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By Charles H. Moore

When lime and magnesia are used as fluxes in the smelting of titaniferous ores fluid, digestible slags low in iron oxide and high in titanium dioxide are produced. The mineral phases present in such slags are (Fe,Mg)O.2TiO2, CaTiO3, and minor amounts of silicate glass (or its devitrification products). The flux additions are added to the ore in relative amounts to crystallize a ratio of (Fe,Mg)O.2TiO2 to CaTiO2, of near the eutectic proportions of 60 pct (Fe,Mg)0.2TiO2 and 40 pct CaTiO3. FeO-Ti02 (ilmenite) remains present in the slag until the FeO content is reduced to approximately 8 pct. Op- timum slag composition is obtained by reducing the FeO content to between 2 and 6 pct. Continued reduction shifts he (Fe,Mg) 0.2Ti02 to oxygen deficient structures classified as MgTi30e and MgTi204. Further reduction yields titanium oxycarbides and freezes the melts.

Jan 1, 1949

By H. J. Rose, J. J. S. Sebastian

When coal is stored under ordinary conditions, progressive changes take place in its chemical and physical properties. These changes are largely caused by the reaction of atmospheric oxygen with the coal substance. Although this "oxidation" or "weathering" occurs slowly in the case of high-rank coals, it is nevertheless a matter of considerable importance, since even a small amount of oxidation may affect the value of coal for carbonization purposes. Coal storage is a necessity at all carbonizing plants. In normal times there are about 5,000,000 tons in storage at by-product coke ovens and gas retorts in the United States, as compared with an annual throughput of about 75,000,000 tons. In other words, the average coal reserve at such plants is slightly less than one month's supply. However, owing to the cost of storage and recovery, coal is usually left in stockpile for as long a time as the management thinks advisable. Storage for six to eight months is common practice and is, in fact, a necessity at certain plants which obtain their coal by water routes that are closed during winter months. Modern by-product coke ovens operate continuously, and they are not cooled down from the time that they arc put into operation until they are shut down for rebuilding—perhaps 20 years later. This continuous operation is imposed by silica-brick construction and high operating temperatures. It is therefore obvious that coke plants must at all times maintain an adequate supply of stored coal, in order to prevent a failure in supply from any cause whatever. Thus when strikes or other emergencies threaten, abnormally large coal stocks are accumulated and held at coke and gas plants. Many of these plants have been forced, at some time or other, to use coal that has been stored for several years. Such coal may fail to coke at all, or it may produce a dirty appearing, weak coke of reduced value. The yields of salable by-products may also be distinctly lowered. However, it must not be assumed that slight oxidation or heat effects are always injurious. Certain high-volatile coals produce a stronger, blockier

Jan 1, 1930

By Robert B. Kistler, Ward C. Smith

The borate industry is one of the few sectors of the mining and mineral-processing industry which the United States still dominates. Since about 1927, the United States has supplied over half of the world's total boron and borate raw materials, and many of the chemical derivatives as well. Chiefly responsible for this record are companies producing sodium borates from two large deposits in southern California, at Boron (Kramer) and Searles Lake. The sodium borates, or products derived from borax and borax-containing brines, are the preferred borates for industry because they are soluble in water and combine readily with most other chemicals. Calcium borates (or sodium-free compounds) are required for certain end uses, but in general, nonsodium borates are used only where borax is not avail- able. During the past hundred years, the use of boron compounds throughout the world has risen from a few tons per year to the equivalent of about a million tons of B2O3. Leadership in supplying borates has shifted from country to country and from region to region during this period, generally as the result of the development of newly discovered deposits that were better in quality, more accessible, or more economically exploitable than previous sources (Table 1). Primary Products and End Uses The principal borate products offered by primary producers in the United States are listed in Table 2. In general, these products are utilized worldwide by almost all consumers, regardless of the original source of the primary borates. In the United States, the primary borates all originate in southern California. Colemanite is produced as crude or processed crude ore from the Death Valley area and is utilized by the fiber glass and ceramic industries without further treatment. Production from Searles Lake, Calif., is from brines that are processed in chemical plants where borax and other compounds are recovered and the principal borate products are produced. At Boron, Calif., the world's leading producer is mining a deposit of mineral borax and operating a chemical refinery. The mineral borax is mined together with included clay, and refined borax or "lo-mol" is one of the refinery products. The mineral and the chemical compound are identical, Na2B4O7- lOH2O. In addition to ship- ping all major refined borate products from Boron, the company ships semiprocessed ore concentrates to treatment plants elsewhere.

Jan 1, 1975

By Robert J. White

Strong's equation for calculating bottom-hole pressure reduction due to gas cutting of drilling mud is corrected, resulting in a simpler equation which is easier to use. Use of the equation is illustrated by examples. It is shown that reduction of weight of a 10 lb/gal mud by 50 per cent at the surface due to gas cutting produces only n 3 per cent decrease in hydrostatic head at the bottom of a 5,000-ft well. It is also shown that at the surface 5 volumes of air per volume of mud are required to reduce the apparent mud weight from 8.5 to 6.5 lh/gal in a 3,000-ft well. Illustrative graphs are included to show the effect of various degrees of gas cutting on apparent mud weight at depths of 2,000, .5,000 and 10,000 ft and to show variation of apparent mud weight, with depth for a 100 lb/cu ft (13.37 lb/gal) mud gas cut to 90 lb/cu ft (12.03 lb/gal) at the surface. INTRODUCTION In 1938, Strong' published the following equation for calculating reduction in bottom-hole pressure due to gas cutting of drilling mud h = 1/D [p + pn/100 In p + p(1-n/100)/p(1- n-100)] where: h = depth in feet P = pressure in atmospheres at depth h due to mud column only D = hydrostatic pressure in atmospheres of a col-umn of uncut mud 1 ft high p = back pressure at well-head (in atmospheres) n/100 = fraction by volume of gas in mud at well-head at back pres-sure p This equation was recently found to contain an error due to an incor-rect expression for variation of vol-ume fraction of gas with pressure. Values calculated by the original equation are close to the correct values for small percentages of gas for which it was derived but become increasingly erroneous as the gas content increases and are completely unusable at the very high gas con-tents employed in aerated mud. DERIVATION The nomenclature used is the same as in Strong's paper. The pres-sure dP exerted by a lamina of thickness dh at a depth h ft is ex-pressed by Eq. 1 where x = volume fraction of gas at depth h dP = D (l - x)dh . . . (1) When we express x in terms of the wellhead per cent gas n, the well-head pressure p and the pressure P at depth h, the result is Eq. 2. x = (np/p+p)/(100-n) + (np/P + p) When this is substituted in Eq. 1 and rearranged to separate the var-iables the result is dh = 1/D [dp + np/100-n dp/(P + p]. Integration between appropriate lim-its results in or if the wellhead is open so that p = 1 atm and we rearrange Eq. 4, the result is loss in head = hD — P = n/100-n In (P + 1) ...(5) Eq. 5 can be solved easily by successive approximation using hD as a first approximation for P on the right-hand side and calculating a first value for loss in head. This can then be used to get a new value of P using the left-hand side of the equation. Values converge very rap-idly even for quite large values of per cent by volume gas n. EXAMPLES The effect on bottom-hole pressure of 50 per cent gas cutting of the mud in a 5,000-ft well using 10 Ib/ gal mud will be calculated, we have: h = 5,000 ft 10 X 7.48 144 X 14.7 = 0.0353 atm/ft hD = 176.5 atm n = 50 Substituting these values in Eq. 5 and using hD as a first approxima-tion of P on the right, we have, approximate loss in head = 50/50 In (176.5 + 1) = 2.30 log 177.5 = 5.17 atm. We calculate a new value of P as follows:

Jan 1, 1958

By J. J. Knoerzer

A full-scale operational test was conducted on the Coaltek preheating and pipeline charging system at the Semet-Solvay Div. of Allied Chemical at Ironton, Ohio, for the purpose of determining whether a high-quality blast furnace coke could be made from blends containing at least 75% Illinois No. 6 Coal and at the same time reduce air pollution during the charging of the ovens. The coke produced had similar physical characteristics as compared to our conventional wet-charged coke, with the exception of smaller size for the preheat coke. Air pollution during charging was con- trolled and there were no serious operating problems. The coking time was reduced 25% from our normal 17 hr for wet charging to 12.8 hr for preheated charges. The blast furnace performance with preheat coke was satisfactory.

Jan 1, 1976

By E. M. Murphy

(Presented by invitation at a meeting of the Spokane Local Section of the Institute, Feb. 17, 1912.) EIGHT years ago the Hecla mine, a lead-silver producer, situated at Burke, Idaho, was producing ore from but two levels, the 300- and the 600-ft. All hoisting was done with a 12- by 16-in. slide-valve, double-reel, hoist. The hoist was being worked to its capacity and was unsuitable for hoisting from greater depths. As the work of opening a new level was about to be started, it became necessary to remodel the then-existing equipment or install a new hoist. The recent advent of electricity from Spokane had made available a cheaper power than steam. By a series of tests conducted throughout the Coeur d'Alène district, it was found that it cost $109 per year to generate a horse-power with steam. Electric power was to be had for $50 a horse-power per year. It was decided to substitute for the engines a motor-drive, of sufficient capacity to operate from the 900-ft. level, and ultimately install an entirely new hoist. After disconnecting the engines, installing a new shaft, and making a few minor changes, a 300-h-p., 2,300-volt, 514-rev. per min., variable-speed motor of the induction type was geared to the reel-shaft. The reels were supplied with 3/8 by 4-in. flat rope, and the duty of the hoist was about as follows: Cage, 1,700; ore, 2,600; car, 1,400; rope, 2,250; total, 7,950 pounds. The Bristol ammeter chart, Fig. 1, shows the combined current-consumption of the hoist- and mine-motors. The large intermittent load is clearly shown ; this produced harmful fluctuations in the voltage of the long, lightly-loaded, 60,000-volt transmission-line from Spokane to the Coeur d'Alènes. The power company received no compensation for the increased cost of producing power for this intermittent or fluctuating load. In order to protect its system from similar excessive

Sep 1, 1912

By F. B. Plummer

GEOLOGICAL engineering as applied to oil fields, or production geology as some prefer to designate the profession, is designed to fill in the border line between pure geology and pure petroleum engineering. Therefore the production geologist may, and frequently does, reach out to grasp much in both professions. Where once the oil geologist was content to pick samples out of a mud ditch and try to identify oil formations from the color or appearance of flakes of rock bailed out of a well, now he has to deal with graphic electrical logs obtained by intricate and highly technical electrical apparatus and to make exact determinations to the fraction of an inch of the depth and thickness of an oil sand 2 miles below the surface.

Jan 1, 1944

By David R. Maneval, H. B. Charmbury

At the turn of the century, iron and coal were the keys to industrial prosperity. At that time, Pennsylvania was the leading mineral producer in the Country, producing 200,000,000 tons of coal in a typical post-World War I year. Close to 90% of the Nation's energy was generated by coal. Today, coal accounts for but 22% of the energy generated, leading to a drastic reduction in Pennsylvania coal output. In contrast with the post-World War I days, 1964 figures showed a drop in production to 93,846,480 net tons. This huge decrease has created a serious economic problem in a state so much dependent on the coal industry. Along with the reduction in coal production, employment has dropped considerably through these years (the number of miners alone has gone from 280,011 to 43,149), thus causing a heavy burden of supporting the unemployed on the taxpayers. As far back as 1939, coal operators and economists saw the problems on the horizon and the need for improvement. Realizing that research was a way to improve and stabilize the industry they demanded legislative action. The Legislature reciprocated with a small grant to The Pennsylvania State University with the provision that each State research dollar be backed with one from the industry. This initial grant laid the foundation for the further growth in coal research.

Jan 3, 1966

By J. D. Hanawalt

Significant strides were made in the year 1948 leading to further recognition of the place of magnesium as a common commercial metal, rather than as just a premium aircraft material. One of the factors contributing to this recognition was the price stability and, in many cases, price reduction of magnesium products in 1948. In contrast to most other metals, manufacturing advances in magnesium outweighed the effects of increased labor and other costs. At the present time, many magnesium extrusions, die castings, and permanent mold castings can be purchased as cheaply as their aluminum counterparts in these forums, though competitive prices for sheet still await the inauguration of a modern tandem rolling mill for magnesium, such as has already been demonstrated.

Jan 1, 1949

By W. V. Green

The creep-rupture behavior of commercial powder-metallurgy tungsten rod is reported for temperatures of 2250°, 2500°, 2700°, and 2800°C, stresses up to 7000 psi, and times up to 4 hr. The temperature dependence and the stress dependence of creep rates are evaluated. Rupture time is fitted to the Larson-Miller parameter and compared to lower-temperature and higher stress results reported by pugh.4 THE tensile strength of single-crystal wire1 and of polycrystalline wire2 have been measured by Goucher. More recently Bechtold3 and pugh4 have studied the mechanical properties of tungsten rod between room temperature and 1200°C. Since tungsten has the highest melting point of all metals, it should retain useful strength to very high temperatures, and should find many applications in missiles, rockets, and so forth. Therefore, the mechanical usefulness of polycrystalline tungsten rod was investigated in the 2250" to 2800°C temperature range by short-time creep-rupture tests. MATERIALS TESTED Creep specimens were machined from 1/2-in. round commercial tungsten rod which was manufactured from powder by cold pressing, sintering, and hot swaging. Purity reported by the vendor was 99.95 pct W. Spectrochemical analyses showed "traces" (less than 0.01 pct) of silicon, iron, and titanium, and "faint traces" (less than 0.001 pct) of calcium and manganese. Carbon content was 30 ppm and nitrogen content was 70 to 110 ppm. No oxygen analysis was obtained. Room-temperature stress-strain tests on the as-received tungsten gave badly scattered results. Threaded end specimens broke at the threads. When these specimens were retested using shoulder grips, the specimens broke at the shoulders. No fractures occurred in the gage lengths. The fracture stresses were: 127,000; 137,000; and 154,000 psi for three specimens which fractured at the shoulders. The microstructure of the as-received tungsten rod is shown in Fig. 1. SPECIMENS USED Fig. 2 shows the two types of creep specimens tested. The threaded-end type specimen, which was used in most tests, had a 3/4-in. gage length and 1/4-in. gage diam. The cone-end specimen, which was used primarily to investigate the effects of a smaller gage diameter and the practicability of the modified grips and specimen, had a 3/4-in. gage length and a 1/8-in. gage diam. In both cases, the gage length terminated at 0.005-in. high shoulders which served as fiducial marks for optical strain measurements. Surface finish on the gage length was 16 µ-in. rms. Creep rates and rupture times were not significantly different for the two types of specimens and were not affected by electropolishing the specimens before testing. TESTING PROCEDURE The constant-load creep-testing machine used has been described by Smith, Olson, and Brown.5 In it the specimen is held vertically by grips of similar material and on the axis of a cylindrical tungsten or tantalum heater-tube. The specimen is loaded by means of the specimen grips, a pull rod (which is sealed to the chamber lid by a vacuum-tight bellows), a mechanical lever system, and hanging dead weights. Both specimen and grips are heated by radiation from the heater-tube, which is heated by its own electrical resistance. An optical system views the incandescent specimen through slits in the radiation shielding and heater-tube. The optical system projects an enlarged image of the specimen gage length on a ground-glass screen. Periodic gage-length measurements are made on this image with two cathetometers. Thorium oxide coatings on the specimen threads or conical end surfaces completely prevented diffusion-welding of specimens to grips, and were used

Jan 1, 1960

By T. W. Guy

DURING recent years, tremendous strides have been made in the economical use of coal. This has resulted in, and to some extent has been a result of, making the fuel specifications more and more rigid. For this reason, all producers have found it necessary to improve their preparation materially, both as to sizing and the elimination of impurities, either by more effective preparation underground or at the tipple and cleaning plant, or both. This cause and its effect in all producing fields seem likely to continue for several years-at least. The splendid inherent qualities of the Pocahontas and New River coals are known all over the world, but their good reputation is only partly due to inherent qualities, and to natural conditions which generally favor loading coal comparatively free from impurities; it is due in large measure to the care and skill used, either with or without the aid of mechanical devices, to ship products consistently low in ash. The first coal from the West Virginia smokeless fields was mined and shipped near Quinnimont, on New River, in 1871, while the first shipments from the Pocahontas field were in 1883. The development of both fields progressed rapidly. At first activities followed the main lines of the Chesapeake & Ohio and Norfolk & Western railroads, and were extended later as branch lines were built from these roads. The Virginian R. R., about 1907, opened up the Winding Gulf territory, which has since become a large producer of smokeless coals from the Pocahontas and the New River measures.

Jan 1, 1931

By Charles H. Foreman

IN JUNE 1921, the Sullivan &lining Co., owned jointly by the Bunker Hill and Sullivan Mining & Concentrating Co. and the Hecla Mining Co, started work on the development of the Star Mine. The development work contemplated called for a crosscut from the Hecla workings on the 2000 level to the Star ledge. The length of crosscut necessary to encounter the Star ledge was approximately 8900 ft. from the Hecla shaft. By using workings formerly made by the Hecla Mining Co., only about 8100 ft. of actual crosscutting was necessary. This crosscut has a direction of S 20° W and would have a tendency to crosscut any ledges in the intervening ground.

Jan 1, 1924

By Arthur S. Dwight

THE last decade of the 19th century was a peculiarly interesting one in. the annals of American metallurgy, especially as concerns the lead and copper- smelting industries; and it may be interesting to review briefly one of the outstanding incidents of that period, the development of the mechanical roasting furnace. I shall not pretend, in these reminiscences, to give with absolute accuracy the sequence of events or dates, nor to present a complete history of the period, but shall seek merely to 'sketch a more or less impressionistic picture with some of the underlying facts and causes as the recollection comes back to me and then point out how the present-day practice grew out of those activities. My acquaintance with the developments in Montana was based on occasional visits and general collateral information, but in Colorado I lived through the episode and was of it.

Jan 1, 1921

By David W. Brunton

The list of our past-Presidents comprises the names of many who, in their official addresses, have sketched the current progress of the arts and professions with which they were familiar. Such addresses are, in my judgment, highly useful, setting forth the results of our own work as a society, and recalling to our minds the particular lines in which discussion would prove most fruitful. Following this course with some hesitation, I venture to offer an outline of the recent improvements and the present situation in mining and metallurgy in the Western United States. The wonderful advances in mechanics, chemistry, and electricity have all combined to aid these arts to such an extent that progress during the last decade has undeniably been more rapid than ever before in the history of the profession. In all mining countries improved transportation-facilities, in many instances called into existence by the traffic created by the mines themselves, have done much to enlarge the field of operations by the reduction of freight-, operating- and living-expenses, thereby bringing lower-grade properties into the producing class. Under normal conditions, as the age of a district increases, all these different factors should combine to off-set the augmented costs attendant on deep mining, and greatly tend to prolong the profitable life of the mines. The more recent and important improvements in our Western mining-practice which have contributed most towards the advancement of the art may be briefly summarized as follows; but, before beginning this portion of my address, I wish to thank most heartily the many engineering friends who have so

Jan 1, 1910

By J. K. Lovrien

A Link-Belt roller-bearing conveyor system was in- stalled recently at the Gross-Marble mine of the Oliver Iron Mining Co. at Marble, Minn., for removal of overburden and lean ore. The material, consisting of clay, sand, gravel, and glacial boulders. is excavated by an electrically operated walking dragline equipped with a 10 cu yd bucket working from a boom approximately 150 ft long. This machine loads into a receiving hopper of a rail-mounted screening plant in 45 second cycles. A manganese steel apron feeder under the receiving hopper delivers to an elliptical grizzly, from which the oversize boulders and extraneous material, by way of an apron conveyor, arc loaded into refuse haulage trucks.

Jan 12, 1951

By Alicia O'Reardon

DIFFIDENTLY, because don'ts are rarely greeted with cheers; humbly, because I, myself, have never lined up with the irreproachables, I venture on the subject of manners for the mining camp matron. Mining camps can be divided roughly into two types-the large, opulent settlement that blooms like the rose about a strong mine in full operation; and the puny group of adobe huts, or calamina shacks, or even canvas tents flung down in the wilderness to shelter the gay pioneers of a shining prospect or the shattered survivors of a lost hope. Of the first, I know nothing; but in the second, I have spent some of my best years, and from its curious code of morals and manners, its comic hates and its unreasoning loves, its high impatience and its engulfing kindness, I have charted the narrow .and pitted path which must be trod by the woman who would success¬fully live therein.

Jan 1, 1936

By T. M. Morris, W. E. Horst

W. E. Horst—In regard to the flotation rate being described as "first orcler" for flotation of quartz particles below 65 p in size (or any size studied in this work) in this paper, it appears that the authors' conception of rate equations is not in agreement with cited references. A first order rate equation has as one of its forms the following: a In.=a/a-x=kt where a = initial concentration, a—x = concentration at time t, t = time, and k = constant. The constant, k, has the dimension of reciprocal time which is similar to the specific flotation rate, Q. described by Eq. 2 in the authors' article, as has been previously discussed by Schumann (Ref. 1 of original article). The plotted data presented in Fig. 4 of the article utilizes the specific flotation rate, Q (min.'); however, there is not adequate data given to indicate the order of the rate equation which describes the flotation behavior of the quartz system studied. Results from the experimental work indicate that the relationship between rate of flotation (grams per minute) and cell concentration (provided the percent solids in the flotation cell is less than 5.2 pct and the particle size is less than 65 p) is described by an equation of the first order (R, = k c+", n being equal to 1 in this size range) and the use of the first order rate equation does not apply. Similarly the relationship for other particle size ranges studied is expressed by equations of the second or third order depending on the magnitude of n. T. M. Morris—The authors are to be commended for the experiments which they performed. As they state in their discussion the concentration of collector ion In solution did change with change in concentration of solids in the flotation cell. Since for a given slze of particle, flotation rate increases with concentration of collector until a maximum is reached, the effect of concentration of particles in their experiments was to vary the concentration of collector ions. A collector concentration which insures maximum supporting angle for all particles eliminates the unequal effect of collector concentration on various sized particles and the effect of size of particles and concentration of particles upon flotation rate could be more clearly assessed. I believe that if the authors had increased the concentration of collector to an amount sufficient to attain a maximum supporting angle for all particles they would find that the specific flotation rate of particles coarser than 65 p would be constant with change in the concentration of solids in the flotation cell, and that a first order rate would apply to the + 65 as well as to the —65 p sizes. It might also be discovered when this change in collector concentration was made that the maximum specific rate constant would be shifted toward a coarser fraction than when starvation quantities of collector are used since this practice favors the fine particles and penalizes the coarse particles. P. L. de Bruyn and H. J. Modi (authors' reply)—The authors wish to thank Professor Morris for his kind remarks and for mentioning the influence of equilibrium collector concentration on flotation rate. With a collector concentration sufficient to insure maximum supporting angle for all particles, a first order rate equation may indeed be found to be generally applicable irrespective of size. Such a concentration would, however, lead to 100 pct recovery of the fine particles and consequently defeat the essential objective of the investigation to derive the maximum information on flotation kinetics. To establish absolutely the validity of any single rate equation for a given size range, the ideal method would be to work with a feed consisting solely of particles of that size range. Use of such a closely sized feed would also eliminate the possibility of the interfering effect of different sizes upon one another. The authors do not believe that increasing the collector concentration would shift the maximum specific flotation rate (Q) towards a coarser fraction. Experimentation showed Q to be independent of solids concentration for all particles up to 65 µ in size, whereas the maximum value of Q was obtained in the range 37 to 10 p. Professor Morris contends that the addition of starvation quantities of collector favors fine particles at the expense of coarse particles, but the reason for this is not entirely clear to the authors. The comments by Mr. W. E. Horst are concerned only with the concept of the term "first order rate equation." According to the usage of this term in chemical kinetics, time is an important variable, as is shown in the equation quoted by Mr. Horst. All the experimental results reported by the authors were obtained under steady state continuous operations when the rate of flotation is independent of time. To be consistent with the common usage of the "first order rate equation," it would be more satisfactory to state that under certain conditions the experimental results show that the relation between flotation rate and pulp density is an equation of the first order.

Jan 1, 1957

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

J. T. Pullon, Rowangarth, Roundhay, Leeds, England :— In discussing Mr. Lee's paper, I wish to call attention to the fact that Mr. B. II. Thwaite (who was heard here yesterday on the subject of the application of blast-furnace gas for the production of power, of which he was undoubtedly the pioneer) read, at the Engineering Congress in Glasgow in 1901, a paper on the profitable utilization of power from blast-furnace gases,' in which he suggested the diversion and cleaning of the whole of the waste gases coming from the blast-furnace and their utilization for power-production, so as to obtain, with proper manipulation, from 4 to 6 times the efficiency of present methods. He suggested also the heating of the stoves with producer-gas of a higher and therefore more suitable calorific value, so as to maintain them in a constant state of maximum efficiency, free from dust, and to avoid the irregular working of the furnace, besides obtaining a maximum supply of air-blast, of 15 or even 20 lb. pressure, by means of internal-conibustion blast-engines driven by the cleaned waste furnace-gases, with a surplus of gas left for other uses. Since that time, in view of the necessity of having a stand-by plant, immediately available, in case of strikes or other reasons causing the banking or blowing-out of the blast-furnace, he has developed, as an addition to his other types of producer, a high blast-pressure gas-generator, producing a gas identical with, or somewhat superior to, blast-furnace gas; and in which all the ash of the fuel is turned into fluid slag, which is available for, the production of slagwool. The gas is a little richer in carbon monoxide than average blast-furnace waste gas, and has only from 1 to 3 per cent. of hydrogen. Fig. I, drawn from a photograph, shows a plant containing this generator, now in operation at Leeds. It is made in units of from 1,000 to 10,000 h.p. capacity for each vessel, and coupled,

Jan 1, 1907

By Donald W. Mitchell, John Nagy, Edwin M. Murphy

In 1957 research was initiated in the U.S. Bureau of Mines experimental coal mine near Pittsburgh, Pa., to study factors affecting foam generation and transport, to evaluate the effectiveness of high-expansion foam for controlling mine fires, and to develop techniques for applying the method under U.S. mining conditions. These investigations showed that high-expansion foam containing at least 0.2 oz of water per cu ft of foam is effective in controlling experimental underground fires burning coal, wood, and oil. Sometimes the fire was completely extinguished, but more often, it was brought under sufficient control to permit either a direct attack on the fire with a stream of water or loading of the hot material into cars. A progress report prepared in July 1958 summarized the initial achievements of the USBM experiments. Since then other phases of the foam-plug method for attacking fires have been studied in the laboratory and in the mine. Previous studies by British engineers of the foam-plug method for fighting mine fires indicated that high-expansion foam was effective in controlling experimental timber fires in an underground passageway. Their subsequent work pertained to the practical aspects of fighting large fires within a mining area with a foam-plug.

Jan 9, 1960