Search Documents

By R. P. Thomas

Secondary fertilizer minerals are the mineral materials used to supply directly and indirectly the secondary and trace plant food nutrient needs of a fertilizer. Since few soils contain sufficient availability of all plant nutrients for their proper growth, man has prepared mixtures of plant food materials to correct these nutrient deficiencies. These mixtures or fertilizers, when added correctly to a soil, make it possible for abundant and economic crop growth. Many kinds of materials are used as sources of these needed nutrients. They come from natural and synthetic materials and minerals including many beneficiated byproduct compounds. A fertilizer consists largely of carriers of one or more of the three major plant foods, namely nitrogen (N), phosphorus-phosphorus pentoxide (P2O5) and potassium-potash (K2O). Many other nutrients are just as essential for plant growth as the three major plant foods. In fact, the efficient use of fertilizers today depends upon an adequate supply of all these other nutrients. Since these additional materials are usually removed from the soil by plants and supplied in fertilizer in less quantities than the major nutrients, they are called secondary and minor nutrients. In the early days these special nutrients were contained as impurities in the primary nutrient carriers. Today, fertilizers are made primarily from concentrated and synthetic materials which carry very few of these other essential nutrients. Consequently, many secondary and trace nutrient carriers, as salts, byproduct compounds and even minerals have to be added to fertilizers. Secondary Nutrient Carriers The secondary plant foods in fertilizer are next to the major nutrients in abundance. They are calcium, magnesium, sulfur, chlorine, silicon and sodium. Although many of these elements are added to a fertilizer as part of the major nutrient carriers, they are also added in special carriers. The large tonnage of these secondary nutrient carriers used in fertilizers represents only a small percentage of the total production of these materials. A fertilizer producer thinks in terms of materials which supply nutrients instead of minerals. Therefore, these materials will be discussed by elements. CALCIUM Soils need calcium to supply the nutrient needs of plants and maintain the desired physical and biological conditions in the soil. The available calcium is usually 40 to 80 pct of the exchangeable bases. (These bases are ones which can be displaced by other cations and determined quantitatively. They are then expressed as milliequivalents per hundred grams of soil-me.) Direct applications of lime materials such as burnt, ground or hydrated limes are the important sources of calcium for the soil. Most crops, especially legumes, have a high requirement for calcium. The average farmer does not use enough lime to maintain the proper level of available calcium. Hence, it is necessary for many fertilizers to contain soluble calcium materials for efficient use of the major nutrients. The following major nutrient carriers supply some calcium: calcium nitrate, ammonium nitrate mixtures and cyanamid, and many of the phosphates. Both synthetic and natural gypsum are used in fertilizer production. Some crops such as peanuts require a large amount of soluble calcium. Gypsum is the important supplier of this soluble calcium. It is not applied with the fertilizer

Jan 1, 1960

By R. B. Moore

IN 1914 the writer and K. L. Kithil announced, through Bulletin 70 of the U. S. Bureau of Mines, that the United States possessed the largest deposits of radium-bearing ore in the world. At that time a small amount of this ore was being, mined and shipped to Europe, and one company was preparing to start the extraction and recovery of radium in this country. The importance of our carnotite deposits in Colorado and Utah up to the publication of Bulletin 70 was not, however, appreciated by anyone.. At that time the total supply of radium in the world was about 10 g., calculated as element, and when I estimated that at least 100 g. of radium element, and probably 200 g., would be produced from our carnotite deposits, there was a considerable amount of skepticism. Up to the present time almost 200 g. have come from this ore, and some writers put this figure a little higher. Uranium ore was found in the copper mines of the Union Minière du Haut-Katanga at Luiswishi in 1913. Later discoveries were made at other places in the Belgian Congo, and the Katanga ores now represent the largest supply of radium-bearing ore in the world. In fact, since 1923 very little radium has been produced from American carnotite, the Katanga ore representing practically the world's supply of. radium since that date.

Jan 1, 1930

By G. Sachs, G. Espey

SIMPLE methods can be used for the determination of the residual stresses in thin-walled tubing if the stresses consist of high tensile stresses at the one surface and high compressive stresses at the other surface Such a stress distribution is approximated in sunk tubing and in deep-drawn shells It is possible to cut sections from such articles in such a manner that a major part of the residual stress is relieved by a bending of the part that is separated from the adjacent metal The circumferential stress is evaluated from the change in diameter D, occurring on splitting a length of tubing (Fig Ib),1-5 or from deflection resulting from the cutting out of a circumferential tongue (Fig Ia) G The bending moment M released by such a flexure is [ ] The release of this bending moment corresponds to the release of stresses, which, in a thin section, vary linearly from one surface to the other, and have the following value in a particular fiber a certain distance (zx from the surface [ ] where C is the section modulus and d is the thickness of the section, the ratio AI C being d 2 for a rectangular section* The maximum stress values at the surfaces are [ ] For most purposes the simpler equations [ ] will be satisfactory, where Dm is the average of the mean diameters of the tubing

Jan 1, 1941

By J. Gurland

The wmk is concerned with the estimate of the degee of continuity of a particulate phase dispersed in a matrix. The first section is a verieu: of the parameters nzeasurable by quantitative rnetallogvaphy, namely the contact area and, under certain conditions, the number of contacts between particles of one phase. In the second section, the frequency of particle contacts is related to the degee of continuity of a randomly embedded phase orz the basis of the lattice-percolation model of Hamrnersley and others. THE extent of continuity of the constituent phases may greatly influence the structure-sensitive properties of phase mixtures, particularly if the phase properties differ significantly. An example from the literature1 is shown in Fig. 1. The marked decrease of the electrical resistivity of sintered silver-alumina bodies near 25 pct by volume of silver presumably occurs because the more conductive phase changes from a discontinuous to a continuous structure. Other example of electrical- and thermal-conductivity transitions are cited by kingery In view of these observations, a knowledge and understanding of the connectivity of the microstructure may be of considerable practical importance. This study is concerned with one aspect of the genera1 problem, namely the estimate of the degree of continuity of a particulate phase dispersed in an opaque matrix. The first section reviews the parameters measurable on a polished cross section by auantitative metallography, such as the contact area and under certain conditions, the number of contacts between particles of one phase. In the second section, an attempt is made to relate the frequency of particle contacts to the degree of continuity of a randomly embedded phase. For the purpose of this discussion, the aggregate has two constituents: the particulate phase and the matrix. The latter is considered to be homogeneous. The term "particle" is used with the meaning of "grain", i.e., a minute unit of matter which is usually a single crystal of a readily distinguishable substance within the confines of a simply connected boundary. While many of the concepts which are used here to describe the structural variables characterizing the microstructure of phase mixtures are qualitative and ill-defined, they are presented with the intent of stimulating further work of a more general and rigorous nature. I) PARTICLE CONTACT, CONTIGUITY, AND MEAN FREE PATH 1) Measurement of Contiguity. The fraction of the total internal surface of a phase a shared with particles of that same phase in a two-phase mixture of and $ is indicated by the contiguity ratio:3 whereis the area of the interface between o particles, and Sap is the area of the interface between a particles and matrix P, per unit volume of mixture. The contiguity ratio ranges from 0 to 1 as the distribution of the a phase changes from a completely dispersed to a completely agglomerated structure. The interfacial areas may be obtained from simple intercept measurements on a random plane, after Smith and Guttman where and N are the numbers of intercepts between a random line of unit length on a plane of polish and the interparticle and interphase interfaces, respectively. The equations are valid for any distribution of particle sizes and shapes.

Jan 1, 1967

By A. S. Michaels, M. C. Porter, A. Stancell

Previous laboratory studies have demonstrated that the injection of small quantities of reverse wetting agents during water displacement can increase oil recovery from unconsolidated porous media.9 In the present investigation, an attempt has been made to determine more fully the effects of reverse wetting treatments and to clarify the mechanism by which increased oil recovery is effected. Water-oil displacements were performed in beds of 140-200 mesh silica sand. Hexylamine slugs (injected after 0.25 pore volume of water throughput), when adequate in size and concentration, were effective in promoting additional oil recovery. Their effectiveness increased with the quantity of amine injected. However, slugs of sufficient size and concentration to stimulate oil production at water flow rates of 34 ft/day did not do so at 4 ft/day. Visual studies in a glass grid micromodel have shown that the stimulation of oil production, via ayueous hexylamine, is a result of transient changes in the oil wettability of the pore walls. if the amine slug is of sufficient size and concentration to induce significant changes in the adhesion-tension, large continuous oil masses will be formed. if the superficial water velocity is high enough to result in rapid desorption of the amine, a favorable "wettobility gradient" may be established across the masses; under such conditions, high oil mobility is observed, and increased oil recovery results. INTRODUCTION It is generally agreed that the efficiency of oil displacement by water in porous media is limited in part by capillary forces which cause the retention of isolated masses of oil — resulting in the so-called "irreducible minimum oil saturation". Recent estimates10 indicate that there are about 220 billion bbl of petroleum in United States reservoirs which are not economically recoverable with present techniques (such as water flooding). This amounts to almost five times the known recoverable reserves. It has been recognized for some time that a suitable alteration in the water-oil interfacial tension and/or the contact angle, as measured between the water-oil interface and the solid surface, should result in better displacement efficiency. Surface active agents can be used as interfacial tension depressants to accomplish this objective,1,2,7 but unfortunately, the additional oil recovery is seldom commensurate with the treatment cost. In contrast to interfacial tension depressants, the effect of contact angle alterations on water-oil displacements has received relatively little attention in the literature. It is known that the wettability affects the displacement process.3,4,11 Displacements in water-wet systems generally result in lower residual oil saturations than those in oil-wet systems. The effect of "'transient" wettability alterations concurrent with the displacement process have been investigated by Wagner, Leach and coworkers,4,11 wherein it has been demonstrated that the establishment of water-wet conditions during water flooding of oil-wet, oil-saturated porous media is accompanied by significant increase in oil displacement efficiency. Michaels and Timminss studied the effects of transient contact angle alterations resulting from chromatographic transport of reverse wetting agents through unconsolidated sand. It was demonstrated that chromatographic transport of short-chain (C4 through C8) primary aliphatic amines can improve oil recovery and that the recovery increases with the quantity of amine injected (i.e., with either the amine concentration or the volume of the slug injected). Circumstantial evidence indicated that the increased displacement efficiency resulted primarily from transient changes in wettability of the porous medium. In the Present investigation. additional information has been obtained on the effects of reverse wetting treatments and the mechanism by which increased oil recovery is accomplished. Hexylamine slugs of varying size and concentration were chromato-

Jan 1, 1965

By J. G. Mravec

The SO-called gas-tube method as developed by Hare, Peterson and Soler for determining the type and content of gases in molten steel is particularly adapted for determining the hydrogen content in molten steel. The development of this method has been quite completely discussed in a paper published by these co-workers in 1937.' The purpose of this paper, therefore, is to familiarize with this method those who arc not well acquainted with it. The principle of the gas-tube method is as fol1ows: One end of an evacuated gas tube is sealed with a very thin copper disk. when this end of the tube is immersed in a test spoonful of molten steel, the copper disk melts almost immediately, allowing a portion of the steel to be drawn up into the evacuated space. Any dissolved gases, and those produced by reactions between the components of the steel during freezing, are liberated into the unfilled portion of the sampling tube. A blob of steel that forms on the immersed end of the tube after the sample is drawn up seals up the end, making it airtight again. The evolved gases are subsequently drawn out of the gas tube through a suitable valve and analyzed by means of an Orsat apparatus. The volume of the sampling tube is sufficiently large so that a pressure considerably below atmospheric is produced after the gas evolution. The low pressure is necessary to effect a nearly complete removal of gases from the steel. Construction oF Sampling Tube The sampling gas-tube apparatus is illustrated in Fig. I. Seamless S.A.E. tubing used for section A is first cut into 7-ft. lengths. Through cxperiencc it was found necessary to use two sizes of tubing for this part, "is-in. and 3/4-in., respectively. The smaller tubing is generally used on the hotter or lower carbon steels. If the inside wall of the tube A is coated with grease or oil, it should be burned out before being machined as follows: One end is machined on the inside diameter to a depth of 34 in., so as to form a seat for a 7/8-in copper disk, which is stamped out from 0.005 to 0.007-in. thick copper sheet. The other end is machined on the outside diameter to a diameter of 1 5/16 in., to take a small reservoir or trap member I?. About 4 in. below the same end, a 1/2-in. hole is drilled to receive the 1/2-in. copper tubing leading to the large reservoir C. The inside of tube A is then thoroughly cleaned with a round wire brush, such as is generally used to clean out shotgun barrels. It is very important that the surface be absolutely free of rust or any nonmetallic coating. Next, the thin copper disk is soldered in place with low-melting silver solder.

Jan 1, 1945

By D. R. Packard, J. D. Verhoeven

The resistivity us atom fraction relationships for dilute solutions of cadmium, mercury, and tin in molten sodium have been determined. With these data and the resistivity capillary-reservoir technique, the electro-transport mobilities, effective valences, and the diflusion coefficients of the three solutes have been determined. The mobilities are found to be higher than in other molten alloys by a factor of around 20. The results are compared to the Mmgelsdorf model for electrotrmtsport. The high values found for the mobility to diffusion coefficient ratio indicate that small quantities of the alkali metals should be susceptible to purification from many solutes by means of electrotransport. PASSAGE of a direct electric current through a liquid metal containing a solute will usually cause a relative motion between the solute and solvent atoms of the alloy. This electrotransport phenomenon may be described experimentally in terms of the mobility of the solute atoms, i.e., the drift velocity of the solute relative to the solvent per unit electric field. In dilute solutions of liquid alloys this relative mobility becomes a measure of the velocity of the solute with respect to the observer since the motion of the solvent is negligible. The mobility is a significant parameter in evaluating the potential usefulness of electrotransport for such things as purification or solute control upon solidification. Prior to around 1958, quantitative data for the mobility of solutes in liquid metals were restricted to some solutes in liquid mercury. Since that time ad- ditional data have been reported for the mobility of solutes in liquid mercury, bismuth, tin, and lead, as shown in Table I. In 1963 Drakin et al.11 reported some values of a transport number for mercury and thallium in molten sodium and potassium. When these values were converted to mobilities, it was found that the mobilities were higher than any of the previously reported values by a factor of around 20, as shown in Table I. Drakin's experimental technique did not eliminate the presence of back-diffusion and consequently his data were expected to be lower than the true values. The purpose of the present investigation was to determine the mobility of a number of solutes in molten sodium with an experimental technique which eliminates back-diffusion errors. EXPERIMENTAL The technique used to determine the mobility was a resistivity capillary-reservoir technique which had previously been used with a high degree of precision on Sn-Bi alloys.4 This technique consists of dipping the vertical Pyrex capillary cell shown in Fig. 1 into a molten bath of alloy while the bath and capillary are under vacuum. The capillary is then filled by intro-

Jan 1, 1969

By R. W. Gurry

THERMODYNAMIC calculations indicate that boron is a better deoxidizer than silicon but probably is not quite as effective as aluminum. Boron should, therefore, be readily oxidized out of the open-hearth bath, which implies that it is not recovered in significant concentration from any scrap charged; also that, if added in the ladle, it tends to oxidize out during teeming unless protected by the presence of a. better deoxidizing agent. These conclusions do not apply to liquid cast iron, in which the oxygen content is much lower than in liquid steel. The possibility of conserving certain strategic alloying elements widely used in steelmaking, notably manganeie, chromium and molybdenum, by the use of boron, which in small concentration appears to be extraordinarily effective in promoting hardenability, raises a question as to what extent any boron present in the scrap charged into the open hearth is oxidized out during melting and subsequent refining. This question is significant because the optimum concentration of boron in the finished steel, which is fairly critical, would be very difficult to attain if the boron in the charge were largely retained in the metal. Moreover, unless boron is substantially eliminated in the open-hearth process its use on a large scale would eventually make it impossible to produce boron-free steel except by restricting the charge to virgin material. There is at present, unfortunately, virtually no satisfactory direct evidence to provide an answer to this question; but there are indications from practice that boron is oxidized out in the open hearth in the production of medium or low-carbon steel, although it may be retained if the carbon content remains fairly high; that is, if the oxygen is kept fairly low. In the absence of direct data, it is necessary to rely upon the indications of indirect evidence, the best approach now available being a thermodynamic calculation of the deoxidizing power of boron in liquid steel by the general method used so successfully by Chipman1 in his study of the reactions in the open-hearth process. The thermal data for boron, upon which such a calculation must be based, are reasonably satisfactory; the only quantities not directly determined are the entropy of melting of boron, the activity coefficient of boron in liquid steel, and the activity coefficient of B203 in an open-hearth slag; but these values may be estimated with ample accuracy. The results of this calculation, which is presented later, are given in Table I, together with corresponding data for other deoxidizing elements. This table shows the calculated residual content of oxygen in equilibrium with different residual concentrations of the deoxidizer in the metal;

Jan 1, 1943

By David H. Browne

One of the most difficult problems in the chemistry of iron-ore, and one, the solution of which, so far as I am aware, has never been attempted, is the distribution, throughout a given vein, of Bessemer ore, and its relation to the formation of the deposit. In those hematite-mines in which both Bessemer and non-Bessemer ore occur, the sorting of the ore as it lies in the deposit becomes a problem of much economic as well as scientific interest. It would seem, from a superficial examination. or, indeed, from any examination not conducted for this especial purpose, as if high- and low-phosphorus ores were mixed in inexplicable confusion ; and a mining-chemist is very apt to fall into a system of adventitious analyses, taking first-class ore wherever he can find it, and overlooking its relation to the formation and position of the vein. I hope that a few notes which I present on this subject may be found worthy of consideration, as throwing a new light upon this obscure topic. During the last three years, while acting as chemist of the Lumberman's Mining Co., I have made some 3000 analyses of iron-ore from the Ludington mine at Iron Mountain, Michigan. These analyses were necessary in order to separate Bessemer and non-Bessemer ore which occurred intermixed in the deposit. During the last year, I attempted in several ways to find some reason or method in the distribution of phosphorus, and have finally become cognizant of the arrangement herein outlined. I have been obliged to confine my attention to our new mine, and, in that, to that portion wherein

Jan 1, 1889

By R. M. Scafe

Although hydrogen has been intensively studied in its relation to steel quality, the methods of sampling and determinations are still open to question. It is true that various procedures have been proposed but actually there has not been sufficient agreement to establish a common base from which to work. As a result, it is difficult, to say the least, to correlate the reported results of some of the investigators in this field. The present symposium, premised on methods rather than effects, should prove of considerable value. For the purpose of this discussion two methods of sampling and analysis will be considered. First, sampling of molten steel in the ingot mold by use of an evacuated tube and cylinder using conventional methods of analysis for the gases collected; second, analysis by vacuum extraction involving the use of heating equipment and the determination of the amount of hydrogen evolved from solid steel samples by measurement at reduced pressures. Both methods have been used at Duquesne Steel Works and it is believed that either may be used with considerable benefit if the limitations of each method are recognized. Evacuated Tube and Cylinder Sampling devices for gases in molten steel suggested by various investigators range from very cumbersome and complicated devices to the relatively simple evacuated tube and cylinder used by Soler for deter- mining the CO content of the bath. This latter device was adopted (Fig. I) and modified to meet conditions at Duquesne Works. The principal modifications were in placing the cylinder at the side of the tube and the use of a sleeve on the immersion end of the tube. The first modification was made so that the cylinder could be readily detached and taken to the laboratory; the second, because of the difficulty encountered in obtaining an airtight seal after sampling and because of our practice of re-using the tube. Rigid control of the method of sampling and of the handling of the sample according to plan are of primary importance in hydrogen determinations. This applies to both the sampling of molten steel and the determination of the hydrogen content of cold steel samples. Except for a few preliminary samples taken from spoons, all work on molten steels using the evacuated tube was confined to the sampling and analysis of molten steel during the pour. As mentioned, uniformity of sampling was a basic consideration. As a result, every effort was made to follow definite sampling techniques and procedures. These included control of the depth below the surface from which the sample was taken, the timing between the shutoff and taking of the sample, as well as maintenance and care of the equipment. The distance below the surface at which the sample was taken was readily controlled bv means of a crosspiece and centering device attached to the tube. The steel was poured into the mold to the hot-top junction, the tube was then lowered into the 75

Jan 1, 1945

By Clarence P. Linville

In an article published in the Iron Trade Review,' I gave a convenient arrangement for the installation of wet and dry bulb thermometers for use in making moisture determinations in the air being blown into a blast furnace, and also gave a chart for use in obtaining moisture values from the thermometer readings. The data from which this chart was prepared were obtained from the tables in use by the U. S. Weather Bureau.2 The work of Carrier3 has shown that these tables are somewhat in error. He has recalculated the values for moisture as referred to wet and dry bulb thermometer readings, and he has prepared a psychrometric chart from the values thus obtained. This work has placed the subject of psychrometry upon a correct scientific basis. I think it is proper that we should recognize the importance of his work and give him credit for one of the most interesting and valuable researches that have been published in recent years. Blast-furnace men are not ready to use, as he suggests14 a value expressed in grains of water accompanying a pound of dry air. However convenient this may be for heating and ventilating work and other engineering problems, there are several reasons for preferring the use of a value expressed in grains of water in a cubic foot of mixed air and water vapor, in connection with combustion phenomena and the effects of moisture on blast-furnace operation. Previous papers presented to the Institute have used such values and we have

Jan 1, 1914

By John H. Melvin

THE Omaha District, Corps of Engineers, has been doing subsurface exploration work for a number of years, both by contract and with its own forces. Certain practices and procedures concerning the recovery of large diameter cores have been developed which will be described in this paper. GEOLOGY Most of the drilling to date has been in connection with structures on the main stem of the Missouri River above Sioux City, Iowa. A wide variety of subsurface conditions has been encountered. The bedrock formations appear in regular order from the oldest to the youngest, traveling upstream; or in other words, the general regional dip is to the northwest. The oldest formation is the Carlile shale, a compaction or noncemented waxy shale of Cretaceous age. Because of its uncemented, soft nature this shale has a tendency to grind or wash away when drilled. It also has a tendency to rebound or expand when the overlying pressures are removed. A 25-ft bed of sharp, friable sandstone called the Codell member is present near the top of the Carlile shale. This member is a cemented sediment, but in drilling, many of the sand grains are broken loose and exert extensive abrasive action on the core barrel and bit. Above the Carlile shale is the Niobrara chalk, a soft calcareous deposit with shaly horizons and some thin beds of bentonitic clay. The average thickness of this deposit is about 145 ft. It is soft enough to be sawed or bored with ordinary woodworking tools, yet is compact enough to be used as building block. The Pierre shale, the formation above the Niobrara chalk, is over 800 ft in thickness and is the most widespread material in the area. It is a dark colored, compaction shale containing numerous thin bentonitic clay seams and at certain horizons, hard manganese concretions. The shale has numerous faults and in addition, along the valley walls, has undergone considerable - slumping. Joints, fault planes and slickensided surfaces are common features encountered in drilling and add to the difficulties of high core recovery. East of the Missouri River the bedrock is generally covered with from 100 to 200 ft of glacial till, composed of clays, silts, sands, gravels and boulders. The valley itself is filled with alluvial deposits, mostly of the sand and gravel sizes, and contains a buried preglacial or interglacial channel over 100 ft in depth. The overburden deposits require sampling in connection with engineering studies and must also be cased before the underlying bedrock can be cored. The diameter of the required overburden samples can thus have an indirect effect on the size of core recovered from the bedrock. West of the river, which in most cases is the western boundary of glaciation,

Jan 1, 1947

By James A. Barr

Phosphate rock is a natural rock containing one or more phosphate minerals usually calcium phosphate, of sufficient purity and quantity to permit its use, either directly or after beneficiation in the manufacture of commercial products.1 The principal minerals in phosphate rock have the apatite structure which may be represented by the type formula: Ca10(X2) (PO4)6 where X represents the hydroxyl group (OH), chlorine or fluorine, either singly or collectively. The calcium may be partly replaced by sodium, magnesium, and other positive ions such as manganese, strontium, lead, uranium, cerium, yttrium and other rare earths. The PO4 radical may be partly replaced by small quantities of UO4, AsO4, SiO4, CO3, SO4, or Vo4. A typical commercial rock is usually a calcium phosphate containing 3 to 4 pct fluorine, the major impurities being limonite or other iron oxides, clay, aluminum phosphates and silica as quartz sand. A little vanadium is present in most of the domestic rock deposits (except the Tennessee Brown Rock), according to Jacob, Hill, Marshall and Reynolds! A little uranium occurs in the Florida leached zone, as will be brought out later. The chemical analyses are reported as P205, or tricalcium phosphate Ca3(PO4)2, the latter often designated by the trade name BPL (bone phosphate of lime). Commercial analyses usually report iron and alumina as oxides, lime as CaO and silica or insoluble. Colony3 examined many samples of apatite, staffelite, dahlite and American phosphorites and concluded that all have identical X-ray diffraction patterns. The phosphates in the phosphate rock have very minute crystalline structures. The mineral apatite Ca3(F.Cl) (PO4) 3 is the principal primary source of the element phosphorus, and occurs widely distributed in igneous rocks but rarely in a minable mass. Only about 12 pct of the world production of phosphate rock comes from primary apatites; the remainder is derived from secondary phosphorites. These phosphorites have been formed by the alteration of sediments by solutions containing phosphoric acid. Such solutions have come from the weathering or leaching of igneous rock containing apatite, bone deposits of prehistoric animals, marine life or guano deposits. These phosphorites are mostly alterations of phosphatic limestones. The sedimentary phosphate deposits are of marine origin and may have been enriched by subsequent solution of the more soluble calcium carbonate by waters containing carbon dioxide, by physical concentration by wave action, and by redeposition of the dissolved phosphate ions. Uses of Phosphate Phosphorus is the spark of life and is the structure builder and one of the main elements of plant food (fertilizer). Without phosphorus, life cannot exist. A "complete" plant food[t] in addition to phosphorus compounds contains potash, which acts as a catalyst to convert nutrients to useful forms, nitrogen to supply the growth element and many minor elements. The cycle of supply of phosphorus is from the apatite to solution and soil, absorption of plant life, decay and return to the soil or by animal life feeding on the plants. With insufficient supply of phosphorus in vegetation, life is not prolific. If crops are removed from

Jan 1, 1960

By Nicholas J. Grant, Bill C. Giessen

The phase diagram Ta-Ni has been treated repeatedly; investigations up to 1958 are summed up in Ref. 1. Since then, an equilibrium diagram has been presented by Kornilov and Pylaeva.2 They found the following intermediate phases: Ta2N; (CuA12 type),3 "TaNi" (p phase, Mo8Co7 type), TaNiz, and TaNi3 (Ticus type).5 Of these, the crystal structure of TaNin remained unknown, and no further literature reference was found. According to Kornilov and pylaeva,&apos; TaNil melts peri-tectically at 1420°C. A 5-g alloy of Ta + 66.7 at. pct Ni was prepared by inert-gas arc melting using 99.95 pct Ta rod (NRC-MG) and 99.9 pct Ni shot (Fisher). The weight loss after three melts was <2 mg; a microscopically homogeneous ingot resulted. As shown in Ref. 6, no oxygen or impurity pickup needed to be considered under these conditions. Specimens were annealed for 15 hr at 1350°C, 15 hr at 1205oC, and 15 hr at 875°C with subsequent powdering and stress relief for 10 min at 1350°C, 15 min at 1205oC, and 1 hr at 875oC, respectively. Micrographs and X-ray analysis (114.6 mm Norelco camera, filtered CuK, radiation) showed homogeneous one-phase alloys in the as-cast state and at all three temperatures, all having the same powder pattern except for broad lines in the as-cast state. From this it is concluded that either TaNi, melts congruently or its melting behavior is a transition between the eutectic and peritectic cases. Since it was found that very slight surface contamination on stress relieving can considerably alter the structure of similar phases (e.g.,TaPt3),7 patterns before and after stress relief were also compared; they were identical except for line broadening in the non-stressrelieved condition, and two faint impurity lines in the stress-relieved samples. The powder pattern is presented in Table I. All lines were accounted for by indexing with a tetragonal lattice, 0Yh- I4/mmm , with a, = 3.154 ± 0.001A, co = 7.905 * 0.002i and c/a = 2.506. The atomic positions are: 1000; 1/2, 1/2, 1/2] + 2Ta(a): 000; + 4Ni(e): *(002); z = 0.333 * 0.002 This proves TaNi2 to be a representative of the MoSiz (Cllb) type. The variable parameter was determined by grouping the visually estimated intensi- ties according to their 2 indices, plotting their F values, and varying z for best fit, which was obtained at z = 0.333= 1/3. Since absorption was not considered, only the relative intensities with similar 28 can be expected to agree. The interatomic distances are presented in Table 11; the standard error is *o.o2A, resulting chiefly from the uncertainty in z. These distances indicate a coordination number 10 for both kinds of atoms and show that the pseudohexagonal layers along (110) are rather un-distorted. The mean atomic volume of 13.1A3 is close to the Vegard&apos;s law value of 13.3A3, showing

Jan 1, 1964

By C. F. Knutson, Martin Felsenthal, J. D. Lung, J. D. Sudbury

This paper has been written to summarize the laboratory and field studies leading to injection of Pacific Ocean water into the Third Grubb formation. Laboratory tests for studying the permeabilities of cores to Pacific Ocean water are described. Resu1ts of these tests showed that the water could be successfully injected if it is chertzically stable, sterile, and properly filtered. Clay swelling was shown to be a comparatively minor factor in permeability reduction. Studies leading to development of an economical system for properly conditioning the ocean water are discussed. It was necessary to control pH, calcium carbonate deposition, bacterial growth, iron solubility. oxygen, and suspended .solids. A relatively simple system combining the use of sulifur dioxide, a quaternary rlmmonium chloride, and filtration was shown to adeqrrately control all these factors. This combination has not previozrsly been used as a water treating technique. Evaluation tests of the water conditioning system prior to injection are described, and results of such tests are presented. Control measures needed to insure a continusously adequate water treatment are reviewed. INTRODUCTION The utilization of sea water for waterflooding has only recently been attempted. Knowledge of treating requirements has been limited, and in most cases no water treating has been done. Prior to the initiation of the Third Grubb zone pilot water flood at Ventura, Calif.,1,2 extensive laboratory research was done in an effort to define the treatment necessary to provide a suitable injection fluid. Close coordination and cooperation between field and research personnel were found to be the foremost requisites in developing the most economical and practical method for treating ocean water. LABORATORY STUDIES Plugging Tendencies of Untreated Ocean Water A program of laboratory studies was initiated for the purpose of evaluating whether ocean water could be injected into the formation for prolonged periods of time without causing plugging of the pore spaces of the formation. Because of the fairly low permeability of the formation (averaging about 40 md), it was realized from the outset that a water of exceptionally high quality was needed. Ocean water used in the laboratory studies was carefully filtered through ultrafine fritted glass filters, having nominal maximum pore sizes of 1.4 microns. Permeability tests were then performed on representative core material from the formation. It soon became apparent in these tests that filtration alone was not a sufficient treatment for the ocean water. Prolonged injection of the filtered water caused rapid plugging of the core samples. The permeability decline of a typical sample is illustrated by Curve A in Fig. 1. The several factors which can contribute to this plugging tendency are briefly reviewed below: Interaction with Formation Clays An evaluation of clay swelling effects on liquid permeability was made using core samples from the Grubb formation. An oil was chosen for determining the reference liquid permeability because it would not tend to react with any clays that might be present in the formation. The samples were then extracted, dried, and resat-urated with either treated ocean water, formation water, or fresh water. Permeabilities to the various waters were then determined. Results of this test series are summarized in Fig. 7. The difference between the oil permeability and water

Jan 1, 1957

THE good and lofty men of intelligence are constantly discoverers of many beautiful things, because of their kindness or because they are driven by necessity. Either they shorten the method of making them after they have seen them, or they think how they can be increased in power or how they can be used for various effects in addition to the one intended by the inventor. Certainly all the effects described to you in this Tenth Book derive from gunpowder. When so many proper- ties and so much strength were observed in this, it was thought that by enclosing it in some strong thing that had the power to resist it, gunpowder would produce a marvelous effect. And thus they made a tube of bronze or iron [160v] which they closed with a wooden plug. They applied fire, and when they saw how forcefully this plug issued they thought of making one that would come out and strike in order to destroy things. They made an instrument of bronze or of iron and put some powder and a round stone inside, and called it a spingard. Developing then from this,

Jan 1, 1942

Tars Committee is the result of a desire of the authorities in charge of the publications of the four national engineering societies to co-operate in this matter. The members of the Committee are the following: Charles WarreN Hunt, Secretary of the American Society of Civil Engineers. D. S. Jacobus, Vice-President of the American Society of Mechanical Engineers. Joseph Struthers, Assistant Editor of the American Institute of Mining Engineers. CaRy T. Hutchinson, Chairman of The Editing Committee of the American Institute of Electrical Engineers. This Committee has held several meetings; it seemed advisable, at the outset, to limit its discussions closely to the general subject of abbreviations. Further, it seemed best to formulate a few general rules to be followed in making abbreviations, rather than to compile a list of forms to be recommended. The Committee decided to limit the subject more narrowly by considering only abbreviations to be used in the text, or general reading-matter, arid not those to be used in special matter,

Jan 1, 1905

By G. C. Wallick, W. R. Foster, J. G. Savins

Inasmuch as the differentiation and integration methods represent different modes of rheological analyses, a dual scheme of analysis using both methods should lead to a generalized method of data analysis. A dual differentiation-integmtion method of analysis is applied here to the Poiseuille flow of a variety of ideal Generalized Newtonian and viscoplastic models. Using machine-processing techniques, the result is a spectrum of response patterns which are expressed in terms of certain derivative functions. It is shown that these characteristic functions form the basis of a highly-sensitive analytic technique for optimizing the selection of the most appropriate functional relationship between shear rate and shearing stress. INTRODUCTION In the first paper of this series, Savins, Wallick and Foster1 presented an historical review of the salient features of the differentiation method of rheological analysis in Poiseuille flow, and also indicated how the method could be applied to problems involving plane Poiseuille flow. It was shown that the differentiation and integration methods, although basically not incompatible, do represent different modes of rheological analysis. This suggests that valuable background information regarding the probable response characteristics of real data obtained with the differentiation method can be obtained from an integration method-differentiation method analysis of the response of a variety of ideal rheological models. The present paper describes how this dual method of analysis has been applied to suites of idealized models representing a wide variety of Generalized Newtonian and viscoplastic behavior which have received attention at various places in the literature.

By W. C. Ellis

IN an ingot of germanium solidified progressively from the bottom by a method&apos; devised by J. H. Scaff and H. C. Theuerer, examination discloses ex- IH. C. Torrey and C. A. Whitmer, Crystal Rectifiers. p. 364. 1948. New York. McGraw-Hill Pub. Co. tensive twin relationships. A slice taken about midway in a cylindrical ingot approximately 3/4 in. in diameter and 1 1/2 in. in length, after etching and polishing to delineate different orientations, is shown in fig. la. The orientations of the regions designated with letters were determined by Laue X-ray back-reflection methods and plotted on stereograms. The orientation relationships of the designated components were determined by comparing the values for the nine angles between the three respective cube poles of each orientation with the values calculated in a formal treatment of octahedral multiple twinning in cubic crystals. Germanium, diamond cubic in structure, has the octahedral twinning habit. I am indebted to K. H. Storks for the calculation of the angular relationships of cube poles in octahedral twinning to four orders. The set of values for the nine angles is distinctive of the order of twinning. Confirmation for a multiple twin relationship is obtained from the determined indices of the mirror planes. These exist for all orders of twinning through the third and for some of the fourth." If the orientations are not those for twinning, then the nine angles for the cube poles do not correspond in value and distribution to those formally calculated. Since all nine angles must correspond in values and distribution of values to the calculated ones, the Laue method with a precision of one or two degrees is adequate to establish or deny with confidence the existence of multiple twins. Regions of the same orientation can also frequently be identified by the optical reflections. For example, the narrow twin bands in A at 2: 00 o&apos;clock have orientation B1. The interesting twin relationships shown schematically in fig. lb were found for the section in fig. la. Most of this slice was made up of orientation, A, appearing in widely separated regions. Of the four possible first order twins of A, three were present in this slice and are designated by B with subscripts. Four second order twins of A are designated by C with subscripts. It is worth emphasizing that two of these, C, and C,, are second orders of A through the first order missing in this section. Two regions, designated by D with subscripts are third order twins of A. D2 is a sixth order twin of D,. All orientations found were ascribable to multiple twinning, as if the orientations in this section originated earlier in solidification from a single nucleus. The presence of extensive multiple twinning to- gether with the absence of other orientations appears to be a characteristic result in many instances of solidification of germanium. Fertile conditions for twinning probably exist in the array of atoms in the diamond cubic structure. The high order twins in the section shown, it is reasonable to presume, are the result of progressive octahedral twinning through several generations in the material freezing earlier. Some of these generations do not appear in this section, it is suggested, because their orientations with respect to the growth direction were unfavorable for survival. The extensive twinning is probably promoted during solidification by constraint imposed by volume increase, and to an irregular growth front. Twinning may also be due, in part, to the attempt of the solidifying region to attain the orientation most favorable to the growth direction (maximum thermal gradient). The nucleus for a twinned orientation could have its origin in a "stacking fault" on the close-packed octahedral plane. Further work is being done in which the course of twinning throughout an ingot is being studied. The results appear to be important in the general theory of solidification.

Jan 1, 1951

By G. Bruggeman, K. G. Kreider

Grain boundary dij]usion coefficienls were measured in tungsten between 1400° and 2200° C and can be expressed by the equation sq cm per sec This activation energy confirms some eavlier estimates made .from tungsten sintering experiments. Grain boundary diffusion was found to occur in sub-bozrndavies having -misorientations of less than 10 deg. The actiuation energy for this subboundavy diffusion is equal to that for dijjusion in incoherent grain boundaries with in the limits of error. This is shown to be consistent with the dislocation model of Low-angle boundaries wheve diffusion occlcvs along- the dislocation &apos;YPipes" comprising -tile boundary. RECENT investigations of the sintering of tungsten powders all report activation energies which are considerably less than the activation energy for tungsten volume diffusion. Kothari&apos; reports a value of 100 * 5 kcal per mole, Hayden and Brophy&apos; obtained 90 kcal per mole, and Vasilos and smith3 found 110.7 kcal per mole from their sintering studies. Since most determinations of the activation energy for volume diffu-sion4-&apos; fall between 120 and 160 kcal per mole (the true value seems most likely to be nearer 150 kcal per mole), the conclusion is drawn that the mass transport leading to densification during sintering is accomplished by grain boundary diffusion. This interpretation is consistent with various diffusion models of the sintering process. 10-12 Vasilos and Smith calculate diffusion coefficients from their data which fit the equation D * 1.36 x 10* exp(-llO,700/HD However, no direct measurements of tungsten grain boundary diffusion have been made. Furthermore, considerable disagreement exists between the directly measured values of tungsten volume diffusion.&apos;-&apos; In order to corroborate the inferred results of the sintering experiments concerning grain boundary diffusion and to provide accurate diffusion data essential to the analysis of the kinetics of creep, oxidation, precipitation, and so forth, the present work was undertaken to measure self-diffusion in single-crystal and polycrystalline tungsten between 1400" and 2200°C. It is within this temperature range that tungsten sintering is done, the re crystallization of tungsten occurs, and the widest application of tungsten as a high-temperature material will probably be made. EXPERIMENTAL PROCEDURE Radioactive WlE5 was produced by irradiating tungstic acid in a neutron flux of 1.2 x 1012 neutrons per sq cm per sec for 36 hr. A 2-week waiting period was allowed for the decay of w"~ also produced by the irradiation. (w"~ has a half-life of 24 hr.) The half-life of the remaining isotope was determined to be 75 days confirming the presence of w lE5 and the absence of any undesired radionuclide. Specimens 4 in. in diam and $ in. thick were cut from polycrystalline swaged tungsten rods (recrystal-lized) and from Linde single-crystal rods. Chemical analyses of these materials appear in Table I. Actually upon closer examination, the single-crystal specimens were found to consist of several subgrains separated primarily by tilt boundaries in which the misor-ientation ranged from 3 to 10 deg. Thus, it was possible to measure boundary diffusion coefficients in these low-angle subboundaries as well as in the incoherent boundaries of the polycrystalline specimens. The two faces of each specimen were ground flat and parallel within 0.0001 in. The radioactive tungstic acid was dissolved in concentrated ammonium hydroxide, placed on the ground flat of the specimen, and evaporated to dryness. The oxide was then reduced in hydrogen at 1000°C resulting in a layer of wlE5 approximately 1 p thick. The diffusion anneals were performed in vacuum in a tantalum resistance furnace. Time at temperature ranged from 10 hr at 1400°C to 2 hr at 2200°C. The penetration profile was determined by measuring the residual activity after successive removal of surface layers by grinding on metallographic polishing paper. Extreme care was exercised to insure that sections were always taken normal to the diffusion direction; this was verified repeatedly by checking that front and back surfaces of the specimen remained parallel. The activity was measured with an end-window Geiger-Mueller counter. The sides and edges of the specimen were well-shielded to eliminate possible effects due to surface diffusion. The weight of the

Jan 1, 1968