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By W. T. Bishop

For many years pine oil has been used extensively as a frother for the flotation of minerals, particularly sulphides, yet the published information available to the average user on its composition, chemical and physical properties, has been rather meager. It is the purpose of this paper to discuss these points and their relationship to the frothing properties of pine oil used in flotation processes. Pine oil, as the name implies, is a liquid obtained from the processing of wood of the longleaf and other southern pines. It is a complex mixture of naturally occurring terpene derivatives, primarily alcohols, and a smaller amount of terpenes, which has found many uses in various industries. Its use as a frother in flotation processes was the first large-scale application in industry and today the mining industry still consumes large quantities of pine oil but the textile and disinfectant industries consume comparable volumes. Much is used in soap manufacture and laundry operations. The surface-active properties of pine oil are in a large degree responsible for this versatility. History The name "Naval Stores" goes back to the days when pine tar and pitch were used to caulk leaky ships and 'Oat their ropes and rigging. Today this term is still used to include not only the oleoresinous products of the pine tree—rosin and turpentine— but other products such as pine oil, pine tar, and the many terpene and resinous compounds obtained by extracting the pine wood or tapping the tree. That part of the industry known as "wood naval stores" dates from about the beginning of this century and today produces a large part of the country's rosin and turpentine by processing pine wood. In addition, all of our natural pine oil is supplied by the wood naval stores industry, as tapping of the live tree gives only rosin and turpentine. This latter phase is known as the "gum naval stores " industry. The first successful commercial operation of the steam and solvent process of the wood naval stores in industry was carried out by Yaryan at Cadillac, Mich., in 1909.1 This operation did not prove profitable, so Yaryan went south to utilize the longleaf pine, and built a plant at Gulfport, Miss.2 Soon after, another plant was built at Brunswick, Ga., which is still in operation, and in 1914 was reported to have processed about 500 tons of wood per day.' In 1921 Hercules Powder Co. acquired the Yaryan interests, at which time the production of pine oil was only 3 to 5 million pounds per year and flotation was the largest customer. As time went on, technological advances were made, other companies entered the field, and the production of pine oil increased many fold. The growth of the industry was especially marked during the past 10 years, and in

Jan 1, 1947

By Fred C. Bond

AN improved method of measuring the surface area of a comminution product down to any desired particle size has been developed. The method is largely graphical, and requires relatively little calculation. It can be used with materials containing large amounts of clay, or excess fines of any kind. The surface area S is expressed in terms of square meters per100 c.c. of solids. This expression is based upon volume rather than weight, and is considered to be more suitable for crushing and grinding problems, where the machines ordinarily are operated under constant volume conditions. It has the advantage that surface areas of different materials can be compared directly, even though their specific gravities may be unknown. The "specific surface" of a material, or the number of square centimeters of surface area per gram, is equal to 100S divided by the specific gravity. Particle diameters are expressed in microns, K being the diameter of the largest particle present and L the grind limit, or lower size limit of the particles formed directly by grinding. The value of K does not always coincide exactly with the diameters of the largest particles retained on the coarsest testing sieve, since the largest particles formed in crushing and grinding are often slabby, or have other irregular shapes. L has been chosen as 0.700 microns, or number 27.5 in the size number series,1 for reasons to be explained later. S is the total surface area of all particles larger than L microns in diameter. When a homogeneous comminution product is separated into fractions whose diameters bear a constant geometrical relationship [p] to each other, and the log per cent weight retained upon each size and passing the next larger size is plotted against the log diameter, a straight line results, which is called the distribution line, and which has a slope in called the distribution modulus. The distribution line can be extended to any desired limiting size, and the total surface area of all particles larger than that size can be calculated. The equation of the distribution line is w = Cxm [I] where w is the per cent weight retained on each successive sieve; x is the particle diameter; and C is the per cent weight retained on an opening of unit diameter.2 Theoretically, the distribution line can be extended to include infinitely small particles. When it is so extended, and the assumption is made that no fine particles are present other than those accounted for by the equation; the log per cent cumulative weight passing any series of sizes, plotted against the log diameter passed, will result in a straight line lying parallel to and above the plotted distribution line.

Jan 1, 1941

By Robert L. Hoss

The application of Muskat's differential equations for predicting the performance of a solution gas-drive reservoir to the Fullerton field indicates that a recovery may be expected of 14,030 bbl per acre under primary depletion, and 15,910 and I7,190 bbl per acre, respectively, under the two pressure-maintenance programs analyzed. In this analysis it is assumed that fluid properties are the same throughout the reservoir, that the core data used are typical of the Clear Fork limestone in the locality, and that injected gas is completely diffused through the pay zones. The economic study of the three recovery programs considered indicates that the one in which 60 pct of the produced gas is returned to the formation is the most profitable. Introduction The purpose of this paper is to consider the effect of pressure maintenance by gas injection on the ultimate recovery of oil from a solution gas-drive reservoir. This prediction of reservoir behavior is the result of calculations based on the equations presented by M. Muskat in the Journal of Applied Physics, March 1945. Reservoir The reservoir analyzed is the Fullerton field in Andrews County, West Texas. It is situated on a broad anticlinal structure with approximately 330 ft of closure, and extends approximately eight miles north and south and five miles east and west. The areal extent is taken as 16,642 acres. The producing horizon is the Lower Clear Fork limestone of Permian age, occurring at depths from 6650 to 7350 ft. It is divided into four zones. For the purposes of this study, the fluid characteristics in all zones are assumed to be the same. Therefore an equivalent zone is assumed of thickness equal to the sum of the thicknesses of the four zones, or an average of 216 ft. The reservoir contains 3,586,991 acre feet of producing limestone, with an initial volume of stock tank oil in place of 918,-403,100 bbl. The average connate water saturation is 24.0 pct. The permeability ranges from 6.7 md. to 12.6 md., and the porosity ranges from 7.7 pct to 11.4 pct, except for occasional cavernous streaks. Based on these values, the limestone may be considered intergranu1ar.l Production histories and material-balance studies have indicated that the driving mechanism is solution gas. Water levels have been established. Theory It is possible to express mathematically the change in residual oil saturation with pressure decline in a solution gas-drive reservoir as being equal to the change in the physical properties of the fluids present in the reservoir as this pressure decline occurs. Essentially these equations, in differential form as presented by M. Muskat,2 express quantitatively the instantaneous net effect

Jan 1, 1948

Engineers who are in charge of industrial operations, and their number is legion, sense as much as anyone the present feeling of unrest in the' country and more than anyone else realize the present inefficiency of labor. Undoubtedly the two phenomena are closely correlated and no doubt are due to a multitude of causes which it will be impossible to enumerate. From my experience in mining I estimate that the present efficiency of labor is only about two-thirds of what it was under pre-war conditions. In the mining industry, at least, we have not a large surplus of men looking for work and usually under these conditions men are rather more independent and will not work as efficiently and faithfully as if they felt there were plenty of men ready to take their places. Wages in metal mining have advanced more than the increased cost of normal and sane living. The result is that the men often work fewer days in a month and do not seem to have very much interest in their work while actually engaged in it. Then again, they have been listening to the more or less vague propaganda of the I. W. W. and the radical wing of the socialists, who are harping on the fact that the distribution of newly created wealth is unfair and that the laborer really is not working for himself or his fellow laborers but is carrying on his exertions for the benefit of a small and lim-ited class of exploiters. A continued harping on this view is bound to influence the judgment of even a conservative workman who is not a student of economics and who hears little or nothing upon the other side. I am a great believer in the common sense of the American people and in the long run I do not think that they will be carried away by unsafe doctrines. The trouble with so many of these propagandists of industrial in-equality is that they do not differentiate between production and dis-tribution. Even if we admit that distribution is unfair, unless goods are produced there will be nothing to distribute. A great many unthinking people seem to feel that wages are paid out of a pot which is inexhaustible and do not realize that eventually what comes out of the pot can never exceed what is put into it. The workman is not paid in money but is paid in goods, money as we all know being used simply as a measure of value and a medium of exchange, and that all that can be used to pay the laborer is what he produces.

Jan 11, 1919

By Albert C. Harding

For several years barite (BaSO4) production has topped such better known minerals as feldspar and fluorspar in annual tonnage and is now well established among our foremost nonmetallic industries. Description Of widespread occurrence in the United States, barite is relatively soft (hardness, 2.5 to 3.5), inert, heavy (specific gravity, 4.5), and is also called "barytes" (sometimes pronounced "bear-i-tease"), "heavy spar" and "tiff." It occurs with granular and earthy structure but usually has coarse, orthorhombic crystallization. It is commonly white, and although occurring in various shades of red, yellow, and gray, barite always gives a white streak and can be scratched by the ordinary prospecting pick. Its softness and weight are usually sufficient to establish field identification. Another aid is the "rotten egg" odor of H2S which sometimes emanates from freshly fractured surfaces. Barite can be readily distinguished from two other minerals which have somewhat similar occurrences and characteristics. The relatively rare celestite, strontium sulphate, has a specific gravity slightly less than 4.00 and gives a distinctively crimson color in a flame test. The very rare wither-ite, barium carbonate, has a specific gravity of 4.3 but readily effervesces with dilute hydrochloric acid. Occurrence All known commercially important barite deposits in the United States occur as re- placements or cavity fillings in schists, shales, limestones, dolomites, and quart-zites, or as residual deposits from such formations. In Georgia, Tennessee, North Carolina, and Missouri, high-grade barite is recovered as fragments from residual clays covering quartzites and dolomites. In Arkansas, Nevada, and California, barite, usually of lower grade, is mined from replacement deposits. These seven states contributed the entire production reported by the U. S. Bureau of Mines for 1945 as given in Table I. Table i—Crude Berile Sold or used by Producers in 1945 State Short Tons Arkansas................... 260.660 Missouri.................... 225.467 Georgia..................... 110,393 Tennessee................... 32,812 Nevada..................... 28,919 Other States............... 37,811 Total..................... 696,062 ('other states,, included only california and North Carolina. Such a large part of this undistributed production came from California that that state probably outranked both Nevada and Tennessee. For the second consecutive year Arkansas was the leading producing state, particularly worthy of note because there was no commercial production of barite there prior to 1941 and because the entire production of Arkansas has come from one large deposit which is being operated by two companies. Consumption The 1945 consumption as reported by the Bureau of Mines was: 482,442 tons as ground barite 139,288 tons in making lithopone 99,173 tons in producing barium ------- chemicals Total 720,903 tons

Jan 1, 1949

By A. A. Jr. Smith, J. S. Smart

The controlled amounts of phosphorus, arsenic, sulphur or selenium found in commercial coppers perform a variety of highly useful functions. Indeed, a large segment of modern copper technology is essentially dependent upon the presence of one or more of these elements. Consequently, the literature contains many references to their effects but the scope is broad and has been only partly covered. New data are presented herewith directed toward a better understanding of the basic behavior of these elements in copper, with particular emphasis on the composition range o to 0.05 per cent. These data are a part of a general program of research on the effects of impurities on the properties of oxygen-bearing and oxygen-free copper, other portions of which have been reported previously. Schematically, the behavior of individual elements is determined from measurements of conductivity and softening temperature,'v2 and the binary alloys employed are synthesized from high-purity copper in order to eliminate interference from the effects of extraneous impurities. Alloys of selected composition were first prepared in the oxygen-free form by continuously casting the melts in the form of %-in. diameter rod. Oxygen was added subsequently to portions of the alloys, either by remelting or by diffusion at 8jo°C. from a surface scale. Test wires wcre drawn one B. and S. number per pass, using four 30-min. 600°C. anneals at 0.3125, 0.257, 0.204 and 0.162 in., and a final cold reduction of 75 per cent to 0.081 in. Oxygen-bearing slugs made by remelting nere hot-rolled to 4ia in.. drawn to 0.162 in., annealed for 30 min. at 6o0°C. and cold-drawn 75 per cent to 0.081 inch. The alloys containing phosphorus, having been compounded very early in the program, were prepared in the form of 3i6-in. rod, and processed to wire with only the last three intermediate anneals listed above, all of these having been conducted in commercial nitrogen. In addition, the conductivity anneals on these alloys were also performed in the same atmosphere, and the small amount of oxygen present as an impurity in the gas resulted in some loss of accuracy at temperatures of 700' to 8o0°C., as will be shown later. Subsequently, the anneals for all oxygen-free alloys were conducted in hydrogen to prevent oxidation, and purified nitrogen was employed only for oxygen-bearing samples. All conductivity anneals wcre of one hour duration followed by a rapid quench in 10 per cent HZSO*. Effect of Phosphorus The widespread use of phosphorus as a deoxidant has resulted in universal appreci-

Jan 1, 1946

By Lloyd R. Jackson

In the past 15 years there has been a great deal of interest in the fundamentals of plastic flow and rupture in metals and a number of papers have presented substantial advances toward a fundamental insight into the mechanism of these two processes. This paper is an appraisal of the present position with respect to the following: 1. The relative importance of shear and hydrostatic stresses in controlling the plastic flow of metals. 2. The relative importance of shear and hydrostatic stresses in determining the amount of flow before rupture in metals. 3. The use of generalized strains in determining the effect of plastic flow on the work-hardening of metals. FundamentalS Involved in Plastic Flow In attempting to devise a quantitative description of plastic flow in metals, it has been customary to assume that metals are homogeneous and isotropic. The fact that neither of these assumptions is correct complicates the experimental appraisal of relations developed. Nevertheless, as will be shown, metals are close enough '0 being isotropic and homogeneous so that considerable insight into the mechanism of plastic flow can be obtained. The assumptions of isotropy and homogeneity allow both the elastic and plastic behavior of metals to be described in terms of 12 variables—six being stress variables, and six being strain variables. From this viewpoint, it should be possible to represent the stress-strain relations in the plastic range for metals by a surface in 12 dimensions. One boundary of this surface would be the surface of transition from elastic to plastic behavior; the other would be the surface of rupture. These two surfaces would be joined by the surface of plastic flow. The shape of this composite surface would depend on the test temperature and speed of straining This paper is concerned only with results obtained at constant temperature and constant speed of straining. While such a representation is conceivable, the demonstration of such a surface would present almost insurmountable obstacles. The most fruitful simplification of this concept has been the recognition that the behavior of metals in the plastic region is primarily a result of shear stresses and strains. Based on this viewpoint, it is possible to utilize stress and strain invariants that are independent of hydrostatic components to define an effective stress and strain. In effect, this amounts to reducing the task of representing stresses and strains in 12 dimensions to one of representation in two dimensions. The two invariants (one for stresses and one for strains) that have received most attention are the following: q2 = ½[(Txx= - Tyy)2 + (Tyy - Tzz)2 + (Tzz - Txx)2 + 3(Txy2 + Tyz2 + 7xx2) [1]

Jan 1, 1947

By Warren E. Wilson

The transportation of solids in pipe lines is a matter of deep concern in many fields of engineering. Much experimental and theoretical work has been done in an effort to devise means of designing pipe lines that will satisfactorily transport given solid loads, but there remain many unanswered questions in this field. The present discussion will be confined to a rather narrow portion of this field and will endeavor to point out certain factors that may well be considered when comparing the relative economy of various installations. The data have been presented previously but a new interpretation was prompted by a suggestion in a paper by Professor O'Brien,' of the University of California, that the friction work per pound of dry material should be considered in determining the relative efficiency of various installations. This method of considering relative economy in various pipe lines leads to some rather unexpected conclusions, especially with reference to the economy of large pipe sizes. A previous suggestion by the writer concerning the economy of a rather peculiar type of installation is strengthened. It is not believed that the considerations set forth herein apply directly in the case of dredge lines, where economy is largely a matter of a high rate of pumping in order to reduce the unit overhead charge. However, it is believed that some value may be gained from these considerations in cases involving the disposal of a fixed amount of solids per unit time with a minimum expenditure of energy and at a low cost for replacement of worn pipes. Such situations are not uncommon in the disposal of mill tailings and the disposal of solids deposited from irrigation waters. It was found that data leading to general conclusions for various pipe sizes were not available but certain definite trends are indicated and methods of analyzing available data are presented in the hope that they may be of assistance in preparing engineering estimates on designs of pipe lines of the type described above. Energy Requirements Carrying out the idea contained in Professor O'Brien's paper concerning the method of computing energy required to transport solids, the following analysis leads to some rather interesting conclusions. Let us represent: Solids load in terms of mass per unit time by w Ratio of mass of suspended solids to total mass of mixture flowing by p Volume rate of flow of mixture by Q Length of pipe by L Slope of energy grade line by s Mass per unit volume of solids by m8. Mass per unit volume of liquid by mi Mass per unit volume of mixture by 11 We then have as an expression for the solids load: w = pqmm The work done per unit mass, p, on the mixture to move it along the pipe the

Jan 1, 1947

By R. S. Busk, E. G. Bobalek

THE relation between gases and metals has been a subject of increasingly active investigation during the past years, principally devoted to the study of metal-hydrogen systems. It has been found that hydrogen is soluble in most molten metals to an appreciable extent and somewhat soluble in most solid metals.1,2 In every known case there is a sudden decrease in solubility at the melting point. Thus a freezing mass of metal containing hydrogen in excess of the solid solubility must in some way expel that excess during the freezing process. This leads to internal blowholes, and such effects as pinhole porosity. Gas trapped in metal that is to be fabricated by a working process such as extrusion or rolling may be the cause of blisters. For some cases, notably in copper and iron alloys, the presence of hydrogen can lead to extreme embrittlement of the metal. The aluminum-casting industry has long recognized the importance of hydrogen in its techniques. Excess gas in molten aluminum alloys often leads to the formation of "pinhole porosity" in the solid casting.3 To prevent this hydrogen pickup it is necessary to avoid overheating the melt and to protect it from such sources of hydrogen as water. In spite of all precautions, it is sometimes necessary to extract hydrogen from the melt just before pouring by bubbling with a gas such as chlorine or nitrogen. Recently it has been found that somewhat similar effects are possible with magnesium alloys, in that the presence of hydrogen can induce or aggravate microporosity.4-6 This paper is primarily concerned with a presentation of some facts concerning the solubility of hydrogen in magnesium and its alloys, with some discussion of the significance of these facts in a practical sense. In any study of gas-metal systems it is important to bear in mind a clear distinction between adsorption on surfaces and absorption within the lattice.1 Considerable attention has been directed toward determining whether hydrogen is truly soluble in any solid metal, or whether the gas extracted from a sample was present at surfaces (external and internal) only.7 Most present day evidence supports the idea of true solution in addition to adsorption. A second important factor when dealing with gas solubility is the dependence of such solubility on external pressure. For diatomic gases such as H2, solubility in both liquid and solid metals apparently is proportional to the square root of the pressure, indicating a breakdown to a monatomic gas before diffusion into the lattice .2 For true equilibrium values of solubility, therefore, the pressure at the metal surface must be constant and, preferably, known. Very little has been published concerning the hydrogen-magnesium system. Winterhager has presented the most

Jan 1, 1946

By L. F. Mondolfo, F. A. Crossley

The mechanism of grain refinement by the addition of small amounts of titanium, molybdenum, zirconium, tungsten, and chromium to aluminum was investigated. The results indicate that the grain refinement is caused by the peritectic reaction which, by transforming the intermetallic compound into crystals of aluminum solid solution, seeds the melt with nuclei above the freezing point of aluminum. THE feasibility of reducing the grain size of aluminum alloy castings by the addition of small amounts of titanium, zirconium, molybdenum, tungsten, columbium, boron, and chromium has been known for a long time, and the use of some of these elements as grain refiners is common practice in the aluminum foundry industry. The purpose of the present investigation was to determine the mechanism by which these additions produce the grain refinement. Asato et al., on the basis of extensive work on copper, antimony, and silver alloys, presented a theory of grain refinement based on the occurrence of the peritectic reaction. Briefly, this theory states that during cooling of the melt crystals of the primary phase form, which react peritectically with the liquid upon further cooling. The peritectic reaction transforms at least partially the primary crystals into crystals of the secondary phase, which then act as nuclei for solidification of the remaining melt. As the peritectic reaction takes place the primary crys- tals break in pieces, and each piece acts as a nucleus. Fine dendritic crystals which can easily break are the most effective for grain refinement. Sicha and Boehm," in investigating the refining effect of titanium on an AI-Cu alloy, concluded that TiA1, crystals serve as nuclei to initiate crystallization, but did not offer further information on the mechanism of refinement. Bonsack in the discussion of their paper suggested that refinement was due to clouds of some solid in the melt, probably TiO² which hindered grain growth. Eborall,' after studying the effect of titanium, zirconium, vanadium, tungsten, columbium, chromium, and boron on some alloys, concluded that the peritectic reaction was not an essential feature of grain refinement. Her conclusion was based mainly upon the observation that under her experimental conditions (sand casting) the Al-Cr alloys, which undergo a peritectic reaction, did not show appreciable refinement. Cibula" investigated the mechanism of grain refinement and reported that two types of grain refinement exist: 1—Grain refinement produced by restriction of grain growth by the concentration gradient mechanism proposed by Northcott.' 2— Grain refinement produced by the presence of particles in the melt, upon which the melt crystallizes easily. He further concluded that very marked grain refinement results from a combination of the two mechanisms. Since Tic was found present in aluminum alloys refined by the addition of titanium, it was identified as the nucleating agent. In the case

Jan 1, 1952

By A. A. Smith, J. S. Smart

THE controlled amounts of phosphorus, arsenic, sulphur or selenium found in commercial coppers perform a variety of highly useful functions. Indeed, a large segment of modem copper technology is essentially dependent upon the presence of one or more of these elements. Consequently, the literature contains many references to their effects but the scope is broad and has been only partly covered. New data are presented herewith directed toward a better understanding of the basic behavior of these elements in copper, with particular emphasis on the composition range 0 to 0.05 per cent. These data are a part of a general program of research on the effects of impurities on the properties of oxygen-bearing and oxygen-free copper, other portions of which have been reported previously.1-2-3 Schematically, the behavior of individual elements is determined from measurements of conductivity and softening temperature,1, 2 and the binary alloys employed are synthesized from high-purity copper in order to eliminate interference from the effects of extraneous impurities. Alloys of selected composition were first prepared in the oxygen-free form by continuously casting the melts in the form of 3/8-in. diameter rod. Oxygen was added subsequently to portions of the alloys, either by remelting or by diffusion at 850°C. from a surface scale. Test wires were drawn one B. and S. number per pass, using four 30-min. 600°C. anneals at o.3125, 0.257, o.204 and o.162 in., and a final cold reduction of 95 per cent t0 0.081 in. Oxygen-bearing slugs made by remelting were hot-rolled to 5/16 in., drawn to 0.162 in., annealed for 30 min. at 600°C. and cold-drawn 95 per cent to 0.081inch. The alloys containing phosphorus, having been compounded very early in the program, were prepared in the form of 5/16-in. rod, and processed to wire with only the last three intermediate anneals listed above, all of these having been conducted in commercial nitrogen. In addition, the conductivity anneals on these alloys were also performed in the same atmosphere, and the small amount of oxygen present as an impurity in the gas resulted in some loss of accuracy at temperatures of 700° to 800°C., as will be shown later. Subsequently, the anneals for all oxygen-free alloys were conducted in hydrogen to prevent oxidation, and purified nitrogen was employed only for oxygen-bearing samples. All conductivity anneals were of one hour duration followed by a rapid quench in 10 per cent H2SO4. EFFECT OF PHOSPHORUS The widespread use of phosphorus as a deoxidant has resulted in universal appreci-

Jan 1, 1945

By Walter Fuchs

IT is now generally conceded that coal is the product of deposition and transformation of debris of forests and swamps.29 Ample data are available to illustrate the metamorphosis of biochemical substances through biological action; other data show the progressive regional metamorphism existing in coal beds ;25 and numerous examples of change effected by intrusion of igneous dikes into coal deposits have been established.23 However, often the relative importance of the biological and the geological factor in determining the character of the various natural coals is a debatable question. Since both biological and geological factors are ever present in nature, the problem, at first glance, would appear to resemble certain probability problems: specifically the simultaneous toss of two coins, with the biological factor as heads and the geological as tails. The probability is 2 : I for the combined effect of both factors, as compared to the exclusive effect of either one, if the a priori probability is the same for each factor. This condition can be analyzed by a thermodynamic treatment of data, which may be obtained from a consideration of pertinent biological, chemical, geophysical and geological facts. SYNOPSIS OF BIOLOGICAL AND CHEMICAL FACTS The biosphere is not sterile; i.e., microorganisms are always present. Microorganisms have been established in the ocean deep, under the ice of the polar regions, in the sand of the deserts, and in swamps far below the surface. The various biological media may be acid, neutral, or alkaline, and they may or may not be readily accessible to air. Microorganisms are encountered almost everywhere, except where the temperature is not within the range tolerable by microbial life. Of course, with changing conditions, the type of microorganisms will change. All chemical products of life-proteins, fats, carbohydrates, lignins, waxes, resins may serve as a habitat of microorganisms. In the decomposition of a medium. some microorganisms macerate organic matter mechanically and remove certain constituents for their own nutrition; others decompose a large part of the organic matter but may leave certain constituents undecomposed. Some attack only certain specific ingredients of the organic matter. All of them build up cell substance. The nitrogen content of the medium largely determines the degree of decomposition. Below 1.7 per cent nitrogen, growth of microorganisms and hence decomposition of organic material is retarded; consequently organic material will accumulate.17, 32 Such accumulations of organic material may give coal eventually. Coals differ in type and rank. The nature of the original vegetation and the conditions attending the transformation of the accumulated debris determine the type of coal such as bright, splint, cannel, and algal or boghead coals. Chemical analysis of representative samples of a given type of

Jan 1, 1941

By Thomas Fraser, H. F. Yancey

PRIOR to the war just ended, Germany was the greatest coal producer in continental Europe. In 1943 the production of coal, bituminous and higher in rank, together with brown coal calculated to the equivalent amount of bituminous coal, is estimated to have been about 240 million metric tons, according to the War Department. Before the war production in Germany exceeded consumption. No other country in continental Europe except Poland had a large surplus. However, England's surplus was the largest in Europe as a whole. Before World War II the Ruhr Basin normally supplied about 70 pct of the total production of high-rank coal, the Saar and Aachen about 6 pct each, Upper Silesia about 14 pct, and Silesia and Saxony the remainder. Nearly one third of the brown coal was produced in the Rhineland, a little less than one half in central Germany west of the Elbe River, and about one fourth east of the Elbe. Bituminous coal and brown coal together constituted by far the most important energy resources of the old German Reich. Bituminous coal furnished nearly 70 pct of the total energy requirement, brown coal supplied about 25 pct, and water power, wood, petroleum and alcohol together aggregated only 7 pct. Because it was the most important single mineral resource of Germany, an excess of coal enabled the Reich to import nearly all the other mineral products that she lacked, such as iron ore from Lorraine. The area adjacent to the coal fields was supplied with gas from an interconnected grid. Similar electric grids are based on brown coal with the power stations at the mines. Coal tar provided the foundation for the development of the extensive German chemical industries as exemplified by the I. G. Farbenindustrie. For almost a century, German scientists have been adequately supported both by the State and by industry in studying improved methods of utilizing coal. In Germany the mineral rights were reserved by the State and ordered extraction of coal was enforced. Each lease comprised a relatively extensive area, which accounts for the generally large size of the mines and mining companies. In 1938 there were 160 mines in the Ruhr, with a total output of 125 million tons but go pct of the production was controlled by 20 companies. By far the largest single coal-mining company in Germany was the Gelsenkirchener Bergwerke A. G., which produced nearly 27 million tons in the Ruhr in 1937. Second was Saargruben A. G., a State-owned company operating in the Saar, which produced more than 13 million tons. Third was Bergwerksgesellschaft Hibernia A. G., with 10 million tons, also in the Ruhr. Briquettes are made from both bituminous coal and brown coal, but in 1938

Jan 1, 1946

By T. W. Lippert

In these opening remarks, I will endeavor to give a background of continuous casting of metals. Only passing attention will be given to the different processes to be described by the authors whose papers are on the program, as they are far more familiar than I am with their subject matter. Suffice to say that over the past several years the brass, copper, aluminum and magnesium industries have shifted practically completely from conventional static molds to continuous casting machines. The Aluminum Company of America alone has more than 60 continuous machines in operation. The product as continuously cast is superior metallurgically, less scrap loss is involved, costs are generally lower, and the equipment requires little floor space. A continuous machine, operating as it does with deadly constancy, is a ravenous consumer of molten metal, and in most plants one or two machines are well able to handle large banks of melting and refining furnaces. In steel, interest in continuous casting is today more serious than ever before in history, and there is every reason to believe that continuous machines may secure a minor place in the ferrous industry, particularly for tool and alloy analyses. In the past, steel has been commercially cast continuously, and today many tons of steel are being turned out in this manner. It has been said that the cradle of every science is surrounded by dead theorists— and certainly there are innumerable examples of this in the metals industries. An excellent illustration, for instance, is the continuous rolling of metal, a tantalizing objective that for decades on end exhausted . the efforts of a long line of famous, infamous and unknown inventors. Finally, in 1922, John B. Tytus, of the American Rolling Mill Co., brought forth what now seems such an obviously simple scheme— a concave roll face, each stand of progressivcly less concavity. And out of this one change in design sprang today's wide continuous mill rolling steel sheet Ioo in. wide at 2000 ft. per minute. Another excellent example is the con- . tinuous casting of liquid metal into an intermediate form, preferably one requiring little subsequent breakdown. First, the casting of liquid metal alone was fascinating enough. Then someone passed the cast metal directly into a rolling mill, and shortly thereafter this continuously rolled strip was passed directly into a stamping machine. This leitmotiv of a continuous flow of metal from the liquid phase to a consumer end product, fast and inexpensive, and all housed within a small space, was enough to drive some 200 or so inventors into frenzy over the past hundred years. All the ideas, however, like mayflies, had only their brief afternoon of existence. They were born and they died on paper, as constant exemplification of that great void that always exists between mental production and commercial production.

Jan 1, 1945

Discussion of the papers of FREDERICH LAIST and HAROLD W. ALDRICH, FREDERICH LAIST and F. F. FRICK, W. L. AUSTIN, and STUART CROASDALE, presented at the Salt Lake meeting, August, 1914, and printed in Bulletins No. 91 and 92, July, and August, 1914. R. C. CANBY, Wallingford, Conn. (communication to the Secretary*). -Apropos of the experimental reduction of copper from cuprous chloride by fusion with ground limestone and coke, as described by Messrs. Laist and Frick, and also proposed for use at Chuquicamata., it might be of interest to refer briefly to the experience at Argentine, Kan., in the smelting of the suboxide of copper (as produced in the Hunt and Douglas process) containing appreciable quantities of chlorides. In the Engineering and Mining Journal of June 10, 1911, I. gave some account of what had appeared to be crucial difficulties with the Hunt and Douglas process, and how the filter-press difficulty had been so rapidly overcome after my discovery of the effect of the sodium salts in the leaching solutions. I also described the effect of the cupola furnace gases upon the lime rock with which I had replaced the coke in the absorption tower, which apparently showed the presence of considerable-chlorine, clue to the imperfect conversion of the subchloride to suboxide, as well as that clue to the difficulties of washing thoroughly the suboxide with the means provided, and also to the presence of chlorides in the cement copper which was smelted With the suboxide. The fumes from the cupola, when issuing direct into the atmosphere, were very dense and white, except when a hot furnace top caused a reddish tinge due to dust. These, fumes had a peculiarly suffocating effect, so that when they were blown over into the town the population suffered the greatest actual distress, not the mere annoyance which would have been clue to a disagreeable odor. The absorption tower had been built at the instance of the city authorities to abate this nuisance, and not with the idea of making any additional metal savings. A serious feature in connection with the Argentine experience with the Hunt and Douglas process was, that it had been implicitly assumed that there could be no metal loss in the Hunt and Douglas process itself, and that all attempts to locate the ruinous copper losses which were accumulating in the metallurgical accounts were devoted to the roasting department. It is possibly unfortunate for metallurgical advance along these particular lines that just about the time of this discovery of this previously unsuspected volatilization loss, in the smelting of the suboxide, the Kansas City company made a contract with the Western Union Telegraph Co. for its supply of copper sulphate and the Hunt and Douglas

Jan 11, 1914

By H. M. Dess, S. R. Bolin

A modifiedl Czochralski technique has been utilized to grow single crystals of YVO, pure or doped with europium or neodymium, from 1 to 2 in. long and 4 to 1/2 in. in dianz. An oxyhydrog-en gas-fired furftace zuas used in this ulork, and melts were contained in iridium crucibles. Successful application of the Czochralski ~vzethod was found to depend upon atmosphere control to prevent crusting and to limit melt decomposition, the establishment of symmetrical thermal gradients in the melt to obtain stable growth, and the selection of high-quality single-crystal seeds to prevent propagation of misorientations during growth and subsequent catastrophic cracking. The suitability of YVO4 as a host for laser-active trivalent rare earth ions has long been recognized. However, the problems associated with the growth of sufficiently large, good-quality single crystals have, until quite recently, seriously hindered satisfactory evaluation of the laser potentialities of this material. Both flux growth and Czochralski growth techniques were investigated at an early stage of interest in YVO,. The former method proved incapable of yielding crystals large enough for practical use,ly2 and the latter was beset with difficulties which took some considerable time to understand and overcome. Recently, however, the Czochralski growth process for YVO, has been improved along separate but similar lines of development by groups working independently in the Crystal Products Department of Union Carbide's Electronics Division and Bell Telephone Laboratories3 so that now good-quality single crystals of satisfactory size can be produced on a routine basis. Stimulated emission from a neodymium-doped YVO4 crystal grown by the Crystal Products Department of Union Carbide was obtained by O'connor4 of MIT, Lincoln Labs. An oxyhydrogen gas-fired furnace was used in this work, Fig. 1, and melts were contained in iridium crucibles. The starting material was 99.9 to 99.99 pct pure YVO4 powder purchased from the Chemical and Metallurgical Division of the Sylvania Electric Products Co. Typical impurity levels, determined by spectrographic analyses, were as follows: Si, 50 to 500 ppm Al, Fe, Mg, 5 to 50 ppm Ni, Pb, Mo, Mn, Ce, Cs, 1 to 10 ppm Initially, YV04 powders predoped with neodymium or europium were obtained from Sylvania. Later, however, because of a desire to grow a series of crystals containing relatively broad concentration ranges of these dopants, it proved more convenient to start with pure YV04 and mechanically admix Nd2O3 or Eu@~ powders plus equimolar amounts of V2O5. The empty crucibles were preheated to 1900" to 1950oC, a temperature range where melting occurred readily. The powdered YVO4 feedstock was then added incrementally. However, a marked tendency toward

Jan 1, 1968

By W. W. Smeltzer

The linear formation rates of wustite films have been determined over the temperature range 590° to 1030°C using a vacuum microbalance technique. These rates are dependent directly on the partial pressure of carbon dioxide, Activation energies for film and scale formation in carbon dioxide and oxygen atmospheres are equivalent to either the dissociation energies of carbon dioxide and oxygen, or the activation energy for the diffusion of cation vacancies in wustite. Of the metals, iron is the most widely used basic constituent of durable alloys despite its intrinsic property of converting at a relatively rapid rate to the oxides from which it is derived. This property has accounted partially for many investigations on the oxidation of iron at low and high temperatures. Interpretation of the results have been complicated by formation of multilayers containing the various oxide phases. To aid in elucidation of the oxidation kinetics, measurements have been carried out in this investigation on the growth of the wustite surface layer. There are several studies directly related to the objective of this investigation. The growth of multilayer scales has been demonstrated to be diffusion controlled in oxygen at atmospheric pressure over the temperature range 450" to 1200°C by Davies, Simnad, and Birchenall.' To gain an insight into the diffusion mechanism, Himmel, Mehl, and ~irchenall' determined the self-diffusion coefficients of iron in wustite, magnetite, and hematite. These results were used to evaluate the oxidation rates of iron and its oxides, taking as a basis the theoretical parabolic rate equation developed by Wagner., The evaluations were compared to experimental data and were shown to provide essential confirmation of this theory. Fischbeck, Neundeubel, and salzer4 have demonstrated that the oxidation of iron in carbon dioxide and other atmospheres at high temperature obeys a linear relationship. Because the Arrhenius temperature coefficients of the reaction rate constants changed at the A, point they concluded that the passage of iron into the oxide controlled the reaction. This viewpoint has been accepted by Benard and ~albot' to explain the occurrence of linear rates in oxygen before the onset of diffusion-controlled parabolic oxidation. This basic premise of a rate-controlling reaction at the iron/oxide interface has been questioned recently by Hauffe and Pfeiffer.' Since the formation of wustite may follow a linear or parabolic relationship depending on the pressure of the gaseous re-actant, they propose that linear oxidation is determined by a chemisorption reaction while parabolic oxidation is controlled by diffusion. As confirmation of this viewpoint, Hauffe and pfeiffer6 and Pfeiffer and ~aubmeyer' have established that the linear scaling constants of wustite formation at 1000°C in carbon-dioxide or low-pressure oxygen atmospheres

Jan 1, 1961

By Lloyd R. Jackson

In the past 15 years there has been a great deal of interest in the fundamentals of plastic flow and rupture in metals and a number of papers have presented substantial advances toward a fundamental insight into the mechanism of these two processes. This paper is an appraisal of the present position with respect to the following: 1. The relative importance of shear and hydrostatic stresses in controlling the plastic flow of metals. 2. The relative importance of shear and hydrostatic stresses in determining the amount of flow before rupture in metals. 3. The use of generalized strains in determining the effect of plastic flow on the work-hardening of metals. FundamentalS Involved in Plastic Flow In attempting to devise a quantitative description of plastic flow in metals, it has been customary to assume that metals are homogeneous and isotropic. The fact that neither of these assumptions is correct complicates the experimental appraisal of relations developed. Nevertheless, as will be shown, metals are close enough '0 being isotropic and homogeneous so that considerable insight into the mechanism of plastic flow can be obtained. The assumptions of isotropy and homogeneity allow both the elastic and plastic behavior of metals to be described in terms of 12 variables—six being stress variables, and six being strain variables. From this viewpoint, it should be possible to represent the stress-strain relations in the plastic range for metals by a surface in 12 dimensions. One boundary of this surface would be the surface of transition from elastic to plastic behavior; the other would be the surface of rupture. These two surfaces would be joined by the surface of plastic flow. The shape of this composite surface would depend on the test temperature and speed of straining This paper is concerned only with results obtained at constant temperature and constant speed of straining. While such a representation is conceivable, the demonstration of such a surface would present almost insurmountable obstacles. The most fruitful simplification of this concept has been the recognition that the behavior of metals in the plastic region is primarily a result of shear stresses and strains. Based on this viewpoint, it is possible to utilize stress and strain invariants that are independent of hydrostatic components to define an effective stress and strain. In effect, this amounts to reducing the task of representing stresses and strains in 12 dimensions to one of representation in two dimensions. The two invariants (one for stresses and one for strains) that have received most attention are the following: q2 = ½[(Txx= - Tyy)2 + (Tyy - Tzz)2 + (Tzz - Txx)2 + 3(Txy2 + Tyz2 + 7xx2) [1]

Jan 1, 1947

By Warren E. Wilson

The transportation of solids in pipe lines is a matter of deep concern in many fields of engineering. Much experimental and theoretical work has been done in an effort to devise means of designing pipe lines that will satisfactorily transport given solid loads, but there remain many unanswered questions in this field. The present discussion will be confined to a rather narrow portion of this field and will endeavor to point out certain factors that may well be considered when comparing the relative economy of various installations. The data have been presented previously but a new interpretation was prompted by a suggestion in a paper by Professor O'Brien,' of the University of California, that the friction work per pound of dry material should be considered in determining the relative efficiency of various installations. This method of considering relative economy in various pipe lines leads to some rather unexpected conclusions, especially with reference to the economy of large pipe sizes. A previous suggestion by the writer concerning the economy of a rather peculiar type of installation is strengthened. It is not believed that the considerations set forth herein apply directly in the case of dredge lines, where economy is largely a matter of a high rate of pumping in order to reduce the unit overhead charge. However, it is believed that some value may be gained from these considerations in cases involving the disposal of a fixed amount of solids per unit time with a minimum expenditure of energy and at a low cost for replacement of worn pipes. Such situations are not uncommon in the disposal of mill tailings and the disposal of solids deposited from irrigation waters. It was found that data leading to general conclusions for various pipe sizes were not available but certain definite trends are indicated and methods of analyzing available data are presented in the hope that they may be of assistance in preparing engineering estimates on designs of pipe lines of the type described above. Energy Requirements Carrying out the idea contained in Professor O'Brien's paper concerning the method of computing energy required to transport solids, the following analysis leads to some rather interesting conclusions. Let us represent: Solids load in terms of mass per unit time by w Ratio of mass of suspended solids to total mass of mixture flowing by p Volume rate of flow of mixture by Q Length of pipe by L Slope of energy grade line by s Mass per unit volume of solids by m8. Mass per unit volume of liquid by mi Mass per unit volume of mixture by 11 We then have as an expression for the solids load: w = pqmm The work done per unit mass, p, on the mixture to move it along the pipe the

Jan 1, 1947

By M. J. Marcinkowski, D. Koskimaki, A. S. Sastri

THIS is the second in a trilogy of investigations carried out in order to understand the solid state transformations and their accompanying effects on the deformation behavior of near-equiatomic Ni-Ti alloys. The first stage of this effort has dealt with the strictly martensitic structures obtainable in these alloys, i.e., those in which diffusion processes were not involved.1,2 These martensites could be produced either by rapid quenching or by plastic deformation of the originally B2 type phase. The present investigation, on the other hand, will deal with those transformations in Ni-Ti which do involve diffusion. A majority of investigators3-10 have shown that the B2 modification of TiNi, which is stable at elevated temperatures, decomposes into one or both of the intermetallic compounds NiTi2 and Ni3Ti below about 650°C. On the other hand, this has been disputed by several Workers was undertaken in order to resolve this discrepancy, as well as to shed more light on the nonmar-tensitic decomposition of B2 NiTi. EXPERIMENTAL PROCEDURE Sample preparation, fabrication, and examination were the same as those described previously in Ref. 2. In addition to the 50 at. pct Ni (55.06 wt pct) hypoeu-tectoid alloy used previously, a second hypereutectoid alloy containing 54.4 at. pct Ni (60 wt pct) was also prepared for this study. RESULTS AND DISCUSSION The equilibrium diagram for the Ni-Ti alloy system in the vicinity of Ni-Ti is shown in Fig. 1. The solid lines have been established by the work of Poole and ~ume-Ftothery4 whereas the dotted lines are based on findings obtained in the present investigation as described below. Structure and Morphology. Fig. 2(a) shows a bright field transmission electron micrograph of a two-phase structure obtained in a polycrystalline Ni-Ti alloy that was furnace cooled (approx 200°C per hr) from 1050' to about 300°C. Large plate-shaped precipitates can be observed in a matrix which was found by electron diffraction to possess the high temperature B2 structure. A selected area diffraction pattern of the region covered by Fig. 2(a) is shown in Fig. 2(b), while Fig. 2(c) is a detailed schematic interpretation of Fig. 2(b). The B2 matrix reflections are illustrated by squares while those of the precipitate are shown as circles. The d values associated with the precipitate reflections could be determined quite accurately since the reflections from the B2 matrix, for which the lattice constant is known precisely, were simultaneously present in the diffraction patterns. All of the reflections

Jan 1, 1970