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By K. R. Janowski, A. B. Chase, E. J. Stofel

Ruby crystals of exceptional optical quality have been grown from fluxes composed of Bi2O3 + PbF2 or Bi2O3 + BiF3. Careful control of growth conditions was required to minimize the number of growth defects consisting primarily of dislocations, occluded flux, and growth twins. Slow growth rates coupled with the addition of small amounts of La2O3 as a flux dopant were helpful in producing nearly perfect crystals. Chromium concentrations up to 1 pet were incorporated into these crystals without adversely affecting their perfection. Crystals up to 10 mm in diameter having as few as one to ten dislocations per crystal were typical of those produced under optimum growth conditions. Under these same conditions the occlusions were eliminated, and growth twins were either eliminated or reduced to one to three twin boundaries per crystal. INTEREST in the nature of lattice imperfections produced during the growth of ruby crystals (Al2O3-corundum structure) has been stimulated recently by the need for ruby lasers of good optical uniformity. As a result, ruby crystals grown by the flame-fusion (Verneuil) process have been studied in detail and have been found to contain high densities of dislocations (106 to 107 dislocations per sq cm) and mosaic structures that impair their optical quality.'-3 Attempts to improve the quality of Verneuil-grown crystals by controlling the growth variables have not been entirely successful. On the other hand, rubies grown by the flux process have received little attention even though their more nearly equilibrium growth conditions suggest that they would have fewer growth defects. Nelson and Remeika have shown recently that small flux-grown rubies can indeed be made into very low-loss lasers. However, they did not report information on crystalline imperfections in these crystals.4 Stephens and Alford have reported briefly on defects found in a flux-grown corundum crystal but they neither described these defects in detail nor related them to the method of growth.5 The present investigation was undertaken to establish the relationship between growth conditions and crystalline perfection of flux-grown rubies, sapphires, and other crystals of the corundum family. EXPERIMENTAL PROCEDURE The corundum crystals used in this study were grown by slowly cooling solutions of A12O3 in molten-salt solvents of PbO + PbF2, Bi2O3 + PbF2 or Bi2O3 + BiF3. The materials employed were Linde A (a Al2O3 powder) with reagent-grade chemicals as solvents. Some of the solutions also contained small additions (1 pet or less) of one or more of the transition metal elements chromium, manganese, iron, and titanium as crystal dopants. La2O3 was added to some of the solutions to alter the growth habit of the crystals. The La2O3 promoted the occurrence of growth facets parallel to (0112) and {1011} planes, where the indexing system is the morphological system described in detail by Kron-berg6 and used throughout this paper. The melts from which the crystals were grown were prepared by mechanically mixing the various constituents and placing them in platinum crucibles. The covered 50- and 100-ml platinum crucibles were heated in muffle furnaces at 1250°C for short periods of time (1 to 4 hr) and then program-cooled at either 2° or 4°C per hr to 1000°C. At this lower

Jan 1, 1965

By P. D. Southgate

VIBRATION, both ultrasonic and sonic, can affect the course of a variety of metallurgical processes. Reports of work on this subject have appeared at intervals over the last twenty years and a thorough review has been made by Hiedemann,' who gives a full list of references. It has been established that both refinement of structure and outgassing of the melt can be produced in most metals with sufficiently intense vibration. Many of the experiments in this field have been carried out using alloys of direct commercial interest in production- type casting equipment. Here a different approach is adopted, and simple binary alloys which exhibit different types of structure are used to facilitate examination of the effects produced under well-controlled conditions. Results from this kind of experiment should enable the basis of larger scale experiments with similar types of materials to be better substantiated. The alloys selected for this work are: 1) aluminum of 99.2 pct purity, the principal impurity being iron, near 0.4 pct; 2) A1-1.8 pct Fe, which is near eutectic composition; 3) A1-4 pct Fe—the second phase, of composition FeAl3, forms distinct acicular crystals; and 4) A1-12 pct Si—although this is of eutectic composition, the silicon normally appears in the form of large plates. Experimental Method There are three practicable methods by which acoustic vibration can be transferred to liquid metals: a) vibration of the whole of the container; b) electromagnetic induction; and c) insertion of a vibrating probe into the liquid. Method c is chosen here, and a frequency of 8 kc per sec is used. The end of the probe is electrically heated so that the metal near it will be the last to solidify. This ensures that vibration is transmitted directly to the liquid metal without passing through any solidifying and pasty intermediate region, which would attenuate acoustic waves severely. In addition, the heating prevents solid metal adhering to the probe, with consequent detuning. The transducer assembly is shown in Fig. 1. A stack of Permendur laminations 30 cm long acts as a half-wave vibrator and a winding along its length carries polarizing and energizing currents. It is joined by a half-wave coupling bar to a mild steel exponential horn, which tapers from 3.8 to 1.1 cm diam. A stainless steel stub 3 cm in length is welded on the free end. The assembly is supported by a plate located at the node of the coupling bar. Acoustic radiation losses are minimized by allowing the free end of the transducer to protrude above the surface of the cooling water. The exponential horn serves the function of matching the acoustic output impedance of the transducer to the radiation resistance of the probe into the melt. Electrical drive is provided by a 1 kw generator. Measurements of probe vibration amplitude during melt treatment are obtained from a gramophone pick-up with the needle attached to the wide end of the horn. This device is calibrated with a microscope before use. Liquid aluminum is very actively erosive and solution of materials with which the molten metal comes into contactcauses difficulties. Erosion of the probes in particular can be severe since it is greatly accelerated by the vibration. Tests of various acous-

Jan 1, 1958

By S. A. Braley

THE first commercial production of bituminous coal in the United States was in 1820, and formation of acid in the areas from which the coal was removed began at that time. Thus it is 130 years since the development of mine acid began. The coal operator has had to deal with the acid water produced in his mines, and his losses from corrosion of pumps and equipment have been tremendous. Other industries and the public have been forced to spend large amounts for their water requirements because of the acid discharge from the mines. There are many contradictions in the literature on this subject probably because of variations in the analytical procedures followed and differences in the methods of calculation and reporting. The opinions previously expressed may be summarized as follows: The production of mine acid has been looked upon as a simple chemical reaction wherein the oxygen of the air has reacted with pyrite to produce ferrous sulphate and free sulphuric acid. This reaction appears in many chemistry texts and generally has not been considered worthy of further study. Since the measurement of hydrogen ion concentration or activity was developed and expressed in terms of pH, indicator and instrumental methods for pH determination have become readily available, making it natural to think of it as a measure of acid content. Special purpose analytical methods applicable to potable waters, sewage effluents, and boiler waters, based in general upon the determination of what may be regarded as impurities, have been applied to more concentrated solutions constituting mine discharges, without reference to the fact that these specialized procedures had been developed to serve as operating guides for water-treatment plants. It has been assumed that the pounds of acid deliv- Table I. Showing pH and Titratable Acid of Varying Concentrations of Ferrous and Ferric Sulphates Ferric Ferrous ion Acldfty Ion Acidity (Fe+++) ppm CaCO3 We++) ppm CaCOa ppm PA equiv. PPm pH equiv. 11.200 1.80 30,000 11,200 3.98 20,000 5,600 2.01 15,000 5,600 4.15 10,000 2,800 2.21 7,500 2,800 4.41 5,000 1.120 2.48 3,000 1,400 4.68 2.500 560 2.60 1,500 140 5.00 250 280 2.65 750 28 5.00 50 112 2.81 300 56 3.07 150 28 3.38 75 ered by a mine was roughly a constant varying with the number of acres mined, and that the concentration of the acid in the drainage was inversely proportional to the volume of flow. Increased flow was thought to result in a dilution of the acid produced. When the Sanitary Water Board of the Commonwealth of Pennsylvania established a fellowship at Mellon Institute, the first approach to the problem was to review some of the chemical reactions involved and their relation to acid production. Since the sulphates of iron were among the principal constituents of coal-mine drainage, the first studies were based upon solutions of chemically pure ferrous and ferric sulphate. These are both neutral salts, that is, the iron and the sulphate are equivalent, but they produce acid reactions in water solution because as salts of strong acids with weak bases, they hydrolyze to form acid solutions. Solutions of each salt, of varying concentrations, were prepared and the pH, titrable acidity and iron and sulphate

Jan 1, 1952

By B. R. Banerjee

MATERIAL used throughout this investigation was high-purity aluminum (99.998 pct). The 1/2-in. cubes were cut out of a cold-rolled slab and annealed at 550°C for 1 hr before deformation. The single crystal specimen was 1 in. in diam x 0.33 in. thick, cut from a cylindrical crystal produced by cooling at about 55°C per hr in a furnace which had a convenient gradient of about 10°C in every 4.5 in. vertical crucible length. Specific data on the ten specimens studied are summarized in table I. Three types of deformation were employed: (I) compression in a hand-operated hydraulic press; (2) impact with a 7-lb sledge hammer; and (3) rolling, using a wedge-shaped specimen' to obtain a gradient of deformations varying from 0 to 50 pct along the length of the wedge. Specimens were either deformed at room temperature, or first cooled in a freezing mixture of dry ice and ether at a temperature of —72°C and then deformed between steel blocks cooled with dry ice. The specimens deformed at the low temperature were ground and polished through 000 emery paper and wheels impregnated with alundum and alumina No. 1. During this entire procedure the specimens were dipped frequently in the freezing mixture of dry ice and ether in order to maintain constantly a frosty surface as insurance against overheating. All specimens were given a final electrolytic polish, using two different electrolytes* to insure that the surface effects observed were not char- acteristic of the polishing technique. With both electrolytes, the annealed specimens gave even surfaces with good polish. Several standard etchants were tried without success. The best results were obtained with an immersion etchant, developed in this connection, containing: hydrofluoric acid, 4 parts; nitric acid, 1 part; glycerine, 3 parts. Discussion of Results Typical strain markings have been observed within deformation bands, as shown in figs. 1, 2, and 4. By stereographic plotting of metallographic measurements, the strain markings within a deformation band in a single crystal of aluminum deformed by compression were found to be traces of (111) planes within a maximum scatter of 6". The edges of the deformation band were found to be traces of the (100) planes also within the maximum scatter of 6" (in agreement with previous workers). At 30 pct deformation, this scatter was considered quite normal because of the fragmentation and rotation of the crystal. This solution, based on the traces on one plane of observation is not unique, but as the planes were observed to be those normally and logically to be expected, further work in this regard was not felt to be necessary. The study of strain markings in a wedge-shaped specimen, rolled to obtain a gradient of deformation from 0 to 50 pct, revealed prominent strain markings at 25 pct reduction in thickness (fig.5). Faint and weak strain markings were visually observable up to a minimum reduction in thickness of about 12 pct. Since strain markings have been observed in other face-centered cubic metals after much smaller deformations;1, 2 and since the rate of recovery in aluminum is high, it is believed that, at lower deformations, self-recovery removes the localized strains at the slip interfaces, thus removing the source of the etching effects that give rise to strain markings. At high magnifications, strain markings sometimes seem to appear as very thin, light-banded re-gions bounded by a pair of dark edges. This so-

Jan 1, 1951

By D. R. Spink

In the preparation of zirconium and hafnium metals, there are many indications that impurity levels control the physical and chemical properties of the metal. The purpose of this work was to develop methods of producing pure raw materials that could be reduced to highly pure metals. Early work by the Carbomcndum Metals Co. and others indicated that certain fused salts were highly efficient in the removal of impurities from gaseous zirconium tetrachloride. We have developed workable fused salts along with a continuous and higly efficient scrubber design which can be used to produce very pure zirconium tetrachloride. Metal made from the purified tetrachloride has been shown to approach crystal bar metal in purity. Scrubber designs are discussed with recommended materials of construction. VARIOUS methods have been used to purify zirconium (and hafnium) tetrachloride. Most of these methods involve thermal degassing initially (the removal of more volatile compounds at temperatures below that where zirconium tetrachloride exhibits a significant vapor pressure) followed by a sublimation step (which conveniently leaves the nonvolatiles behind.) While these procedures effect definite purification, such processing is batchwise and does not result in optimum purification. Early work by The Carborundum Metals Co. and others indicated that fused salts were highly efficient in the removal of impurities from gaseous zirconium tetrachloride. The objective of this work was to develop a continuous fused-salt scrubbing process that would yield high-purity zirconium and hafnium tetrachlorides. The term "fused salt" refers to the molten state of ionic compounds and as used here, specifically refers to alkali metal and alkaline earth halides. Fused salts, because of their many valuable properties, are becoming increasingly im- portant industrially. These valuable properties of the fused salts are: 1) stability at elevated temperatures; 2)low vapor pressure; 3) low viscosity; 4) ability to dissolve many different materials; and 5) good elctctrical conductivity. All but the last property enhances the use of fused salts as scrubbing agents for zirconium and hafnium tetrachlorides. Fused-salt scrubbing may be defined for our purpose as the intimate contact between a gaseous compound and a molten salt with the purpose of removing impurities from the gaseous compound. In this case, the gaseous compound is zirconium tetrachloride which submlimes at 331°C. When this gas is contacted with a molten salt, impurities such as aluminum, iron, and titanium are removed and the resulting product is considered fused-salt scrubbed. Zirconium and hafnium are sold to a purity specification. Generally speaking, normal production without scrubbing is capable of meeting specifications. There are, however, several considerations That make the knowledge of methods of additional purification highly desirable. These are: 1) the control of product analysis; 2) the production of a pure product for special applications; 3) the salvaging of off-specification material; and 4) the use of raw materials with higher impurity levels than 1 he present raw materials. You will note that items 1 and 2 are somewhat complementary to each other and that item 4 assumes that The present process has impurity removal limitations. To better understand the part that fused-salt scrubbing of zirconium tetrachloride plays in the manufacture of zirconium, Fig. 1 contains an illustrated flow sheet of the industrial production of zirconium metal. In referring to Fig. 1, we can point out the specific benefits derived from our ability to purify zirconium tetrachloride. Purification of the crude (hafnium-containing) zirconium

Jan 1, 1962

By A. J. May

THE Star shaft is near the north boundary of the group of mining claims belonging to the Ground Hog Unit of the American Smelting and Refining Co., near Vanadium, N. Mex. The shaft bins and surface plant are served by a siding from the Atchison, Topeka and Santa Fe railroad, and this factor of railroad transportation influenced the choice of site. This paper describes the shaft sinking only, and does not cover the surface plant or other parts of the mine or its equipment. Experience with this shaft seems of interest because of the mechanical mucking, good rate of progress, and the costs obtained at the present level of labor and material costs. The shaft has four compartments, as shown in fig. 1. Equipment: Riddell Mucker: The mucking was done by a clamshell bucket and a Riddell mucker, which, as in other shafts sunk with this machine, consisted of a carriage mounted on axles with double flanged wheels that traveled back and forth on a swinging track, parallel to the long axis of the shaft (fig. 2 to 6). Three air motors were mounted on the carriage; one hoisted the clam, one operated the bucket opening and closing device, and the third moved the carriage along the track. The carriage was designed with guide shoes and could be hoisted to the surface in either skip compartment without trouble (fig. 4). During blasting operations the clam was tied on the rails and the carriage was hoisted up a few sets to protect it from flying rock. No attempt was made to hoist the carriage and clam together lest the clam catch in the timbers. The track on which the carriage operated was built of extra heavy 6 in. pipe with 1x2 in. strap welded on top for rails. A 1/2x4 in. angle was welded on the bottom of the 6 in. pipe with a 1 in. round rod welded in the angle for a filler and additional strength. The end or cross pieces of the track which kept the track to gauge, were also made of reinforced, heavy 6 in. pipe and were bolted to the long members on which the carriage traveled (fig. 2 and 3). This section of track was used, instead of heavy railroad rails, for two reasons: (1) this section would bend before it snapped and was much safer for the men in the bottom; and (2) it was a better blasting shield, and protected the timbers better, in fact, only five wall plates were broken by blasting in 1926 ft of shaft, although 150 to 225 lb of 40 pct powder was loaded per round, depending on the ground conditions. The swinging track was supported by four 5/s in. hoisting cables anchored to the end plates. There were also four safety cables fastened two to three sets above the carriage, which would catch the carriage if one of the supporting cables should fail for any reason (fig. 7). Clamshell Buckets: Two clams were used, each of 3/s yard capacity, both manufactured by Blaw Knox, Nos. 662 and 663. The No. 663 clam was 4 in. wider and 5 in. shorter than the No. 662, but seemed to dig and load more satisfactorily. It was easier to hoist and lower when it came up for repair. It did not turn over as easily, had less spill

Jan 1, 1950

By E. L. Dougherty, J. W. Sheldon

Using the numerical techniques shown in this paper it is possible to compute the simultaneous dynamical behavior of multiple fluid-fluid interfaces in two dimensions. Hence, fluid-fluid inter face models of several oil recovery processes can be constructed which allow prediction of the effect of fluid flow in two dimensions on the behavior of these processes while taking into account various physical effects, such as saturation gradients, phase changes and thermal stimulation. Techniques for constructing fluid-fluid interface approximations for several oil recovery processes are reuiewed. The validity of these techniques is established by comparison to experimental results. The availability of a computer program for computing the behavior of multiple fluid-fluid interface problems makes the use of potentiometric models uneconomic. The results indicate the areal sweep efficiencies obtained from potentiometric model studies at high mobility ratios may be somewhat optimistic. The results also indicate that the areal sweep efficiency curves obtained at high viscosity ratios 2—4 using miscible fluids in porous media are misleading and that considerable care must be taken in defining the mobility ratio for a displacement process, especially for miscible fluids. INTRODUCTION Many of the methods used to estimate areal sweep efficiency assume that the oil recovery process can be represented by one or more fluid-fluid interfaces. When the mobilities of the displaced and displacing phases are assumed equal, this quantity can be computed using analytical mathematical methods.l.2 For non-unit mobility ratio, experimental methods based upon the fluid-fluid interface concept include potentiometric and electrolytic blotter models. Scaled models of porous media have also been used to study this problem. Fay and Prats3 and Aronofsky4 used numerical techniques to compute breakthrough sweep efficiency, but neither of these studies were extended beyond breakthrough. Numerical techniques which have been developed for solving a general fluid-fluid interface problem are presented in a companion paper.5 These techniques have been incorporated into a program for a large-scale digital computer which can treat simultaneously the dynamical behavior of as many as six fluid-fluid interfaces. Thus it is possible to simulate the behavior of several oil recovery processes taking into account such effects as saturation gradients. Techniques for representing several oil recovery processes by fluid-fluid interfaces are presented. Processes considered are conventional water flooding with and without a mobile gas phase, hot water flooding, miscible flooding and enriched gas drive. Other processes, whose effects could be studied by this technique, but are not considered in detail here, are underground combustion and steam injection processes and various slug processes such as gas-water injection and alcohol-solvent processes. Theoretical results obtained with single interfaces for mobility ratios of 0.25, 1, 2, 4, 8, 16, 32 and 64 in a repeated five-spot are compared to experimental results for this geometrical configuration obtained using miscible fluids and conductive analogs. Predicted recovery curves for water flooding in a repeated five-spot are compared to experimental results reported in the literature. Example calculations are shown for a conventional water flood in the presence of a free gas phase and for a hot-water flood. MATHEMATICAL PRELIMINARIES We assume that the rock matrix is homogeneous with constant thickness, absolute permeability and porosity. The fluids are incompressible. We also neglect the effects of gravity.

Jan 1, 1965

By A. R. Denison

The area discussed in this report comprises a group of 38 counties lying in the northeast corner of Texas. It covers all, and extends beyond, the borders of what is commonly described as the East Texas Basin. It includes two major oil fields, Van and East Texas; two major gas fields, Bethany and Waskom; and a number of fields, both oil and gas, of lesser importance. All commercial oil production comes from beds of Upper Cretaceous age and almost exclusively from the basal member, the Woodbine sand. Gas is produced from both Upper and Lower Cretaceous beds with the newer production from the older beds. East Texas Field This field continued as in 1932 and 1933 to dominate the drilling and production situation throughout the oil business. A total of 3681 producing wells was completed in this field during 1934. This is an increase of 1215 over the 2466 producers completed during 1933. Total wells

Jan 1, 1935

By Albert Sauveur

(Cleveland Meeting, October, 1912.) ALTHOUGH many metallurgists know that some pearlitic special steels can be made troostitic, martensitic, and even austenitic, without quenching, and, therefore, without exposing them to the dangers of the quenching-bath, the practical significance of such possibility does not seem to have received the attention it deserves. Let us recall briefly the mechanism of the transformation alluded to. In Fig. 1 (after Guillet) is shown the constitutional diagram of nickel-steel that; is, of alloys of iron, carbon, and nickel. Any steel the composition of which falls within the area LPO is pearlitic after slow cooling; any steel the composition of which is represented by a point within the area MLO is martensitic, and any steel within the area MNO is austenitic. Starting with pearlitic steel, then by increasing the carbon-content or the nickel-content, or both, the metal becomes martensitic and eventually austenitic; that is, its composition crosses first the boundary-line LO and then the line M0-and it remains martensitic or austenitic after slow (air) cooling.1 We have inn this way imparted to the metal without quenching it the properties of hardened carbon-steel. In other words, the steel is now self-hardening. Nickel cannot be introduced into solid steel, but by the well-known process of case-hardening it * Professor of Metallurgy and Metalllography in Harvard University. + Assistant in Metallurgy and Metallography in Harvard University. 1 The boundaries between the various zones are not, as a matter of fact, as sharp as indicated in the diagram, because pearlite is not transformed abruptly and in its entirety into martensite when a certain critical composition is attained, nor is martensite suddenly and completely converted into austenite. Greater refinement in the construction of the diagram would undoubtedly result in the introduction of troosto-pearlitic, troostitic, and troosto-martensitic zones between the pearlitic and martensitic areas and-of a martenso-austenitic zone between the martensitic and austenitic areas. Fur the purpose of this note, however, the existence of these transition-conditions may be ignored.

Nov 1, 1912

By William F. Harris, Joseph Easha

FOR many years basic control of refinery operations depended on visual observation of small chill specimens poured at various intervals during processing. The oseto of these samples was related to the physical and chemical properties of the metal. Since the =setn is dependent on many factors other than oxygen content, this method, while giving a general indication of the condition of the copper, does not accurately measure the oxygen content. For the last 3 years a modified vacuum fusion procedure which enables the operator to determine the oxygen content of the copper within 1 5 min of sampling has been in use at the Westinghouse Copper Mill. For use with this apparatus a sampling technique has been developed which gives oxygen values representative of the oxygen content of the wire bar. The sampling technique is based on a statistical study, which compared the oxygen content of the laboratory sample of copper poured at the same time a wire bar was being poured, with the oxygen content of the wire bar. The apparatus used for the determination of oxygen in copper is shown in Fig. 1 and is essentially the same as previously described but with one important modification. A very porous fritted glass disc has been inserted in the tubing between the manom- eter and 40/50 ground glass joint. The fritted disc retains the copper vapor and copper particles in the furnace section and prevents contamination of the mercury in the manometer. Without the disc the manometer became difficult to read after a few weeks of operation. In earlier work1 it had been established that the simplified vacuum fusion apparatus used at the Copper Mill gave essentially the same results as a con-vential vacuum fusion apparatus. However, for this study it was necessary to determine the difference, if any, between the oxygen content of the wire bar and the oxygen content of the small chill sample used for the oxygen analysis. This correlation was established by taking a chill sample at the same time wire bars were being poured. The wire bar being poured at the time the chill sample was taken was marked and removed for further analysis. The copper is sampled at various times during refining and cast into laboratory size samples with the mold shown in Fig. 2. The mold is made of cold rolled steel and is 2 in. high and 2 1/2 in. in diam. The large upper portion of the cast sample is used for measurement of the conductivity of the copper, The lower portion which is a rod about 1/4 in. diam by 3/4 in. long is used for determination of the oxygen content. This portion of the sample weighs about 5 g which is approximately the size sample used for the analysis. The only preparation neces-

Jan 1, 1962

By R. P. Smith

Iron-carbon alloys containing a single-phase austenite region and a two-phase azcstenite + cementite region at the desired temperature were prepared by partial carburization of iron or partial decarburization of carburized iron. Each sample was held at a fixed temperature until equilibrium was achieved. Analysis of the austenite for carbon then gave the solubility of cementite in austenite. Solubility measzcrements were made for the temperature range 734° to 1012°C. These values together with other data give 7560 cal for the mean heat of solution of cementite in austenite, and 0.765 pct C for the eutectoid composition of austenite. They also indicate that graphite is the stable phase at all temperatures between the eutectoid and eutectic temperature. Measurements of the solubility of cementite in austenite at 927oand 1011 "C, using a method based on the equilibration of iron with boro-cementites, are reported. The solubility of cementite in austenite (?-iron) has been computed by Darken and Gurry1 from the observed solubility of graphite in austenite, and the thermodynamic properties of pure iron and of iron-carbon alloys. They have shown that the solubility of cementite is greater than that of graphite in the temperature range between the eutectoid and eutectic, and thus that cementite is metastable with respect to graphite and austenite saturated therewith. Since their computation is not in accord with the earlier experimental work of Mehl and wells,' the present direct determination of the solubility of cementite in austenite was undertaken. EXPERIMENTAL PROCEDURE Each iron rod about 1/2 in. O.D. by 4 in. was first carburized at a temperature and with a H2-CH4 gas mixture such that the carbon content would be greater than that corresponding to the solubility of cementite in austenite at the desired (lower) temperature; sufficient carburizing time was allowed that the carbon content became substantially uniform, as illustrated by Curve A, Fig. 1. The sample was then partially decarburized with a hydrogen-water vapor mixture, giving a carbon distribution as schematically illustrated by Curve B. The sample was then held in a helium atmosphere at the temperature at which the solubility was to be determined until the decarburized portion of the sample came to equilibrium with that containing cementite. Curve C of Fig. 1 represents schematically the final carbon distribution; the horizontal portion corresponds to the carbon content of austenite saturated with cementite. To bring the sample to room temperature without change in the carbon distribution and in machinable condition, it was first quenched in a salt pot at 480°C, then in water at room temperature. Successive layers were machined from the center 2 in. of the sample and analyzed for carbon by the usual

Jan 1, 1960

By Nathaniel Arbiter, Arthur F. Taggart

THE fact that the floatability of minerals with fatty-acid collectors changes as the pH of a pulp varies was utilized in the early days of flotation, when sulphuric acid was used with oleic acid to float sphalerite and galena from gangues which themselves float with fatty acids in alkaline pulps. Gaudin1 showed that this difference in floatability is a regular function of the extent of the change in pH. The present paper offers an explanation of the phenomenon, and on the basis thereof sets up recommendations for control of soap-flotation operations. EXPERIMENTAL Parallelism between floatability of a mineral in a given environment and its contact angle in that environment is so well established,' and the contact angle is so readily and rapidly measurable, that contact angles have been used throughout the experimental work to indicate relative floatability. Experiments comprised contact-angle measurements on a number of representative minerals and metals, and a variety of subsidiary tests designed to check and to amplify the contact-angle indications. Contact-angle measurements were made by the method described in detail by del Giudice.3 Sequence of procedure for determination of the points of Fig. I was: 1. Polish specimen. Most specimens yielded zero contact angle after polishing; a few showed a slight "cling." Cling is characteristic of specimens that pit on polishing; it is due to a residue of organic contamination, originally on the particle surface, which persists in the pits. The cling did not change total contact angle after conditioning, and is not, therefore, additive in the upper part of the curves of Fig. I. It may have broadened the bases of the curves for the affected minerals slightly. 2. The specimen was next conditioned in soap solution for 5 minutes. 3. The conditioned particle was transferred, under conditions that precluded surface drying, to an aqueous solution of the pH desired and contact angle determined. 4. The particle was thereupon transferred, again without surface drying, to water. The confirmatory tests will be described at the places pertinent in the argument. DISCUSSION OF RESULTS Gaudin and Vincent4 have shown that contact angles with heptoic acid as a collector decrease for a given specimen when the concentration of collector present falls below a certain value. A similar reduction in angle occurs with collector-conditioned particles that are visibly slime-coated, and varies roughly with the extent of coating. Since in the last case the reduction in angle is certainly due to reduction in the proportion of total conditioned mineral surface presented to the bubble, the authors believe that the same condition prevails in the first case cited, and that similar reduction in angle and floatability will occur whenever starvation quantities of collector are present, whether

Jan 1, 1943

The Bougainville ore body was discovered in 1964 by a partnership of Conzinc Rio Tinto of Australia and New Broken Hill Consolidated Limited. The ore body is a porphyry copper in a fine-grained quartz diorite, which intrudes andesite volcanics and is located at an elevation of about 2, 000 ft in the Crown Prince Range of Bougainville in the Solomon Islands. Mineralization is predominantly chalcopyrite with some bornite and some gold and silver present. Rainfall in the area amounts to 200 in. (5. 08 m) per year. An active volcano is situated only 24 miles (38.4 km) from the mine, and all structures were designed to resist seismic shocks. An interesting and unique feature of the Bougainville operation was that the overburden was stripped with hydraulic monitors. Bougainville Copper, at 90,000 tpd, is the largest copper concentrator to be designed and constructed at one time; and besides the twin 54 in. by 74 in. Allis-Chalmers gyratories, it features seven 7 ft (2. 13 m) standard and fourteen 7 ft shorthead crushers, in addition to nine 18 ft diameter by 21 ft long (5. 5 m by 6. 4 m), 4250 hp, single -stage ball mills. During the design stage of the Bougainville primary crushing plant, several alternates were studied because the ore was expected to break with the production of large amounts of small-sized particles but with a minimum of fines. These alternates included two 54 in. by 74 in. gyratories with grizzlies, two 60 in. by 89 in. gyratories, and one 72 in. by 96 in. gyratory, the latter two installations without grizzlies. The two 54 in. units with grizzlies were finally selected as giving good reliability and the ability to handle the large amounts of small material in the feed. As originally installed, grizzly bars were set at 8 in. (203 mm); but, in an effort to perform more interparticle crushing in the primary and less rock-on-steel crushing in the secondaries and tertiaries, a test is underway (1976) to determine the effect of using 6 in. (152 mm) grizzly spacings (see write -up on Anaconda's crusher at Butte). The Bougainville ore is mined with 17 cu yd (13 cu m) shovels and hauled in 105, 170, and 210 st trucks to the crushers, which are equipped for two-side dumping. Up to 40% of the ore passes the grizzlies, which are equipped with splitters; and additional horizontal splitter bars are located directly above the spider caps. Because of the grizzlies, the crushers are supported by unique U-shaped enclosures, which are in turn supported by the end and center walls of the installation.

Jan 1, 1978

By W. B. Stephenson

In the pumping of sands, slurries and slimes, practices developed over the years are the real keystones of 'successful operation. These practices are necessarily based on modifications of familiar theories. Practical methods used in the solution of problems involving the pumping of materials are set forth in the following discussion. Basic Requirements To pump sands and slurries economically, a few basic requirements must be met by the pumping system as a whole. A pipe-line velocity must be established that will move the fluid mixture throughout the entire system without any possibility of the solids settling out. To accomplish this, the velocity of flow must be slightly in excess of the critical velocity of the mixture. The critical velocity of a mixture varies from 3 ft. per sec. to 18 ft. per sec., depending on the screen analysis, concentration, and specific gravity of the solids in the mixture. Most tailings are pumped at a minimum velocity of 4 ft. per sec. if they include slimes, whereas the pipe lines of sand and gravel dredges require velocities as high as 18 ft. per second. A number of articles have been written on the determination of the minimum velocities required to maintain solids in suspension. Studies have also been made on the friction and pumping heads developed when handling solids in suspension.1-4 Our experience so far has shown that, within the normal operating limits of a pumping system, the friction factor follows more nearly the basis described by Howard,' who says, among his conclusions: "... values of f (friction factor) . . . will decrease with an increase in velocity." This conclusion is borne out by our actual experience. When the velocity in a pipe line is not sufficient to keep the solids in suspension, the total friction head' is greater than when the velocity is increased to a point where the solids are in suspension. A slight increase in the volume of feed to the pump and a slight increase in the pump speed are usually all that is necessary to put the system in balance. Maintaining Constant Volume Within reasonable limits, the volume of mixture to be handled through a pipe line should be held constant, so that the required velocity will be provided at all times. There are several ways in which this can be accomplished. The commonest is to provide a sump of sufficient capacity to take care of slight surges in the volume of mixture being fed to the pumping systen]. This sump, however, should not be as large as a settling chamber. The use of a float-controlled, fresh-water make-up valve in a sump will guarantee a constant volume. Where variations in volume are slight,

Jan 1, 1947

By W. B. Stephenson

In the pumping of sands, slurries and slimes, practices developed over the years are the real keystones of 'successful operation. These practices are necessarily based on modifications of familiar theories. Practical methods used in the solution of problems involving the pumping of materials are set forth in the following discussion. Basic Requirements To pump sands and slurries economically, a few basic requirements must be met by the pumping system as a whole. A pipe-line velocity must be established that will move the fluid mixture throughout the entire system without any possibility of the solids settling out. To accomplish this, the velocity of flow must be slightly in excess of the critical velocity of the mixture. The critical velocity of a mixture varies from 3 ft. per sec. to 18 ft. per sec., depending on the screen analysis, concentration, and specific gravity of the solids in the mixture. Most tailings are pumped at a minimum velocity of 4 ft. per sec. if they include slimes, whereas the pipe lines of sand and gravel dredges require velocities as high as 18 ft. per second. A number of articles have been written on the determination of the minimum velocities required to maintain solids in suspension. Studies have also been made on the friction and pumping heads developed when handling solids in suspension.1-4 Our experience so far has shown that, within the normal operating limits of a pumping system, the friction factor follows more nearly the basis described by Howard,' who says, among his conclusions: "... values of f (friction factor) . . . will decrease with an increase in velocity." This conclusion is borne out by our actual experience. When the velocity in a pipe line is not sufficient to keep the solids in suspension, the total friction head' is greater than when the velocity is increased to a point where the solids are in suspension. A slight increase in the volume of feed to the pump and a slight increase in the pump speed are usually all that is necessary to put the system in balance. Maintaining Constant Volume Within reasonable limits, the volume of mixture to be handled through a pipe line should be held constant, so that the required velocity will be provided at all times. There are several ways in which this can be accomplished. The commonest is to provide a sump of sufficient capacity to take care of slight surges in the volume of mixture being fed to the pumping systen]. This sump, however, should not be as large as a settling chamber. The use of a float-controlled, fresh-water make-up valve in a sump will guarantee a constant volume. Where variations in volume are slight,

Jan 1, 1947

By William B. Stephenson

IN the pumping of sands, slurries and slimes, practices developed over the years are the real keystones of successful operation. These practices are necessarily based on modifications of familiar theories. Practical methods used in the solution of problems involving the pumping of materials are set forth in the following discussion. BASIC REQUIREMENTS To pump sands and slurries economically, a few basic requirements must be met by the pumping system as a whole. A pipe-line velocity must be established that will move the fluid mixture throughout the entire system without any possibility of the solids settling out. To accomplish this, the velocity of flow must be slightly in excess of the critical velocity of the mixture. The critical velocity of a mixture varies from 3 ft. per sec. to 18 ft. per sec., depending on the screen analysis, concentration, and specific gravity of the solids in the mixture. Most tailings are pumped at a minimum velocity of 4 ft. per sec. if they include slimes, whereas the pipe lines of sand and gravel dredges require velocities as high as 18 ft. per second. A number of articles have been written on the determination of the minimum velocities required to maintain solids in suspension. Studies have also been made on the friction and pumping heads developed when handling solids in suspension.1-4 Our experience so far has shown that, within the normal operating limits of a pumping system, the friction factor follows more nearly the basis described by Howard,1 who says, among his conclusions: " ... values of ƒ (friction factor) .. . will decrease with an increase in velocity." This conclusion is borne out by our actual experience. When the velocity in a pipe line is not sufficient to keep the solids in suspension, the total friction head is greater than when the velocity is increased to a point where the solids are in suspension. A slight increase in the volume of feed to the pump and a slight increase in the pump speed are usually all that is necessary to put the system in balance. MAINTAINING CONSTANT VOLUME Within reasonable limits, the volume of mixture to be handled through a pipe line should be held constant, so that the required velocity will be provided at all times. There are several ways in which this can be accomplished. The commonest is to provide a sump of sufficient capacity to take care of slight surges in the volume of mixture being fed to the pumping system. This sump, however, should not be as large as a settling chamber. The use of a float-controlled, fresh-water make-up valve in a sump will guarantee a constant volume. Where variations in volume are slight,

Jan 1, 1946

By A. T. Beckwith

This paper concerns measurements of low-velocity air currents and investigations on mine ventilation by means of chemical smoke. The chemical smoke used is produced without flame and at ordinary mine temperatures, and therefore presents no ignition hazard in gaseous mines. Mining men who have worked in open-light mines are familiar with the use of tobacco smoke in determining the direction of air travel and approximately measuring low-velocity air currents. The use of chemical smoke is merely a refinement on the use of tobacco smoke and the flameless low-temperature source of chemical smoke has the additional advantage that it can be used in gaseous mines. Ventilation smoke apparatus, Fig I, is a simple device for producing dense white smoke. The apparatus as shown consists of a rubber aspirator bulb which is used to force air through a glass "smoke tube" containing a chemical substance that produces a dense white smoke on contact with air. The apparatus was developed by engineers of the U. S. Bureau of Mines.' It is inexpensive, weighs less than 3 oz, is easily carried in a pocket, and requires no skill to operate. Smoke apparatus is invaluable in practical mine ventilation work for: (I) measuring low-velocity air currents, (2) detecting air leakage, (3) observing airflow characteristics. This paper is written to show the merits of the apparatus, and is based upon findings through its extensive use, during the past six years, in mines operated by the Lehigh Navigation Coal Co. Inc. The Apparatus Certain chemicals, such as stannic chloride (SnCl4) and pyrosulphuric acid (H2S2O7) produce "white smoke" when exposed to air. Stannic chloride gives off vapors which on contact with moist air cause the formation of solid hydrates, of which SnCl4.5H20 is the most important. Pyrosulphuric acid decomposes when exposed to air with the evolution of sulphur trioxide (SO3) fumes, which become white upon contacting moisture in the air. A chemical, such as one of the above, is the active substance in a smoke tube. The glass tubes are hermetically sealed during manufacture, and are made ready for use by merely breaking off the tips at the conveniently located file cuts. When the smoke tube is connected to the aspirator, depressing the aspirator bulb forces air into contact with the chemical, and smoke discharges from the open end of the tube. A white solid (a hydrate if stannic chloride is used, or sulphur trioxide if pyrosulphuric acid is used) may occasionally form a cake in the outlet opening of a smoke tube. A small wire such as an ordinary paper clip can be conveniently employed to dislodge the cake should it seal the tube. When the assembled apparatus is not

Jan 1, 1949

By Arthur F. Taggart, Nathaniel Arbiter

The fact that the floatability of minerals with fatty-acid collectors changes as the pH of a pulp varies was utilized in the early days of flotation, when sulphuric acid was used with oleic acid to float sphalerite and galena. from gangues which themselves float with fatty acids in alkaline pulps. Gaudin1 showed that this difference in floatability is a regular function of the extent of the change in pH. The present paper offers an explanation of the phenomenon, and on the basis thereof sets up recommendations for control of soap-flotation operations. Experimental Parallelism between floatability of a mineral in a given environment and its contact angle in that environment is so well established,2 and the contact angle is so readily and rapidly measurable, that contact angles have been used throughout the experimental work to indicate relative floatability. Experiments comprised contact-angle measurements on a number of representative minerals and metals, and a variety of subsidiary tests designed to check and to amplify the contact-angle indications. Contact-angle measurements were made by the method described in detail by del Giudice.3 Sequence of procedure for determination of the points of Fig. I was: I. Polish specimen. Most specimens yielded zero contact angle after polishing; a few showed a slight "cling." Cling is characteristic of specimens that pit on polishing; it is due to a residue of organic contamination, originally on the particle surface, which persists in the pits. The cling did not change total contact angle after conditioning, and is not, therefore, additive in the upper part of the curves of Fig. I. It may have broadened the bases of the curves for the affected minerals slightly. 2. The specimen was next conditioned in soap solution for 5 minutes. 3. The conditioned particle was transferred, under conditions that precluded surface drying, to an aqueous solution of the pH desired and contact angle determined. 4. The particle was thereupon transferred, again without surface drying, to water. The confirmatory tests will be described at the places pertinent in the argument. Discussion of Results Gaudin and Vincent4 have shown that contact angles with heptoic acid as a collector decrease for a given specimen when the concentration of collector present falls below a certain value. A similar reduction in angle occurs with collector-conditioned particles that are visibly slime-coated, and varies roughly with the extent of coating. Since in the last case the reduction in angle is certainly due to reduction in the proportion of total conditioned mineral surface presented to the bubble, the authors believe that the same condition prevails in the first case cited, and that similar reduction in angle and floatability will occur whenever starvation quantities of collector are present, whether by design or by reason of excessive consumption.

Jan 1, 1943

By Nathaniel Arbiter, Arthur F. Taggart

The fact that the floatability of minerals with fatty-acid collectors changes as the pH of a pulp varies was utilized in the early days of flotation, when sulphuric acid was used with oleic acid to float sphalerite and galena. from gangues which themselves float with fatty acids in alkaline pulps. Gaudin1 showed that this difference in floatability is a regular function of the extent of the change in pH. The present paper offers an explanation of the phenomenon, and on the basis thereof sets up recommendations for control of soap-flotation operations. Experimental Parallelism between floatability of a mineral in a given environment and its contact angle in that environment is so well established,2 and the contact angle is so readily and rapidly measurable, that contact angles have been used throughout the experimental work to indicate relative floatability. Experiments comprised contact-angle measurements on a number of representative minerals and metals, and a variety of subsidiary tests designed to check and to amplify the contact-angle indications. Contact-angle measurements were made by the method described in detail by del Giudice.3 Sequence of procedure for determination of the points of Fig. I was: I. Polish specimen. Most specimens yielded zero contact angle after polishing; a few showed a slight "cling." Cling is characteristic of specimens that pit on polishing; it is due to a residue of organic contamination, originally on the particle surface, which persists in the pits. The cling did not change total contact angle after conditioning, and is not, therefore, additive in the upper part of the curves of Fig. I. It may have broadened the bases of the curves for the affected minerals slightly. 2. The specimen was next conditioned in soap solution for 5 minutes. 3. The conditioned particle was transferred, under conditions that precluded surface drying, to an aqueous solution of the pH desired and contact angle determined. 4. The particle was thereupon transferred, again without surface drying, to water. The confirmatory tests will be described at the places pertinent in the argument. Discussion of Results Gaudin and Vincent4 have shown that contact angles with heptoic acid as a collector decrease for a given specimen when the concentration of collector present falls below a certain value. A similar reduction in angle occurs with collector-conditioned particles that are visibly slime-coated, and varies roughly with the extent of coating. Since in the last case the reduction in angle is certainly due to reduction in the proportion of total conditioned mineral surface presented to the bubble, the authors believe that the same condition prevails in the first case cited, and that similar reduction in angle and floatability will occur whenever starvation quantities of collector are present, whether by design or by reason of excessive consumption.

Jan 1, 1943

By O. Schaaber

THE existence of isothermal martensite without the presence of the athermal form thus far has been established only in a 6 pct Mn, 0.6 pct C steel' and a 23 pct Ni, 3.5 pct Mn-Fe alloy.' " Theoretical calculations, moreover, predict this phenomenon to be observable only within narrow composition limits.' In all other steels, it is generally considered that martensite inevitably forms upon cooling below the M, temperature. Even the possibility of isothermal martensite transformation has been questioned for the common steels, although Averbach and Cohen" showed that martensite formation does not stop when the cooling is arrested and that as much as 5 pct retained austenite may transform isothermally to martensite at room temperature. This note presents some observations made on a number of low alloy steels by dilatometric and inductive measurement of isothermal austenite transformation at various temperatures close to the Ms. In the dilatometer studies reported previously, austenitized specimens were immersed in a salt bath maintained at proper temperature and immediately inserted into the dilatometera8' already at thermal equilibrium with the bath. The dilation was read on a dial gage divided into 0.001 mm intervals. Induction measurements were made with a separate excitation source and a test coil, sealed together in a salt-tight case. The increase in the induced voltage caused by the transformation products was recorded at a paper speed of 4 mm per sec. The steels studied are listed in Table I. Specimens prepared from steels 1 and 2 were in the form of hollow cylinders 60 mm long, 10 mm ID, 14 to 16 mm OD, while specimens of steels 3 and 4 were in the form of notched-bar impact test specimens, DVM type. Specimens of steel 5 were in the form of strip, 7x0.3 mm. In the bainitic range, curves representing the amount of transformation vs log time have a single step appearance, as is shown by the curve of isothermal transformation at 320°C in Fig. 1.Y ransformation proceeds in accordance with the Austin-Rickett equationo P -----------= k t" 100-P where P is the percentage of transformed austenite, t is time, and k and n are constants. Near the M, temperature, however, complex curves having two steps are observed. As shown in a previous papera for steel 3 isothermally transformed at 245"C, such complex curves can be separated into two separate transformations or reactions each following the Austin-Rickett equation. The values of n in the equation for a number of such two-step transformations are listed in Table 11 for steel 1. At transformation temperatures of 250" and 235"C, evidence of a second transformation is very

Jan 1, 1956