Search Documents

By D. A. Dukelow, G. Derge

THE Fe0-Mn0-Si0, system has many properties of fundamental interest besides its occurrence in steel-making. The system is the simplest ternary complication of the FeO-SiO, binary whose electrochemical properties have been explored. Therefore, knowledge of the conformance of Fe0-MnO-SiO, melts to Faraday&apos;s laws, as investigated by current efficiency measurements, would be of particular value in interpreting the observed variations of electrical conductivity, while at the same time furthering understanding of this type of molten oxides. Pertinent to the present study are conductivity data of FeO-SiO, and Fe0-Mn0-SiO2, and current efficiency data of FeO-SiO,. Concerning conductivity measurements, Inouye, Tomlinson, and chipman&apos; studied the specific conductivity, a, of molten wüstite as a function of temperature and oxide addition. Liquid FeO in equilibrium with an iron crucible was found to have a o whose magnitude and positive temperature coefficient were undeniably semiconductor in nature (o1400°C = 269 ohm-1cm-&apos;). Additions at 1400°C of 5 mole pct MnO decreased o to 227 while a similar addition of SiO2, dropped o to 125. Additional SiO2 produced an exponential decline of o. It was reasoned that because wüstite is known to be oxygen excess and since there is no pronounced change in oFeO upon melting, that UFeO(L)is p-type semiconduction. Björling2 gives o data for the ternary FeO-MnO-SiO, using fayalite, 2 FeO-SiO,, as the base substance. Upon addition of tephroite, 2 MnO-SiO, he noted a small decrease in o. Taking his data for 1400°C with one-half of the fayalite replaced by tephroite, o shows a decrease of some 40 pct relative to o for fayalite, i.e., 5 ohm-&apos; cm-&apos; to 3. In line with this observation, Mori and Matsushita3 reported that substituting MnO for FeO in the silicate de- creased o slightly except at high SiO, contents where the decrease was somewhat larger. Investigating the ionic nature of FeO-SiO2 melts, Simnad, Derge, and George4, found the anode current efficiency, C,, as calculated from iron anode weight loss, was temperature invariant and in general increased with SiO2 concentration. The authors suggested the possible presence of electronic conduction to explain why C+ < 100 pct. Fig. 4 includes their results as curve (b). EXPERIMENTAL METHOD Apparatus—Fig. 1 is a schematic section of the electrolysis cell used in all the current efficiency runs. The melt was contained in an iron crucible that rested on an alundum ring. A centered silica tube came within 1 in. of the surface of the melt and initially served as a thermocouple well and then as the guide for the anode.

Jan 1, 1961

By John M. Kelly

New Mexico produced 31,913,816 bbl. of oil in 1942, the lowest annual production since 1936, and dropped one place to rank eighth among oil-producing states. This production decreased 7,838,052 bbl., or 19.71 per cent, from the 1941 figure is the result of transportation difficulties caused by the dislocation of tanker sailings to east coast ports. The average per-well allowable in New Mexico on Jan. I, 1942, was 43 bbl. and at the end of the year was 38 bbl. Allocations as set by the New Mexico Oil Conservation Commission followed the recommendations of the Petroleum Administrator for War. After setting the daily outlet, however, the average daily pipe-line runs were 87,545 bbl.—11.06 per cent short of these allocations. Production for Lea County was 26,812,949 bbl., Eddy County 4,624,578 bbl., northwestern New Mexico 473,609 bbl., Chaves County 2,680 barrels. Drilling activity for New Mexico in 1942 was approximately 84 per cent of that in 1941 with 339 completions. Of these completions 254 were oil wells, II gas wells, and 74 dry holes. Proven fields accounted for 55 of the dry holes and 19 were wildcats. Three new oil fields and one new gas field were discovered as the result of wildcat drilling. Extensions were made to one oil field and one gas field. By the close of the year, the New Mexico Oil Conservation Commission had designated 59 areas as proven for oil and/or gas. Southeastern New Mexico Lea County Monument was again the largest producing field in the state, with 5,729,336 bbl.; Eunice was next, with 5,217,965; Vacuum produced 3,295,624 and Hobbs 2,973,488. The Hobbs field has the largest accumulated production, which at the close of 1942 totaled 100,381,417 bbl. The 100-million-barrel mark for Hobbs focused attention on the fact that this is the first field in the state to attain this figure, and also that, as Hobbs has been under continuous proration since July 1930, or approximately the entire life of the field, this 100-million-barrel recovery was obtained with 86 per cent of the wells in the pool still flowing and having a drop in bottom-hole pressure of only 3.5 Ib. per million barrels recovered. Hobbs stands out as perhaps the best regulated major oil field in the world. Two new oil fields were discovered in Lca County, the most inlportant being the area designated as East Lusk, consisting of the south 4 tiers of Sections in T. 19 S., R. 32 E. The discovery well was drilled in the SW. SW. 1/4 of sec. 21, T. 19 S., R. 32 E., by Culbertson and Irwin, Inc., and others. It was completed at a total depth of 2751 ft. in the Seven Rivers formation of Permian age. The initial potential of the well was 237 bbl. per day on pump. The oil produced has a gravity of 24.10 A.P.I., with sulphur content of 0.9 per cent. This oil has an asphaltic base and because

Jan 1, 1943

By John M. Kelly

New Mexico produced 31,913,816 bbl. of oil in 1942, the lowest annual production since 1936, and dropped one place to rank eighth among oil-producing states. This production decreased 7,838,052 bbl., or 19.71 per cent, from the 1941 figure is the result of transportation difficulties caused by the dislocation of tanker sailings to east coast ports. The average per-well allowable in New Mexico on Jan. I, 1942, was 43 bbl. and at the end of the year was 38 bbl. Allocations as set by the New Mexico Oil Conservation Commission followed the recommendations of the Petroleum Administrator for War. After setting the daily outlet, however, the average daily pipe-line runs were 87,545 bbl.—11.06 per cent short of these allocations. Production for Lea County was 26,812,949 bbl., Eddy County 4,624,578 bbl., northwestern New Mexico 473,609 bbl., Chaves County 2,680 barrels. Drilling activity for New Mexico in 1942 was approximately 84 per cent of that in 1941 with 339 completions. Of these completions 254 were oil wells, II gas wells, and 74 dry holes. Proven fields accounted for 55 of the dry holes and 19 were wildcats. Three new oil fields and one new gas field were discovered as the result of wildcat drilling. Extensions were made to one oil field and one gas field. By the close of the year, the New Mexico Oil Conservation Commission had designated 59 areas as proven for oil and/or gas. Southeastern New Mexico Lea County Monument was again the largest producing field in the state, with 5,729,336 bbl.; Eunice was next, with 5,217,965; Vacuum produced 3,295,624 and Hobbs 2,973,488. The Hobbs field has the largest accumulated production, which at the close of 1942 totaled 100,381,417 bbl. The 100-million-barrel mark for Hobbs focused attention on the fact that this is the first field in the state to attain this figure, and also that, as Hobbs has been under continuous proration since July 1930, or approximately the entire life of the field, this 100-million-barrel recovery was obtained with 86 per cent of the wells in the pool still flowing and having a drop in bottom-hole pressure of only 3.5 Ib. per million barrels recovered. Hobbs stands out as perhaps the best regulated major oil field in the world. Two new oil fields were discovered in Lca County, the most inlportant being the area designated as East Lusk, consisting of the south 4 tiers of Sections in T. 19 S., R. 32 E. The discovery well was drilled in the SW. SW. 1/4 of sec. 21, T. 19 S., R. 32 E., by Culbertson and Irwin, Inc., and others. It was completed at a total depth of 2751 ft. in the Seven Rivers formation of Permian age. The initial potential of the well was 237 bbl. per day on pump. The oil produced has a gravity of 24.10 A.P.I., with sulphur content of 0.9 per cent. This oil has an asphaltic base and because

Jan 1, 1943

J. E. Stead, Middlesborough, England (communication to the author): Prof. Howe&apos;s valuable paper on cast-iron brings forward most prominently the correct explanation of the part played by combined carbon in pearlite and cementite, in determining the strength and hardness of cast-iron. On a previous occasioil I have shown that castings made by melting a white Cleveland iron and glazed iron, one containing 1.5 and the other from 4 to 5 per cent. of silicon, and each about 3 per cent. of carbon, were stronger than those made of ordinary foundry-iron; the difference in the final castings being a differ-

Jan 1, 1902

By R. Ruka, E. A. Gulbransen

ONE of the interesting questions in the understanding of the reaction of iron with oxygen is the kinetics and the mechanism of the crystal structure changes occurring in the formation and breakdown of the oxide film. In a recent work&apos; the electron diffraction method was applied to the study of the solid phase reactions occurring internally in the oxide film on iron above 570°C and under vacuum conditions. The higher oxides which form under oxidizing conditions are reduced internally by the diffusion of iron into the oxide leaving the bulk of the oxide FeO (wüstite). This paper will ask and consider three questions. These are: (1) What is the nature of the depressed transformation temperature for the Fe3O4 + Fe ? 4Fe0 reaction in very thin oxide films?; (2) What is the mechanism of the forward transformation of Fe3O4 to FeO at or near 570°C?; and (3) What is the nature and mechanism of the slow reverse transformation of FeO to Fe3O4 and Fe below 570°C?. The composition of the oxide as well as its electrical, magnetic, mechanical, and chemical properties depends upon the kinetics of these reactions. Literature Survey The composition of the oxide film on pure iron at temperatures up to 570°C has been studied extensively by the electron diffraction method. Nelson,&apos; Jackson and Quarrell,3 and Gulbransen and Hick-man4 have shown that Fe3O4 and a-Fe2O8 are formed in the temperature range of 225" to 570°C, while y-Fe,O, is most likely formed below 225°C for long oxidation times. In very thin films FeO (wüstite) is found to form at temperatures as low as 400°C, and its existence depends essentially upon the extent of initial oxidation. FeO is not found in the formation of thick films below 570°C. On the other hand X-ray5 and micrographic8 studies show that Fe3O4 may exist as the main com-ponent in thick films up to 650°C, well above the equilibrium temperature for the reaction Fe3O4 + Fe ? 4FeO. The kinetics of the forward and reverse trans-formations of the reaction Fe3O4 + Fe ? 4FeO have not been studied in oxide films. However, analysis of the data of Gulbransen and Hickman4 on the heat-ing and cooling of iron oxide films of known thick-nesses in high vacua shows that the forward reac-tion proceeds rapidly even for a 4000 A film at temperatures of 575" to 600°C. The reverse reaction or decomposition of wüstite (FeO) occurs at tem-peratures below 450°C. Thus, there appears to be a slow process in the decomposition which is in marked contrast to the rapid forward reaction. The decomposition of a bulk sample of FeO free from the metal has been studied extensively by Chaudron, Benard and coworkers using the micro-graphic, X-ray diffraction, and thermomagnetic methods. Chaudron7,8 first observed that the de-composition of FeO (wüstite) below 570°C occurs by the reaction 4FeO ? Fe3O4 + Fe. Later work by Chaudron and Forestier5 showed that the rate of de-

Jan 1, 1951

By C. S. Giggins, F. S. Pettit

The oxidation of Ni-Cr alloys in 0.1 atm of oxygen has been studied at temperatures between 800" and 1200°C. For alloys with 30 wt pct or more Cr, continuous layers of Cr2O3 are formed during oxidation. In the case of alloys with chromium concentrations between approximately 5 to 30 wt pct, external scales of Cr203 are formed over grain boundaries whereas internal precipitates of Cr2O3 and external layers of NiO are formed at other areas on the alloy surface. When such conditions are present on the alloy surface, chromium diffuses laterally from those areas covered with a continuous layer of Cr2O3 to areas where a Cr2O3 sub scale exists and it is possible for the sub-scale zone to become separated from the alloy by a continuous layer of Cr2O3. Whether such a state will be attained depends upon the initial grain size of the alloy and the oxidation time. When the concentration of chromium in the alloy is less than 5 pct, Cr2O3 is formed internally both at grain boundaries and within the interior of grains and the alloy is covered with an external layer of NiO. MECHANISMS which describe the growth of oxide scales on nickel-base superalloys are complex and the effects produced by the various elements in these alloys on the oxidation behavior of superalloys are not clearly understood. In order to determine the influence of the different elements on the oxidation behavior of superalloys, it is first necessary to examine the oxidation properties of binary nickel-base systems which contain the principal elements present in the superalloys and then progressively more complex systems until compositions typical of the superalloys are attained. Chromium is present in virtually all nickel-base superalloys and the purpose of the present studies was to examine the selective oxidation of chromium in Ni-Cr alloys. The oxidation characteristics of Ni-Cr alloys have been extensively studied1-" to date principally as a result of the high oxidation resistance exhibited by some of these alloys. Ni-20Cr* has long been known *All compositions are given as wcight percent unless specified otherwise. to be oxidation resistant and is commonly used as resistance heating elements for service temperatures up to 1100°C. This alloy cannot be used for extended periods of time at higher temperatures because of the apparent reaction of the external scale with oxygen to form gaseous CrO3. In spite of the considerable work cited above some important aspects of Ni-Cr oxidation still remain unresolved. Virtually all of the previous studies agree that small additions of chromium to nickel, e.g., <10 wt pct Cr, result in increased oxidation rates as compared to that of pure nickel, whereas larger additions, e.g., 20 to 30 wt pct Cr, form alloys with substantially lower oxidation rates. The controversial aspects of the oxidation mechanisms for these alloys that still remain unresolved are as follows: 1) A description of the oxidation mechanism for the low chromium alloys. 2) A description of the oxidation mechanism for the high chromium alloys, particularly with respect to the composition of the external scale which results in the lower oxidation rates. 3) The specific alloy compositions at which the oxidation mechanism changes from that obtained for low chromium contents to that of the high chromium alloys and the reason for this transition. EXPERIMENTAL The Ni-Cr alloys listed in Table I were prepared from high purity metals by nonconsumably arc melting and casting as buttons. These alloys were then given a preliminary annealing treatment in argon at 815°C for 100 hr to promote homogeneity. Each button was cut into 0.250 in. thick sections that were subsequently cold-rolled to 0.050 in. thicknesses and annealed in argon at 815°C for 48 hr to provide a twinned, equi-axed grain structure. The grain size for these alloys was not uniform and the limits, within which the average grain size lies, are given in Table I for the single-phase alloys. All the alloys were single phase with the exception of the Ni4OCr alloy in agreement with the Ni-Cr phase diagram.&apos;&apos; Rectangular specimens were cut from the sheet to provide surface areas of approximately 2.5 sq cm. Exact areas were determined with a micrometer after surface preparation was completed. All of the specimens except the Ni-40Cr alloy and pure chromium were polished through 600-grit Sic abrasive paper, ultrasonically agitated in ethylene trichloride, rinsed with ethyl alcohol, and electro-polished. The specimens were electropolished in a 10 vol pct H2SO4 (conc), 6 vol pct lactic acid, methyl alcohol solution at 70" to 80°C for 2 min at a current density of 0.8 to 1.2 amp per sq cm. This electro-polishing procedure did not produce acceptable surfaces on the Ni-40Cr alloy nor on pure chromium and the oxidation properties of these materials were obtained for specimens polished through 600-grit Sic

Jan 1, 1970

By C. S. Barrett, C. T. Haller

TWINNING in magnesium is known to occur profusely under certain conditions, and when it occurs in polycrystalline materials it brings about a partial or even a complete change in the preferred orientation. The amount of research on this subject, however, has not been in proportion to its importance as a mechanism of deformation and reorientation. Much of the research has been limited to twinning in single crystals. The present study&apos; concerns polycrystalline sheet, and is an investigation of the twinning produced by plastic deformation as a function of the following variables: I. Direction and type of deformation. 2. Amount of deformation. 3. Speed of deformation. 4. Temperature of deformation. 5. Composition and temper of the sheet. 6. Twins previously produced. 7. Twins previously produced, then annealed. By proper control of these variables it is shown that, on a laboratory scale, samples can be produced that are free from preferred orientations. MATERIALS AND METHODS The materials used were samples of commercial magnesium-alloy sheets with nominal compositions given in Table I. [ ] X-ray diffraction was used in most of this work to detect the twins and to estimate the amount of twinning. Since twinning on {102} planes causes a reorientation of the crystal lattice by 86°, it is very easy to study with X-ray diffraction patterns, particularly if one notices the diffraction ring from the basal plane the 002 reflection. By properly directing the X-ray beam, it is possible to produce 002 reflections from twinned material at, say, the 6 and 12 o&apos;clock positions on the 002 ring, with the untwinned material reflecting to 3 and 9 o&apos;clock positions; and by judging the relative intensity of the arcs on the diffraction ring at these positions, it is possible to judge the amount of twinned material relative to the untwinned. This X-ray method of estimating the amount of twinning is generally superior to metallographic observation, for it was found

Jan 1, 1946

By Y. Nakada, U. F. Kocks, B. Chalrners

THE orientation dependence of work hardening has previously been studied over the entire range, i.e., including special orientations of high symmetry, in aluminum1-3 and silver.* The differences between various orientations are substantial, and the trend is the same in all fcc crystals. However, there are quantitative differences in behavior between aluminum and silver at room temperature, particularly in the (100) orientation. While many experiments on gold have been reported,5&apos;9 none included the special orientations. We therefore undertook tension tests on gold crystals of the axial orientations (100),(110), (Ill), (211), and, as a representative of single slip, one whose Schmid factor was 0.5 (hereafter referred to as m = 0.5). Single crystals of dimensions 1/4 by .1/4 by 6 in. were grown from the melt1&apos; at a rate of 4 in. per hr, using gold of 99.99 pct purity obtained from Handy and Harman. A growth rate of 1/8 in. per hr, or a purity of 99.999 pct,ll produced no difference in results. The crystals were annealed at 1000°C in air for 24 hr and furnace-cooled down to room temperature, after which they were electro-polished in a solution of potassium cyanide (40 g), potassium ferrocyanide (10 g), soda (20 g), and enough distilled water to make 1 liter of solution, at a current density of 0.02 amp per sq mm. After 2 or 3 hr, a very smooth surface was obtained by this method. Nine m = 0.5, two (loo), one (110), three (Ill), and one (211; crystals were tested at room temperature in a floor-model Instron machine at a tensile strain rate of 0.5 pct per min. The accuracy of the stress measurement was k10 g per sq mm up to 500 g per sq mm, k2 pct for higher stresses. The strain measurement was accurate to t2 pct. The scatter of stress at a given strain among the crystals of the same orientation was small, *5 pct being the largest. The representative stress-strain curves for various orientations are shown in Fig. 1. Table I summarizes the work-hardening parameters as used by seeger.12 Results of other investigators are also included in this table for comparison. There are no previous data for the corner orientations. Values for m = 0.5 crystals agree fairly well with those of Berner. Tm is defined as the stress at which the stress-strain curve begins to deviate from linearity of Stage 11. However, in practice this is a very difficult value to estimate because each investigator has a different idea of linearity. Therefore, the comparison with the values of other investigators may not be valid. In the present experiment, (100) crystals had the highest 111, followed by (111) crystals. The work-hardening rate in Stage I1 was highest for the (111) crystal followed by the (100) crystals. Our value for 0x1 of m = 0.5 orientation agrees very well with those of other investigators. 1) Single-Slip orientation (m = 0.5). These crystals were oriented so that the primary-slip vector was contained in one side face. The dimension perpendicular to this side should then not change if single slip indeed takes place. Within the accuracy of measurement, this dimension did not change during the deformation. Since the accuracy is k0.2 pct, the amount of secondary slip is less than 0.7 pct of the slip on the primary-slip system at 30 pct tensile strain. This is in conformity with the results obtained by Kocks" for aluminum crystals. The tensile axis moved toward (211) during the deformation. Slip bands, Fig. 2(a), were very fine and closely spaced. Some deformation bands were observed. There were no clear-cut cross-slip traces such as the ones observed on aluminum m = 0.5 crystals. 2) (111) Crystals. The orientation of the tensile axis was stable during the deformation. From this observation, one can deduce that at least three slip systems must have operated, and probably all six because the remaining three all have cross-slip relation to one of the first three.&apos; It was very difficult to observe the slip markings. Consequently, we could not confirm by this method that six systems were operative during the deformation. At high strains (above 50 pct shear strain), this orientation had the highest stress-strain curve. At 80

Jan 1, 1964

By Y. Dardel

Since the first determination of Dumas1 in 1880, many authors have tried to measure the solubility of hydrogen in solid aluminum, or at least the amount of dissolved gas in it. However, the interpretation of the results which have been obtained is still difficult. Sieverts? then Baukloh and Oesterlen,a during their gassing experiments could not determine any solubility of hydrogen in solid aluminum. On the other hand, Portevin, Chaudron and Moreq4 leaving the determination of the hydrogen solubility beyond the scope of their experiments, measured only the amount of gas that they could extract by high voltage positive ion bombardment and found up to 151 cm3 of gas per I00 g of metal. Winterhager,6 by repeated vacuum extraction during severe cold rolling, extracted up to 161 cm3 per 100 g. In both series of experiments, the extracted gas contained chiefly hydrogen with a small amount of nitrogen, carbon monoxide, carbon dioxide and methan. Later, Schmidt and von Schweinitze as well as Chaudron and Moreau7 showed the importance of the adsorbed layer of hydrogen, the extracted quantities being proportional to the surface and not to the weight of the sample, when its cleaning was not perfect. In earlier experiments, Steinhausers extracted from more massive samples nothing but a little amount (< 0. 5 cm3 per I00 g) of hydrogen, carbon monoxide and methane. Thus, according to these experiments the quantity of dissolved gas is probably very small and the effect of the surface could falsify the results of the extraction. However, owing to the care taken by Chaudron and his coworkers, it was clear that all the hydrogen extracted could not come from the superficial layer, or that the links which bound hydrogen to the surface were so strong that the usual method of cleaning could not destroy them. After the main parts of the experiments reported here had already been carried out, Eborall and Ransley9 published the results which they obtained with an analysor having an accuracy of 0.03 cm3 per I00 g, while that of the usual apparatus was only about 0.2 cm3 per I00 g. During all their experiments the adsorbed layer would have been a difficulty, for the value of the adsorbed hydrogen was approximately equal to that of the dissolved amount. Table i—Amount of Adsorbed and Dissolved Hydrogen (After Eborall and Ransley) Extraction Hz Adsorbed „ h2 dissolved Temperature Calculated Extraction OCcma 500 0.057 0.050 600 0.062 o.096 Since always keeping the same adsorbed layer is very difficult, an error in the correction for the adsorption can be made when using the apparatus of. Eborall and Ransley, as well as the earlier apparatus.

Jan 1, 1949

J. E. Stead, Middlesborough, England (communication to the author): Prof. Howe&apos;s valuable paper on cast-iron brings forward most prominently the correct explanation of the part played by combined carbon in pearlite and cementite, in determining the strength and hardness of cast-iron. On a previous occasion I haveoshown that castings made by melting a white Cleveland iron and glazed iron, one containing 1.5 and the other from 4 to 5 per cent. of silicon, and each about 3 per cent. of carbon, were stronger than those made of ordinary foundry-iron; the difference in the final castings being a differ-

Jan 1, 1902

By John Henderson

FOR some time now the most commonly accepted description of liquid silicate structure has been the "discrete ion" theory, proposed originally by Bockris and owe.&apos; This theory is that when certain metal oxides and silica are melted together, the continuous three dimensional silica lattice is broken down into large anionic groups, such as sheets, chains, and rings, to form a liquid containing these complex anions and simple cations. Each composition is characterized by "an equilibrium mixture of two or more of the discrete ions",&apos; and increasing metal oxide content causes a decrease in ion size. The implication is, and this implication has received tacit approval from subsequent workers, that these anions are rigid structures and that once formed they are quite stable. The discrete ion theory has been found to fit the results of the great majority of structural studies, but in a few areas it is not entirely satisfactory. For example it does not explain clearly the effect of temperature on melt structure,3 nor does it allow for free oxygen ions over wide composition ranges, the occurrence of which has been postulated to explain sulfur4 and water5 solubility in liquid silicates. In lime-silica-alumina melts the discrete ion theory is even less satisfactory, and in particular the apparent difference in the mechanism of transport of calcium in electrical conduction8 and self-diffusion,&apos; and the mechanism of the self-diffusion of oxygen8 are very difficult to explain on this basis. By looking at melt structure in a slightly different way, however, a model emerges that does not pose these problems. It has been suggested5" that at each composition in a liquid silicate, there is a distribution of anion sizes; thus the dominant anionic species might be Si3,O9 but as well as these anions the melt may contain say sis0:i anions. Decreasing silica content and increasing temperature are said9 to reduce the size of the dominant species. Taking this concept further, it is now suggested that these complexes are not the rigid, stable entities originally envisaged, but rather that they exist on a time-average basis. In this way large groups are continually decaying to smaller groups and small groups reforming to larger groups. The most complete transport data 8-10 available are for a melt containing 40 wt pct CaO, 40 wt pct SiO2, and 20 wt pct Al2O3. Recalculating this composition in terms of ion fractions and bearing in mind the relative sizes of the constituent ions, Table I, it seems reasonable to regard this liquid as almost close packed oxygens, containing the other ions interstitially, in which regions of local order exist. On this basis, all oxygen positions are equivalent and, since an oxygen is always adjacent to other oxygens, its diffusion occurs by successive small movements, in a cooperative manner, in accord with modern liquid theories." Silicon diffusion is much less favorable, firstly because there are fewer positions into which it can move and secondly, because it has the rather rigid restriction that it always tends to be co-ordinated with four oxygens. Silicon self-diffusion is therefore probably best regarded as being effected by the decay and reformation of anionic groups or, in other words, by the redistribution of regions of local order. Calcium self-diffusion should occur more readily than silicon, because its co-ordination requirements are not as stringent, but not as readily as oxygen, because there are fewer positions into which it can move. There is the further restriction that electrical neutrality must be maintained, hence calcium diffusion should be regarded as the process providing for electrical neutrality in the redistribution of regions of local order. That is, silicon and calcium self-diffusion occur, basically, by the same process. Aluminum self-diffusivity should be somewhere between calcium and silicon because, for reasons discussed elsewhere,&apos; part of the aluminum is equivalent to calcium and part equivalent to silicon. Consider now self-diffusion as a rate process. The simplest equation is: D = Do exp (-E/RT) [I] This equation can be restated in much more explicit forms but neither the accuracy of the available data, nor the present state of knowledge of rate theory as applied to liquids justifies any degree of sophistication. Nevertheless the terms of Eq. [I] do have significance;12 Do is related, however loose this relationship may be, to the frequency with which reacting species are in favorable positions to diffuse, and E is an indication of the energy barrier that must be overcome to allow diffusion to proceed. For the 40 wt pct CaO, 40 wt pct SiO2, 20 wt pct Al2O3, melt, the apparent activation energies for self-diffusion of calcium, silicon, and aluminum are not significantly different from 70 kcal per mole of diffusate,&apos; in agreement with the postulate that these elements diffuse by the same process. For oxygen self-diffusion E is about 85 kcal per mole,&apos; again in agreement with the idea that oxygen is transported,

Jan 1, 1963

CARL HENRICH (communication to the Secretary*).-I have read with much interest the discussions of my paper by Messrs. A. S. Dwight, E. P. Mathewson, Win. B. Boggs, Jos. W. Richards, and W. C. Smith. Mr. Dwight&apos;s acknowledgment that he always-in lead smelting¬obtained better results by figuring A1203 as an acid in his slags, I may take as a confirmation of my views, notwithstanding his later conversion by, the late T. S. Austin to the latter&apos;s empirical view and way of neglecting the consideration of A1203 altogether in the composition of slags-letting the slags "dissolve" in Al203. I have a strong suspicion that Mr. Austin, in a large custom smelting plant at El Paso, has been able to keep the alumina percentage of his slags sufficiently low, not to give him much trouble, although I have also a suspicion that his furnace foreman may have had a somewhat differing opinion of the practical working of the "dissolving" theory,, whenever its applicability was tested to its limits. That Austin should have conceived the notion that the Ca of CaF2 would enter into a slag as CaO, seems hardly in accord with the recognized ability of that late metallurgist. It is a well-recognized fact that even small amounts of CaF2 will reduce the viscosity of a slag; but I did not think anyone ever had an idea that CaF2, in some mysterious way, parted with its F and coupled itself with 0 to satisfy a craving for CaO on the part of 802-least of all in a lead furnace. The "dissolving" theory for CaF2 was doubtless appropriate, and an improvement on figuring the Ca of CaF2 as CaO to satisfy the demand of Si02 for RO bases. However, I cannot understand the rationality of extending this "dissolving" theory to A1203 and to ZnO. It would be interesting to have more specific data from Mr. Mathewson in regard to the actual composition-analyses-of the slags made, when he had these unusually high alumina slags in Colorado. We "old" smelters all know that within certain limits, usually found out by rather tough experience, we could safely "disregard" A1203. In fact, I believe, we never really analyzed for alumina, except in slag analyses, when we

Jan 6, 1917

By F. C. Schora, H. P. Meissner

Iron ore from Cerro Bolivar, Segre&apos;, and Sierre Grande was reduced in fluid beds at about SOOT, using gas analyzing 20.5 pct CO, 41 pct Hz, and 38.5 pct N2. Except in the early stages of reduction, the rate of oxygen loss from the bed was directly proportional to the oxygen concentration in the bed, independent of gas composition as long as the gas was reducing, and little affected by temperature. The percentage reduction of the bed solids at any time was independent of particle size. I HE reduction of spheres or cubes of dense iron ore in a slowly moving stream of either pure H, or pure CO has been found to take place at distinct interfaces between well defined layers of iron and the iron oxides.&apos;y4 These interfaces generally penetrate the ore lump in topochemical fashion, remaining parallel to the original contours of the specimen. Thus in the earlier stages of reducing hematite, the specimen&apos;s core is Fe,O, surrounded by successive shells of the lower oxides, and finally by an exterior shell of iron. McKewan5 assumed that the rate limiting step occurred at the Fe-FeO interface, with reducing gas penetrating up to this interface through the external porous iron shell, and reduction of the higher oxides within the ore lump occurring by diffusion of iron through the dense FeO shell. He developed an analytical expression based on this model relating the amount of oxygen removed from

Jan 1, 1962

[Trans. No. Place Date Vol. Page 1. Wilkes-Barre, Pa.*.. *May: &apos;71.. 1 3 2. Bethlehem, Pa Aug. &apos;71.. 1 10 3. Troy, N. I X Nov. &apos;71.. 1 13 4. Philadelphia, Pa Feb. &apos;72.. 1 17 5. New York, N. Y.*.... May, &apos;72.. 1 20 6. Pittsburgh, Pa Oct., &apos;72.. 1 . 25 7. Boston, Mass Feb., &apos;73 1 28 8. Philadelphia, Pa.*.... May, &apos;73 2 3 9. Easton, Pa Oct., &apos;73 2 7 10. New York, N. Y Feb., &apos;74.. 2 11] [ ]

Jan 1, 1925

By A. Goldberg, T. E. Tietz, J. E. Dorn

INTRODUCTION THE concept that the flow stress for plastic deformation of metals in the work hardening range is a function of the instantaneous values of the strain, strain rate and test temperature was promulgated by Ludwick1 many years ago. This thought has been more or less a guiding principle throughout the immediate period of development and growth of mechanical metallurgy. It has been tacitly assumed or knowingly applied to many investigations on the plastic behavior of metals. Spurred by the theoretical interest and practical importance of the plastic behavior of metals, many investigators have attempted to determine empirical, semi-empirical, and theoretical equations2-18 relating the flow stress with the strain, strain rate, and temperature. Although the applications of such equations have been extensive, the experimental verification of the existence of a mechanical equation of state is weak. Furthermore, some of the available evidence on plastic flow appears to suggest that no simple functional relation between stress, strain-rate, strain and temperature can exist. The mechanical equation of state demands that [a = a(e, E, T)[I]] Where o = true stress = load/instantaneous area e = true strain = In Instantaneous gauge lengths initial gauge length e = true strain rate T = temperature] This formulation implies that [da] is an exact differential. Therefore the flow stress (o) is a function of the instantaneous values of the strain (e) the strain rate (e) and the temperature (T), independent of the previous mechanical or thermal history. Having reached a certain strain, strain rate, and temperature, by any path whatsoever, a definite and fixed value of the flow stress should be obtained. One check on the validity of the mechanical equation of state is easily obtained. Consider the following three tests on the stress-strain curve at constant temperature: [A. Strain at rate [ei] B. Strain at rate i2 C. Strain at rate [Ei] to [ei] and continue test at i2] A graphical representation of possible results of such tests are shown in Fig I. If, for strains greater than [el], test (C) data coincide exactly with the data from test (B), as shown in Fig Ia, a limited verification of the mechanical equation of state is obtained for the range of strain rates from [ii] to [e2]. But if the data from test (C) differ from those of (B) beyond strain [el] where the strain rate is changed from [e,] to [€2i] the mechanical equation of state is not

Jan 1, 1948

By R. E. Somers

I. Introduction...........................604 1. Location, Topography, and Climate...............604 2. Scope of Work and Acknowledgments...............606 3. History and Mining......................606 11. General Geology.........................609 1. Introduction...........................609 2. Granite. :..........................610 3. Quartz Porphyry......................... 612 4. Monzonite........................... 614 5. Volcanic Breccia........,................ 618 6. Gravels............................. 619 111. Economic Geology......................... 619 1. Introduction........................... 619 2. Mineralogy........................... 619 3. Occurrence of the Ores...................... 622 4. Oxidation and Downward Enrichment............... 630 5. Rock Alteration........................639 6. Genesis of the Ores........................ 643 I. Introduction 1. Location, Topography, and Climate The Burro Mountains are located in the southwestern part of New Mexico, in Grant county. The group is made up of two distinct mountain masses, known as the Little Burros and the Big Burros, the former lying about 6 miles southwest of Silver City, and the latter about 9 miles farther in the same direction. They are separated by the valley of the Mangas River, a tributary of the Gila, and a stream only in name, except after a heavy downpour of rain. The Little Burros attain an elevation of 6,625 ft. above sea level, and the Big Burros 8,054 ft., with the surrounding country averaging about 6,000 ft. To the south of these mountains stretches the desert plain, while to the north are the more frequent elevations of the mountainous country.

Jan 1, 1916

By K. Tanaka, J. D. Mote, J. E. Dorn

It) an attempt to ulLcoce.lP the operative strain-rate-contl-olliy: dislocation nieclzanistns, specially oviented sizgle clystals of the intel-nzediate 1zexagonal phase containing Ag plus 33 at. pct A1 were tested in tension over a wide range of temperatures. Slip was observed to take place by the {0001} <1120> {l100} mechani fracture took place across the(i100) plane and winning occurred by the (i01Z) ?lechanisn. Basal slip exhibited a strong yield point over the -alzge from 77 to 450°K, the upper ,esolved shear st]-ess having the exceptionally high value of 10,500 psi over this entire ?-a?zge of tenzpei,atuves. The critical 9-esolved shear stress for prismatic slip decreased f7-om 48,000 psi at 4.3"K to 23,000 psi at 170°K (Region 1) follozcirg zt:lzich it decl>eased sloz&ly to 21,500 psi at 475°K (Res&apos;on II); from 475" to 575°K (Regioz III), the c7-itical esolced shear stress dec&apos;-eased precipitously to 2000 psi; and from 575" to 750°K (Region IV) it decreased less afi&apos;dly to a low value of about 500 psi. Pvistintic slip in Region I was pobably controlled by the tliel-nally activated riecharzisui of nucleation and g,-ozcth of kinks in dislocations lying in Peierls potential troughs. In Region II for prismatic slip the critical 1-esolved shear stress was slzocn to be deteemined by sh0l.t-range 01-dering, Overall the forgiorz fo basal slip, 7.c.lre1-e a Strong yield-point phenorlienu ia7as observed, the critical vesolved slzea?-stress was shoztn to be determined by n conibirzation 0-f Szizuki locking and short-range-order Izavderzizg, The precipitous decrease in the critical resolved shear stress with increase in ter,/pe7-atrir-e over Region HI was tentatively ascribed to a decrease in the degree of slort-)ange 07-del;iqq (0)- clusteing) and also the effect of fluctuations the degree of o?der, It is at pgreser2t zrtzce)taitz as to 1t1hethe1- these or other possi1)le effects are also ,esponsible. fo- the data obsel-ved 172 Region IV. 1NTEREST in inter metallic compounds stems not only from their role in dispersion hardening of polyphase alloy ystems but equally from their potentialities for high strength, hardness, and stability not only at atmospheric temperatures but especially at elevated temperatures. As summarized in a re- cent symposium of the Electrochemical Society on "Mechanical Properties of Inter metallic Compound", most of the experimental evidence regarding the mechanical behavior of intermetallic compounds centers about the effect of temperature on the hardness and ductility of polycrystalline specimens. The available data reveal that the plastic behavior of intermetallic compounds might be rationalized in terms of the usual dislocation mechanisms appropriate to a solid solutions providing the additional complexities arising from crystal structure, long-range ordering, short-range ordering, and defect lattices are taken into consideration. It is apparent, however, in terms of the history on a solid solutions, that a complete detailed mechanistic rationalization of dislocation processes may not be possible until the deformation processes are studied in single crystals of intermetallic compounds. The present paper contains a preliminary report on the plastic behavior of single crystals of the hexagonal Ag-A1 intermetallic phase over a wide range of temperatures. The results confirm the thesis that single crystal data provide a most effective method of identifying operative dislocation mechanisms in intermetallic compounds. EXPERIMENTAL TECHNIQUES Several factors prompted the selection of the hexagonal Ag-A1 intermetallic phase for this preliminar investigation on the plastic properties of single crystals of intermetallic compounds: 1) This phase has a wide solubility range5 which would permit future investigations on the effect of composition and axial ratios on slip mechanisms. 2) Although it undoubtedly exhibits short-range ordering (or clustering) this intermetallic phase is free from complexities arising from long-range ordering.6 3) Since the atomic radii of aluminum and silver are practically identical, the possible complications due to Cottrell locking are minimized. 4)Whereas the dislocations on the basal planes are expected to dissociate into Shockley partials and are thus susceptible to Suzuki locking, those on the prismatic planes probably remain complete. 5) The axial ratio, being 1.61, is almost ideal, suggesting that short-range ordering may be almost spherically symmetrical. The present investigation was conducted exclusively with the hexagonal Ag-A1 alloy containing 33 at. pct Al. Preliminary investigations revealed that this alloy undergoes basal slip by the (0001)

Jan 1, 1962

By K. A. Gschneidner, O. D. McMasters

DgIel-ential thermal, nretallographic, and X-ray paramzetric methods were used to establish the Yb-Pb phase dingram. The terminal solid solubilities in the system are less than 0.2 at. pct. Lead additions lower the 792°C transformation tewzperature of pure ytterbiun~ at 787°C by means of an inverted peritectic veaction. Ytterbium additions raise the 327oC melting point of lead to 329°C by means of a perilectic reaction. Three intermetallic compounds Yb2Pb, YbPb, and YbPb, melt congruerttly at 1246", 1116o, and 740°C. respectively. YbsPb3 forms by a peritectic reacliorz at 1250°C. YbzPb crystallizes in the PbCh (C23) type structure and the orthorhombic latliceo constants are a, = 7.478. bo = 5.225, aud C0 = 9.549A. YbsPbs crystallizes in the hfnsSi3 (D8a) type structure. The hexa~nal lattice constants for this phase are a, = 9.325 and co = 6.92d. YbPbl crystallizes in the cubic AuCU3 (Ll2) type structure with a: = 4.8628 + 0.0008A. YbPb is diwrorphic with the structure change occurring al 507°C upon healing. The crystal structures of the two forttzs were not determined. Eulectic reactions occur at 5.1 at. pct Pb and 769oC, 41.5 at. pct Pb and 1086oC, and G8.0 at. pct Ph and 717°C: RELIABLE information concerning the alloying behavior of most of the rare-earth metals is scarce. A systematic study of the rare earth-lead alloy systems now in progress is an effort to supply such information. Determination of the phase diagram of the Yb-Pb alloys is the first step of this study. Variations in the valence of normally divalent ytterbium may be studied by comparing the characteristics of the Yb-Pb alloys to those of the trivalent rare earth-lead and of the divalent alkaline-earth-lead systems. Of particular interest are the melting temperatures of the intermetal-lic compounds since these are known to be high relative to the melting points of the constituent metals. Crys-tallographic and magnetic susceptibility data for the rare earth-lead alloys are to be included in the comparative study. Results from this and subsequent investigations should provide a better understanding of alloy formation. EXPERIMENTAL PROCEDURE Materials. The major impurities in the ytterbium and lead used in this investigation are listed in Table I. The lead was obtained from Cominco Products, Inc., and was specified to be 99.99 pct pure. The ytterbium was prepared in this laboratory by the lanthanum reduction of the oxide followed by a distillation of the ytterbium. Alloy Preparation. The alloys were prepared by

Jan 1, 1968

By R. C. Gifkins, K. U. Snowden

The value of the index n in power ktivs for the stress sensitivity of minimum creep rale at lead is derived front results drawn from lite literature and from previously unpublished nork on commercial (99.99 pel) and high-purity (99.999 pel) lead polycryslalline and hi crystal specimens. In tests al 0.5Tm (22 to 50&apos;C) for slvesses below 250 psi, n fulls to mily for poly-cr,yslullirle specimens, single crystals, and bicrystals, and toy grain boundary sliding in bicrystals. Between 250 and 500 psi there is a tyansilion range and, for the polycrystalline specimens al least, u high-stress regime for 500 to 1500 psi where n is 5 or 6. These results are such that none of the suggested stress taws can he used to extrapolate to very loir stresses. Meclianisms for deformation in Ike grains and toy grain boundary sliding in the low-strcss regime are outlined. In particular, the mechanism for grain boundary sliding involves sliding controlled by diffusion from tensile to compressire Ledges. predictions based on this model give promising numerical agree-nicul with experiment. II is suggested that the mechanism for grain boundary sliding may he important in other circumstances, e.g., in creep of ceramic materials or superplaslicity, because it can operate with lille or no dislocation aclirity. WhEN the stress dependence of secondary creep rate is represented by a power law the values taken by the stress exponent n are found to vary between 1 and 7, see, c.g., Garofalo.&apos; In Eq. 1 11 u is the applied stress and A a constant. The case for accepting values of v = 1 rests principally upon tests at high temperatures (>0.9Tm) and there have only been isolated tests at lower temperatures (rather than plots of creep rate against stress) for which the creep rates are such that some form of Nabarro-Herring creep with n = 1 is applicable. Hanson5 and Greenwood and cole6 plotted creep rate against stress for tests made in the vicinity of 0.5Tw, and found a "creep yield", so that below a certain low stress the creep rate was linearly related to stress: these observations appear to have been subsequently ignored. Various models have been proposed which agree with a large body of experimental results in which n equals -5 at high stresses (e.g., weertman7 and McLean8). Various alternatives to Eq. [1] have been proposed principally as a means of unifying creep data, but sometimes, it seems, in order to obviate the necessity for assuming a series of regimes of deformation associated with the various values of n; further refer- ence to these will be made in the section on stress laws. This paper calls attention to extensive results which show n = 1 for the creep of lead at room temperature (0.5 T,). RESULTS Fig. 1 is a composite diagram based on figures in the literature6,9,10 with additional results obtained by the present authors and their colleagues11,12 in the course of a number of investigations not directly concerned with stress sensitivity. In Fig. 1 In creep rate is plotted against In stress. The curves show results for two kinds of material. Lead I is of commercial purity (99.99 pct Pb) and lead IT a specially refined material, hydrogen-purified to remove oxygen; it contains 99.999 pct Pb. Curve A is for lead I in polycrystalline form (grain diameter 0.02 to 0.05 cm) at room temperature (22&apos; to 26°C). Curve B1 is for lead I, polycrystalline, tested at 50C. Curve B2 is for lead 11, polycrystalline (grain diameter 0.02 cm), tested at room temperature (22 O- Curves C to F relate to tests made of bicrystals of lead 11: all of the same nominal orientation ("Y" in Ref. 12). Curves C and V are for creep within the component crystals of the bi crystals at 22°C (AB and CD in Fig. 2). Curve E is for creep measured in a gage straddling the boundary, approximately 0.15 mm either side (BC in Fig. 2). Curve F shows rates of grain boundary sliding (as distinct from strain rates in the other curves), obtained by averaging the offsets of six marker lines on the bi-crystal boundaries. The principal feature of the results is that the stress sensitivity falls into two distinct regimes, according to whether the stress is below approximately 250 or above 500 psi (there is a transitional range between 250 and 500 psi). The new result is that below -250 psi two of the curves (A and BI) give a value of n 1, and the other curves also drop below n - 2 to -1.5 but do not extend to low enough stresses to show clear evidence of n 1. At very high stresses the curves tend to give values of n - 6, as previously determined in other investigations. Curve R2 for the high-purity lead in polycrystalline form at room tenlperature almost merges with B, and thus gives new significance to the values for stresses of 150 and 200 psi; previously&apos;3 these points had seemed to fall away from the curve of slope -3, but they now can be seen as almost completing a transition to n = 1. It should be noted that there was originally considerable apparent scatter in the results for the high-purity lead. However, this was found to be associated with annealing conditions or variations in residual content of oxygen and curve B2 was constructed using the highest rate (i .e., the rate for the purest lead) determined for each stress during the course of various investigations over the years: altogether, some forty tests were used in constructing curve R2.

Jan 1, 1968

By Henry S. Washington

Introduction. It Still Rains On The Choco ! I Well Remember One Evening A Dozen Years Ago, While. Traveling Toward The Town Of Negua In A Small Champa Or Dug-Out Canoe, The Rain Fell So Heavily That I Had To Work My Hardest To Bail Out The Water With A Large Totuma Or Gourd In Order To Keep The Canoe Afloat, The Senegambian Meanwhile Plying His Paddle In The Stern. If Any One Thinks Bailing Is Easy Work, Let Him Scoop Out A Quart Or More At A Stroke, 40 Times A Minute For Half An Hour, And I Venture That He Will Change His Opinion. These Small Canoes Required Only One Paddler, To Make The 3 Miles An Hour Which Is The Standard Rate Of Aquatic Progress On The Choco. Another Time, On The Atrato River, About Six O&apos;clock In The Afternoon, The Rain Fell So Heavily Than An Empty Gourd, 9 In. In Diameter And 4.5 Deep, Was Filled To The Brim In 90 Sec., Timed By A Watch. Such Downpours Are Typical, But Unless Caught In One It Is Not Specially Noticed. These Downpours Seldom Last More Than An Hour, And Frequently Cover Only A Limited Area, Occasionally Falling On One Bank Of A River And Not On The Other. During The Night-Time,&apos; The Rain, If Gentle, Will Usually Last Until Dawn, And Sometimes An Intermittent Drizzle Will Keep Up All Day As Well, Although, As A Rule, It Rarely Rains During The Day. The Rise Of The Rivers, Due To The Rain-Fall, Varies From A Few Inches To Several Feet. One Night In August, 1899, The Spuds Of The Dredge Margaret, Operating On The Atrato River, Showed A, Rise Of 16 Ft., And For 3 Days Thereafter Occurred The Greatest Flood Known In That District For 32 Years. The Dredge Had All Three Spuds Clown, And The 2-Yd. Shovel Dragging On The Bottom. A 0.75-In. Cable Fast To A Stout Tree, 700 Ft. Away, Stretched Tight

Sep 1, 1908