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By W. Jolley

Decarburized iron and Fe-3.28 pct Ni alloys were impact and tension tested in the temperature range of ambient to 4°K. It was found that alloying with nickel improves the fracture properties of the ferrite matrix. The improvement in toughness of iron alloyed with nickel is attributed to the effect of the nickel addition on the temperature and strain rate dependence of the yield stress as well as on slip behavior. The Fe-Ni alloy exhibits wavy slip when strained at temperatures down to at least 50°K. This behavior contrasts with that of the unalloyed iron where a change It is a generally accepted fact that of the common alloying elements of steel only nickel and manganese improve both the room-temperature yield strength and the notch impact properties. It has been argued for a number of years that manganese refines the ferrite grain size, the pearlite spacing, and the grain boundary carbides in medium- and low-carbon steels and thereby increases resistance to brittle fracture.''' This hypothesis recently was confirmed for a 0.04 pct C iron containing manganese, but at the same time from wavy to planar slip occurs at about 120°K. The observed lower temperature and strain rate dependence of the lower yield stress in the Fe-Ni alloy as compared to the unalloyed iron may be attributed to this difference in slip behavior. In contrast to suggestions published previously, transmission electron microscopy showed that the uniform dislocation distributions and the lack of dislocation tangles which are produced by low-temperature straining of bcc materials cannot be attributed to the absence of cross slip at these temperatures. no increase in notch toughness was observed in a decarburized Fe-Mn alloy.3 It thus appears that manganese only increases the toughness of Fe-Mn-C alloys by refining grain boundary carbides and has no toughening effect in carbon-free iron. On the other hand, the mechanism whereby nickel improves toughness has not been established. Hodge et a1.4 have clearly shown that a 3.28 pct Ni addition lowers the impact transition temperature of 0.02 pct C steel approximately 35°C when the grain size is maintained constant. Recently, Wullaert and Tetelman6 stated that nickel refined the grain boundary carbides of an Fe-C alloy and consequently increased the toughness. They also observed the previously reporteda-'

Jan 1, 1969

By H. B. Smith, B. Egeberg

Britannia metal is a white alloy consisting primarily of tin and antimony, the tin greatly predominating. The alloy usually contains a small amount of copper and occasionally very small amounts of one or two other metals, such as bismuth, zinc, and lead. It is capable of being cold-rolled, it takes a high polish, and it is fairly noncorrosive; properties which make it a popular metal for many household and traveling utensils. Britannia metal is similar in many respects to pewter and has largely replaced pewter in the arts, but it should not be confused with that alloy, because pewter is essentially a tin-lead alloy, while Britannia is a tin-antimony alloy. In view of the fact that so little has been published concerning Britannia metal, the authors feel justified in presenting the results of their investigation, particularly since the behavior of this alloy under cold rolling and heat treatment differs so greatly from that of other metals and alloys. The old craftsman, engaged in the making of ornaments or tableware, heated the cold-rolled sheet metal or his finished product to a straw color corresponding to about 375" I?., claiming to produce thereby a harder and more rigid article. The fact that possibly led him to this heating was that a reheated article or sheet made from Britannia metal has a distinct metallic ring when struck a sharp blow, whereas an unheated article or sheet has a leady, dead note. No doubt he has associated the metallic ring with a greater rigidity and strength, and justly so, as will be seen later. The approximate analysis of the metal we investigated was 91 Sn, 7 Sb, 2 Cu, and the molten metal was bottom-poured into an iron mold yielding an ingot 7 3/4 in. wide by 11 in. long and % in. thick, the casting temperature being 800" F. The ingot was cold-rolled to a sheet 0.032 in. thick, sufficiently large samples for experimental purposes being cut from the sheet at intermediate stages. The samples were all tested for hardness with scleroscope and Brine11 machine, then heated to 212" F. for 30 min., and again tested after cooling to room temperature. The same samples were heated successively at 300°, 400°, and 440" F., followed

Jan 1, 1929

By Emil Gathmann

Through wide experience at numerous mills in the United States I have found that there is a decided difference of opinion among the producers of steel as to what constitutes commercially sound steel. Some metallurgists insist upon having, for certain grades of steel, a so-called "open steel," i.e., one which contains numerous blowholes of varying sizes, and consequently but little volume of true pipe, although a central intermittent shrinkage cavity often extends well down into the ingot. Such blowholes and pipe are expected to weld up during rolling or forging, because their surfaces are not oxidized. Even if this be admitted, included slag particles and a high degree of segregation are bound to be present in the product of such ingots. Blowholes are the result of an oxidized heat, and all heats, unless made or finished in the electric furnace, are oxidized more or less. Subsequent deoxidation, or rather degasification, either in the ladle or in the mold, or in both, is necessary to reduce or prevent blowholes. As is well known, a greater yield of billets or sheets is secured from the ingot by allowing the formation of blowholes, but this is undoubtedly obtained at the expense of the quality of the product. Decided segregation of carbon, phosphorus, and sulphur, as well as small included slag particles, undoubtedly exists throughout the greater portion of all so-called open steel, and cannot be removed by cropping. The first requisite for sound, homogeneous steel ingots and blooms is therefore, in my opinion, so to treat the steel in the furnace, ladle, and mold that "piping" steel is produced. The line of demarcation between harmful and so-called "harmless" blowholes is practically impossible to define. Is it not, therefore, the better and safer practice to use means for the elimination of blowholes and correspondingly reduce the segregation and allow the formation of a well-defined shrinkage cavity or pipe at the upper end of the ingot? With the relatively cheap deoxidizers available at the present time, e.g., ferro-silicon, aluminum and titanium, there is no commercial reason why all steel should not be thoroughly degasified. A degasified steel being provided, the method of freezing or solidifying the liquid steel into an ingot, and the subsequent working into blooms and thence into various products, is of great importance in reducing the crop or scrap portion of the steel, due to segregation and pipe. How to ac-

Jan 1, 1916

By Kenneth R. Hancock

Iron oxides are unique in that they are the only significant colored mineral found in a natural state suitable for use as a pigment after it has been pulverized to pigmentary size. The current world production of iron oxide pig¬ments is estimated by the author to be between 450,000 and 550,000 tons based on 1969 data. The fact that highly colored natural deposits of iron ore are found throughout the world ac¬counts for its use in prehistoric man's artistic cave paintings. These early artists did not realize that they had established man's first paint test fence which now has some 20,000 years of exposure. In addition to abundance, constituting about 7 % of the earth's crust, iron oxides have the advantages of low cost, permanency, and are not toxic. Through the centuries, succeeding civilizations have utilized iron oxides as a major source for decoration and protection when coloring was desired. In the last century the chemical industry has improved on nature by developing a complete range of synthetic iron oxide pigments which surpass the pigments pro¬duced from natural iron ores in uniformity, color quality, and chemical purity. In the United States alone, the combined production of natural and synthetic iron oxides produced sales of over $28,000,000 in 1970 (Stipp, 1970). Nomenclature With the increasing importance of the syn¬thetic iron oxides it is necessary to make a distinction between the natural or mineral pig¬ments and the synthetic pigments. Natural pigments are those products which are derived from selected ores and should not be confused with iron ores mined for steel production. Iron ores that are mined for steel must be capable of being mined and reduced to iron on a com¬mercial basis. These ores are selected on the basis of iron content and processing economics. It is therefore unusual when iron ores for steel production are suitable for use as mineral pig¬ments. Natural pigment ore sources are se¬lected for their special physical-chemical prop¬erties and can command a premium price. Synthetic pigments, and in this instance iron oxides, are those pigments produced from basic chemicals. Through chemical synthesis pig¬mentary sized particles are produced as opposed to comminution, the major procedure common to all natural iron oxide pigments.

Jan 1, 1975

By Colin C. Harris, Nathaniel Arbiter

Flotation kinetics is the study of the variation in amount of froth overflow product with flotation time, and the quantitative identification of all rate con- trolling variables. With such variables maintained constant, the algebraic relationship between the proportion of mineral floated and flotation time is a flotation rate equation. This contains the constant values of all the rate determining variables implicit in one or more rate constants which must be evaluated from experimental data. The form or forms of the rate equation can either be deduced from assumptions or facts established about the mechanism of the process, or, more commonly, determined empirically or by analogy with similar rate process. (See pages 215 to 226 and 221 to 227.) The earliest contributions on flotation kinetics came in the mid- ~hirties,3,27,31 with interest increasing in recent years. The broad goal of these studies is the reduction of the total variability of a flotation system to equations among the individual variables, or among a lesser number of dimensionless groups.43 Although the goal is at present far from realization, its attainment will yield many practical advantages. The quantitative under- standing of the process should lead to improvements both in metallurgical results and flotation cell design. It should lead also to reliable methods for scaling-up* of laboratory and pilot plant results to full size operation without the need for expensive and time-consuming mill tests on commercial machines. Finally, this type of quantitative information will assist the automation of flotation cells and circuits as well as control by computers. Replacing present methods of control based on post-mortem assays and trial and error manipulation of reagents and cell variables by control through exact process analysis should yield higher levels of grade and recovery through reduction of the large variability of present-day results. CHEMICAL ENGINEERING ANALOGIES: Industrial flotation always involves flow of pulp through a series of stirred tanks. It thus bears formal analogy to many chemical engineering processes, the kinetics of which in flow systems has been studied for many de- cades.38,39,73,83 It will be useful to review these studies before considering flotation kinetics. Batch and continuous treatment are classified in Fig. 1. Batch operation in the true sense is unknown in flotation where concentrate is always removed

Jan 1, 1962

By Arthur Gibson

Synopsis.-A new feature in coal mining, where the coal is to be conveyed from a high to a lower elevation and the topography of the country is such as to preclude surface haulage. The distance from the mine to the tipple inn this instance is about 3,000 ft. and the difference in elevation between the terminals 321 ft., of which 225 ft. occurs in the first 1,300 ft. from the loading terminal. A mine car was designed especially for this plant consisting of two tramway buckets on one pair of trucks, the buckets being lifted from the truck, attached to the train line automatically, and conveyed to the tipple. THROUGHOUT eastern Utah, in the Book Cliff range and the Wasatch plateau, the coal-bearing measures are admirably exposed, in the bold and for the most part bare escarpments. The geology is simple, the rocks being almost flat, or at the most dipping not more than 10 per cent. The coal beds occur in a formation, or group of strata, consisting of sandstone and shale, 600 to 800 ft. thick, which has been correlated with the Mesaverde formation of the Cretaceous. Above this occurs about 2,000 ft. of alternate layers of buff-colored sandstone and shale. Below the coal lie the Colorado shales, which are estimated to be about 1,500 ft. thick, below which are the red rocks of the Jura-Trias. As a rule the coal beds all clip in a northerly direction and under the high mountain. The canyons opening out into what is known as Castle valley all cut the coal beds, and the beds rising in the direction of the valley are found frequently high up on the escarpment, often as much as 1,000 ft. above the valley. The surface features of the region have an economic bearing on the availability of the coal. The valleys and gulches in the Colorado shale extend out from the coal areas across the edge of the plain, so that it is impracticable to build transportation lines parallel with the boundaries of the field within several miles of the coal land. It will be necessary, therefore, to build branch lines up to the coal lands from points on the Denver & Rio Grande Railroad traversing Castle valley.

Jan 10, 1914

By C. R. Fulton

The idea of making permanent magnets by sintering is not a new one, but until the introduction of the iron-nickel-aluminum permanent-magnet alloys there was little need for such a process. Permanent-magnet alloys in use up to the time of this development could be forged and machined to the exact size or shape required without too much difficulty. These new Fe-Ni-A1 alloys, which have become known as Alnico in this country, soon became very popular because of their superior magnetic properties, but when they were made by casting they did have some disadvantages when compared with the older type of permanent-magnet steels. Among these disadvantages were the following: 1. It was almost essential that they be cast to size, since they could not be readily forged or machined. The material could be ground but this was quite expensive, particularly for small magnets in large quantities. 2. The material had a large grain size and was mechanically weak. 3. Close tolerances could not be held and on small magnets this meant grinding almost the entire magnet. Because of the brittle nature of the material, there was considerable loss due to chipping and cracking during these grinding operations. 4. Because of its high aluminum content, the molten alloy had a high surface tension. It was difficult to prevent loss of aluminum by oxidation during the melting operation. In view of these difficulties it is not hard to understand why a process for sintering alnico was developed, or why sintered alnico has come into such widespread use in recent years. It might be well to qualify this by saying that it has come into widespread use for small magnets weighing 2 oz. and less, of the type shown on Fig. I. In this size range, sintered alnico has been able to compete in price with cast alnico. Magnets larger in size, of the type shown on Fig. 2, can be made but they do not compare favorably in price with the cast material. An idea of the range of sizes that have been produced is given by Fig. 3, which shows a small magnet weighing 0.006 oz. and a large magnet with a steel insert weighing 4 lb., both made from sintered alnico. Magnets weighing more than 2 oz., however, should not be made from sintered

Jan 1, 1945

By Nicholas J. Grant, Noboru Komatsu

Metallographic and X-ray studies were made of oxide dispersion strengthened Cu-12 vol pet SiO2 and Cu-3.5 vol pet Al2O3 alloys following time exposures at temperatures approaching the melting. point of the matrix metal. Changes in hardness, oxide particle size and crystal structure were studied to determine the time-temperature stability of these alloys. An interpretation of the mechanism of oxide agglomeration is proposed. One of the most striking features of dispersion strengthened metal-metal oxide alloys is their stability at elevated temperatures, both with respect to recrystallization and maintenance of mechanical properties after exposure at high temperatures. A small amount of work has been done on the re-crystallization phenomenon in dispersion hardened metal-metal oxide alloys'l and several theoretical treatments have been advanced regarding the stability of these alloys by Lenel and Ansell,8 and by Grant and his co-workers.9, 10 This paper reports on metallographic and X-ray studies following various heat treatments of Cu-AI2D3 and Cu-SiO2 alloys at elevated temperatures and the effect of subsequent cold work on the recrystallizalion temperature. An interpretation of the recrystallization behavior of this type of alloy, based on the decomposition and agglomeration of oxides, is proposed. EXPERIMENTAL PROCEDURE Cast ingot bars of copper-1.59 pet Si and Cu-0.77 pet Al, 7/8 in in diam, were annealed in argon for 80 hr at 1000CC for homogenization. The homogenized rods were machined into fine chips and ball milled. Milled particles in the range minus 20 to plus 60 mesh were separated for internal oxidation. The internal oxidation was accomplished by the same method used by Preston and Grant,9 except that the oxidalion temperature for the Cu-Si alloy was 750°C, and for the Cu-A1 alloy was 800°C. These powders were then hydrogen-reduced at 450°C, compacted in a copper container, evacuated at room temperature to 0.04 µ, and sealed for extrusion. They were extruded at 1400°F (760°C) with a ram speed of 55 in. per min for an extrusion ratio of 15.6 to 1 to give a rod 0.38 in. diam by about 3 ft long.

Jan 1, 1962

US 4,134,944-Production of iron oxide ore pellets of uniform size and excellent strength. Small pieces of ore are rolled into nuclei in a first pellet-rolling circuit in the presence of a binder, the nuclei sized and hardened by sintering or cold-bonding of the binder, the nuclei rolled in additional ore to form product pellets, the pellets sized, the suitable size fraction taken as product, and undersize pellets returned to the rolling operation. P. A. Ilmoni and R. Drugge, assigned to Luossavaara-Kiirunavaara AB Jan 16, 1979. 5 pp. (264-37) Filed- 5-25-77 (800,278) Priority: Sweden, 6-2-76 (76/06,¬241). Same British 1,553,763, dated Oct 10, 1979. US 4,145,210-In the induration of pellets of iron oxide ore or iron works dust or sludge, a charge of dried pellets and 2-20% by weight of coke having a size range of from 5 to 30 mm, a drum index of more than 70, a reactivity index of less than 50, and a tumbler index of more than 50 is charged into a rotary kiln The charge is heated and passed through the rotating kiln to indurate the dried pellets without burning the coke Powder-coated coke is recovered from the kiln for reuse. Ring formation in the kiln is substantially prevented. K. Kato and K Kadota, assigned to Sumitomo Metal Industries, Ltd, and Sumitomo Heavy Industries, Ltd. Mar 20, 1979 10 pp (75-3) Filed- 2-22-77 (770,947) Priority: Japan, 2-24-76 (51/19,754) US 4,145,211-Method of cooling hot metallized iron oxide ore agglomerates from a direct reduction furnace Agglomer¬ates ranging from 3/a in to 41/2 in in cross-section and at a temperature of 1000-2000°F are formed into a moving bed while at rest relative to each other Air at ambient tempera¬ture is passed through the bed at a velocity sufficient to cool the agglomerates rapidly to a temperature no greater than about 500°F without substantial reoxidation of the metal in the agglomerates and by using air as the sole cooling gas. C A Czako, A Berzins, and M J Greaves, assigned to Arthur G McKee & Co Mar. 20, 1979 15 pp. (75-34) Filed: 7-18-77 (816,467)

Jan 1, 1980

By E. R. Stover, J. Wulff

A tentative 870°C isothermal section, the solidus equilibria, and the solubility of Tic and graphite in the nickel solid solution have been determined with arc-cast specimens. Each of the Ni-Ti intermetallics forms two-phase fields with Tic; only Ti,Ni has a measurable solubility for carbon. A quasi-binary eutectic exists between Tic: and a titanium-rich nickel solid solution; ternary eutectics occur on either side, with TiNis or with graphite. Graphite is in equilibrium with a nickel solid solution containing a ratio of Ti/C which increases below the solidus. DURING the past decade, titanium-carbide cermets containing nickel or cobalt alloy binders have been widely studied for high-temperature and wear-resistant applications. Recent work has emphasized control of the carbide grain size and distribution2's and the thermal exparision match between the phases/ The present study was initiated to determine the phase compositions during the sintering or infiltration process, and during subsequent heating. Although the effects of additives and impurities in commercial compositions are important, it was necessary to consider first the pure ternary, Ni-Ti-C. Emphasis was placed on the nickel corner, since the nickel solid solution is the continuous phase in compositions having highest strength. Early metallographic work by Zarubin and Molkov- showed that solid solubility at either end of the section Ni-Tic is small. Edwards and Raine reported that nickel dissolves between 3 and 5 wt pct Tic at 1250° C, on the basis of microstructures of annealed, vacuum-melted powder mixtures. Although the solubility of nickel in Tic has not been measured, Tic formed by the menstruum process in liuid-iron solution contains as little as 0.06 wt pct Fe. BINARY SYSTEMS The most recent determinations of the three binary systems are summarized in Fig. 1. Titanium carbide (6) is predominant among the binary phases, and it melts above the boiling point of nickel. The Ni-C binary is based on separate liquid solubility' ) and solid solubilitylo measurements. The eutectic temperature, 1328OC, is taken from the solidus determination described below. However thermal analysis data by Morrogh and williams also show eutectic arrests in this vicinity in the absence of supercooling. The Ni-Ti binary is taken from the work of Poole

Jan 1, 1960

By John H. G. Monypenny

The range of chromium content of stainless steel is, in most cases, included in the limits 11 to 14 per cent., or the middle part of the range, 9 to 16 per cent., specified by the discoverer. For some time after the steel was produced commercially, the carbon content was about 0.3 to 0.4 per cent. and occasionally higher; only rarely was material with 0.25 per cent. carbon or less produced. The reason for this is obvious from the nature of the alloys of chromium available for making such steels; as the lowest carbon content generally available was about 1 per cent., and this in conjunction with a chromium content of about 60 per cent., the production of a 12-per cent. chromium steel with less than 0.25 to 0.30 per cent. carbon was impossible. The advent, on a reasonable commercial scale, of carbonless ferrochromium has modified this condition, however, so that for the last three years stainless material containing 0.1 per cent. or less carbon and the normal amount of chromium has been on the market. As far as the author is aware, the material was first made on a commercial scale by the firm with which he is associated in June, 1920, when a 5- or 6-ton cast of material containing 0.07 per cent. carbon and 11.7 per cent. chromium was made and cast into 12-in. ingots. The necessity for using a totally different raw material, carbonless ferrochromium, instead of the ordinary low-carbon ferro (0.6 to 1.0 per cent. carbon) has led to the idea that stainless iron is a quite distinct product and quite different from stainless steel. While this may be true from a commercial aspect, it is wrong metallurgically. The name stainless iron is unfortunate as the material is a very mild stainless steel and forms the lowest carbon member of a series of steels of continuously varying content which are, in many respccts, the counterpart of the series of ordinary carbon steels ranging from "dead soft" to tool steels. In an article on stainless steel in the Journal of the Society of Chemical Industry, November, 1920, the author said "Just as in the far-off days 'steel' was regarded as a hard product of iron, and little or no attempt was made to grade it into harder or softer varieties, so at present stainless

Jan 1, 1924

By John H. G. Monypenny

The range of chromium content of stainless steel is, in most cases, included in the limits 11 to 14 per cent., or the middle part of the range, 9 to 16 per cent., specified by the discoverer. For some time after the steel was produced commercially, the carbon content was about 0.3 to 0.4 per cent. and occasionally higher; only rarely was material with 0.25 per cent. carbon or less produced. The reason for this is obvious from the nature of the alloys of chromium available for making such steels; as the lowest carbon content generally available was about 1 per cent., and this in conjunction with a chromium content of about 60 per cent., the production of a 12-per cent. chromium steel with less than 0.25 to 0.30 per cent. carbon was impossible. The advent, on a reasonable commercial scale, of carbonless ferrochromium has modified this condition, however, so that for the last three years stainless material containing 0.1 per cent. or less carbon and the normal amount of chromium has been on the market. As far as the author is aware, the material was first made on a commercial scale by the firm with which he is associated in June, 1920, when a 5- or 6-ton cast of material containing 0.07 per cent. carbon and 11.7 per cent. chromium was made and cast into 12-in. ingots. The necessity for using a totally different raw material, carbonless ferrochromium, instead of the ordinary low-carbon ferro (0.6 to 1.0 per cent. carbon) has led to the idea that stainless iron is a quite distinct product and quite different from stainless steel. While this may be true from a commercial aspect, it is wrong metallurgically. The name stainless iron is unfortunate as the material is a very mild stainless steel and forms the lowest carbon member of a series of steels of continuously varying content which are, in many respccts, the counterpart of the series of ordinary carbon steels ranging from "dead soft" to tool steels. In an article on stainless steel in the Journal of the Society of Chemical Industry, November, 1920, the author said "Just as in the far-off days 'steel' was regarded as a hard product of iron, and little or no attempt was made to grade it into harder or softer varieties, so at present stainless

Jan 1, 1924

By C. E. Turner, J. R. Elenbaas, R. D. Grimm, J. A. Vary, D. L. Katz

A technique is presented by which well samples and core plugs of dolomite formations are classified by microscopic examination into seven different porosity grades. Quantitative values of porosity and permeability are determined for each grade by a statistical correlation of the core plug test data with the porosity grading system. These quantitative values are applied directly to the grades exhibited in the well samples for the purpose of estimating the reservoir void space for wells that were not cored. The procedure is described for estimating the gas reserves per unit area lor the South Hugoton gas field. but a reserve estimate for the field is not given. INTRODUCTION The miscroscopic examination of well sample; and the graphic recording of their lithologic qualities and other distinguishing characteristics of various geologic formations drilled is both a science and an art of long standing and wide application. Usually the primary objective of a geologist who "sits on the well" and examines the samples are: to identify the formation being drilled, determine the total depth, casing point. and completion interval. In most cases the porosity is described. if done at all, in general terms. such as: trace, scattered, fine, poor, fair, medium. good, excellent, or in some other relative terms. In fields where various geologists have examined samples and recorded observations on many wells considerable variations in lithologic terms and porosity descriptions occur unless there is primary effort to establish uniformity of logging observations and standards of recording observable porosity. When an estimate of the pore volume of a reservoir is made a geologic concept of the processes that control the magnitudes of porosity and permeability is developed by microscopic examination of well samples. The characeristics and appearances are then mentally related to rather general quantitative units of porosity based on physical core data from the same reservoir or on such data or experience in other reservoirs that have similar qualities. The reliability of such estimates depends largely on the variations of the lithology of the formations, the geometric properties of its void system. the extent of comparisons of sample appearances with porosity data, as well as the uniform recording of all relevant characteristics. This statement is particularly significant for dolo-mitized limestone formations of substantial thicknesses and heterogeneity such as the Permian Dolomites of the Hugoton gas field. Jn this field, as well as in most of the Permian Dolomite fields, the producing formations are of relatively great thicknesses in which the porosity and permeability of the reservoir varies substantially in all directions, depending on the crystalline structure. degree and kind of impurities, kind of fossils anti cementation thereof, degree of dissolution. and fracturing. The variations of the lithologic texture of the dolomites and post deposition alterations have resulted in porosities and permeabilities of such magnitudes that only a part of the gross thickness can be counted as "pay." At the time of this study insufficient gas production had been experienced to apply the pressure decline production method in the South Hugoton Field and the electric logs are not definitive enough. The problem of estimating gas reserves in the south part of the Hugoton Field is primarily one of determining the pay thickness and porosity from well samples and core data. The area studied embraced all that part of the field lying south of an east-west line through Guvmon, Okla., anti containing approximately 1.000,000 acres. This paper describes a technique of correlation of physical core data with well samples so that quantitative values of pay thickness, porosity. Permeability, and connate water may be assigned to well samples that are representative of a given interval, and thereby permitting the estimation of gas reserves lor a given unit area. The procedure was developed by a uniform microscopic qualitative porosity grading of the dolo. mite core plugs.. and relating these grades to the respective physical core data on a statistical basis The well sample-were also graded in a Similar manner in order that the quantitative values established lor the core plugs could be applied to the well Sample for wells that were not cored. GRADING OF DOLOMITE A group of experienced geologists was given the assignment of examining the samples on all wells in South Hugoton in order that they could log their observations in a uniform and standardized manner and grade the observed porosity so that it could be related quantitatively to the core data. The group initiated the study 011 chips from cores which bad been tested for porosity and permeability. This study continued until all of the geologists developed a common knowledge of lithologic terms and of the characteristic appearances of the samples and their relations to measured porosity. The characteristic appearances of the dolomite samples under twelve-power magnification as related to their qualitative porosities afforded a classification of the dolomite into :even grades of porosity, ranging from dolomite of no-visible porosity under twelve-power magnification to dolomite of excellent porosity. The assigned grade for a specific 10-ft interval is a weighted average of all visible grades of porosity exhibited by the cuttings representing that interval. The porosity characteristics were recorded by a color graph adjacent to the lithology column in conjunction with a numerical system for further definition of relative porosity as shown in Fig. 1. The three vertical lines to the right of the lithology column each represent 33 1/3 per cent. which lines were used to record the percentage of the samples, for any particular interval. that showed porosity under the microscope. The colors were used to denote actual pore size. i.e., orange. blue and I-ed for pore diameter of one-fourth or less. one-fourth to one-Ilalf. and greater than one-half millimeter, respectively. The area colored 1)). one or more colors represents the percentages of the samples exhibiting pores of the respective size or sizes. The numerals from one to six inclusive shown on the log in

Jan 1, 1952

By S. R. Krom

IN Mr. Hoffman's papers, and in the discussions attending them, the claim is apparently made for the Sturtevant mill that it produces

Jan 1, 1893

By C. Norman Cochran

The pllnse diagvam for the NaF-AlF3 system was used to calcutate an ionic model for the NaF-AlF3 system. Assuming an ideal solution,a series of simultaneous equations expressing equilibria be-tween solid and liquid phases at the euleclic, perilec-tic, and melting points were solved for the activities of the ionic species, the dissociation constants, and the entropies and heats of fusion. The calculations suggest the existence of A13F1415 ions in addition to the F-1+AlF6-3 , and AlF4-4 ions previously proposed by others. The calculaled valnes give better agreement with vapor pressures than the previous model without Al3Fl14-5. Additional possible vefinements of the model are proposed. CRYOSCOPIC1 investigations and density data2 for the NaF-A1F3 system have previously been used to study the dissociation mechanism of Na3A1F6 and to derive equilibrium constants for its dissociation to NaF and NaAlF,. Depending primarily on the heat of fusion assumed for cryolite, the dissociation constants ranged between 0.02 and 0.18 from cryoscopic studies, and from 0.09 at 1273°K to 0.16 at 1363°K from density data. In most cases the values were unable to reproduce satisfactorily the experimental liquidus lines very far on the A1F3 side of the Na3A1Fe composition. This suggested the existence of at least one other ionized compound in the melt besides NaA1F4 in the Na3A1F6-A1F3 side of the system. This is assumed to be liquid Na&13F14 (chiolite), which is already established as a stable solid in phase studies of this system. MODEL FOR THE MELT The melt is assumed to be an ideal solution with ion activities equal to anion fractions. The only cation in the model is sodium so that Temkin and simple anionic activities are identical. Although the compounds are completely ionized to Na' and the respective anion in the melt, molecular rather than ionic notation is used throughout this work. The Na3A1Fe is assumed to dissociate to NaA1F4 and NaF as in the former model, and Na&13F14 to dissociate to Na3A1Fe and NaA1F4. Other valid dissociation equilibria can be written involving these four compounds, but all of these can be obtained by combinations of the two described dissociation reactions and, thus, are automatically considered in these calculations. The model allows for no free AlF3 so that compositions for NAIF3 > 0.5 (mole fraction A1F3 on the NaF-A1F3 basis) cannot be treated. The question of the existence of free AlF3 in the melt will be discussed again later. The constants in the model were evaluated from points along the entire known liquidus line of the NaF-A1F3 system. Previous work employed only the liquidus line or densi- ties near the Na3A1F, composition. The liquidus line compositions used in the solution of the model are from unpublished work by Mr. P. A. Foster, Jr., for compositions between the Na3A1F6 melting point and the Na&13F14-A1F3 eutectic, and from the published works of Grjotheim,1 Phillips,3 and Foster4 for the remainder of the system. The relationships used in solving for the desired dissociation constants and heats and entropies of fusion are listed in Table I, and the points along the liquidus line at which each apply are indicated to the right of the relationships. The mole fractions of each of the separate species in the melt are symbolized by N. Relationships [I] and [2] are the respective dissocia-ation constants, Kl and K2, of Na3AIF6 and Na5A13F14 for this model. For simplicity, these constants will be assumed to be independent of temperature. Relationship [3] follows from the assumption of the ideal solution. The expression relating the values of N to the experimental values of NAIf3, is given in Relationship (41. Relationships [5], [6], and [7] each state the equilibrium between a compound in the melt and its pure solid phase for the portion of the liquidus lines where it precipitates. The heats of melting, AH,, and entropies of melting, AS,, used in [5], [6], and [7] are assumed to be independent of temperature. The compositions and temperatures of all five invariant points (two melting points, two eutectics, and one peritectic) along the liquidus lines from NAIF3 = 0 to NAIF3 = 0.5 were employed in the solution. The eutectic and peritectic compositions were particularly useful because each of these is involved in one more equation than other points along the liquidus lines and thus reduces the number of points required to solve for the constants. Also, their use assures that the inflection points in the derived liquidus line will correspond exactly with those on the experimental liquidus line. The total number of equations is 5k1 — 1, where n is the number of experimental composition points used. The number of unknowns is 4n + 5 (4n- 3 values of N, 3 values each of AH, and AS,, and 2 values of K). Thus, six points must be used in the solution to obtain an equal number of equations and unknowns. The one additional required experimental composition was taken on the liquidus line between the Na3A1Fe melting point and the Na3A1F6-Na5A13F14 peritectic. Previous work indicated this was a difficult portion of the curve to fit. The temperature used for the point was 1161°K, the same as for the NaF-Na3A1Fe eutectic. This choice of temperature gave two points with identical NNa3AIF6 values which simplifies the algebraic solution. The second point at this temperature is denoted 1161°'K. PROCEDURE FOR SOLUTION OF EQUATIONS Values were assumed for NNa,AIF and NNaF at the NaF-Na3A1F6 eutectic at 1161°k. By an iterative procedure, the corresponding values for NNa5A13F14 and NNaAlF4 at 1161°K were determined from 131 and 141. A value was assumed for NNaAlF4 at 1161°'K and

Jan 1, 1968

By E. V. Potter

For a nurnber of years, it has been known that manganese made by electro-deposition under certain conditions is ductile while under other conditions it is very brittle. The ductile metal is gamma manganese normally stable only between 1100 and 1138°C1; the brittle metal is alpha manganese, stable up to 727OC. The ductile metal is not stable, but gradually changes to the brittle form; the time required to complete the transfornlation is about 20 days at room temperature. Other observations have indicated that the transformation is completed in 10 to 15 min. at about 125°C, while at — 10°C, no appreciable change occurs in 9 months. The properties of gainma and alpha Illanganese in the pure state are ordinarilj difficult to determine because the gamma structure cannot be retained by normal quenching procedures and alpha manganese is so brittle, it is difficult to obtain specimens free from flaws. In a recent investigation2 some properties of gamma and alpha manganese were determined by studying the ductile electrolytic metal and determining the changes in its properties as it transformed to the brittle alpha form. These investigations provided an excellent opportunity for following the progress of the transition and studying its mechanism. The results of a series of such investigations are reported in this paper. Procedure Various properties of manganese were determined starting with the metal in the original ductile gamma form and following the subsequent changes in its properties as the metal transformed to the brittle alpha form. These observations were made at various temperatures, the data providing information regartling the mechanism of the transformation as well as the effect of temperature 011 the transition rate. Structure and resistivity values gave the most significant results, so this paper is concerned primarily with them. The structure was studied microscopically as well as by X ray diffraction. The resistivity was determined on strips of the metal by measuring the potential drop across a given length of the specimen. Current was passed through the specimen by wires soldered to its ends, and the potential connections were made by wires looped around the specimen near its center. The current was determined by the potential drop across a standard resistor connected in series with the specimen, the potential drop being measured on a potentiometer. In the temperature range from room temperature to 100°C an ordinary drying oven was used to heat the specimen. This was entirely satisfactory except at 100°C, where the time required to heat the specimen was long compared to the transition time, making the initial section of the resistivity curve unsatisfactory. To overcome this limitation, at 100°C and higher a thermostatically controlled oil bath was used to heat the specimens. The block on which the specimen was mountetl was plunged into the hot oil at the start of each test. The heating time was thereby reduced from 5 min. to about 6 sec, and dependable resistivity values could be obtained through 160°C. At this point the whole transition, including the warm-up time for the specimen, required only about 20 sec and it was not considered worth while trying to extend the temperature range further. Aside from the heating problem, the problem of making a sufficient number of accurate resistivity determinations became more and more difficult as the temperature was raised. Using the manually operated potentiometer, 100°C was about as far as it was possible to go. At this temperature and above, a self-balancing photoelectric recording potentiometer was used. Its response was quite rapid, and it proved to be entirely satisfactory all the way through 160°C, where the tests were stopped because of the specimen heating problem rather than any limitation of the potentiometer recorder. The metal used in these tests was prepared at the Salt Lake City laboratory of the Bureau of Mines. The method of preparation is discussed in a paper by Schlain and Prater.3 The sheets were about 2 3/8 by 5 3/16 in. and varied from 10 to 16 mils in thickness. They could be cut readily into pieces suitable for the various tests. X ray and microstructure determinations were made on pieces about 1/8 to 1/4 in. wide and about 1 in. long, while resistivity measurements were made on strips as long as possible and about 55 in. wide. The thickness of each sheet was not uniform over all its surface. This had no bearing on the X ray and microstructure determinations, but sections as nearly uniform and free from flaws as possible were chosen for the resistivity determinations. The gamma manganese was electro-deposited at 30°C, the time of deposition ranging from 5 to 12 hr for each sheet. Whenever possible, the tests were started directly after the metal was stripped from the cathode; otherwise the sheet was placed immediately

Jan 1, 1950

By J. R. O’Connor

Stimulated emission from Nd+3 in yttrium uanadate fYVOJ is reported. Single crystals of YVO4:Nd, obtained from Linde Col-p., have improved substantially in the last several months. Pulsed thresholds of YVO, laser rods are now approximately 2 to 3 5, cowparable to tliose for YAG:Nd. Yttrium uanadate crystalli~es irz a space group similar to zircon. All rare-earth vanadates have this structure. Rare-earth ions sucll as Nd+3 which substitutes for Y+3, aye situated irz a strong tetragonal crystal field which lacks inversion symmetry. This condition increases the p'robability of the parity-forbidden f — f transitions. Yttrium anadate has strong absorption bands beyond -1000A. These are clue to Y-O, V-O charge transfer and molecular transitions. Under 2537 and 3660A irradiation pure YVO, fluroresces u bright yel-LOLO. This fli&orescence is corrzpletely quenched in YV04:Ncl crystals. This and other evidence of energy trut~sjer from the lattice is repovted. Optzcul atz 1user pvope 1-ties o! YI'U4:E[t are brieJy described. THIS paper describes some of the optical and laser properties of Nd+3- and Eu+3-doped yttrium orthovana-date (YVO4). It reports laser action for the first time in this low-symmetry host. For some time we have pursued a research program concerning laser hosts' wherein the rare-earth (RE) ion is situated at a site of low crystal symmetry so as to increase the probability of radiative transitions. Single crystals of doped and undoped YV04 are grown from iridium crucibles in an oxyhydrogen gas-fired furnace by a modified Czochralski technique.' This material crystallizes in a D4li tetragonal space group of the zircon (ZrSiO,) type.3 All RE vanadates have the same structure and form solid solutions with YVO4. Therefore, it will be possible to investigate a variety of cross-pumped laser systems, as in the case of yttrium aluminum garnet (YAG).4 At present, ~d'~-doped YAG is one of the most efficient solid-state lasers.5 Accordingly, most of the material to follow will compare the properties of YV04 to those of YAG. Fig. 1 shows the relative transmission of YAG and two types of YVO4. "Pure" YVO4 has a normal absorption edge and is colorless. A second type has a broad absorption peaking near 4200A and is yellow. Rubin and Van uitert6 suggest the yellow material is slightly reduced. Samples of each type are being investigated by electron spin resonance,7 but these studies are so far inconclusive. The pulsed laser threshold is much lower in the yellow material than in the colorless. Therefore, the absorption at 3500 to 5000.4 transfers energy to the Ndi3 ions. Photons of wave length between 2000 and 4500A cause undoped YVO4 to fluoresce at 4800, 5250, 5460, 5540, and 5750A. This emission, previously reported by Brixner and Abramsom,8 is partially quenched by EU'~ and completely quenched by Ndt3 at room temperature due to energy transfer from the lattice to the RE ions. At low temperatures, some lattice fluorescence is present. This implies that the energy-transfer process is in part phonon-assisted. Although the YVO, single crystals used in this work were prepared from Y2O3 containing less than 0.01 pct rare-earth impurities, there is aopossibility that emission lines between 4800 and 5750A are due to dysprosium, terbium, and so forth. However, these lines are not observed in other compounds, prepared from Y2O3, such as YP04, Y2MoO6, and so forth. Furthermore, extensive absorption measurements on our "pure" YV04 single crystals between 0.4 and 5.0 failed to reveal any characteristic rare-earth lines. Fig. 2 compares the absorption spectra of Ndt3-doped YAG and YVO4from 0.6 to 1.0 . The Ndt3 absorptions are labeled according to free ion, R-S coupling. These term designationsQ are appropriate for YAG:Nd. They appear to be inappropriate for YV04:Nd. In YVO, neodymium must substitute for yttrium. The yttrium site is situated In a strong tetragonal field, where point symmetry is (42m) or possibly lower.1° However, the reduced splitting of the Stark components of the YV0,:Nd spectrum implies that the NdT3 ion is in a cubic site. The only plausible explanation for this discrepancy is that the Ndt3 ion is in a low-symmetry site, lacking inversion symmetry, so that a substantial admixture of 4f and 5d wave functions occurs. In this case, R-S coupling is not valid and J is no longer a good quantum number." Consistent with this view, the 4~ metastable level of YV04:Nd has an oscillator strength larger and a

Jan 1, 1968

By P. L. De Bruyn, R. J. Charles

THE transfer of kinetic energy of translation into other forms of energy by impact is a fundamental process in most crushing and grinding operations. During and after the impact process the original source energy may be accounted for in any of the following possible forms: 1) Kinetic energy of translation of both the impacted and impacting objects. 2) Kinetic energy of vibration of the components of the impact system. 3) Potential energy as strain energy of the components of the system or in the form of residual stresses. 4) Heat generated by internal friction during plastic deformation or during damping of elastic waves. 5) New surface energy of fractured materials. At any instant during the impact process only the strain energy of the components of the system can contribute directly to the brittle fracture process. If fracture is the desired result, as in comminution, it would seem advantageous to choose or arrange the conditions of impact so that a maximum amount of the original kinetic energy could be converted to strain energy at some moment during a single impact. The present work deals with determination of these desirable conditions for a simple case of impact and application of the principles involved to general cases of impact. Experimental Method: Longitudinal impact of a rod with a fixed end was chosen as the impact system for investigation. The rod was mounted horizontally and the fixed end was formed by butting one end of the rod against a rigidly mounted steel anvil. The rod, of pyrex glass, was 10 in. long by 1 in. diam with both ends rounded to a 6 in. radius. The rounded ends permitted reproducible impacts on the free end of the rod and assured a symmetrical fixed end. Pyrex was selected as the rod material because of the marked elastic properties of such glass and the similarity of fracture between pyrex and many materials encountered in crushing and grinding operations. The frequency of natural longitudinal oscillation of the rod was 10 kc, and thus simple electronic equipment could be used for observation of strain changes occurring in the rod at this frequency. As shown in Fig. 1, impacts on the free end of the rod were obtained either by a pendulum device or by a spring-loaded gun. Relatively heavy hammers (100 to 600 g) of mild steel were used in the pendu- lum impacts, while fairly light projectiles (20 to 80 g) were fired from the spring-loaded gun. One of the main objects of the experimental work was to obtain the strain-time history of the rod as a function of the mass and kinetic energy of the impacting hammers. For this purpose a technique involving wire resistance strain gages and a recording oscilloscope was employed. Five gages were applied at equidistant sections along the rod, and by means of a switching arrangement the strain-time history at any section, and for any impact, could be obtained in the form of an oscillograph with a time base. The equation relating strain and voltage change across a strain gage through which a constant current is flowing is as follows: e = ?v/iRF [1] ? = strain, ?v = voltage change, i = gage current, R = gage resistance, and F = gage factor (from manufacturer's data — SRA type, Baldwin Lima Corp.). With the above equation an oscillograph depicting voltage change vs time on a single trace can be converted directly to a strain-time diagram if a calibration of the vertical response on the oscilloscope screen for specific voltage inputs is available. In the present case the calibration was obtained by photographing precisely known audio frequency voltages on the same oscillograph as that on which a voltage-time trace from a strain gage had been made. Synchronization of the beginning of the single trace with the beginning of the impact was accomplished by permitting contact of the impacting objects to close an electrical circuit from which a voltage pulse, sufficient to initiate the trace, was obtained. The struck end of the rod was lightly silvered for purposes of electrical conduction so that it would form one of the electrical contacts. Markers every 100 micro-seconds on the traces served for a time base calibration. Determinations of the kinetic energies of translation prior to impact were made in the case of the pendulum hammers by measuring the height of fall of the hammer and in the case of the projectiles by measuring the exit velocity from the gun barrel by means of an electrical circuit employing light sources, slits, and phototubes.' During the experimental work it became evident that the time of contact between the impacting object and the rod was an important variable in the impact process. Measurements of the times of contact were made, therefore, for every impact for which a strain-time record was obtained. The time of contact was determined by permitting the impacting components, when in contact, to act as a closed switch and discharge a condenser at relatively constant voltage. The discharge was observed and photographed with a time base on the oscilloscope screen.

Jan 1, 1957

By N. A. Gokcen

THE data of Chaudron,1 Tonosaki,2 and Collins³ on the thermodynamic properties of MOO, disagree widely. These authors, by using essentially similar methods, studied the following reaction: 1/2MoO2(s) + H2(g) == i/2Mo(s) + Ph,o H2O(g),K = —----- [1] Ph2 Tonosaki used a vacuum system consisting of a furnace containing MOO, and a water saturator whose temperature was kept at 25 °C with a thermostat. After repeated evacuation, hydrogen was admitted slowly into the system. The experiments were based upon the fact that at a constant furnace temperature and constant partial pressure of water, the total pressure of gas mixture over MOO? + Mo is constant. Any attempt to vary the pressure by external forces would vary only the amounts of MoO2, and Mo, after which the pressure should return to the equilibrium value in accordance with the equilibrium constant of reaction 1. The actual value of K was determined from the total equilibrium pressure (sum of Ph2o + Ph2) at each temperature. The total pressure of gas was varied within the range of 80.2 to 125.4 mm Hg, within a temperature range of 645" to 823 °C. The results were summarized as log K = 0.9413 — 1444.6/T for reaction 1. The ratio of H2O/H2 was considered to be uniform in spite of the presence of a thermal gradient across the static gas phase. It was shown by Rosenqvist and Cox,' however, that in somewhat similar circumstances the error resulting from thermal diffusion may be large. Collins³ improved Tonosaki's method by attempting to avoid thermal diffusion errors. His equilibrium data were obtained at 700°, 800°, and 900° C, and the result for reaction 1 was expressed as log K = 1.258 — 1822/T. The purpose of this investigation was to study reaction 1, avoiding the thermal diffusion errors, and to obtain equilibrium data in a considerably wide temperature range for the reliable extrapolation of the resulting thermodynamic functions. Experimental Procedure The diagram of the apparatus is shown in Fig. 1. Tank hydrogen was passed through a tube containing platinized asbestos at 425 °C in order to convert a trace of oxygen into water vapor. The flow rate was carefully controlled with a capillary-type flow-meter B and a bubbling column D. The gas was then presaturated sufficiently at P and led into a condenser system immersed in a thermostat, controlled to within ±0.002C. The temperature of the thermostat was measured with a thermometer calibrated against a certified standard. The temperature of P was adjusted to avoid the condensation of unduly large amounts of water as judged from the rate of flow out of the capillary tube M. Argon was purified by passing it through magnesium chips kept at 630°C. After passing through the flowmeter B', it was mixed with moist hydrogen emerging from the thermostat. The resulting gas mixture was then led into the hot zone of the furnace through the heated glass tubing and the silica tube S, thus insuring the same ratio of PII2o/Ph2 from the condenser to the reaction chamber, thus avoiding thermal diffusion. The entire gas system was of all-glass construction, except at the magnesium train. The furnace comprised a glazed alumina tube over which a 15-in. platinum coil was wound. The lower end of the alumina tube was tightly closed with a brass bottom and a silicone rubber gasket, and the upper end with two glass disks, each with a hole of 1/16 in. in diameter, through which the gas mixture escaped into the atmosphere. A back-up coil of kanthal wire facilitated the temperature control of the furnace. A coil of annealed molybdenum strip of 99.99 pct purity, 0.005 in. thick and 0.050 in. wide, and weighing 17 g was hung in the furnace with a 0.010-in. platinum wire attached to one end of a sensitive analytical balance. The temperature of the furnace was measured with a Pt-Pt-10 pct Rh thermocouple checked against a standard. The experimental procedure consisted of heating the gas purification trains, adjusting the gas flow rates, attaining a constant thermostatic temperature, flushing the entire system for 2 hr while heating the furnace to well above the expected equilibrium temperature and then cooling it at a rate of 0.3°C per min during which time the change in the weight of molybdenum was observed on the balance. For a given thermostatic temperature, i.e., a constant Prr,o/Px,, molybdenum oxidized upon cooling slightly below the equilibrium temperature. The procedure was then repeated by heating the furnace and thus reaching a temperature slightly above the equilibrium value. The average of the two temperatures, differing by 2" to 3"C, was considered to be the true equilibrium temperature. In order to determine the stoichiometric composition of the oxide phase present in this investigation,

Jan 1, 1954

By John Henderson

Densities of melts 0f the lime-iron oxide-silica system in contact with solid iron have been measured by the maximum bubble pressure method in the temperature range 1250° to 1440°C and the composition range 0 to 40 mol pct lime, 15 to 100 mol pct iron oxide, and 0 to 55 mol pct silica. Densities range from 4.65 g cm 3 for wustite at 1440°C to 2.75 g cm-&apos; at 1350°C for a melt containing 30 mol pct lime, 20 mol pct iron oxide, and 50 mol pct silica. The results are interpreted in terms of a postulate that the melts can be regarded as a random array of oxygen ions in which regions of local order exist to satisfy the coordination requirements 0.f the cations. An understanding of the nature of metallurgical slags is basic to the development of a sound theoretical description of heavy metallurgical extractive and refining processes. Because these liquids are complex, direct measurements of their properties has not thrown much light on their structure. This has led to the approach of measuring the properties of simpler liquids, and building up their complexity until slag compositions are reached. In this way the density of liquid iron silicates was measured in a previous study1 and the present work represents a further stage in this synthesis. EXPERIMENTAL The technique used in the measurement of density was the maximum bubble pressure method. Details of the apparatus and procedure were similar to those previously reported,&apos; with the exception that a constant voltage transformer was used to supply the power input to the furnace and six silicon carbide resistance elements were used in place of the molybdenum winding. With these modifications melt temperature could be maintained within 1 centigrade degree during the course of a run. The silica used to prepare the melts was washed natural quartz ignited at 1000°C; wustite was prepared by air-melting A.R. grade ferric oxide in an iron crucible and lime was prepared by air ignition, at 1000°C, of weighed quantities of A.R. grade calcium carbonate, previously air-dried at 110°C. The finely ground constituents were intimately mixed in a glass ball mill prior to melting. Temperatures quoted are accurate to * 5°C and the standard deviation of the density values, calculated by the method of least squares, ranged from 0.5 to 1.8 pet. However, replicate determinations of density on different melts of the same nominal composition at the same nominal temperature did not vary by more than 1 pct, Table I, and this figure has been taken as an estimate of the accuracy of the density results. The density of carbon tetra-chloride was also measured as a check on the absolute performance of the experimental method. At 20°C a value of 1.593 * 0.002 g cm"3 was obtained; this compares with the literature value2 of 1.595 g cm"3. Results of experiments designed to measure the dependence of the density of lime-iron oxide-silica melts, in contact with solid iron, on composition and temperature are shown in Table I. Because iron sometimes precipitated in the sample during quenching, the Fe203 chemical analyses were only poorly reproducible and should be taken as a guide rather than as absolute values. Fig. 1 shows the data from various sources for the density of liquid iron silicates and Fig. 2 shows isodensity contours at 1410°C for lime-iron oxide-silica melts, calculated by graphical interpolation of smoothed curves drawn through the experimental results, together with the 1400°C results of Adachi and ogino3 and Pope1 and Esin.4 Fig. 3 shows the isothermal variation with composition of the volume of melt per gram ion of oxygen at 1410°C and Fig. 4 shows regions in which the temperature coefficient of this volume is negative, positive, or negligible (<0.005 cm3 deg-I). DISCUSSION a) Disparity Between Reported Density Results. Consider the system iron oxide-silica, the results for which are summarized in Fig. 1. Although there is some difference in the temperatures at which the various densities apply, this difference is not sufficiently large to account for the observed discrepancies. The reliability of the present results for the low-silica region has been confirmed by measurement of the density of liquid wustite by three different techniques. At 1410°C the density measured by a balanced-column method was 4.55 g cm"3, by a combination balanced-column and gas-densitometer method 4.59 g emd3, and by a pycnometer method 4.53 g cm"3. Schenck, Frohberg, and Hoffermann&apos; have also reported a value of 4.55 g cm"3 for the density of liquid wustite at 1400°C. It must be concluded, therefore, that neither Pope1

Jan 1, 1964