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By D. A. Kraai, S. Floreen

The effect of 1 to 50 ppm S on the ductility of nickel at 800° to 1400°F was studied. Results at each temperature showed a decrease in the reduction of area from approximately 95 to 5 pet over the sulfur range studied. Ductility varied with grain size, but only to a minor extent relative to the sulfiw effect. The effects of sulfur were completely offset by the addition of small amounts of magnesium. The results indicate that the "hot-short" loss in ductility is not an inherent property of nickel. Some possible mechanisms which cause the loss in ductility are described. MANY metals or alloys that normally possess high ductility exhibit a ductility loss at intermediate temperatures. This loss in ductility is often called "hot-shortness". Numerous examples of this phenomenon have been reported in the literature. Much of this work has been reviewed by McLean1 and by Rhines and Wray.2 To date there is no fully satisfactory explanation of the cause of this intermediate-temperature hot-shortness. It is generally recognized that impurities, and particularly impurities that form low-melting phases, can cause embrittlement. Examples of hot-shortness have been reported, however, where there were no obvious impurities present which would lower the ductility. Thus there has been some basis for believing that hot-shortness is an inherent property, and that even the purest metal would display a hot-short loss in ductility. This latter hypothesis was recently put forward by Rhines and wray2 based on studies of nickel and nickel alloys. In the discussion of this paper, however, Guard noted that high-purity nickel showed no hot-shortness.3 Thus there is reason to doubt whether pure nickel, or by inference any other pure metal, will inherently exhibit hot-shortness. The present work was initiated to determine the extent to which hot ductility was sensitive to very small amounts of an impurity element. If it could be demonstrated that hot-shortness could be induced by only minor amounts of an impurity, then it might be argued that hot-shortness in general is an impurity effect, and not a fundamental property of pure metals. The particular impurity studied was sulfur in nickel. The deleterious effects of sulfur are well- known. It is also well-known, and will be shown below, that additions of magnesium will render sulfur innocuous. When no such refining agents are added, however, the Ni-S system is a very useful one for studying the influence of small amounts of impurities. EXPERIMENTAL PROCEDURE Two heats containing -24 ppm S were vacuum-melted and small amounts of magnesium were then added under an argon atmosphere. These alloys were used to show the effectiveness of the normal magnesium treatment in overcoming the influence of sulfur. A second series of alloys with a sulfur range of 1 to 50 ppm was then prepared by vacuum melting nickel in alumina crucibles. No elements, such as magnesium, which tend to combine with sulfur were added. The higher sulfur contents were attained by adding nickel sulfide. Lower sulfur contents were prepared using a method in which the melt was oxidized under vacuum to produce the reaction S + 2O = SO2 These heats were subsequently deoxidized with carbon. Ten- to twenty-pound ingots were cast of all of the alloys studied. The compositions are given in Table I. The ingots were forged and hot-rolled to 3/4-in. bar. They were then annealed at either 2000" or 1600°F to produce different grain sizes. One-quarter-in.-diam tensile specimens were machined from the bars. These were tested at 800°, 1000o, 1200°, and 1400°F. The specimens were held at temperature approximately 45 min before testing. The strain rates were 0.005 min-1 to yielding, and 0.05 min-' after yielding. No extensometers or gage marks were placed on the specimens because the higher sulfur heats tended to fracture at the knife-edge indentations or gage marks. The properties measured were ultimate tensile strength and reduction of area. The analytical technique for determining sulfur at low levels was that developed by Burke and Davis.4 They reported a standard deviation of 1 ppm at an average sulfur level of 4 ppm in NBS standards. A standard deviation of 3 ppm is probably more realistic for the alloys used in this investigation considering the possibility of some segregation in the ingots. RESULTS A summary of the tensile results is given in Table I. As shown in the table, both heats to which

Jan 1, 1964

By Dale A. Vaughan, Oliver M. Stewart, Charles M. Schwartz

A. U. Seybolt (General Electric Research Laboratory)—The authors should be commended for adding some important information to our knowledge of the solubility of interstitial elements in metals. It is becoming increasingly evident that the effect of even traces of such elements have very far-reaching effects upon the mechanical properties of the body centered cubic metals. Those who have worked in this area know that the accurate determination of the small solid solubility limits in systems of the type reported by the authors is a quite difficult task, and it is therefore not surprising that frequently the results of different workers are not in agreement. It is instructive, and usually helpful, to plot the solubility results on log weight or atomic percent -1/T coordinates to find out if a straight line is obtained. A straight line is expected because in systems displaying solubilities of the order of 1 to 3 at. pet or less, Henry's law is usually obeyed—or at least well enough obeyed so that the deviation from linearity is not very appreciable. If Henry's law is obeyed, one canthen use the Van't Hoff Equation in the form In N = ?H/RT + C, where N is mole fraction, at. pet, or wt pet for small values, and AH is the partial molal heat of solution of the solute. R and T have the usual significance, and C is an integration constant. If one plots the reported nitrogen solubility values as indicated above, the three points fall reasonably well on a straight line. The oxygen values for the two upper temperatures fall very closely to the nitrogen values as shown in the authors' Fig. 15. However, the value at 500°C departs widely from the straight line established by the data at 1500" and 1000°C. It is, of course, true that one cannot place too much emphasis on the significance of a line established by only three points, but in the absence of reasons for anticipating deviations, data exhibiting wide departures from linearity should at least be examined closely. Fig. 16 shows the log at. pct -1/T plots for the authors Ta-O and Ta-Ndata including a solid circle point at 500°C and 1.8 at. pet for Ta-O, which is simply extrapolated from the two higher temperature points. In addition, the data of R. P. Elliott9 for Nb-O are shown. These points were picked off his curve and are not very exact, but as can be seen they line up well on a straight line. It is interesting, and probably significant, that the slope of Elliott's results is not far from those of Vaughn, et al. This is probably to be expected because one would anticipate that the partial molal heats of solution of oxyten in these two very similar metals should be not too far apart. AH for Ta-O is about -1900 cal per mol, while for Nb-O it is near -2300 cal per mol. Hence, this lends some support to the thesis that the point at 500°C for Ta-O is much too high. The data of Gebhardt and Preisedanz10 are also plotted, and it is seen that their data while lying on a linear plot, have an appreciably steeper slope. The possible reasons for this will not be discussed here except to point out that their pressure-composition data show anomalies which suggest that they may have been dealing with a different equilibrium from that being discussed. There is another consideration which would also suggest that the solubility at 500°C is lower than shown. The solubility values were obtained by the classic method of first establishing a lattice parameter-composition curve. This the authors did, and there is probably little doubt that it is quite accurate. Such a plot is generally almost error-free because it has a self-correcting feature in that any deviation from linearity makes a data point immediately suspect, and subject to confirmation. Unfortunately, this is not true with respect to the actual solubility values. These are obtained ordinarily by taking an alloy containing more solute than is soluble at some temperature and then thermally

Jan 1, 1962

By L. Ekstrom, J. P. Dismukes

The homogeneity and microstrcture of zone-leveled Ge-Si alloys haw been investigated by sellera1 physical techniques and by metallography as a function of growth rate in the range 3 x 10 1x10 cm-sec', and as a system of alloy composition throughout the system. The temperature gradient at the solid-liquid interface was about 50 deg-cm-' Cellular or dendritic structures char-acteristic of constitutional supercooling were ob-served except at very slow growth rates, which ranged from about 2 x 10 cm -sec for Ge 1 sio alloy to about 2 X 10'5 cm-sec'1 for Ge .sSio.s alloy. Using a simple model similiar to that employed for dilute solid the dependence upon compo-sition over the entire system of the critical growth rate for the onset of constiutional supercooling was calculated, and was .found to he in good agreement with the experimental results. THE recent discovery of the low thermal conductivity of Ge-Si alloys' at high temperatures has revealed that these alloys have high efficiencies for thermoelectric-power generation.', Therefore, a reliable method was needed for the preparation of homogeneous samples required for definitive measurements throughout this alloy system. Due to the low diffusion rates in the solid alloys, the segregated samples obtained by quenching a melt are not readily homogenized by annealing.475 However. isothermal solidification from a melt of constant composition can produce uniform material. Of the available semiconductor crystal-growth procedures, the zone-leveling technique6 applied to a complete solid-solution alloy system by Wang and Alexander' and by others provides a simple method of doing this. In the present work, the homogeneity and microstructure of zone-leveled alloys have been correlated with growth conditions, and the conditions for preparing homogeneous Ge-Si alloys have been established. This has provided insight into the solidification process of alloy semiconductors. EXPERIMENTAL PROCEDURE Sample Preparation. The Ge-Si alloy phase diagram4 shown in Fig. l(a) consists of a complete series of solid solutions. The zone-leveling technique used to prepare most of the samples consists of moving a zone of liquidus composition (C1) through charge material of the corresponding solidus composition (C,), as is illustrated in Figs. l(b) and l(c). To prepare the charge materials, high-purity germanium and silicon were pulverized in a steel hammer mill, cleaned magnetically, and melted together to make uniform chill castings. The zone leveling was carried out in a resistance-heated furnace similar to that of Mitrenin et al.' shown in Fig. 2. However, a few specimens of high silicon content were prepared by the Czochralski technique. The growth rate ranged from 3.5 x X6 to 1.2 X 10~3 cm-sec-'. Temperature gradients in the solid and in the melt were determined by recording the temperature as the molten zone passed over a Pt-Pt 13 pct Rh thermocouple contained in a small

Jan 1, 1965

By N. A. D. Parlee, N. M. El Tayeb

Fe-V alloys with small percentages of vanadium show no deviations from Sieverts' Law up to P~, = 1 atm in the 1600º to 1750ºC region. At somewhat under 8 pct V and up to at least 20pct V, at 1604" and 1661 °C, nitrogen absorption follows Sieverts' Law at low Pn2 values, but deviates from this law beyond critical values of pn2, due to formation of a nitrzde phase of approximately VN composition. The behavior below these solubility limits can be described at all temperatures by the equations: RAO and parlee1 suggested that the nitrogen absorption curve for liquid iron alloys takes the general form shown in Fig. 1 when an alloy nitride precipitate is formed. They showed that the precipitation of 6 titanium nitride from liquid Fe-Ti alloys follows this general scheme and dealt with the general theory involved. Recently, Evans and Pehlke2 reported their research on the precipitation of aluminum nitride from liquid Fe-A1 alloys. Fountain and Chipman's recent paper3 on the precipitation of boron nitride from solid solution contains a fine example of the analogous behavior which they have been studying in the solid state. Researches on the absorption of nitrogen by liquid Fe-V alloys have been described by various authors.1,4-7 Most of this work has been confined to fairly low vanadium concentrations and rather high temperatures because of difficulties variously described as, formation of surface scums, bridging, and so forth. This behavior and the rough thermo- dynamic calculations made by chipman,8 over eleven years ago, indicated that excessively high vanadium concentrations should not be required for vanadium nitride precipitation. It seemed desirable to look for and study this precipitation in order to fill out the thermodynamically interesting nitrogen absorption data on these alloys. EXPERIMENTAL METHOD The general method used was essentially the same as employed by Rao and parlee,1 in which a Sieverts type of apparatus was used and the precipitation of the nitride detected by the "break-point" in the Sieverts' Law line, and by the visual observation of the formation of the new phase on the surface of the melt. There were, however, a few differences in apparatus and technique as described below. The oil manometer used by Rao and parlee' to measure low partial pressures of nitrogen was not employed. The present authors sought to avoid as much as possible the exposure of the liquid alloy to low total pressures of gas during the 6 to 10 hr long runs because of the heavy iron evaporation-loss errors involved. This was achieved, partly by keeping evacuation times to a minimum with fast pumping but largely by the use of two burettes, one for argon and one for nitrogen, and using them to equilibrate the alloy with mixtures of argon and nitrogen rather than nitrogen alone. Each run involved a careful sequence of operations. After melting, de-

Jan 1, 1963

By John E. Conley, John A. Ruppert

W. B. Mather—A minor recommendation that may be offered to improve the paper is the inclusion of a map of Oregon showing the general location of the various deposits. This is of especial importance to persons like myself who are not familiar with the various areas and counties mentioned. N. S. Wagner and R. S. Mason (authors' reply)—We agree that an index map of Oregon showing the location of the various nonmetallic deposits would add to the paper (fig. 1).

Jan 1, 1951

By John A. Ruppert, John E. Conley

W. B. Mather—A minor recommendation that may be offered to improve the paper is the inclusion of a map of Oregon showing the general location of the various deposits. This is of especial importance to persons like myself who are not familiar with the various areas and counties mentioned. N. S. Wagner and R. S. Mason (authors' reply)—We agree that an index map of Oregon showing the location of the various nonmetallic deposits would add to the paper (fig. 1).

Jan 1, 1951

By W. L. Fink, L. A. Willey

During the war there was introduced a new higher strength aircraft alloy designated 75S.1,2,3 The properties of this alloy assure extensive applications in both military and commercial aircraft. It is therefore important to understand its limitations as well as advantages. The properties of 75.5 alloy in the heat-treated tempers, like those of many other aluminum alloys, are affected by the rate of quenching. In general, low quenching rates tend to cause low strengths and to adversely affect the resistance to corrosion. Commercial quenching procedures are usually sufficiently rapid to permit the development of maximum properties. However, in the center of heavy sections, such as large rolled and extruded shapes, the quenching rates may not be rapid enough to develop maximum strength or resistance to corrosion. The investigations of 75s alloy described herein reveal the most critical range of temperature and the effects of quenching sheet and extrusions at different rates through that temperature range, on the tensile properties and resistance to corrosion. Procedure Preparation of Specimens Sheet specimens (3 in. by 9 in.) were prepared from a commercial lot of 75s "as rolled" sheet (0.064 in. thick). The composition4 was as follows: Weight Percentage Cu Mn Mg Zn Cr A1 with Normal Impurities 1.64 0.16 2.58 5.66 0.27 Remainder The specimens employed for the determination of the time-temperature relations during quenching of sheet were prepared by the following procedure: the hot junction of a 28-ga. iron-constantan thermoelement (asbestos insulated) was brazed to a thin strip of aluminum which was in turn brazed into the end of a 3/16-in. id by %-in. od by 30 in. long aluminum protection tube. Before brazing, the tube was flattened to 0.064-in. thickness over the junction and adjacent lead wires for a distance of I 1/2 in. The flattened end of the tube was fitted into a slot cut from one edge to the center of the 3-in. by 9-in. by 0.064-in. sheet and brazed into place. The brazed joint was dressed to the thickness of the sheet and the entire specimen buffed to approximately the brightness of "as rolled" material. Because of the brazing operations required, these specimens were prepared using 3S alloy. For the investigation of quenching rates in heavy sections, there were used 75s extrusions which had compositions similar to that of the sheet. The specimens consisted of 14 in. lengths of 3i-in., 2-in., 3-in, and 4-in. diam cylindrical rods and a roughly rectangular extruded section which was approximately 4 in. by 7 1/2 in. Thcrmocouple~ were peened into the bottoms Of .1/8-in. diam wells drilled into one end and parallel to the axis to a depth of

Jan 1, 1949

By G. M. Ritcey

Continuous contacting equipment for solvent extraction can be divided into two major areas, according to whether their mode of operation is stagewise or differential (Figure 1). Mixer settlers and the recent Kenics and Sulzer mixers typify the stagewise contactors. In these counter- current contactors, the aqueous and the organic phase are mixed and then separated in a large settling area before the next stage of mixing. Countercurrent differential contact- ors, such as centrifuges and various types of columns, are more compact in that they require less ground area than mixer settlers. [ ] Contactors, in addition to being either stagewise or differential, can be further subdivided into non-agitated and agitated depending on the method used for mixing the phases and producing the countercurrent flow. The simplest contactors such as spray, packed, or perforated plate columns achieve both the mixing and countercurrent flow by means of the gravity difference between the two phases. In agitated contactors such as the Scheibel, Reciprocating Plate, and Sieve-Plate Pulse, mechanical agitation is introduced but gravity differences still produce countercurrent flow. To conserve plant space, and for large throughput with short contact time, centrifugal contactors are used where possible. The reader can refer to reviews on the subject (1-11).

Jan 1, 1978

By T. F. Witherbee

That the single charging-bell, properly proportioned, is a good all-around device for distributing material in a blast-furnace can scarcely be questioned; yet it is equally true that, in some cases, it has not given perfect satisfaction; as has been demonstrated by the substitution of double bells, at furnaces under the beat management—generally in cases where anthracite, either alone, or with a portion of coke, was used as fuel. The defect of the single bell seems to be that it does not permit, beyond very narrow limits, such changes in charging as may be required by the temporary conditioil of the furnace. Modern furnaces using Connellsville or other good coke and Lake Superior ores seem to be well served with a single bell. At least, up to a certain size, somewhere about 18 by 85 ft. to 19 by 90 feet, these furnaces make low-silicon pig-iron with about 1,800 lb. of fuel, or in some cases very much less. The following instances occur to me, in which other forms of charging-apparatus have been employed with advantage: 1. A charcoal-furnace, 61 ft. high, 11 ft. in diameter at bosh, and 8 ft. 2 in. at stock-line, with a rectangular crucible, 42 by

Jan 1, 1905

By H. S. Chiang, S. S. Peng

INTRODUCTION Underground coal mining disturbs the original in-situ conditions which induces a series of strata activities and results in creating "mine pressures," the source of all ground control problems. Adoption of self advancing powered supports in modern longwall mining adds a new dimension to ground control problems and thus research. Roof stability, in general, refers to the integrity and stability of the immediate roof which is measured by the maximum exposed area and time duration without support. There are many factors that con- tribute to roof stability problems. In addition to mining height, rock property and stratum components and caving angle of the immediate roof, characteristics of joints and fissures and their degrees of development, faults and underground water, the operational techniques also play a very important role. This paper summarizes these operational techniques and methods of controlling stable and unstable roof. CLASSIFICATION OF THE IMMEDIATE ROOF There are many ways of classifying the roof (1). For practical purpose, the immediate roof in this paper is divided into three groups, i.e. unstable. medium stable and stable. Unstable Immediate Roof It has the following features (1) It consists of weak or soft carbonaceous shale, black shale, clay shale and well-jointed or fractures sandy shale

Jan 1, 1983

By W. V. Vietti, W. A. Oberlin

Crude petroleum produced in the Texas Panhandle oil field is both an asphalt and a paraffin-base oil and is further characterized by being a high-gravity crude with an extremely high cold test,. An eight-well composite of Panhandle crude showed the following characteristics: Gravity, 36.6° A. P. I. Viscosity: 61 sec. Saybolt at 100° F. 170 sec. Saybolt at 75° F. 1560 sec. Saybolt at 50° F. (stirring) Cold Test, 60° F. Distillation Test: Per Cent. Per Cent. Gasoline........................ 28.8 Wax........................... 19.2 Kerosene........................ 4.8 Asphalt........................ 13 .0 Gas oil......................... 30.7 Sulfur1......................... 0.8 Fuel oil......................... 34.7 Subsurface Conditions The original pressure in the formation in the Panhandle field closely approximated 420 Ib. gage or 435 Ib. absolute pressure. Temperatures taken indicate that the formation temperatures do not exceed 90° F. The temperatures in Table I are typical measurements taken on one lease. * A contribrition from the research department of the Marland Refining Co. of Oklahoma and the production engineering department of the Marland Oil Co. of Texas. 1 Smith [Analysis of Panhandle and Rig Lake Crudes. U. S. Bur. Mines, Circular No. 6014 (December, 1926)] found an average sulfur content of 0.6 per cent.

Jan 1, 1928

By C. A. Shook, W. H. W. Husband, D. B. Haas

Introduction Although previous studies1,2,3 have been made, no correlations for pressure drop have been proposed. This is probably because severe particle breakage occurred and pressure drops changed substantially with time. A quantitative statement of the relationship of pressure drop to the parameters of the system is desirable for lignite since, unlike higher rank coals, lignite slurries are thixotropic. The present investigation was undertaken to quantify the pipeline behavior and required continuous monitoring of pressure drop and size distribution.

Jan 1, 1980

By T. D. Tiemann

Extraction of silica from the taconites of the Wisconsin Gogebic range by high temperature digestion in caustic solutions has been described.1,2 The ores consist essentially of hematite, goethite, and microcrystalline quartz, detailed descriptions of which appear in the literature.1,3 It is the purpose of this communication to describe some results obtained from a laboratory investigation of an alternative method, that of sintering the ore with sodium carbonate followed by water extraction of the sodium silicate produced. This is analogous to the Deville-Péchiney4,5 soda ash sinter process for the production of alumina from bauxites in which soluble sodium aluminates are formed. Raw mixes of the desired composition were prepared from 10.0 g minus 200 mesh samples of taconite and sintered in nickel crucibles in a muffle furnace controlled to within ±10°F of the operating temperatures. The resulting sinters were pulverized and then leached in distilled water with continuous agitation for 30 minutes at 95°C. The suspensions were vacuum filtered and the residues dried, ignited and weighed. Iron assays on the ignited samples were made by the standard dichromate procedure after dissolution in hydrochloric acid. The percentage of extraction was calculated from the iron assays by the relation:

Jan 1, 1964

By E. P. Jennings

The abundance and value of the tellurium minerals of Colorado is well known, but, as yet, few analyses have been made of them, and I offer these as a small contribution to the chemistry of these valuable ores. 1. Native Tellurium.—The specimens from which the analyses of this mineral were made are from the " John Jay" Mine, Boulder County, Colorado, where it occurs in quite large masses, though mixed with more or less silica and iron pyrites. It is usually a finegrained, tin-white mineral, but sometimes occurs in distorted, hexagonal prisms in cavities in the quartz. Before the blowpipe it gives the reactions for tellurium, sulphur and iron; by cupellation, it yields a small amount of gold. An analysis of a coarsely crystallized specilnen gave the following results : Specific gravity, 5.10.5. Tellurium,.........68.40 Gold, :.........1.36 Iron pyrites,........24 92 Ferric oxide,.....4.37 Silica and silicates,........11.54 Silver, lead, and mercury,... traces. 100.59 Deducting the pyrites, iron oxide and silica, we have for the con]position of the mineral: Tellurium,..........97.78 Gold,.......... 2.27 100.00 Or, considering the gold to be in combination with tellurium to form sylvanite, we have : Nativc tellurium,........96.50 Sylvanite (An, Te3,),........4.50 100.00

Jan 1, 1879

By J. D. Pennock

The different samples of brick examined were Grecian magnesite, American magnesite; silica brick and coke-oven tiling made in Belgium and used in retort coke-ovens. The Grecian magnesite was furnished by a New Pork party. The American magnesite and the silica brick were furnished by a manufacturing company in Pittsburgh. From these brick were made cylindrical cores, '79 inches long and 15/8 inches in diameter. At one end of each was drilled a hole about 1/4-inch in diameter and 11/4 inches long, into which the thermometer was inserted during the experiment. Conductivity.—The apparatus used for determining the conductivity, as shown in Fig. 1, is a sheetriron drum, 18 inches in diameter and 8 inches high. In the center is a little combustion-chamber with walls of split fire-brick, 39 inches square and about 6 inches high. The fire-brick, however, pass through the drum to the table on which the drum stands. The cores are placed horizontally, half-way between the top and bottom of drum and on the line of diameters at right angles. In the four walls of the combustion-chamber are cut holes just large enough to allow the cores to pass through. The cores extend

Jan 1, 1897

By R. C. Ferguson, Harlowe Hardinge

Oscar Johnson—In my opinion, the effect of mill speeds on grinding costs must be studied along with capital investment and dollars gathered together as profits. Comparing the entire groups of operators with those who have had the opportunity to make slow-speed mill studies, I think you will find the latter small in numbers. Most managers want the equipment worked to its maximum output. There are, however, some installations where plant and mill sizes are such that they can do the job with reduction of mill barrel speeds. The past and the present installations of the industry are laid out to get the most capacity for the least capital outlay. This is the case even with the plants of Chile Exploration, International Nickel, Morocco, and Anaconda, now under construction or being changed. The industry recognizes that most all equipment it buys today is good and can be depended upon for efficient performance. Under this scheme of things, I am doubtful that slow-speed ball mill operation will be generally applicable. With reference to the U. S. Bureau of Mines laboratory tests, I think table II could have been omitted. It is inconclusive as to maximum efficiency for the low-pulp level mill on hard ore. There should be no question about this point. However, data on mill speeds can be found to substantiate various theories as well as refute them. Gow, Guggenheim, Campbell and Coghill, in their paper on Ball Milling,' believe their 2 x 2 ft laboratory mill reflects results that can be expected from large mills. If so, then referring to their table 11, they state, "The conclusion to be drawn from this second series is that high speed, not exceeding 72 pct of the critical, favors capacity, as before, but that with proper conditions of operation high speeds may give as good efficiency values as low speeds. In this case the efficiency values are nearly constant. A horizontal curve would indicate that the amount of grinding was directly proportional to the power expended, and these tests suggest that such a coildition can be made to exist in commercial operations." Table II (From Paper by Gow et a1)2 Speed. Pot Critical 32 42 52 62 72 82 Capacity: Surface tons per hr (65- mesh) 266 42.1 54.4 65.9 74.3 74.1 Surface tons per hr (200- mesh) 56.1 87.4 112.7 137.1 154.2 153.0 Efficiency: Surface tons per net hp hr (65-mesh) 35.7 36.3 36.3 35.4 34.3 32.3 Surface tons per net hp hr (200-mesh) 75.3 75.3 75.1 73.7 71.0 66.0 Ore in mill, 1.b. 98 100 100 113 122 165 The field performance data, table 111, represents much effort in its collection and preparation. But, one must realize that there are many variables that effect the efficiency of grinding mill operation, and too much must not be assumed as to the effect of some specific change. Possibly with changes in mill speed, the results might be more consistent by also a change in ball rationing, type of ball, volume of ball charge,. p.ulp level and amount of pulp in the mill, pulp consisting, design of liner, circulating load, etc. Also, changes in ore character must be reckoned with when evaluating grinding performance. At present the Climax Molybdenum Corp. is running at much reduced capacity. Mr. James Duggan informs me that at mill speeds of 17 rpm, they save a $0.025 per ton on liners and $0.025 per ton in power, but, if the demand for molybdenum increased, he would go back to higher speed to obtain maximum tonnage, as the values from the increased tonnage would far more than offset the one half saving at the slower speed. The Jnspiration ran a six months' test between mills running 21 rpm and 23.5 rpm. The slower mills ground 10 pct less ore with a slight saving per ton, but when the reduced plant tonnage was checked back into the actual cost figures of concentration, the high-speed mills with their greater tonnage showed considerable advantage. To be convinced of possible practical results from the predictions in the conclusions, I think we would have to rely on the analysis of expert cost accountants to furnish the necessary proof figures. Hardinge and Ferguson are to be commended for the work in preparing this paper. I am convinced that our Massco engineers should go into higher speeds with our equipment. Harlowe Hardinge (authors' reply)—For one, I heartily agree with Mr. Johnson's opening statement that the effect of mill speeds on grinding costs must be studied along with capital investment and dollars gathered together as profits. It was on this basis and for this reason the paper was written. Mr. Johnson, on the other hand, takes the position that, on the whole, low speeds are not justified from the economic standpoint, basing his principal reason on the fact that lower mill speeds cut mill capacities and hence reduce the gross income from the product produced. There is no denying this point. It is almost axiomatic. It is for this very reason that the overall advantage of lower mill speeds has been discounted and even overlooked. It was for this reason mainly that the paper was written in the first place. It is one thing to plan an efficient operation at the outset, basing one's figures on the tonnage requirements at the time, and it is quite another to be confronted with the problem of increasing the output of an existing installation at a minimum of capital expenditure. Economic consideration of a new installation is greatly influenced by referring to an old one. Too often, the analyst assumes that if this practice is followed in the new installation, one would not go wrong. It is just here that he may be wrong. Past practice and low capital expenditure are all too frequently given priority over the engineer's analysis of operating costs. When we are able to start fresh, we should give proper weight to other economic factors which do not exist in an old installation. It is these economic factors that make it possible to spend at the outset just a little more money and get it back in a matter of months and effect big savings for years to come. F. C. Bond—This paper is of considerable importance in that it emphasizes a modern trend to operate ball mills at somewhat slower speeds than formerly. We have checked the data in the paper with that obtained

Jan 1, 1951

By Harlowe Hardinge, R. C. Ferguson

Oscar Johnson—In my opinion, the effect of mill speeds on grinding costs must be studied along with capital investment and dollars gathered together as profits. Comparing the entire groups of operators with those who have had the opportunity to make slow-speed mill studies, I think you will find the latter small in numbers. Most managers want the equipment worked to its maximum output. There are, however, some installations where plant and mill sizes are such that they can do the job with reduction of mill barrel speeds. The past and the present installations of the industry are laid out to get the most capacity for the least capital outlay. This is the case even with the plants of Chile Exploration, International Nickel, Morocco, and Anaconda, now under construction or being changed. The industry recognizes that most all equipment it buys today is good and can be depended upon for efficient performance. Under this scheme of things, I am doubtful that slow-speed ball mill operation will be generally applicable. With reference to the U. S. Bureau of Mines laboratory tests, I think table II could have been omitted. It is inconclusive as to maximum efficiency for the low-pulp level mill on hard ore. There should be no question about this point. However, data on mill speeds can be found to substantiate various theories as well as refute them. Gow, Guggenheim, Campbell and Coghill, in their paper on Ball Milling,' believe their 2 x 2 ft laboratory mill reflects results that can be expected from large mills. If so, then referring to their table 11, they state, "The conclusion to be drawn from this second series is that high speed, not exceeding 72 pct of the critical, favors capacity, as before, but that with proper conditions of operation high speeds may give as good efficiency values as low speeds. In this case the efficiency values are nearly constant. A horizontal curve would indicate that the amount of grinding was directly proportional to the power expended, and these tests suggest that such a coildition can be made to exist in commercial operations." Table II (From Paper by Gow et a1)2 Speed. Pot Critical 32 42 52 62 72 82 Capacity: Surface tons per hr (65- mesh) 266 42.1 54.4 65.9 74.3 74.1 Surface tons per hr (200- mesh) 56.1 87.4 112.7 137.1 154.2 153.0 Efficiency: Surface tons per net hp hr (65-mesh) 35.7 36.3 36.3 35.4 34.3 32.3 Surface tons per net hp hr (200-mesh) 75.3 75.3 75.1 73.7 71.0 66.0 Ore in mill, 1.b. 98 100 100 113 122 165 The field performance data, table 111, represents much effort in its collection and preparation. But, one must realize that there are many variables that effect the efficiency of grinding mill operation, and too much must not be assumed as to the effect of some specific change. Possibly with changes in mill speed, the results might be more consistent by also a change in ball rationing, type of ball, volume of ball charge,. p.ulp level and amount of pulp in the mill, pulp consisting, design of liner, circulating load, etc. Also, changes in ore character must be reckoned with when evaluating grinding performance. At present the Climax Molybdenum Corp. is running at much reduced capacity. Mr. James Duggan informs me that at mill speeds of 17 rpm, they save a $0.025 per ton on liners and $0.025 per ton in power, but, if the demand for molybdenum increased, he would go back to higher speed to obtain maximum tonnage, as the values from the increased tonnage would far more than offset the one half saving at the slower speed. The Jnspiration ran a six months' test between mills running 21 rpm and 23.5 rpm. The slower mills ground 10 pct less ore with a slight saving per ton, but when the reduced plant tonnage was checked back into the actual cost figures of concentration, the high-speed mills with their greater tonnage showed considerable advantage. To be convinced of possible practical results from the predictions in the conclusions, I think we would have to rely on the analysis of expert cost accountants to furnish the necessary proof figures. Hardinge and Ferguson are to be commended for the work in preparing this paper. I am convinced that our Massco engineers should go into higher speeds with our equipment. Harlowe Hardinge (authors' reply)—For one, I heartily agree with Mr. Johnson's opening statement that the effect of mill speeds on grinding costs must be studied along with capital investment and dollars gathered together as profits. It was on this basis and for this reason the paper was written. Mr. Johnson, on the other hand, takes the position that, on the whole, low speeds are not justified from the economic standpoint, basing his principal reason on the fact that lower mill speeds cut mill capacities and hence reduce the gross income from the product produced. There is no denying this point. It is almost axiomatic. It is for this very reason that the overall advantage of lower mill speeds has been discounted and even overlooked. It was for this reason mainly that the paper was written in the first place. It is one thing to plan an efficient operation at the outset, basing one's figures on the tonnage requirements at the time, and it is quite another to be confronted with the problem of increasing the output of an existing installation at a minimum of capital expenditure. Economic consideration of a new installation is greatly influenced by referring to an old one. Too often, the analyst assumes that if this practice is followed in the new installation, one would not go wrong. It is just here that he may be wrong. Past practice and low capital expenditure are all too frequently given priority over the engineer's analysis of operating costs. When we are able to start fresh, we should give proper weight to other economic factors which do not exist in an old installation. It is these economic factors that make it possible to spend at the outset just a little more money and get it back in a matter of months and effect big savings for years to come. F. C. Bond—This paper is of considerable importance in that it emphasizes a modern trend to operate ball mills at somewhat slower speeds than formerly. We have checked the data in the paper with that obtained

Jan 1, 1951

By J. F. Radavich

Many heats of steel of low carbon value have been known to produce brittle pieces of steel. The brittleness is believed to be due to the impurities located within the grain boundaries. Such brittle steels have been examined with an optical microscope to ascertain the nature and the amount of the impurities present at the grain boundaries. Due to the relatively low resolving power of the optical microscope, the impurities are not visible in fine detail. The writer obtained some sheet steel and proceeded to determine the location of the impurities and to show the application of the electron microscope to the study of grain boundaries. One sample was known to be capable of becoming embrittled, whereas another sample was believed to be much less susceptible to embrittlement. Treatment of Specimens The specimens were embrittled by annealing above the A3 point under mildly oxidizing conditions. One piece of ingot iron could not withstand a 90" bend, whereas another piece of ingot iron was not affected and could withstand a 90" bend. The brittle piece was then annealed at a high temperature in a hydrogen atmosphere. The annealed ingot iron was termed cured and could withstand a 90" bend very easily. The three specimens examined will be designated as brittle, good. and cured in the discussion that follows. Procedure The sizes of the specimens were as follows: one piece of brittle ingot iron-3/8 by 35 in.; one piece of good ingot iron-96 by 1/8 in.; one piece of cured ingot iron-36 by 54 in. The specimens were too small to be polished by hand and therefore were mounted in bakelite. The polishing procedure was carried out in the conventional manner with the use of 1/0 through 3/0 papers, and the final polish was done with alumina on a billiard cloth. The specimens were then etched in a 4 pct solution of picral in alcohol, and then they were examined through an optical microscope. An area was chosen that showed distinct grain boundaries, and an effort was made to keep near this area when pulling the replicas REPLICA TECHNIQIJE The replica technique used in the preparation of the replicas for examination under the electron microscope is described in Electron Metallography.' It consists essentially of the following steps: 1. Obtaining a suitably etched specimen. 2. Applying a swab of ethylene di-chloride on the surface. 3. Applying a formvar solution on the surface. 4. Placing a screen on any desired spot. 5. Breathing on the fornivar layer. 6. Applying scotch tape on the screen and film. 7. Pulling the film and the screen up with the Scotch tape. 8. Separating the screen from the Scotch tape. This replica technique is very similar to the one described by Harker and Shaefer. However, with the added step, the percentage of replicas removed is very much higher regardless of the length of the time from the etching of the specimen to the actual pulling of the replica. The replicas were then shadow cast with manganese at a filament height to replica distance ratio of 1 1/2:7. This produced a very high contrast replica for use in the electron microscope. One of the dificulties encountered with this study was the restricted area of the specimen. The width of the specimens was the same as that of the 200 mesh nickel supporting screen. In order to increase the effective area, the screens were cut down as shown in Fig 1. The arrow indicates the direction in which the replica was pulled. This operation made it possible to obtain a large percentage of good replicas. Fig 3 shows an electron micrograph of a brittle piece of ingot iron and a grain boundary that was polished mechanically. The surface is very rough probably due to the incomplete removal of the flowed layer by the picral etchant. The grain boundary does show evidence of impurities. It was decided to electropolish the specimens to obtain a much smoother surface than the one obtained by mechanical polishing. ELECTROPOLISHING The specimens were cut in half to expose the metal on the back side. The exposed metal had sufficient area to make good electrical contact and electropolishing was carried out easily. The conditions for electropolishing were 0.9 amp, 35 volts, and 25 sec. in an electrolyte composed of 850 cc of ethyl alcohol, 100 cc distilled water, and 50 cc of perchloric acid. The polished specimens were then etched in the 4 pct picral solution for a shorter time than was necessary for

Jan 1, 1950

By A. U. Seybolt

The solubility limit of oxygen in columbium has been determined in the range between 775' and 1100°C by means of lattice parameter measurements and microscopic examination. The solubility is a function of temperature and varies, in the range given above, from 0.25 to 1.0 pct O, respectively. BECAUSE of the marked deleterious effect of oxygen upon the mechanical properties of some of the transition metals, it is desirable to know something about the solubility of oxygen in these metals. The brittleness caused by oxygen in solution is particularly marked in the case of the group VA elements, vanadium, columbium, and tantalum. The solubility of oxygen in vanadium has already been reported in an earlier paper,' and Wasilewski2 has given a value (0.9 wt pct) for the solid solubility of oxygen in tantalum at 1050°C. Brauer3 in 1941 investigated the Cb-0 system up to Cb2O5, but made no real effort to investigate the extent of oxygen solubility in the metal. He made the observation, however, that this solubility must be less than 4.76 atom pct (0.86 wt pct) oxygen. This estimate was made from X-ray diffraction results on the alloys CbO, CbO, and CbO; all alloys consisted of the terminal (Cb) solid solution plus CbO, but the last alloy containing 4.76 atom pct 0 showed only three very weak CbO lines. It is surprising that Brauer, by examining only three alloys, arrived at an estimate of the solubility which agrees very well with the results to be reported herein. Experimental Procedure A columbium strip obtained from Fansteel Metallurgical Products was cut into strips, 0.020x1/2x2 in. Two holes, about 3/16 in. in diameter, were made near the ends of the strips in order to hold them against a flat steel block for mounting in a General Electric X-ray spectrometer for lattice parameter measurements. The same holes were used to hang the specimens inside a fused silica vacuum furnace tube which was part of a Sieverts' gas absorption apparatus. The apparatus and method of adding oxygen gas has been previously described.1 According to the supplier, the columbium obtained had the analysis given in Table I. After degreasing the samples, approximately 0.001 in. was etched from each side of the samples in order to remove possible surface impurities from the last rolling operation. For this purpose the following cold acid pickle was found satisfactory: 8 parts HNO3, 2 parts H2O2 and 1 part HF. Various Cb-O compositions were obtained up to 0.75 wt pct O by the gas absorption and diffusion technique. After the sample had absorbed all the oxygen gas added at 1000°C, an additional 24 hr was allowed for homogenization. This treatment appeared to be adequate, as shown by the linearity of the lattice parameter-composition plot. More concentrated alloys were prepared by arc melting mixtures of Cb and Cb2O5 since it was very time-consuming to make Cb-0 alloys in the neighborhood of 1 pct O, or over, by the diffusion method. When the flat strip specimens were used, they were ready for the X-ray spectrometer after cooling from the Sieverts' apparatus. The cooling rate obtained by merely allowing the hot fused silica furnace tube to radiate to the atmosphere (when the furnace was lowered) was sufficiently fast to keep the dissolved oxygen in solution. Arc-melted alloys were reduced to —200 mesh powder in a diamond mortar, wrapped in tantalum foil, sealed off in evacuated fused silica tubes, and then heat treated as indicated in Table 11. The fused silica tubes were quickly immersed in cold water without breaking the tubes after the heat treatments. The tantalum foil prevented reaction between the fused silica and the sample; there was no reaction between the powdered samples and the foil at 1000°C, but some trouble was experienced at 1100°C. At this temperature level a reaction between the sample and the foil was sometimes observed, which resulted in erroneous parameter values. Experimental Results Hardness Tests: Since most of the X-ray samples were in the form of flat strip, it was convenient to obtain Vickers hardness numbers as a function of oxygen content. Compared to the V-O case,' oxygen hardens columbium much more slowly, presumably because of the larger octahedral volume in colum-bium (about 12.0 compared to 9.3Å3 in vanadium), hence, requiring less lattice strain for solution. The plot of VHN vs wt pct O is shown in Fig. 1.

Jan 1, 1955

By R. D. Carter

Nurnerical .solutions are presented to some problems of unsteady-state radial flow of gas in which Darcy's law holds. These solutions are intended to aid in explaining the observed behavior of gas wells during drawdown tests. The variation of viscosity and Z-factor with pressure is accounted for in the solutions. Results are presented for three types of problems: (I) unfractured wells producing at a constant rate, (2) fractured wells producing at a constant rate and (3) unfractured wells producing through a critical flow prover. In the critical-pow-prover solutions, a correction of the calculated well-bore pressure to account for non-Darcy flow is made. A good correlation is shown between the solutions to the problem of Type 1 and the corresponding diffusivity-equation solution. Using this correlation, the diffusivity solution may be used to obtain gas-well solutions. The solutions to the problems of Type 2 illustrate the difference in drawdown-curve behavior to be expected between fractured and unfractured gas wells. Methods for estimatting fracture radius and flow capacity are presented and verified from solutions of Type 2. The solutions to the problems of Type 3 illustrate the differences to be expected between critical-flow-prover drawdown tests and constant-rate tests. An equation is presented for correcting critical-flow-prover data to constant-rate conditions. A description of the methods used in obtaining the solulions appears in the Appendix. INTRODUCTION It is necessary for many engineering purposes, such as predicting future deliverability performance, to be able to relate bottom-hole flowing pressure, formation pressure and flow rate for conditions of stabilized flow in gas wells. This information is customarily given as a plot of on logarithmic co-ordinates. It is desirable to be able to predict stabilized performance curves for gas wells based on data obtained from drawdown tests of short duration. Tests of long duration may be wasteful of gas, and low-permeability wells do not stabilize in a short-duration test. Although it is now commonly recognized that non-Darcy flow plays a significant part in gas-well behavior, it is believed that an understanding of transient behavior of systems obeying Darcy's law is still important in the interpretation of short-term test data, and the prediction of stabilized performance curves therefrom. In this connection, an equation for correcting Darcy flow It seems likely that solutions of the type presented herein, combined with the non-Darcy flow correction of the type of Eq. 1 and the usual laminar-flow skin factor, could provide a model which would adequately explain transient gas-well behavior for times after the non-Darcy flow region (which should be confined to a small area surrounding the well) has been established. The solutions presented in this paper are for three types of problems: (1) unfractured wells producing at a constant rate, (2) fractured wells producing at a constant rate and (3) unfractured wells producing through a critical flow prover. In the problems of Types I and 2, no corrections for non-Darcy flow were made in the results presented, since it was reasoned that the constant-rate boundary condition would facilitate such a correction if it was desired later. For the problems of Type 3, however, a condition of varying flow rate required that a non-Darcy flow correction of the type of Eq. 1 be included. This was done. Based on the numerical results presented, a number of approximations and a correlation are presented which may be useful in analyzing gas-well test data. It is assumed that the system can be described as a finite cylindrical gas reservoir produced by a single cylindrical well located at the center of the reservoir. Flow is strictly radial.