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Discussion of the paper of C. W. WASHBURNE, presented at the Pittsburgh meeting, October, 1914, and printed in Bulletin No. 93,. September, 1914, pp. 2365 to 2378. ROSWELL H. JOHNSON, Pittsburgh, Pa.-It seems to me rather important to bear in mind one thing which is sometimes lost sight of, that the marine sedimentary rocks are laid down in water. We have to start with an initial charge of water. That being so, and the surface tension between the water and the -oil being as slight as it is, as referred to by Mr. Washburne,. the phenomena of capillarity are bound to be most important as between the liquid surface and the gas surface. So far as the liquid-gas surface is concerned, capillarity, in my opinion, is of the utmost importance, and it seems to me this paper of Mr. Washburne's is of great value to us for that reason. Starting out as we have, with our attention concentrated upon gravitational sorting, we have had to wait for the discussion of movement furnished by Munn, and this discussion of capillarity by Washburne, for a more balanced view of the situation. It seems to me that in the accumulation of oil and gas we have a problem of the interworking of gravitational sorting, capillarity, viscosity, immiscibility, and movement. All five things seem to me to be important. I would have expected Mr. Washburne to have given a fuller treatment of the relation of movement to capillarity. In my own experiments I find that gravitation and capillarity alone seem remarkably impotent when everything is at rest, but if I furnish a little movement, gravitation and capillarity step in and accomplish a great many results that one would not expect. Take a horizontal tube and fill a portion at the middle with an ordinary sand saturated with oil, and then put water and sand in each end, and the tube may remain at rest a very long time without that oil distributing itself along the top of the tube. But with a little motion that oil will gradually work up to the upper side. So gravitation and capillarity alone are rather impotent unless they get this element of movement. It would not be necessary to have very extensive movement, but some degree of movement is essential. Now if natural gas, in addition to the method of origin by the action of bacteria on organic matter in mud, may also arise by pressure at great depth, as the overburden is added, a great deal of motion may result. I think more motion is produced in this way than by the descent of meteoric waters.

Jan 4, 1915

By Frank C. Schrader

Page Introduction.............................. 196 Geology of the District......................... 196 Ore Deposits of the District....................... 198 Gcncral Description........................ 198 The Cerbat Mountains Group................... 199 General Description...................... 199 Tennessee Mine....................... 203 Midnight Mine........................ 203 Mineral Park........................ 204- Golconda Mine........................ 204 Other Ore-bearing Districts.................. 205 Lost Basin District ...................... 205 The Black Mountains Group.................... 206 Tom Reed-Gold Road District...................... 208 General Dcscription........................ 208 Development........................... 209 Topograplly............................ 210 Geology.............................. 210 Ore Deposits........................... 213 General Dwcription...................... 213 Zones.......................:....215 Structure of Ore Shoots.................... 217 Gold Road Mine ......................... 218 General Description...................... 218 Geology........................... 218 Ore Deposits......................... 219 Tom Reed Minc......................... 222 General Description..................... 222 • Ore Deposits.......................... 222 Development......................... 223 Character of Ore....................... 224 Other Mines........................... 224 Fields Similar to the Ton1 Reed-Gold Road District......... 227

Jan 1, 1917

By Waldemar Dyrssen

I CANNOT agree with the results obtained by the committee. The gas obtained per pound of coal is too high in calorific value and the amount of gas is too large. It should require about 190 cu. ft. of oxygen per 1000 cu. ft. of gas and not 75.14 cu. ft. as is given on page 35 of the report, or about 2.5 as much. Calculating the calorific value per pound of coal from the coal analysis given on page 34, according to Dulong's formula, the gross and net calorific heat are about 12,890 and 12,430 B.t.u., respectively, which is about 18,600 and 17,900 B.t.u., respectively, per pound of carbon in the coal. This is an unusually high figure, as ordinary bituminous coal has less than 18,000 gross B.t.u. per pound of carbon. Assuming, however, that the calorific values calculated are correct, the following results are obtained. On page 35, the net calorific heat in the gas per pound of coal is given as 12,856 B.t.u. and calculation for the gross value shows it to be about 13,950; in other words, the gas contains (13,950 - 12,890) ÷ 12,890 = 8.2 per cent. more heat than the coal on a gross basis and (12,856 - 12,430) ÷ 12,430 = 3.4 per cent. more on a net basis. The calculated amount of carbon in this gas per pound of coal gasified is about 0.688 lb., or nearly the same as in the coal (0.6972) and the gross and net calorific heat per pound of carbon in the gas are 20,300 and 18,710 B.t.u. which are 9.1 and 4.5 per cent. more than for the carbon in the coal. These calculations show that the results given in the report cannot be correct. There must always be some heat losses in the gasification of coal, in radiation from the producer, and in sensible heat in the gas; there must be some loss of carbon in ashes and in soot, and there are always tarry vapors in the gases that are condensed and do not appear in the fixed gases. From the excessive heat in gas per pound of carbon contained therein, it can also be concluded that the percentage of hydrogen in the gas is too high, from which it follows that the moisture decomposed is too high and that more free oxygen must be used.

Jan 11, 1924

By A. H. Daane, B. J. Beaudry

The yttl-irtm-nickel system has been investigated by metallo-graphic, thermal ard X-ray methods. There are nine intermetal-lic compounds present: Y3Ni, Y3Ni,, YNi,, YNi,, Y,Ni,, YNi,, and Y,Nil, which rodergo peritectic decomposition and YNi and YNi, which melt congruently. There are eutectics at 34.8, 57.5 and 93.3 at pct Ni which melt at 805°, 950 and 1285 C, respectively. Crystallographic data are given for YNi, YNi,, YNi,, YNi5and Y,Ni,. The terminal solid solubility is low. In recent work by Fisher and Fullhart' in which yttrium crucibles to be used for containers of uranium-chromium eutectic were clad with a high nickel steel, a low melting phase formed where the yttrium was in contact with the steel. To investigate the cause of this phenomenon, Daane, et al. made a survey study of yttrium systems with chromium, manganese, iron, and nickel and found an 18 wt pct Ni (weight percent) alloy to melt at approximately 950°C. voge13 in a study of the systems of cerium, lanthanum, and praseodymium with nickel found six compounds of the same formula in each system, i.e., R3Ni, RNi, RNiz, RNi3, RNi4, and RNi5. Since there is a great similarity between yttrium and the rare earths, compound formation was likely to occur also in the yttrium-nickel system. voge13 observed that the ability of transition metals to form compounds with the rare earths diminishes in the order nickel, cobalt, and iron while no compounds are formed with manganese, chromium, and titanium. Available data on yttrium systems with these elements indicate similar behavior, except that a slightly greater tendency toward compound formation is apparent. Simple eutectics with limited solid solubility have been found in the yttrium-titanium4 and yttrium-chromium5 systems, but at least one compound is present in the yttrium-manganese system.' In the case of yttrium-iron, at least three compounds are present,5 while only two are present in the cerium-iron,' and no compounds are present in the lanthanum-iron5 system. On the basis of both the trend in the alloying behavior of yttrium and rare-earth metals with the first transition series metals and the large number of compounds in the cerium-nickel system, one might expect six or more compounds to form in the nickel-yttrium system. A consideration of Hume-Rothery's rules of alloying based on size factor, electronegati-vity, and valence predicted low terminal solid solubility and possible compound formation. The present study was undertaken to confirm these predictions of

Jan 1, 1961

By J. B. Warriner

S. A. TAYLOR, Pittsburgh, Pa.-What was the distance of haul? J. B. WARRINER.-There is practically no limit to the haul. The length is determined entirely by the feasible location for a dump. -I have known of hauls up to 2 miles in length. R. V. NORRIS, Wilkes-Barre, Pa.-This paper was originally presented to the Anthracite Section as the result of the appointment of Mr. Warriner as the Chairman of the committee to study this matter and present this paper. As he has stated, he obtained data very freely from all the stripping operations in the region, and it is a type of paper of which we should have more in the Transactions. Two or three things in it strike me as particularly valuable. The two tables, 1 and 2, showing the coal remaining, have been the result of a great amount of study, as it is not an easy matter to obtain data as to the amount of coal left in mining. As an example, one of the, anthracite mines was mined and robbed out in 1850, so the maps show. That mine is today producing 250,000 tons of coal, over 50 per cent. from the bed which on the maps is marked as exhausted. What actually happened is that the seam was on a light pitch inconvenient to mine. There was ample thickness of coal and the chambers were driven at a convenient pitch through this 30,-ft. bed, leaving top and bottom, taking out about 10 ft. The pillars were removed and the working caved and marked as gone. That is the type of area that is now being stripped, which explains the reason for the enormous amount of coal left in, and the fact that Mr. Warriner has worked out the actual results from a large number of strippings is of great interest to the operators in any region handling thick coal which has been mined over in the past, generation. The modern mining, of course, is different. We do not have all the coal we want in big veins, and we do not mine it that way. Another interesting feature of the paper to me was the study of losses. It is not uncommon to assume that after you have stripped off the overburden all the coal goes to market. Mr. Warriner has shown that there is a loss ranging up to 10 or 15 per cent. that does not go, so 'that estimates made on stripping, figuring on all the coal, are subject to this very material correction.

Jan 4, 1917

By Robert A. Colten, Frederick C. Hull, Robert F. Mehl

It is known that pearlite forms from austenite by a process of nucleation and growth, and that the rate of formation of pearlite may be described by a rate of nucleation and a rate of growth.l,2 The manner in which these two quantities operate to produce the observed isothermal reaction curve has been analyzed in a paper published in I939.3 Two types of process were described: (I) that in which nucleation occurs at the grain boundaries of the parent phase, with the nodules growing toward the centers of the grains, initially as hemispheres and then after impingement as roughly radial-columnar structures; and (2) that in which nucleation occurs generally, with the nodules growing to full spheres until impingement with other growing nodules restricts growth. Both cases are met in the formation of pearlite from austenite (Fig. I);2,4 the former, occurring near the knee of the S-curve, has been named "grain-boundary transformation," and the latter, occurring at temperatures near Ael, has been named "group-nodule transformation." In developing our knowledge of the factors that determine the rate of formation of pearlite from austenite, it is important1,2 to obtain data on the rate of nucleation and the rate of growth of pearlite. Such data, when obtained near the knee of the S-curve, will furnish information of use in understanding the factors that affect hardenabil-ity; when obtained at higher temperatures, such data will be useful in understanding the behavior of steels that during heat-treatment react to pearlite.2 It is the purpose of this paper to present data on the rate of nucleation and the rate of growth of pearlite in dependence upon composition, grain size, temperature, and the degree of homogeneity of the parent austenite. The studies are restricted chiefly to plain carbon commercial steels." Previous Data on Rate of nucleation and rate of Growth Data on the rate of nucleation and the rate of growth of pearlite have been published by Scheil and Lange-Weise,5 by Mirkin and Blanter,6,7 by Meh1,l and by Dorn, De Garmo and Flanigan.2, It is difficult to interpret the data, for in most cases too little information is given on austenitizing temperatures and times, the state of homogeneity of the austenite (presence or absence of carbide, etc.), austenite grain size, and mode of formation of pearlite at the temperatures given. Except for the approximations of Mehl and the work of Dorn, austenite grain size was disregarded, though it is well known

Jan 1, 1942

By Robert A. Colten, Frederick C. Hull, Robert F. Mehl

It is known that pearlite forms from austenite by a process of nucleation and growth, and that the rate of formation of pearlite may be described by a rate of nucleation and a rate of growth.l,2 The manner in which these two quantities operate to produce the observed isothermal reaction curve has been analyzed in a paper published in I939.3 Two types of process were described: (I) that in which nucleation occurs at the grain boundaries of the parent phase, with the nodules growing toward the centers of the grains, initially as hemispheres and then after impingement as roughly radial-columnar structures; and (2) that in which nucleation occurs generally, with the nodules growing to full spheres until impingement with other growing nodules restricts growth. Both cases are met in the formation of pearlite from austenite (Fig. I);2,4 the former, occurring near the knee of the S-curve, has been named "grain-boundary transformation," and the latter, occurring at temperatures near Ael, has been named "group-nodule transformation." In developing our knowledge of the factors that determine the rate of formation of pearlite from austenite, it is important1,2 to obtain data on the rate of nucleation and the rate of growth of pearlite. Such data, when obtained near the knee of the S-curve, will furnish information of use in understanding the factors that affect hardenabil-ity; when obtained at higher temperatures, such data will be useful in understanding the behavior of steels that during heat-treatment react to pearlite.2 It is the purpose of this paper to present data on the rate of nucleation and the rate of growth of pearlite in dependence upon composition, grain size, temperature, and the degree of homogeneity of the parent austenite. The studies are restricted chiefly to plain carbon commercial steels." Previous Data on Rate of nucleation and rate of Growth Data on the rate of nucleation and the rate of growth of pearlite have been published by Scheil and Lange-Weise,5 by Mirkin and Blanter,6,7 by Meh1,l and by Dorn, De Garmo and Flanigan.2, It is difficult to interpret the data, for in most cases too little information is given on austenitizing temperatures and times, the state of homogeneity of the austenite (presence or absence of carbide, etc.), austenite grain size, and mode of formation of pearlite at the temperatures given. Except for the approximations of Mehl and the work of Dorn, austenite grain size was disregarded, though it is well known

Jan 1, 1942

By J. Stuart Warner

The reaction COSO4(c)?CoO(c) + So3(g)was investigated from 950° to 1170OK by two different methods. The sulfate was decomposed in a previously evacuated space and Pso3 calculated from the measured total pressure on the assumption that Pso2 = 2P02. The sulfate was also decomposed under conditions of controlled oxygen pressure. The difference in the results obtained by these experimental techniques is attributed to the effects of thermal diffusion. The standard free energy change for the reaction is given by ?F° = 66,292 + 17.273T log T — 102.57 T (±300 cal/mole). It was found by DTA and X-ray diffraction studies that CoS04 undergoes a transformation at 617°± 4°C. THE metal sulfates may decompose directly to the oxide or pass through one or more intermediate basic sulfates. Provided the oxidation state of the cation does not change in the course of the reaction, the decompositions may be described in general as follows: One of the major objectives of this work was to determine the validity of Eq. [3] as much of the existing sulfate data has been calculated from decomposition pressures by Eq. [5]. The type of apparatus generally used for these measurements consists of a reaction vessel at high temperature which communicates with a manometer at room temperature. A temperature gradient is thus imposed on the gas phase causing thermal diffusion which brings about a partial separation of the different gaseous species present in an initially uniform mixture. The basic theory and experimental facts associated with this phenomenon are summarized elsewhere1 and it will suffice to state here that the heavier gaseous species diffuses down the temperature gradient. Since thermal diffusion destroys the homogeneity of the gas phase, it is not necessarily true that Pso2 = 2Po2 in any particular volume element of the gas phase even though there are twice as many molecules of SO, as of 0, in the gas phase considered as a whole. Under these conditions, the decomposing sulfate gives off SO, which dissociates to SO, and 0, and all three species are distributed throughout the system by thermal diffusion. However, the sulfate will continue to dissociate until the equilibrium value of PSo3 is established on the hot zone. Thermal diffusion may distribute SO2 and O2 throughout the gas phase in any way so long as Eq. [2b] is satisfied in the hot zone; i.e. Pso2(Po2)1/2=K3pso3. When a steady state is reached, we can characterize Pso2 in that

Jan 1, 1962

By Ottar Dragge, C. Danielsson, Bo Kalling

THE desulphurizing of pig iron has been accomplished with a number of different additions. The oldest and still most commonly used agent is soda, the extensive use of which commenced about 1925, when it was used principally for cupola furnace iron. More recent experience' seems to show that better results can be obtained with sodium hydroxide. The well-known desulphurizing properties of lime have also been exploited in different technical processes. Another material with even more powerful effect is calcium carbide.' The desulphurizing ability of manganese, when added to the ladle in sufficient quantity, should also be mentioned in this connection. During recent years increasing attention has been paid to the desulphurizing properties of metallic magnesium." An addition of a suitable alloy of magnesium is now in use purely for the purpose of sulphur elimination. Of the desulphurizing agents mentioned, lime is by far the cheapest, provided that the reaction can be brought about rapidly and completely. Therefore, a method that makes full use of the desulphurizing ability of lime may be able to compete with other processes. A method developed at the Dom-narfvet Iron and Steel Works (Sweden) will be described, which enables pig iron to be rapidly desulphurized to very low sulphur contents by using a burnt lime powder. as the desulphurizing agent. Lime in Older Processes In cases where lime has been used for the desul-phurization of pig iron, it has generally not been used alone, but mixed with other substances such as fluorspar, to obtain the formation of a molten slag during the process. This method has been tried by Tigerschiold,' who treated the iron with a lime-fluorspar mixture, the stirring of the iron being brought about inductively with low frequency alternating current. Very good results were obtained. A process of this type has also been suggested by R. P. Heuer, U. S. A. The principles of this method, which has been tested in Great Britain by Newell. Lanener. and Parsons." re that a mixture of lime and fluoispar is added to the hot metal in the ladle, while a powerful stream of nitrogen gas is blown into the bath to produce the required intermixing. The results of the tests were unsatisfactory, however. A similar process has been developed at The Steel Co. of Canada, according to a statement by H. M. Griffith.' Here the tests were carried out in a carbon-lined ladle provided with carbon tuyeres in the side wall for blowing nitrogen into the bath. The addition consisted of about 20 lb of a mixture of burnt lime and fluorspar per ton of pig iron. Good results appear to have been achieved. The sulphur content of the pig iron is stated to have been reduced from 0.025 to 0.050 pct down to 0.006 pct. Various methods of desulphurizing pig iron have been tried using lime powder without fluxing material for fusing. Eichholz and Behrendt7 have experimented with blowing a powdered limeicoke mixture with air into the ladle. Their results were, however, not conclusive and the experiments do not appear to have been continued. Similar experiments have been carried out at Domnarfvet, using nitrogen instead of air in order to avoid oxidation. But these attempts were not particularly successful. It appears to be difficult to achieve the required agitation by this means. The strong cooling effect of the gas on the iron is also a serious drawback. A method in many respects similar to that tried at Domnarfvet was tried by Eulenberg and Krus at the end of the 1930's. Here again desulphurization was carried out with lime alone, brought into contact with the molten iron in a rotary furnace. The temperature was kept at the required level, 1400" to 1500°C, by the introduction of a pulverized coal burner in one end of the furnace. The speed of rotating was not given. A paper by Bading and Krus states that, in one of the first experiments, the sulphur content in 56 tons of pig iron was brought down from 0.186 to 0.035 pct in 117 min, but that a considerable shortening of the time would be possible. According to later reports by Eichholz and Behrendt,' it should be possible by this process to achieve a desulphurization speed of 0.35 pct S per hr for a consumption of 6 to 10 pct limestone and 2 to 3 pct coke, as fuel exclusively. The final sulphur content is, however, not stated. Domnarfvet Method After a number of different procedures had been investigated, the tests at Domnarfvet were directed to desulphurization with lime in a rotary furnace. Before going into the practical details of the method, the theoretical aspects will be discussed briefly. If the pig iron does not contain alloying elements other than carbon, the reaction can be expressed most simply by the usual equation: FeS + CaO + C = Fe + CaS + CO [I] 4H,. ~ 34,000 cal That this reaction can be carried through to a very complete desulphurization of pig iron has been shown by OelsenD in a discussion in connection with the Eulenberg and Krus' method. He mentions two laboratory tests, in one of which the sulphur content in the pig iron at 1400°C was reduced from 0.540 to 0.006 pct after treating with 3.35 pct lime. The pig iron had a low manganese content, but other analysis is th. given. Mention also should be made of the recently published investigations by Fischer and Cohnen'" dealing with the influence of the carbon content of the iron on desulphurization with lime, although in this case fluorspar was added also. The tests show that efficient desulphurization is possible with lime in the steel bath, provided that the carbon content is sufficiently high. The temperature employed in these tests was considerably higher (1620") than that normal for treatment of pig iron. The author concludes that the product S% X C% - 0.011 at the temperature in question.

Jan 1, 1952

By G. W. Healy, N. R. Griffing

The activity coefficient of sulfur in Cr-Fe-S melts was determined by measuring the values of Ph3Rh,in equilibrium with such melts. The results showed that chromium has a pronounced negative effect on the activity coefficient of sulfur, which up to about 20 pct Cr may be represented by the equation: log f; = - 0.019 pct Cr It was also found that the influence of chromium was not altered by the presence of appreciable amounts of carbon or silicon. The influence of alloying elements on the activity of sulfur in molten iron has been the subject of many investigations; however the effect of one important alloying element, chromium, has not been reported, and the object of the present investigation was to determine its effect on the activity coefficient of sulfur in liquid Fe-Cr-S alloys both in the absence and in the presence of carbon and/or silicon. EXPERIMENTAL PROCEDURE The general method employed consisted of passing mixtures of hydrogen and hydrogen sulfide over the sulfur-containing melt of interest and analyzing the outgoing gas to determine the equilibrium value of which resulted from the reaction shown in Eq. 111. H, (gas) + S (dissolved in melt) = H,S (gas) 111 The activity coefficient of sulfur, fs, was then calculated with Eq. [2] in which K, is the known equilibrium constant of Eq. [I] for dilute solutions of sulfur in iron. Raw materials used in the preparation of the charges included commercial grades of electrolytic iron and chromium and carbon-reduced, acid-treated silicon of 99.9 pct purity. Oxygen in the former presented no problem since it was removed by hydrogen in the normal course of an experiment. Carbon was added in the form of premelted iron-carbon and chromium-carbon master alloys. Sulfur was charged as iron sulfide prepared by first heating powdered iron and sulfur in air in an alumina dish until reaction occurred, and then deoxidizing by melting in a hydrogen atmosphere. Commercially bottled hydrogen and hydrogen sulfide were used after being passed through purification systems containing palladium, "Drierite," and magnesium perchlorate in the case of hydrogen, and "Drierite" alone in the case of hydrogen sulfide. Lamp-grade cylinder argon served as a flushing agent without further purification. Charges weighing from 300 to 500 g were placed in a high-purity alumina crucible of 0250-ml capacity and heated in an argon atmosphere in the induction-heated carbon-tube furnace illustrated in Fig. 1. During heating, a dry hydrogen atmosphere was substituted for argon in order that deoxidation of the charge and flushing out of argon would be accomplished sooner. After the charge melted, a Pt-Pt 10 pct Rh thermocouple contained in an alumina protection tube was immersed in the melt, and the desired melt temperature (usually 1600°C) was established. Higher temperatures up to 1760°C were required for some chromium-rich alloys because of their higher melting points, and in these cases a Pt 6 pct Rh-Pt 30 pct Rh thermocouple was used. The thermocouple output was fed to an automatic controller which provided straight line temperature

Jan 1, 1961

By J. W. Martin, L. K. Singhal

Grain boundary M23CB precipitates have been shown to form by a process involving the migration of an austenite grain boundary, and each plate of precipitate is in parallel orientation with one of the austenite grains constituting the boundary. The carbide distribution and morphology appear to be sensitive to grain boundary mis orientation. Some areas of austenite grain bowzdary permit the development of an array of M,C, particles, some of which are in parallel orientation with one grain and some with the other grain constituting the boundary. Massive carbide at grain boundary triple points is also shown to be in parallel orientation with one constituent grain. PREFERENTIAL precipitation during aging of carbides of the type (Fe,Cr)23C6, usually written MZ3C6, in grain boundaries of quenched austenitic stainless steels has been widely recognized. M23C6 has a complex cubic crystal structure' which contains ninety-two metal atoms and twenty-four carbon atoms per unit cell. Less energy is involved in forming grain boundary precipitates than in the formation of intragranular precipitates, and the process is further enhanced by the accelerated diffusion rates in the boundaries and by the probability of segregation of chromium atoms and carbon atoms to the region of the grain boundaries during prior solution heat treatment in order to reduce lattice strain. Early electron micrographic studies2, 3 involving either extraction replica or normal replica techniques established the geometric or dendritic form of the carbide particles, although this approach led to dis- pute as to whether the particles grew within the plane of the boundary or grew into the matrix.4-6 More recent thin-foil studies' have claimed to identify a discontinuous precipitation process involving M23C6 at grain boundaries, and the object of the present work was to attempt to clarify the situation using modern electron micrographic and diffraction techniques. 1) EXPERIMENTAL 1.1) Material. The steel selected for this work had a base composition of 24 pct Ni-25 pct Cr-3 pct Ti and contained about 0.04 pct C. The full analysis if given in Table I. This alloy was in the form of strip which had been hot- and cold-rolled to a thickness of 0.6 mm. 1.2) Heat Treatment. Specimens 4 cm long by 1 cm wide were solution-heat-treated for 3 hr in argon at 1150°C, followed by water-quenching. Specimens were subsequently aged in vacuo at 750°C for periods up to 500 hr. 1.3) Preparation of Electron Microscope Specimens. The heat-treated strips were cut bv spark machining into discs of 3 mm diam and 0.6 mm thickness. he-discs were dished on both sides using an electrolytic jet of 15 pct HCl electrolyte at 80 v. Final electro-polishing of the discs was carried out using 10 pct perchloric acid, 20 pct glycerol, and 70 pct ethanol at 10 v. The current density was kept below 300 ma. cm"2 by cooling the electrolyte to 0" to 5°C. As soon as a small hole appeared, the electropolishing was stopped and the specimen was quickly washed with ethanol.

Jan 1, 1969

By M. Cohen, C. Wagner, J. E. Reynolds

If the total volume of a diffusion couple changes during the diffusion, the measurement of distance becomes ambiguous. Use of distance parameters as suggested by Hartley and Crank is discussed. For small concentration differences, the standard form of Fick's second law is retained with conventional length units and the in- terdiffusion coefficient D. It is shown how D can be calculated from experiments involving large concentration differences and analyzed in terms of distance parameters. 'The merits of incremental diffusion couples involving small concentration differences are emphasized. THE conventional form of Fick's second law for one-dimensional diffusion of component B in a binary solution of A and B is where c, is the concentration of component B; x, the distance; t, the time; and D, the interdiffusion coefficient which may depend on ca. Hartley and Crank' have pointed out that Eq. 1 applies only if the total volume of the diffusion couple does not change during the diffusion process; otherwise, the definition of x becomes ambiguous. No change in total volume takes place if the specific volume of the solution is a linear function of the weight fraction Wb, or if the molar volume is a linear function of the mol fraction N. In some alloys, however, these relationships do not hold, and then it is necessary to introduce a modified measure of distance, 4 in order to retain the general form of Eq. 1. The application of Hartley and Crank's suggestions to diffusion in alloys has been discussed by Wagner.' Relation Between Measure of Distance and Units of Concentration The definition of [ depends on the choice of units for the concentration c,, as follows: 1—If the concentration ca is measured as the weight fraction W, (or weight percent), [ = 5, has to be defined so that equal increments of contain equal increments of mass m of the solution, e.g., dm = pSdx = Sdw [2] where p is the local density of the solution, and S is the cross-sectional area in sq cm which is taken to be constant in this problem of one-dimensional diffusion." * da Silva and Mehla have demonstrated the constancy of the cross-sectional area in the usual type of diffusion couple. However, experiments involving diffusion into thin wires4, 5 may exhibit changes in cross-sectional area, and therefore are excluded from the present treatment. Thus and the unit of is gram per sq cm instead of cm. 2—If the concentration c, is the mol fraction N, must be defined so that equal increments of contain equal numbers of mols of solution, e.g., dn= (S/V)dx= Sd [41 where V is the local molar volume of the solution. Thus dt, = dx/V [51 and the unit of is mols per sq cm. 3—If, as may be advisable in the case of interstitial solutions, the concentration C is measured in terms of the molar ratio of components B and A (c,, = Y, = nH/nA, where n and nl are numbers of mols of B and A), = Y has to be defined so that equal increments of contain equal numbers of mols of A, e.g., dnA= (NAS/V)dx = Sdf [6]

Jan 1, 1954

By Cecil Desch

THIS annual lecture, under the auspices of the Institute of Metals Division, and which was illus- trated by lantern slides, has been printed in full and a limited number are available for distribution on request. Some excerpts from the lecture are given below: Ever since the simple geometrical relations of crystals were discovered, it has been recognized that their proper-ties are best explained by assuming that their ultimate particles are arranged on a space lattice, and that the char-acteristics of that lattice determine the shape of the crystal and its physical and mechanical properties. Modern ex-amination by means of X-rays has widened that concep-tion and given it greater; definiteness, and the atoms are now regarded as the particles forming the space lattice. The splendid achievements of investigators in this field have made it possible to state, for a large number of sub-stances, the form and dimensions of the lattice. The char-acteristic of a lattice is that a unit of simple geometrical form is repeated at regular intervals in three dimensions so as to fill the entire crystal. It follows that there must be certain planes in which the atoms are more closely packed than in planes drawn at any angle to them, and it is these planes of closest packing which play the greatest part in determining the growth and other properties of the crystal. There are actually two stages in crystallization, what-ever be the medium in which it occurs. The first is the ap-pearance of crystal nuclei; the second the growth of those nuclei to form crystals of appreciable .size. The first is clearly a kinetic phenomenon. In the molten mass, solu-tion, or vapor, the molecules are in a state of rapid motion and frequent collision. When the temperature has fallen so far. that it is possible for a crystal to exist, a few col-liding molecules may fail to rebound, and so become at-tached to one another, the balance between the attracting and repelling forces-between them causing them to arrange themselves on a space lattice, to which other molecules sub-sequently attach themselves. It was once maintained that the X-ray evidence demanded that the molecule should dis-appear in the solid crystal, but this was a wrong inference, and in many crystals, but not in all, the chemical molecule retains its identity in the solid state. In pure metals the atom and the molecule are identical, so that the conditions are unusually simple. How many. nuclei will be formed in a given mass is evi-dently a problem in probability. Experiments to deter-mine the relation between the temperature and the number of nuclei formed in a given time have been made with some success by using viscous organic substances, but metals offer much greater difficulties, and the few determinations which have been published are vitiated by serious errors. However, the examination of sections of ingots of the same composition and cast at 'the same temperature in similar molds will show, that the number of crystals does not vary widely.

Jan 3, 1927

By D. C. Hilty

C. E. SIMS*—This is a most interesting and important paper. It is important from two standpoints. First, it has as-spects of being highly accurate and therefore extremely useful to the operating man in showing how far he can go in oxidizing carbon from a steel bath while retaining chromium and the effect of temperature on this limit. Fig 5 is undoubtedly the highlight of the paper, and in checking it against available data, it seems capable of predicting actual results. The other important aspect is the apparently significant fact that reactions within a steel bath, such as between carbon and an oxide, are homogeneous reactions which do not require equilibrium with an external phase. In this case, it seems obvious that the reaction and the equilibrium established were between dissolved carbon (or carbide) and dissolved CrO. The classic reaction which requires equilibrium with solid Cr2O3, did not fit the data. It was recognition of this principle that made Fig 5 possible. G. R. FITTERER*—It might be in assuming the CrO is dissolved in the metal that you are actually approaching the correct factor for activity. If that is true and if the percentages that were used represent an equilibrium constant, this would mean, in effect, that the minimum temperature at which chromium would be reduced by an equivalent percentage of carbon would be about 2400°F from your equation. I believe that is in line with my experience particularly if you deal only with low percentages. J. CHIPMAN†—The author in discussing the equilibrium of the reaction offers two choices of explanation. One postulates an effect of chromium on the activity coefficient of carbon; it would require perhaps more data than are available to us at the present time to test this thoroughly. The other postulate which he offers is a reaction with CrO. This explanation is consistent with physical and chemical principles provided that a solid phase CrO is present, and that is essentially what he is postulating. If that oxide were present one would expect and, I think, almost require the kind of results that he obtained. The weakness of that postulate lies in the lack of confirmatory evidence regarding the presence of solid CrO as such. This should offer an interesting subject for further study. It seems a pity that the theoretical arguments revolving around CrO should have obscured for a moment the very real excellence of this paper. E. CARTER*—I think there is a problem that presents itself in practical application where the metal temperature is from 3200 to 3300 and the temperature desired in pouring is considerably less. B. M. LARSEN†—I get the impression from some of the work that was done earlier that there is probably a localized zone of high temperature at the slag metal interface which effects the removal of the carbon. Without that I wonder if the effect is possible to have a localized superheat and an equilibrium there favorable to low carbon content and

Jan 1, 1950

By R. L. Perrine

The rise of drain holes drilled from a well to improve productivity is becoming increasingly common. This paper presents data on the productivity increase that may he expected. The data were obtained by use of an electrolytic tank mode1 of a reservoir. Parameter varied in the study to show their effect on productivity include the length, number, and arrangement of drain holes, formation thickness, and damage near the well-hore. The most important results are that very large increases in productivity can be expected only ill damaged wells. The distance, to which drain holes penetrate is of primary importance. Additional length is more effective than increasing the number of drain holes. INTRODUCTI O N In planning the use of drain holes to improve productivity, it is important to he able to estimate the increase in production that can be obtained for a given expenditure. It is also important to know what combination of parameters related to the use of drain holes can he chosen to give the largest production increase. This paper presents data on the productivity increase that may be expected, as obtained by use of an electrolytic tank model of the reservoir. In this study, :! number of parameters were varied to show their effect on productivity. These included the length, number, and arrangement of the drain holes. The presence or absence of a damaged zone of low permeability around the well-bore and the thickness of the producing formation were also considered. The productivity increase that might be expected due to drain holes is presented as the ratio: productivity of a well after drain holes are drilled and completed to the productivity of the same well in an undamaged state without drain holes. The symbol Q/Qo is used to represent this productivity ratio. Thus, the comparison in each case is with a formation of uniform and undamaged permeability. Additional notation includes I;, for the radial extent of the damaged zone, which is assumed to be cylindrical and concentric with the wellbore. Thus the effect of an actual block is approximated by a discontinuous varia-tion in permeability. For purposes of this paper, the permeability within the damaged zone, denoted by kb, is assumed to be 1/25 that in the remainder of the formation, or k. A necessary assumption in making comparative tests using an electrolytic model is that reservoir flow behavior can be approximated by single-phase, steady-\tate flow according to Darey's Law. In addition, the formation must be assumed to be homogeneous with equal horizontal and vertical permeability. The well-hore diameter in this study is assumed to be 11¾ in. and the drainage radius of the well equal to 500 ft. The drain holes are considered to have been completed without damage. THE ELECTROLYTlC MODEL 'She producing formation was modeled by forming a sheet of phosphor-bronze into a cylinder 40% in, in diameter to represent the boundary of the drainage area. This was enclosed in a waterproofed plywood box, and the box filled to an appropriate level with a dilute sodium chloride solution. Solution concentration was adjusted to give a total resistance from

Jan 1, 1956

By Edward Martinez

The reactions occurring in the copper segregation process were studied by heating mixtures of chryso-colla, salt, and a reducing agent. The techniques used in this investigation were differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). The initial chloridizing of the oxide copper occurs below 500°C and cupric chloride may be the compound formed. Volatilization and reduction of the copper chloride take place above 550°C, although these reactions do occur to some extent below 550°C. A difference in the distribution of the metallic copper in the reducing agent was found when sodium chloride was used compared to magnesium or calcium chloride. Segregation was obtained with mixtures of cupric oxide, salt, and charcoal with no quartz or silicate present. Preliminary tests indicate that segregation may occur even in the absence of water vapor. The DTA and TGA techniques were found to be of great value in studying these reactions. The copper segregation process is a method for treating oxide copper ores. The ore is heated, most commonly in a kiln, with a reducing agent and a halide salt, generally sodium chloride, to approximately 700°-750°C and held for 30 to 60 min. The addition of the salt results in the migration and reduction of the oxide copper to metallic copper on the surface of the reducing agent rather than in the original mineral structure. The metallic copper can then be recovered by a subsequent leaching or flotation step.1-4 Experimental work in 1923 on oxide copper ores from the Sagasca mines in Chile led to the discovery of the reduction process. It was found that during the reduction of the copper mineral with coal, at about 700°C, the copper migrated to the surface of the coal instead of remaining disseminated in the ore. The unusual behavior of the copper, which caused it to migrate from the ore particles to the coal, was traced to the presence of a small quantity of sodium chloride occurring in the ore. Further experiments with oxide copper ores proved that the presence of a halide, either occurring naturally or admixed with the ore, caused the copper to migrate from the ore particles and to segregate in the charge. The ratio of salt to reducing agent may vary somewhat, but in general 0.5% to 1.5% sodium chloride and 0.5% to 1.0% coal or coke have been mixed with the ore. Less than stoichiometric amounts of salt are required to convert all the oxide copper to a chloride, so that a cycle of reactions appears to be occurring. Several investigations reported in the literature have proposed reactions to explain the mechanism of the process.5-10 There appears to be general agreement that water is necessary for the reactions to occur; that once the sodium chloride reacts with silica or silicates in the ore, the hydrochloric acid formed will convert the cupric oxide in the mineral structure to cuprous chloride. However, there appears to be a conflict of opinion on the reactions involved in the reduction of the cuprous chloride to metallic copper on the surface of the carbon. Rey has indicated that salt, water vapor, and

Jan 1, 1968

By A. J. de Witte

INTRODUCTION The importance of determining dips of subsurface formations in wells, especially in wildcat wells, is self-evident and need not be enlarged upon. Various dipmeter instruments have been described in technical literature1,2,3,4 over the years. The introduction of the continuous dip-meters3,4 has made the earlier types obsolete. Continuous dipmeter logs are run by at least two different major service companies. Included as part of the service are a limited number of dip calculations—usually 10—made at different levels from the log. Very frequently this is the total result of a dip survey. It is believed that dipmeter surveys would be of considerably more advantage if geologists and engineers were able to make their own calculations from the original records. Determination of dips from the dipmeter record starts with the correlation of three log curves taken at different sides of the borehole. It cannot be over-emphasized that the quality of the results hinges primarily on this correlation. Nobody should be better qualified to correlate logs than a subsurface geologist or field engineer. The next requirement is to have an easy yet accurate way of computing the dip from the correlated points. Service companies use a mechanical device for this purpose. Directions for a graphical method were given in a recent article by B. 0. Prescotts. This paper describes a different graphical technique which, in our experience, is simpler, faster and at least as accurate. The entire manipulation is carried out on the stereonet in a number of easy moves. The paper is divided into two parts. This first part contains the introductory sections and full explanation of the geometry involved. The second part reviews the reading of data from an actual field log and summarizes the practical rules for computation of dips, the whole process being illustrated by an example. Following the outlined procedure, one could calculate a good many levels in a relatively short time, thus being able in particular to check suspected anomalies such as fault zones or unconformities in as close detail as the log will permit. GENERAL EXPOSITION OF THE METHOD Prnciple of the Dipmeter The position of a plane in space is defined by the location of three points, not on a straight line. Referring to Fig. I, if a borehole traverses a bedding plane, we can determine the strike and dip of the bed by finding three points which are not in line along this plane. Such points as A, B, and C are obtained with the dipmeter. The device consists of three electrodes (or caliper arms)1, 2, and 3 spaced at 120 angles, as schematically indicated, whose readings are separately recorded (Curves 1, 11, 111, to the right). When electrode 1 passes the boundary of the bed, Curve I will kick, etc. From these curves, we know the relative distances of points A, B, C, measured along the axis of the hole. If A is at zero, then B and C are at levels d1 and d2 up the hole,

Jan 1, 1957

By G. H. Lair, B. J. Langford, S. H. Rockwood

Volumetric reservoir analysis is dependent upon a firm relationship between porosity, connate water, and net pay. Capillary presswe data on core samples interrelate these three factors. It is shown that other reservoir problems may be resolved: (I) whether water production is indigenous or extraneous to the oil producing interval, (2) an oil-water contact is being approached, and (3) whether the oil-water contact is remotely situated. INTRODUCTION Volumetric analysis of carbonate reservoirs challenges the ingenuity of the reservoir engineer due to an absence of data on the minimum oil-bearing and oil-producing pores of a given reservoir rock. Many studies with this as the ultimate objective are available on the physical characteristics and fluid-flow behaviors of the carbonate reservoir. Some of these publications are: Hassler, Brunner and Deahl's1 study of the role of capillarity in oil production; Jan Law's' and A. C. Bulnes3 statistical treatment of core analysis data; Chalkley's method4,5 or estimating specific surface areas and porosity; Walter Rose's9 report on porosity, reserves, and recovery; Archie's78 tex-tural classification of carbonate rocks; Stewart and Spurlock's9 large core analysis; Purcell'sl0 mercury injection method in studying capillary pressure phenomena; Stewart, Craig, and Morse's" model multiple-phase flow test in investigating the relative permeability effect; and Fatt's12 illumi-nating network model of porous me-dia. The present study shows that the static reservoir parameters of porosity, connate water, and net productive thickness may be interrelated by utilizing a statistical arrangement of mercury capillary pressure data in addition to routine core analysis. This report summarizes the techniques that are followed to obtain these relations which are applicable to carbonate and sandstone reservoirs that do not contain clays. Capillary pressure statistical studies may be extended to include clay-bearing rocks by utilizing water capillary pressure data. POROSITY It is necessary that the laboratory determine the porosity value that includes the pores that are filled with hydrocarbons and water in the reservoir. This is the reservoir's total porosity. When true total porosity values are not available, correlations between porosity and capillary pressure characteristics lose their significance since they cannot be related through oil-base mud core data to the porosity and connate water values found in reservoirs. Methods used to obtain reliable porosity data will not be discussed; however, care should be exercised in selecting samples for measurement. In homogeneously porous formations, small core plugs sampled frequently will furnish adequate information. Where heterogeneity, particularly vugginess, is present, large-core porosity data may be required; in such reservoirs a suite of capillary pressure samples may be selected from small plugs. CAPILLARY PRESSURE Capillary pressure data provide a method for relating two carbonate reservoir parameters, porosity and connate water saturation, which in turn permit delineation of productive rock types necessary for selecting the third parameter, productive thickness. Specific applications of capillary pressure data to petroleum reservoirs were suggested by Archie8 and Pur-cell."' Their work demonstrated that in preferentially water-wet rock, porc

Jan 1, 1958

By Robert M. Keeney, Jay Lonergan

The electric smelting of manganese ore and the production of ferro-manganese did not exist as an industry, in the United States or elsewhere, previous to the outbreak of war in 1914. Ferromanganese had been produced, electrically, during times of high prices by two companies at Niagara Falls and by several European companies, but the production was spasmodic, and none was electrically produced when ferromanganese sold at from $35 to $40 per ton. Thus the electric smelting of manganese ore must be considered as a development caused by the high prices prevailing during the years 1916, 1917 and 1918, and the necessity of smelting domestic ore in order to fill the ferromanganese requirements of the steel industry of the United States, which increased from 189,088 tons in 1914 to 356,356 tons in 1918. The electric furnace is well adapted to smelting domestic ore because it can be located in small units near the source of ore supply. In 1918, the ferromanganese production of the United States was 333,027 tons, of which about 7 per cent., or 23,000 tons, was produced in the electric furnace. The electric furnace not only assisted materially in the development of a domestic-ore supply but made a considerable saving of coke, as it requires about 11/4 tons of bituminous or lignite coal per ton of ferromanganese compared with a blast-furnace consumption of 2.9 tons of coke per ton of ferromanganese. Some of the plants in the United States that smelted manganese orc in the electric furnace during the war and in 1920 are listed in Table 1. From early in 1919 to about February, 1920, little ferromanganese was produced in the electric furnace. During this period the price of ferromanganese (78 to 82 per cent. manganese) was about $100 per ton. During the first half of 1920, several plants resumed operation when the price of ferromanganese (76 to 80 per cent. grade) gradually increased to $200 per ton, delivered.

Jan 1, 1922

By Jay Lonergan, Robert M. Keeney

The electric smelting of manganese ore and the production of ferro-manganese did not exist as an industry, in the United States or elsewhere, previous to the outbreak of war in 1914. Ferromanganese had been produced, electrically, during times of high prices by two companies at Niagara Falls and by several European companies, but the production was spasmodic, and none was electrically produced when ferromanganese sold at from $35 to $40 per ton. Thus the electric smelting of manganese ore must be considered as a development caused by the high prices prevailing during the years 1916, 1917 and 1918, and the necessity of smelting domestic ore in order to fill the ferromanganese requirements of the steel industry of the United States, which increased from 189,088 tons in 1914 to 356,356 tons in 1918. The electric furnace is well adapted to smelting domestic ore because it can be located in small units near the source of ore supply. In 1918, the ferromanganese production of the United States was 333,027 tons, of which about 7 per cent., or 23,000 tons, was produced in the electric furnace. The electric furnace not only assisted materially in the development of a domestic-ore supply but made a considerable saving of coke, as it requires about 11/4 tons of bituminous or lignite coal per ton of ferromanganese compared with a blast-furnace consumption of 2.9 tons of coke per ton of ferromanganese. Some of the plants in the United States that smelted manganese orc in the electric furnace during the war and in 1920 are listed in Table 1. From early in 1919 to about February, 1920, little ferromanganese was produced in the electric furnace. During this period the price of ferromanganese (78 to 82 per cent. manganese) was about $100 per ton. During the first half of 1920, several plants resumed operation when the price of ferromanganese (76 to 80 per cent. grade) gradually increased to $200 per ton, delivered.

Jan 1, 1922