. Plates of suitable size, 12 by 3 by 1 in., or by + in., were cut under a water jet from the stock material and examined ultrasonic -ally for homogeneity of grain size and absence of voids. The acceptable plates were solution-treated at 2150°Ffor 1 hr and air-cooled. These plates were then reduced in thickness by cold rolling 0, 10, 15: or 20 pct along the original rolling direction. The plates were machined into buttonhead tensile specimens with a gage diameter of 0.125 in., with a gage length of 1.125 in., and with their tensile axes parallel to the rolling direction. The specimens were examined for quality of finish with a penetrant dye, ultra son ically checked for voids, and finally given a dimensional tolerance check with an optical comparator. The acceptable specimens were aged for 24 hr at either 1000" or 1500 F and air-cooled. These specimens were then held at 540°F in a water loop for approximately 18 days to qualify as controls for similar specimens irradiated under the same conditions of time, temperature, water chemistry, and flow rate. Table U summarizes the treatments. These treatments were investigated to establish whether prior precipitation and stabilization of carbide phases at strain sites within the matrix could reduce the amount of carbides available for precipitation at grain boundaries during service. Tensile-Test Conditions. Specimens were tested to fracture at room temperature or 1350 F in air on an Instron tensile-testing machine at a crosshead speed of 0.05 in. per min. The time for the furnace to reach equilibrium at 1350°F was approximately 30 min; soak time prior to testing was 15 min; and test duration was approximately 5 min.

Jan 1, 1968

(There are 67 Student Chapters in the United States, 2 in Canada ) University of Alabama-University, Alabama, Mining & Metallurgical Society, James W Stewart University of Alaska-College, Alaska, Mining Society of the University of Alaska, Guinn Metzger University of Arizona-Tucson, Arizona, Miners' Society, A E Gorum Birmingham-Southern College-Birmingham, Alabama, Pick & Hammer Club, Daniel D Arden University of British Columbia-Vancouver, British Columbia, G M Dawson Club, A Gunning University of California-Berkeley, California, Mineral Technology Association, Bernard York Carnegie Institute of Technology-Pittsburgh, Pennsylvania, The Metals Club, Gerhard Derge Case Institute of Technology-Cleveland, Ohio, Pick and Shovel Club, Gerald M Cover City College of New York-New York, New York, CCNY Student Chapter AIME, Daniel T O'Connell

Jan 1, 1954

By George W. Lower, William A. Hockings, Donald A. Kaczynski

The rate of dissolution of polycrystalline metallic copper in aqueous cupric ammonium nitrate solutions in the non-film-forming region was investigated by the rotating disc method. The investigation was performed in solution concentration ranges applicable to hydrometallurgical processes. This investigation was an extension of a study on the cupric ammonium carbonate system previously reported by Smith, Lower and Hockings, in which the following kinetic model was proposed: (1) Diffusion of cupric ammine ions to the copper surface; (2) Forward reaction - first order reaction of cupric ammine ions with metallic copper; (3) Reverse reaction - disproportionation of cuprous ammine ions to metallic copper and cupric ammine ions ; and (4) Diffusion of cuprous ammine ions from the copper surface. The nitrate system was selected for this study because it simplified the determination of the ionic composition of the solutions. The variables studied were stirring speed and cupric, ammonia, and nitrate concentrations. The dissolution rate increased linearly with at low values of but exhibited increasingly negative deviations from linearity at higher values of m. The rate also increased with increasing cupric concentration but decreased with increasing ammonia and nitrate concentration. Good agreement was obtained between the experimental rate data and the proposed model. Further verification of the model was indicated by the close agreement of the diffusion coefficient calculated from the data and comparable literature values.

Jan 1, 1974

By Ming-Kao Yen

S. E. MADDIGAN*—I think Mr. Yen should be complimented on doing a very excellent and a very comprehensive piece of work. I was particularly pleased to note the use of X rays in a somewhat less tedious technique than pole figures. In the past I think many workers have been diverted away from the use of X rays in such investigations because of the large amount of work involved in pole figures if one is dealing with a great number of specimens. The same thing, I think, applies to the determination of orientations by counting of twins which is also a very tedious procedure; as a result several papers which have otherwise been of excellent quality have depended upon etching techniques for determination of orientation. The present paper indicates that the results reported in those previous papers were correct, but I think the use of etching techniques alone is a rather shaky basis for setting up theories in the literature. W. M. BALDWIN, JR.*—This discussion will be a short note of correction and apology. In my discussion of Brick, Martin and Angier's paper I incorrectly reported the orientation of phosphorus deoxidized copper annealed at temperatures. When I learned that Mr. Yen was preparing the present paper I asked that he correct this previous error, which he most graciously consented to do. However, through my ambiguity the correction noted on p. 59 of Mr. Yen's paper is still not the proper one. For this I take full responsibility. The orientation which I observed in phosphorus deoxidized copper at high temperatures is the (112) [111] which agrees with the pole figure given in Fig 8a, on p. 65 of Mr. Yen's paper. Our observations were made on the basis of twin counts rather than X ray determinations and therefore serve as an independent confirmation of Mr. Yen's data. M. K. YEN (author's reply)—The author wishes to thank Dr. Maddigan for his comments in regard to the application of glancing technique to textures. As a matter of fact, considerable work has been done recently in connection with

Jan 1, 1950

By Paul Weir

BLEACHING clays have been used extensively in the oil-refining industries for a number of years. Their use in water purification is relatively recent and less extensive. They are frequently classified as (1) those naturally active and (2) those active after artificial activation with acid. Fuller's earths fall within the general group of bleaching clays and gradually the commercial term "fuller's earth" has been applied to natural clays originating, for the most part, in the south-eastern section of the United States. Bentonitic clays are usually classed as activable and are prevalent in the southwestern section of the United States.1 Bleaching clays vary considerably in chemical and physical properties throughout the country, or even in different parts of one deposit (Table 1). TABLE 1.-Physical and Chemical Composition of Different Types of Clays Composition, Per Cent Constituents and Properties Bentonite Fuller's Mud Clay (Wyoming) Earth (P Peak)' (Alluvial) Silica (SiO2) 60.0 69.6 61.67 Alumina (Al203) 19.0 14.3 20.34 Ferric oxide (Fe203) 2.8 3.90 7.70 Titanium oxide (Ti02) 0.13 0.70 1.01 Lime (CaO) 0.5 0.80 0.00 Magnesia (MgO) 2.0 1.00 0.24 Soda (Na2O) 2.4 0.40 0.31 Ignition loss 4.7 6.77 8.51 Moisture content 8.0 10.0 20.0 Isoelectric point, pH 9.2 9.2 6.5 Average swelling volume 15.0 0.0 0.0 Weight per cubic foot, lb 55.0 40.0 65.0 Material passing 200-mesh sieve, per cent 90.0 85.0 50.0

Jan 1, 1939

THE activity of the principal oil fields of Rumania followed the same course as in 1939. It was marked by (1) collaboration between the various companies, particularly in exploiting oil at great depths with a view to rationalizing the exploitation and decreasing the difficulties inherent in very deep drilling; and (2) economy in the exploitation of the older pools in reducing to a minimum the cost of the extraction and working over of wells by the concentration of productive wells in groups. The pooling arrangement continued at Tintea as a measure of conservation, and exploitation of the unitized region went forward on the basis of the norms established in 1939. The same methods were applied in the fields of Liesti, Ceptura and Boldesti. The petroleum industry had some difficulty in providing the necessary material and the hands for work. Importation of material and machines from the United States was virtually stopped. Substitutes were provided from Germany but particularly useful were certain dispositions made by the local metallurgical industry. Despite the higher cost of the production of local material and machines, they were superior to the German product, the difference in quality justifying the higher price charged as the materials were found to be particularly adapted for the purposes of the petroleum industry. The cost of production was still further raised by the work that was imposed for national defense. The rise in costs per meter drilled was 50 per cent over those of 1939. According to bimonthly tables furnished by the Moniteur du Petrole Roumain, the deepest well completed in 1940 was an exploratory well, No. 201 of the Concordia company, drilled at Tintea and suspended at 3338 meters. This depth was reached toward the close of 1939 and the well was not deepened in 1940 became of large deviation from the vertical. The record for productive wells had been held by No. 429 at Tintea, drilled by Unirea to a depth of 3200 m., and in 1938 well No. 317 Cocorasti-Mislea, of the Colombia company, but these records were passed in 1940 by well No. 613 Liliesti of the Con-cordia company, which reached a depth of 3294 m. and had an initial production of 10 tons per day. In 1940, the same number of wells, II, had been drilled to a depth of over 3000 m. as in 1939. Five of these wells are at Tintea and six at Liliesti. Table I lists these very deep holes in the order of their depth. Table i.—Deep Wells Drilled in Rumania in 1940 Initial No. Produc- of Company Field Meters tion, Well Meters Tons per Day 405 Colombia......... Liliesti 3,001 10 629 Unireu............ Tintea 3,005 73 426 Unirea............ Tintea 3,050 48 410 Colombia. ........ Liljesti 3,055 30 627 Concordja (Unirea). Liliesti 3,072 75 430 627ConcordjaConcordia (Unirea). (Unjrea 3,II9 30 618 Colombia......... Liliesti 3,168 70 24 Steaua Romana. . . Tintea 3,184 18 412 24Unirea............ Tintea 3,211 23 613 Concordia......... Liliesti 3,294 10 Production in Rumania in 1940 reached 5,813,000 tons, in contrast to 6,~40,0oo tons in 1939, a decline of 427,000 tons, or 6.8 per cent. Drilling reached 241,500 m., in

Jan 1, 1941

THE activity of the principal oil fields of Rumania followed the same course as in 1939. It was marked by (1) collaboration between the various companies, particularly in exploiting oil at great depths with a view to rationalizing the exploitation and decreasing the difficulties inherent in very deep drilling; and (2) economy in the exploitation of the older pools in reducing to a minimum the cost of the extraction and working over of wells by the concentration of productive wells in groups. The pooling arrangement continued at Tintea as a measure of conservation, and exploitation of the unitized region went forward on the basis of the norms established in 1939. The same methods were applied in the fields of Liesti, Ceptura and Boldesti. The petroleum industry had some difficulty in providing the necessary material and the hands for work. Importation of material and machines from the United States was virtually stopped. Substitutes were provided from Germany but particularly useful were certain dispositions made by the local metallurgical industry. Despite the higher cost of the production of local material and machines, they were superior to the German product, the difference in quality justifying the higher price charged as the materials were found to be particularly adapted for the purposes of the petroleum industry. The cost of production was still further raised by the work that was imposed for national defense. The rise in costs per meter drilled was 50 per cent over those of 1939. According to bimonthly tables furnished by the Moniteur du Petrole Roumain, the deepest well completed in 1940 was an exploratory well, No. 201 of the Concordia company, drilled at Tintea and suspended at 3338 meters. This depth was reached toward the close of 1939 and the well was not deepened in 1940 became of large deviation from the vertical. The record for productive wells had been held by No. 429 at Tintea, drilled by Unirea to a depth of 3200 m., and in 1938 well No. 317 Cocorasti-Mislea, of the Colombia company, but these records were passed in 1940 by well No. 613 Liliesti of the Con-cordia company, which reached a depth of 3294 m. and had an initial production of 10 tons per day. In 1940, the same number of wells, II, had been drilled to a depth of over 3000 m. as in 1939. Five of these wells are at Tintea and six at Liliesti. Table I lists these very deep holes in the order of their depth. Table i.—Deep Wells Drilled in Rumania in 1940 Initial No. Produc- of Company Field Meters tion, Well Meters Tons per Day 405 Colombia......... Liliesti 3,001 10 629 Unireu............ Tintea 3,005 73 426 Unirea............ Tintea 3,050 48 410 Colombia. ........ Liljesti 3,055 30 627 Concordja (Unirea). Liliesti 3,072 75 430 627ConcordjaConcordia (Unirea). (Unjrea 3,II9 30 618 Colombia......... Liliesti 3,168 70 24 Steaua Romana. . . Tintea 3,184 18 412 24Unirea............ Tintea 3,211 23 613 Concordia......... Liliesti 3,294 10 Production in Rumania in 1940 reached 5,813,000 tons, in contrast to 6,~40,0oo tons in 1939, a decline of 427,000 tons, or 6.8 per cent. Drilling reached 241,500 m., in

Jan 1, 1941

By W. F. Dietrich

Mineral fillers are relatively inert chemically under the conditions of use but have physical properties* that modify those of the materials • The properties. uses, and other data on 15 classes of important *The pro listed in the second edition of Industrial Minerals and Rocks.l A third edition of this reference is in preparation. in which they are incorporated. The mineral fillers considered in this article are asbestos, barite, clays, diatomite, crushed limestone, limestone whiting and lime, mica, silica, talc and soapstone, and pyrophyllite. Slate and stone, other than limestone and its derivatives, are excluded because, even though used in large quantities, they are exceptionally low-cost materials generally produced close to the area where they are used. Carbon black is excluded because it is manufactured from natural gas and more than 90 pct of the output is used in rubber; hence the factors for estimating requirements are easily evaluated. OVERALL GROWTH FACTORS Table I gives the population, retail sales, and value added by manufactures in the U. S. and in the eleven western states in 1954. These data are rough guides to the proportionate part of total U. S. markets for products containing mineral fillers that may be expected in a given area. For example, the population of the eight Mountain states in 1954 was 3.6 pct, and retail sales in these states were 3.8 pct of the U. S. total, but the value added by manufactures was only 1.3 pct of the U. S. total. On the other hand, the three Pacific Coast states, with 10.3 pct of the total population, had 12.0 pct of the retail sales and produced 9.6 pct of the value added by manufactures. On an industry-by-industry basis the correlation between the three guideposts will not be as close as shown in the 1954 data for the Pacific Coast states, but in the long-term view the continuing rapid population growth in the western states is certain to result in expanded industrial production at an even more accelerated pace, which will shorten the gap between local consumption and production in most major groups of manufactured consumer goods. Of course, there will always remain favorable areas for production of specific products. Such special situations must be individually analyzed. Fig. 1 compares the population trends in the U. S., the western states, and California with Real Gross National Product from 1910 to 1957, with forecasts to 1970. It is estimated' that the U. S. Real Gross National Product, as measured by the value of goods and

Jan 1, 1960

ANNUAL MEETING OF THE NEW YORK SECTION - The annual meeting of the New York Section was held at the Machinery Club, May 7. While the dinner, at which fifty attended, was in progress, the names of the nominees for next year's officers were posted. The result of the election was as follows: Chairman, E. P. Mathewson; vice-chairmen, William Y. Westervelt, R. M. Atwater, Jr.; treasurer, Wilber Judson; executive committeemen, Lucius W. Mayer, Edwin S. Berry. The subject for the evening was "Organization and Campaign in France of the 27th Engineers." Colonel O. B. Perry described the many difficulties surmounted, for it was necessary to work with untrained men ALLEN H. ROGERS WALTER S. DICKSON CHAIRMAN OF NEW YORK SECTION SECRETARY OF NEW YORK SECTION and shortage in supplies. He described the unusually fine character and physique of his officers, which made it possible to make the untrained men most efficient. He described in some detail the work of building bridges over the Meuse River and the bringing up of supplies to the first army base, in particular at the Argonne-Meuse sector; General Pershing gave a personal commendation of the work undertaken by this regiment. The Colonel described the methods of operating the transportation of ammunition and supplies to the "army dumps," by which at the time of signing the armistice there had been brought up 600,000 tons of equipment for use in the projected campaigns. An interesting item was that 3,600,000 sand bags had been provided, in case the Germans should be able to turn the line of the American troops. Captain Edwin S. Berry described the methods of sending materials to the front lines and gave figures to indicate the huge quantities required, adding that the order of preference was troops, ammunition, food, and engineers' supplies. The speakers then answered several questions given by the members present. WALTER S. DICKSON, Secretary.

Jan 6, 1919

By P. E. Demmler

Phosphorus combines with copper in various proportions, forming true alloys, some of which are of commercial importance. These materials find wide application as deoxidizers and as a means of introducing phosphorus into other alloys, as in phosphor-bronze. Phosphor-coppers containing 10 and 15 per cent. of phosphorus are the commercial grades that are most generally offered. Each has certain advantages when used in making other alloys. The 10 per cent, grade of phosphor-copper has an advantage over the 15 per cent. in that it has a much lower melting point and can be prepared by certain methods with a much lower loss in phosphorus. The 15 per cent. grade has the advantage of lower freight rates per unit of phosphorus and, by the method to be described, a uniform product can be prepared with practically no loss of phosphorus. Alloys of copper and phosphorus containing any desired percentage of phosphorus lower than 15 per cent. can be prepared by melting together the requisite amounts of copper and 15 per cent. phosphor-copper. Processes for making phosphor-copper may be divided into two classes as follows: (1) Those depending on the smelting of phosphate rock or superphosphate of calcium with copper or copper-bearing materials, and coal or other carbonaceous material; (2) those depending on the direct combination of metallic copper and elemental phosphorus. A number of formulas for preparing phosphor-copper according to the first method have been published. The Metal Industry' gives the following: Superphosphate of calcium, 60 lb.; granulated copper, 30 1b.; finely powdered coal, 10 1b. Similar formulas are given by Brannt2 and others, and detail variations are covered by patents, such as those of L. A. Jeffs3 and H. A. Webster.4 Among the objections to this method of producing phosphor-copper are the large amounts of raw material and resulting slag to be handled, and the difficulty of getting a satisfactory fusion. S. Skowronski5 found that at 1300' C. (2372' F.) it was impossible to get a good fusion

Jan 1, 1921

By T. R. Ingraham

The thermal decomposition of Nickel (II) sulfate was examined by determining the total pressure of SO3, SO2, and O2 developed over a sample when it was heated in an evacuated system fitted with a Pyrex-bellows mercury manometer. The equilibrium pressures were combined with previously published data on the oxide and sulfide systems to establish a predominance volume diagranz for the Ni-S-O system over the normal range of roasting temperature and gas composition used in the treatment of nickel minerals. The protective coating of NiSO4 which forms on the oxide during roasting, and which causes the sulfation reaction to almost cease, may be disengaged readily by temperature cycling. When nickel sulfide is roasted in air, either nickel sulfate or nickel oxide may be formed by altering the experimental conditions. Because of the differing stabilities of various metal sulfates and oxides, possibilities exist for separating some of the constituents of mineral mixtures by the technique of selective sulfation and oxidation roasting. The experimental information required to make reasonable predictions of the possibilities of this technique is incomplete and, in some cases, in conflict. As part of a general program of providing some of the required information, a study EXPERIMENTAL Materials, Apparatus, and Procedure. Fisher certified reagent-grade nickel sulfate hexahydrate was used in the source material for both nickel sulfate and nickel oxide. The manufacturer's analysis indicated: 0.001 pct Fe, 0.005 pct Cu, 0.003 pct Co, 0.001 pct C1, other 0.15 pct. The material was dehydrated, before use, by heating at 420°C for 5 hr. The oxide was prepared by roasting the sulfate in an open tray in a muffle furnace for 10 hr at950°C. Preliminary experiments which were made by thermogravimetric analysis and X-ray diffraction analysis established that only one crystal form of nickel oxide and one of nickel sulfate were involved in the equilibrium shown in Eq. [I]. The apparatus used in the experiments was described previously.1,3 The main feature is a corrosion-resistant, flexible Pyrex bellows which is used to protect the mercury in a u-tube manometer. Before a run was begun, the apparatus was washed thoroughly with hot hydrochloric acid and water and dried by heating under vacuum. The mixed sulfate -oxide sample was contained in a platinum bat rest-

Jan 1, 1967

By Morris J. Elsing

FOR MANY YEARS lead and zinc have had the so-called protection of a tariff and it is the purpose of the following brief discussion to show what' such protection actually accomplishes with a view to forecasting the possible results of the present copper tariff. In analyzing the subject, tabulations of the United States production, consumption, imports and exports, including ore and concentrates and all of the metallic products, of both lead and zinc have been made for each year since 1900. Of these data, the relationship of the imports and exports and the relative foreign and domestic prices are shown in Table 1. The conclusions drawn from these figures are listed below. 1. The United States is an exporter of zinc. 2. The United States is an importer of lead. 3. The average price of zinc at St. Louis for the last 32 years has been no higher than on the London market even though zinc and zinc ore have "enjoyed" a protective (?) tariff of varying amounts per pound for 22 years of this period. 4. The average price of lead on the New York market for 32 years has been 1.2c. per pound higher than on the London market, the tariff varying from 0.75 to 1.5c. per pound of lead in ore, and 1 to 2c. or more on manufactured lead.

Jan 1, 1932

By Paul Gordon

The distribution coefficient, k, of interest in zone refining is generally defined as the ratio of the solid to the liquid solubilities of one element in another at the normal melting point of the solvent. In practice, distribution coefficients are frequently calculated from solubilities at temperatures well below the melting point of the solvent, e.g., at a eutectic temperature. This is done because of the general lack of accurate data on the liquidus and solidus curves in most phase diagrams. The practice is equivalent to assuming that the liquidus and solidus curves are straight lines in the temperature range between the melting point of the solvent and the temperature at which data for the solubilities are known. It is recognized that the k values so derived may be in serious error; we have found evidence in recent zone-refining operations that a case in point is silicon in aluminum. The phase diagram found in the literature for silicon in aluminum indicates a eutectic on the aluminum-rich side at 12.5 at. pct Si and at 577°C,1 and a solid solubility of silicon in aluminum at this temperature of 1.59 pct.2 It also shows the liquidus and solidus as nearly straight lines from 577°C to the melting point of aluminum (660°C)1,2 The k value obtained from this data is 0.13. This is almost exactly the same as the k value (about 0.14)' obtained in a similar way for copper in aluminum. Yet we have found by mass-spectrograph analyses* of three bars of zone-refined aluminum that copper is efficiently removed from aluminum by zone refining but silicon is not. Two of the three bars of aluminum were zone-refined in our laboratories, the other in the laboratories of AIAG Metals, Inc. The former two bars, designated bars PG2 and PG3, were 30 in. long by 1 in. in diameter during refining; each was processed in a high-purity graphite boat* and kept under refining stage of the process consisted of thirty unidirectional zone traverses at rates of about 1 to 2 in. per hr, with a zone length of 1 to 2 in. At approximately the middle of the refining period a 6-in. piece of the impurity-laden finishing end of the bar* was cut off and replaced with new start- ing material. Following refining, the purest 20-in. section of the bar (obtained by discarding approximately 2 in. of the starting end and 8 in. of the finishing end of the bar) was leveled and then analyzed. The AIAG bar was 16 in. long and about 1.2 in. in diameter; it was purified by eight passes of a 2-in. zone at a rate of 1.6 in. per hr, the bar being contained in a sintered alumina boat lined with loose alumina powder of the highest purity. Data for the silicon and copper contents of the three refined bars are given in Table I. Derived data for the efficiencies of the zone-refining operations are listed in Table 11. It is clear from these two tables that the copper is removed much more efficiently—by a factor of 10 to 50 times—from aluminum during zone refining than is silicon. For example, in bar PG3 the thirty zone passes reduced the copper content from 10 to 0.02 ppm, i.e., by 500 times, whereas the same treatment lowered the silicon content by only a factor of about 16. It seem virtually certain, therefore, that the distribution co efficient, k, for silicon in aluminum is well above that for copper and is very likely not much below unity. This also implies that the solidus line on the aluminum-rich side of the A1-Si phase diagram is very probably appreciably curved near the aluminum melting point since the phase-diagram data indicate such curvature is unlikely in the liquidus.

Jan 1, 1965

By B. Haimson, C. Fairhurst

A criterion is Proposed for the initiation of vertical hydraulic fracturing taking into consideration the three stress fields around the wellbore. These fields arise from (1) nonhydrostatic regional stresses in earth, (2) the difference between the fluid pressure in the wellbore and the formation fluid pressure and (3) the radial fluid flow through porous rock from the wellbore into the formation due to this pressure difference. The wellbore fluid pressure required to initiate a fracture (assuming elastic rock and a smooth wellbore wall) is a function of the porous elastic constants of the rock, the two unequal horizontal principal regional stresses, the tensile strength of the rock and the formation fluid pressure. A constant injection rate will extend the fracture to a point where equilibrium is reached and then, to keep the fracture open, the pressure required is a function of the porous elastic constants of the rock, the component of the regional stress normal to the plane of the fracture, the formation fluid pressure and the dimensions of the crack. The same expression may also be used to estimate the vertical fracture width, provided all other variables are known. The derived equations for the initiation and extension pressures in vertical fracturing may be employed to solve for the two horizontal, regional, principal stresses in the rock. INTRODUCTION Well stimulation by hydraulic fracturing is a common practice today in the petroleum industry. However, this stimulation process is not a guaranteed success; hence, the deep interest shown by the petroleum companies in better understanding the mechanism that brings about rock fracturing, fracture extension and productivity increase. Geologists and mining people became interested in hydraulic fracturing from a different point of view: the method may possibly be employed to determine the magnitude and direction of the principal stresses of great depth. Numerous articles in past years have dealt with the theory of hydraulic fracturing, but they all seem to underestimate the effect of stresses around the wellbore due to penetration of some of the injected fluid into the porous formation.1-4 Excellent papers on stresses in porous materials due to fluid flow have been published5,6 but no real attempt has been made to show the effect of these stresses in the form of a more complete criterion for vertical hydraulic fracturing initiation and extension. This paper is such an attempt. ASSUMPTIONS It is assumed that rock in the oil-bearing formation is elastic, porous, isotropic and homogeneous. The formation is under a nonhydrostatic state of regional stress with one of the principal regional stresses acting parallel to the vertical axis of the wellbore. This assumption is justified in areas where rock formations do not dip at steep angles and where the surface of the earth is relatively flat. This vertical principal regional stress equals the pressure of the overlying rock, i.e., S33 = —pD, where S33 is the total vertical principal stress (positive for tension), p is average density of the overlying material and D is the depth of the point where S33 is calculated. The wellbore wall in the formation is considered to be smooth and circular in cross-section. The fluid flow through the porous elastic rock obeys Darcy's law. The whole medium is looked upon as an infinitely long cylinder with its axis along the axis of the wellbore. The radius of the cylinder is also very large. Over the range of depth at which the oil-bearing formation occurs, it will be assumed that any horizontal cross-section of the cylinder is subjected to the same stress distribution, and likewise that it will deform in the same manner. STATE OF STRESS PRIOR TO DRILLING OF WELLBORE At a depth D from the earth surface within the oil-bearing strata, it is assumed that the following are 1References given at end of paper.