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By M. S. Seltzer

High temperature steady-state creep rates have been determined jor lead sulfide single crystals whose defect concentrations were fixed by equilibration under controlled sulfur pressure. The activation energy of creep, Qc , for undoped lead sulfide, is a function 01 composilion, decreasing from 2.9 to 2.2 ev as the carrier concentration increases from 9 x 1016 to 8 1018 electrons cm-3 for lead excess crystals, and increasing from 1.7 to 2.3 ev as the concentration of holes increases from 4 x 1017 to 1 x 1018 cm-3 in sulfur excess material. For five different composilions, Qc for undoped and bismuth-doped crystals has been found to be equal to Qpb + Qs, the self-diffusion activation energies for lead and sulfur in PbS. It is well-established1 that high-temperature steady-state creep of pure metals is a diffusion-controlled process, where the activation energy of creep is equal, within experimental error, to the activation energy of self-diffusion. The relationship between the activation energy for steady-state creep and those for self-diffusion in binary compounds is more complicated, however, because two different diffusing species must be considered, and becayse the activation energies may be influenced by compositional variations and by foreign atom additions.2-4 In some cases experimentally determined creep activation energies are correlated with those for self-diffusion of the slower-moving species, but such agreement is by no means universal. Interpretation of experimental results is difficult because few investigations include measurements of creep rates and self-diffusion coefficients of both diffusing species on single crystals of similar composition and foreign atom concentration. The objective of this investigation, therefore, is to determine the influence of stoichiometric defects and foreign atoms on steady-state creep and self-diffusion for a well-characterized binary compound. Lead sulfide, a compound semiconductor which crystallizes in the NaC1-type structure, and whose homogeneity range includes compositions on either side of the 1:l atom ratio, was chosen for study in this investigation. The pressure-temperature-composition relations for PbS are available,5,3 and deviations from stoichiometry may be monitored by electrical measurements.7 Single-crystal specimens are available to allow observation of effects due to bulk phenomena without interference from grain-boundary effects. These crystals have been employed to determine steady-state creep rates under compressive stress for "pure" and bismuth-doped PbS as a function of sulfur pressure and temperature as well as crystal orientation and applied stress in order to establish the relationships between defect concentrations and creep rates. EXPERIMENTAL PROCEDURES Crystal Growth. Lead sulfide crystals, prepared by the Bridgman method, are grown in evacuated quartz crucibles, filled with almost equal atomic proportions of high-purity (99.999 pct) lead and sulfur, and heated to a temperature above the melting point of PbS (about 1127°C) so that the lead and sulfur react to form molten PbS. The crucible and melt are dropped through the hot zone of the crystal-growing furnace at the rate of 1 cm per hr. The maximum melting point of PbS is slightly on the lead-rich side of the 50:50 composition; hence crystals grown from a near stoichiometric melt are usually n-type semiconductors containing excess lead atoms. Typically the lead excess concentration in solid solution with the PbS is 3 x 1018 atoms cm-3. Crystals containing either 1/20 or 1/2 mole pct Bi2S3 were prepared by addition of the foreign atoms prior to crystal synthesis. Preparation of Specimens of Controlled Stoichiom-etry. Since it is difficult to grow crystals of desired composition, the process of crystal growth and control of stoichiometry are separated into two distinct operations. Equilibration of as-grown PbS to a desired composition is most easily accomplished by first annealing the n-type crystals under high sulfur pressure (about 1 atm) at temperatures above 700°C. This process serves to put excess lead precipitates into solution, yielding 0 -type crystals upon quenching to room temperature. Inter diffusion occurs readily in crystals so treated, and the methods described by Bloem may then be employed to obtain crystals of controlled stoi-chiometry. For the creep measurements made in this study, this involves heating crystals in mixtures of H2 and H2S The equilibrium constant for H2S is given by: Thus the sulfur partial pressure is obtained from knowledge of the H2/H2S ratio and Kh2S for the temperature in question. Fig. 1 shows the p-T-x diagram for PbS. It can be seen that, within the stability limits for single-phase lead sulfide, desired compositions may be obtained by equilibrating under a specified sulfur pressure and temperature. Characterization of Crystals. The principal methods for evaluating PbS crystals include measurement of electrical properties and mass-spectrographic analysis. The measured electrical parameters include Hall coefficient, conductivity type, and electrical resistivity Bloem7 has shown that there is a 1:l relation between the defect concentration and carrier concentration obtained. Hence, if the contribution to the carrier con-

Jan 1, 1968

By D. R. Mitchell

MEETING for the thirteenth time in New York as part of the five-ring circus known as the Annual Meeting A.I.M.E., the Coal Division experienced a wartime boom in attendance. Technical sessions were crowded and whereas 65 seats were set up for the annual luncheon meeting of the Division over 100 members showed up, many of whom had to be fed elsewhere. Possibly the Coal Division should adopt "13" as its lucky number. Discussions at technical sessions, formal and informal, were lively. Those papers containing material directly concerned with the war, or containing information that might be usable for war industries, were enthusiastically received. Some criticism was made in regard to the present method of handling discussions and it was suggested that better success would be had in getting discussions in the record by the use of hired reporters. This is being considered by the executive committee of the Coal Division.

Jan 1, 1943

By W. M. Yim

Experimental results are presented which indicate that transverse striations in horizontal zone-leveled Bi-Sb alloy crystals are due to irregular growth rate resulting from thermal fluctuations in the melt (Iring gowth. Thc thermal fluctutations arose from two different sources. The first type was brought about by periodic fluctuations in the furnace temperature. The second type can be attributed to turbulent therrrol conlcclion in the trzelt near the solid-liquid inteyace. Tile arrzplitlcde ond fvequency of the tetiperaticre fluctlrations vesultity from llle lhevnal con1,ecrrell. The striation spacings in Lhe crystals covvelale well with the periodicity 0.f the tempevature flueluatiors. Altliough the strialiors represenl corrlpositiozul inhoiHogeneity oh a rzicroscule, less than f.z cil. be1 S6 in Best's as deterrirzed by electron-pro be chalq'sis, the slriations roerre fbund to ILUL' no rrleusuanble effect on electical vesistirity rwr on weak field macgnetoresistance of. the Bi-Sb a1lu.y in the ternpevutue ),unge 4.Polo 300°K. DURING the course of an investigation on the horizontal growth of semimetals,' it was found that crystals of Bi-Sb alloys contained many closely spaced parallel arrays of striations. These striations occurred perpendicular to the growth direction and parallel to the solid-liquid interface. We shall refer to them as transverse striations, or just striations'', to distinguish them from lineage substructures or longitudinal striations which form parallel to the growth direction and have been known to be associated with cellular structures.' Similar transverse striations have been reported previously to occur in other materials prepared by horizontal growth: metals,4 semiconductors,5 as well as their alls. - Various methods of crystal preparation have apparently little effect on the occurrence of the transverse striations. They form whether the crystals were grown by the vertical Czochralski technique, withe1' or without'3- rotation, or by the horizontal zoning methd.- Thus, the transverse striations are not limited to any one class of materials, nor to any particular method of preparation. It is likely, therefore, that all of the observed transverse striations may have some common cause. Previously, workers agreed that periodic changes in the growth rate bring about the striations. However, no agreement exists as to the origin of the growth-rate fluctuations. Some attributed the discontinuous growth to a purely external cause, such as fluctuations in the furnace temperature, jerky motions in the crystal pulling mechanism, or a nonsymmetrical temperature distribution in the melt (in the case of crystals grown by the Czochralski technique with rtation). Others looked for the cause in some fundamental property of the growth process itself. For instance, a certain degree of supercooling is required to initiate growth from the melt. But, with further growth, the degree of supercooling decreases because of the liberation of the heat of solidification at the solid-liquid interface. Thus, crystal growth would be brought to a halt until sufficient supercooling is resotred and the cycle begins again.3'11 According to this model, periodic fluctuations in the melt temperature should exist at the solid-liquid interface. Since the periodic fluctuations in growth rate would result in changes in the segregation coefficient of solute atoms, crystals containing the transverse striations may, in some cases, show a periodic impurity fluctuation along the length, resulting in a degradation of electrical properties. The resistivity striations in doped germanium'9-10 or lnsbB are well-known examples of this microsegregation. The present work was undertaken to explain the exact origin of the transverse striations, and to assess the extent of their effect on chemical homogeneity as well as on electrical properties of Bi-Sb alloy crystals. Results from our previous study of the crystal growth of Bi-Sb alloys1 indicated that the transverse striations may arise from the temperature fluctuations in the melt during growth. This paper will show that the melt temperature fluctuations are indeed responsible for the occurrence of the transverse striations. I) EXPERIMENTAL Although the transverse striations have been observed in all slow-grown Bi-Sb alloys across the entire compositional range, we selected a composition, Big3Sbs, for the present study in view of the extensive data available on the crystal growth of this alloy from a previous study.' High-purity bismuth and antimony, both a 6-nine grade by the manufacturer's emission spectrographic analysis, were used throughout. Independent mass-spectrographic analysis showed, however, that the starting materials were more nearly a 5-nine grade. each containing metallic impurities of approximately 10 ppm atomic. In zone-leveled Big5Sb5 alloys, the total metallic-impurity content was slightly lower, about 7 ppm atomic, indicating that some degree of purification was achieved during the growth. None of the electrically active impurities, such as tin and lead (acceptors) and tellurium and selenium (donors), were present in significant quantity in undoped Bi95Sb5. Typical analysis of the undoped Bi95Sb5 alloy is shown in Table I. Nonmetallic impurities, such as carbon and oxygen, were detected, sometimes as much as 100 ppm, in both the starting materials and the zone-leveled alloys: but the data were only qualitative. Temperature fluctuations in the melt were monitored over 1 or more days by means of a 5-mil chromel-

Jan 1, 1967

By H. H. Hausner, H. S. Kalish

M. Hansen—This paper certainly is an interesting study. Although I have not had too much experience in the powder metallurgical methods of studying phase equilibria, I would like to say the following concerning the interpretations of the results obtained: 1. The existence of a zirconium-rich eutectic having a melting point close to 950°C and containing approximately 5 pct beryllium is well established. 2. Undoubtedly sintering of the original compacts (i.e., without repressing and resintering at 1350°C) resulted in a condition being far from equilibrium, even in the low-melting point zircon-rich region where undissolved zirconium particles have been observed. This means that only partial reaction between the component powders has taken place. 3. In preparing and handling powder mixtures for pressing and sintering, we have found that with powders differing considerably in density, and also in particle size, separation in layers of different composition may occur. This means that a concentration gradient would exist within such samples. This phenomenon may, at least to some extent, account for the difference in microstructure of the top and bottom regions of some of the sintered samples. If this is the case, density figures for some of the nominal compositions would not represent actual densities of those mixtures. 4. Fig. 1 shows that the low densities of mixtures with 40 and 60 pct beryllium sintered at 1350°C are changed to much higher densities if the products sintered at 1100°C are repressed and resintered at 1350°C, whereby an approach toward equilibrium takes place. This would mean that the low density and growth in volume is due to nonequilibrium conditions. If this is true, would it be justified, then, to conclude that "the remarkable growth of the alloys in the vicinity of 40 to 60 pct Be indicates the formation of a high-melting point phase, probably accompanied by a considerable change in volume due to a large alteration of the crystal structure from that of the original compounds"? If some compound formation has taken place already during the first sintering at 950" to 1350°C, more compound would be formed by repressing and re-sintering of the 1100" samples. This treatment, however, results in higher, rather than lower, densities. In general, the density-composition curve of alloy systems containing one or more intermediate phases is characterized by a more or less defined contraction (decrease in specific volume, increase in density) over the "theoretical" density. Does not discrepancy exist between the two statements that "growth of the alloy indicates the formation of a high-melting phase . . ." and "even at 1350°C, no indications of sintering have been observed"? 5. I am not sure that the explanation given for the fact that fig. 4 did not reveal as much eutectic as the top portions of the mixture with 2 pct Be, is correct. The density of the melt containing only 5 pct Be or even perhaps less, is not too much different from that of the nominal composition. The reason might be also that there was already some separation of the components in the pressed compact. 6. I do not understand why the microstructure of the bottom regions of the compact with 5 pct Be (fig. 6) is so different from that of the top regions (fig. 5). The compact was melted on sintering at 1100°C. Its composition lies close to the eutectic point. There should be at least some lamellar structure in the bottom regions too; otherwise, the composition of top and bottom must have been very different after sintering, because the eutectic is said to extend as far as the composition ZrBe2. In case the white and gray areas of fig. 6 are both gamma, and the black areas undissolved zirconium, this composition would be close to the phase coexisting with zirconium, that is, ZrBe2, according to the hypothetical diagram, or a compound richer in zirconium. 7. Figs. 9 and 10 are not mentioned in the text. 8. The great difference in microstructure of the composition 20 pct Be of figs. 8 and 14 on one side and fig. 15 on the other side proves that sintering at 950" and 1100°C results only in partial reaction of the powers. 9. The mixture with 60 pct Be (fig. 19) seems to consist of two phases, rather than one phase, one interspersed in a matrix of another. 10. The statement that the eta phase "may be an intermetallic compound or the product of a peritectic or monotectic reaction" seems to be misleading, because the product of a peritectic or monotectic reaction in this region of the system must be an intermetallic compound. 11. If there is some solid solubility of Be in alpha and beta-Zr, it would be expected to be higher in beta-Zr (b.c.c.) than in alpha-Zr (h.c.p.). The temperature of the polymorphic transformation of zirconium then would be lowered, rather than increased. In accordance with this, Battelle has found that the transformation point of titanium is decreased by beryllium. 12. In case the phases present in alloys with 80, 90, and 95 pct Be are identical (which appears to be correct), it is striking that the relative amounts of both phases (eta and beryllium) are not too different within this wide range of composition. With 60 to 65 pct Be

Jan 1, 1951

By Winston A. Wong, John J. Jonas

Commercial purity aluminum was deformed by extrusion over the temperature range 320° to 616°C and the strain rate range 0.1 to 10 per sec. Flow stresses and strain rates were calculated from the experimenLa1 ram pressures and speeds. The stress-strain rate-lemperature relationship in extrusion was found to be similar to that in creep. Extrusion, torsion, compression, and creep data extending over ten orders of magnitude of strain rate and over two orders of magnitude of stress were correlated by a single creep equation. It was concluded that hot-working is a thermally activated process, in which the rate-controlling mechanism is either the climb of edge dislocations or [he motion of jogged screw dislocations. The microstructural changes observed during extrusion were consistent with the proposed deformation mechanisms. ALTHOUGH great progress has been made in understanding the technology of extrusion, very little is known about the actual deformation mechanisms operating during flow. Previous accounts describing extrusion have indicated that the relationship between ram speed (V), pressure (P), and temperature (T) can be given as follows:1 V = apb and P = A' exp(-AT). In these equations, a and b are constants which depend on temperature, A' is a constant which depends on ram speed, and A is a "coefficient" with a different value for each metal. Although these equations have fairly wide application, they do not contribute much to a fundamental understanding of the deformation. Furthermore, extrusion has not hitherto been considered as a thermally activated rate process. This lacuna is surprising because hot-working is similar to high-temperature creep in several respects. There is, in fact, a fair body of experimental evidence suggesting that the material response under hot-working conditions is similar to that occurring under creep conditions, in spite of the many orders of magnitude difference in strain rate.2"4 Since creep has been extensively analyzed in terms of dislocation mechanisms, the comparison of hot-working to creep is useful, for it can suggest the possible deformation mechanisms operating during hot-working. In this paper, the hot extrusion of aluminum will be examined from the point of view of thermally activated deformation mechanisms, such as operate during creep. EXPERIMENTAL PROCEDURE The experimental procedure consisted of extruding commercial purity aluminum* over a range of ram velocities and temperatures at constant die reduction by the direct method. Details of the experimental equipment have been published elsewhere.5 Extrusion was carried out at each of the following billet temperatures: 320°, 376°, 445°, 490°, 555°, and 616°C at the following constant ram speeds: 0.002, 0.008, 0.02, 0.1, and 0.2 in. per sec.* All results were obtained using a square-shouldered die with an extrusion ratio of 40:1, giving a reduction in area of 97.5 pct. The ram force was the dependent variable, and was measured by means of strain gages on the ram and was plotted as a function of ram travel. The sequence of events before making an extrusion was duplicated before each run so as to minimize as much as possible variations in experimental conditions. For example, after the equipment had been assembled, the billet was allowed to heat up to temperature inside the insulated container. Once the container attained the desired temperature, a period of 1/2 hr was allowed to elapse before the extrusion was made. This time was found to be required to allow the billet to reach a steady-state temperature, as determined from previous tests. When all was ready, extrusion was carried out without interruption; that is, the billet was upset and extruded in one operation. EXPERIMENTAL RESULTS AND DISCUSSION The two usual experimental approaches for investigating high-temperature deformation exhibit an important common feature. In the first approach, which corresponds to creep, a constant stress (or load) is applied to the material at constant temperature and the resultant strain is recorded against time. After an initial transient stage, a state of constant strain rate exists (secondary creep), in which a steady-state condition is established which is sensitive to variation in either applied stress or temperature. In the second approach, a constant strain rate is applied and the resultant flow stress is recorded. This corresponds to the situation in hot torsion or hot compression, where it is observed that, for a constant test temperature, there is an initial rise in stress to a steady value which is maintained up to very high strains. In tests of this type, a steady-state region is also established in which the stress is sensitive to variation in either the strain rate or the temperature.3,4,6-16 In both types of tests, therefore, a steady-state region is established after an initial transient. In the case of hot-working this region may be called steady-state hot-working, and it is analogous to steady-state creep with which it has many common features. Stress Dependence of the strain Rate in Extrusion. In order to assess the stress dependence of the strain rate under extrusion conditions, and to compare it to that of creep, as well as of hot torsion and hot compression, the extrusion data were analyzed according to power, exponential and hyperbolic sine creep equations.

Jan 1, 1969

By Thomas L. Watson

My thanks are due to Mr. Frank Firmstone, Easton, Pa., who has called my attention to the statement in my paper' that " Barite, fluorite and quartz, thougll not observed in the Tennessee area," ... as possibly misleading to the reader, if construed to mean that such a discovery had never been made. Mr. Firmstone is correct in assuming that this statement referred only to the study of the worked areas of the metallic ores, especially zinc, made in the course of the survey upon which my paper was based. The occurrence of barite and fluorite with lead-ores in Tennessee was reported by Prof. Safford? in 1869, and by Safford and Killebrew? in 1887, with the further statement that about 1,000,000 lb. of barite were annually mined in Greene, Washington and Jefferson counties, Tenn., and that considerable deposits occur also in McMinn, Smith and other counties. It is also noted that the barite " usually occurs in veins, associated with galena." The present worked areas of barite are, however, distinct barite propositions, without workable quantities of either lead or zinc, so far as mining operations have gone, and the areas are more or less removed from the present areas of zinc-ores. Mr. Firmstone informs me also that, in 1892, he observed, in the magnesian limestone at Watauga Point, in Carter county, on the left bank of the Watauga river, a little below the mouth of Buffalo creek, small quantities of galena and some fluorite.

Jan 1, 1907

The following communication was recently sent President Wilson by J. Parke Channing, Chairman of the Engineering Council: The transportation systems of our country are largely the creations of its professional Engineers. This statement can be made without disparagement to the statesmen, the financiers, the manufacturers, the lawers, the educators, the mechanics, the laborers and many others, who, with the Engineers, have contributed to the development of transportation. Through all stages of preliminary exploration, final survey, construction, upkeep and operation, in financial management, and in adjustment of the relations of transportation to the public, the genius and knowledge of the Engineer are essential. Not only in technical physical matters, but also in determinations of policy, his contributions have supplemented and must ever supplement those of other men. These declarations hold good for all the carriers of commerce, by rail, by highway, by water, by pipe-line, by wire, or by air. Hence, it follows that the body established by Government to regulate the commerce, the carriers and the ways of communication, embracing so many engineering features, should number among its nine members, men of engineering training and experience. Engineering Council, being aware of a vacancy on the Interstate Commerce Commission, begs leave to request the Chief Executive that in filling this vacancy, he give earnest thought to the selection of a man who, to his other qualifications, adds the training and experience of an engineer familiar with transportation problems.

Jan 9, 1919

FRANCIS B. SILSBE,* Washington, D. C. (written discussion?). ?This paper is an interesting example of the -solution by the methods of metallography of what seemed at first a purely chemical problem. The authors have shown: in detail, how the well-known corrosion of spark-plug terminals is due to the dropping out of the individual crystals of the metal as it becomes surrounded by an oxide film. This corrosion is usually quite slow but in special cases may become a serious factor in limiting the life of spark plugs. There still remains the problem for the metallurgist to produce a material that will be entirely free from, this trouble. One of the most startling results of the work is. the demonstration that it affords of the deleterious effect of a mechanical stress continuously applied to material that is at the same time subject to adverse chemical or thermal conditions. The particular style of spark plug shown in the illustration, and in which serious trouble was caused by this corrosion, has the side terminals fastened at both ends and the method of assem-bling is such that a considerable initial tension is applied to the wire. It is without doubt this superimposed tension that causes the inter-crystal-line network to line up, as it were, into a few continuous and deeply penetrating transverse fissures instead of forming a great number of shallow surface cracks. This result is clearly shown both in the case of

Jan 11, 1919

By J. D. Mooney

(San Francisco sleeting, September, 1915) THE accompanying chart has been drawn for the convenience of engineers as a means of quickly determining the correct number of plies of conveyor belts operating under specific conditions. The calculations are based on the average safe strength (factor of safety, 15) of the various standard rubber conveyor belts. The, calculations assume maximum loading conditions; that is, the belt is considered as carrying the greatest load that it will handle without spillage at ordinary belt speeds. This not only produces the most economical operating conditions, but also the maximum tension in the belt. The chart is a graphical representation of the formula: p = kgW (L + 1OH) Where, p = the correct number of plies k = a constant, depending on the type of drive g = the weight in pounds per cubic foot of material handled W = the width of the belt in inches L = the length of the belt in feet (approximately twice the center distance). H = the difference in elevation between the head and tail pulleys, in feet. For a simple drive, with a bare pulley, k = 1/250,000 For a simple drive, with a rubber-lagged pulley, k = 1/300,000 For a tandem dive, with bare pulleys, k= 1/375,000 For a tandem drive, with rubber-lagged pulleys, k = 1/455,000 The chart is drawn for a simple drive, with a bare pulley (k =1/250,000;

Jan 9, 1915

Engineers and masters of enterprise are waking fast to the realization that there is something more in the relations of employer and employee than mechanical output, which can be measured mathematically, and that the human side of service must receive greater consideration for the future. So much has been said and written on this subject that it has passed into a truism. Should not the same element, long neglected, be considered as of even greater importance than questions of "administration and membership, in the plans of engineering societies? Should mutual service and interest end with mere technical output by members and the rendering of care and management by officers? The world is recognizing, as never before, obligations for service to fellowmen clue from all, high or low, in rank or wealth. Our technical societies, organized for professional protection and advancement, are, insensibly to themselves, almost without conscious intent, widening their field of service to members and dealing heartily with questions broader than technique. Those who are doing such service find unconsciously more and more satisfaction in work so rendered. The growth of knowledge that comes to subaltern engineers or veterans by converse and contact with their fellows, working along and versed in the same subjects, brings interest and friendship. In this way are built some of the warmest friendships of life, coming as incidental and pleasurable result of meetings undertaken for other purposes. Should not the friendly purpose, the desire for service one to another, and es-

Jan 1, 1919

Man is born on Mother Earth without knowledge or skills. Soon he finds physical needs for food, clothing, shelter, exercise, and relaxation. His personal needs are self-expression, new experiences, and amusements, while his social needs have been classified as work, status, security, friendship, companionship, and love. He finds himself infinitesimal in comparison to the whole. Often- times when he feels smug, he is actually riding for a fall. And nothing is much worse than frustrated man. The postwar world does not provide the Utopia of peace and prosperity of which man had dreamed. In fact, it seems that the sacrifices and waste of that great struggle are being lost in the morass of stupidity, selfishness, and cupidity which unfortunately are still the most conspicuous traits of the human race. Perhaps it is too soon to expect the blessiilgs which are supposed to appear in a peaceful world, and man's thought is clouded with a pessimism engendered by the conflict itself, in which all activities tend to enhance his pessimistic nature. Must man submit that it is a law of nature for nations to go to war? The war has demonstrated that when faced with a common danger, peoples differing in antecedents, language, forms of government, and resources can unite for a time, pool their skills and abilities, and emerge victorious from a contest unparalleled in magnitude, ruthlessness, carnage, waste, and cost. This has been accomplished by great individual and national sacrifices, the

Jan 1, 1950

By A. V. Quine

FOUR years ago several mining operators shook their heads and predicted that Goldfield Consolidated Mines Co. would never be able to mine the zinc-lead ores from the 550 to 650 level areas of the Deep Creek mine. Their prediction was not without apparent justification, for everywhere one gazed, water was spurting or dripping; every hole that was drilled produced more and more water under pressures of 220 to 250 psi, all from apparently unrelated channels. When the volume of water from one level alone reached 2200 gpm with a possible flow of 5000 to 6000 gpm if the area were fully tapped, development work was brought to a halt and the few holes into the water area were grouted off under contract. As zinc prices had completely deteriorated, the workings were allowed to flood. Upon reopening the mine, in late 1950, it was discovered that the relatively few sacks of cement used in the previous grouting operation had done a tremendous amount of good. Consequently it was decided to systematically drill test holes with a longhole machine and diamond drill and to seal all holes with a cement grout solution. After 30,000 ft of drilling, and the pumping of over 20,000 sacks of cement, 15,000 of which were placed in the supposedly impossible 650 level, the company was successful in literally forcing the water out of the ore zones and opening up large tonnages for subsequent extraction.

Jan 3, 1954

GEO. F. COMSTOCK,* Niagara Falls, N. Y. (written discussion?).¬A study of this paper raises a question on which it is hoped Mr. Stork will throw more light; that is, why does an oxygen content generated on poor melting conditions have a deleterious effect on the properties of the iron, while an oxygen content generated by the oxidation of steel scrap in the cupola is beneficial to the strength and chilling ability? In each case the oxygen is absorbed at the same time and place in the process of melting and it is by no means clear why the superiority of semisteel should be assigned solely to its oxygen absorption, when oxygen absorbed without the steel addition is admitted to be injurious. It is not apparent why oxygen caused to be absorbed by the steel addition should not pro-duce the effects of burning, sluggishness, slag inclusions, gas occlusions, etc., the same as oxygen absorbed by the iron in the cupola for any other reason, and it would seen that other factors to which he has not given sufficient emphasis must enter into the author's results. To an impartial reader of this paper, who was most favorably inclined toward J. E. Johnson, Jr.'s theory of the improvement of cast iron by oxygen, the discrepancy in the author's reasoning or statements is difficult to accept, and it is hoped that an explanation will appear in the final discussion.

Jan 11, 1919

Geologist or Mining Engineer who has had sufficient experience to make examination of a large area and who can report upon economic value of any minerals found. Work will extend over a period of 2 or more years. Location, India. R-1660. Assistant Superintendent of malleable and gray iron foundry, young man. Must have thorough molding experience, especially on squeezers, knowledge of mixture control and operation of air furnaces, cupolas, and annealing ovens college graduate preferred. R-1727. Engineer thoroughly familiar with distilling, evaporating and drying machinery. Capable of taking charge of entire evaporator department, including engineering and selling. New Jersey. R-155C. Experimental Draftsman familiar with small automatic mechanisms, principally those produced in large quantities by punch-press methods, such as adding machines or typewriters. New York City. R-1566. Patent Draftsman.-At least 2 years' experience on perspective rend-ering of small automatic machinery. New York City. R-1570. Designer.-Familiar with hydraulic work and capable of going ahead with detail and design work without supervision. Pennsylvania. R-1575. Superintendent or Foreman. Knowledge of ceramics, clay products, electric porcelain, tile, factory materials, etc. New York State. Good salary to right man. R-1578. Designer. Experienced in designing mining machinery, including electric hoists. Canada (Quebec). R-1589. Construction and Operating Superintendent. Executive and thor-oughly experienced in the zinc melting industry. Will have charge of construction of plant and its operation. Salary $6000 to start; increase to $8000 later. India. R-1593.

Jan 11, 1919

By John W. Pack

AT present the manufacture of metallic zinc, or spelter, in Missouri, is carried on only at the establishments located at Carondelet, or South St. Louis. Although the development of the industry has not yet reached that fulness which it has attained elsewhere in the United States, still the commanding advantages of position of these establishments are so evident that the prospective importance and magnitude of spelter manufacture in this State, and especially at this locality, can hardly be doubted. A study of the chemical and technical aspects of the business of these points cannot be without interest to the metallurgist as well as to the capitalist. I have endeavored to investigate, as far as was practicable, within the limits of a paper of this character, some of the problems connected with this industry, at the same time making a few comparisons of the results attained at some of the Carondelet works with those of other establishments with regard to which information could be obtained. In the prosecution of these studies I have been kindly aided by the managers of Carondelet establishments, and by Prof. Charles P. Williams, Director of Rolla School of Mines. To the latter I am especially indebted for assistance in regard to methods of analysis. To all these gentlemen I return my thanks for their valuable aid. Other sources of information will be duly credited in their proper places.

Jan 1, 1875

By George W. Maynard

In the Journal of the Iron and Steel Institute for the year 1878, in the account of the proceedings of the annual meeting in March of that year, when Mr. Bell read his paper On the Separation of Phosphorus from Pig-Iron, occurs the following statement, as part of the reported discussion of that paper: " Mr. Sidney Thomas stated that he had succeeded in effecting the almost complete removal of phosphorus in the Bessemer process. Experiments had been carried on at Blaenavon, with the co-operation of Mr. Martin, on quantities varying between 6 lbs. and 10 cwt., and some hundred analyses made by Mr. Gilchrist (who had the conduct of the experiments from the first) showing the removal of from 20 per cent. to 99.9 per cent. of phosphorus in the converter. He believed the practical difficulties in the way had been overcome, and that Cleveland pig might be made into good steel without any intermediate process. He hoped on a future occasion to lay full details before the Institute." I was present at that meeting, and I doubt if any one in the hall knew, either by sight or name, the young man who had dared to rise in that august body and claim that he had accomplished that after which the great metallurgists of Europe had been unsuccessfully striving ever since Mr. Bessemer's great discovery. I remember distinctly the pitying smile of derision and the stony stare

Jan 1, 1885

By H. O. Hofman

Lime-roasting is a term proposed by Ingalls' for the operation of forcing air under pressure through a mixture of galena and lime at the kindling-temperature with the object of oxidizing lead and sulphur and of fritting or fusing the charge. If finely-divided galena were treated in this manner without the addition of lime, the heat set free by the oxidation of part of the lead and the sulphur would be sufficiently great to fuse un-decomposed sulphide, and thus stop desulphurization. Besides the chemical action that the addition of lime, limestone or gypsum to the charge may have, the admixture has the physical effect that it keeps the particles of galena separated from one another and accessible to the oxidizing effect of the air. At present, three methods of lime-roasting are carried out on a working-scale,—the Huntington-Heberlein, the Carmichael-Bradford and the Savelsberg2 processes. In the last, which interests us here, an 8-ton charge is made up of galena, limestone and perhaps some siliceous or ferruginous flux; the whole is crushed to pass a screen with 3-mm. holes and moistened with 5 per cent. of water. It is fed gradually into a bowl-shaped converter, 6.56 ft. in diameter, supported by trunnions attached to a truck. On the bottom the converter has a grate with blast-inlet beneath. In starting, the truck with the converter

Jan 1, 1908

By F. Weinberg

Lead single crystals have been deformed in tension over the temperature range of 4.2°K to the melting point. Changes in flow stress resulting from temperature cycling and strain rate cycling have been measured as a function of temperature for crystals of different orientations and purity. It was found that the flow stress ratio, after correcting for the temperature dependence of the shear modulus, decreased progressively with temperature above approximately 0.5Tm. The activation energy calculated from the high-temperature portion of the curve was found to be markedly higher than that of self-diffusion. For single glide crystals, the corrected flow stress showed an increase above 0.5 Tm before decreasitzg with temperature. This increase is attributed to static recovery occurrittg during temperature cycling. THE temperature dependence of the flow stress, based on temperature cycling and strain rate cycling, has been extensively investigated,' and on the basis of these results dislocation models of the work-hardening process have been proposed. In general, the flow stress is divided into two parts, ts, the short-range interaction term, which is only effective at low temperatures and which decreases with increasing temperature, and TG, the long-range stress term, which is independent of temperature after allowing for the temperature dependence of the shear modulus. The observations demonstrating that tG/µ is independent of temperature were generally carried out at low temperatures to minimize recovery effects. Several investigations have been reported on flow stress measurements at high temperatures2"5 which demonstrate that TG/µ does not remain constant at temperatures above 0.5Tm (where Tm is the melting temperature of the material in OK). Specifically, Hirsch and warrington3 carried out temperature cycling tests at two strain rates on single and polycrystalline aluminum up to 0.8 Tm and on polycrystalline copper. For aluminum they found that the flow stress ratio (the flow stress at temperature T2, divided by the flow stress at the reference temperature T1 in one temperature cycle) dropped progressively with increasing temperature above 0.5Tm. From the slopes of the high-temperature portions of the curves, they determined an activation energy for the deformation process of 1.6 ev (at best) which they considered was in agreement with the activation energy of self-diffusion, 1.35 ev. Calculations of the activation volume demonstrated that the deformation was not controlled by dislocation climb. They proposed a mechanism in which the rate-controlling process at high temperatures was due to the rate of move- ment of vacancies away from jogs, i.e., that of self-diffusion. Results of Lucke and Buhler4 on single crystals of aluminum confirmed this conclusion. They measured the critical resolved shear stress of aluminum over a wide range of temperature and strain rates. They found that the temperature dependence of the critical resolved shear stress was similar to that of the flow stress ratio, as determined by Hirsch and Warrington, and from their data calculated an activation energy for high-temperature deformation of 1.35 ev identical to that of self-diffusion. More recently Gallagher5 has carried out a detailed investigation of the temperature dependence of the flow stress ratio of copper, silver, and gold. In all cases, he found that the flow stress ratio, after adjusting for the shear modulus temperature change, drops at high temperatures. The activation energies he determined were found to be appreciably higher than the activation energy of self-diffusion of the material being considered. The flow stress ratio was found to be dependent on the orientation of the material, and, in addition, an anomalous increase in the flow stress ratio for copper, oriented for single glide, was observed above 0.5Tm. The purpose of the present investigation was to measure the critical resolved shear stress, the flow stress ratio, and the strain rate sensitivity of lead, primarily as a function of temperature. The results should indicate whether, following Lucke and Buhler, the critical resolved shear stress of lead has the same temperature dependence as the flow stress, and, following Hirsch and Warrington, whether the activation energy for high-temperature deformation in lead is the same as that of self-diffusion. Lead deforms as a normal fee material,6'7 is available in high-purity form, can readily be grown as single crystals, and, for this investigation, has the very considerable advantage of having a low melting point, 327°C. The observations of the critical resolved shear stress of lead have been published elsewhere.' EXPERIMENTAL PROCEDURE The experimental procedure was essentially the same as that used in the critical resolved shear stress measurements.' Single crystals of 99.999 pct (59) and 99.9999 pct (69) lead were deformed in tension with a table-model Instron in a silicone oil bath above room temperatures and in a cooled methyl alcohol or liquid-nitrogen bath below room temperatures. The test specimens were rectangular in section, 0.65 by 0.33 cm, and had a 5-cm gage length. The specimens were grown as single crystals with tapered ends, which fitted into matched tapered grips for testing. To obtain the flow stress between two temperatures, specimens were first deformed approximately 1.0 pct at the higher temperature. The test was then stopped, the load relaxed, the oil bath removed without disturbing the specimen, the grips and specimen cooled with a fan and then immersed in liquid nitro-

Jan 1, 1969

By J. E. Campbell, G. D. Calkins, N. M. Ewbank, M. Pobereskin, A. Wesner

GRINDING for size reduction affects the economics of many processes and products. It is essential as the first step in many industrial processes and is also a finishing step for materials with properties depending on particle size, such as talc, cement, and silica sand. Intermediate and fine grinding are vital operations in the U. S. cement industry, which is producing more than 250 million bbl of cement per year.' Wear of the grinding media is a large part of the grinding operation cost. Problems encountered in grinding cement are so complex that evaluation of efficiency and economy of grinding media is difficult.2 It has been especially difficult to evaluate the relative effectiveness of different types of balls because there are no good testing techniques. Many other industrial operations can be evaluated on a laboratory scale with reasonable accuracy. This does not hold true for evaluation of grinding balls. The consistent results obtained in a laboratory test under a given set of conditions are not always borne out in field application. Rough evaluations of the effectiveness of various compositions and types of grinding balls have been made in the field by using a full charge of one type in a mill and comparing the production record with another run using another type of ball. This method is time-consuming and not very precise, as the second run may not have been carried out under identical conditions. Laboratory-scale tests, on the other hand, have yielded inconclusive results, and many investigators have turned their attention to the development of a field testing technique. Field testing small sample lots of grinding balls has been impractical because it is difficult to identify and recover the test specimens from the grinding mill, and individual groups of balls that have undergone different heat treatments can not be separated.".4 To overcome these difficulties, previous investigators have identified the balls by distinctive marks, notches, and drilled holes, but this procedure has three serious drawbacks: 1) Grinding characteristics and quality of the steel balls may be affected. 2) Physical markings may be worn away in the grinding process, especially during a prolonged run. 3) Recovery from the bulk of the charge will be extremely difficult because the markings are hard to see and may be masked by a coating of the product. To circumvent these difficulties, a radioactive-tracer technique was proposed for recovery and separation of steel grinding balls and subsequent evaluation of the various compositions of the balls. The proposed technique involved five basic operations: 1) Thermal-neutron irradiation activation5 of each group of test grinding balls to a different level of specific radioactivity. 2) Addition of groups of radioactive steel-ball specimens into a ball tube mill. 3) Recovery of radioactive steel-ball specimens from the bulk of the mill charge. 4) Separation of the various groups by their specific radioactivity. 5) Evaluation of actual grinding ball wear. Before any physical tests were performed, required neutron irradiation intensity and time were calculated. Probable composition of the steels to be used was ascertained. An examination was made of the radioactive nuclides8 to be formed which would contribute measurably to the radiation level immediately after irradiation and during the test operation. The radioisotopes formed, their types of radiation, and their half lives are listed in Table I. Of these radioisotopes only iron-59 and chromium-51 were significant for the actual wear test. The intensity of radiation that could be detected by a Geiger counter when the test was completed was the basis for the minimum activation level established. The intensity of radiaton that could be safely handled at the beginning of the test was the basis for the maximum activation level, although this was not considered a major problem. Ten groups of grinding balls of various composition and/or surface or heat treatment were to be tested. One group was designated for the minimum irradiation time. The remaining groups were designated for irradiation periods that increased by increments of 33 pct from that of each preceding group. This difference was considered enough for separation and identification of the groups by comparison of specific activity. Potential Hazards: Possible radiation hazards that might be encountered during this experiment were evaluated for the three important phases: 1) the radiation hazard of placing balls and removing them from the mill, 2) contamination of the product cement by radioactive material worn from the balls, and 3) contamination of the steel by the radioactive balls left in the mill. The radiation intensity expected from the whole group of radioactive balls was calculated to be 250 milliroentgen per hr at 1 ft. This meant the balls would require special shielded packaging and warning labels on the shipping containers. In a radiation field of 250 mr per hr a man can work for 1 hr without exceeding maximum permissible weekly exposure. Since the balls could be dumped into the mill in a matter of seconds, relatively little radiation exposure was anticipated at this stage of the operation. If the weight loss in the balls was 7.7 pct per month and the cement feed through the mill was

Jan 1, 1958

By Rees D. Rawlings, C. W. A. Newey

The aging characteristics of an Fe-11 at. pct Mo alloy have been studied by means of light metallography together with density, Young&apos;s modulus, and hardness measurements. The results were consistent with the precipitation of a single intermetallic compound during aging; overaging was slow relative to that in other iron-based binary alloys. The solution treatment temperature had a small effect on the rate of hardening whereas deformation prior to aging had a marked effect on both the rate of hardening and the peak hardness. The density data indicate that the compound precipitated is Fe3MO2 and not the Laves phase Fe2Mo. Analysis of the modulus and density results gave values for the time exponent for precipitate growth of approximately 1.0 and 1.5 for the alloy aged with and without prior deformation, respectively. DETAILED studies of precipitation hardening in bcc matrices have been confined largely to the effects of carbides and nitrides. In view of this and the growing technological interest in intermetallic compound strengthening, e.g., in maraging steels, a study of precipitation in iron-based alloys with a low interstitial content has been undertaken. This paper is concerned with the aging behavior of an Fe-11 at. pct Mo alloy; the mechanical behavior of the alloy will be reported later. The early work of sykes on Fe-Mo alloys showed that precipitation of the intermetallic compound was accompanied by an increase in hardness and a decrease in volume of the material. More recent surveys of the strengthening associated with precipitation have been made3-5 and, in particular, Elsen and wassermann4 showed that deformation prior to aging increased the rate of hardening. These latter workers also followed the precipitation process by means of dilatometry, electrical resistivity, and lattice parameter measurements. Their results confirmed that there is a decrease in volume on aging. Except for the work of Hornbogen on an Fe-20 at. pct Mo alloy, neither clustering nor the precipitation of a nonequilibrium phase has been observed in Fe-Mo alloys. Studies of alloys of lower molybdenum content475 indicate that the equilibrium intermetallic compound is precipitated during aging. However, there is some doubt concerning the nature of the equilibrium precipitate phase. According to the phase diagram constructed by Hansen,8 the phase should be precipitated. This phase has a rhombohedra1 crystal structure which is characterized by the formula Fe706,&apos; although the composition of the molybdenum-rich boundary corresponds approximately to Fe3Mo2. The version of the diagram proposed by Sinha, Buckley, and Hume-Rother indicates that the A phase, a Laves phase Fe2Mo, should be precipitated. Their observation of a Laves phase supports the earlier findings of Bechtoldt and Vacher,13 although, in a recent study of the system by means of diffusion couples, Rawlings and Newey did not detect the phase. The work presented here describes the effect of solution-treatment temperature, aging temperature, and prior deformation on the aging characteristics of the alloy as revealed by light metallography together with hardness, density, and Young&apos;s modulus measurements. In addition the density data are used in an attempt to determine the compound precipitated during aging. EXPERIMENTAL PROCEDURE A 29-kg ingot of the alloy was cast at R.A.R.D.E., Fort Halstead, from deoxidized, Japanese electrolytic iron and sintered molybdenum. The ingot was homogenized for 6 hr at 1473°K and then worked, with intermediate anneals, into 6- and 16-mm-diam rods and 6-mm plate. Chemical analysis of the alloy gave, wt pct: Mo, 17.5 (11 at. pct); C, 0.003; Si, 0.002; S, 0.005; P, <0.002; and02, 0.0098. Solution treatments were carried out under a dynamic argon atmosphere in a vertical, "crusilite" element, furnace which had a facility for rapid quenching into iced water. Except for the study of the effect of solution treatment temperature, all specimens were solution-treated at 1573" * 2°K for 1 hr. Salt baths were used for the aging treatments. Specimens for hardness, density, and Young&apos;s modulus measurements were produced, after heat treatment, from the stock rod or bar using a precision silicon carbide slitting wheel. As described later, the quenching treatment produced local plastic strain in the stock material; consequently, care was taken to ensure that the specimens were not prepared from these regions. Those specimens used in the studies of the effects of prior deformation on the aging behavior were strained in compression in a Denison universal testing machine. Specimens for light metallographic observations were mechanically polished on successively finer grades of diamond paste down to and then etched in either alcoholic ferric chloride or in a 2 pct nital solution. Vickers diamond pyramid hardness data were obtained using a 30-kg load. At least five impressions were averaged for each determination. Density measurements were made using a displacement technique in which each specimen was weighed in air and in dibromoethane at 296°K. The specimens were cylindrical and weighed 3 to 4 g; all weighings were made on a balance reading to 1 x 10"5 g. For each specimen the mean value of five weighings was used to calculate the density. The density of the dibromoethane was determined using the displacement procedure and a standard nickel specimen. The error in an absolute density value was estimated to be HI.01 pct. To obtain the density as a function of aging time a single specimen was used and the density meas-

Jan 1, 1969