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By H. E. Wilborg, G. V. Henderson

This chapter deals with those sands employed by foundries for the manufacture of cores and molds used in the casting of such common metals as steel, gray iron, ductile iron, aluminum-based alloys, and copper-based alloys. Most metal is cast in "green sand" molds in which the sand mixture, consisting primarily of silica, clay, and water, forms a plastic material. This plastic material is rammed around a pattern in a split box called a flask, then the box is separated, the pattern is withdrawn, and the metal is poured. These green sand molds are broken apart when the metal has solidified. The sand is then remixed and a new mold made for the next casting. To a lesser extent silica sand is mixed with resins or oils and, after forming, the mixture is hardened by either heat or chemical reaction. In any case, the foundry mold or core is used just once before being broken up and remixed for manufacturing another core or mold. By far the greatest consumption in the foundry is of those types of sand high in silica, low in clay (under 0.5%), and occurring in numerous locations thoughout the United States. Consumption End Uses Foundry sands fall into four distinct categories: silica sand, lake sand, bank sand, and natural molding sand. Silica sand is a general term used to describe washed, graded, dried, and cooled clay-free sands which are found in many parts of the United States. They generally contain 90 to 100% silica but vary greatly in chemical analysis and grain structure. Lake sand is the sand dredged from Lake Michigan or dug from the dunes bordering that lake. Bank sand is composed primarily of silica grain but containing up to 5% clay. It is shipped in both the damp and dry state but the normal processing of bank sand consists only of drying and scalping. Occasionally two different grades of bank sand are blended prior to or during loading. Natural molding sand is a term used to describe a sand containing sufficient clay as mined to be suitable for molding purposes. Clay content may vary from 10 to 24% with the balance of the material consisting primarily of silica sand. These sands range in fineness from one peaked on the 20 mesh to one which contains more than 50% of the particles passing the 270 mesh. Lake sands are relatively coarse and are used in great quantities for the production of automotive castings. Bank sands and natural molding sands are gradually phasing out as the production of castings becomes more a science and less an art. The vast majority of foundry sands used today are those known as the silica sands and lake sands. Foundry sands are used in two basic ways. The majority are used in the green or uncured state with the balance used in the cured or set state. Green sand is grain bonded with clay and contains varying amounts of water to plasticize the clay in order to bond the grains together. Green sand is either naturally bonded or "synthetic" sand. The naturally bonded molding sands are generally found in the Hudson River Valley of New York State, Cumberland County in New Jersey, and in Tennessee and Mississippi. Synthetic sand is molding sand compounded in the individual foundry. It is made up primarily of graded silica sand, western or southern bentonite, water, and carbonaceous and/or cellulosic materials. Green sand is used primarily in making molds. The use of naturally bonded green sand has been declining for many years, primarily because naturally bonded sands are more difficult for the foundryman to find and control. Synthetic green sand, on the other hand, can be

Jan 1, 1983

By H. M. Myers, J. E. Funk

The two-phase flow of a drilling fluid in a diamond drill bit is investigated by deriving and solving the steady-state continuity and momentum equations. Parameters in this analysis are rotational speed of the bit, local rate of addition of drill solids, non-Newtonian nature of the drilling fluid and drilling rate. The describing equations relate the flow and pressure drop to the design characteristics of the bit. The equations are integrated numerically yielding the flow-rate pressure drop characteristics for the bit, flow distribution in the bit and velocity and static pressure as a function of position in each flow channel of the bit. Results are presented for a particular bit design. This paper shows that under normal drilling conditions certain parameters may be neglected in the hydraulic calculations for a diamond drill bit. Therefore, shortened forms of the equations presented can be used to fit the proper diamond bit to the drilling fluid hydraulic system. INTRODUCTION Like the conventional bit, the diamond drill bit is a key component in the circulating system of a well. The conventional rock bit is fitted to the circulating system by selecting the flow nozzles which provide the system with the proper flow-rate pressure drop relationship. Fluid behavior across the face of the diamond bit must be better understood so the bit can also be fitted to the circulating system. Data from field-operated diamond bits are presently available and do yield some information regarding the flow-rate pressure drop relationship. However, the number of factors affecting this relationship is quite large. Drilling parameters and conditions such as bit penetration rate, bit weight and rotational speed are important. Moreover, flow channels in the bit are part of the cutting head, and introducing drilled solids into the flow channels reduces the flow area, causes additional drag and influences the pressure drop. Many tests would have to be performed if field tests were required to study all parameters which might influence fluid behavior in the bit. A logical approach to this problem is to investigate analytically the fluid behavior in the bit, including parameters that are present under normal drilling operations. This approach, which seems to offer the best method for future studies, is presented in this paper. Following is the general procedure. 1. Equations describing the most general flow channel are written and include the addition of drilling solids (which is related to penetration rate), rotation of the bit, design parameters of the bit and non-Newtonian properties of the fluid. 2. A typical bit is designed and the bit parameters are substituted into the equations. 3. Parameters are assumed (penetration rate, rotational speed of the bit, mud weight, etc.). 4. The describing equations are numerically integrated to obtain the pressure drop across the face of the bit as a function of flow rate. 5. The pressure-drop contribution of each component (friction, acceleration, etc.) is obtained from the numerical solution, and those factors which largely influence the total pressure drop are identified. Classifying the drilling fluid is important in establishing the friction factor relationship since the frictional pressure losses are the main contributors to the total pressure drop. High-density drilling fluid is commonly assumed to be a Bingham plastic. 1-3 Govier4 presented a method for selecting a friction factor in the laminar flow region from the rheology properties of the mud and a modified Reynolds number. Metzner5 presented a criterion for selecting the friction factor in the turbulent flow region. The bit design used in conjunction with the solution of the equations has divergent flow channels. Stall, which is the backflow of fluid in the channels due to eddies that occur on the outer perimeter of the flow stream, can occur in these divergent channels (or diffusers). When stall does occur the static

By R. S. Shoemaker, D. L. Harris

PST investigations into the possibility of concentrating the low-grade iron ores of the Gogebic Range in Wisconsin have been hampered by the complex association of the constituent minerals. In part the problem arises from the fact that the iron occurs essentially as two minerals, hematite and goethite, having nearly the same chemical composition but exhibiting different physical properties. Individual grains of these minerals are usually so small that the ore must be ground to a size finer than 325 mesh if substantial liberation of the minerals is to be secured. Appraisal of beneficiation tests on this iron ore requires, therefore, some method of determining quantitatively the contents of constituent minerals in the various products of the beneficiation. Because of the chemical similarity of the two iron minerals, chemical analyses do not provide a means of differentiation. Although the minerals are different physically, they are both opaque and friable, and as the ore must be ground to a very fine size for liberation to be secured, quantitative microscopic methods of analysis are extremely difficult at best. In an effort to overcome these analytical problems, a quantitative X-ray diffraction analysis method has been developed at the University of Wisconsin for the research program on iron ore beneficiation. The X-ray diffraction analysis of chemical compounds of crystalline form has proved of inestimable value for structure studies and rapid qualitative analytical purposes in a number of fields.' In some cases X-ray diffraction analysis has been found suitable for quantitative determinations. H. P. Klug2 found that quantitative procedures for quartz powders when mixed with calcium fluoride were reproducible within ±1.0 pct. Talvenheimo and White3 reported quantitative analyses of clay minerals to be accurate within 10 pct and also detected 1 pct of bentonite in 99 pct illite. In other investigations,'" powders of quartz and mica have been analyzed quantitatively with accuracies from 1 to 5 pct. A powder of tungsten carbide was analyzed similarly by Redmond7 and Rooksby8 reported the determination of small amounts (0.11 pct) of calcium oxide in magnesium oxide. In the most generally practiced use of X-ray diffraction, traces of the diffracted beam are recorded as lines on a film much as lines of elements are recorded on an optical spectrograph film. As with the spectrograph, the darkness of the lines denotes the amount of the constituent in the sample. If the film is replaced by a Geiger tube assembly and a graphic recorder or a scaling unit, the intensity of the diffracted beam can be registered as a peak on a chart or energy impulses per unit of time on the scaler. Several methods of quantitative measurement have been investigated and reported in literature. Klug2 used manual operation of the goniometer and a counting technique to determine the difference in counting rates at the diffracted angle and for the background. In another case3 the area under the recorded diffracted peak was the basis for the determination. In other instances the height of the recorded diffraction peak above background, measured while the goniometer was moving, has been the basis for the measurement. The sizes of particles most suitable for diffraction techniques are reported in the literature as follows: for tungsten carbide a maximum of 40 microns7 and for quartz a maximum of 5 microns.' Very fine sizes of crystals are known to cause a broadening of the diffused beams; hence some workers have set a lower limit of 0.1 micron for quantitative results. Guinier10 has indicated that broadening of the diffracted X-ray beam is not appreciable for crystallites larger than 0.02 to 0.03

Jan 1, 1956

By M. E. Wadsworth, C. H. Pitt

Nickel corrosion in sulfuric acid solutions at elevated temperatures and oxygen wer-pressures was imestigated. Weight loss was 1inear with time and varied directly with oxygen concentration. Independent variation of the possible active species in solution indicated that the undissociated sulfuric acid molecule plays an important part in the corrosion mechanism. The rate determining step was considered to be the adsorption of oxygen on a site containing adsorbed H2SO4. THE tendency for a metal to go into solution depends on a number of factors some of which are: 1) the position of the metal in the electrochemical series; 2) the type and concentration of corroding species in solution; 3) the concentration of oxygen in solution; 4) the type of film formed at the liquid-metal interface; and 5) the physical state of the metal. The corrosion of a metal in an aqueous solution may be considered to be a heterogeneous reaction that occurs at the liquid-metal interface. The reaction is generally considered to occur as a result of electrochemical potential differences within the system. Little work has been published in the literature concerning the corrosion of pure nickel. A great deal has been publistled dealing with the experimental and theoretical aspects of the over-all corrosion process. Evans,1 Uhlig,' and recently Todt 3 and Tomashoff,4 have published books which review the results of experiments which have been conducted on corrosion, and have developed some of the basic ideas of the more widely accepted theories of corrosion. Friend5 states that. nickel does not readily discharge hydrogen from any of the common nonoxidiz-ing acids and that a supply of some oxidizing agent is necessary for appreciable rates of corrosion. He further notes that at temperatures between atmospheric and close to boiling, corrosion rates tend to vary with concentration, temperature, and aeration in acid concentrations up to 25 pct. Whitman and Russel6 studied the effect of dissolved oxygen on a number of metals in acid solutions and found that oxygen accelerates the rate of corrosion of nickel in sulfuric acid. Flowers and Kelley7 in studying the action of dissolved CO, on electroplated nickel postulated that nickel dissolves as NiHCO3 in the presence of CO, and air. It was found that oxygen was necessary for corrosion to take place and that the rate increased with increasing amounts of oxygen in solution. Flowers and Kelley attributed the oxygen effect to cathodic depolarization. MacGillavry, Rosenbaum, and wensson' determined metal solution potentials of nickel in various electrolytes. They found that nickel has no tendency to corrode in alkaline solutions in the presence or absence of air. In acid solutions in the presence of air, metal solution potential increases in the order of 1/2 v were observed. This increase was attributed to probable chemisorption of oxygen on the nickel surface and the corrosion mechanism suggested was the interaction of H+ ions with the nickel oxide formed at the surface. Delahay9 observed the reduction of oxygen on various metals. A polarograph was used to measure the course of the reaction. With some metals hydrogen peroxide was produced as an intermediate compound. However, nickel was not considered to be a hdrogen peroxide producer. Van Rysselberghe 10,11 and associates attributed the accelerating effect of carbon dioxide on the corrosion process to the presence of percarbonic acid produced in solution reacting with the hydrogen peroxide. The percarbonic acid can be reduced at less negative potentials than hydrogen peroxide and as a result accelerates the reaction. EXPERIMENTAL Since a complete description of the apparatus used can be obtained elsewhere,12'13 no attempt will be made here to describe the equipment other than to note that it consisted essentially of an autoclave unit from which samples could be withdrawn periodically without disturbing the interior state of the autoclave. A titanium autoclave liner was used to protect the autoclave from the solution.

Jan 1, 1961

By M. S. Hunter, D. L. Robinson

An extremely fine subgrain structure found in aluminum and aluminum alloys is shown and a method for revealing this structure is described. The appearance and some of the characteristics of this structure are described and the possible significance of subgrain structure in terms of chemical, electrochemical, and metallurgical processes is considered. GRAINS and grain boundaries, which constitute the principal manifestations of the crystalline aggregates known as metals, play such an important part in determining the characteristics and properties of metals and alloys that their nature and behavior have long been of much concern to the met-allographer. Many investigators have speculated on the possible existence of a finer structure within the usual grain structure and, through X-ray diffraction and metallographic techniques, have revealed evidence that such finer structures exist. Among these structures are the mosaic blocks and domains described by Burgers1 and others in their contributions on crystalline structure and the dislocation theory, the small units associated with polygoniza-tion described by Cahn,2 and the intragranular blocks revealed more recently by Lacombe and Beaujard.3 his paper describes some novel methods for clearly revealing a very fine granular substructure within the usual grains of pure aluminum and aluminum alloys. It also compares the characteristics and behavior of this subgrain structure with those of the ordinary grain structure and gives some examples of the manner in which this substructure may influence the characteristics of aluminum alloys. Metallographic investigations of aluminum and its alloys have dealt extensively with the functions and behavior of grains and grain boundaries and have evolved a definite concept of the relation between grain structure, orientation and physical, mechanical, chemical, and electrochemical behavior. During the examination of etched samples, a roughening or mottling of the body of certain grains has occasionally been observed. Such roughening obviously represented differential attack by the etching solution, but its true significance was not at first realized. It is now known that this roughening probably rep- resented a subgrain structure, although the particular etching treatments used were not capable of revealing this subgrain structure clearly. Also, in practically all cases, the subgrains were apparently far too small to be resolved by the light microscope. Recently, a method has been developed for revealing clearly the subgrain structure of most aluminum alloys. This method is somewhat unique in that it eliminates much of the usual tedious mechanical polishing and the attendant danger of a surface layer of flowed metal and at the same time is simple, rapid, and effective. It involves the use of the Alcoa R5 Bright Dip, a patented chemical polishing treatment licensed by Aluminum Co. of America. This treatment produces a bright, highly polished surface at least the equal of any mechanical polish and also etches the subgrain boundaries as well as the ordinary grain boundaries to reveal both the grain and subgrain structure simultaneously. Metallographic specimens to be examined are taken through the customary grinding and polishing operations used for aluminum alloys.' The usual care required in the final polishing operation to prevent a flowed surface layer and to obtain a high polish is not necessary, however, because any flowed layer is eliminated and a high polish is produced by the final immersion in the Alcoa R5 Bright Dip. Depending on alloy type, this dip takes from a few seconds to about 3 min, after which the sample is rinsed well, blown dry, and is ready for examination. The substructure can be revealed by some of the usual metallographic methods such as electropolish-ing or mechanical polishing and etching but no method has been found which is the equal of the new chemical polishing treatment. Mechanical polishing followed by the usual metallographic etching is not entirely satisfactory for revealing this substructure, probably because of the flowed surface layer resulting from the mechanical polish. If the usual etching methods are prolonged sufficiently to remove this layer, the specimen surface becomes quite rough and the substructure is not defined clearly.

Jan 1, 1954

By Irving Cadoff, Kurt Komarek, Edward Miller

THE lead-telluride phase diagram as compiled by ansen' has one intermetallic compound, PbTe, with solid-solubility limits extending from 22 to 45 wt pct Te (31.4 to 57.1 at. pct). Pelzel2 redetermined the solubility limits on the lead-rich side of the compound by measuring the relative areas of the two phases in samples annealed in the liquid + compound region, and obtained data that agreed with that of Hansen. Recent studies of the semiconducting properties of PbTe3 however, have indicated that addition of either lead or tellurium to PbTe does not produce samples having carrier concentrations greater than about 10 19 cm-3. Assuming that each impurity atom results in one ionized charge carrier, this carrier concentration corresponds to a solubility range of less than 0.04 at. pct. Fritts and Karrar4 have also observed two phases in samples containing from 0.15 to 3.0 pct excess Pb. To resolve the discrepancy between these data, the solid solubility limits of the compound PbTe were reinvestigated, using several other techniques. Ten 25-g samples with compositions of 1/2, 1, 3, 5, and 10 wt pct excess Pb and Te and two 100-g samples of 15 and 65 wt pct Te were prepared, sealed in evacuated quartz capsules, and melted at 950oC. The 1 pct excess Pb and Te and the 15 and 65 wt pct Te alloys were homogenized for 96 hr at 450°C; the remaining specimens were annealed 50°C below the solidus temperature reported in Hansen. The specimens were polished and etched with dilute HNO,. All the samples were two phase, the second phase appearing at grain boundaries or as spheroidized inclusions in the grains. In the case of the tellurium rich specimens, the second phase could be identified as a eutectic. Debye-Scherrer powder diffraction patterns of the i, 1, 3, 5, and 10 pct excess samples were obtained using CuKa filtered radiation. The films were indexed as the B1 or NaCl structure. The calculated lattice parameter of PbTe was the same for all the specimens, with an average of a0 = 6.460 ± 0.0005A. Lines due to excess lead or tellurium were very faint but could be clearly seen in all the films. The relative areas of the two phases in the 15 and 65 wt pct Te samples were corrected for the differences in density of Pb, Te, and PbTe, and taken as proportional to the relative volumes of the two phases. The corrected relative volumes agreed with a phase diagram having negligible solubility of both lead and tellurium in lead tellurium. The density of the two specimens was obtained to give a third independent determination of the phase limits. The specimens were broken into small pieces to eliminate any internal porosity, and adherent air bubbles were removed by vigorous shaking under water for several hours. The density of lead (11.34 g per cm3) and of tellurium (6.25 g per cm3) was taken from the International Critical Tables and that of stoichiometric PbTe (8.25 g per cm3) calculated from the lattice parameter. For the 15 wt pct Te samples, the density assuming no solubility was calculated to be 9.89 g per cm3; the observed density was 9.86 g per cm8. For the 65 wt pct Te alloy, the density calculated for the case of no solubility was 7.24 g per cm3; the measured density wag 7.22 g per cm3. These results are consistent with those of planimetry and X-ray. SUMMARY Data have been presented which show that the solid solubility of both lead and tellurium in PbTe is

Jan 1, 1961

By John Chipman

THE equilibrium between titanium in liquid iron and titanium oxides has been studied by Hadley and Derge.' They have shown that a minimum occurs in the oxygen content of the metal between 0.1 and 1.0 pct Ti, but its exact level was not fixed. The oxide phase in this minimum range was principally TiO, containing some iron oxide. On the other hand, for concentrations above 5 pct Ti the oxide phase was TiO and the oxygen content of the metal increased rapidly with increasing titanium content. From their observations and the free energy of Ti0 and TiOz reported by Kelley and ah,' it is possible to derive approximate values for the activity coefficients of titanium and oxygen in liquid iron-titanium alloys and the conditions for equilibrium in steel deoxidation. Neglecting possible departures from the stoichio-metric composition, the condition of equilibrium with Ti0 may be expressed as follows: TiO= Ti_ + C) log K = log NTl + log [% O] + log yTi + log fQ Here as a matter of convenience the titanium concentration is expressed in mol fraction while that of oxygen is in weight percent. The activity coefficients are yTi and fo. The value of log fo approaches zero as the concentration of titanium approaches zero, while that of log yTi approaches a limiting value of In Fig. 1 the sum of log NTi + log [% 0] is plotted for mol fractions of titanium between 0.05 and 0.50. The smooth extrapolation gives a value of —4.15 which corresponds to log K — log y:i . We therefore have the equation: According to the data of Kelley and Mah,' the free energy of formation of Ti0 at 1900°K is -82,400 cal. The free energy of solution of half a mol of oxygen in iron, taking 1 pct 0 as the standard state, is -29,300 cal. From these we write: From these equations the activity coefficient of titanium at infinite dilution in iron is found to have a value of 0.011 or log y°. = -1.96. This is only an approximate value but is certainly better than the estimated 0.05 in Basic Open Hearth Steelmaking To obtain approximate values for the activity coefficient at intermediate concentrations, it is as- sumed that log yTi(l is constant and equal to -1.96. This corresponds to a value of E;: = 3 In yTi/aNTi = 9.0 which is not unreasonable We now have the value for the activity of titanium and the percentage of oxygen in equilibrium with TiO. It is therefore a simple matter to calculate the activity coefficient of oxygen which is shown in Fig. 2. The effect of titanium is rather large, being comparable to that of vanadium, but not so large as has been reported for aluminum. The slope of the line at low concentrations corresponds to E: = aln yo/ aNTi=-0.37. At concentrations below 1 pct Ti the deoxidation constant and oxygen content for equilibrium with TiO, can be calculated from the foregoing data and the free energy of formation of TiO,, which according to Kelley and Mah is -144,600 cal at 1900°K. The free energy of solution of oxygen has been given; that of Ti to form a dilute solution with 1 pct Ti as the standard state is RT ln (0.5585 y:i/47.9) = -34,800 cal. From these data we find (for concentrations in wt pct): TiO, = Ti + 2 -0; hFTgO0= + 51,200 cal log if =-5.89 The interaction coefficients, concentrations being expressed as wt pct, are e;: = alogfTi/a[% Ti] = +0.048 and e:' = a logfo,/a[ojTi] = -0.187. The calculation gives the following results which, in view of the impurity of the oxide phase, must be regarded as approximate:

Jan 1, 1961

By G. S. Coe, G. F. Bolling

The columnar-to-equiaxed transition (CET) has often been studied as a function of concentration, C, temperature gradient in the melt, G, and rate of solidification, R. Although it may not be immediately obvious it is sure that the CET, expressed as some ratio G/R necessary to suppress equiaxed nucleation for a given C,' cannot be a single-valued function of C. This restriction which is ignored in theoretical presentations is most trivially illustrated by the following simple reasoning. An ordinary casting is an unconstrained system where the thermal conditions change continuously with progressive solidification, and thus where the ratio G/R decreases from the outset. A CET occurring early in a casting (much equiaxed material) must then mean a higher value of G/R at transition, in comparison with the late CET which implies a more columnar ingot. Therefore, when we choose to experiment under constant superheat for all alloys across the simplest binary, and we find an inversion in the amount of equiaxed material, we shall find two values of C satisfying the G/R condition. However, in addition to this simple instance, the early experiments of ~orthcott' seem to show that the amount of equiaxed material in cast ingots may be a multivalued function of composition in a given binary system. In the present investigation, the CET has been examined in Pb-Sb, Pb-Ag, Pb-Sn, and Sn-Pb under several types of casting conditions. First, we have used the "bidirectional" ingot section Simulation;~ and we have used .'i~z situ" ingot solidification where a hot mold already filled with liquid is chilled so that there is no disturbance provoked by pouring. Differences in method are trivial to our purpose except for the fact that certain variations are more simply observed by one technique than by the other. Second, we have varied the mode of superheating from the simple extreme of casting all alloys from the same temperature regardless of composition to the careful casting at a standard superheat, calculated with respect to the alloy liquidus. Third, we have made provisions for decanting and interface observation, so that some "castings" were not completed. The results obtained with Pb-Sb are exemplary; some of these are shown in Fig. 1 along with explanatory captions. At 9 to 10 at. pct Sb, and thus above the solid-solubility limit Cs = 5.8 at. pct Sb and yet below the eutectic concentration Ceu = 17.5 at. pct Sb, there is a persistent anomaly in all the variations. Measurement was easy enough and standard enough so that we may forgo discussion of either method or possible error, in view of the forceful self-consistency shown by experiment. Solute distributions were measured along the bidirectional ingots in order to determine if a solute buildup had occurred at the CET. No anomalous changes in concentration were observed along the bars at either side of the solute anomaly of 10 at. pct Sb. The microstructures of the ingots were also examined across the range of composition investigated. At concentrations less than 9 at. pct Sb the micro- and macrostructures were typical of the cellular-dendritic growth usually reported for the columnar zone. Above the anomaly, both the columnar grain size and the amount of primary phase decreased. This microstruc-tural observation can be correlated with observations made of decanted interfaces. Below 9 at. pct Sb, the interface reveals the "normal" columnar dendritic structure; however above the anomalous concentration range, preferential growth of certain dendrites appears to form a "super dendrite" pattern. In Fig. 2 a microstructural view of the etched '(super dendrites'' shows their constitution both in terms of relative phase proportion and in terms of the ordinary smaller dendrites.

Jan 1, 1969

By D. L. Martin

THAT small amounts of impurities have a harm-J- ful effect on the malleability of metals and alloys is well-known. One common type of em-brittlement involves the formation of a small quantity of eutectic at the grain boundaries, and is typified by sulfur embrittlement of nickel. Another example of eutectic embrittlement—sulfur embrittlement of cobalt—is described in this report. In the preparation of specimens for a study of Co-Pt alloys, it was observed that the hot swagabil-ity of the alloys appeared to be influenced by the grade of cobalt used as melting stock. The cause of the hot-shortness was not traced to any particular impurity, although sulfur was suspected.' The damaging action of sulfur on the malleability of cobalt has not been generally recognized,'; in spite of the fact that the Co-S phase diagram8 eveals the same basic conditions—low solubility and eutectic formation—responsible for sulfur embrittlement of iron and nickel.7, 8 Apparently sulfur embrittlement has not been a serious problem in the fabrication of cobalt alloys. One related factor is likely the limited commercial experience with high cobalt alloys, since the predominant use of cobalt has been in alloys containing less than 75 pet Co. A series of Co-S alloys was prepared and studied to establish the effect of sulfur on the hot working characteristics of cobalt. Specimens, 5/8 in. diam by 4 in. long, were prepared by vacuum melting in magnesium oxide crucibles and casting in a copper mold. Two grades of low sulfur electrolytic cobalt were used as the basic material for the study, one from Johnson, Matthey and Co. and the other from the International Nickel Co. Each contained about 99.5 pet Co and had a nominal sulfur content under 0.005 pet. The sulfur was added initially as cobalt sulfide powder. Later, some low sulfur alloys were prepared by diluting the high sulfur alloys with cobalt. Trouble was experienced in controlling the sulfur content. Apparently much of the cobalt sulfide powder was lost during melting, as most of the samples contained a lower sulfur content than was added. The alloys were evaluated for hot brittleness by heating to 1000°C in a hydrogen furnace and swaging in air. The results of these tests are summarized in Table I. All the alloys containing less than 0.008 pet S were successfully hot swaged to 1/4 in. diam. The bars containing more than 0.015 pet S could not be swaged because of the formation of intercrystal-line cracks similar to those illustrated in Fig. 1. Examination of the microstructure of the cast bars revealed cobalt sulfide eutectic at the grain boundaries, Fig. 2. The sulfide was not always continuous at grain boundaries in bars that were hot embrittled but, in general, the particles did form a network that could account for the brittleness above the eutectic temperature, 880°C. There is no question about the brittle nature of a specimen exhibiting a continuous sulfide network such as is shown in Fig. 2b, though a sulfide distribution similar to that in Fig. 2a is marginal. This particular bar cracked when hot-swaged. However, other bars with lower sulfur content but with some sulfide phase at grain boundaries were successfully worked. The reduction of area of a hot tensile test specimen was also found to be a sensitive indicator of sulfur embrittlement. The variation of reduction of area with sulfur content is shown in Fig. 3 for specimens fractured at 900°C in an evacuated capsule. The ductility of cobalt is greatly reduced when the sulfur content exceeds 0.005 pet. Similar results were obtained for alloys tested at 800°C, below the eutectic temperature. The upper sulfur embrittlement limit of 0.015 pet, Table I, agrees with the observation of Kalmus8 hat

Jan 1, 1957

By Gordon W. Hodgson, Edward Tipman

INT'RODUCTION An appreciable number of the oil fields in Western Canada are accumulations of heavy black oils in more or less unconsolidated sandstones. When the crude oils are produced by conventional means, they are frequently contaminated with both sand and oilfield water. The water is usually present as emulsified water, and the sand and other solid materials are suspended in the emulsions. The presence of the solid material in the crude oils is troublesome and, in general, little is known about the behavior of suspended solid particles in emulsions. The Stokes equation describes the behavior of suspended particles in homogeneous fluids in terms of particle size, density differential, and fluid viscosity. In the case of an emulsion, particle size and density differential introduce no difficulties, but considerable doubt centers around the viscosity term. It has been reported1 that the viscosity of an emulsion is related to the viscosity of the continuous phase by an expression of the type: n = a, (1 + a C) where n is the viscosity of the emulsion, n,, is the viscosity of the continuous phase, a is a constant, C' is the volume concentration of the disperse phase. The value of 17, the coefficient of the concentration term, has been determined for various systems, and has been found to vary from a value of 1 to 4.75. The value of 2.5 has been found to be applicable to a large number of systems, and this is the value that is widely used in the equation which then becomes the Einstein equation for the viscosity of emuls~ons. It is of considerable significance that neither the particle size nor the viscosity of the disperse phase enters the expression; the expression for the viscosity of the enlulsion is based solely upon the viscosity of the continuous phase and the concentration of the disperse phase. For crude oil emulsions the Simha equation and the data presented by Fukushima and lchimurai show a non-linear dependence of the viscosity ratio on the water concentration. While it is undoubtedly reasonable to use these data for predicting the viscosity of a specific emulsion, and while it is equally reasonable to expect the calculated viscosity to predict the settling rate of a solid spherical particle in the emulsion by means of Stokes equation, there seems to be no direct evidence that this calculation is indeed sound for describing the settling rates of solid particles in emulsions of water in crude oils. PROCEDURE A direct approach to the problem was thus indicated. Laboratory equipment was designed and built for the direct determination of the rate-of-fall characteristics of solid particles in emulsions of water in oil. Although the apparatus incorporated the basic design of conventional falling-ball viscometers, the study was concerned directly with the rate-of-fall characteristics of particles in emulsions, rather than with the viscosity of the emulsions as such. The crude oil used in this study was a very heavy black crude oil—the McMurray oil obtained from oil-soaked sands outcropping on the Athabasca River in northeastern Alberta. It was produced from the sands by strip mining followed by hot-water separation of the oil in the separation plant of the Alberta Government at Bitumount'. The primary plant product was a wet crude oil containing about 5 per cent solids and 35 per cent water. The final plant product was only slightly different from the native oil, having lost only about 4 per cent of its bulk as light ends during dehydration distillations. In the present investigation two kerosene dilutions of the McMurray oil were used in addition to the dry plant product. The McMurray oil contained 1.92 per cent solids. Analysis of the solids by X-ray diffraction showed the presence of kaolinite, pyrite, and illite as major constituents. with lesser amounts of quartz. Particle size of the pyrite and quartz was less than 10

Jan 1, 1957

By G. K. Manning, W. E. Few

T has been known for some time that both'inter-granular carbide and intergranular oxide phases cause brittleness in molybdenum. Parke and Ham' indicated that 0.0025 pct 0 present in molybdenum after solidification from the melt was sufficient to induce intergranular brittleness during forging. However, material containing 0.06 pct C could still be forged. However, adding this amount of carbon to insure deoxidation causes the formation of carbides on freezing. These carbides are precipitated at grain boundaries, and Rengstorff and Fischer' have shown they have an unfavorable effect on the room-temperature ductility of molybdenum. Take? in 1928 proposed that the solubility of carbon was a constant value of 0.30 pct from room temperature up to 1800°C. In 1935, Sykes, Van Horn, and Tucker' obtained X-ray data suggesting that the solid solubility of carbon in molybdenum was between 0.07 and 0.09 pct at temperatures from 1500" to 2100°C. The a-solubility line for carbon was included in the Mo-C diagram given in the Metals Handbook as a tentative line based on the data of Sykes, Van Horn, and Tucker. In order to determine the partial phase diagrams for these systems, it was necessary to construct a high-temperature furnace suitable for heat treating molybdenum at temperatures up to 4000°F. A molybdenum resistance furnace was built for this purpose in which samples could be heat treated in a purified atmosphere and quenched from any desired temperature.' Experimental Work Solubility of Carbon: Arc-cast molybdenum supplied by the Climax Molybdenum Co. and 18-gage molybdenum wire samples produced by powder metallurgy at the Fansteel Metallurgical Co. were used in determining the a-solubility line for the MO-C system. The cast molybdenum contained 0.032 pct C initially. Two lots of 18-gage wire were used, one containing 0.011 pct C and the other 0.005 pct C initially. All material contained a carbide phase as received. Fig. 1 illustrates the carbides found in the untreated material. Heat treatment in a purified hydrogen atmosphere was found to reduce the carbon content in the as-cast molybdenum. Purified argonT also decarburized molybdenum samples at temperatures above 3500°F; however, the carbon content remained constant during heat treatment in purified argon at lower tem- peratures. The argon was purified by passing it over titanium at 750 °C and then through a magnesium perchlorate drying tower. The hydrogen was purified by passing it through a commercial hydrogen deoxidizer, followed by a drying tower. Specimens having different initial carbon contents were heat treated in argon at 3500°F for periods ranging from 5 min to 5 hr and were analyzed for carbon. Samples of the same final carbon content had the same microstructures regardless of time at temperature. Furthermore, a gradient between center and surface in the amount of undissolved carbide particles present was never observed. It was concluded that at these low carbon levels, and at the high temperatures involved, diffusion proceeds so rapidly that the specimen is always substantially homogeneous in carbon content, in spite of the gradual loss in carbon. Based on the above findings, the following procedure was used to determine the carbon-solubility limit at 3000°, 3500°, and 4000°F. At each of these temperatures, a number of samples were heat treated, as shown in Table I, and rapidly cooled to room temperature. Since the samples lost carbon in proportion to the length of time heated, a series of samples were obtained of varying carbon contents. By use of a rapid cooling rate, the phases present at the high temperature were retained at room temperature. All samples were examined microscopically. Those found to contain either no excess carbide phase or only a very small amount were then analyzed for carbon. The samples actually analyzed for carbon

Jan 1, 1953

By G. Krauss, J. M. Thompson, H. Y. Kumagai

Boron-doped p-type and arsenic-doped n-type source materials were used to deposit thin silicon films on amorphous fused quartz substrates by cathodic sputtering in argon atmospheres. All as-sputtered films were found to have high electrical resistivities of about 104 ohm-cm, despite controlled variation of the substrate temperature from 50O to 400°C. The high resistivity of the n-type films persisted even after postdeposition heat treatments as high as 1000°C, while p-type films showed a sharp decrease in re-sistivity to values on the order of 1 ohm-cm or lower after heat treatments above 650°C. X-ray and electron diffraction, together with transmission electron microscopy of the p-type films, revealed that the improved electrical properties resulted from two distinct processes. A primary crystallization or recovery within the pains, which were approximately 200Å diam in the as-sputtered films, accompanied the initial sharp drop in resistivity at 650°C. Following this process, a secondary recrystallization or discontinuous grain growth was nucleated in films heated at 1000°C. The resulting significantly increased size of certain grains and the corresponding decrease in grain boundary area accompanied an additional decrease in resistivity after heat treatment at 1000°C. The properties of thin silicon films are of interest because of their possible application in device technology. Although evaporated silicon films on amorphous substrates1-3 and both sputtered and evaporated germanium films4-' have been studied in some detail, sputtered silicon films have not been widely investigated. It has been observed that evaporated silicon films deposited at substrate temperatures below approximately 600°C are amorphous.1,3,9,10 At substrate temperatures higher than this, the films are polycrys-talline, sometimes exhibiting a fiber texture with the fiber axis normal to the substrate surface.' Similar results have been obtained with germanium films, although in this case the substrate temperature for the amorphous to crystalline transformation is reported to be as low as 150OC.5 The mechanism of film deposition by cathodic sputtering differs markedly from that of thermal evaporation. It might be expected, therefore, that the properties of sputtered and evaporated silicon films would also differ. The purpose of our study was to determine the effects of deposition conditions and heat treatments on the electrical resistivity, structure, and composition of thin silicon films sputtered on fused quartz substrates. EXPERIMENTAL DETAILS Apparatus. A schematic diagram of the sputtering apparatus is shown in Fig. 1. The vacuum chamber was enclosed by an 18-in.-diam by 12-in.-high Pyrex bell jar mounted on a stainless-steel base plate. Access holes in the base plate were used to supply argon gas to the chamber, to allow for various electrical feedthroughs, and to provide mechanical motion to the shutter between the source material and substrate. The chamber was evacuated by a pumping system consisting of a 720 liter per sec oil diffusion pump backed by a 13 cu ft per min mechanical pump. Ultimate pressures of less than 1 x 10-6 torr could be achieved. The substrates were securely mounted on the stainless-steel substrate holder by quartz tabs held in place by stainless-steel screws. Temperatures of the substrate holder were measured by a thermocouple inserted within the holder. A quartz lamp was used to heat the holder and temperatures as high as 420°C could be maintained. Deposition Conditions and Procedure. The substrates used were polished fused quartz slides 116 by 1-12 by 3 in. and were outgassed at 200°C for 1 hr at a pressure less than 1 x 10-5 torr before film deposition. This was followed by a presputtering period of 2 hr during which the movable stainless-steel shutter was so positioned that deposition on the substrate was prevented. At a sputtering voltage of 5000 v dc and an argon pressure of 0.03 torr, the cathode cur-

Jan 1, 1967

By Archer Wheeler

The Boston & Montana Reduction Works at Great Falls, Mont., was formerly the reduction works of the Boston & Montana Consolidated Copper & Silver Mining Co., and continued as the reduction plant for the independent company until .June 1., 1910, when the consolidation of a large number of the operating companies of Butte was effected. It then became merged in the Anaconda Copper Mining Co. as the Boston Montana Reduction Department of the Anaconda Copper Mining Co. The history of copper converting at this plant, while not covering the entire period of the commercial use of the process in this country, does cover by far the larger part of it, and as the operations and appliances of the process have undergone many changes during the time, it may, perhaps, be of some interest to put the record of these changes into permanent form. The plan followed in the preparation of this paper has been to give first a brief chronological record of the principal events and changes and then, even at the risk of some repetitions, to give more detailed account, of some of these changes under separate headings. The headings for the complete paper are as follows: 1. General Chronological Review. 10. Development of Different Classes 2. Mechanical Manipulation of Converters After Class I. 3. Casting of Finished Copper. 11. Basic Lining. 4. Tamping of Linings. 12. Number and Size of Tuyeres. 5. Early Acid Linings. 13. Cast Copper Tuyeres. 6. Acid Linings With the Use of Ore. 14. Efficiency of Air. 7. Introduction of Flux Through the 15. Size of Converter Mouth. Tuyeres 16. Height of Converter. 8. Bottom Blast. 17. Summary. 9. Disposal of Converter Slag.

Jan 8, 1913

By A. C. Heath, E. H. Dix

THE importance of aluminum-silicon alloys in the light alloy field is now generally recognized. Where silicon was once considered detrimental to the properties of aluminum, useful alloys now contain as much as 13 per cent. Furthermore, silicon is present as an impurity in aluminum of even the purest grades. Iron is another important impurity in aluminum and like silicon is found in small quantities in the purest aluminum available today. The manner of occurrence of iron and silicon in commercially pure aluminum and many of its alloys exerts a very pronounced influence upon their properties. The effect of large quantities of iron in aluminum-silicon alloys is so detrimental that it has been found necessary to limit the allowable maximum percentage to as low a figure as is consistent with quantity production and satisfactory physical properties. The intimate relation existing between iron and silicon in aluminum and aluminum alloys makes necessary a more complete knowledge of this ternary system. This paper is divided into two principal parts, dealing respectively with aluminum-silicon solubility equilibria and the constitution of aluminum-iron-silicon alloys. PART I.-ALUMINUM-SILICON ALLOYS The early work on this system was largely confined to determining the general form of the diagram and in this respect the results are in good agreement. Briefly, aluminum and silicon form a simple eutectiferous series without compounds. Until recently the solid solubility of silicon in aluminum had not been accurately determined. Fraenkel1 (1908) stated that aluminum will retain 0.5 per cent. silicon in solid solution. Rosenhain, Archbutt and Hanson2 gave the maximum solubility as about 1.50 per cent. and added that "this solubility does not appear

Jan 1, 1928

By Edward W. Parker

At the Seventy-sixth meeting of the Institute, held in New York, N. Y., February, 1899,I presented a paper on this subject entitled, Coal-Cutting Machinery,' which has become somewhat out of date, in view of the decade's development in this feature of the coal-mining industry. It should be explained that the present paper is limited to the use of mining-machines in bituminous mines. Practically all of the anthracite mined is "shot from the solid," no undercutting being done. Anthracite-mining is therefore not considered in the statistics or other references. The statistical record as compiled by the U. S. Geological Survey shows that in 1898, the year preceding the presentation of my former paper, there were 32,413,144 short tons of coal undercut by the use of machines. In 1907 the machine-mined coal-product amounted to 138,547,823 short tons. In sympathy with the general decrease in coal-production during 1908, the output of machine-mined coal decreased to 123,183,334 short tons, but the proportion of machine-mined coal to the total output, nevertheless, showed an increase, from 35.1 per cent. in 1907 to 37 per cent. in 1908. In 1898 only 19.5 per cent. of the total product was unclercut.by the use of machines. The number of in use in the bituminous mines of the United States has increased from 2,622 in 1898 to 11,144 in 1907, and to 11,569 in 1908. The total production of bituminous coal in the United States in 1908 mas almost exactly double that of 1898, while the machine-

Jan 1, 1911

By G. M. Webster, G. E. Dawsongrove

The use of percussion-type side-wall cores as an aid in detection and evaluation of hydrocarbon shows and in examination of rock properties has become increasingly popular in recent years. Sidewall coring has an advantage over normal bottom-hole coring methods in that the zones may be surveyed with the electric log prior to selection of sample depths. This allows an efficient sampling of all zones of interest, a procedure not possible with bottom-hole coring techniques unless the costly procedure of continuous coring is utilized. Percussion sidewall coring presently provides the most rapid and lowest cost method of obtaining sidewall cores. It has been recognized for some time that certain discrepancies exist between core analysis data obtained from percussion cores and data obtained from other types of core Samples. This paper presents existing field and laboratory data that were available to the authors. Several examples of comparative core analysis data obtained from various fields are presented along with photomicrographs of thin sections of conventional and percussion cores. The results of this investigation are presented to throw more light on the possible disturbed condition of percussion sidewall cores. SAMPLE DISTURBANCE AND FRACTURING The principal cause of discrepancy between conventional core analysis data and percussion sidewall core analysis data is believed to be the shattering and re-adjustment of the grains due to the large impact shearing forces produced by mechanics of percussion coring. Figs. 1 through 5 are photomicrographs of thin section slides of formation samples obtained by means of diamond cores, conventional cores, and percussion sidewall cores. Figs. 1 and 2 show samples of the

By Glenn C. Waterman, Scott Hazen

3.1-1. Purpose. Development drilling is directed towards determining the grade, volume, and three-dimensional outline of a mineralized zone previously located by exploration. It is distinguished from exploration or reconnaissance drilling, which has as an objective the discovery of new mineralized areas. A development drilling and bulk sampling program should furnish the following information: 1. Geology of the mineralized zone. 2. Quantitative data on grade and tons of material within pertinent cutoff limits. 3. Physical size and shape of the deposit. Areas underlain by waste as well as ore. 4. Mineralogica1 and metallurgical characteristics of the ore. 5. I1hysical characteristics of the ore. 6. Hulk samples for metallurgical testing and grade check. 7. Data on other factors that could affect mining operations, such as ground water, ground conditions, etc. 3.1-2. Procedures. There are numerous methods and techniques that are used to acquire pertinent data on a potential ore deposit. The total cost and accuracy of a development program depends on significant evaluation of the geology, proper selection of a drilling method, thorough analysis of sample data, and accurate evaluation of all the information. Knowledge of the geology of the mineral deposit is important in planning the development testing program and in evaluating the data obtained from such a program. Exploration work usually provides some significant information on the general size, shape, thickness, grade, and geology of the deposit. In some cases no further data are needed; in many cases geological complexities suggested by the preliminary work require further geological study. Of considerable importance may be the following:

Jan 1, 1968

By D. L. Gardner, H. L. Barr

The following report covers the history of the development of the mine, present equipment, methods and costs of mining and milling. In addition, a description of the ore deposit is given with emphasis on the origin of the fractures, mode and types of ore occurrence, and mechanics of granite emplacement. An endeavor has been made to present a complete and accurate statement of the San Mauricio mine, the highest grade gold mine in the Philippine Islands. Credit is gratefully acknowledged to the mine staff for descriptions and details regarding their particular field of work. All analyses were made by Mr. T. A. DeVore, head chemist, San Mauricio Mining Co. Messrs. Edward Wisser, J. E. Fyfe, A. F. Skerl and W. B. Meek, geologists, have contributed geologic information and ideas, for which thanks are extended. The Executive Committee of Marsman and Co., Inc., Managers of the Company, has kindly given permission for publication. Mr. J. B. Stapler, Division Manager, Marsman and Co., has had the courtesy to read the manuscript and to give critical and helpful suggestions. Location of Area and Scope of Work San Mauricio Mining Co. controls a group of 113 claims that lie immediately north of the town of José Pafiganiban (formerly Mambulao), Camarines Norte, Luzon, P. I. (Fig. 1). Exploration work commenced in the spring of 1934; active development began in the fall of that year and has continued to the present date. Mill construction was begun Ocl,. 15, 1935, and production started March 10, 1936. Total production to June 1, 1939, is P10,499,105.15 ($5,249,552.57).

Jan 1, 1941

By D. L. Gardner, H. L. Barr

The following report covers the history of the development of the mine, present equipment, methods and costs of mining and milling. In addition, a description of the ore deposit is given with emphasis on the origin of the fractures, mode and types of ore occurrence, and mechanics of granite emplacement. An endeavor has been made to present a complete and accurate statement of the San Mauricio mine, the highest grade gold mine in the Philippine Islands. Credit is gratefully acknowledged to the mine staff for descriptions and details regarding their particular field of work. All analyses were made by Mr. T. A. DeVore, head chemist, San Mauricio Mining Co. Messrs. Edward Wisser, J. E. Fyfe, A. F. Skerl and W. B. Meek, geologists, have contributed geologic information and ideas, for which thanks are extended. The Executive Committee of Marsman and Co., Inc., Managers of the Company, has kindly given permission for publication. Mr. J. B. Stapler, Division Manager, Marsman and Co., has had the courtesy to read the manuscript and to give critical and helpful suggestions. Location of Area and Scope of Work San Mauricio Mining Co. controls a group of 113 claims that lie immediately north of the town of José Pafiganiban (formerly Mambulao), Camarines Norte, Luzon, P. I. (Fig. 1). Exploration work commenced in the spring of 1934; active development began in the fall of that year and has continued to the present date. Mill construction was begun Ocl,. 15, 1935, and production started March 10, 1936. Total production to June 1, 1939, is P10,499,105.15 ($5,249,552.57).

Jan 1, 1941

By Carlo Massa

THE Societá Auonima di Miniere e di Alti Fourni, familiarly known as the " Elba Company," works the rich ore-deposits of the Island of Elba under a long-term contract with the Italian Government. The ore-deposits are scattered over the eastern and southeastern coast; but as those parts of the island are not well provided with ports, the blast-furnaces were built at Portoferraio, the principal town of the island, situated on the northern shore, and possessing a magnificent natural harbor where even vessels as large as the battleships of the Italian navy can comfortably anchor. In the selection of Portoferraio. the cost of transporting the iron-ore from the different mines to the blast-furnaces has been reduced to a minimum, and shelter has been provided for the Company's flotilla of tugs and barges, as well as for the steamers carrying coal and pig-iron. The whole plant, of which a general view is given in Fig. 1, comprises 1. A discharging-pier with unloading-cranes. The ore and coal are transported from this pier by means of an aerial cable-rail¬way to the coal- and ore-storage yards. This cable-railway is supported by an iron bridge extending from the pier to the shore and by a wooden trestle extending from the shore to the yards. , 2. Blast furnaces, two in number, with all the accessory appa¬ratus, such as blowing-engines, dry purifiers, Cowper hot-blast stoves, hoists, etc. 3. Coke-ovens, two batteries, with coal-bin, crushers and boilers. 4. Engine-house containing the blast-engines and the electric generating-station. 5. Pumping-plant. 6. Narrow-gauge railways.

Mar 1, 1905