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By K. Takahashi, I. Iwasaki

The methyl stretching vibrations for a series of normal xanthates, isoxanthates and normal amines were determined with the aid of an infrared spectro-photometer, and the results were compared with published information on the corresponding alcohols. The frequency shifts of methyl stretching vibrations may be attributed to the inductive effect of polar groups. The hydrogens in the shorter chain alkyl groups are somewhat polar and can be expected to interact with water molecules by hydrogen bonding. Contact angle, surface tension lowering, solubility, and critical micelle concentration appear to be related to the induced polarity of the alkyl groups. Traube's rule states that in homologous series of compounds solubility decreases and surface activity increases regularly with the size of the hydrocarbon group. Analyzing the work of transfer of a solute from solution to surface, Langmuir' interpreted this rule to mean that each CH2 group added to a molecule produced its effect independently of the others. It is also well known2 that the maximum equilibrium contact angle with sulfhydryl collectors is independent of the polar groups and of the sulfide minerals, and that it increases to a certain limit with the number of carbon atoms in the alkyl group. This observation is thought to demonstrate the orientation of the collector molecules at the sulfide surfaces. The dependence on the hydrocarbon chain length is usually explained as due to the screening of the force field of polar mineral surfaces.3-5 Here again, Langmuir's principle of independent surface action appears to be implied. Heteropolar compounds consist of nonpolar and polar groups, the former being the hydrocarbon group and the latter containing such electronegative atoms as O, N, S, P, or halogens. According to Palit6 the hydrogens in the alkyl groups are more electroposi- tive than in the paraffins owing to the negative inductive effect of the polar groups and a possibility that a hydrogen bond with water molecules ensues. Goto and Takenaka7 provided direct evidence of the inductive effect by measuring the shift of the C-H stretching vibrations of alcohols, acids, and alkyl bromides with an infrared spectrophotometer. Their approach appeared to be directly applicable to the studies of surface activity both at air-water and water-mineral interfaces encountered in flotation systems. The present article attempts to relate the C-H stretching vibrations of alkyl xanthates, alcohols, and amines with such flotation chemistry parameters as contact angle, surface tension lowering, solubility, and critical micelle concentration. MATERIALS AND METHODS Normal xanthates from methyl to octyl inclusive and the isopropyl, isobutyl, and isoamyl xanthates used in this investigation were prepared in the usual manner.8 Normal amine hydrochlorides with carbon chain lengths of 1, 2, 4, and 6 were from Distillation Products Industries, of 8 from Archer-Daniels-Midland Co., and of 10, 12, 14 and 16 from Armour and Co. Normal propylamines, pentylamines and heptylamines from Distillation Products Industries were used both as received and as hydrochloride formed by converting the amines according to the procedure described by Li9 Perkin-Elmer Model 521 and 621 infrared spectro-photometers were used to investigate the spectra in the frequency region of 3050 to 2800 cm-' with frequency scale expansion. The accuracy of the frequency readings was within + 1 cm-1. The KBr micropellet technique was used to prepare the xan-thate samples for measurements, and the halocarbon mull technique was used for amines and amine hydrochlorides. EXPERIMENTAL RESULTS Fig. 1 shows the CH3 asymmetric stretching vibrations as a function of the number of carbons in the alkyl group for normal xanthates, isoxanthates and amines. Also included in the figure are data for normal alcohols and isoalcohols taken from the article

Jan 1, 1970

By E. Martinez

Samples of chrysocolla, a hydrated copper silicate, from several sources were submitted to differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). Pure samples of chrysocolla are difficult to obtain, but comparison of the thermograms revealed that certain reactions occurred in all the samples and it is believed that these are due to chrysocolla. Endothermic reactions occurred at 50' to 175°C, 350° to 650°C, and 980° to 1100°C each of which caused a weight loss. The first was due to loss of absorbed water, the second to a dehydroxyla-tion, and the last to conversion of cupric oxide to cuprous oxide. In addition, two exotherms were detected at 685° to 695°C and 935° to 950°C. Infrared spectra of heated samples indicated the exotherms were due to changes in the Si-O bonds leading to the formation of cristobalite. The results suggest that thermoanalysis may be a more sensitive and reliable method for detection and identification of chrysocolla than X-ray diffraction, infrared spectroscopy, or optical techniques. The recovery of copper from oxide ores has been the subject of much research in recent years. One of the principal oxide copper minerals is chrysocolla, a hydrated copper silicate. The information available indicates that it has widely varying properties depending on the origin of the sample. Chrysocolla usually is found associated with cuprite, malachite, azurite, and native copper. Most of these other minerals are recoverable by present day flotation practice, but chrysocolla is lost in the tailings.1,2 Reagent combinations that are successful in laboratory chrysocolla flotation with ore from one source have been found to be ineffective with another. 3 The copper segregation process offers an altemative to beneficiation of oxide copper ores.4'5 The process is of particular interest in processing ores that cannot be treated by conventional hydrometal-lurgical methods because of high acid consumption.6 Fuller understanding of the properties of chryso- colla may prove of value in the search for improvements in both the flotation and segregation processes. Chrysocolla samples from Arizona, Nevada, Chile, Australia, and South Africa were studied by differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). In addition, a sample from Miami, Ariz., was submitted to X-ray diffraction, infrared spectrophotometry, and surface area determination. EQUlPMENT Differential thermal analysis (DTA) detects, amplifies, and records exothermic-endothermic reactions occurring in a sample as its temperature is raised at a constant rate, usually 10°C per minute. A unit made by the Robert L. Stone Co. was used in this study. The tests can be run if desired with a gas streaming through the sample. A thermobalance records weight losses or gains in a sample as its temperature is raised at a uniform rate. The gravimetric analyses (TGA) were run on a Chevenard thermobalance converted electronically for graphic recording. A heating rate of 5°C per minute up to 1100°C was used in these tests. A Perkin Elmer Infrared Spectrophotometer, Model 221, was used with sodium chloride optics obtaining IR spectra in the 2 to 15 region. A pressed pellet technique with potassium bromide was used in preparing the samples. DESCRIPTION OF SAMPLES Chrysocolla is found in the oxidation zones of copper deposits commonly associated with malachite, azurite, and limonite. It is described as varying in composition and in color from bluish green to brown or black. Inclusions of other minerals are usual so chemical analysis of chrysocolla samples may be suspect. However, it is considered by many to be a solid solution of CuO, SiO2 and H2O with a general formula of CuO.SiO2.2H2O or 2CuO.2SiO2. 3H20. Chukhrov7 has described a sample from the Urals as CU3,5(OH)2 (A1Si3) O10.nH2O and stated that chrysocolla is a montmorillonite-type mineral. On the basis of X-ray analyses, DTA, and infrared spectra of chrysocolla from the Inspiration Mine, Ariz., Sun8 concluded that there was no substantial evidence to classify it as a montmorillonite mineral. Chrysocolla samples from many sources throughout the world were used in this investigation. The following is a brief description of each:

Jan 1, 1963

A LARGE attendance at the annual dinner of the Institute, to be held this year on Tuesday eve-ning of convention week, is already assured. Presentation of the Douglas, Hunt and Saunders medals will attract unusual attention since not only in Blaylock, Mathews and Hoover the Institute will be honoring men who have made notable contributions to the advance-ment of their profession, but as to one of them each person as he passes down the reception line will be won-dering whether in renewing acquaintance with our past-president and present Secretary of Commerce, he is not greeting the next president of the United States. Elsewhere in this issue accounts of the professional careers of these three men appear as also of the two younger men, Charles H. Herty, Jr., and P. H. Royster, who are to receive the Robert W. Hunt and the J. E. Johnson awards. Institute honors go for technical achievement, but the Institute will be proud and happy if the nation should later confirm its own judgment by placing larger responsibilities on one of its members. The medals are to be presented at the annual dinner following the President's reception and preceding the dance. There will be no. other speeches and since the occasion falls on Carnival Night a particularly gay evening is anticipated. The event will be at the Wal-dorf as usual, and members are urged to return prompt-ly the reservation cards sent them by mail. Other entertainment features will include a Smoker, Monday evening at 8.15, held at Mecca Temple and in charge of a new committee with Fred Kay of the Petro-leum Division as chairman. He promises that vocal music will not be allowed to interrupt conversation. Lunch will be served each day on the Fifth Floor of the Engineering Societies Building, and ten special luncheons and dinners have been arranged for particu-lar committees and groups as shown by the detailed program. The Woman's Auxiliary has laid out a gen-erous program including luncheons, teas, a theater party on the night the men folks go to the Smoker, visits to museums and, not the least important, a round of the leading shops. The Excursion Committee is arranging for an excur-sion sure to be of interest. The American Smelting and Refining Co. has opened its great Perth Amboy plant to the Institute, and on Thursday, Feb. 23, a party will be taken to it by bus traveling through the Holland Tunnel en route. Full opportunity will be afforded those interested to see the workings of the ventilation system of that great public work. If a sufficient number indicate interest, arrangements will be made for group excursions to other plants in the vicinity of the city.

Jan 2, 1928

By Frederick Sharpless

THE term "segregation," as here used, means the separation of certain natural resources into groups, consisting of one or more members, with the idea that when thus segregated, each group may be more easily and effectively administrated. We may, for example, consider surface rights as distinct from underground rights, and stop there; or we may go further, and deal separately with timber, water, and agricultural rights, or, going underground, we might deal separately with such groups as precious and base metals, clay, oil, gas, etc. The present paper contemplates only the separation so far as practicable, for administrative purposes, of surface from mineral rights. "Classification," in this paper, has reference to the groups into which the government has divided, is dividing, or will hereafter divide its natural resources; first, into the broad classes of mineral and agricultural lands; and, second, into coal, oil, phosphate, brine lands, etc., the central idea being the separation into natural groups for the purpose of simplifying administration and for the purpose of encouraging maximum development and minimum waste. The two subjects are in some respects quite distinct, but as my argument develops, I think it will be obvious why they are discussed in the same paper.

Jan 4, 1914

By T. I Harkins, J. Brian Eby

This paper outlines the geophysical investigation of the area covering the Darrow salt dome, Louisiana. Surveys with the refraction seismograph and torsion balance failed to disclose the dome, but reflection dip shooting was successful and was confirmed by later drilling. Introduction The Darrow salt dome and oil field lies in western Ascension Parish, Louisiana, on the outside of a sharp bend and on the east bank of the Mississippi River. The dome occurs about 30 miles south of Baton Rouge and 80 miles northwest of New Orleans. Its geology, shape and structure have been ably described in detail by Carroll E. Cook1 and, except for the general features, will not be repeated here. The purpose of this paper is to record some of the interesting and pertinent geophysical data contributing to the discovery of the dome and eventually the oil field. The salt dome is circular in outline and comes to within about 4625 ft. of the surface. At this depth the diameter of the salt plug is approximately 4800 ft. The dome has only a thin cap rock of less than 75 ft. Some oil has been found and is being produced in Miocene sands above the cap rock, but most of the field's production comes from a narrow ring of wells around the east and south flanks of the dome. Producing horizons on the flank are found at 5670 to 5840 ft. in the Miocene and 6890 to 6985 ft., 7028 to 7060 ft. and 8260 to 8270 ft. in the Oligocene. The deepest well that has been drilled is the Humble Oil and Refining Company's Community B-5, on the south flank of the structure, which reached a depth of 10,013 feet. The size and shape of the field and the area of production are indicated on Fig. I. The line showing the area of production encloses all wells now producing and all abandoned producers, both on the top and flank of the dome. This line of production is shown on all subsequent geophysical maps as a direct means of comparing the early geophysics to later drilling development. Darrow dome occurs on the low, flat flood plain of the Mississippi River; it is protected from flood overflow by high artificial levees. The rich loamy soil supports a high degree of cultivation, principally sugar cane. Drainage is secured by many small canals and the water table of the area is at or near the surface. These particular conditions of topography, drainage and top soil greatly influenced the early geophysical picture, and the influence was always unfavorable. Surveys with Refraction Seishograph and Torsion Balance A reported oil show in a water well drew attention to the lands of the Belle Helene

Jan 1, 1943

By W. B. Stephenson

In the pumping of sands, slurries and slimes, practices developed over the years are the real keystones of 'successful operation. These practices are necessarily based on modifications of familiar theories. Practical methods used in the solution of problems involving the pumping of materials are set forth in the following discussion. Basic Requirements To pump sands and slurries economically, a few basic requirements must be met by the pumping system as a whole. A pipe-line velocity must be established that will move the fluid mixture throughout the entire system without any possibility of the solids settling out. To accomplish this, the velocity of flow must be slightly in excess of the critical velocity of the mixture. The critical velocity of a mixture varies from 3 ft. per sec. to 18 ft. per sec., depending on the screen analysis, concentration, and specific gravity of the solids in the mixture. Most tailings are pumped at a minimum velocity of 4 ft. per sec. if they include slimes, whereas the pipe lines of sand and gravel dredges require velocities as high as 18 ft. per second. A number of articles have been written on the determination of the minimum velocities required to maintain solids in suspension. Studies have also been made on the friction and pumping heads developed when handling solids in suspension.1-4 Our experience so far has shown that, within the normal operating limits of a pumping system, the friction factor follows more nearly the basis described by Howard,' who says, among his conclusions: "... values of f (friction factor) . . . will decrease with an increase in velocity." This conclusion is borne out by our actual experience. When the velocity in a pipe line is not sufficient to keep the solids in suspension, the total friction head' is greater than when the velocity is increased to a point where the solids are in suspension. A slight increase in the volume of feed to the pump and a slight increase in the pump speed are usually all that is necessary to put the system in balance. Maintaining Constant Volume Within reasonable limits, the volume of mixture to be handled through a pipe line should be held constant, so that the required velocity will be provided at all times. There are several ways in which this can be accomplished. The commonest is to provide a sump of sufficient capacity to take care of slight surges in the volume of mixture being fed to the pumping systen]. This sump, however, should not be as large as a settling chamber. The use of a float-controlled, fresh-water make-up valve in a sump will guarantee a constant volume. Where variations in volume are slight,

Jan 1, 1947

By S. L. Hoyt

The writer has long been interested in seeking an explanation of the upper heat effect in the copper-tin alloys over the a + b range, first described in 1913. These notes are offered, not at all as the final explanation 'of this heat effect, but rather to indicate certain progress which has been made toward establishing what happens over this temperature interval. While working on the thermal analysis of the copper-rich kalchoids (copper-tin-zinc alloys), it was noted that those alloys containing major portions of tin and minor portions of zinc exhibited two marked heat effects, one at about 520' C. and the other at about 600" C., instead of the single effect which is generally observed in either of the two binary series. This matter was discussed with Dr. Guertler, who suggested that a heat effect at about 600" C. in the pure copper-tin alloys might be expected. This led to a more searching examination of the thermal critical points in the pure copper-tin alloys, with the result that a marked, although somewhat weak, heat effect was located at about 600. Somewhat later, this upper heat effect was discussed with Dr. Burgess, and it was requested that the Bureau of Standards make heating and cooling curves of one of these alloys for the purpose of removing any possible doubt as to the actual presence of the heat effect. Results obtained by the Bureau are given in Plate I. In an earlier paper1 differential curves were published showing that the heat effect occurred at constant temperature over the a + B range and increased in magnitude with the amount of B up to a point somewhat above 20 per cent. tin. No heat effect was noticed at this temperature in the eutectoid alloy. The existence of this heat effect seems to require a modification of the present copper-tin diagram in the a + B field, and it has been the object of the work here presented to secure the evidence upon which such a change should be based.

Jan 1, 1919

By J. Brian Eby, T. I. Harkins

This paper outlines the geophysical investigation of the area covering the Darrow salt dome, Louisiana. Surveys with the refraction seismograph and torsion balance failed to disclose the dome, but reflection dip shooting was successful and was confirmed by later drilling. Introduction The Darrow salt dome and oil field lies in western Ascension Parish, Louisiana, on the outside of a sharp bend and on the east bank of the Mississippi River. The dome occurs about 30 miles south of Baton Rouge and 80 miles northwest of New Orleans. Its geology, shape and structure have been ably described in detail by Carroll E. Cook1 and, except for the general features, will not be repeated here. The purpose of this paper is to record some of the interesting and pertinent geophysical data contributing to the discovery of the dome and eventually the oil field. The salt dome is circular in outline and comes to within about 4625 ft. of the surface. At this depth the diameter of the salt plug is approximately 4800 ft. The dome has only a thin cap rock of less than 75 ft. Some oil has been found and is being produced in Miocene sands above the cap rock, but most of the field's production comes from a narrow ring of wells around the east and south flanks of the dome. Producing horizons on the flank are found at 5670 to 5840 ft. in the Miocene and 6890 to 6985 ft., 7028 to 7060 ft. and 8260 to 8270 ft. in the Oligocene. The deepest well that has been drilled is the Humble Oil and Refining Company's Community B-5, on the south flank of the structure, which reached a depth of 10,013 feet. The size and shape of the field and the area of production are indicated on Fig. I. The line showing the area of production encloses all wells now producing and all abandoned producers, both on the top and flank of the dome. This line of production is shown on all subsequent geophysical maps as a direct means of comparing the early geophysics to later drilling development. Darrow dome occurs on the low, flat flood plain of the Mississippi River; it is protected from flood overflow by high artificial levees. The rich loamy soil supports a high degree of cultivation, principally sugar cane. Drainage is secured by many small canals and the water table of the area is at or near the surface. These particular conditions of topography, drainage and top soil greatly influenced the early geophysical picture, and the influence was always unfavorable. Surveys with Refraction Seishograph and Torsion Balance A reported oil show in a water well drew attention to the lands of the Belle Helene

Jan 1, 1943

By J. J. Jakosky

A REVIEW of the progress in applied geophysics during the recent depression years reveals marked advances "over the methods employed several years ago. Of late, geophysical work has been curtailed to a con-siderable extent in the fields of oil and base-metal exploration, its especial domains a few years ago. Greater attention has been directed toward the use of geophysical technique in other engineering problems. Constantly maintained research programs have developed new instruments and per-fected better field, laboratory and interpretation techniques based on experience and skill acquired from years of application in the older geophysical field. During the past two years, geophysical methods have been employed in problems that required information on thickness of fill materials and subsurface bedrock contours. Considerable success has been attained, with subsequent drilling checking the predicted depths within one to five per cent. In general, these problems were similar as far as the fundamen-tal physical and geological conditions were concerned, but they have varied widely in specific detail and in engineering aspects. Character-istic of the different problems are: (1) yardage and bedrock profile in gold-placer mining; (2) water supply, involving underground drainage and storage conditions; (3) bedrock contours in dam-site and other structural investigations; (4) gravel and fill yardage, and other structural features along rights of way and in rock and gravel quarrying. Of particular interest, perhaps, to mining men are the problems of gold placer deposits and water supply. Geophysical work on gold placers is of especial interest because of the present expanded activity in all phases of gold mining. The development of a suitable water supply at, an economical cost is often of prime importance in insuring a successful mining venture. Particularly is this true in the arid Southwest. How-ever, the use of geophysical work in water supply is not confined to the needs of mining development.

Jan 1, 1933

By Andrew B. Crichton

THE oft repeated statements of the United States Geological Survey and the Bureau of Mines that the coal reserves in the United States are sufficient for 3000 yr have given us all a sense of security hard to disturb. If we discount that statement 66 pct, which to the uninformed seems drastic, we would still have 1000 yr supply, and why should mortal man worry about the difference between 1000 and 3000 yr supply of coal. That is exactly the attitude which many who should be better in- formed have taken toward the problem. A recent brochure "How Strong is America," by the New York Herald Tribune, states there is "no end to coal * * The truth is staggering * * U. S. has enough coal to last 4000 years." What the statement actually means is that the calculator got as high as 4000 yr and decided it was pointless to go on. The President's ERP Committee on Natural Resources and others in high places continue to assure the country of our superabundance of coal. In the past few days the “Wall Street Journal" carried an item from Director Boyd of the Bureau of Mines saying that within a hundred years we would need to triple our annual coal production of 6oo,ooo,ooo tons, making it 1,800,000,000 tons annually, and at that rate we had coal reserves sufficient for 1000 yr. In my humble opinion, we cannot now or ever produce 1,800,000,000 tons annually, be- cause we do not have the reserves in the producing districts to do it. Past reckoning in geology may be, as in the Psalms, a thousand years are as yesterday, but the future must be considered more realistically, and "a thousand years" is really a "heck" of a long time. In most developed areas, mining engineers can count the coal reserves in terms of a hundred years or less, and in some important areas now producing large annual tonnages in much under fifty years. They think when they hear of thousands of years coal reserves, reference is made to distant fields and "the fields are always green far away." The estimates of our coal reserves upon which we are relying were made in 1907 under the direction of Marius R. Campbell, Director of the United States Geological Survey. It is apparent this work was not well done. It was necessarily based on rather meager data because of the little development and prospecting as of that date. There were mistakes in the correlation of seams, and they assumed the continuity of thick seams throughout large coal bearing areas where coal often did not exist. The overstatement of coal bearing areas in the Campbell figures are common. The 1907 survey includes all coals over 14 in. in thickness to a depth of 3000 ft. The total coal reserves according to Campbell were 3157.2 billion tons. The production and mining losses that year would amount to -570 million tons and

Jan 1, 1948

By E. C. Houston

The presence in the Tennessee Valley of extensive deposits of olivine, a silicate of magnesium and iron that contains approximately 28 per cent magnesium, has been recognized since 1896 when Lewis8 published a survey of basic magnesium rocks of western North Carolina. A recent field survey by T.V.A.7 showed that more than two hundred million tons of high-grade olivine occurs above local drainage levels in western North Carolina and northern Georgia. Except for sporadic attempts to work the olivine for its nickel and chromium contents,10 the ore received little attention industrially until 1926 when Goldschmidt3 suggested its use in the manufacture of refractories. Only one instance is recorded of an attempt to utilize the ore commercially for its magnesium content;" in this case a process was used in which olivine was treated with sulphuric acid, the resultant mixture was leached with water, and the leach solution was purified and evaporated to form epsom salts, which was the end product. As a part of its program of contributing to the development of the natural resources of the region, the Tennessee Valley Authority became interested in the olivine deposits as a source of metallic magnesium because of their high magnesium content and proximity to hydroelectric power. Studies were undertaken to determine the feasibility of producing magnesium chloride by extraction of olivine. The experimental work was carried out successively at the T.V.A. Minerals Testing Laboratory, Norris, Tenn., at the Georgia State Engineering Station,* Atlanta, Ga., and at the T.V.A. laboratory at Wilson Dam, Ala. The present paper describes a process. developed through the pilot-plant stage, whereby magnesium chloride suitable for reduction to metallic magnesium can be prepared from olivine by extraction with hydrochloric acid and subsequent purification. Research on the magnesium-from-olivine process, originally intended for peacetime use, was given impetus by the shortage of magnesium that existed at the beginning of the current world war. By the time the process was sufficiently developed to justify a proposal for its inclusion in the war program, the shortage had been met by expansion and development of other processes. However, it is believed that the magnesium-from-olivine process may have advantages that will warrant consideration of its use after the war, when the economics of the various processes rather than production on a wartime scale will be the criterion for commercial production of magnesium. Description OF Process Metallic magnesium is produced electro-lytically by the Dow and the Elektron

Jan 1, 1949

By W. B. Triplett, H. I. Aaronson, G. M. Andes

A detailed morphological study has been made of the pro-eutectoid TiCr, and the eutectoid reactions in a Ti-17.42 pct Cr alloy isothermally transformed at temperatures from 775° through 5561°C. The morphologies of proeute,ctoid TiCr2 were found to be subject to description by the Dube morphological classification system. Grain boundary allotriomo.lphs are the dominant plpoeutectoid morphology throughout the temperature range investigated. lntragranular plates, and especially Widmanstatten sideplates, form only in small numbers. This morphological pattern differs markedly from that of the proeutectoid a reaction in hypoeutectoid Ti-Cr alloys (AIME Trans., 1957, vol. 209, p. 1227; 1958, vol. 212, p. 624), in which plates form prolifically throughout wide ranges of temperature. The eutectoid reaction is nonlamellar in character at 675°C. An increasingly prominent lamellar component develops at lower temperatures. The proeutectoid TiCr 2 and the eutectoid transformations have been studied metallographically in a hypereutectoid titanium-chromium alloy. This investigation was undertaken with the immediate objective of comparing these transformations with their counterparts in hypoeutectoid titanium-chromium alloys, studies of which have been recently completed.1,2 It was also intended, however, to contribute to the general literature on transformations of these types. Especially in the proeutectoid case, this literature is still sufficiently sparse to make difficult the testing of generalizations on the mechanisms of these transformations. TiCr, is the only intermetallic compound in the titanium-chromium system.3-5 The TiCr2 phase field extends to a maximum temperature of 1350°C) and encompasses the approximate composition range of 62 to 68 pct Cr at lower temperatures.3'4 At temperatures below 1000°C, TiCr2 has a MgCu,-type fcc structure, with 24 atoms comprising a unit cell.6,7 Only fragmentary observations on the morphology of proeutectoid TiCr2 have been previously reported. An observation which is of considerable importance with respect to the results obtained during the present investigation was made, however, on anisother-mally transformed alloys with high chromium (48 to 70 pct Cr) contents.3"8 Despite the occurrence of extensive impingement, it is apparent that a substantial proportion of the proeutectoid TiCr, which precipitated in these alloys grew in the form of Widmanstatten plates. Several observations have been made on the eutectoid reaction in hypereutectoid alloys during investigations of the titanium-chromium phase di-

Jan 1, 1961

By O. P. Chisholm

Dross emerges from the blast furnace either with the lead through a lead well or by tapping from a forehearth or settler, but until a dozen years or so ago few dross reverberatories were used in western lead smelters because it was the usual procedure to circulate the dross from the drossing lead kettles back to the blast furnace. It was quite customary for lead smelters to produce matte in their blast furnaces, as this was the form in which copper could be collected, concentrated if necessary, and shipped to the copper smelters for further treatment. The main prerequisites for good matte formation arc., of course, a more or less definite amount of copper on the charge and sufficient sulphur. Such troublesome impurities as arsenic and antimony were ignored, in so far as possible, although they contaminated the bullion and thereby increased refinery costs. At the same time stocks of blastfurnace speiss containing gold, silver, lead and copper in addition to iron, arsenic and antimony, were being accumulated for want of a market to absorb them. As the dross was being fed back to the furnaces as rapidly as it was being produced, arsenic and antimony tended to build up until the arsenic could effect a combination with copper and iron and an alliance with lead, and the antimony a combination with copper and an alliancc with lead. Sulphur, being the most active agent in taking up the copper, left little of that element for the arsenic and antimony, so that on the whole a somewhat unsatisfactory metallurgy resulted. During this same period, certain lead plants were beginning to encounter trouble with zinc due to the replacement of crude ores of lot zinc content by concentrates containing high percentages of lead and zinc in sulphide form, the blast-furnace slags resulting from the smelting of such concentrates being characterized by a decidedly increased zinc content. It was soon realized that zinc plus sulphur was "poison" to a lead blast furnace and steps were taken to reduce the sulphur content,. At this stage some plants found that any substantial matte fall was out.

Jan 1, 1937

By W. B. Stephenson

In the pumping of sands, slurries and slimes, practices developed over the years are the real keystones of 'successful operation. These practices are necessarily based on modifications of familiar theories. Practical methods used in the solution of problems involving the pumping of materials are set forth in the following discussion. Basic Requirements To pump sands and slurries economically, a few basic requirements must be met by the pumping system as a whole. A pipe-line velocity must be established that will move the fluid mixture throughout the entire system without any possibility of the solids settling out. To accomplish this, the velocity of flow must be slightly in excess of the critical velocity of the mixture. The critical velocity of a mixture varies from 3 ft. per sec. to 18 ft. per sec., depending on the screen analysis, concentration, and specific gravity of the solids in the mixture. Most tailings are pumped at a minimum velocity of 4 ft. per sec. if they include slimes, whereas the pipe lines of sand and gravel dredges require velocities as high as 18 ft. per second. A number of articles have been written on the determination of the minimum velocities required to maintain solids in suspension. Studies have also been made on the friction and pumping heads developed when handling solids in suspension.1-4 Our experience so far has shown that, within the normal operating limits of a pumping system, the friction factor follows more nearly the basis described by Howard,' who says, among his conclusions: "... values of f (friction factor) . . . will decrease with an increase in velocity." This conclusion is borne out by our actual experience. When the velocity in a pipe line is not sufficient to keep the solids in suspension, the total friction head' is greater than when the velocity is increased to a point where the solids are in suspension. A slight increase in the volume of feed to the pump and a slight increase in the pump speed are usually all that is necessary to put the system in balance. Maintaining Constant Volume Within reasonable limits, the volume of mixture to be handled through a pipe line should be held constant, so that the required velocity will be provided at all times. There are several ways in which this can be accomplished. The commonest is to provide a sump of sufficient capacity to take care of slight surges in the volume of mixture being fed to the pumping systen]. This sump, however, should not be as large as a settling chamber. The use of a float-controlled, fresh-water make-up valve in a sump will guarantee a constant volume. Where variations in volume are slight,

Jan 1, 1947

By J. L. Huitt, B. B. McGlothlin

The introduction of new fracture propping agents that are brittle but much stronger than sand created the problem of what loading strength is required for a propping agent to be effective in a given formation. It is shown that the load at which the propping agent crushes should exceed the load at which total embedment in the fracture faces is possible. Simple laboratory tests to determine loading strength of the propping agent and embedment in the fracture faces, and use of these data in selecting a propping agent for a given formation, are discussed. INTRODUCTION One of the most important factors in the design of hydraulic fracturing treatments is the selection of a propping agent that can effectively provide the fracture flow capacity needed for stimulation of a well. Sand, once generally accepted as being synonymous with propping agent in hydraulic fracturing, is now recognized as having limited effectiveness in many formations because of its low resistance to crushing. Sand particles are brittle and have relatively low strength. Because of this property, sand particles are crushed in rocks that offer high resistance to the penetration of fracture faces by the proppant particles when the fracture attempts to close under the action of the overburden load. For rocks that offer a high resistance to penetration, deform able particles are more effective propping agents than sand. However, for this same type of rock, a propping agent that does not deform, yet does not crush, is often more effective. Thus, a rigid propping agent with sufficient strength to prevent crushing is desirable. A method for determining the strength required for a rigid propping agent to function effectively in given formations is discussed. BEHAVIOR OF RIGID PROPPANTS AND FRACTURE FACES RELATED STUDIES An early qualitative description of the reaction of propping sand in fractures was given by Hassebroek et al.' In discussing fracturing in deep wells, the authors mentioned that even though propping sand entered the fractures, a high flow capacity did not result due to crushing or embedding of the propping sand. Dehlinger et al.2 in discussing the reaction of propping sand surmised that, because of the hardness of sand particles, deformation occurred in the fracture faces contacting the propping sand. In later studies,3,4 methods of determining the embedment of propping sand in fracture faces of soft rock and the critical load at which propping sand is crushed by the fracture faces in hard rock were discussed. In working with de-formable proppants, Kern et al. considered proppant particles to be deformed into cylindrical disks by action of the overburden and then pressed slightly into the fracture faces by further action of the overburden. Rixie et al.'0 reported on embedment pressure and presented a method of selecting a propping agent for use in given formations. The propping agents included sand, walnut shells and aluminum pellets. All these studies have contributed materially to a better understanding of propping agent behavior; however, the strength of brittle proppants (sand, glass and ceramics) required to result in embedment rather than crushing has not been discussed. This topic will be covered in the ensuing discussion. PROPPANT PARTICLE CRUSHING—-EMBEDMENT For this discussion, a rigid propping agent is considered to be one that is brittle and fails under tensile stress when loaded to a critical value. In an earlier study4 it was shown that the Hertzian4 loading theory could be applied to a spherical brittle propping agent if the propping agent and fracture faces behaved elastically. At the failure of the proppant, the ratio of the load to the square of the diameter of the particle should be constant for a given material combination, or: Lc/dp2=C ............(1) A partial derivation of this equation from proppant and formation properties is included in the Appendix. Should a rigid particle not be crushed as a load is applied, it embeds in the fracture faces. A study3 of particle embedment in fracture surfaces has been published. The embedment can be described by an equation based on Meyer's metal penetration hardness relationships: d1/dp=B 1/2[L/dp2]m/2..........(2) In Eq. 2, B and m are constants that are characteristic of the rock; the significance of the other terms is shown in Fig. 1. A STANDARD DEFINITION FOR PROPPANT LOADING STRENGTH Eq. 1 is useful in appraising propping agent strength," but it is strictly applicable only when the area of contact between a particle and a fracture face (or loading plate)

Jan 1, 1967

By John Johnston

When I was honored by being invited to give the Howe Memorial Lecture, I decided to read Howe's book, "The Metallography of Steel and Cast Iron," published in I9I6—that is, about 25 years ago—in search of a text. I found the book written in fine, clear, attractive, yet precise style, as I expected, knowing that his father— Dr. Samuel Gridley Howe, his mother— Julia Ward Howe, and all of his four brothers and sisters had lived in a New England literary atmosphere and had written books. This leads me to suggest that many authors of metallurgical papers and books could well study Howe's writings with a view to the improvement of their own. I failed to find a specific text, but did find a subject, for in reading his book I was struck by the few instances in which time is considered explicitly as a factor in the phenomena examined, and by the fact that many of the hottest arguments would have been settled had time been taken properly into account. Indeed, Howe hardly mentions time except in a rather incidental way, as in a few references to lag; for instance: The lowering of temperature at which the transformation occurs by rapid cooling . . . is a phenomenon of undercooling or lag. It is in part explained by the fact that the transformation itself is a time-consuming reaction which, setting in during a rapid fall of temperature, is naturally protracted till the temperature has sunk far below that at which it is due. He does discuss, quite fully, the iron-clrbon equilibrium diagram, as known at that time, introducing it by stating: As he is a reasonable man who is not deterred from using a hand truck for moving his trunk by the consideration that he has thus to move a trunk plus a truck, so am I reasonable in putting into your hands this useful, indeed indispensable. tool for mastering the ABC of iron metallurgy. Somewhat later, in introducing a discussion of the phase rule, which "it would be hardly proper to pass ... by without an attempt to outline its meaning," for "a clear exposition of its applicability or jurisdiction is needed to restrain the half-initiated from misusing it and the uninitiated from being misled by these misuses," he writes—and I quote his statement because we cannot properly discuss the influence of time on a process until we know the state of equilibrium which would ultimately be reached by the system under consideration: It is a most remarkable and valuable generalization, its conceptions help greatly toward getting a broad outlook on metallography, but its misconception has brought out a flood of obscuring writings. it tells us about the constitution towards which alloys tend, that which they reach when equilibrium is complete, when all tendencies have corrected themselves and have been complied with completely. Its application, in absence of true equilibrium, is like determining density with a telescope or even with a tuning fork; it is like the mad tea party at which the butter put into the works of the watch was the best butter. If the reader learns no more than to beware of attempts to dccipher the conditions of inequilibrium by a law which touches only the conditions of exact

Jan 1, 1942

By John Johnston

When I was honored by being invited to give the Howe Memorial Lecture, I decided to read Howe's book, "The Metallography of Steel and Cast Iron," published in I9I6—that is, about 25 years ago—in search of a text. I found the book written in fine, clear, attractive, yet precise style, as I expected, knowing that his father— Dr. Samuel Gridley Howe, his mother— Julia Ward Howe, and all of his four brothers and sisters had lived in a New England literary atmosphere and had written books. This leads me to suggest that many authors of metallurgical papers and books could well study Howe's writings with a view to the improvement of their own. I failed to find a specific text, but did find a subject, for in reading his book I was struck by the few instances in which time is considered explicitly as a factor in the phenomena examined, and by the fact that many of the hottest arguments would have been settled had time been taken properly into account. Indeed, Howe hardly mentions time except in a rather incidental way, as in a few references to lag; for instance: The lowering of temperature at which the transformation occurs by rapid cooling . . . is a phenomenon of undercooling or lag. It is in part explained by the fact that the transformation itself is a time-consuming reaction which, setting in during a rapid fall of temperature, is naturally protracted till the temperature has sunk far below that at which it is due. He does discuss, quite fully, the iron-clrbon equilibrium diagram, as known at that time, introducing it by stating: As he is a reasonable man who is not deterred from using a hand truck for moving his trunk by the consideration that he has thus to move a trunk plus a truck, so am I reasonable in putting into your hands this useful, indeed indispensable. tool for mastering the ABC of iron metallurgy. Somewhat later, in introducing a discussion of the phase rule, which "it would be hardly proper to pass ... by without an attempt to outline its meaning," for "a clear exposition of its applicability or jurisdiction is needed to restrain the half-initiated from misusing it and the uninitiated from being misled by these misuses," he writes—and I quote his statement because we cannot properly discuss the influence of time on a process until we know the state of equilibrium which would ultimately be reached by the system under consideration: It is a most remarkable and valuable generalization, its conceptions help greatly toward getting a broad outlook on metallography, but its misconception has brought out a flood of obscuring writings. it tells us about the constitution towards which alloys tend, that which they reach when equilibrium is complete, when all tendencies have corrected themselves and have been complied with completely. Its application, in absence of true equilibrium, is like determining density with a telescope or even with a tuning fork; it is like the mad tea party at which the butter put into the works of the watch was the best butter. If the reader learns no more than to beware of attempts to dccipher the conditions of inequilibrium by a law which touches only the conditions of exact

Jan 1, 1942

CONTENTS PAGE PEIRCE, CARL-Making Rimmed Steel. Discussed by L. F. Reinartz. H. D. Hibbard, C. L. Kinney, Jr., A. H. Woodward, V. B. Buck, A. L. Feild, J. V. W. Reynders 1 SCHROEDER, F. W., and LARSEN, B. M.-Progress Report of the Effect of the Open-hearth Process on Refractories. Discussed by D. A. Lyon 12 KEATS, J. L., and HERTY, C. H.-Elimination of Metalloids in the Basic Open-hearth Process. Discussed by J. V. W. Reynders 14 Making Rimmed Steel Discussion of paper by CARL PEIRCE, presented at the New York fleeting and issued, as Paper No. 1563-C, with MINING AND METALLURGY, March, 1926. L. F. REINARTZ, Middletown, Ohio.-Mr. Carl Peirce has presented a valuable paper on a subject that has been very widely discussed in recent years, especially since the demand for high finish, deep drawing and other grades of sheet steel in the lower carbon ranges has become an important factor in the steel business. Steel of this analysis has been produced for many years, but the product for which it was made did not require the extra care in the steel plant that it does today. It must now be worked down into thin sheets for special purposes and undergo many severe finishing processes both in the steel mill and in the fabricating plants. Mr. Peirce's paper has outlined in a concise and logical manner the steps which must be taken in manufacturing such steels. The secret of successs is attention to details of well known steel practices. I agree with him that quality steels of this class cannot normally be made out of inferior raw materials. Scrap should be clean and if possible not too variable in analysis. Galvanized scrap or babbit are particularly objectionable. Scrap should be in such physical condition that undue delays are not encountered in charging the furnace. Limestone should preferably contain over 95 per cent. available calcium carbonate, and be free from clay or other foreign substances. Almost universal practice shows that 10 per cent. limestone is required for proper slag volumes to protect the metal from over oxidation. The use of 8 per cent. limestone makes the operation less fool-proof.

Jan 4, 1926

By C. F. Clausen

"Cement" means binding agent or glue. It is derived from the Latin word "Caementum," the name of a limestone, chips of which were used in mortar more than 2,000 years ago in Italy. During the middle ages "cement" or "cement" generally denoted mortar. Today it means any binding material. The Thomas Register lists nearly 200 classifications for "cement" including automobile cement, household cement, rubber cement, etc. The material most commonly associated with this word, however, is portland cement which, when mixed with water and allowed to hydrate, is a ceramic binding material used to cement aggregates (crushed stone, gravel and sand) together in "concrete," the most universally used building material of today. It is estimated that more tons of concrete are used annually than all other building materials put together including steel, lumber, gypsum, bricks, tiles, aluminum and glass. Its use in foundations, building construction, sanitary work, dams, railroads, and highways, makes it difficult to conceive of modem civilization without concrete. A survey made in October 1955 showed the following uses of portland cement: [Percent Highways20 Nonresidential buildings20 Residential buildings15 Military construction10 Sewer and water works8 Public utilities10 Other (conservation, farm, and maintenance and repair)17 100] As of today, the percentage for highways is probably even higher. Ceramic binding materials have unquestionably been used in construction work for thousands of years. The mortar between the blocks of the great pyramids was calcined gypsum (plaster of paris). The use of calcined and slaked limestone goes back earlier than the Roman Empire. Gypsum, however, is relatively soft, and common lime mortar is not "hydraulic," i.e., it does not harden under water. The Greeks and Romans discovered later that an addition of a finely divided active siliceous material (Santorin earth or Pozzolana) would react with slaked lime to form a stronger, and hydraulic, cement. The Appian Way in Italy, Colosseum, and the great Aqueducts built by the Romans were made with this type cement, and some of these structures are still in existence today. However, not until 1756 did some serious research result in the development of better cements. In that year the English engineer, John Smeaton produced a stronger cement by burning a limestone containing considerable proportions of clayey impurities. Other investigations and improvements were made by Bryan Higgins, Bergmann, Joseph Parker, L. J. Vicat, J. F. John, James Frost, and I. C. Johnson.2 Traditionally, but perhaps unfairly to others, the invention of the prototype of today's portland cement is credited to the English mason Joseph Aspdin who in 1824 obtained a patent and gave the product its name, because in color the mortar produced from it resembled a natural building stone obtained from the British Isle of Portland. The contributions of Johnson and Aspdin were primarily the important step of preparing a synthetic mixture of lime and clay without depending on raw materials found in nature which might contain such elements in desirable proportions. However, even these early

Jan 1, 1960

By K. A. Jackson, G. A. Chadwick, A. Klugert

The diffusion field ahead of a lamellar interfnce is analyzed using an electrical analog. A self-consistent solution is obtained for the shape of the interfnce and the diffusion field by an iterative process. The solutions presented here are for a 50-50 eutectoid or eutectic, The shape of the interface is found to he independent of growth velocity and lamellar spacing, and to depend on the relative values of interfacial free energies at the phase houndaries . The mode of growth of lamellar eutectics and eutectoids has been a subject of much interest for many years.1-4 Mehl and Hagel 1 have shown photomicrographs taken by Tardif when he attempted to determine experimentally the shape of an advancing pearlite interface; the results are completely ambiguous. Brandt' and schei13 have made approximate calculations of the composition ahead of a lamellar growth front. The shape of the advancing front and the composition distribution ahead of the front are difficult to calculate because one depends on the other. It is the purpose of the present paper to describe a method by which this calculation has been done. Lamellar-eutectic growth usually occurs under conditions where the growth is fairly rapid, and the interface temperature is close to the eutectic temperature. The growth rate is usually determined by heat flow. Eutectoid growth, on the other hand, can best be studied by quenching to some temperature, and allowing growth to proceed isother-mally. In both cases the growth is believed to be controlled by diffusion* rather than by the atomic kinetics of the transformation. This being the case, a single treatment of the diffusion equation will apply to both cases, provided the region of the interface in a eutectic may be considered to be isothermal. If a part of the interface could appreciably change its thermodynamic driving force by advancing ahead of or lagging behind the mean interface, then the two cases would not be similar. Eutectics normally grow in temperature gradients of the or-der of a few degrees per centimeter. The normal eutectic spacing is the order of a few microns. Part of the interface would have to extend many lamellar spacings ahead of the mean interface before it experienced sensibly different conditions. The interface temperature is usually a few tenths of a degree below the eutectic temperature so that temperature differences of the order of one-thousandths of a degree (a displacement of one lamellar spacing) would be unimportant. Protrusions large compared to the mean spacing do occur when one phase only grows into a eutectic liquid. This is usually a dendritic type of growth, and easily distinguishable from the lamellar mode of growth. A single treatment of lamellar growth will apply equally well to both eutectic and eutectoid decomposition. At the interface, which as shown above is essentially isothermal, the difference between the equilibrium eutectic temperature Teu and the actual interface temperature Ti, can be divided into two parts: 1) the composition varies across the interface, so that the local equilibrium temperature is not Teu; and 2) the interface is curved, so that the local equilibrium temperature is depressed according to the Gibbs-Thompson relationship. This undercooling can be written as Teu-Ti =?T = mAC(x) + a/r(x) [1] where ?C(X) is the departure of the composition at a point x on the interface from the eutectic composition, see Fig. 1, r(x) is the local radius of curvature at a point x on the interface, m is the slope of the liquidus line on the phase diagram, and a is a constant given by where s is the interfacial free energy, TE is the equilibrium temperature, and L is the latent heat of fusion. The calculations in this paper will be made only for the case where the phase diagram is symmetric, that is, the eutectic occurs at 50 pct, the liquidi have the same magnitude slope m at the eutectic temperature, and C,, the amount of B rejected when unit volume of a freezes, see Fig. 2(a), is the same for both phases. As shown in Fig. 2(b), the composition ahead of the a phase will be rich in B, the composition ahead of the ß phase will be rich in A. The composition at the phase boundary is the eutectic composition. The difference between the local liquidus temperature and the actual tempera-

Jan 1, 1964