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By D. N. Seidman

In the course of a study of the electronic and thermodynamic properties of Pb-Se alloys it was found necessary to have an accurate knowledge of the phase diagram. However, the literature is in disagreement as to whether or not a monotectic reaction occurs in the lead rich portion of the phase diagram. Pelabonl reported only a two-phase region consisting of lead-rich liquid and solid PbSe extending from almost pure lead to the compound PbSe, and gave the melting point of PbSe as 1065°C. The data of Friedrich and Leroux2 are in general agreement with this type of diagram, with the melting point of the compound being 1088°C. However, Nozato and Igaki by inverse rate thermal analysis observed a monotectic reaction isotherm exlacing at 860°C with a monotectic composition of 20.5 at. pct Se. The miscibility gap in the liquid state extends from 7.5 to 20.5 at. pct Se. Hansen and Anderko4 accepted Nozato and Igaki's phase diagram in the region of the lead-rich monotectic. To reinvestigate this portion of the phase diagram, both thermal analysis and metallographic examination of various compositions were performed. The thermal analysis apparatus was constructed according to the specifications of the National Bureau of Standards. A t/t-l pct Rh thermocouple was calibrated against the melting point of copper (NBS), zinc (NBS), and antimony (A. D. Mackay), the emf being measured with a Rubicon Type B potentiometer sensitive to lpv. The absolute accuracy of the thermal analysis obtainable with this system is ± 0.5oC. Starting materials were semiconductor grade lead and selenium purchased from the American Smelting and Refining Co. Both elements were 99.999 pct pure with only trace impurities detected upon spectroscopic examination. One hundred galloys were sealed in quartz crucibles with a central thermocouple well under a vacuum of less than 1 p. This procedure prevented any composition change due to vaporization during the run. Cooling curves were obtained on the alloys listed in Table I. Data was taken by the direct method at cooling rates ranging between 1/2 to 2°C per min. The alloys were heated well above the liquidus and shaken vigorously to insure homogeneity. No evidence of an arrest indicative of the monotectic reaction was observed, and the two-phase region reported by Pelabonl and Friedrich and Leroux? was confirmed in general, although our data give higher liquidus temperatures than Friedrich and Leroux. The melting point of stoichiomet-ric PbSe determined for two different samples was 1080.7 0.5oC. The results of this investigation are compared with Nozato and Igaki's data in Fig. 1. To Complement the thermal analysis data, an 86 at. pct Pb specimen was examined microscopically. This composition was in the center of the miscibility gap reported by Nozato and Igaki.3 The alloy was heated to 1000°C, held for 1/2 hr, and water quenched. The specimen was polished using standard metallographic techniques for lead. The alloy was etched with an acetic-nitric acid etchant for 10 min at 45°C. Microscopic examination did not indicate the existence of two separate layers or solidified droplets imbedded in a matrix, as would be expected if a miscibility gap were present. The mi-crostructure shown in Fig. 2 consists of uniformly dispersed, dendritic PbSe in a lead-rich matrix.

Jan 1, 1962

By Thomas L. Kesler

Essentially all of the barite produced in Georgia has come from the Carters-ville district in the northwest part of the state. The earliest recorded shipment of ore, 60 tons, was made in 1894.' With the exception of the four-year period 1931 to 1934, the separate yearly output has been recorded and published since 1915, whereas the total yearly output of the United States has been published since 1880. The separately recorded production of Georgia (Cartersville) through 1947 is 2,232,544 short tons valued at $14,900,746,2 but unpublished data on the period 1931 to 1934, plus the estimated unrecorded output prior to 1915, make the actual total about 2,400,000 short tons. This is about 21 pct of the total production of the United States, which, through 1947, is 11,328,440 short tons valued at $71,683,386.2 The barite-producing part of the Cartersville district is relatively small, having from north to south a length of 4.5 miles, and a width of 2 miles. This small area, containing 35 barite mines, is the source of practically all of the barite produced in the state. The area is hilly, and has a total relief of 500 ft. The west-flowing Etowah River crosses the middle of the area, and is an unfailing source of water for operations on properties near its course. Opencut mining is carried on during the entire year, but is hampered by rain in the winter and early spring. Three railroads, two U.S. highways, and a network of graded roads provide access to and within the district, as well as excellent shipping facilities for ore and supplies. In addition to the barite, the district contains deposits of manganese, brown iron, ocher, umber, and specular hematite. Geologic Setting The area containing the barite deposits is underlain by Lower Cambrian rocks and their weathered residua. These rocks are grouped in three formations; in ascending order, these are the Weisner, the Shady, and the Rome. The Weisner formation consists mainly of finely micaceous metashale containing many random beds of quartzite, a few beds of conglomerate and metasiltstone, and beds of crystalline limestone that is apparently scarce. The formation is more than 1000 ft thick, and the base is not exposed. On account of their resistance to weathering, the rocks of the Weisner formation have sustained the higher elevations and therefore crop out on the ridges that characterize the area. Nearly all of these ridges are underlain by asymmetric anticlinal folds, and conversely the intervening valleys are underlain by synclinal folds. A diagrammatic section, showing typical mode of exposure of the Weisner rocks and their relation to overlying formations, in the limb of a fold, is shown in Fig 1. The Shady formation here consists of a lithologically distinctive series of variably siliceous specular hematite beds and thin beds of dolomite, which in places contain abundant fossils. In the zone of weathering, the dolomite has been leached and most of the hematite hydrated to ocherous and umber-ous clays, hut bedding planes in these weathered materials are commonly well preserved with or without distortion effected by slumping. This preservation of structure during weathering is lacking in the residuum that rests on the Rome dolomite, which is described below. The maximum thickness of the

Jan 1, 1950

By E. Miller, J. M. Eldridge, K. L. Komarek

The thermodynamic properties of- liquid Mg-Pb allojs have been determined by an isopiestic method from 18 to 42 at. pct Pb and by a thevmodynumic analysis of the phase diagram frofiz 0 to 100 at. pct Pb. In the overlapping composition range the magneszupn activity values derived by the two methods are in excellent agreement, thus mutually supporting the correctness of the Mg-Pb phase diagram previously determined by the authors and of the acticitzes deriz~ed isopiestically. SEVERAL studies have been made of the thermody-namic properties of liquid Mg-Pb alloys. Wagner and Engelhardt,1 Lantratov,2 Knappwost,3 Sryvalin et al.* and Wilson5 used the electromotive-force method, Scheil and Wolf8 and Schmahl and Sieben" applied the transpiration technique, and the present authors8 utilized the phase diagram to determine the activity of magnesium in the Mg-Pb system. The results of these studies are not in very good agreement and could not be incorporated into a general systematic analysis of the thermodynamic properties of the homologous series of the Mg-Group IV B systems Mg-Pb,8 Mg-Sn,° Mg-Ge,10and Mg-Si.11 The thermodynamic properties of the Mg-Pb system were therefore re investigated by an isopiestic technique which has been developed for similar studies in the Mg-SnB and Mg-Ge10 systems- Lead specimens, contained in iron or graphite crucibles, were heated in a temperature gradient in an evacuated and sealed titanium reaction tube and equilibrated with magnesium vapor of known vapor pressure to form alloys of compositions which depended on their temperatures, the temperature of the magnesium vapor source, and the thermodynamic properties of the system. EXPERIMENTAL PROCEDURE Magnesium (Dominion Magnesium Ltd., Toronto, Canada) of 99.99+ pct purity and lead (American Smelting and Refining Co.) of 99.999 pct purity were used. In the early experiments, Runs 2 and 3, the alloys were contained in uncovered high-purity iron crucibles. Alloys formed in the uncovered iron crucibles had to be chemically analyzed owing to the slight volatility of lead under the imposed experimental equilibration conditions. The compositions of these alloys were determined by a gravimetric analysis of lead as lead chromate. To avoid this problem, the remaining runs were made in covered graphite crucibles machined from high-density (1.92 g per cu cm) graphite rods (Basic Carbon Corp., Sanborn, N.Y.) which had a maximum ash content of less than 0.04 pct. The non- i reactivity of graphite with lead and magnesium has been previously established,' and the experimental procedure has been described in full detail.' In the runs using covered graphite crucibles it was found that the weight increases of the crucibles and their contents after equilibration equaled the magnesium contents of the alloys within the accuracy of the chemical analysis (i0.3 at. pct Pb). Clearly, the small lid openings of the graphite crucibles prevented significant lead losses during a run, and the weight increase was therefore taken as the magnesium content of the alloys. EXPERIMENTAL RESULTS At thermodynamic equilibrium the magnesium partial pressure of the specimens equaled that of the reservoir. Since the magnesium reservoir was always maintained at the temperature minimum of the system, the activity of magnesium of any specimen was given by the ratio of the magnesium reservoir pressure to the vapor pressure of pure magnesium at the specimen temperature. The standard state was chosen as liquid magnesium and the vapor pressure of liquid magnesium

Jan 1, 1968

By H. P. Stuwe

It is investigated whether a model of sphere packing permits the computation of the lattice parameters and their variation with concentration in various a phases; it does, except in phases containing silicon. Several observations indicate that a particular role is played by the "E-atoms" in the lattice. THE phase is formed by many alloys of the transition elements.'-' Its structure has been described by Bergman and Shoemaker,5,8 Dickins, Douglas, and Taylor,7 and Kasper, Decker, and elanger.' There are five kinds of crystallographically equivalent positions for the 30 atoms in the unit cell which have been designated by these authors I, 11, 111, IV, and V or, in the same sequence, A, B, C,D, and E, as shown in Fig, 1. For the purposes of the present paper two elements of the lattice will be discussed separately: The lattice planes perpendicular to the c-axis which are made up by the atoms A, B, C, and D and which determine the a-parameter; and the close-packed "vertical rows" of E-atoms which determine the c-parameter. asper,9 and Frank and kasper10 described the a phase and other complex structures as sphere packings. In these papers particular attention is paid to the coordination polyhedra. Lattice positions with an equal number of nearest neighbors are considered equivalent regardless of their crystallo-graphic description. This seems to work very well for the explanation of ordering phenomena in the a phase as far as information on this is available." If the description of the phase as a sphere packing is valid it should be possible to draw two further conclusions: 1) It should be possible to calculate the lattice parameters from the atomic radii of the components, and 2) It should be possible to predict the variation of the lattice parameters with concentration within one phase field. Both points are discussed in this paper. PROCEDURE Measurements of lattice constants were done with a symmetrical back-reflection X-ray camera. With Cr-radiation, about a dozen a1 lines could be observed with most samples. From the (550/710)- and 720-lines the a-value was computed. With this value the c-parameter was calculated from the (333)- and (413)-lines. Finally, the position of all the other lines was computed from the lattice parameters thus obtained. In this way the validity of the indexing could be checked and, at the same time, this proce- dure gave an estimate of the accuracy of the lattice parameters. A correction was made for film shrinkage. The atomic radii used in the computations are the Goldschmidt radii for coordination number 12. Actually, some of the atoms have a coordination number of 14 or 15, but the error thereby introduced is small. * For the computation of lattice constants from the atomic radii an "average atomic radius" of all components was used, i.e., complete disorder was assumed. Although this seems to be true for some systems like OS-Cr,4 it is not true in others.11,13,14 The ordering model, however, which has been suggested by Kasper on the basis of extensive research lets both kinds of atoms contribute to both the ''vertical rows" and the lattice planes perpendicular to them, so that even with ordering of this kind the assumption of complete disorder cannot introduce a very serious error in calculating lattice parameters. RESULTS Bergman and shoemaker6 gave a table of the interatomic distances in the Fe-Cr phase. If we disre-

Jan 1, 1960

By Harry M. Mikami

Chromite is the only ore mineral of metallic chromium and chromium compounds and chemicals. Because of this fact, chromite and chrome ore are used synonymously in trade literature. In commercial market quotations, chrome ore is the term commonly used. Chromite per se, because of properties imparted by its chromium content, is used in refractories and in special purpose molding sands for metal casting. There are many other minerals containing some, generally minor, amounts of chromium, but none are commercial sources of the element (Thayer, 1956). Chromium and chromite have many diverse uses that, directly and indirectly, critically affect vast segments of our modern industrial system. Most important are probably the metallurgical applications wherein chromium is a component of heat-, abrasion-, corrosion-and oxidation-resistant and high-strength alloys of many types. Stainless steels are the largest volume category of chrome-bearing alloys. Chromium chemicals are used in leather tanning, in pigments, dyes and mordants, printing, chemical process industries, photography, pharmaceuticals, metal plating, pure chromium metal production, and for many other purposes. Chromite is a necessary constituent in basic refractories indispensable for the production of steel, copper, cement, and glass. Under present conditions, the US and North America, with the possible exception of Cuba, have no commercial ore reserves. There are chromite deposits, as will be described, but they would be used only under highly abnormal conditions if all outside sources were cut off for an extended period. All chromite used in the US is imported from the eastern hemisphere in which are contained the principal world reserves. The main suppliers in 1980 were the Republic of South Africa (43%), the USSR (21% ), the Philippines (12%), Albania (11 %), Turkey (8%), and others (5%). The strategic nature of chromite is obvious. End Uses-Grades and Specifications As noted before, the three principal uses for chromite are metallurgical, refractories, and chemical with a fourth minor use as foundry molding sand. For metallurgical applications chrome ore is first reduced in electric carbon arc furnaces to various types of ferrochromium alloys. There are high, medium, and low carbon ferrochromiums with carbon ranging from 0.01 up to 10%. Chromium itself ranges from 50 to 73 %. Ferrosilicon chromium and ferrochromium-silicon grades have chromium from 33 to 67% and silicon from 3 to about 48%. Since iron is reduced with chromium, the Cr:Fe ratio of the ore will determine the ultimate grade of the ferrochromium whereas carbon and silicon can be controlled during processing. MgO, A12O3, CaO, and excess SiO2, are removed in slag. A small amount of pure chromium metal is prepared by alumino-thermic and electrolytic processes from essentially iron-free chrome components that have been made via the chemical route. The higher grades of ferrochromium with chromium in the 66 to 73% range can only be made from ores with not only high chromium content, but low iron, i.e., high Cr:Fe ratio. These ores, conventionally termed metallurgical grade, have Cr2O3 contents of 45 to 56% with Cr: Fe ratios of 2.5 to 4.3. A standard composition is generally 48% Cr2O3 and 3:1 Cr:Fe ratio. Very high grade ores are often blended with lower grades even with the high iron chemical grade. For some ferrochromiums, additions of high alumina refractory grade are used as slag conditioners to facilitate smelting while still contributing chromium values. A lower grade ferrochromium, the high carbon charge chrome, has become the predominant grade in use today for making chromium-bearing steel alloys. This

Jan 1, 1983

By R. C. Gifkins

R. C. Gifkins (CSIRO)—In this paper evidence is put forward to support the idea of grain boundary shearing in aluminum at 4.2°K and the phenomenon is explained in terms of a low-temperature "equicohesive temperature". It is stated that these findings show that grain boundary shear cannot be ruled out in any situation by temperature arguments alone. We believe, from our own recent study of "apparent grain boundary sliding'' at temperatures below 0.45 Tm, that it can be ruled out on temperature arguments alone.45 Our experiments were made principally with magnesium and a Ms-A1 alloy ("Magnox A12"). Careful examination of offsets of marker lines or steps at grain boundaries produced by deformation at room temperature (-0.3 Tm) showed many of these to result from curvature over narrow zones along the grain boundaries. A significant residuum did, however, appear as a sharp offset or step. It was found that the mean value of this step rose to a small value during the first 0.5 to 1 pct strain and then remained at this level with further strain. Moreover, exactly the same values were obtained (at the same stress) at 75°C instead of 21°C. That is, in this range of temperature the "apparent sliding" was not temperature-sensitive. At 125°C and above there was sliding which increased with strain and which was temperature-dependent. When this temperature-dependent sliding was used to calculate the sliding to be expected at room temperature, this underestimated the "apparent sliding" by a factor of 104. The conclusion drawn is that the "apparent sliding" consists of shear localized in a zone of a width measured perhaps in microns, whereas it seems that true sliding occurs on the boundary surface.46 A model for such localized shear has been developed in general terms, following a similar model of Urie and Wain.47 Other strong evidence for low-temper- ature sliding has been based on the offsets of marker lines consisting of a substructure seen using the electron microscope to resolve these.48 We have repeated this work and found that the effects can be accounted for in terms of cracks in an oxide film which is produced when the substructure is etched up; these cracks form over zones of shear rather than at actual interfaces. However, in aluminum at room temperature (-0.3 Tm) there is no "apparent sliding" which is optically detectable. We suggest that, when the temperature is much lower (and possibly the rate of strain higher, too), as in the experiments of Chin et al., then aluminum behaves like magnesium at room temperature, and a narrow zone of shear develops to accommodate differences in strain across the grain boundary. Such a zone could well give rise to triple-point cracks. It is hoped to investigate these suggestions further. B. Y. Chin, W. F. Hosford, Jr., and W. A. Backofen (authors' reply)—It is interesting to have Dr. Gif-kin's comments, although it is somewhat difficult to reply in detail without the reference containing the work that he describes. Apparently though, he does find a low-temperature temperature-independent sliding that would seem to be related to the observations reported here. Perhaps some of the difficulty has semantic origins, growing out of the distinction between ('true sliding" and "apparent sliding".

Jan 1, 1965

P. W. BRIDGMAN.-Owing to a misunderstanding, I did not see Dr. McAdam's and Dr. MacGregor's remarks on my paper on Flow and Fracture (Metals Technology, December 1944, Pp. 32-38), until after their publication. Both Dr. McAdam and Dr. MacGregor speak of my analysis for the stress distribution at the neck of a tension specimen as containing several assumptions; in particular, that the strain is uniform across the section of the neck, that there is no hoop tension at the periphery, and that the plasticity conditions of von Mises hold. As far as the mathematics goes, the situation is no different in this problem of plastic flow than in a conventional problem of elasticity. That solution is unique which satisfies the boundary conditions on the stresses, the stress equations of equilibrium, and in addition the constitutive equations connecting stress and strain in the elastic case, or a corresponding set of equations, of which the von Mises relations are a special form, in the plastic case. In the particular case of the necked tension specimen I have found that there is a solution satisfying the boundary conditions, the stress equations of equilibrium, and the von Mises plasticity conditions in which the strain is uniform across the section, and there is no hoop tension at the periphery. This is therefore the solution, and the uniformity of strain and vanishing of hoop tension at the periphery are to be described as discoveries, over which the operator has no control, rather than as assumptions. The only part of the solution that can properly be described as an assumption is the von Mises plasticity condition. With regard to this it is to be noted that the condition is needed only in a much weakened form, for the analysis uses the condition only at the neck, where the strain is approximately constant. Thus, in the extreme case referred to in a footnote of my paper (p. 37, Met. Tech. Dec. 1944) the actually measured strain across the section varies from 2.4 to 2.6. Obviously it is a much weaker assumption to postulate that the von Mises condition holds in the strain range 2.4 to 2.6 than to assume it to hold for the entire range of strain from o up to 2.6, which would be necessary if the solution applied to the entire tension specimen rather than to the immediate region of the neck only. Furthermore, it is to be commented that under the special conditions of this problem the von Mises condition becomes identical with the maximum shearing-stress criterion of plastic flow; this amounts also to a weakening of the restrictions imposed by the von Mises condition. Dr. MacGregor refers to actual experiments of his own in which the strain was found not to be uniform across the neck. It is to be emphasized, however, that these were experiments on bars of rectangular section, and that the nonuniformity established was a nonuniformity around the perimeter, not a nonuniformity from the surface toward the axis. My method of solution applies only to a circular cross section. It can be said that the solution that satisfies the boundary conditions, etc., would definitely not be expected to demand a uniform strain for noncircular sections. In discussing my results, Dr. McAdam uses a definition of "flow stress" different from mine, so that the immediate applica-

Jan 1, 1945

By Lars Rossemyr, Terkel Rosenqvist

The equilibrium Mn + 2 IiCl = MnCl2(g) + H2 has been studied at 1090°C for pure manganese and for Mn-Si alloys. For this reoction a standard free energy of Fo1363, = - 19,700 i 300 col ioas found. Combined with other thermal data, the standard free energy of the reaction Mn(s, ß) + Cl2 = MnCl2(g) was derived: Fo=- 56,140 + 9.78 T log T - 40.10 T For the formation of the various manganese silicides the following free energies were obtained. 5 Mn + 3 Si - M1z5Si3 ?F°1363 = -41,500 i 1500 cal Mn + Si - h.lnSi ?F°1363= -10,000 i 500 cnl Mn + 2 Si = MnSiz ?F°1363= -11,500 ± 500 cal In the search for a method suitable for the study of thermodynamic properties of certain alloy systems, it was found that the heterogeneous equilibrium between the alloy and a gas mixture consisting of hydrogen chloride, hydrogen, and volatile metal chlorides has considerable advantages. In addition to giving thermodynamic information about the alloys, such measurements may be used to derive thermodynamic data for the volatile metal chloride itself. The present paper gives some results which were obtained for manganese silicides and manganous chloride. Similar studies are presently being carried out for the iron silicides. The phase diagram of the Mn-Si system is rather well known,' but no information exists to the authors' knowledge about the thermodynamic properties of manganese silicides or about the chemical activities in molten Mn-Si alloys. At elevated temperature, manganese may react with hydrogen chloride according to the equation: Mn(s, ß ) + 2 HC1 = MnC1, (g ) + H2 [ 1] with the equilibrium constant The value of K, may be determined from measurements of the gas composition in equilibrium with pure manganese. When this value is used in connection with measurements on manganese alloys, the chemical activity of manganese in the alloy may be derived. Initial calculations showed that around 1000" to 1200°C the equilibrium constant K1 has a value of a few thousand, i.e., the reaction is shifted far to the right. In order to study this rather unbalanced gas composition, a flow method was used in two slightly different modifications. For all experiments with manganese silicides and for some experiments with pure manganese the apparatus shown on Fig. 1 was used. A bed of the metal or alloy was placed in a tube furnace. The refractory tube had an internal diameter of 14 mm and the bed was 75 mm long. Electrolytic manganese of high purity and silicon, 99.95 pct Si, were used as raw materials. All alloys were prepared by melting weighed amounts of the elements in a high frequency induction furnace in argon atmosphere. The melting was done in a silica crucible which was placed inside a graphite shell. The alloys were crushed to - 10 +40 mesh and analyzed chemically. Also, for the pure elements, the same size fraction was used. A controlled gas mixture of purified hydrogen and from 3 to 12 pct HC1 was passed through the bed where it reacted with manganese according to Eq. [I]. The volatile manganese chloride was collected in a condenser placed in the cooler part of the furnace tube. The gas mixture before and after the furnace was sampled and analyzed by absorption of

Jan 1, 1962

By Raymond B. Ladoo

Wollastonite is a calcium metasilicate, with the formula CaSiO3; containing theoretically 48.3 pct CaO and 51.7 pct Si02. It is one of many natural and synthetic silicates with varying CaO/SiO2 ratios, with and without water of crystallization. While it is a very common mineral, deposits of sufficient size and purity to be of commercial interest are unusual. There is only one producer (1958) of wollastonite for industrial use in the United States, Godfrey L. Cabot, Inc. at Willsboro, New York. There has been a small production of surface material for ornamental use from near Blythe, California. Carload tests have been made on California wollastonite for making mineral wool and a commercial plant for this purpose was projected in 1957. Properties Wollastonite is monoclinic and commonly occurs in masses or aggregates of bladed or needle-like crystals. It has a perfect cleavage parallel to the long prismatic axis. It is rather brittle and some types grind easily to a very finely fibrous product, but other types, due to interlacing of fibers, are tough and difficult to grind. Mobs hardness is 4.5 to 5; specific gravity 2.8-2.9; index of refraction 1.616 to 1.631; melting point 1,512°C. Color when pure is a brilliant white, but when less pure it may be gray or brown. Luster is vitreous, transparent to translucent. Common mineral associates are garnet (several varieties), diopside, calcite and quartz. The nature of the mineral impurities determines to a large degree the commercial value of a deposit. At Willsboro, New York, the impurities consist chiefly of iron garnet and iron diopside which are both magnetic and so are easily removable by magnetic separation, yielding a nearly theoretically pure product. Some deposits in California contain calcite and quartz which cannot be removed cheaply, thus limiting market possibilities. Occurrence Wollastonite is a contact metamorphic mineral occurring in most places within or associated with impure limestones. The deposits at Willsboro, New York1,2,3,5 consist of two or more beds dipping 15-50°E and striking NW-SE. The main bed, 30 to 70 ft thick, may be traced on the surface for at least 2 ½ miles. In this belt, the Pre-Cambrian Grenville limestone has been injected and partially replaced by the more liquid portions of an anorthositic magma. Buddington and Whitcomb3 have described the rock as "Mixed gneisses, pyroxenite and garnetiferous gneisses and skarns." Prospecting revealed the wollastonite at ten different places in the belt, overlain in most places by a garnet rock. Diamond drilling has proven several million tons with probable reserves around 15 million tons. Interbedded with the wollastonite are beds of garnet from a few inches to several feet in thickness. In the wollastonite ore itself the chief and almost only associated minerals are garnet (mostly almandite but some andradite and grossularite) with small amounts of green hedenbergite. Inasmuch as the almandite and diopside are magnetic they are easily separated from the wollastonite in high intensity magnetic separators. If grossularite should occur in quantity other means of separation would be needed. Wollastonite has been reported at 35 localities in California12 but only those in the Big Maria and Little Maria Mountains, 16 to 20 miles north of Blythe, Riverside County, are

Jan 1, 1960

By F. G. Stone

A strain anneal process has been developed for the production of iron tensile test specimens, the gauge length consisting substantially of a single crystal. Since the method has been quite successful and the results of general interest, the process will be described in detail. The essential feature of the method is the continuous, slow increase of furnace temperature during the grain growth annealing treatment. Briefly, the procedure is as follows: I. Heat machined bars to 950°C in vacuum, hold I hr, furnace cool. 2. Strain to 3.5-3.8 pct elongation (axial loading). 3. Anneal, continuously raising furnace temperature from 450 to goo°C at a rate of so0 per day. 4. Hold at 900°C for 100 hr, furnace cool. Tensile test bars with a 1/4- X I-in. gauge section have been machined from 35 in. Armco iron plate and from 3/8 in. rounds of Puron, a high purity laboratory iron. The axes of the test bars were parallel to the rolling direction. During the machining operation the bars were polished in the lathe with No. 600 emery paper, and this polished surface proved satisfactory for subsequent macrographic examination. A micrographic examination of the materials showed that both were high in FeO inclusions, those of the Puron being smaller but much more numerous. An initial vacuum anneal of I hr at 950°C followed by furnace cooling resulted in a ferritic grain size of ASTM No. 3 for Armco and No. I for Puron. Special heat treatments which reversed these initial grain sizes produced no marked improvement in single crystal production after subsequent treatments. The strain for subsequent grain growth was determined by measuring the decrease in diameter of the tensile bar during elongation. The change in diameter could be measured with a micrometer to +0.0001 in., corresponding to an accuracy of 0.08 pct for the elongation. The accuracy of the diameter measurement is also dependent on grain size because of surface roughening during elongation, and for this reason, a No. 3 grain size is preferable. Optimum grain growth was obtained for strains between 3.5 and 3.8 pct elongation. Once this critical range had been cstablished, all tests were held within it, and thus only meager data were obtained on grain growth following strains outside this range. In general, grain size decreased with increasing strain to about 5.5 pct elongation. Grain growth was occasionally ohserved with less than 3.5 pct elongation although this may have been the result of error in measurement. The program control device for the grain growth anneal consisted of a I rpm motor and worm gear drive, operating the dial shaft of a pyrometer controller through a pulley. Dial speeds of 33 and 50°C per day were tried, but the results at the slower speed were not sufficiently better to warrant the increased furnace time. The furnace tube was evacuated at intervals during the run and kept sealed the remainder of the time. When the controller reached 900°C, it was stopped and the temperature held for 100 hr. This eliminated most of the numerous minute crystallites of about 0.5 mm dimension usually visible on the etched surface of the single crystal. Since recrystallization occurs at the A3 point, the top temperature of 900°C provided a 10"

Jan 1, 1949

By N. V. Peterson, R. S. Mason

The violent explosion of Mount St. Helens in the state of Washington on May 18, 1980 showered volcanic ash over vast areas of the Northwest. It was another eruptive episode in a long history of similar occurrences in the region, which extends from Canada to California and reaches several hundred miles inland from the Pacific Ocean. Pumice, pumicite, and cinders are products of explosive volcanic eruptions. Pumice and pumicite are produced by the violent expansion of dissolved gases in a viscous silicic lava such as rhyolite or dacite. Scoria is the mafic counterpart of pumice. Pumice is a light-colored, cellular, almost frothy rock made up of glass-walled bubble casts. It may occur as coherent, massive blocks composed of highly vesicular glassy lava in either a flow or vent filling, or it may be more or less fragmented by violent eruption. Pumicite, the diminutive of pumice, has the same origin, chemical composition, and glassy structure, differing only in particle size. Particles less than 0.16 in. in diam are designated pumicite. Pumice usually is found relatively close to the vent from which it was expelled, while pumicite may be carried by winds for great distances before settling as an accumulation of fine-grained ash or tuffaceous sediment. Mount St. Helens lofted an estimated 5 billion cu yd of ash and pumicite. The volcano, unlike most of the High Cascade peaks, is composed largely of dacitic material with only minor amounts of andesite and basalt. Volcanic cinders are the reddish to black vesicular fragments which pile up during explosive eruptions of volcanoes of basaltic composition. Most cinder deposits occur as cones or mounds of stratified fragments ranging from a fraction of an inch to several inches in diameter. Individual cones or mounds may be several hundred feet in diameter and up to 500 ft high. Properties and Uses Low bulk density, good heat and sound insulating properties, and excellent abrasive capabilities make pumice and pumicite useful in industrial applications. Cinders, though less cellular and somewhat heavier, also have a variety of industrial uses. The main use of pumice and cinders continues to be in the construction industry as road-surfacing material, railroad ballast, and building block aggregate. Pumicite is used in sizable quantities as a pozzolanic additive to monolithic concrete where it increases workability, strength, and durability of the concrete and reduces the heat of hydration. Volcanic cinders generally are denser and more coarsely cellular than most pumice. Markets for cinders include aggregate for road construction and surfacing and use in lightweight concretes, particularly blocks. Some producers having access to both pumice and cinders offer a variety of blends of the two materials to block manufacturers. Table I lists the principal applications of industrial pumice. Tables 2 and 3 show US sales and uses of volcanic products. Most pumice deposits are unconsolidated and usually have a minimum of overburden. Mining is by open pit and can be easily carried out with conventional loading equipment. Sometimes air drying precedes hauling to a crushing and screening plant which yields the size product desired. Multiple bins at railroad hauling facilities permit blending if desired. Pumice for abrasive use may require more sophisticated processing by fine grinding and air classification before being bagged for market.

Jan 1, 1983

By O. N. Carlson, D. G. Alexander

THE hardness anisotropy of metals and alloys has been of increasing interest in recent years but silicon ferrite,1 niobium,2 and tungsten3,4 are the only bcc metals about which this type of information has been reported. This investigation was carried out on vanadium and chromium single crystals in an effort to determine to what degree the hardness variations observed in these metals are due to orientation effects and to compare their behavior with other bcc metals. In earlier work the authors had observed a small angular dependence in the Diamond Pyramid Hardness of single crystalline vanadium on the (100) plane but no anisotropic effects were noted on either the (110) or (111) planes. At the suggestion of R. G. wheeler5 it was decided to investigate this effect in greater detail using the more asymmetric Knoop indentor. The vanadium metal used in the study was prepared by the aluminothermic reduction of V2O5 followed by electron beam melting.6 The principal analyzed impurities were 230 ppm C, 230 ppm O, 65 ppm N, 90 pprn Al, Cr not detected, 50 ppm Fe, 60 ppm Ni, and 200 ppm Si. The chromium was an iodide-refined product obtained from the Chromalloy Corporation. Analysis of this material showed the following amounts of impurities present: 10 ppm C, 9 ppm O, 2 ppm N, 0.4 ppm H, 3 ppm Al, 2 ppm Ca, 2 ppm Cu, 20 ppm Fe, 1 ppm Mg, 0.3 ppm Mn, 1 ppm Mo, 3 ppm Ni, 10 ppm Si, and 1 ppm V. Single crystals of both metals about 1 cm in diam and 10 cm in length were grown by an arc-zone melt- ing technique.7 The chromium crystal was annealed at 1600°C for 6 hr in a purified argon atmosphere to remove any strains or inhomogeneities, but the vanadium was tested in the as-grown condition. The crystals were oriented by the Laue back-reflection method and then sectioned with a spark cutter into individual specimens with a (loo), (110), or (111) plane parallel to the crystal surface. They were mounted in Lucite and carefully ground to a flat surface. The vanadium specimens were then electropolished in a 6 pct perchloric acid-methanol mixture while the chromium specimens were mechanically polished on a Syntron vibratory polisher using an alumina abrasive. The orientation of each crystal was then rechecked by the back-reflection X-ray method. All of them were found to lie within 2 deg of the desired orientation with the exception of the (110)-Oriented chromium crystal which was within 4 deg. Microhardness impressions were taken at 10 deg intervals from the common (110) direction by rotating the crystal in the plane of the crystal surface. A Knoop indentor was used with a 400-g load on the vanadium crystals and an 800-g load on the chromium. The hardness values are averages of 6 impressions and standard deviations were calculated for each set of data. The values reported for the (111) plane of vanadium are based on from 10 to 15 measurements for each point. The microhardness results for vanadium and chromium are plotted as a function of the angular rotation of the long axis of a Knoop indentor from the (110)

Jan 1, 1970

By J. L. Martin, W. M. Campbell

A new electric logging method, called displacement logging, often gives a direct indication of the presence of mobile hydrocarbons in hydrocarbon-bearing formations. This method is based on the detection of a bank of connate water which is formed between the invading mud filtrate and virgin formation fluids in these cases. The existence of this phenomenon has beer, verified by laboratory studies and by actual field logs taken in known oil sands. INTRODUCTION During the past decade increasing use has been made of conventional electric logs to determine the amount of oil or gas in formations traversed by a borehole. This determination requires knowledge of several factors, such as true resistivity of the formation, formation factor, and water resistivity. Sometimes all of the factors necessary to make a reliable saturation calculation are not available. Also, the computations and corrections which are necessary in such a study often require the services of an experienced log analyst. It has long been the desire of exploration people to have a logging device which will locate hydrocarbon-bearing formations directly without requiring complex interpretation methods. The displacement log, while not completely fulfilling this desire, appears to be a Step in that direction. Basis for the Device The basis for this device stems from a phenomenon which occurs when mud filtrate invades a formation which contains displaceable hydrocarbons. As the mud filtrate invades the formation, most of the oil or gas is pushed out of the invaded zone, leaving residual oil. However, in addition to displacing most of the oil or gas, the connate water is also swept out, since the originally irreducible water is mobile in the presence of a water phase.1,2,3 Tonsequently, this irreducible water piles up as a bank between the virgin oil zone and the invading filtrate. If the mud filtrate is of higher resistivity than the formation water— as is commonly the case—the resulting annular zone, containing the bank of formation water, will be of lower resistivity than either the virgin oil-bearing formation resistivity or the invaded zone resistivity. This resistivity configuration, going from high to low to high again as the distance from the borehole increases, is found only in those zones which contain displaceable hydrocarbons. A device which would reliably detect this low resistivity zone would give a direct indication of mobile hydrocarbons. Illustrations This phenomenon is illustrated in Fig. 1 and 2. Fig. 1 shows a sketch of a zone containing salty connate water plus displaceable hydrocarbons, along with graphs showing fluid content and electrical resistivity vs distance from the borehole, before invasion occurs. Fig. 2 shows this zone, together with fluid content and resistivity graphs. after invasion by a fresh water mud. The resistivity pattern on moving away from the borehole is high: low: high. The absence of the low zone phenomenon in water zones is illustrated in Fig. 3 and 4. Fig. 3 shows a sketch of a zone containing salty formation water and residual oil, along with graphs showing fluid content and electrical resistivity vs distance from the borehole, before invasion occurs. Fig. 4 shows this water zone, together with fluid content and resistivity graphs, after invasion bv a fresh water mud. In this case the resistivity pattern on moving away from the borehole is high: low since there is no change in water saturation at the head ol

Jan 1, 1956

By Renato G. Bautista, Theodore D. Tiemann

A kinetic study of the hydrogen reduction of taconite from the Wisconsin Gogebic range was made over the temperature range from 500° to 1000°C on eleven size fractions from 4 to 150 mesh. Two stages of reduction were observed, a rapid initial reaction followed by a slower reaction presumably taking place at an internal receding FexO-Fe interface. Calculated mean activation energies for the two reactions were 7800 and 14,600 cal per mole respectively. In recent years there has been an increased interest in the direct reduction of iron oxide ores to metallic iron by means of gaseous reducing agents such as hydrogen and carbon monoxide.1,2 These investigations have been motivated by the desire to develop a process that will by-pass the blast furnace in the production of steel. The majority of these processes have been developed to produce metallic iron by direct reduction from high-grade iron oxide ores.3"5 Very little work has been done on the low-grade siliceous iron oxide ores.6"8 The work reported here is directed principally towards the fundamental aspect of the reduction reactions of siliceous iron oxide ores, since the practical aspects of the gaseous reductant process were discussed previously. The ore used in the investigation was obtained originally from the United States Bureau of Mines10 trench sample of the Yale member of the Wisconsin Gogebic range iron formation. The Yale taconite has an average analysis of 28.2 pct Fe and approximately 50 pct SiO2. Chemically, these nonmagnetic taconites contain on the average about 53 pct silica and 30 pct Fe. An average analysis calculated fron the USBM10 figures for a composite of the five members (Norrie, Plymouth, Pence, Pabst, and ale) of the iron formation is given in Table I. Mineralogically, based on previous X-ray diffraction and other studies, the principal minerals are hematite (Fe2O3), geothite (Fe2O3.H2O), and quartz (SiO2). Minor amounts of iron containing silicates, siderite (FeCO3) and magnetite (FeO. Fe2O3) are present.10,11 The iron minerals and the quartz are finely disseminated requiring extremely fine grinding for liberation. For the experimental work, the ore sample was screened into a number of size fractions, the analyses and densities of which are given in Table II. EXPERIMENTAL PROCEDURE The reduction experiments were carried out in a 24 in. by 2 in. ID nichrome-wound vertical-tube furnace mounted on a stand. A 1 1/2 in. OD zirconium-oxide combustion tube was used inside the furnace to contain the atmosphere. To the top of this combustion tube was joined a pyrex ground-glass joint to which was attached a glass bulb with a small (1.0 mm) opening at the center, and with two outlets controlled with a stopcock on each side. A pyrex-glass joint with connections to three stopcock joints for introducing hydrogen, nitrogen, and mixtures of hydrogen and nitrogen gas was joined to the tapered bottom of the combustion tube. The sized ore fractions were contained in a 1 in. diameter by 1 1/2 in. 150-mesh nickel screen basket. The basket was suspended in the furnace from a balance by means of a supporting nickel wire which hung freely inside the combustion tube. The furnace temperature was controlled by a Leeds and Northrup Speedomax Type G controller, connected to a chromel-alumel thermocouple placed

Jan 1, 1962

By Walter J. Karplus

By means of a finite difference expansion a fluid flow field in cylindrical coordinates with axial symmetry, is simulated by a network of electrical resistors. A series of DC analog computing units, connected to the network bounrlary corresponding to the free surface effectively adjust the network parameterr to satisfy simultaneously Laplace's equation and the borrndary conditions. The system automatica1ly "re1axes" to the correct boundary shape in a fraction of a second. A detailed application of the method to the water coning problem in oil wells is presented. INTRODUCTION The water coning problem in petroleum production is a prime example of a class of problems known as free surface problems. A free surface arises in fluid flow regions when the shape of the boundary of a single phase flow region is affected in some manner by the pressure or potential gradients within the region. When there exists an interface of two fluids of different densities, the shape of this interface will be determined by the relative velocities of the two fluids and will therefore comprise a free surface. Other free surface problems of interest to petroleum engineers include the gas coning, water injection, and gravity drainage probIcms. In each case it is desired to predict the shape of the boundary of the oil zone as a function of the flow rate, the well penetration and the physical parameters and dimensions of the system. Such problems do not lend themselves to the classical analytical treatments of boundary value problems because in this case the boundary of the potential field and the potential distribution within the field are interdependent and must be calculated simultaneously. A further difficulty arises from geometric considerations. Since the fluid flow is of the radial type in most cases, such effective methods as conformal transformation and the hodograph are not applicable. It is the purpose of this paper to present a method whereby free surface problems of this type may be solved rapidly to the desired order of accuracy by means of a combination of a network of electrical resistors and conventional analog computer units. The water coning problem is treated in some detail. Then the procedure for extending the technique to other free surface problems is indicated. FORMULATION Most commercial oil reservoirs consist of an oil-saturated sand, bounded above by an impermeable strata and below by a water-saturated sand. Gravimetric separation results in a horizontal oil-water interface. When an oil well is drilled so that it partially penetrates the oil zone, and production is initiated at a constant rate, the oil-water interface will assume a new shape as a result of the pressure gradients in the oil zone. It should be emphasized that this is a steady phenomenon. After an initial transient period the water phase will be completely static and only the oil will be in motion. The new steady-state shape of the interface, as shown in Fig. 1, depends upon the depth of penetration, d, the thickness of the oil zone, I, the production rate, q, the hydraulic permeability zone of the sand, k, the viscosity of the oil, µ, and the densities of the oil and water, p.,. and pw.. The problem is to determine this relationship. Darcy's law + = - (P f g p z).....(1) it.

Jan 1, 1957

By H. R. Ogden, E. S. Bartlett, A. G. Imgram

Notched and unnotched tensile specimens of wrought and recrystallized, oxygmted and hydro-genated tantalum and columbium were tested over a range of temperatures selected to encompass the ductile-to-brittle transition. Increasing the oxygen content of tantalum and columbium increased their strength, and raised their ductility transition temperature, but did not cause a marked deterioration of notch properties below that of commercially pure material. The adverse effects of oxygen were more pronounced for recrystallized structures than for wrought material. The effects of hydrogen are complicated by strain aging or slow strain rate hydrogen embrittlement at -105°F. However, in general, hydrogen had only a minor effect an strength, but markedly increased the effective transition tem-terature and caused a deterioration of notch properties . BCC metals including the refractory metals in Groups Va and VIa (V, Cb, Ta and Cr, Mo, W) can be expected to undergo a ductile-to-brittle transition and exhibit brittle fractures at low temperatures.' Notch embrittlement is associated with this phenomenon, and can be a serious design problem. Table I compares the tensile transition behavior and notch sensitivity of commercially pure Group Va and VIa refractory metals. The Group VIa refractory metals have considerably higher transition temperatures, and become notch sensitive at higher temperatures, than do the Group Va refractory metals. In addition, the Group VIa refractory metals are sensitive to metallurgical structure. Recrystallized structures generally have higher transition temperatures than wrought material of the same composition. The relatively poor transition behavior of the recrystallized structures of these metals is generally attributed to the segregation of interstitial impurity atoms at grain boundaries. Pronounced sensitivity to structure is not evident with commercially pure Group Va refractory metals, however. Since these metals have higher solubilities for interstitial elements than do the Group VIa metals ,4 it can be expected that higher total interstitial concentrations are necessary to develop a comparable degree of grain boundary segregation and to produce a similar sensitivity of transition temperature to structure. Increasing only the concentration of interstitial atoms in solution would tend to increase the flow stress of a metal in relation to its cleavage fracture stress and thereby raise its transition temperature, but would not be expected to cause a marked sensitivity of transition temperature to structure. A research program has been conducted at the Battelle Memorial Institute to evaluate the effects of interstitial oxygen and hydrogen on the transition behavior and notch sensitivity of tantalum and columbium, and to evaluate the effects of structure on "contaminated" material. EXPERIMENTAL PROCEDURES Notched and unnotched tensile specimens of oxygenated and hydrogenated tantalum and columbium with both wrought and recrystallized structures were tested over a range of temperatures selected to encompass the ductile-to-brittle transition Oxygen levels selected for study in both tantalum and columbium were nominally 500 and 1000 ppm, whereas nominal hydrogen contents were 150 and 500 ppm in tantalum and 150 and 300 ppm in columbium. Oxygen and hydrogen additions were made directly to 6-in. lengths of 1/2-in.-diam electron beam melted wrought bar stock, in a Sieverts Apparatus. Subsequent high-temperature annealing was required for homogenization of the oxygenated material, but was not necessary in the case of hydrogenated stock. The oxygenated and hydrogenated bars were then swaged to 1/4-in.-diam rods. Tensile specimen blanks were cut from the 1/4-in.-diam rods and annealed to achieve stress-re-

Jan 1, 1963

By H. J. Beach

This paper describes the properties and uses of cementitious mixtures containing 10 to 20 per cent bentonite and 2 per cent or more sodium chloride. Salt additions improve bentonite cement by increasing early strength and stabilizing viscosity without changing thickening time. The volume yield of cement is increased 20 per cent or more without lowered early strength. The unique properties of salt in this type of system make savings of more than 10 per cent possible where light-weight, low-strength cementitious material is adequate to fill behind pipe. The density range of these mixtures is 12 to 13 1b/gal and the filtration rates are medium-low, aiding the placement of long columns in primary cementing. Where available, sea water is an ideal salt source in preparing these slurries. INTRODUCTION Accelerators increase the rate of cement hydration. In speeding reaction with water, they can affect cement performance by reducing thickening time and increasing early strength after set. Accelerators that cause both effects can be considered "total", and those which produce only one effect can be called "partial". Materials that act conversely to accelerators are retarders. and they also can be total or partial. Partial retarders. make high-temperature cementing possible by prolonging thickening time while impairing early strength only slightly. Most known accelerators are total. A useful partial accelerator would increase strength without altering thickening time. This report concerns material combinations in which a normally total accelerator exerts unique partial properties. Utilizing these limited effects improves bentonite cement. SEPARATE EFFECTS OF SODIUM CHLORIDE AND BENTONITE ON CEMENT Sodium chloride and calcium chloride are commonly used in cement, and at low concentrations their effects are similar. Ludwig1 studied sodium chloride in API Class A and Class E cements.' Figs. 1 and 2 sum- marize his data taken at 140°F on slurry pumpability and early strength. Normal water-to-cement ratios are 0.46 and 0.40, respectively, for Class A and Class E cements. At saturation the salt content is 12 to 14 per cent of the weight of cement solids. The illustrations, therefore, cover the range of salt solubility in the mixing water. The data show that sodium chloride is a total accelerator of the Class E cement studied over the range of solubility. It is total in Class A cement to 6 per cent. Above this concentration salt becomes a retarder— partial from 6 to 10 per cent and total above. These results are general for different brands of Class A cement, although the shift from acceleration to retardation may occur at different salt concentrations for different temperatures. The results are specific for the Class E brand studied. In discussing his data, the investigator emphasized that different Class E cements might respond erratically to salt, depending on the brand chosen. Morgan and Dumbauld3 escribe the properties of bentonite cement in a paper that is a standard reference in using these systems. Bentonite functions in cement as an enabling agent; each bentonite addition equal to 1 per cent of the weight of dry cement makes possible the further addition of 4.5 per cent water.' Thus, 10 per cent bentonite in Class A cement, normally slurried neat with 46 per cent water, enables the slurry to contain another 45 per cent before settling. Water is one of the lightest and cheapest cement extenders; it reduces density and cost. Bentonite cements produce uniform slurries having low susceptibility to solids separation. After set, they offer low resistance to perforation.

By T. R. Ingraham

When aluminum sulfate was decomposed in an evacuated apparatus and the sample cooled, Q alumina was found. The thermodynamics of the decomposition reaction were resolved by measurements of the total pressure of SO3, SO2, and O2 generated over the sample at various temperatures. The results were correlated with other published data to calculate the rmges of thermodynamic stability of the various compounds involved. The thermal decomposition of aluminum sulfate was studied by Wijhler, Pluddeman, and Wöhler1 and by Warner and Ingraham.2 The results of both studies were critically reviewed by Kellogg,3 who observed that "each set of data shows considerable scatter and strong curvature on a plot of log pso3 vs 1/T".3 He agreed with Warner and Ingraham2 that both the discrepancy in the two sets of results and their curvature may arise from the indefinite properties of the particular form of A12O3 which is formed during the decomposition. While studying the thermal stability of other sulfate systems, we had noted the presence of nonequilibrium oxide properties in both the cobalt4 and manganese5 systems, but neither had shown any appreciable curvature on a logPSO, vs 1/T relationship, and the data from both systems agreed reasonably well with prior work. It therefore seemed reasonable to reexamine the technique which had been used in our earlier work on aluminum sulfate.2 The principal difference was that a tightly compacted pellet had been used for the earlier aluminum sulfate work, whereas a loose powder, contained in a platinum boat, was used for our work on other sulfate systems. In addition, a better technique had been developed for dehydrating the samples. From work done on the nickel system,6 we had become aware of the highly protective nature of some sulfate layers on their oxjdes, and hence of the necessity of providing a large surface area of P3e sample when equilibrium was to be attained in a reasonable time. That observation suggested that perhaps a steady state, rather than equilibrium, had been reached in the earlier work on aluminum sulfate. This paper reports a repetition of the experimental work with large, finely divided samples of anhydrous aluminum sulfate. APPARATUS AND PROCEDURE The apparatus used in the experimental work was described in earlier papers.2,7 The source material was Anachemia reagent-grade Al2(sO4)3 - 18H2O which was first partly dehydrated by heating at 400°C for 48 hr and then completely dehydrated by repeated baking of an aluminum sulfate-oleum slush to dryness at 450°C. ? Alas was prepared by decomposing some of the sulfate in a muffle furnace at 800° C overnight. Approximately equal amounts of the 7) alumina and aluminum sulfate were used in the experiments. The finely divided samples were handled under dry box conditions, and in addition some of the aluminum sulfate was decomposed in the apparatus while it was under vacuum, to ensure its complete dehydration prior to sealing the apparatus. The samples were heated to a series of constant temperatures on both increasing- and decreasing-tem-perature programs. Two to three days were required to obtain steady readings of the total decomposition pressure on an increasing-temperature program, and 5 to 6 days on a decreasing-temperature program. Three samples were examined on both programs. Within experimental error, the results for each sample and each program could not be distinguished.

Jan 1, 1969

By G. H. Tausch, T. A. Huber

Very encouraging progress has been made ill the develop-ment of the permanent-type well completion which decreases considerable the cost of completions and workovers and aid-in the acquisition of reliable reservoir information at low cost. Completion and remedial operations are performed with tool,; which pass through the well tubing. Perforating and plug-hack operations can be done with the tubing in place and do not require pipe-handling equipment. Because of the many advantages afforded by this method, development work is going forward in anticipation of ultimately being able 10 use it to perform all usual well completion and workover operations. Effort is also being directed to the development of a more permanent type of lift equipment suitable for use with the permanent-type well completion. INTRODUCTION The permanent-type well completion in one in which the tubing and well-head are set in place only once in the life of the well and the completion or remedial work is performed through the tubing with a tubing-type perforator. a retrievable tubing extension. and other wire-line tools. This new type completion has made possible the saving of one to two days' rig time in the completion of each of several hundred wells During the last two years, and use of equipment developed for this type of completion has resulted in a 75 per cent reduction in cost. of certain types of workovers. In addition. the more reliable indication of the commercial value of a reservoir and the more accurate general reservoir information made Possible promise to be of even greater value in oil recovery than the reduction of costs for completions and workovers Recently. several well.. were worked over by using the retrievable tubing extension suspended on a swab line to plug back with cement and then perforating a higher producing interval with the tubing-type perforator, thus opening the way for complete through-the-tubing workovers which may be performed without pipe-handling equipment or mud. Those items attendant to the use of pipe-handling equipment and mud. such as hoard matting rig substructure. and pits. were also eliminated. There are indications that the elimination of drilling mud during completion and workover operations will frequently give increased well productivity, as plugging of the perforation. will not occur. It ii now possible to perforate selectively small sections of the producing interval and to test a well through these sections prior to perforating more interval. The perforating of additional interval will not entail the costly operations of killing the well and pulling tubing, nor will the old or the new perforations be plugged. The productivity of .mall sections of a reservoir and the actual gas-oil or oil-water contacts may now be determined economically under flowing condition.. Selective completions can be made in this manner to delay gas and water problems and bring about maximum oil recovery. At the present time, gas lift appears to offer the greatest potentialities for artificial lift in the permanent-type well com"letion since it can provide full-open tubing to accommodate the through-the-tubing tools and it may be ultimately developed into a fairly permanent type of lift. With precent-day pas-lift equipment. valve or mandrel failure necessitates occacio11al removal of the tubing. thereby reducing to some extent the permanence of the completion. New gas-lift valves are now

Jan 1, 1953

By M. T. Simnad, C. E. Birchenall, M. H. Davis

The transport mechanisms previously proposed in wustite and hematite have been confirmed by movement of inert markers during the growth of these phases. By similar measurements the mechanism for magnetite has been determined. The rates of growth of multilayer scales on iron, magnetite and hematite on wustite, and hematite on magnetite have been measured. All rates are found to be diffusion controlled under the conditions of the experiments. MANY studies have been made of the rate of oxidation of iron in both the low temperature, film-forming region and the high temperature scaling range. The interpretation of the results has been greatly complicated by the formation of multi-layered scales containing the various phases of iron oxides. In most cases no attempt has been made to determine the composition of the scale and its dependence on time of oxidation in a quantitative manner. However, several recent studies'" have taken this variable into account. It is generally agreed that the growth of thick scales on iron follows a parabolic rate law for the increase of total thickness. In the thin film region agreement has been claimed with parabolic equations of various forms and with logarithmic equations. The discussion here will be concerned only with the formation of scales of considerable thickness, greater than several microns, although some of the conclusions may be applicable to thin films. A brief survey will be given of the solid phases of the iron-oxygen system, the stability of wiistite in bulk and in thin films, the relative densities of iron in the metal and oxides, and the kinetics of forma- tion of oxide scales on iron. New experimental results will be introduced at several points during the discussion, and an attempt will be made to formulate a mechanistic picture consistent with these observations. The experimental techniques are described in an appendix. Iron-Oxygen System Fig. la shows the iron-oxygen phase diagram. Wüstite ("FeO"): The lowest of the oxides has a NaCl type cubic lattice formed by close-packing of the relatively large oxide ions with the smaller iron ions arranged in the interstices. The ionic radius for 0' is about 1.3 A, while Fe++ has a radius of about 0.8A and Fe"' about 0.7A. Its range of existence on the phase diagram is very wide for an ionic material of this type and does not seem to include the stoi-chiometric composition FeO. These deviations appear to be well established as vacancies on iron lattice sites by the comparison of lattice parameters and densities for a series of compositions by Jette and Foote.4 The limits of the field are disputed, but the work which seems most reliable" indicates vacancies in from 5 pct to more than 12 pct of the iron sites. In order for the crystal to be electrically neutral, there must be electron holes which correspond to the formation of trivalent iron ions equal to twice the number of vacancies. Magnetite ("Fe³O4"): Considerable disagreement also exists in the literature about the stable range of the Fe³O4 field. Some diagrams show the Fe³O4 composition to be lower in oxygen than the formula indicates, but Schenck6 gives a diagram from the

Jan 1, 1952