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By Gerald C. Mathis

FERGUS County, Mont., shown in Fig. 1, is known for its once famous gold mines near the old towns of Gilt Edge, Maiden, and Kendall. But at Heath, a small farming community near the foothills of the Snowy Mountains, thousands of tons of gypsum have been mined since 1916. The value of the gold taken from the mines of Fergus County runs into millions of dollars; the value of the products made from the gypsum of the Heath mine is also in the millions. The gypsum mine will continue to produce for many years, while the gold mines are closed today. The Heath gypsum mine was developed by the Northwest Gypsum Co. in 1916. The products of the small mill built by this company were plaster, agricultural gypsum, and raw gypsum for cement manufacturing. The United States Gypsum Co. prospected the adjacent property in 1916 and 1917 by means of two adits and some exploration drill holes. During World War I, the company abandoned operations at Heath, but again became active in this area in 1928 hen it purchased all the property of the Northwest Gypsum Co. A long range program of expansion was begun with the building of a block plant and the purchase of additional land and mineral rights. A modern wall board plant was built in 1936. When the old wooden mill purchased from the Northwest Gypsum Co. burned in 1937, an all-metal calcining plant located at Blue Rapids, Kansas, was dismantled, moved to Heath, and erected on the site of the mill. In August 1951 a new mine was opened 3000 ft north of the mill. Rock is conveyed from the mine to the mill by an 18-in. belt conveyor. The Heath gypsum deposit lies at the base of the Ellis formation of Jurassic Age. The Ellis at Heath lies unconformably on the black fissle shale of the Heath formation of the Big Snowy Group, which is Mississippian in age. The strike of the gypsum bed is N45°E and the dip approximately 3" NW; the regional strike and dip of the area. The gypsum lies in a series of six layers separated from each other by thin seams of shale. The lower layer is composed of' gypsum and shale intermingled and is not of commercial grade. The upper five layers are high in purity, but only the middle four layers are mined on the advance, as the top layer is left for roof support. This top layer is mined on retreating operations at the same time the pillars are robbed. Total thickness of the gypsum layers varies from 12 to 14 ft. Fig. 2 shows the average thickness and arrangement of the layers. Mining Methods The mine was originally developed by driving an adit into the gypsum horizon. The Northwest Gypsum Co. mined in the top four layers, the top layer being split, leaving about 12 in. for roof support. A modified room and pillar method was used: entries were 15 ft wide and rooms varied between 20 and 30 ft and were turned on 90" from the entries. Crosscuts between the rooms left pillars from 10 to 20 ft square. The rock was loaded by hand into 1-ton mine cars and pulled to a central gathering point by mules; from the gathering point, mules or horses were used to pull the string of cars to the mill tipple. This method was continued by the United States Gypsum Co. from 1928 to 1937.

Jan 1, 1954

By A. S. Appleton, M. B. Bever

The stored and expended energies of an Au-Ag alloy deformed in torsion were investigated as functions of strain, strain rate, and temperature. At room temperature, the stored energy, measured by tin solution calorimetry, increased linearly up to an intermediate strain, above which it was nearly constant; at 78 °K the relation was linear up to fracture. Approximate values of the energy stored at 4 OK indicate a rapid increase below 78 OK. The energy stored by specimens deformed successively at 4o and 78oK changed slowly with increasing second strain from the curve for energy stored at 4 OK (measured after annealing at 78oK) to that for deformation at 78°K. The ratios of the stored to the expended energy at room temperature and 78 oK were unusually large. The additional amount of energy stored at the lower temperature is attributed mainly to an increase in the number and energy of dislocations. The stored energy as a function of strain rate at 4oK (measured after annealing at 78oK) increased to a sharp maximum over a narrow range of strain rates, whereas the expended energy changed only slightly. These effects are explained by the generation of point defects resulting from the enforced nonconservative movement of jogs in fast moving screw dislocations. The effect of straining successively at two strain rates at 4oK was also investigated. Stress-strain curves for 4o, 78oK, and room temperature and the results of micro examination of specimens deformed at these temperatures are also reported. THIS investigation is a continuation of a research program primarily concerned with the effects of variables on the energy relations involved in the deformation of metals. The variables investigated in earlier work have included strain, strain rate, temperature of deformation (room temperature and 78oK), and the type of deformation process. Most of this work has been carried out with Au-Ag alloys. In the investigation reported here, the deformation process was torsion, which had not been used previously in the program. The stored and expended energies involved in the deformation process were measured as functions of strain, strain rate and the temperature of deformation in the range 4" to 373" K. The microhardness and microstructure of deformed specimens were also investigated. The relation between stored energy and strain differs for different deformation processes.1,2 In general, the stored energy increases with strain and may attain a nearly constant value at large strains. This value and the rate at which it is reached, however, depend on the process of deformation. This dependence has been attributed, at least in part, to differences in the effective strain rate and rise in temperature of the specimen during deformation. The effects of the temperature of deformation on both the stored energy and the energy expended in the working process have been the subject of only a few investigations.3-6 Values of these quantities at low temperatures are of special interest as they yield information on point defects which, for many metals, is not obtainable at higher temperatures. The effect of the strain rate on the stored and expended energies has received little attention The strain rate has usually been measured only in relative terms, and hence the interpretation of its effect on the stored energy has been mainly comparative.

Jan 1, 1963

By M. Prats, D. G. Russell

The performance of a well in a bounded, layered reservoir with interlayer crossflow has been investigated mathematically. The system studied comprises a centrally located well in a bounded cylindrical reservoir composed of two layers of contrasting physical properties. The reservoir contains a single fluid of small and constant compressibility. In the case of a well producing at constant pressure, the production rate of the crossflow system declines exponentially after the early transient behavior dies out. For wells which produce with constant rate, the pressure-time relationship is linear following the transient. For very early production time, the production rate of the two-layer crossflow system behaves as that of the two-layer stratified system (the case in which the layers are in communication at the well only). Except for early time, in most practical cases the performance of a two-layer reservoir with cross-flow can be duplicated by that of a single-layer reservoir. The equivalent single-layer reservoir must have the same pore volume and the same drainage and wellbore radii as in the two-layer case. In addition, the equivalent reservoir must have a "kh" (permeability x thickness) product equal to the sum of the "kh" products of the respective layers in the crossflow system. If the porosity and permeability distributions are known, the production and pressure behavior of a well with and without crossflow can be predicted. From a comparison of the observed pressure or production performance of a well and the theoretical behavior, the occurrence of interlayer crossflow can be detected. INTRODUCTION When flow is possible across the bedding plane from a low-permeability layer into an adjacent layer of moderate or high permeability, the earlier depletion of the more permeable layer will cause such flow to occur. If this situation exists, the oil recovery from tight layers can be appreciable; thus, the economic ramifications of interlayer crossflow are apparent. The possible importance and extent of flow between adjacent and connected layers — whether resulting from capillary, gravitational, or viscous forces — have been the subject of considerable speculation for many years. Jacquard1 presented a rigorous analysis of the crossflow due to single-fluid expansion occurring between two adjacent and connected layers when the well produces at constant rate. His presentation was entirely mathematical, however, and no numerical results from evaluation of the mathematical solutions were presented. Our objectives in the preparation and presentation of the present paper are essentially twofold— (1) to analyze the behavior of a well which produces a single compressible fluid from a bounded, layered reservoir with interlayer crossflow, and (2) to present practical numerical results and simplified formulas to facilitate engineering analysis of reservoirs with crossflow. The constant-terminal-pressure case was analyzed rigorously, whereas the constant-terminal-rate case was treated only for semisteady-state conditions. DESCRIPTION OF THE IDEALIZED TWO-LAYER RESERVOIR The reservoir to be studied is assumed to be bounded and cylindrical in shape, with a completely penetrating well at its center. The reservoir is composed of two adjacent horizontal layers between which fluid is free to flow. Each layer is assumed to be homogeneous, isotropic and completely filled with a fluid of small and constant compressibility. The total thickness of the reservoir is small enough

By M. Bevis, A. G. Crocker

A. G. Crocker and M. Bevis (Battersea College of Technology)— Richman and Richman and conard17 have recently published the very interesting results of their studies on the plastic deformation of Fe-Ni-C martensites and of an Fe-5 wt pct Be alloy. Other work on the range of Fe-Be alloys containing between 16 and 27 at. pct Be has also been reported by Richman." One of the fascinating features of this work is that the materials investigated deform primarily by means of twinning and that several twinning modes are operative in addition to the well-established (112 ) mode of bcc materials The composition planes of these unusual twins were determined using a single-surface analysis and reported as (0131, "{045)" or "{089)", and "{2,3,10)" or "(127)". (It is now thought1' that the "{0,1,13)" habit reported for the Fe-Ni-C alloys'' is more likely to be near "{127)". Although the full twinning elements of these unusual twinning modes could not be determined directly from the experimental results, the authors attempt to deduce the elements by considering twin intersectionslQ and by using the projection technique of Jaswon and Dove.' The basic assumption of their approach is that the (013) habits are truly rational planes but that the other habits are irrational and merely approximated to by the indices quoted above. They thus deduce that the twinning mode describing the (013) habit is either Type I or compound and that the modes describing the other habits are Type 11. This deduction must however be false as all twinning modes in cubic structures obeying the classical orientation relationships of deformation twinning must be compound. Type-I and Type-I1 modes can occur in all of the other crystal systems (indeed in the triclinic system compound modes are not allowed), but in the cubic system only compound modes can arise. This fact, which does not appear to be well-known, fol- lows immediately from the relations between the four twinning elements defining a twinning mode. Thus for a Type-I mode which is uniquely defined by the rational twinning elements K1 = hi and tj2 = vi (i = 1, 2, 3), the Kz qd 771 elements are given by: where the summation convention of the tensor calculus has been adopted. For cubic materials the metrics cij Iand cij reduce to the unit tensors 6ij and 6ij so that we have It is clear from these equations that both ki and ui must take on integral values; i.e., Kz, and ql must be rational, if hi and vi are integers, i.e., if K1 and 77~ are rational. Thus for cubic materials a Type-I mode must degenerate into a compound mode and the same result also arises for Type-II modes. The apparently irrational habits observed by the authors can thus not be explained in terms of Type-I1 twinning if the classical laws of deformation twinning are to be obeyed. An alternative explanation of the irrational habits is that they may arise from twinning modes with four irrational twinning elements. These modes, which do not obey the classical orientation relationships associated with deformation twinning, have been shown to arise as the result of double twinning processes in magnesium,22 but may also describe a simple shear on an irrational plane in an irrational direction. Indeed double twinning processes in bcc

Jan 1, 1963

By Noel Jarrett, Allen S. Russell, Bernard M. Starner, Stanley C. Jacobs

A process has been developed to refine high-grade commercial aluminum to 99.99 pct purity. This enzploys precipitating titanium, vanadium, and zirconiu~ as borides. The upgraded liquid is partially crystallized under conditions that prevent massive freezing. The resulting crystals are compacted and washed free of adhernig impure liquid aluminum by melting the top crystals while draining off the liquid. Finally, the bottorn portion of the crystal bed is melted and removed as the pure product. Leakage from the crystallizat~on vessel is prevented by a layer of alumina granules that are not wetted by the aluminum. ALUMINUM of 99.99 pct purity is desired in a variety of applications. These include electrolytic capacitors, catalyst carriers, decorative trim for automobiles, aluminum powder, and high-strength alloys. This market was for many years filled by refining commercial-purity aluminum in a three-liquid-layer electrolytic cell of the type originally proposed by Hoopes. To meet the expanding need for lower-cost high-purity aluminum, a refining process based on chemical precipitation and fractional crystallization was developed. The availability of this super-purity metal was announced in November 1961, and three patents1-3 relating to the process were issued in 1965. An alternate process, comprising continuous fractional crystallization of a portion of a liquid-aluminum feed stream under conditions of strong agitation at the surface of the growing crystals, was published by Dewey4 in 1965. Earlier proposals by Larsen 5 and by Regner6 also emphasized the advantage of rapid agitation of the melt in the region of the crystallization zone. johnson 7 more recently proposed extracting purified aluminum from an alloy by mixing crystals of pure aluminum into the molten alloy, allowing them to grow, and removing the pure aluminum as by casting. Aamot's 8 recent patent describes a freeze refining process that involves controlled partial freezing against cooled moving retort walls. The Alcoa process to produce high-purity aluminum is schematically described in Fig. 1. Relatively pure aluminum is treated with boron in a furnace (a) to precipitate high melting point impurities, the supernatant liquid is transferred to a crystallization vessel (b), the liquid is partially crystallized with mechanized "tamping" (c), the remaining impure liquid is tapped out and the crystal bed partially and directionally re-melted to wash the underlying crystals (d), and the balance of the crystals is melted and withdrawn as high-purity aluminum (e). PRINCIPLES OF FRACTIONAL CRYSTALLIZATION Commonly encountered impurity elements form two types of systems with aluminum. Titanium, vanadium, and some other transition elements in periodic groups IV, V, and VI are the high melting point impurities. Initial solidification of aluminum containing small percentages of these elements will produce solid markedly enriched in them at temperatures slightly above the freezing point of high-purity aluminum. Most other elements, such as silicon and iron, produce eutectic type reactions with aluminum. In this case the first solid formed on initial solidification at temperatures slightly below the freezing point for high-purity aluminum is markedly depleted while the remaining liquid is enriched in these elements. The equilibrium change in composition during solidification of aluminum contaminated with silicon, iron, or titanium is illustrated in Fig. 2. Here, for clarity, the temperature scale is expanded beyond the

Jan 1, 1968

By C. M. Wayman, J. F. Breedis

The crystallography of the martensitic transformation in the Fe-30 Ni alloy was reinvestigated. The scatter in the habit Plane as determined from measurements on the mid-rib plane was smaller than reported previously, and the orientation relationship was determined from a martensite plate having known direction cosines. From agreement with crystallographic theory and from observations of the morphnlogy of the martensite plates, it is suggested that the mid-rib plane represents the starting region of the transformation. THE crystallography of the martensitic transformation in the iron-nickel system has been the subject of many investigations.&apos;-7 However, for iron alloys containing approximately 30 wt pct Ni, a wide scatter in the reported habit planes exists. In only one instance has a Laue determination of the orientation relationship been made, but the habit plane of the martensite plate studied was not determined experimentally. Because the most successful thermodynamic and kinetic analyses8 of the martensite transformation have been based on Fe-30 Ni alloys, it was considered desirable to reinvestigate the crystallographic features of the transformation in this alloy. Lieberman9 suggested that the most significant information for use in a theoretical treatment involves the determination of all the crystallographic observables from a single plate of the product phase. This was first done in essence by Greninger and Troiano10 for Fe-22 wt pct Ni-0.8 wt pct C, and is the method followed in this investigation. Some theoretical approaches11-13 in describing the martensitic transformation consider the overall transformation distortion to be comprised of a Bain distortion, or lattice deformation (PI, which produces the structure change, and a lattice invariant deformation (G), such as twinning, which together leave the interface or habit plane un-distorted. The incorporation of a rigid body rotation (R) results in a transformation distortion (E) such that the interface plane is left both undistorted and unrotated. In matrix notation, E = RPG where the lattice invariant deformation has "taken place" in the austenite. Bowles and Mackenzie14-16 in formulating a theoretical approach proposed an adjustable scaler quantity, denoted as 6, which represents a uniform dilation in the interface plane. This dilation acts to adjust the lattice spacings of the parent and product structures at the plane of contact. Using the dilation parameter as a variable, these authors were able to account for a continuous variation of habit planes in steels along a curve in the stereogram between {225}A and {259}A. she invariant line strain14 of the transformation is 6 RP, and the corresponding transformation distortion is E/6.) With the dilation parameter known, the invariant line is computed as the triple coincidence of the habit plane, the shear plane of the lattice invariant deformation, and the initial Bain cone.14 The contraction axis for the Bain distortion can be taken9&apos;17 as [010]A, and the correct permutation of the habit plane indices used. Kelly and Nutting 18 have established the shear plane (of twinning) in the tetragonal martensite of Fe-22 Ni-0.8C to be {112)M by means of transmission electron microscopy. The reasonable shear system is then {112}M which is equivalent to {011}A <01l>A. The as-

Jan 1, 1962

By L. Guttman, C. S. Barrett, J. S. Bowles

THE transformation from the face-centered cubic (Al) to the face-centered tetragonal (A6) structure in certain alloys of the indium-thallium system reported in the preceding paper1 exhibits many interesting crystallographic and metallo-graphic features, most of which presumably are similar to those of other cubic to tetragonal transformation such as, for example, the one which occurs in the chromium-manganese system,2 the one which, judging by microstructures and X-ray pat-terns,3 probably occurs in the copper-manganese system, the ones accompanying ordering in FePt,4 Copt,&apos; and AuCu,5 and the transformation near 115°C in barium titanate.6,7,8 If, as mentioned in ref. 1, the transformation is second order, the phases in equilibrium do not differ in composition, and it is both possible and likely that the mechanism is a diffusionless one. The present paper reports the results of a detailed study of the indium-thallium transformation and presents a theory for the atomic movements of the transformation which accounts for the observations. Experimental Crystallography of Transformation Markings The transformation from cubic to tetragonal in the indium-thallium alloys produces microstruc-tures of the type illustrated in fig. 1. These structures are observable either as relief effects produced on a smooth surface by the transformation, or after polishing and etching. These microstruc-tures are markedly similar to those found in copper-manganese alloys: iron-platinum alloys," and barium titanate,7,8 where it has been demonstrated that the lamellae are parallel to the (101) planes of the original cubic crystal. That the observed lamellae in indium-thallium alloys are also parallel to the (101) planes was proved by the following analyses performed on single grains in polycrystal-line samples containing 20.75 atomic pct T1. A study of the microstructures of a number of specimens revealed the fact that in many specimens the transformation markings continued unchanged in direction across the (111) interfaces of annealing twins. This at once demonstrates that the lamellae are parallel to a plane that is common to both parent and twin orientations, i.e., a plane in the zone <112>. This conclusion is compatible with the lamellae being parallel to (101) planes. To make a more complete determination of the habit plane of the lamellae, two grains were selected in which annealing twins ({Ill) twins) had been present in the high-temperature modification (cubic). The traces of the annealing twins, and of the transformation markings in both parent and twin crystals, were plotted together in stereographic projection, and a parent-twin pair of orientations was found that accounted for all lamellae as (101) planes. The projection of one of these twinned grains is reproduced in fig. 2. In view of these results the probability of there being another solution for the habit plane remote from (101) is very small, but to explore the possibility that the habit plane deviates slightly from (101), a more precise analysis was undertaken. In this, the orientation of a grain in the cubic modification was determined from a Laue back-reflection photograph taken with the sample at 90°C. The traces of the lamellae that formed in this grain on cooling were plotted in the stereographic projection

Jan 1, 1951

By B. A. Shaw

Historically, microwave tubes have been fabricated from massive metal and ceramic components. The current trend is to lighten tibes for airborne applications. The reqciiremenls of light weight and also reduced cost have created a novel approach to tube structure in which thin-film technology plays a major role. Although the electrical requirements of thin-film circuits in microwave tubes differ from those required or se,niconductor integrated circuits. the technology is basically similar. The stringent requirements of the micvowave tube have created sophisticaled thin-film techniques thut are of interest to the integrated-circuit industry in general. This paper describes a nunzber of thin-jilm techniques recently developed and discusses in detail the application of the technology in microwave tubes. The particular areas of interest are: 1) ceramic mounted thin-film slow-wave structures; 2) thin-film secondary emitters; 3) suppression of tube environnental multipactor by semiconducting&apos; thin films; and 4) age-hardenable and dispersion-hardened thin metal films. SEVERAL thin-film techniques specifically applied to microwave power tubes are discussed in this report. There are two reasons for this work. One is the necessity of reducing weight and cost of microwave tubes and the other is related to overcoming problems in the tube operation by the use of applied thin-film technology. The major emphasis of this work has been on tube slow-wave structures. Other work in the area of secondary emission, either its suppression or its enhancement, is continuing; the most satisfactory results to date have been by utilization of thin-film technology. The requirements of high thermal and electrical conduction together with greater strength than normally obtained with elemental materials have led to the development of dispersion-hardened films. The paper will discuss: 1) ceramic-mounted delay-line microwave tubes; 2) multipactor and secondary emission; 3) hardened films. I) CERAMIC-MOUNTED THIN-FILM SLOW-WAVE STRUCTURES In a conventional crossed-field microwave tube, the slow-wave or delay-line structure is produced from two carefully machined components. One half of the structure is shown in Fig. 1. The other half is the mirror image of the first but is rotationally offset by a half a period. The combined structure now forms an interdigital type of slow-wave structure and is the anode of the tube as shown in Fig. 2. The period and finger length of an interdigital slow-wave structure are prescribed by the desired dispersion characteristics. The typical design is as shown in the first figure; it can be noticed that the finger width is several times greater than the finger thickness. Even assuming that it were mechanically possible to produce free-standing fingers of extremely small cross-sectional dimension, for example, 0.002 in. thick by 0.005 in. wide by 0.500 in. long, decreasing this finger width would increase the tube efficiency but would also decrease the thermal-conduction path, causing an increased temperature rise from intercepted rf current which in its extreme could easily cause finger melting. Hence, for free-standing lines of this type, the design is a compromise between mechanical capabilities, tube efficiency, and thermal dissipation. These structures are also expensive and tend to be heavier than purely electrical considerations would demand. In the present approach, we have transposed the three-dimensional structure previously shown into an essentially two-dimensional structure as shown in Fig. 3. The linear structure is used here for clarity of detail. The support member is a ceramic material and the line is deposited copper. The final tube design is shown in Fig. 4. Because of the backwall sup-

Jan 1, 1967

By R. Fawley, M. A. Quader, R. A. Dodd

Stacking fault energies and annealing twin frequencies have been measured for austenitic stainless steels having a) constant 20 wt pct Cr and varying nickel contents, and b) constant 20 wt pct Ni and varying chromium contents. The effect of nitrogen has also been studied and, to a lesser extent, so has the effect of carbon. All measured stacking fault energies plot linearly against the corresponding annealing twin frequencies, suggesting that, for constant prior deformation and grain size, twinning frequency can be used to estimate stacking fault energy. Compositions low in nickel possess the lowest fault energy, while the maximum fault energy within the investigated composition range occurs mound 20 pct Cr-20 pct Ni. Nitrogen has practically no effect on stacking fault energy when increased from 0.005 to 0.05 wt pct, although Planar dislocation glide is associated with higher nitrogen contents; this may be a short-range order effect. Carbon may raise the stacking fault energy a little, and causes pronounced dislocation tangling in deformed alloys. The basically different dislocation structures promoted by nitrogen and carbon, respectively, are not associated with large variations in stacking fault energy, and the reason for the difference remains unknown. INTEREST in the dislocation configurations developed in plastically deformed alloys arises principally from a desire for an understanding of mechanisms of plastic deformation and fracture. Comparatively little basic work has been concerned with austenitic stainless steels, although considerable interest has developed in the fundamental aspects of deformation of these alloys since the suggestion that those compositions deforming essentially by planar glide are particularly prone to transgranular stress corrosion cracking.&apos; Certain facts are well-established. An 18 Cr-8 Ni steel (type 304) has a low stacking fault energy which is increased by higher nickel contents, and the structure of these steels when moderately plastically deformed changes concomitantly from planar to less planar to distinctly tangled dislocation configurations. These changes are thought to relate to changes in stacking fault energy, and considerable effort has been expended in measuring stacking fault energies of austenitic stainless steels through the determination of node curvatures2"4 even though the method has limitations due to formula approximations,5 an upper limit of measurement of 50 erg cm-2 at the most,5 and the necessity of an extremely meticulous experimental technique. Therefore, it is not surprising that only qualitative agreement between different investigators is generally to be found.&apos;-&apos; At high energies where node radius measurements are inappropriate, some use has been made of annealing twin frequencies to estimate relative stacking fault energies, although a recent critical evaluation of the method suggests that it should be used cautionsly with due regard to effects of grain size and prior deformation.6 Finally, there is a question as to whether the structures of some deformed steels are due to ordering effects. In particular, the role of nitrogen in promoting planar dislocation motion has been suggested to be due to ordering,&apos; but similar suggestions have been made for steels having low interstitial contents.4 EXPERIMENTAL Small ingots of austenitic stainless steels (-50 g) were prepared from components exceeding 99.99 pct purity, the nickel and chromium being Johnson Matthey "Specpure" metals. Carbon was added as pure graphite, and nitrogen as CrN. The components were accurately weighed, and it was assumed that the final composition was the same as the nominal composition

Jan 1, 1969

By E. H. Rennhack, J. F. Libsch

Definite transition behavior was found in unalloyed titanium at 0.13 pct 0 equivalent. The addition of 0.5 Sn, 1.0 Al, 0.5 Al, and 1.0 Sn lowers the tvansition temperature of titanium at oxygen equivalents exceeding 0.22, 0.29, 0.40, and 0.51, respectively. Metallographic evidence indicates that progressive amounts of oxygen restrict deformation at low temperatures resulting eventually in brittle fracture. The presence of tin or aluminum is thought to alter the atomic distribution of oxygen within the titanium lattice in such a manner as to facilitate some degree of slip and twinning. 1 ITANIUM-like iron and zinc experiences a transition from ductile to brittle fracture with decreasing temperature. The presence of sufficient quantities of the interstitial elements, carbon, oxygen, and nitrogen in solid solution, has been shown to progressively lower the room-temperature impact resistance of titanium with increasing interstitial content.1"1 Ogden,et al,2 reported finding no transition from ductile to brittle fracture with decreasing temperature in iodide titanium. However, a definite transition was found to occur at 0.36 pct 0 equivalent in an alloy containing 0.47 pct carbon in solid solution. The oxygen equivalent in this case was obtained by assuming the effects of carbon, oxygen, and nitrogen in combination on the impact properties of titanium to be additive on the same basis as their separate effects on tensile strength, namely: Oe = 2/3 (pct C) + pet 0 + 2 (pet N) They concluded that the tendency toward transition behavior is dependent on the total interstitial content in solid solution and not on any one particular interstitial element. Rennhack,4 however, recently found transition behavior in iodide titanium at an oxygen equivalent of 0.17 pct. Ogden, etal3, reported that the strengthening effects of carbon, oxygen, and nitrogen in titanium decrease with the addition of tin. They showed that tin additions increase the tolerance of titanium for the interstitials, that is, 10 pct Sn permitted individual additions of up to 0.4 wt pct of the interstitial elements without any significant loss in ductility. Aluminum tends to decrease ductility and impact strength of titanium for a given interstitial ~ontent.3 Van Thyne and Kessler5 found that the solid solubility of carbon in titanium doubled in the presence of 10 pct Al. The precise effects of tin and aluminum in the nrespncp of rorvfen nn the impact properties of titanium had previously not been determined. The high oxygen tolerance of titanium containing tin may provide a suitable means for improving the impact properties of titanium containing the interstitial elements, particularly oxygen. Unlike tin, however, aluminum has a high affinity for oxygen and will reduce rutile titanium dioxide (TiO2)by a thermit-type reaction.6 Thus, the atomic distribution of oxygen in titanium might be different in the presence of aluminum. The present work was undertaken to: 1) Determine the effect of oxygen on the transition behavior of unalloyed iodide titanium. 2) Determine the effect of small amounts of tin and aluminum on the transition behavior of iodide titanium in the presence of oxygen and other interstitial~. EXPERIMENTAL Three different lots of iodide titanium were employed to prepare the alloys studied in the present work. Their chemical composition is presented in Table I. The compositions of the tin and aluminum used for alloying are shown in Table 11. Oxygen additions were made using calcined rutile titanium dioxide (TiO2)of 99.7 pct purity. Alloy Preparation—Four titanium-base alloys containing separate additions of 0.5 and 1.0 pct each

Jan 1, 1960

By T. E. Leontis

ONLY a limited amount of information has been published on the effect of thorium as an alloying ingredient in magnesium. McDonald13&apos;2 showed that the addition of thorium in amounts up to 3 pct increases significantly both the ductility and the strength of rolled magnesium sheet. A recent publication by Sauerwald" indicates that thorium contributes strength and creep resistance at elevated temperatures to magnesium in both the cast and wrought states. The observations of Sauerwald are confirmed in this paper, which presents the results of a systematic study of the effects of compositional variation on the tensile properties, creep resistance, conductivity, density, and metallography of Mg-Th alloys containing up to 50 pct Th both in the sand-cast and in the extruded states. The effect of the addition of cerium to Mg-Th alloys is also reported. Experimental Methods The alloys studied in this investigation were pre.pared in small laboratory melts according to the melting practice described by Nelson4 as the crucible method. Electrolytic magnesium was used as the starting material to which the thorium* was introduced in metallic form. It was observed that the behavior of thorium in molten magnesium with respect to reaction with protective fluxes is similar to that of rare-earth metals. In order to obtain the highest possible alloying efficiency, it is necessary to use non-MgC1, fluxes and to apply all the precautions described by Marande6 for melting, alloying, and casting magnesium-rare-earth alloys. .Under these conditions it is possible to obtain an alloying efficiency in the range of 85 to 95 pct. The Mg-Th-Ce alloys were made with cerium of the highest purity available, not with the commercial product "misch-metal" which contains approximately 50 pct Ce. The total rare-earth content of this material was 97.1 pct, of which 0.3 pct was rare-earth metals other than cerium; the major impurities comprising the balance were iron and magnesium. The thorium and cerium contents of each alloy were determined chemically. Test bars 6% in. long with a 2% in. long reduced section of % in. diam were cast in sand molds using a four-baf pattern. In most cases, a 3 in. diam extrusion billet 10 in. long was cast in a steel mold from the same melt used for making the sand-cast test bars. For the higher thorium alloys, it was necessary to remelt the foundry scrap from the test bars in order to make the extrusion billets. The billets were scalped to a diameter of 2 15/16 in. and the ends faced to a length of 9% in. as limited by the size of the extrusion container. The alloys were extruded into % in. diam rod on a 500-ton direct-extrusion press. The details of the extrusion process are as follows: Billet preheat 925°F (2 to 16 hr) Container temperature 900 °F Die temperature 900°F Extrusion speed 10 ft per min Reduction ratio 36:1 Percent reduction 97.3 Alloys containing up to 10.2 pct Th were preheated at 925°F for 2 hr; all alloys with higher thorium contents were preheated for 16 hr. In order to establish the effect of extrusion temperature, billets of

Jan 1, 1953

By J. A. Hren, G. Thomas

A high-temperature stage has been used to study precipitation and dissolution in thin foils of Al-20pct Ag alloy directly in the electron microscope. The results show that the aging characteristics are similar to those observed for bulk materials, and in addition, direct evidence is presented for clustering at the solid solution temperature. The limit of solubility of G. P. zones is-350°C. The heterogeneous precipitation, the growth and dissolution of ?&apos;have been studied in detail. Growth of ?&apos; parallel to the basal planes, occurs by continuous motion of inter -facial partial dislocations. Growth stops at intersecting particles due to formation of sessile a/6 <110> interfacial dislocations. Growth normal to the habit plane occurs by the spontaneous nucleation of partial dislocations on alternate (111) planes and the thickening rate is --10-3= times the lengthening rate. The precipitates dissolve in layers and the final product is a whole a/2 <110> dislocation . The nucleation -growth -dissolution processes are thus completely reversible. Kinetic data obtained from the dissolution rates of ?&apos;particles enable the diffusion coefficient to be determined and the activation energy is found to be 37.5(±4) kcal mol-1, which is that expected for dzffusion of silver in aluminum. The velocity of the interfacial dislocations is thus dependent solely on the rate of diffusion of silver atoms. RECENTLY it was demonstrated that a high-temperature stage could be effectively used in the electron microscope to follow directly the processes of precipitation and dissolution in thin foils of A1-4 pct Cu alloy.&apos; These experiments also provided kinetic data which enabled the diffusion coefficient to be estimated. This new development of electron metallography opens up many fruitful areas of research and it was decided to investigate the aging behavior in thin foils of A1-20 pct Ag alloy, particularly the mechanism of heterogeneous precipitation (i.e., precipitation on lattice defects). This system was chosen because the aging characteristics of bulk specimens are now well known,2"7 and because we wished to obtain more details of the role played by partial dislocations and stacking faults in the nucleation growth and dissolution of the hcp ?&apos; phase. This is of interest for the general case of fcc-- hcp transformations. Part of the A1-Ag phase diagram is shown in Fig. 1. The use of a high-temperature stage also enables a study to be made of the clustering process (formation of G. P. zones) and to determine the structure of the solid solution prior to the usual quenching and aging procedures. It is also possible to obtain kinetic data from measurements of the rates of dissolution of precipitate particles. Unlike the results of previous experiments on A1-4 pct CU 1 where much of the initial precipitation occurred on the foil surfaces, the results on the A1-20 pct A1 alloy were identical to those reported for bulk specimens6,7 and no surface precipitation was ever observed. Thus, it was possible to follow the aging sequence: G.P. zones — ?&apos; — ? directly in the thin foils. This paper is concerned with the formation and dissolution of zones and the ?&apos; phase, and no attempt has been made so far to follow the mode of discontinuous precipitation of ?. I) EXPERIMENTAL DETAILS The high-purity A1-20 pct Ag alloy was prepared by the Aluminum Co. of America in the form of 0.001-in.-thick sheets. These were cold rolled with intermediate anneals to a thickness of 0.0004 in.,

Jan 1, 1963

By C. A. Stout, S. W. Nicksic

The materials that stubilize emulsions of some Southern California crude oils were isolated from the produced crude. These substances were separated into acidic and nonionic fractions by ion exchange chromatography. Each fraction was further broken into groups of homogeneous molecular weight composition by gel permeation chromatography. Both ionic character and molecular weight of the individual fractions are reflected in the properties of the original crude oil emulsion. Specifically, the more acidic and the higher molecular weight fractions appear to be the most effective stabilizers. INTRODUCTION The treatment of oilfield emulsions is a continuing problem for the oil industry. In almost all cases, these are water-in-oil emulsions. Much more is known about the formation and stabilization of oil-in-water (O/W) emulsions than of the water-in-oil (W/O) type. To understand W/O emulsions, more information is needed on the materials responsible for their formation and stabilization. This is especially true in the case of oilfield emulsions where the stabilizing materials are complex mixtures of large asphaltene-like molecules. To study the chemical and physical properties of these emulsion stabilizers, it is necessary first to separate them from crude oil. This separation was achieved in the case of two Southern California crude oils. The materials that were isolated appear at first to be little different from an asphaltene mixture. However, if a mixture of distilled water and mineral oil containing about 1 percent of the natural emulsion stabilizers is passed through a colloid mill, the W/O emulsion formed may be stored in the laboratory for many months without any sign of breaking. This could not be done using undifferentiated asphaltenes from the same wells, indicating that there is a real difference between these materials and ordinary asphaltenes. The colloid mill used to generate the emulsion was required because tile natural emulsion stabilizers had very little effect on oil-water interfacial tension. The one characteristic — complexity of composition — that emulsion stabilizers share with asphaltenes makes virtually impossible the exact structure determination of the components of the mixture. For this reason, it was decided to investigate first the influence of molecular weight on the ability of these materials to stabilize emulsions. The emulsion stabilizers were first separated into acidic and neutral fractions according to whether or not the material was retained on a weakly basic ion exchange column. The extraction procedure was not designed to remove basic components from tile oils, and no attempt to isolate such a fraction was made. Following this separation, selected fractions were analyzed by gel permeation chromatography. Gel permeation separates according to molecular size, largely independently of chemical or polar characteristics. A heterogeneous mixture is separated into a number of fractions having much more homogeneous molecular weight distribution. A number average molecular weight of each fraction is therefore close to the true molecular weight of the principal component of that fraction. The fraction weights, expressed as weight percent of the sample, and the number average molecular weight of a representative selection of the fractions, will be referred to in this paper as the molecular weight profile of the original sample. DESCRIPTION OF GEL PERMEATION ANALYSIS The first reported gel permeation analyses were for separating partially hydrolyzed protein molecules in an aqueous system using expanded starch granules. Most of the theoretical work on gel permeation has been done by biochemists.1 This theoretical treatment is still incomplete, but the

Jan 1, 1969

By A. O. P. Casbarian

An analytical method is developed to determine the variation of the ultimate lateral resistance of a plate in a cohesionless soil with depth. This analysis is based on a modification of Rankine&apos;s classical earth pressure theory and the theory of plasticity as applied to soils. The ultimate resistance is defined as the product of the effective stress at the midpoint of the plate, the area of the plate and a dimensionless variable termed the ultimate resistance factor. This variable has been plotted us the depth ratio: i.e., the ratio of of the depth of embedment us the height of the plate. The resistance of a plate may then be calculated using the values af the ultimate resistance factor from the chart provided or the equation may be programmed for use in an analysis of anchor systems in cohesionless soils. It is emphasized that the analysis is semitheoretical. The theory has been compared with experimental results reported in the literature and results indicate general agreement. Actual field tests are necessary to further verify this theory. INTRODUCTION With the exploration for oil offshore in waters all over the world, it is of importance to determine the behavior of the various soils in relation to their ultimate resistance to deformation. Examples of such problems are the holding capacity of anchors and the lateral resistance of piles. Very little information is available in the published literature on the design and performance of anchors, in either cohesive or cohesionless soils. The analysis developed in this report is the first step in obtaining a solution for the determination of anchor holding capacity in a cohesionless material. DISCUSSION The theory used in the analysis is based on the ultimate strength of the soil and is the maximum resistance developed by the plate against further movement. In such a state the elastic deformations are disregarded in comparison with the plastic deformations. Hence, the plate can be considered as completely rigid. The theory of plasticity determines the three unknown stresses at any point by means of two equilibrium conditions for a small earth element in combination with the failure condition. However, the exact solutions can only be carried out in a few simple cases such as, for example, when the rupture or failure lines are straight (Rankine theory) or with spiral and straight rupture lines (Prandtl theory).l Kiitter 2 derived a single equation expressing the variation of the stress in any given rupture line. To utilize this equation, it is necessary to know the stress in the rupture line at a certain point. Unfortunately, this is difficult to obtain unless the rupture line intersects the free surface at a certain angle or when the earth is cohesion-less and unloaded. A method to overcome this is to consider only the boundary conditions at both ends of a rupture line without investigating the equilibrium of the earth above the rupture line. This assumes that the rupture lines meet the surface at statically correct angles, so that boundary stresses may be determined. As Kiitter&apos;s equation furnished a relation between these stresses, the unit earth pressure may be calculated at the point where the rupture line meets the wall. Another way in which Kotter&apos;s equation may be applied is in investigating the equilibrium of a soil mass above a rupture line. This method assumes that the failure or rupture line is known and that the boundary stresses in the rupture line at the ground surface can be determined. In this case it is possible to determine the earth pressure from the equations of equilibrium.

Jan 1, 1967

By M. C. Flemings, T. S. Piwonka

Pore formation is examined analytically in cellu-larly solidified single crystals, in cylindrical castings of pure metals and alloys, and in unidirectionally solidified castings. Effects are considered of fluid flow. dissolved gas, and surface tension. Experimental results show that flow through a partially solid "mushy" aluminum alloy obeys relations similar to those applicable for flow through other types of porous beds. Flow rate is proportional to the square of the fraction liquid (fL) for fL less than 0.3. Results indicate models chosen for mathematical description of pore formation in alloy solidification are valid. ONE of the solidification variables which is influential in determining mechanical properties of castings and of wrought material produced from cast ingots is porosity. This porosity may result from shrinkage, dissolved gases, or a combination of both, and may take the form of either macroscopic pores in localized areas of the casting or microporosity evenly distributed throughout large areas of the casting. In alloys which freeze over a range of temperatures some microporosity is generally found after solidification. There has been much discussion as to whether the micropores are caused primarily by shrinkage, by gas, or by a combination of both.&apos;-3 There has, however, been little experimental or analytical work performed to delineate the relative contributions of shrinkage and gas in causing microporosity or to quantitatively describe the influence of processing variables on microporosity. Porosity other than microporosity (e.g., center line shrinkage) has also received only limited quantitative treatment.495 The aim of this work is to examine analytically the general problem of pore formation in solidification and to perform limited confirmatory experiments. Consideration is first given to shrinkage porosity in pure and nearly pure metals (shrinkage in cellular growth, centerline shrinkage in cylinders). Next, a discussion is given of formation of shrinkage-caused microporosity in unidirectional solidification and in "mushy" solidification. Finally, influences of dissolved gas and surface tension on microporosity are examined. Numerical results are given for aluminum and an aluminum alloy. Typical examples of microporosity are shown in Figs. 1 to 3, for 1) cellularly solidified aluminum, 2) sand-cast aluminum alloy, and 3) low alloy steel. SHRINKAGE POROSITY IN PURE AND NEARLY PURE METALS 1) Cellular Growth. In cellular freezing of an impure liquid, liquid grooves may exist over a considerable length of the growing crystal.6 The cross-sectional area of the grooves decreases with increasing distance from the cell tips; the root of the groove is blunt if the liquid at this point reaches eutectic composition. As a result of volume contraction during solidification, flow occurs down the groove, parallel to the growth direction; hence, there must be a pressure drop from the groove entrance to points within the groove. The geometry of the groove is simplified to that of a circular cylinder of radius r and length L, Fig. 4, L » r, and a simple and useful limiting case is obtained. This is that, in the circular cylinder freezing at constant velocity, the pressure at the root of the groove is lower than that pressure at radius r in grooves of other geometries where r decreases continuously to a lower limit at L. As discussed below, a pore resulting from a given pressure difference

Jan 1, 1967

By G. Donald Emigh

Nothing is more important to life-plant and animal-than phosphate. Its compounds are essential to the energy functions of all living systems and for the formation of bones and teeth. Animals get their phosphate from eating plants and other animals, or domestically from feed supplements. Plants get their phosphates from the soil. Man&apos;s most important use of phosphate is for fertilizer; approximately 95% of the world&apos;s phosphate rock production is consumed by fertilizers. Most of the balance is processed in electric furnaces into elemental phosphorus, the important raw material for making industrial phosphates. Recovery of uranium from phosphates has been possible but not widely used. However, recent significant developments have generated interest in such recovery in the US and elsewhere. Phosphate occurs in all igneous and sedimentary rocks, and in all fresh and salt water. However, economical recovery is limited to deposits where natural concentration of the phosphate mineral has occurred. Occasionally natural concentration is great enough that the material can be used as mined; generally, however, the ore is low grade_ and must be concentrated. Phosphate rock is produced in 31 countries. Fig. 1 shows the location of major phosphate rock producers as well as some of the known phosphate deposits not yet in production. In the last decade the world phosphate industry has experienced steady growth. World production rose from 98 Mt of phosphate rock in 1973 to 140 Mt in 1982. Fig. 2 shows the growth curve of rock production and graphically illustrates the almost straight-line rise since 1945 in both US and world production. Table 1 gives the breakdown, by countries, of world rock production, 1974 through 1979. Table 2 shows US rock production by producing areas. Definitions of Terms Used in the Phosphate Industry Phosphate Rock: Commonly called rock in sedimentary deposits and apatite in igneous deposits. Those expressions generally include any mined, or mined and beneficiated, fluorine-containing calcium phosphate used as the raw material for the next stage of manufacturing. The average phosphate content in rocks is 0.1 to 0.2% P2O5, as documented by McKelvey (1973). About 200 minerals contain more than 1 % P2O5. However, the important mineral in igneous rocks is fluorapatite, [Ca5 (PO4),3 F], containing about 42% P205 and 3.8% F2; in sedimentary rocks the important mineral is francolite, a carbonate fluorapatite containing up to 2% molecular CO2. Both are in the apatite family of minerals. Most phosphate rock, whether beneficiated or not, is a fine-grained material. The expression phosphate rock has no relation to its phosphate content. For example, phosphate rock from Idaho used in the production of phosphorus may contain about 24% P205, whereas rock from Morocco may contain 36.6% P2O5. Phosphorite: A deposit of phosphate directly or indirectly of sedimentary origin, which is of economic interest. Grade of Phosphate Rock: The calcium phosphate content of phosphate rock is expressed in different world areas by one of the following terms: BPL (bone phosphate of lime) TPL (triphosphate of lime) P2O5 (phosphorus pentoxide) P (phosphorus-not commonly used) An illustration of relationship is: 80% BPL = 80% TPL = 36.6% P5O2 = 16% P

Jan 1, 1983

By John W. Cahn

Tile avevage value of the mean curvature of surfaces in a specimen can be precisely delermined by sitrlple measurements performed on random sections or on 1 vojectiotzs of these surfaces. For surjaces enclosing particles, the quanlity is sllown to be velated to the probable tlurrrhev ot particles intevcepted by a random platne and, under certain conditions, to the perimeter of their Projected image and to the increuse in surjace area when the particles grow. Many of the velalionsl~ips are valid for any shape or size of the particles. THE recent growth of the field of stereology or quantitative microscopy is largely the result of the discovery of a limited number of rigorously defined geometrical parameters that can be precisely measured on random sections or projections of a structure without assumption about particle shape.&apos; Such parameters have been the volume fraction and surface area and line length in a unit volume. The present paper introduces the average of the mean curvature of surfaces in a volume, and shows that it can be rigorously measured by counting methods alone. AVERAGE CURVATURE ON A PLANE Consider a curve y = v (x) on the xy plane. The curvature Kp in the plane at any point is given by Kp = (dZy/dx2)/[1 + (dy/dx)2]3/2. The average curvature along the curve may be defined as Kp = (1/L) fKpdl |1] where dl = [(dx)&apos; + {dy)2]1/2 is the length of an element of the curve and .(dl = L is the total length of the curve. The integral on the right-hand side of Eq. [l] will be called the total curvature, It is dimensionless and readily evaluated by substituting d = arctan (dy/dx) to give ah which is the change in direction of the tangents to the ends of the curve, Fig. 1. Hence, Kp = (1/L)(?h) [2] It can also be seen that Eq. [2] is applicable in the limit of sharp corners. Even though the curvature is infinite at a corner, f Kpdl remains integrable and equal to the change of angle. The signs of the quantities Kp and dl are arbitrary and, if the areas adjoining the curve are equivalent, there seems to be no compelling reason to fix the signs. For a closed curve, however, it becomes worthwhile to use the signs to distinguish among different types of areas or phases enclosed. For such a closed curve AO = t2r and As a convention, we shall take the direction of the integration along the curve in such a way that the area or phase under consideration (henceforth called a) is kept to the left side of the curve, Fig. 1. Then Kp is positive where the curve is concave and negative where the curve is convex. For a closed curve Ad - +2n if the curve encloses a, and Ad = —2n if the curve is surrounded by a. PLANAR SECTIONS OF THREE-DIMENSIONAL STRUCTURE OF ISOLATED a PARTICLES Consider next a planar section of a microstructure containing particles of a in a matrix. We place no restriction on shape of connectedness of these particles, and begin by considering the curvature of only the boundary between a particles and matrix&apos; Clumps of contiguous a particles are then treated as a single a particle. The two-dimensional section will show in a unit area na simple closed curves enclosing a particles and nh closed curves of holes, in-

Jan 1, 1968

By R. D. Young, E. A. Harre

Nitrogen exists in two broad categories commonly designated as elemental nitrogen and fixed nitrogen. Elemental nitrogen is found in nature as a diatomic molecule and constitutes about 78%, by volume, of the earth&apos;s atmosphere. Fixed nitrogen is a common term used for nitrogen that is chemically bound to other elements. Although elemental nitrogen is very abundant, nonleguminous plants cannot utilize nitrogen unless it is in the chemically combined form. The content of this chapter is confined to fixed nitrogen since the uses and properties of elemental nitrogen and the fixed nitrogen compounds are different. Certain bacteria associated with legumes are able to fix atmospheric nitrogen, but not to the extent required by succeeding nonleguminous crops. The need to use fertilizers containing fixed nitrogen compounds to grow food crops has been recognized for hundreds of years, and from antiquity farmers have used organic wastes such as animal manures, vegetable wastes, sewage sludge, fish scraps, etc., containing these compounds for fertilizers. These organic materials have a low nitrogen content, however, and cannot support large-scale food production. Known commercial-size deposits of natural nitrates containing much higher nitrogen content exist only in Chile, and the possibility of the discovery of other significant deposits is remote. The Chilean deposits were the major source of nitrogenous fertilizers until the Haber-Bosch process for the production of synthetic ammonia was developed. In the Haber-Bosch process, nitrogen reacts with hydrogen at high temperatures and pressures and in the presence of a catalyst to form ammonia. Modern plants use air, water, and natural gas or other hydrogen sources to produce the ammonia that is now the key building block of the fixed nitrogen industry. Several major problems that developed in the 1970s continue with the nitrogen industry into the 1980s. These are (1) the continuing sharp escalation in the cost of feedstocks for ammonia production as well as all energy sources, and (2) the very steep increase in the investment cost of production facilities. More than 75% of the fixed nitrogen produced domestically is consumed as fertilizers. The types of materials used as fertilizers have changed significantly during the past years. There has been a trend from the use of low-analysis fertilizers to types which contain high percentages of plant nutrients. The average plant nutrient content (N + P2O5 + K2O) of fertilizers used in the United States has increased from 18% in 1930 to 32% in 1960 and today approaches an average of 44%. In the case of nitrogen fertilizers, the low analysis natural nitrates (16% N) gave way to ammonium sulfate (20% N) after about 1920. After World War II, ammonium nitrate (33.5% N) previously used in munitions, became established as the leading nitrogen fertilizer. Urea use as a fertilizer (46% N) began in the 1960s, and in the past 10 years has become the world&apos;s leading solid nitrogen fertilizer. Nitrogen Materials Anhydrous Ammonia-Anhydrous ammonia is a colorless gas at ambient temperatures and pressures and has a sharp pungent odor. Anhydrous ammonia is stored and transported as a liquid in high-pressure cylinders and tanks at ambient temperature, and in low-pressure tanks, barges, and ships at -28°F. Anhydrous ammonia is applied directly at 4 to 7-in. depths in the soil as a high-pressure liquid by special applicators, after which it expands to a gas that dissolves in the soil moisture or is absorbed on soil colloids. In other systems ammonia is metered into irrigation water and is thereby introduced into the soil.

Jan 1, 1983

By R. W. Heckel

The growth and shrinkage rates of second-phase particles of various size distributions are analyzed in terms of five mathematical models. These models apply to various forms of diffusion-controlled growth (one model) and interjace-controlled growth (four models). The expression for diffusion-controlled growth assumes local equilibrium at the interface between the second Phase and the matrix and through the choice of the proper flux area perrnits the definition of minimum diffusion-controlled growth kinetics. The interface-controlled kinetics models consider the situations where the rate-controlling step occurs at either the interlace undergoing solution or the interface undergoing deposition. In addition, each of these interface-controlled kinetics models is analyzed for interface reaction rates which are independent of the thermodynamic activity gradient across the interface or proportional to the gradient. THE variation of the size distribution of second-phase particles in a solute-saturated matrix has been a stimulating topic for many years. Research has been carried out in this area for situations where the matrix was either liquid or solid. It is well-understood that the over-all process results in an increase in the average particle size, a decrease in the total number of particles per unit volume, and a net decrease in surface area. Greenwood1 has presented a mathematical model based upon the mass balance existing between growing and shrinking particles. His analysis is stated in terms of Fick&apos;s First Law using concentration gradients set up between particles of different size as a result of the effect of surface curvature on solubility. Greenwood&apos;s analysis indicates that the mean particle size should increase approximately as the cube root of time. Asimow2 has shown that several of the simplifying assumptions employed by Greenwood may be eliminated from this diffusion-controlled model with little increase in complexity. Lifshits and Slyozov3-5 have also considered the growth-shrinkage problem involving diffusion-controlled kinetics. Their analysis was extended to include the effects of interacting particles ("kinetic approximation"), particle shape, and elastic strains. These authors also show that the mean particle size varies as the cube root of the reaction time. wagner6 has formulated expressions for both diffusion-controlled kinetics and interface-controlled kinetics in the growth-shrinkage problem. Wagner&apos;s diffusion-controlled kinetics is based upon the same form of mass balance using Fick&apos;s First Law as used by others and is shown to be applicable to situations where kr >> D (k is the interface reaction constant, r is the particle radius, and D is the diffusion coefficient). This analysis also yields a mean particle size which varies as the cube root of time, in agreement with other workers. Wagner also developed interface-controlled kinetics to handle kr « D. This model was based upon the fact that the interface reaction rate is proportional to the interface area. Wagner assumed that the rate was also proportional to the thermodynamic activity difference, ?a, existing across the interface. Thus, the specific reaction rate at the surface of radius r was defined as k • 4nr2 . ?a. It is the purpose of the present paper to reconsider the processes of diffusion-controlled growth and interface-controlled growth in the variation of particle-size distributions as a function of time at constant second-phase volume. The analyses are formulated in a manner which permits data obtained

Jan 1, 1965

By Jim D. Mote, Eugenia M. Howard, Willis L. Barmore, John E. Dorn

The effect of stress and temperature on the creep rate of Ag-33 at. pct A1 and Ag-33 at. pct Al-1 at. pct Zn for prismatic slip was determined over a range of temperatures from 440º to 700°K. The alloys exhibited a brief initial inverted transient creep over which the creep rate increased slightly to a steady-state value which depended only on the stress and temperature, regardless of the previous strain history. The steady-state creep rates were found to be given by: where the activation energy is independent of the stress and strain and agrees fairly well with that estimated for diffusion. The observed creep behavior was shown to be in qualitative agreement with a model based on the stress-induced local disordering in the vicinity of a dislocation. OVER the past fifteen years, considerable progress has been made in correlating the experimen-entally observed plastic behavior of pure metals over each temperature range with one or more of a series of theoretical strain-rate controlling dislocation mechanisms. Despite the current interest in the plastic behavior of intermediate phases and inter metallic compounds, however, very little has been done in identifying the operative dislocation mechanisms in these materials. It is anticipated that the plastic behavior of intermediate phases can be rationalized in terms of the same dislocation mechanisms that are appropriate to pure metals and a solid solutions, provided the additional complexities arising from crystal structure, bonding, long-range order, short-range order, and defect lattices are taken into account. As part of a more extensive investigation on the plastic behavior of intermediate phases, Mote, Tanaka, and Dorn1 recently reported on the effect of temperature on the yield strength for prismatic slip in the hexagonal Ag-33 at. pct A1 intermediate phase as recorded in Fig. 1: Over Region I the deformation was observed to take place as a result of the thermally-activated Peierls mechanism, and over Region II the athermal disordering mechanism applied. The experimental data at that time, however, were not sufficiently extensive to identify the thermally activated mechanisms operative over Region III. It is the purpose of this investigation to attempt to identify the mechanisms that are operative over this high-temperature region. It will be shown that the same mechanism operates all over Region Ill, although the activation energy for this mechanism is in good agreement with that for diffusion, the process cannot be attributed either to the motion of jogged screw dislocations or the climb of edge dislocations. The results, however, are in good qualitative agreement with stress-induced disordering localized at dislocations. EXPERIMENTAL PROCEDURE The alloys studied in this investigation were prepared from silver, aluminum, and zinc (each of purity greater than 99.995 pet) by induction melting under an argon atmosphere and chill casting in a copper mold. Rectangular bar single crystal specimens (1/4 by 1/8 in. in cross-sect ion) of Ag-33 at. pct Al were grown in vacuum by a modified Bridgman technique. Similar Ag-33 at. pct Zn specimens were produced by an identical technique employing an argon atmosphere. The specimens were so oriented that the angle 90-Xo between the tensile axis and the normal to the prismatic plane and the angle A, between the tensile axis and the slip direction were 45 ± 1 deg. The effect of a change in temperature on the creep rate and a change in stress on the creep rate were determined over the temperature range

Jan 1, 1963