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By C. R. Dale

IT IS the purpose of this paper to point out a number of the most common causes of crooked holes; to outline methods of drilling and straightening which to my personal knowledge have proved successful in numerous cases; to describe some of the characteristics of holes which, though not crooked in an exaggerated sense, may still cause serious mechanical trouble if not recognized and properly remedied; and to define clearly the part of oil-well surveying in the concerted effort operators generally are making to keep their wells straight from spudding to completion

Jan 1, 1931

By M. E. Wadsworth, J. R. Lewis, J. M. Quets

Samples of snythetic magnetite were reduced in hydrogen at various partial pressures and temperatures. The reaction mas found to be surface controlled and directly proportional to hydrogen partial pressure over the temperature range studied (400° to 1000°C). A transition in the mechanism occurred at approxirnately 590°C. This has been attributed to a change in the slow step of the reduction reaction resulting from the presence of stable wüstite at higher temperatures. Below 590°C the heat of activation for the reduction was found to be 14,700 cal per mole and it was 3,200 cal per mole above 590°C. THE reduction of the oxides of iron has been a subject of study and interest for many years. Edstrom1 has reviewed the work up to 1953 and his findings provide much basic information concerning details of the reduction of hematite (Fe2O3 ) and magnetite (Fe3O4) with both H2 and CO. He concluded that below 600°C the reduction of both hematite and magnetite was essentially identical, since the rate was controlled by a surface reaction at a magnetite gas interface and the iron formed was very porous. The decrease in the reduction rate for both hematite and magnetite immediately above 600°C was attributed to the formation of a stable wüstite phase across which diffusion was very slow. The wide difference in reduction kinetics for hematite and magnetite above 600°C was explained in terms of the character of the wüstite formed. The rate of magnetite reduction increased slowly with temperature beyond the minimum immediately above 600°C and rates equivalent to those observed at 550°C were not obtained until the temperature was increased beyond 850oC. Edstrom and Bitsianes2 studied the solid-state reduction of magnetite, the reaction of which can be written (4x-3)Fe + Fe3O4—4 FexO [1] where x is between 0.83 and 0.95. The rate was found to be controlled by the kinetics of transport of iron ions through the wüstite phase. Bogdandy and Riecke3 studied the kinetics of reduction of small grains of iron oxide in hydrogen and qualitatively attributed the slow step in the reduction process to the diffusion of hydrogen and water vapor through pores. McKewan4 has analysed the data of Joseph,5 Stalhane and Malmburg,6 and Lewis7 and has demonstrated that the kinetics of reduction of both hematite and magnetite are controlled by surface reactions and also that the variation in surface area during reduction must be accounted for. McKewan was able to correlate the reduction data by the equation rodo[1-(1-R)1/3] = Kt [2] where ro is the initial particle radius, do is the density of the iron oxide, R is the fraction reduced at time t, and K is a rate constant. The applicability of Eq. [2] for temperatures above 600°C where a stable wüstite phase is present, indicates the slow step in the over-all kinetics does not result from diffusion unless diffusion occurs laterally along the oxide metal interface or through a wüstite layer of constant thickness. Diffusional control through a layer of wüstite is unlikely, however, in view of the pressure effects demonstrated by Tenenbaum and Joseph,' Diepschlag,9 McKewan,10 and the results of the present study. McKewan has demonstrated a linear rate dependence on the hydrogen partial pressure over the temperature range 400" to 1050°C for the reduction of hematite.

Jan 1, 1961

By Paul A. Beck, John Towers, W. D. Manly

Recent work on grain growth in high purity aluminum and in a solid solution type alloy of aluminum and magnesium1 showed that the isothermal increase of the average grain diameter D with time follows the equation D = K(tg + A)2 Eq 1 Here tg is that portion of the total annealing time 1, which is available for grain growth, that is the annealing time less the time necessary for complete recrystallization. The parameters A and n depend only on the temperature. A has the dimension of time, and is usually of the same order of magnitude as the time for recrystallization: R. In some instances R may be substituted for A in Eq I. This is the case for example at long periods of annealing or at high temperatures, where both A and R become small in comparison with t. In such instances Eq I is simplified to D = K, tn Eq 2 For high purity aluminum the exponent n increases in the ratio of about I to 5 in. the temperature range of 350' to 6w°C. 70-30 brass has been long known to exhibit grain growth of the continuous type, such as occurs in pure metals. For this reason, it was of interest to determine whether grain growth in brass also follows Eq I and 2 as it does in aluminum. Isotherma1 grain growth data for 70-30 brass were published in recent years by R. S. French2 and by H. L. Walker.' Fig I shows a log D vs. log t plot of French's data, together with the 500, 600 and 700°C data by Walker for 42.8 pct reduction by rolling. In such a log D vs. log t plot Eq 2 corresponds to a straight line with a slope of n. As seen in Fig I, the data of French and the 600°C data of Walker can be represented by straight lines. However, the 500 and 7c0°C data of Walker give curved lines and the average slope of his 500°C line is very different from the slope of the line representing French's data for the same temperature. Furthermore the curvature of the 700°C line suggests a tendency for grain growth to stop after 8 hr. If confirmed, this would constitute a definite deviation from Eq 2, not explainable on the basis of the specimen thickness effect found in high purity aluminum.' Walker's specimens were 0.125 in., or 3.18 mm thick, while the deviation occurs at a grain size of approximately 0.4 mm. A further point of divergence arose recently, when J. E. Burke suggested4 on the basis of Walker's data, that, instead of Eq 2, grain growth in 70-30 brass follows the equation D - D, = K . tgn Eq 3 Here D, is the grain size as recrystallized at the temperature in question. Although it was possible to show5 that, for pure aluminum, for which isothermal grain growth has been carefully investigated, Eq 3 is incompatible with the experimental facts, the situation remained somewhat obscure with respect to 70-30 brass. In view of the discrepancies between the published data on brass from different

Jan 1, 1949

By John Towers, Paul A. Beck, W. D. Manly

Recent work on grain growth in high purity aluminum and in a solid solution type alloy of aluminum and magnesium1 showed that the isothermal increase of the average grain diameter D with time follows the equation D = K(tg + A)2 Eq 1 Here tg is that portion of the total annealing time 1, which is available for grain growth, that is the annealing time less the time necessary for complete recrystallization. The parameters A and n depend only on the temperature. A has the dimension of time, and is usually of the same order of magnitude as the time for recrystallization: R. In some instances R may be substituted for A in Eq I. This is the case for example at long periods of annealing or at high temperatures, where both A and R become small in comparison with t. In such instances Eq I is simplified to D = K, tn Eq 2 For high purity aluminum the exponent n increases in the ratio of about I to 5 in. the temperature range of 350' to 6w°C. 70-30 brass has been long known to exhibit grain growth of the continuous type, such as occurs in pure metals. For this reason, it was of interest to determine whether grain growth in brass also follows Eq I and 2 as it does in aluminum. Isotherma1 grain growth data for 70-30 brass were published in recent years by R. S. French2 and by H. L. Walker.' Fig I shows a log D vs. log t plot of French's data, together with the 500, 600 and 700°C data by Walker for 42.8 pct reduction by rolling. In such a log D vs. log t plot Eq 2 corresponds to a straight line with a slope of n. As seen in Fig I, the data of French and the 600°C data of Walker can be represented by straight lines. However, the 500 and 7c0°C data of Walker give curved lines and the average slope of his 500°C line is very different from the slope of the line representing French's data for the same temperature. Furthermore the curvature of the 700°C line suggests a tendency for grain growth to stop after 8 hr. If confirmed, this would constitute a definite deviation from Eq 2, not explainable on the basis of the specimen thickness effect found in high purity aluminum.' Walker's specimens were 0.125 in., or 3.18 mm thick, while the deviation occurs at a grain size of approximately 0.4 mm. A further point of divergence arose recently, when J. E. Burke suggested4 on the basis of Walker's data, that, instead of Eq 2, grain growth in 70-30 brass follows the equation D - D, = K . tgn Eq 3 Here D, is the grain size as recrystallized at the temperature in question. Although it was possible to show5 that, for pure aluminum, for which isothermal grain growth has been carefully investigated, Eq 3 is incompatible with the experimental facts, the situation remained somewhat obscure with respect to 70-30 brass. In view of the discrepancies between the published data on brass from different

Jan 1, 1949

By K. Torssell, U. Lindborg

The kinetics of precipitation deoxidation is considered from a theoretical point of view. The size distribution and the total content of deoxidation products are estimated statistically as a function of time, taking into account Stokes and gradient collisions between the particles and separation at the top surface of the bath. The assumption is made that two particles coalesce into one larger particle as a result of a collision. General expressions are derived and calculations are carried out numerically for the case of silica particles in liquid iron. The analysis predicts a three-stage behavior for the removal of oxygen, an incubation stage, a stage of rapid separation, and a slow final stage where the content approaches the equilibrium value. The agreement with experimentally determined size distributions and deoxidation times is considered to be good. A quantitative estimation of such growth mechanisms as diffusion from the melt and redistribution of oxygen from small particles to large ones shows that these latter mechanisms cannot explain the experimentally observed gvowth of inclusions. This also indicates that collisions provide the important growth mechanism. OXIDE inclusions precipitate when a deoxidizer like silicon or aluminum is added to a steel bath. The inclusions grow and the large particles tend to separate from the bath. For each type of oxide the growth determines the sizes of the final inclusions as well as the total inclusion content of the steel. The mechanism of growth is controversial, however. It has been suggested that an inclusion grows principally by diffusion of atoms through the melt to the inclusion particle or principally by collisions and coalescence with other inclusions. Diffusion growth is always present to some extent but recent experiments and calculations by Torssell,' Kniippel et 'a1.,2 Sano et al. and Miya-shita4 indicate that collisions may be more important than previously realized. A detailed analysis has so far been lacking. The present paper is a quantitative, statistical analysis of the growth and separation of inclusions and is based on a collision theory. Nuclea-tion is not considered. The numerical estimates are based on the experimental conditions of Torssell's' investigation and comparisons are made with his observations. Torssell' studied the growth and separation of silica particles in liquid iron. Samples were taken from a 0.6 kg iron bath at various times after the addition of silicon. By a particle-counting technique developed by Bergh and Lindber~the size distribution of the inclu- sions was determined. The number of particles at the first sampling, 10 sec after silicon addition, was of the order of 3 x lo7 to 10' per cu cm, the largest particles having a radius of 2 to 4 pm. The volume fraction was 0.001 to 0.004; i.e., the dispersion was very dilute. During subsequent holding the largest particles increased their radius by a factor of 10 after about a minute, and the whole size distribution was displaced toward larger values. These results were obtained with allowance for precipitation of the equilibrium concentration of oxygen during solidification. The bath contained less than 0.01 pct of C. Figs. 1 and 2 show the typical appearance of the inclusions. Most particles are very closely spherical and appear to have been liquid or semiliquid in the melt. The observed number of inclusions, about 5x 10' per cu cm, is of the same order of magnitude as found by ~er~h.' This is a large value. It follows that the diffusion distances are very short and that the precipitation

Jan 1, 1969

By E. W. Cawthorne, R. I. Jaffee, C. M. Craighead

SOLUTION of a solid metal or alloy in a molten metal bath is used daily in melting operations, extractive metallurgical processes, and in brazing. It is generally recognized that temperature, time, agitation, and the composition of the solute metal and the solvent bath all affect solution rate. However, there is little information available in the literature on the kinetics of the process or the relative effect that these variables have on solution rate. In connection with an aluminum brazing study, data on the solution of aluminum in an A1-Si* bath to promote rapid solidification. The chemical analyses were made on drillings taken from the cast plates. The results of this work are listed in Table I. The thermal-analysis data were obtained on 200 gram samples cooled at approximately 1.5" per min. A calibrated chromel-alumel couple was used. The thermal arrests were recorded autographically on a General Electric photoelectric potentiometer recorder. The instrument was calibrated to 22.5 pct. The thermal emf was bucked with a Leeds and Northrup semiprecision potentiometer so that 1 mv represented the full scale of the GE recorder. Referring to Table I, it will be noted that the analytical results tend to be lower than the intended compositions by about 0.3 pct Si in the higher ranges. In view of the known difficulties in obtaining accurate silicon determinations by wet analysis when the silicon content is high and in view of the care that was employed in weighing and preparing the alloys, the intended compositions are believed to be more accurate than the analyses. Furthermore, when the thermal-arrest data are plotted against the intended compositions, a smooth curve is obtained, as shown in Fig. 1. This is not the case when the data are plotted against the analytical results. It will be noted from Table I that the 12.5 pct Si alloy (melt 4) showed a primary arrest at 577.6"C and the eutectic at 576.l°C. The metallographic examination of this chill-cast plate sample showed a small amount of primary silicon. These results, Fig. 1, place the eutectic at slightly less than 12.5 pct Si and are in rather good agreement with the unpublished Hanford data. In all of the subsequent work, the composition of the A1-Si dipping baths was determined by thermal analysis (spread between the primary arrest and the eutectic temperature) employing 12.5 pct Si and 577.2 °C as the composition and temperature of the eutectic. Material Preparation and Selection of the Techniques: At the beginning of this work, it was anticipated that, owing to oxide film present on the surface of the aluminum, difficulty would be encountered in obtaining rapid uniform wetting of aluminum specimens dipped in the A1-Si bath. The following etchants were investigated as possible methods of providing a thin uniform oxide film on the specimen surface: 1—phosphoric acid (H³O4), 2—fluoboric acid (HBFI), 3—sodium hydroxide (NaOH), and 4—hydrofluoric acid (HF). Tests with sheet .specimens (2x½x0.06 in.) of 2s aluminum prepared with these etchants indicated that the fast uniform wetting required for this work could not be obtained if any oxide film existed on the specimen surface. Tests were then conducted by dipping similar specimens etched in 5 pct NaOH and given a thin

Jan 1, 1956

By Charles Law McCabe, Lyndon H. Everett, Edna A. Dancy

It has been found that the carbide phase present at equilibrium in the system M-H2-CH4, at about 600°C, is MC for the rare-earth metals Ce and Pr. X-ray diffraction analysis showed that the monocarbides have fcc structures with lattice constants of 5.036 + 0.009Å and 5.131 + 0.001Å for CeC and PrC respectively. Gaseous equilibrium measurements were used to calculate the standard free energy of formation of the monocarbides from the elements. for the formation of (+ 1300) for the formation of PrC. THE rare-earthdicarbides, and their crystal structures, have been known for some years,l but only more recently were the carbides CeC,2,3 Ce2C3 2 and CeCS3 reported. In 1958 to 1959, Spedding et al. published work on the lanthanum-carbon system4 and other rare-earth metal-carbon systems,5 proving the existence of M2C3 and MC2, and measuring the lattice constants. They also demonstrated that tri-rare earth carbides, M3C, exist for the rare-earth metals samarium through ytterbium. However, they concluded that the cerium monocarbide reported by Brewer and Krikorian2 and by Warf,3 and given a fcc structure with a lattice constant of 5.130Å bythe former workers, was, in fact, cerium metal with carbon dissolved in it. They were also unable to find any evidence for the existence of Warf's CeC3, for which no structural details had been given. Even more recently, Palenik22 reported the existence of only M2C3 and MC2, having been unable to find any evidence for the existence of any other rare-earth carbides. There are no published experimentally derived thermodynamic data for the formation of any of these carbides, although Brewer and Krikorian6 have estimated values of for CeC, Ce2C3 and CeC2. The objective of the present investigation was; to determine experimentally the free energy of formation of any of the reported carbides of cerium and praseodymium, through a study of the rare-earth metal-hydrogen equilibrium. EXPERIMENTAL A methane-hydrogen mixture was circulated, in a closed system over previously prepared cerium or praseodymium hydride, and when equilibrium had been attained, the gas mixture was analyzed by selectively oxidizing the hydrogen and condensing out the water formed. The metal hydrides were used as starting material for convenience because, otherwise, the hydrogen in the gas mixture would immediately dissolve in the metals; in addition, the metals would not react with methane alone at the experimental temperature (around 600°C). The circulating system was based on that used by Browning, DeWitt, and Emmett7 for similar studies on iron carbides. It consisted of a quartz reaction vessel, all-glass circulating pump, analysis tube containing copper oxide that could be heated to 300" C by means of a small furnace, a solid CO2-methanol trap, and a double limb absolute manometer, Fig. 1. A cathetometer, capable of reading to 0.005 cm, was used to measure the difference in height between the two columns of mercury. In its final form, the reaction vessel was enclosed in an outer jacket, containing approximately the same pressure of hydrogen as that within, to reduce errors due to diffusion of hydrogen out through the fused silica of the reaction vessel., The circulating system was supplied with

Jan 1, 1962

By Renato G. Bautista, Theodore D. Tiemann

A kinetic study of the hydrogen reduction of taconite from the Wisconsin Gogebic range was made over the temperature range from 500° to 1000°C on eleven size fractions from 4 to 150 mesh. Two stages of reduction were observed, a rapid initial reaction followed by a slower reaction presumably taking place at an internal receding FexO-Fe interface. Calculated mean activation energies for the two reactions were 7800 and 14,600 cal per mole respectively. In recent years there has been an increased interest in the direct reduction of iron oxide ores to metallic iron by means of gaseous reducing agents such as hydrogen and carbon monoxide.1,2 These investigations have been motivated by the desire to develop a process that will by-pass the blast furnace in the production of steel. The majority of these processes have been developed to produce metallic iron by direct reduction from high-grade iron oxide ores.3"5 Very little work has been done on the low-grade siliceous iron oxide ores.6"8 The work reported here is directed principally towards the fundamental aspect of the reduction reactions of siliceous iron oxide ores, since the practical aspects of the gaseous reductant process were discussed previously. The ore used in the investigation was obtained originally from the United States Bureau of Mines10 trench sample of the Yale member of the Wisconsin Gogebic range iron formation. The Yale taconite has an average analysis of 28.2 pct Fe and approximately 50 pct SiO2. Chemically, these nonmagnetic taconites contain on the average about 53 pct silica and 30 pct Fe. An average analysis calculated fron the USBM10 figures for a composite of the five members (Norrie, Plymouth, Pence, Pabst, and ale) of the iron formation is given in Table I. Mineralogically, based on previous X-ray diffraction and other studies, the principal minerals are hematite (Fe2O3), geothite (Fe2O3.H2O), and quartz (SiO2). Minor amounts of iron containing silicates, siderite (FeCO3) and magnetite (FeO. Fe2O3) are present.10,11 The iron minerals and the quartz are finely disseminated requiring extremely fine grinding for liberation. For the experimental work, the ore sample was screened into a number of size fractions, the analyses and densities of which are given in Table II. EXPERIMENTAL PROCEDURE The reduction experiments were carried out in a 24 in. by 2 in. ID nichrome-wound vertical-tube furnace mounted on a stand. A 1 1/2 in. OD zirconium-oxide combustion tube was used inside the furnace to contain the atmosphere. To the top of this combustion tube was joined a pyrex ground-glass joint to which was attached a glass bulb with a small (1.0 mm) opening at the center, and with two outlets controlled with a stopcock on each side. A pyrex-glass joint with connections to three stopcock joints for introducing hydrogen, nitrogen, and mixtures of hydrogen and nitrogen gas was joined to the tapered bottom of the combustion tube. The sized ore fractions were contained in a 1 in. diameter by 1 1/2 in. 150-mesh nickel screen basket. The basket was suspended in the furnace from a balance by means of a supporting nickel wire which hung freely inside the combustion tube. The furnace temperature was controlled by a Leeds and Northrup Speedomax Type G controller, connected to a chromel-alumel thermocouple placed

Jan 1, 1962

WE the undersigned, being ell persons of full age and citizens of the United States, and a majority resident of the State of New York, desiring to form a corporation pursuant to the provisions of the membership Corporations Law for the purpose of incorporating, as provided in section 5 of Article I. of said law, the existing unincorporated association known as American Institute of Mining Engineers, do hereby make, acknowledge and file this Certificate for that purpose, and do Certify as follows: I. That the American Institute of Mining Engineers is an unincorporated association organized and existing with the object of promoting the arts and sciences connected with the economic production of the useful minerals and metals and the welfare of those employed in these industries by means of meetings for social intercourse and 6he reading and discussion of professional papers, and to circulate by means of publications among its members and associates the information thus obtained. II. That the persons duly appointed or designated to manage the affairs of said association are designated by the rules thereof Members of its. Council; that the undersigned are all members of said Council as the same was constituted on the 296h day of December, 1904. III. That on said last-mentioned date a regularly called meeting of said association was held at its office in the Borough of Manhattan, City of New York; that thirty days before such meeting notice of the intention to incorporate said association was given by mail to each member thereof whose residence or post-office address is known; that at said meeting the following resolutions were offered, seconded and duly adopted by the unanimous vote of all its members then present, to wit: "Resolved, That it is the sense of the members and associates of the American Institute of Mining Engineers in general meeting assembled that it is desirable and necessary for the well being of said association and its members and for the furtherance of the objects for which the same has been formed, that said association incorporate under the Membership Corporations Law of the State of New York; "And Further Resolved, That the Members of the Council of this Association, or a majority thereof, be and they hereby are authorized, in accordance with the provisions of Section 5 of Article I. of the Membership Corporations Law, to incorporate this association for the same purposes for which it has been organized and conducted, in the manner provided in Article 11. of said law; "And Further Resolved, That the name of said corporation as hereby adopted by this meeting shall be American Institute of Mining Engineers; "And Further Resolved, That the said incorporators shall be named in the Certificate of Incorporation as directors of such corporation until its first annual meeting, and that such directors and their successors in office shall be and they hereby are authorized to enact and adopt a Constitution and By-Laws for the government of said corporation." IV. That the name of the proposed corporation is American Institute of Mining Engineers. V. That the purposes for which this corporation is to be formed are: To promote the arts and sciences connected with the economic production of the useful minerals and metals, and the welfare of those employed in these industries by all lawful means; to hold meetings

Jan 1, 1928

By J. C. Scully

In June, 1965, Sanderson and scully5 reported at the Conference on Environment Sensitive Mechanical Properties of Materials at the Research Institute for Advanced Studies at Baltimore that thin foils of titanium could be prepared by chemical polishing in a mixture of 44 pct HF and 73 pct HNO3 in the volumetric ratio 2:3. The technique is simpler than that since reported by Rice and Orava. As-received annealed titanium (containing 0.8 pct Fe and 30 ppm H) in the form of sheet 0.05 cm thick is placed in the solution and moved up and down. The reaction is violent but suitable foils are obtained very easily and consistently. A typical micrograph is shown in Fig. 3. The small precipitates were not identified. Yamane and ueda6 observed many spotlike features which they referred to as small dislocation loops. While their spots may be due to the reaction of the warm foil with the air as suggested by Rice and Orava, the precipitates in Fig. 3 are also found when foils of titanium are prepared by electro-polishing at low temperatures and subsequently examined in the electron microscope without any inter- mediate warming. Furthermore, they are not a surface effect. It is necessary to add that alloys of titanium cannot be so easily thinned by the chemical polishing solution described above since it contaminates the a, phase with hydrogen and produces y hydride. These matters are described at length in a paper7 and their relevance to stress corrosion is considered elsewhere.'-* Author's Reply The authors are grateful to Dr. Scully for bringing to our attention his hitherto unpublished technique for thinning unalloyed titanium, and deeply regret the unintended apparent duplication. The chemical thinning solution (7 parts HNO3 and 3 parts HF, by volume) reported by us is the same as that with which, for some period in the past, we had experienced success in the preparation of foils from single and polycrystalline niobium. Its subsequent effective application to titanium was a logical step, which, clearly independently of Scully, was conceived by Mr. Rice, to whom full credit is due. A few comments are warranted concerning some of the details of the preceding Discussion. It is evident to the discerning reader that the two thinning techniques under consideration are chemically almost identical, and in that sense are equally "simple". The chemical aspect is, of course, the one of primary importance in both communications. Thereafter, the relative simplicity is dictated by the mechanics of the actual thinning operation selected by the individual investigator. Our standard dimpling, or dishing, procedure was chosen with a view toward providing, for the electron transparent areas of the sample, the maximum protection from extraneous deformation during handling. That the long, straight dislocations visible in Scully's electron micrograph of a seemingly recovered structure closely resemble handling dislocations would tend to indicate the merit of our adopted technique. Features similar to those which Scully has attributed to precipitates, without any apparent diffraction contrast confirmation, were not observed in any of our clean foils taken from annealed or deformed specimens. This was admittedly somewhat surprising since the 3700 ppm (nominal) Fe in the A-70 commercial-grade titanium examined should have given rise to TiFe precipitates. Presumably these existed but were un-resolvable. Curiously, Scully's "precipitate1' density is fairly high although the iron content quoted was less than one-fourth of that in our material. One is forced to conclude from the evidence that prior thermal and mechanical treatments are responsible for the two different types of structure observed.

Jan 1, 1968

By M. E. Learmont, R. J. Lipp, I. Iwasaki

In the selective flocculation of iron ores, the concentration of alkaline earth ions in pulp solutions plays a critical role. Sodium silicate, alone or with sodium tripolyphosphate, has been used as a dispersant. When Ca+ + concentration exceeds 15 to 20 ppm, however, only a strong complexing agent, such as ethylenediaminetetraacetate (EDTA) was found to be effective (Heerema, Lipp, and Iwasaki, 1979). Some iron ores release Ca+ + in excess of 20 ppm. With ores that contain gypsum, the Ca+ + concentration may reach several hundred ppm. The purpose of this investigation was to compare the effectiveness of EDTA with nitrilotriacetate (NTA) in countering the adverse effects of Ca+ +, particularly at high Ca+ + concentrations. Emphasis was placed on the use of NTA since it is more cost-effective than EDTA. It is also used in detergents in some countries (Malaiyandi, Williams, and O'Grady, 1979). NTA, like EDTA, forms a soluble complex with Ca+ + with a 1:1 molar ratio. Its structure and the value of log Kca are given below together with EDTA (Shibata, 1963). [ ] For experimental materials, an equal weight mixture of Lac Jeannine hematite and a high-purity quartzite from Thompson, MN, both ground to - 30 µm (- 560 mesh) was used. Selective flocculation test conditions and procedures were identical to those used in previous investigations (Heerema, Lipp, and Iwasaki, 1979). The optimum level of starch addition for the above mixture was determined to be at 300 g/t (0.6 lb per st). Initially, a series of selective flocculation tests were performed on the mixture pulped with 10-3M CaC12 (40 ppm Ca + +) at pH 11. With no NTA present, flocculation of the entire suspension resulted. The selectivities achieved in tests with 90, 100, and 150% of the stoichiometric amount of NTA were virtually identical to each other and also to the selectivity of separation obtained in the absence of Ca+ + Such an observation could have been expected since Ca+ + concentrations up to a few ppm may be tolerated in selective flocculation (Krishnan and Iwasaki, 1982). A similar series of tests were performed at 10-2M CaC12 (400 ppm Ca+ +). The results are shown in Fig. 1 as grade¬recovery curves. For comparison, the results obtained in the absence of Ca++ are included. At 90% of the stoichiometric amount of NTA, a large enough concentration of uncomplexed Ca+ + was left in solution to cause indiscriminate flocculation. Note in this figure that NTA is capable of countering the adverse effect of Ca+ + even at this high concentration when it is used in excess of stoichiometric amounts. The free Ca+ + concentrations at 100 and 150% are calculated to be 2.5 and 0 ppm, respectively. [ ] The relative effectiveness of NTA and EDTA was then compared at 100% of the stoichiometric amount using 10-2M and 10-3M CaCI2 (Fig. 2). EDTA appears to be slightly more effective than NTA. The free Ca++ of 0.02 ppm in 10-2M CaC12 with EDTA compared to 2.5 ppm free Ca+ + with NTA might account for the difference. As evident, prohibitively high additions of EDTA and NTA were required to complex high concentrations of calcium ion. The use of both of these agents would result in the accumulation of complexed Ca+ + in recycle water.

Jan 1, 1985

By Randolph C. Specht

A two year study was made of the waste disposal of the pebble rock phosphate industry. Solid slimes are impounded in large settling areas and the process water is re-used. Clear effluent was not found to be toxic to fish, or animal life in field tests or in controlled experiments.

Jan 1, 1950

By Y. C. Liu, G. A. Alers

The anisotropy of Young's modules has been measured in a series of Cu-Zn alloys containing from 1 to 28 wt pct Zn and cold-rolled to 97.5 pct reduction in thickness. These modulus data show a transition in texture as a function of zinc content. In alloys containing 3 pct Zn or less, the texture is essentially that of copper. A transition is clearly seen to develop in 5 and 8 pct Zn alloys, and to have been completed in a 12 pct Zn alloy. Increasing the proportion of zinc to 28 pct does not produce any further changes in texture. The ease and clarity with which this texture transition can be seen in the modulus data is in great contrast with the inccertainty in the visual detertiination of the range of texture transition from a series of pole figures. It is also shown that the rolling texture of the high zinc content alloys cannot be a one-COIIIponenl texture, characterized by the (110)(112) ideal orientations, as usually assumed. A second, quite important component must also be present. Furthermore, the present data are inconsistent with matrix orientations on which the "oriented growth" hypothesis of the Formation of recrystallization textures is based. THE rolling textures of binary fcc alloy systems have generally been considered to lie between two terminal textures. One of these terminal textures is the copper type and the other is the 70:30 brass type. Alloys of intermediate solute content exhibit a texture which is said to be a transition between the two terminal textures. On the basis of efforts to correlate rolling and recrystallization textures, two concepts have been advanced in the literature on the nature of these transition textures. One school1 suggests that the addition of alloying elements, e.g., zinc, causes a gradual rotation about one of the (111) poles from the (358)( 523) ideal orientation of the copper-type rolling texture to the terminal {1 10)( 112) ideal orientation used to describe the rolling texture of 70:30 brass. This concept is depicted in Fig. 1 with the angle of rotation corresponding approximately to the zinc content and is designated here as the "rotational concept", since the ideal orientation of the transition textures varies continuously with alloy content. The other concept,' the "mixture concept", suggests that the copper-type rolling texture is a two-component texture. {358) (523) and {110)(112). The addition of alloying elements affects only quantitatively the relative amounts of these two components—a decrease in the amount of material in the {385}(523) orientation and an increase of that in the {110)(112) orientation with increasing solute content. An experimental distinction between these two concepts is essential to a better understanding of both the mechanism of formation of rolling textures and the subsequent formation of recrystailization textures in fcc metals. Because of the lack of resolution inherent in pole figures, it has not been possible to differentiate between the two concepts on the basis of this data. Both concepts, in fact, make use of the same set of pole figures but interpret them in a manner acco-rding to the view held.'" Experimental results obtained from inverse pole figures or selected-area electron diffraction3j4 simply -yield more refined pole figures but do not eliminate the ambiguity of interpretation. Quantitative measurement of an entirely different, orientation-dependent property must thus be considered

Jan 1, 1967

By John J. Gilman

BECAUSE of their layerlike structure, zinc crystals exhibit strong anisotropies for almost all physical and chemical properties. This should, and indeed does, greatly influence the plasticity of zinc for various crystal orientations. At low temperatures, the investigator of this plastic anisotropy is plagued by the great variety of deformation modes that operate. However, at high temperatures (250° to 419°C) only two deformation modes predominate: basal (0001) and prismatic (1010) glide. Furthermore, since strain hardening is virtually absent at high temperatures, the plasticity for these two modes of deformation can be very simply described by means of two equations of state. It is the purpose of this paper to describe the experimental behavior of basal and prismatic glide in zinc crystals, and to interpret this behavior in terms of other physical properties (in particular, the thermal expansion coefficients and the elastic constants) using the theory of dislocations. Fig. 1 defines the two planes of the zinc structure that will be discussed. Glide occurs very readily on the basal planes at all temperatures, and there is a very large literature on this subject. Much of the literature has been reviewed by Schmid and Boas;' it will not be reviewed here. Kolesnikovl was the first to show that if basal glide is circumvented by stressing a zinc crystal parallel to the basal planes (giving zero shear-stress on the basal planes) then, at temperatures above about 320°C, glide on the first-order prism planes occurs. His results have recently been confirmed by Cahn, Bear, and Bell." These previous workers have established the existence and crystallographic elements of prismatic glide; the present paper is concerned with the stress, strain rate, and temperature relations of prismatic glide as contrasted with basal glide. Experimental Methods The crystals were square ones, 6x6 mm, that had been grown in precision Pyrex tubes by a method that is described in detail elsewhere.' Most of the crystals were 99.999+ pct Zn (New Jersey Zinc Co. CP grade). Some were alloyed with 0.1 -+-0.005 atomic pct Cd, and chemical analysis showed that almost all of the added cadmium persisted through the crystal-growing process. For measurements of nonbasal glide, crystals were oriented with their basal planes parallel to both the rod axis and one of the flat faces of the square cross section. However, the orientation of the close-packed directions [1210] with respect to the rod-axis was variable. For basal glide measurements, the angle between the basal plane and the specimen axis was 35". The orientations were measured by the Gren-inger back-reflection X-ray method. The problem of finding a suitable method of gripping the crystals was the most serious experimental obstacle that arose. Because of the large plastic anisotropy of zinc, the usual gripping methods were unsatisfactory. Some methods that were tried were: high melting-point solder, making heads on the ends by locally melting a crystal, and electroplating nickel on the ends to form enlarged portions. For all these methods, the regions of the grips were weaker than the crystals themselves. Finally, two methods were decided upon: bend tests and direct machining of tensile specimens. In the bend tests, specimens were loaded as simple beams so that gripping was not a problem. The beams were 1 in. long and the axis of bending was parallel to the hexagonal axis of the crystals. For the crystals that were machined into tensile specimens, brass bars with slots in them were used to support the crystals, and thereby minimize the distortions due to machining. The crystals were glued into the brass bars with plastic cement which was later dissolved away with acetone. See Fig. 2, left. No clamps were used near the crystals and the machining was done using a milling machine with a fly-cutter. The tool bit was very sharply pointed to minimize burnishing. The feed was less than 1 mil per cut. The depth of cut was 2 mil for roughing cuts, and % mil for the finishing cuts. This machining method produced surface layers of tiny recrys-tallized grains only 2 to 3 mil deep, and the bodies of the crystals were not measurably disturbed. After the crystals had been machined and removed from the brass holders, they were chemically polished until about 5 mil had been removed from all their surfaces. The polishing reagent consisted of equal parts of concentrated HNO,, 30 pct H3O and ethyl alcohol; it is described in detail elsewhere." A typical crystal is shown in Fig. 2, right. The I-shaped faces are normal to the hexagonal axis of the crystal; otherwise the projections at the ends would simply shear off when the crystal was loaded. The cross section in the 2?-in. gage length is 0.215x0.115 in. It was found that the polished

Jan 1, 1957

By H. E. Exner

This article is a critical review of the influence of surface preparation on crack formation at Vickers indentations in the test used by Palmqvist3-7 to evaluate the toughness of cemented carbides. Experimental results are presented which clearly show that grinding introduces compressive surface stresses into the cobalt phase and thus reduces the crack length. The deformed surface layer is removed by polishing and a stress pattern is approached corresponding to that in the bulk material. Cracks of maximum length are characteristic of this stress state. Deformation stresses can be removed by annealing above 800°C. On the basis of these results , sample preparation for the crack length test can be simplified, the accuracy of measurement is improved, and a simple and significani parameter is found to describe crack resistance of cemented carbides. FOLLOWING suggestions by Ammann and Hinniiber,1'2 Palmqvist3-7 developed a method for testing the toughness of cemented carbides using as a measure the sum of crack lengths at the four corners of a Vickers hardness indentation. This method has several advantages over the bend test commonly used in carbide technology: a) specially formed samples are unnecessary; b) sufficient information can be obtained from one sample; c) the scatter is relatively small; d) the range of actual values for commercial cutting alloys is wide. Thus, this test is both cheaper and more precise than the bend test. Nevertheless, Palmqvist's method is not widely used, mainly for two reasons: a) The relationship between crack length and the technological properties of the material (wear and shock resistance) is not clear. b) The crack length is strongly dependent on surface treatment. It is necessary, therefore, that surface preparation be very precise and reproducible, conditions usually hard to obtain. While any other simple mechanical test has this first drawback, the second became crucial in the application of the crack length method as a practical test. The reasons that this drawback could not be eliminated are, in our opinion, misleading and inconsistent interpretations of the influence of surface preparation on the crack length given in literature. In the following, after a short review of previous experimental results the interpretations given by different authors,4?'-11 cf. Table I, are discussed critically and a consistent explanation is presented on the basis of which improvements of the method of crack length testing are proposed. 1) PREVIOUS EXPERIMENTAL RESULTS In his first attempt to use the cracks at Vickers impressions as a quantitative measure of the toughness of cemented carbides, palmqvist3 calculated the work necessary to initiate cracks by the formula: Sk =k.Pk. [I] where k = numerical constant = 6.49, Sk = critical work to initiate cracks (gf cm), Pk = critical load (load necessary to initiate cracks) HV = Vickers hardness (kp per sq mm). The difficulties involved in experimental determination of the critical load were overcome by the observation that a linear relation holds between the applied load and the sum of the crack lengths at the four corners of the indentation. This linear function, given by Eq. [2] below, was confirmed by Dawihl and Alt-meyer9and by our experiments, see Fig. 1: I = a1.P +a2 [2] where 1 = sum of the crack lengths at a Vickers indentation, P = applied load, al, a2 = parameters dependent on the toughness of the alloy and the surface preparation. The critical load, Pk, is now given by a2, which can be obtained by extrapolating the load vs crack length line to zero crack length, see Fig. 1. This simple relationship, Eq. [2], led Palmqvist1,7 to a parameter which was more reproducible and easier to obtain experimentally than the critical work: the work, S300, put into the sample to produce an average crack length of 300 µm per indentation. This parameter is calculated using the formula: where the load, P3oo, giving a crack length of 300 µm, can be taken from the load-crack length plot, Fig. 1,

Jan 1, 1970

By Grimes, J. A.

EXTENSIVE discovery 'and rapid exploitation of orebodies within the past half century have attracted many able geologists to the mining industry and furnished them a wealth of data from which to develop theories concerning ore genesis. By tosting and elimillating theories which are not sufficiently sup- ported by fact, or which are based on inaccurate observation of field data, the trend of geological opinion has . moved strongly in certain directions until, at the present time, large numbers of geologists subscribe to a broad concept of .ore genesis that I would summarize as below:

Jan 1, 1928

By H. E. Cline

Calculations of the formation and growth of faults caused by a variation in lumellar widths were made for a two-dimensioml three-plate problem. The angle between the a-ß boundary and the growth direction was allowed to vary and the time evolution was studied using a quasisteady state approach. At spacings smaller than a critical spacing given by X V = AO variations in the larrlellar widths grow in time to produce faults that coarsen the structure, while at spac-ings larger than this critical spacing, variations in the lamellar widths decay in time. If small plates are introduced into the structure they may grow only at large spacings to refine the structure. The time evolution and shape of faults were calculated for the three plate-problem and then the three dimensional problem and rod-like eutectic were qualitatively discussed. UNDERSTANDING of the mechanism by which the spacing of directionally solidified eutectics is determined may allow one to control their structure better. Steady state solutions for the growth of lamellar structures have been found for a range of lamellar spacings A and growth velocities V. To obtain a unique solution for the isothermal growth of pearlite, Zener1 assumed that growth occurs at a maximum velocity, while Tiller2 assumed that a eutectic alloy, grown under an imposed velocity, will choose a spacing corresponding to minimum undercooling. These assumptions are equivalent and have been referred to as "extremum growth". The extremum condition predicts the observed relation between velocity and spacing as given by V = constant [I] but does not provide a mechanism for changing the lamellar spacing. Jackson and Hunt3 calculated the interface shape by using solutions to the diffusion equation for a planar interface and a relation of the interface composition to the local curvature. If the spacing is much larger than the extremum spacing, the interface breaks down catastrophically to form forked plates. However, the catastrophic breakdown cannot account for the small adjustments in spacing that must occur in practice..3 Direct observations during the growth of organic eutectics4 and the Pb-Sn eutectic5 show that spacing changes occur by the formation of faults. A fault in a plate-like eutectic is the edge of a plate. Once the faults form, they may move to make small adjustments in the spacing.6,3 The motion of faults intersecting the growing interface was shown by an approximate analysis to give Eq. [I].6 A perfectly regular lamellar structure should be able to persist over a range of lamellar spacings. However, during growth small perturbations in the structure may occur. If the amplitude of the perturbation increases in time the structure is unstable, while if all possible perturbations decrease in time the structure is stable. In a previous paper7 variations in the shape of the solid-liquid interface were considered, while this paper considers only variations in lamellar widths while maintaining a macroscopically planar solid-liquid interface. Previously, theories of lamellar growth1"3 have artificially contrained the growth to give a regular periodic structure. To allow for a variation in spacing, the three phase intersections and groove angles were allowed to change with time as determined by assuming local equilibrium. THREE-PLATE PROBLEM Since the spacing changes in eutectics by local formation of faults,4'5 it is suggested that local variations in spacing are responsible. The interaction between neighboring plates will be greatest because they have the smallest diffusion distance. For simplicity, as a nearest neighbor approximation, a three-plate problem will be considered, as illustrated in Fig. 1. The structure consists of a periodic array in which all the plates are allowed to vary in width. As in steady state growth it is assumed that the average composition in the solid remains constant. A variation in plate widths, that maintains the composition in the solid, was introduced by making the first a-phase plate thinner by an amount A, keeping the width of the second B-phase plate constant, and increasing the width of the third a-phase plate. If the structure were not perturbed, as in the regular two-plate problem previously described,' then the groove angles at the three-phase junctions are the equilibrium angles, 0, and ? B, and the solid-solid boundary is normal to the interface. In the three-plate problem with a variation in plate widths the phase boundaries are assumed to be related to the three-phase junction by equilibrium angles, but the a/B boundaries may be rotated by an angle 0 from the growth direction. The angle H be-tween the tangent to the a/B boundary and the growth direction may vary during growth and determine the —> — — —.A_ Q-0 / 0 x, X2 Fig. 1—Schematic of the three-plate problem showing a variation in the spacing and the effect on the angles at the three phase intersections.

Jan 1, 1970

By James K. Richardson

Today, the enigma of the "missing man" in the metal mining industry equals, and frequently surpasses in objective importance, the problems of ore development, drilling, sampling, pumping, milling techniques, geophysical prospecting, or any one of a hundred highly technical subjects. Unfortunately, as engineers, we have confined our attentions, in the main, to the scientific phases of mineral technology, relegating our man power problems to the background. But what good has all our scientific study and preparation been if we can't get the ore mined, milled, or smelted? What has happened to our labor supply? Where is the good old miner who could timber, drill a round, lay track, or do any job underground?

Jan 1, 1949

By Albert A. Mathews

OUTCROPS of gypsum rock near the present site of the city of Gland Rapids, Mich., were known to fur traders early in the nineteenth century. However, the deposits seemed without value and were not worked for some time. So far as cat1 be learned, Michigan gyp- sum was first used by a plasterer who settled in Grand Rapids in 1834 as a member of its fourteenth white family. In building a house for one of the early traders, be used some otnamental stucco mouldings manufactured from the local gypsum deposits for decorations in the gables and around some circular windows. The gypsum was broken out with a hammer, ground in an Indian corn mill, and burlled in a caulclron kettle,. After two attempts, the ornaments were successfully set, and remained on the house until it was destroyed by fire in 1850.

Jan 1, 1936

By F. R. Hensel

THE demand for clean steel is increasing daily. New processes of refining steel are being developed in order to remove all nonmetallic inclusions as completely as possible, as it is the general opinion that. inclusions affect the dynamic properties of steel and iron to such an extent as to justify great expense for their removal. It is surprising to note at the same time the commercial development of a new process for making artificial wrought iron. By this process slag and steel are thoroughly mixed, the amount of nonmetallic inclusions usually exceeding 2 per cent in weight. The contradiction in these two efforts is obvious and is responsible for the investigation reported in this paper. H. W. Gillett also has recently emphasized the need for further research on wrought iron.1

Jan 1, 1932