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By W. T. Thom

In previous classifications of coal, it has been customary to regard moisture eliminated from coal samples between 20 and 100 C. as extraneous matter, rather than as a constituent part of the coal. It seems, however, that the physical character and use properties of the low-rank coals are directly related to the amount of such moisture present, and recent chemical work has shown' that such coals contain unstable groupings which decompose between 20 C. and temperatures somewhat above 100" C., with the splitting off of moisture. According to this view, the moisture eliminated from air-dried coal below boiling point is similar in all essential respects to moisture eliminated above 100" C., and is produced by analogous reactions; and inasmuch as the moisture given off above 100" C. has always been treated as a constituent of the volatile matter of coal, it would seem that consistent usage would include as a part of the volatile matter all moisture present as an essential component of the coal as it occurs in nature. As a matter of experience, it seems clear that the general physical and chemical characteristics of the low-rank coals are largely determined by or related to the moisture, whether chemically or physically combined, present in air-dried coal; it is also demonstrable by trial that the low-rank coals cannot be satisfactorily classified on a purely chemical basis by using the moisture free form of analysis. The low-rank coals of the western United States include numerous well-defined types, many of which were referred to in a classification proposed by Ashley,2 in which the physical and use properties of the coals were made the primary basis for their systematic grouping. When testing this classification by replotting analyses of these type coals according to the Seyler scheme of classification,3 a satisfactory parallelism between use properties and chemical constitution of the dry coal was found among

Jan 1, 1925

By B. W. Roberts, V. A. Phillips

A copper alloy containing- 25.5 at, pct Zn and 19.0 at. pct Ni, which was previously found to show an anoma1old.s hardening effect on quenching- from 600 "C and aging- at 400oc, has now been examined by neutron diffraction. No evidence of long-range order was found. The aged sample showed diffuse scattering- consistent with clustering. The anomalous hardening effect is now attributed to lattice strains caused by clustering rather than (long-range) order hardening. SOLID-solution Cu-Ni-Zn alloys (the commercial 'nickel silvers") have been reported to show anomalies in: change of resistivity on cold working,1-6 temperature coefficient of resistance,2-12 resistivity at low temperatures,13,14 parameter (vs temperature),2"4 calorimetric data,2,4 specific heat,15,16 dilation,2-4 and elastic modulus.17 The structure responsible for the anomalies is produced by annealing typically near 400°C and is rather loosely referred to as the ('K-Zustands" (K state), a term coined by Thomas1' who apparently meant simply that the arrangement of atoms on the sites deviated from that expected statistically. Thomas proposed that the K state occurred in a variety of (solid-solution) alloys such as Cu-Ni-Zn, Ni-Cr, Ni-A1, Ni-Cu, Fe-A1, and Fe-Si and is recognized because its formation is strongly temperature-dependent and results in an increase in electrical resistance which can then be decreased by cold working. Later workers on ('nickel silver" have interpreted the K state variously as short-range order, long-range order. or a combination. The present work was prompted by the discovery by Phillips and Jones19 of a substantial hardening effect when an 18 pct "nickel silver" alloy which is fairly close to the Cu2NiZn composition, was reheated in the range 150" to 450 C after previously quenching from 600°C or, alternatively. was slow-cooled from 600°C or above. The phenomenon was attributed to (long-range) order hardening. Due to the similarity in the atomic scattering factors of copper. nickel, and zinc atoms, the ''nickel silvers" are unfavorable for X-ray diffraction studies aimed at detecting ordering. Nevertheless Bialas et a1.,20 using a powder sample containing 47.96 wt pct Cu, 24.03 wt pct Ni, and 27.98 wt pct Zn, slow-cooled from 400" to 200°C taking 500 hr, observed weak super lattice lines. Further unpublished work" using an anomalous dispersion X-ray technique indicates that zinc atoms are regularly ordered at the corner points of the lattice cell, while the nickel and copper atoms are statistically distributed on the remaining sites. Köster 17 also observed X-ray superlattice lines, for example, in an alloy containing 43.5 wt pct Cu, 28.6 wt pct Ni, and 27.9 wt pct Zn superimposed on the basic fcc cell with a = 3.62 kX. He proposed a Cu3Au-type superlattice with the Ll2 structure in which the A sites were statistically occupied by copper and nickel atoms and the B sites by zinc. He adds that substitution must be possible so that zinc atoms partly occupy A sites. Below about 35 pct Cu, Koster had some evidence for a CuAu-type superlattice with the Llo tetragonal fcc structure with a = 3.82 kX, c/a = 0.88 which could be preserved by quenching. This is suggested17722 to correspond to CuNiZn. While the present work was in progress Hirabaya-shi et a1.23 made an independent comprehensive neutron-diffraction study of a single crystal containing 50.05 at. pct Cu, 26.57 at. pct Ni, 0.25 at. pct Mn, 0.13 at. pct Fe, balance zinc. The presence of manganese and iron is surprising since the crystal was supposedly grown from high-purity metals. The homogenized crystal showed evidence of long-range ordering after an anneal of 5 months at about 300°C. Three possible crystal models were proposed. A curious feature of their results23 is that they could not find any neutron-diffraction evidence of ordering in a powdered polycrystalline near-stoichiometric Cu2NiZn alloy. There appears to be some essential difference between a near-stoichiometric Cu2NiZn alloy and one somewhat further off stoichiometry as used by the present authors. Thus Sato14 was able to reproduce the low-temperature resistivity anomaly reported by one of the authors13 on the present alloy if he used a similar composition, but found the normal behavior of the residual resistivity in a near-stoichiometric alloy. satol2 found that the resistivity of a cold-drawn slightly off-stoichiometric alloy increased to a maximum on isothermally annealing at 300°C and then decreased ("over-aged"). Since he could not explain this on the basis of ordering phenomenon, he proposed that zinc atoms were segregating to stacking faults (Suzuki effect) and found etching bands on the surface by replication which were attributed to the widening of faults. Sato suggested14 that the hardening effect observed by Phillips and Jones19 is partly due to the Suzuki effect. EXPERIMENTAL The starting material was 1/4-in.-diam hard-drawn rod of a commercial 18 pct "nickel silver" alloy identical with that used in a previous study by Phillips

Jan 1, 1967

By K. R. Carson, J. Weertman

An attempt is made to ascertain the mechanism of tangle and cell formation and its dependence upon dislocation-interstitial carbon interactions. The strain-hardening behavior of single crystals of 3.25 pct Si-Fe was determined at 300° and 425°K and under conditions of both continuous and interrupted tensile strain. Significantly enhanced hardening was observed in crystals deformed at the elevated temperature, and it was further accentuated by interrupted straining. Transmission electron microscopy was used to study the resultant dislocation structures. Strain aging was found to aid tangle and cell formation at 425°K, but at both temperatures embryo tangles formed solely from primary glide dislocations, presumably by a process involving cross slip and "mushrooming". IN the course of plastic deformation all bcc metals and alloys develop a dislocation structure characterized by loose-knit groups of tangled dislocations. With increasing strain the tangles become more tightly knit and grow larger; finally a three-dimensional cellular substructure is formed:1 This process has been observed with the transmission electron microscope.'-l7 However, most investigations were confined to the study of nearly pure polycrystalline metals at relatively low temperatures. At intermediate temperatures, 0.17 to 0.14 Tm where T, is the melting temperature in degrees absolute, the mobility of interstitial impurities such as carbon is high enough to permit migration to nearby glide dislocations but is still low enough so that a significant drag force is exerted.18,19 it is also in this temperature range that a hump occurs in the curve of work-hardening rate vs temperature for iron. Analogous plots for tantalum" and columbiumzo show a definite upward trend in the work-hardening rate. Keh and Weissman1 have pointed out that this behavior may be explained solely on the basis of changes in the dislocation configuration: at low temperatures the dislocations tend to be relatively straight and uniformly distributed, but at intermediate temperatures tightly knit tangles and cellular substructure appear. The interference of these tangles with glide dislocations causes the observed increase in the work-hardening rate. This explanation appears reasonable, yet one might ask what factors cause tangle formation to be so favorable at intermediate temperatures. It seens likely that the strong dislocation-interstitial interactions which are known to occur in this temperature range are at least partly responsible," with the magnitude of the effect being proportional to the interstitial concentration. The purpose of the present work is to study the relationship between tangle formation and strain hardening in a bcc metal in the temperature range 0.17 to 0.4 Tm. Particular emphasis was placed upon a study of the effects of interstitial-dislocation interactions. Single crystals of 3.25 pct Si-Fe containing about 200 ppm of C in solid solution were used in the investigation for the following reasons: 1) The mobility of interstitial carbon in 3.25 pct Si-Fe is negligible at 300°K but increases rapidly at slightly elevated temperature22. Hence, differences between the flow curves and dislocation structures of crystals deformed at 300°K, 0.17 T,, and crystals deformed, say, at 425°K, 0.24 Tm, should be appreciable because of the enhanced dislocation-carbon interactions at the elevated temperature. This effect was accentuated in some samples by interrupted straining, thereby introducing a certain amount of aging. 2) Near room temperature, slip in suitably oriented 3.25 pct Si-Fe single crystals is largely confined to the (110) planes.23'24 Dislocation structures formed under conditions of single glide are the least complicated and their method of formation is the most easily discernable. 3) Dislocations in Si-Fe can be tightly locked with carbon atmospheres by a low-temperature aging treatment. The subsequent thinning of samples to foil thicbess causes little or no rearrangement in the dislocation structure.25 EXPERIMENTAL PROCEDURE Large single-crystal sheets of 3.25 pct Si-Fe were donated by Dr. C. G. Dunn of the General Electric Research Laboratory, Schenectady, N. Y. The orientations of the sheets were determined and slabs 1.0 by 0.25 by 0.05 in. were cut such that the desired tensile axis corresponded to the long dimension. The slabs were mechanically polished and subsequently decar-burized by heating at 1000°C for 3 days in a flowing wet-hydrogen atmosphere. A carbon content of about 200 ppm was introduced by heating at 805°C for 25 min in a flowing atmosphere of dry hydrogen containing heptane vapor. Shaped copper tools were then used to spark-machine at 0.125 by 0.50 in. gage length onto each slab. Vacuum annealing at 1225°C for 2 days followed by a quench into the cold end of the furnace to retain carbon in solid solution concluded the soecimen preparation. Continuous tensile flow curves for crystals of severa1 orientations Were obtained both at 300' and 425°K. A strain rate of 6.67 x 10-4 Per set was used in these and all other tests. Crystals oriented for single glide, B and D in Fig. 1, were subjected to a 3.5 pct plastic elongation to insure uniform slip along the gage length; they were then immediately subjected to interrupted strain cycling as indicated in Fig. 2(a). Each cycle consisted of unloading to 1.5 kg per sq mm, holding

Jan 1, 1969

By W. T. Jr. Thom

IN PREVIOUS classifications of coal, it has been customary to regard moisture eliminated from coal samples between 20° and 100° C. as extraneous matter, rather than as a constituent part of the coal. It seems, however, that the physical character and use properties of the low-rank coals are directly related to the amount of such moisture present, and recent chemical work has shown1 that such coals contain unstable groupings which decompose between 20° C. and temperatures somewhat above 100° C., with the splitting off of moisture. According to this view, the moisture eliminated from air-dried coal below boiling point is similar in all essential respects to moisture eliminated above 100° C., and is produced by analogous reactions; and inasmuch as the moisture given off above 100° C. has always been treated as a constituent of the volatile matter of coal, it would seem that consistent usage would include as a part of the volatile matter all moisture present as an essential component of the coal as it occurs in nature. As a matter of experience, it seems clear that the general physical and chemical characteristics of the low-rank coals are largely determined by or related to the moisture, whether chemically or physically combined, present in air-dried coal; it is also demonstrable by trial that the low-rank coals cannot be satisfactorily classified on a purely chemical basis by using the moisture free form of analysis. The low-rank coals of the western United States include numerous well-defined types, many of which were referred to in a classification proposed by Ashley,2 in which the physical and use properties of the coals were made the primary basis for their systematic grouping. When testing this classification by replotting analyses of these type coals according to the Seyler scheme of classification,3 a satisfactory parallelism between use properties and chemical constitution of the dry coal was found among

Jan 5, 1925

By K. J. Miller, R. E. Hucko

The Coal Reparation Division of the Pittsburgh Mining Technology Center conducted an investigation to assess and compare the pyritic sulfur reduction potential of coal-pyrite flotation and high-gradient magnetic separation (HGMS). Tests were run on three coals - an Upper Freeport bed coal, a Lower Kittanning bed coal, and a Pittsburgh bed coal - to establish grade-recovery relationships characteristic of both processes. Representative portions of each coal sample were crushed to two top sizes-nominal - 500 pm (-35 mesh) and nominal - 149 pm (-100 mesh)-and subjected to conventional froth flotation. The froth product was then beneficiated by coal- pyrite flotation or HGMS, to provide a direct technical companion of the two processes. At - 500 pm (- 35 mesh), the size normally employed for coal flotation, both coal-pyrite flotation and HGMS effectively separated pyrite from coal, and the performance of the two processes was essentially the same. At a - 149 pm (- 100 mesh) sire, however, the performance of HGMS exceeded that of coal-pyrite flotation. The separation effected by HGMS were more efficient at - 149 pm (- 100 mesh) than at - 500 pm (- 35 mesh). On the other hand, it was concluded that either the effectiveness of coal-pyrite flotation decreases with diminishing top size or the process has not been optimized to treat material finer than 500 pm (35 mesh).

Jan 1, 1983

By E. A. Gulbransen, J. W. Hickman

IN a previous paper1 the authors have investigated the structure of the oxide films formed on most of the metals that make up the alloys of this study. The metals were studied in order to provide basic information on the structures, both physical and chemical, of the oxide films and to determine how these structures are effected by the temperature, time of oxidation, and surface preparation. It was felt that an understanding of the physical and chemical structure as well as the stability of the oxide film might furnish clues as to the nature of the reaction process and the protective quality of the film. The oxidation of the metals was studied over the temperature range 300° to 700°C. except for copper, where the range selected was 100° to 500°C. The results of these studies were presented in graphical form as existence diagram, of the oxides on a time-temperature scale. For some of the metals the existence diagrams were simple and showed few chemical transitions, but there were numerous cases where the physical state of the oxide surface was a function of time and temperature. In general the physical state of the oxide surface changed with increasing temperature so as to increase the sharpness of the diffraction patterns and to cause orientation effects to be more pronounced. Deviations in lattice parameters from X-ray values were noted. In general these deviations were of positive nature and may be due to solid solution of the metal in the oxide lattice. This effect might be expected in thin oxide films. In a study of the oxidation of alloys containing two or more metals, there may arise the complicating factor of identification of the oxides formed. A thorough understanding of the oxides formed on the pure metals, therefore, was, essential before investigation of the oxidation of alloys. In this paper it is our purpose to present a study of the following problems: I The existence diagrams of various alloys. [2.] The effect of the structure of the [ying] metal on the existence diagram of Iron. 3. The effect of the percentage of chromium on the oxides formed on Fe-Cr alloys. 4. The relationships, if any, between the oxides formed and the protective quality of the oxides. The following alloys are included in this study: alloys of iron with body- centered cubic, face-centered cubic and other metals, 13 Cr-Fe, 18-8 stainless steel, K42B1 Nichrome V, Hipernik, Inconel, Stellite " 21," Refractaloy, Kovar, mild steel, a series of Cr-Fe alloys and a series of Co-Fe alloys. Since many of the commercial alloys in this list contain more than two metals, various complicating factors in the identification of the oxides formed may arise.

Jan 1, 1946

By J. W. Hickman, E. A. Gulbransen

In a previous paper' the authors have investigated the structure of the oxide films formed on most of the metals that make up the alloys of this study. The metals were studied in order to provide basic information on the structures, both physical and chemical, of the oxide films and to determine how these structures are effected by the temperature, time of oxidation, and surface preparation. It was felt that an understanding of the physical and chemical structure as well as the stability of the oxide film might furnish clues as to the nature of the reaction process and the protective quality of the film. The oxidation of the metals was studied over the temperature range 300' to 7o0°C. except for copper, wherc the range selected was 100' to 500°C. The results of these studies were presented in graphical form as existence diagrams of the oxides on a time-temperature scale. For some of the metals the existence diagrams were simple and showed few chemical transitions, but there were numerous cases where the physical state of the oxide surface was a function of time and temperature. In general the physical state of the oxide surface changed with increasing temperature so as to increase the sharpness of the diffraction patterns and to cause orientation effects to be more pronounced. Deviatiois in lattice Darameters from X-ray values were noted. In general these deviations were of positive nature and may be due to solid solution of the metal in the oxide lattice. This effect might be expected in thin oxide films. In a study of the oxidation of alloys containing two or more metals, there may arise the complicating factor of identification of the oxides formed. A thorough understanding of the oxides formed on the pure metals, therefore, was, essential before investigation of the oxidation of alloys. In this paper it is our purpose to present a study of the following problems: 1. The existence diagrams of various alloys. 2. The effect of the structure of the alloying metal on the existence diagram of iron. 3. The effect of the percentage of chromium on the oxides formed on Fe-Cr alloys. 4. The relationships, if any, between the oxides formed and the protective quality of the oxides. The following alloys are included in this study: alloys of iron with body-centered cubic, face-centered cubic and other metals, 13 Cr-Fe, 18-8 stainless steel, K4²B, Nichrome V, Hipernik, Inconel, Stellite "²I," Refractaloy, Kovar, mild steel, a series of Cr-Fe alloys and a series of Co-Fe alloys. Since many of the commercial alloys in this list contain more than two metals, various complicating factors in the identification of the oxides formed may arise.

Jan 1, 1947

By E. A. Gulbransen, J. W. Hickman

In a previous paper' the authors have investigated the structure of the oxide films formed on most of the metals that make up the alloys of this study. The metals were studied in order to provide basic information on the structures, both physical and chemical, of the oxide films and to determine how these structures are effected by the temperature, time of oxidation, and surface preparation. It was felt that an understanding of the physical and chemical structure as well as the stability of the oxide film might furnish clues as to the nature of the reaction process and the protective quality of the film. The oxidation of the metals was studied over the temperature range 300' to 7o0°C. except for copper, wherc the range selected was 100' to 500°C. The results of these studies were presented in graphical form as existence diagrams of the oxides on a time-temperature scale. For some of the metals the existence diagrams were simple and showed few chemical transitions, but there were numerous cases where the physical state of the oxide surface was a function of time and temperature. In general the physical state of the oxide surface changed with increasing temperature so as to increase the sharpness of the diffraction patterns and to cause orientation effects to be more pronounced. Deviatiois in lattice Darameters from X-ray values were noted. In general these deviations were of positive nature and may be due to solid solution of the metal in the oxide lattice. This effect might be expected in thin oxide films. In a study of the oxidation of alloys containing two or more metals, there may arise the complicating factor of identification of the oxides formed. A thorough understanding of the oxides formed on the pure metals, therefore, was, essential before investigation of the oxidation of alloys. In this paper it is our purpose to present a study of the following problems: 1. The existence diagrams of various alloys. 2. The effect of the structure of the alloying metal on the existence diagram of iron. 3. The effect of the percentage of chromium on the oxides formed on Fe-Cr alloys. 4. The relationships, if any, between the oxides formed and the protective quality of the oxides. The following alloys are included in this study: alloys of iron with body-centered cubic, face-centered cubic and other metals, 13 Cr-Fe, 18-8 stainless steel, K4²B, Nichrome V, Hipernik, Inconel, Stellite "²I," Refractaloy, Kovar, mild steel, a series of Cr-Fe alloys and a series of Co-Fe alloys. Since many of the commercial alloys in this list contain more than two metals, various complicating factors in the identification of the oxides formed may arise.

Jan 1, 1947

By John Chipman, Carl F. Floe

A year ago the authors published a paper on the solubility of sulphur dioxide in molten copper.l The data in that paper agreed closely with that obtained by previous investigators, which, however, did not agree with the theoretical predictions for solubility of triatomic gases of this type. It has generally been assumed that the reaction of solution is: 6Cu(l) + SO2(g) = Cu2S (in Cu) + 2 Cu2O (in Cu) [I] _ (CU2S)(CU2O)2 K = (Cu)6(Pso2) [2] Neglecting the slight change in copper concentration and considering that the concentrations of sulphur and oxygen are both proportional to the volume of gas absorbed, it follows that this volume should be proportional to the cube root of the pressure. It was found that a plot of the volume absorbed versus the cube root of the pressure gave a straight line, but that this line did not pass through the origin. Calculations of the equilibrium constant for the reaction showed that it was fairly constant for pressures above 100 mm. but that actually it approached zero at lower pressures. The conclusion was made therefore that the solubility as determined could not be expressed by Eq. I or by any other simple equation, particularly at low pressures. Other investigators have concluded that the solubility of sulphur dioxide in copper as well as in several copper alloys is more nearly proportional to the square root of the pressure.* Such a conclusion, however, does not satisfactorily account for the results, even when rather complicated mechanisms for the solution are assumed. The highly improbable speculations of Lepp2 and of Schneider and Esch3 based upon hypothetical dissociation pressures of Cu2O and CU2S dissolved in copper illustrate the type of reasoning that has been used to account for the discrepancy. In the discussion of the previous paper, the authors pointed out that the discrepancy might possibly be due to impurities in the copper, although the purest form available was used. Further consideration of the problem suggested that the impurities likely to have the greatest effect on the solubility of so2 in copper were oxygen, sulphur and carbon. Accordingly, further experiments have been made to show the effects of these elements. Experimental Methods The apparatus used for measuring solubility was essentially the same as that shown in the previous paper. However, since it was desired to make measurements at low pressures, a McLeod gauge was added and 6-mm. glass tubing was substituted for the capillary. This increased the "hot volume" considerably but was necessary in order to obtain good vacuums in a reasonable length of time. A mercury diffusion pump was also installed.

Jan 1, 1942

By Carl F. Floe, John Chipman

A year ago the authors published a paper on the solubility of sulphur dioxide in molten copper.l The data in that paper agreed closely with that obtained by previous investigators, which, however, did not agree with the theoretical predictions for solubility of triatomic gases of this type. It has generally been assumed that the reaction of solution is: 6Cu(l) + SO2(g) = Cu2S (in Cu) + 2 Cu2O (in Cu) [I] _ (CU2S)(CU2O)2 K = (Cu)6(Pso2) [2] Neglecting the slight change in copper concentration and considering that the concentrations of sulphur and oxygen are both proportional to the volume of gas absorbed, it follows that this volume should be proportional to the cube root of the pressure. It was found that a plot of the volume absorbed versus the cube root of the pressure gave a straight line, but that this line did not pass through the origin. Calculations of the equilibrium constant for the reaction showed that it was fairly constant for pressures above 100 mm. but that actually it approached zero at lower pressures. The conclusion was made therefore that the solubility as determined could not be expressed by Eq. I or by any other simple equation, particularly at low pressures. Other investigators have concluded that the solubility of sulphur dioxide in copper as well as in several copper alloys is more nearly proportional to the square root of the pressure.* Such a conclusion, however, does not satisfactorily account for the results, even when rather complicated mechanisms for the solution are assumed. The highly improbable speculations of Lepp2 and of Schneider and Esch3 based upon hypothetical dissociation pressures of Cu2O and CU2S dissolved in copper illustrate the type of reasoning that has been used to account for the discrepancy. In the discussion of the previous paper, the authors pointed out that the discrepancy might possibly be due to impurities in the copper, although the purest form available was used. Further consideration of the problem suggested that the impurities likely to have the greatest effect on the solubility of so2 in copper were oxygen, sulphur and carbon. Accordingly, further experiments have been made to show the effects of these elements. Experimental Methods The apparatus used for measuring solubility was essentially the same as that shown in the previous paper. However, since it was desired to make measurements at low pressures, a McLeod gauge was added and 6-mm. glass tubing was substituted for the capillary. This increased the "hot volume" considerably but was necessary in order to obtain good vacuums in a reasonable length of time. A mercury diffusion pump was also installed.

Jan 1, 1942

By Bernard Kopelman, C. C. Gregg

THE reduction of tungstic oxide to tungsten metal powder by hydrogen is a process by which one might expect the resultant metal powder to be porous. In- [ ] deed, sponge iron, prepared by reduction of the oxide in a reducing gas, is generally accepted as quite porous, with pores large enough to be seen readily under the optical microscope at relatively low magnifications. However, any pores that may exist in tungsten metal powder are not resolved by the optical microscope, and apparently, not even by the electron microscope. Fig I shows commercial tungsten powder magnified at 10,000X by the electron microscope,1 both etched and unetched. In an earlier paper by one of the authors,2 the existence of pores in tungsten powder [ ] was required to explain adequately the particle size changes occurring during the reduction of tungstic oxide. The inability to detect these pores under the electron microscope at 10,000 X implies that these pores are of a size of 100 A units or less. (This in itself is by no means proof that pores above 100 A would not exist, since polishing effects on the specimen might smear up holes of such small magnitude). If, then, these pores are less than 100 A, and of the order of molecular size, then the density of the metal powder should be

Jan 1, 1948

E. P. Pfleider, University of Minnesota I would like to ask Bob Merrill whether he considers that horizontal concave curvature of a slope has any stabilizing effect, such as Jenike 1 suggested several years ago. R. H. Merrill, U. S. Bureau of Mines, Denver Federal Center The stabilizing effect is due to the restraint offered to radial movement by the curvature. We found in laboratory tests that if we constrained the rock with the same stresses as those measured in the pit then it would sustain a maximum stress about two or four times greater than when the same rock type was unconstrained. We are therefore definitely of the opinion that a constrained situation in a slope is favorable towards stability. G. A. Leonards, Purdue University I was interested in Mr. Lane's observations concerning the correspondence between rate of slide movement with rise of reservoir. Perhaps the most interesting feature is that the rate of movement at the time the rock slope failed was less than the rate at an earlier time when it did not fail. This is difficult to explain from current slope stability theory. K. S. Lane, U. S. Army Corps of Engineers I believe that reduced rate of movement is the result of the progressive type of failure, such as described by Patton and Deere. which occurs along the sliding surfaces. It is difficult to analytically define the progressive failure condition for inclusion in slope stability conditions, but its existence should be recognized in design. We should also realize that many apparently stable slopes undoubtedly contain overstressed regions. To design a slope with no overstressed region would be uneconomical and conservative. D. H. Deere I would pose the question-"What is the meaning of a factor of safety of one?" We were involved in the design of a large, irregularly shaped, underground cavity with an unsupported span of several hundreds of feet. Tests on rock specimens indicated a strength of 1300 lb per sq in. The RQD would have been between 90 to 100 percent indicating excellent structural continuity. In-situ stress determinations indicated an approximately hydrostatic state of stress at a level of 1400 lb per sq in. Calculation of stress concentrations at the walls indicated that the stresses there would be about 3000 to 4000 lb per sq in. Admittedly the rock is in a confined condition everywhere except at the very skin of the wall and the rock walls would thus on the average be somewhat stronger. Allowing for the effect of restraint the factor of safety was found to be less than 0.5 over a region several feet into the wall. Construction was started, using rockbolts only to support the walls. Failure around the immediate skin occurred after each

Jan 1, 1967

By M. Muskat, H. H. Evinger

A METHOD has been developed whereby one may calculate the productivity factors of producing formations from a knowledge of the reservoir conditions. Account is taken not only of the heterogeneous character of the gas-oil flow system but also of the detailed variations with pressure of the shrinkage and viscosity of the oil, the solubility of the gas in the oil, and even the variability of the gas viscosity and the deviation of the gas from ideal behavior. Curves are shown giving the results of numerical calculations on the production rate as a function of the pressure differential for a high-pressure and a low-pressure system, three values of gas-oil ratio being treated in each case. Curves are also given showing the variation with distance from the well of the pressure, oil saturation, and permeability. The effect of connate water is briefly discussed in relation to the apparently large discrepancies between the calculated and observed productivity-factor values. INTRODUCTION The significance of the productivity factor as a measure of the capacity of an oil-bearing formation to produce is well recognized; for it is the composite and integrated resultant of the physical properties of both the porous medium and the fluid stream passing through it with respect to the ease with which the particular petroleum fluids present in the formation can flow through it and into producing wells. The most direct method of determining the productivity factor of a well consists, as is well known, in the simultaneous measurement of reservoir-pressure differentials and rates of production and the expression of the data in terms of rate of flow per unit pressure drop.1 Actual measurements carried out in this manner on producing wells have given factors that generally lie in the range of 0 to 100 bbl. per day per pound pressure drop. This wide range arises not only from variations in permeability but also from the varying sand thickness of producing formations. One of the aims of developing a theory of the mechanics of oil production obviously is that of predicting what the productivity factor should be from a knowledge of the individual characteristics of the producing formation and the fluids produced. For homogeneous fluid systems passing through a porous medium into a producing well, it has been known for some time that the steady-state rate of liquid flow Q is given by the formula:* [ ] where k is the sand permeability, h its thickness, µ the liquid viscosity, [Ap] the pressure drop between the well and the distant parts of the reservoir, in particular that at a radius [ro ]and [r ] is the well radius. This gives the productivity factor: [ ] which will have a numerical value for a liquid of I centipoise viscosity of 0.9316 or

Jan 1, 1941

Representatives from 100 countries will focus on aspects of energy, ocean mining, safety, and manpower training at Houston's Astrodomain.

Jan 4, 1978

By W. C. Winegard, A. Galibois, C. J. Beingessner

The effects of solutes on the distribution of two-dimensional configurations of grains in zone-refined tin have been studied. When solutes with partition coefficients (ko) greater than unity are added, three-sided pains become more prevalent and the growth law changes. It is shown by electron-Probe micro-analysis that a solute buildup occurs ahead of a moving grain boundary when ko > 1. It has been found recently1, 2 that solutes with partition coefficients greater than unity have a larger retarding effect on grain growth than solutes with k, less than unity. ko is defined as the ratio of the concentration of solute in the solid to the concentration of solute in the liquid with which the solid is in equilibrium. Niessen and winegard2 have suggested that this effect is probably due to the complex shape changes which occur during the process of grain growth and that no theory based on single boundary motion3-5 can explain the results. They suggested that the dissociation of the unstable fourfold junction was delayed in alloys where ko was greater than 1 because the boundaries at the junction had to move into a region of high solute concentration. If indeed this mechanism were correct, it was felt that not only would the dissociation of fourfold junctions be affected by the solute buildup ahead of the boundaries, but the collapse of three-sided grains would be impaired. These combined effects would naturally lead to a modification in the distribution of the number of sides per grain seen on a two-dimensional section. The present investigation was undertaken to test these hypotheses by examining the grain-growth process in detail. EXPERIMENTS The Distribution of Grain Configurations in Zone-Refined Tin as Seen on a Two-Dimensional Section. Following the method of Bolling and Winegard,6 zone-refined tin was cast into button-shaped specimens and, subsequently, plastically deformed under a drop hammer at room temperature. The resulting flat coin-shaped samples were annealed at 200°C, some for 50 sec and others for 100 sec. The specimens were then examined to determine the distribution of the number of sides per grain, i.e., the num- ber of crystals adjacent to any particular grain in the section. For simplicity, the grains were classified as three-sided, four-sided, and so forth; this concept is schematically illustrated in Fig. 1. As indicated by smith,' it was necessary to examine every grain within an enclosed area to obtain a proper distribution of the relative frequency of each type. The distributions for the two annealing times are illustrated in Fig. 2. The total number of grains examined is also indicated on the figure. It is evi-

Jan 1, 1965

By A. Timur

Fluid flow properties of porous media have long been of interest in such varied disciplines as geology, geophysics, soil mechanics, and chemical, civil, and mechanical engineering. This interest has resulted in numerous models of porous media that have been proposed, tested, and found to be useful under, at best, only special circumstances. A critical review of most of these models is given by Scheidegger. 1 The application of each new tool to the study of porous media has helped to test some of the existing theories and to form new ideas based on the new parameters being measured. In the application of nuclear magnetic resonance (NMR) techniques to the study of the properties of fluids in porous media, the theoretical studies of Korringa et al.2 resulted in a model for the relaxation of spin polarization of protons in a hydrogenous fluid in a pore of a solid. Seevers3,4 verified this model, established a method for measuring the surface-to-volume-ratio distribution in a porous medium, and proposed a technique for determining specific permeability in sandstones. In the present investigation, the uses of NMR methods are extended and a simple model of porous media is developed from an analysis of pulsed NMR measurements. In this model, the pore spaces of a porous medium are divided into three groups on the basis of their surface-to-volume ratios. To evaluate predictions of the NMR model, laboratory measurements of spin-lattice relaxation time, porosity, permeability, and residual (irreducible) water saturation were conducted on more than 150 sandstone samples obtained from four oil fields in North America. Applications are discussed for estimating the volume of movable fluid, ?p, and the specific permeability, k, of sandstone samples. The former parameter, which can be considered as producible porosity, is expressed by ?p = [1 -- (Swr/100)]? , .... (1) where + is porosity in percent of bulk volume and Swr is the residual (irreducible) water saturation in percent of pore volume at a capillary pressure of 50 Psi. Fast, nondestructive laboratory methods are described for determining porosity, movable fluid, and permeability of sandstone samples from measurements with a pulsed NMR (spin-echo) apparatus. Procedures are given for adapting these methods to samples of irregular shape and small size. Theory General In the Korringa, Seevers, and Torrey2 (KST) model the observed decrease in the spin-lattice relaxation time, T1, of protons of a hydrogenous liquid contained in the pore spaces of a porous solid is attributed to an increase in the correlation time for the random motion of the water molecules and to the presence of paramagnetic centers at the liquid-solid interface. This KST model predicts the observed relaxation time of a hydrogenous liquid in a pore of a solid through

Jan 1, 1970

By J. C. Bradbury

The year of the Centennial is upon us. Not only is AIME marking its 100th birthday, but the cement industry is also celebrating 100 years of activity (see article by Roy Grancher, page 48). Fort Dodge, Iowa, and gypsum also tried to get into the act but missed by one year. Frank Apple-yard's gypsum article (page 53) informs us that the Fort Dodge area has been producing gypsum continuously for 99 years. That would seem to make AIME and the industrial minerals doddering oldsters. Not so-our Institute shows more energy than ever, and the word for industrial minerals is growth. These are the mineral resources of the future, the raw materials for the abundant life to come

Jan 1, 1971

By Fred D. DeVaney

Probably no ferrous metallurgical process has ever found such ready acceptance and rapid expansion as the pelletizing of iron ores. The process was first commercialized in the early 1950's and since then it has grown to the point where the amount of material pelletized worldwide will approach 100 million tons in 1971. The term agglomeration is used to describe any process by which fine material is formed into larger shapes or agglomerates and includes, in addition to pelletizing, such processes as sintering and briquetting. Sintering cannot be used to efficiently agglomerate iron materials containing a high percentage of 100-mesh fines but the method has been widely used over many decades for agglomerating flue dust, mill scale and iron ore finer than 3/8 in.

Jan 1, 1971

By D. W. Duncan, A. Bruynesteyn

An ore containing chalcopyrite was microbiologically leached in 6 ft columns at particle sizes ranging from -2 +1 ½ inches, to -3/8 + 3/16 inches. The rate of leaching increased exponentially as the particle size decreased. The controlling factor was the active leaching volume made up of the particle surface area and the depth of penetration of the bacteria and leach liquor into the particle. This volume became an increasingly larger part of the total volume as the particle size decreased. The sample under test leached poorly at larger particle sizes and it was calculated that under commercial conditions, it would produce at best a pregnant solution containing 100 mg/l (0.2 lb/ ton) of copper per 100 ft of dump height.

Jan 1, 1974

W. M. PEIRCE, Chairman J. L. CHRISTIE, Past-chairman E. H. DIX, JR., Vice-chairman ALBERT J. PHILLIPS, Vice-chairman E. M. WISE, Secretary International Nickel Co., Bayonne, N. J. W. M. CORSE, Treasurer Executive Committee W. H. BASSETT, JR. R. H. LEACH' D. K. CRAMPTONR. F. MEHL J. A. GANN W. E. REMMERS G. O. HIERS H. J. ROAST JEROME STRAUSS Finance Committee J. L. CHRISTIE, Chairman W. M. CORSE C. H. MATHEWSON T. S. FULLER H. S. RAWDON

Jan 1, 1934