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The Inspiration ore body was discovered in 1904, but a 50 -ton mill which was installed to treat the disseminated copper ore promptly failed. The original Inspiration Company then gave way to another, backed by W. B. Thompson, which found 40 million tons of ore. Control then passed to Anaconda and Dr. Louis Ricketts took charge as consulting engineer. He abandoned the mill which had been partially built (to the horror of the stockholders, according to Ira Joralemon) and spent a year and a million dollars experimenting with flotation. The first large copper flotation plant was then built and recovered 50% more copper than had previous gravity mills. It, of course, was highly successful and became the forerunner of modern flotation plants. Inspiration is distinctive as the first fully integrated copper operation in the United States. Three open pits supply sulfide ore to the concentrator and mixed oxide and sulfide ore to a vat leaching and electrowinning operation with leached ore also being sent to the concentrator. In addition, dump leaching supplies pregnant solution for scrap iron precipitation. Inspiration has recently constructed an electric furnace smelter and also operates a continuous casting and rod plant. The new primary 54 in. by 74 in. crusher was completed in May of 1972 and replaced an older unit which was in the way of the open pit development. It is of an unusual circular silo design, which permits dumping 0 from two positions at 90 from each other. One dumping position is in line with the spider, while the other one is at right angles to it. A box girder splitter bar hung from the dump pocket slopes downward from the second dump point, across the spider cap, and rests on the pocket bottom. This splitter was not installed to protect the spider but was to aid in distributing wet ore being dumped from that position to both sides of the spider. Any large amount of wet ore delivered to one side of the spider would pack in the crusher cavity. The round front wall of the 18 ft (5.5 m) deep pocket is unlined except for light steel protection at the top, while the straight back wall is lined with vertically positioned railroad rails. Water for dust suppression is sprayed into the pocket through a cluster of 3/8 in. (9.5 mm) nozzles at the back of the pocket. About 5 gpm (19 lpm) of water are mixed with 90 psi (620 kPa) air upstream of the nozzles to produce a fog which is effective in dust control. The 54 in. Allis -Chalmers gyratory is placed mostly within one quadrant of the circular enclosure to permit placement of the apron feeder on the lowest level in the proper position to transfer crushed ore to the

Jan 1, 1978

By A. B. Cox, L. W. Wark

An attempt has been made to compare the influences of the two most widely used depressants—alkalis and sodium cyanide—and the most widely used activator—copper sulfate—on the air-mineral contact induced by five sulfur-bearing compounds: (1) sodium di-ethyl dithio-phosphate (sodium Aerofloat); (2) potassium ethyl xanthate; (3) sodium di-ethyl dithiocarbamate; (4) potassium iso-amyl xanthate; (5) potassium di-n-amyl dithiocarbamate. Three different organic types are included in lhis group and for two of these types a higher and a lower homologue have been tested. The study of potassium ethyl xanthate, the preliminary results of which have been described,' was continued until there had been obtained a comprehensive account of the influence of variations in pH value and in the concentrations of xanthate, sodium cyanide and copper sulfate on the adsorption of this xanthate by galena, sphalerite, pyrite and chalcopyrite. With concentrations of copper sulfate and collector that the work with ethyl xanthate indicated would give the most illuminating. results, the other four collectors were tested, in a less exhaustive way. The same general principles determine the influence of alkalis, cyanide and copper sulfate, no matter to which type the collector belongs, but there is a gradation in the quantitative measure of such influence. In the list above, the five collectors are cited in the order of their capacity to withstand the depressants, sodium Aerofloat being the least resistant, potassium di-n-amyl dithiocarbamate the most resistant. This order coincides substantially with that of the solubilities of the heavy metal salts formed by double decomposition with the collectors, those formed from sodium Aerofloat being most soluble. There is little difference between the third and fourth members of the series, and under certain conditions their positions are reversed. In general, then, of the three types of collectors investigated, the dithiophosphate type is most easily influenced by depressants, and the

Jan 1, 1935

By Bob J. Rawicki

TYPES OF WET DUST COLLECTORS Basically, there are two types of wettype dust collectors. One is mechanical, incorporating pumps, motors, fans, sprays, filters, or flooded beds. These come in many forms, but their operating principle is basically the same. The screen or flooded bed is wetted by a series of sprays. Polluted air is drawn in through a fan; here the dust particles impinge on the screen and are flushed off into a settlement tank. The air then passes through spray eliminators to the atmosphere. A great deal of time and money has been spent developing this type of collector. In laboratory tests where clean water at constant pressure, air at constant volume, and dust at low but constant mass to volume were applied, these collectors gave high percentage dust collection efficiencies. Theoretically and technically, they are very good. In practice, however, under rugged mining conditions where there are no constants, and dust load, particle size, water pressure, and volume of air vary with time, their efficiency varies dramatically. Some of the most common problems are: 1. clogging of screens 2. blocking of nozzles 3. replacement. of damaged pump stators Any of the above result in loss of air flow and dust collection efficiency. Generally, there are so many mechanical moving parts, something is always breaking down. This type of collector is very expensive in parts and labor to maintain. The second type of dust collector, which I personally developed, with the help of the British National Coal Board of Great Britain, has none of the above mentioned problems and it works on a completely different principle. My collector, the Mark III Precipitaire Wet-Type Dust Collector, (an improved version of previously successful models) has no internal moving parts, no flooded beds, screens, spray nozzles, etc. It is highly efficient - 99.8% efficiency on total collected dust and 97% on respirable dust. The pressure drop through the collector is constant, hence, air flow remains constant. There is no maintenance expenditure, be it labor or parts. The only maintenance that there is, is desludging. This, of course, varies with the dust load. With a low dust load, desludqinq may only be required every 4 weeks, but this is a very simple operation that can be handled by unskilled men and it takes only a very short time. My collector is powered by a ventilation fan that is placed on the clean air side for a longer fan and motor life. Dust is extracted solely by water action. The collector's operating principle is: Dust laden air is drawn in along ducting into a tapered scrubber section, shaped to create a self-induced curtain of water. This action washes the dust particles from the air and the collected dust settles into the bottom of the tank. Cleaned air is then exhausted via a series of spray eliminators where it is completely dried and on into the atmosphere. These collectors have been sold in Great Britain, to the National Coal Board, and throughout Europe. They have been working very well for many years now. GENERAL APPLICATIONS Dust is very dangerous; silicosis and black lung kill and disable many workers each year. Many of the mine explosions can be attributed to coal dust. By the use and application of dust collectors, these deaths and disasters can be avoided. There really is no excuse. However good and efficient a dust collector may be, it's positioning and installation arrangement is critical. The collector may remove 99% of dust supplied to it, but it takes the skill and experience of a dust control engineer to design and fit ducting, hoods, etc. to remove polluted air at source and deliver it to the collector. In some cases this is very simple; in the case of longwall machines, it is very difficult. In general, dust collectors should be used to collect dust at every point of dust generation. I have noted a great reliance on dilution as a means of dust control. I personally think this is a dangerous and unreliable method. As mines become deeper and the use of larger and more productive equipment becomes more common, reliance on dilution will be impossible and dust collectors will be essential.

Jan 1, 1982

By E. E. Malouf

Rapid depletion of the world's mineral deposits combined with the expanding demand for metals places great pressure on our ability to provide technologically and economically feasible processes to recover greater amounts of metals from progressively lower grade sources. Chemical mining is one area in which expanding research and development can provide new processes or refinements to existing ones. These new techniques could result in increased production of metals from materials now considered uneconomic to process by current technology. To mine by chemicals requires the interaction of such disciplines as hydrometallurgy, microbiology, chemistry (both organic and inorganic), fluid flow, mineralogy, geology, and of course, economics. One of the least understood areas but one which may end up being an essential part of any chemical mining process is microbiology, i.e., the role of microorganisms in altering minerals and metals in solution.

Jan 1, 1971

By George R. Ensminger, E. Heaton Hemingway

During the past year, the Watertown Arsenal has been interested in the occluded gas and oxide content of certain ordnance steels in order to determine, if possible, whether some of the peculiar failures in their physical properties might not be traced to these causes. For the purpose of best accomplishing a study of this nature, it was decided to heat the various samples of steel in a vacuum for definite periods of time at high temperatures and carefully examine the quantity and composition of the gases evolved. By the use of a fused quartz tube fitted with a water-cooled, ground-glass stopper, it was possible to maintain a vacuum at a temperature of 1000" C. for 10 hr. without perceptible leakage being evidenced as measured by a McLeod gage. The silica tube was connected with an evacuating system so constructed that the volatilized gases could be removed from time to time and a low vacuum of 0.0002 to 0.0010 mm. of mercury continuously maintained. At no time during the period of heating or in the removal of the gases did the evacuated system come in contact with rubber stoppers or any rubber connections, making contamination from such a source, impossible. In other words, the only volatile products that could be: obtained must necessarily have come from the steel itself or from the glass and fused quartz system or from the mercury used as a sealing agent. In the carlier experiments, the steel treated was in the form of turnings, but this practice was discarded because the weight's of the turnings before and after being heated were widely inconsistent,, even when taken from the same piece of steel. This discrepancy developed largely through variation in the amount of metal volatilized with the gases; this metal could always be seen in the form of a ring where it condensed in the cooler portion of the tube in either the amorphous or crystalline condition. Because of the frequency in occurrence and the variation in the manner of deposition, this material was roughly analyzed and found to consist for the most part of iron. At the same time two samples of steel that had been

Jan 1, 1922

By E. Heaton Hemingway, George R. Ensminger

During the past year, the Watertown Arsenal has been interested in the occluded gas and oxide content of certain ordnance steels in order to determine, if possible, whether some of the peculiar failures in their physical properties might not be traced to these causes. For the purpose of best accomplishing a study of this nature, it was decided to heat the various samples of steel in a vacuum for definite periods of time at high temperatures and carefully examine the quantity and composition of the gases evolved. By the use of a fused quartz tube fitted with a water-cooled, ground-glass stopper, it was possible to maintain a vacuum at a temperature of 1000" C. for 10 hr. without perceptible leakage being evidenced as measured by a McLeod gage. The silica tube was connected with an evacuating system so constructed that the volatilized gases could be removed from time to time and a low vacuum of 0.0002 to 0.0010 mm. of mercury continuously maintained. At no time during the period of heating or in the removal of the gases did the evacuated system come in contact with rubber stoppers or any rubber connections, making contamination from such a source, impossible. In other words, the only volatile products that could be: obtained must necessarily have come from the steel itself or from the glass and fused quartz system or from the mercury used as a sealing agent. In the carlier experiments, the steel treated was in the form of turnings, but this practice was discarded because the weight's of the turnings before and after being heated were widely inconsistent,, even when taken from the same piece of steel. This discrepancy developed largely through variation in the amount of metal volatilized with the gases; this metal could always be seen in the form of a ring where it condensed in the cooler portion of the tube in either the amorphous or crystalline condition. Because of the frequency in occurrence and the variation in the manner of deposition, this material was roughly analyzed and found to consist for the most part of iron. At the same time two samples of steel that had been

Jan 1, 1922

By J. W. Peirce

Advances in instrumentation now make it possible to measure accurately flaw of such difficult-to-mea-sure liquids as mining slurries. A mass flowmeter, which introduces no restrictions in the line, will measure the mass flow of slurry equal to the volume flow times the mms/unit volume. In the mass flowmeter system a volume flow measurement is electrically multiplied by a density measurement in order to give mass flow. Fig. 1 shows a typical mass flow measuring system. The volume flow is measured by a magnetic flowmeter and the density is measured by a gamma gauge cell, neither of which have any restrictions in the line. Consequently, there is no clogging and no more loss of head than there would be in a similm length of standard pipe. None of the parts extend into the flowing stream and there are no moving parts in the measuring elements. PRINCIPLE OF OPERATION OF THE VOLUME FLOW TRANSMITTER The magnetic flowmeter, which is used for the volume measurement, operates on the principle of a generator (Fig. 2). This principle states that when a moving conductor cuts lines of force in a magnetic field, a voltage is induced in it. Moreover, if the dimensions of the conductor remain constant, then the induced voltage is directly proportional to the velocity of the conductor. Since the voltage is strictly a function of flow velocity, the transmitter output can in no way be influenced by such factors as temperature, viscosity, turbulence, or conductivity. The linear output is detected by flush mounted electrodes (as shown) and transmitted to a potentiometer flow receiver. Magnetic Meter Construction: The metering tube is constructed of nonmagnetic stainless steel. (See Fig. 3.) To prevent shortcircuiting of the generated voltage, the tubes are lined with a suitable liner, depending upon the corrosive, erosive or other properties of the liquid or slurry to be measured. A uniform magnetic field is produced by two saddle-shaped coils of insulated copper wire. A laminated iron core focuses the magnetic field at a 90' angle to the flowing liquid. The voltage generated by a flow of liquid through the magnetic field is detected by two point electrodes mounted flush with the inner wall of the metering tube, 180' apart. Electrodes are made of Type-316 stainless steel or other material suitable to the application . Volume Flowmeter Operation: The millivolt output of the metering transmitter is transmitted to a potentiometer-type receiver (Fig. 4). The self-balancing, self-standardizing receiver has a drive unit for circuit rebalancing. The measurement change imposes an unbalanced input on the twin windings of the drive unit. The resulting unequal pull on a segmental rotor provides the motion which drives a pen, while simultaneously and steplessly repositioning a rebalancing element. Changes in conductivity have no effect on the accuracy of the measurement or the calibration of the instrument. The minimum conductivity values are determined by the length of the transmission cable and the size of the transmitter. They can be as low as five micro mhos, since there is such a small load on the electrodes. Because the meter electrically averages all of the incremental velocities in an irregular flow profile, it is ideally suited for turbulent flow and suspended solids. Straight runs of pipe are therefore not required. The transmitter can be installed close to

Jan 1, 1962

Jan 1, 1968

Jan 1, 1968

By D. F. Strong

Most Newfoundland mineral deposits can be clearly classified as within rocks formed either as accreting plate margins (ophiolitic pyrite-chalcopyrite massive sulfides such as Betts Cove, Whalesback, York Harbour, chromite at Lewis Hills, and asbestos at Baie Verte), at consuming plate margins (Kuroko-type polymetallic massive sulfides such as Buchans and Pilleys Island, porphyry-type Mo-Cu at Rencontre, fluorite at St. Lawrence), or within plates (zinc deposits at Daniels Harbour, sedimentary iron ores at Wabana, manganese in Conception Bay.) As these metallogenic patterns can be convincingly extrapolated southward into the Appalachians and northward to the Caledonides, they provide an important means of eliminating and selecting areas for particular exploration targets. Some criteria are described for the recognition of these environments of differing economic potential.

Jan 1, 1975

By S. R. Mitchell, M. C. Fuerstenau, A. M. Gaudin

The two principal attributes of a thickener pulp are its settling rate and the ultimate pulp density of the thickened mud. Testing for evaluation of thickening attributes of a pulp has usually been done batch-wise by placing the pulp in a one-liter glass graduated cylinder and noting the position of the boundary between clear liquor and mud as a function of time. Refinements in testing have included repulping a thickened mud to various dilutions and evaluating the settling rate on these various repulped muds. This is considered to make possible an estimate of the settling rate as a function of pulp density and therefore to pinpoint the slowest settling pulp which ought to be critical from the standpoint of thickener plant design. Finally, tests are sometimes made with model-size continuous thickeners of arbitrary size. In batch tests it is generally accepted that the behavior of a pulp is described by a curve such as the one shown in Fig. 1, in which the position of the boundary between clear liquor and mud (the mudline) is plotted against time. It has also been assumed that the initial settling rate (the slope of the line segment AB) is descriptive of the pulp and independent of the size and shape of the container. Where the settling rate is slower and clearly a function of time (portion CD of the settling curve), it has been assumed that the data are not of much use because of the intrusion of compacting phenomena. The next important datum is the height. PE, which is a measure of the so-called ultimate pulp density. This quantity is assumed to be characteristic of the pulp and independent of the container. When actual data are recorded, results are rarely exactly according to this theory and numerous deviations may be noted. For example, some pulps seem to require an appreciable delay before beginning to settle, as in line AF. This is spoken of as representing the need for an induction time for flocculation. It has seemed desirable to explore thickener data with a more sensitive charting tool than is afforded by the coordinates of Fig. 1. Instead of relating the position of the mudline to time, it has seemed desirable to relate the rate of descent of the mudline to time. This, in effect, amounts to charting the slope of the line in Fig. 1, or the derivative of its ordinates, against the same abscissas. Fig. 2 shows the new chart for the curve ABCDE of Fig. 1. When this new tool was applied to data obtained, for example, with sized clay pulps, astonishing differences appeared. Apparently the traditional tool conceals differences instead of revealing them, whereas the new method emphasizes them. It seems, also, that both charting methods have their uses. In this article attention is focused on the effects of pulp density and container height as they affect the settling behavior of flocculated suspensions of a sized kaolin. The thesis by M. C. Fuerstenau' gives more details than this summary, as well as some information about the effect of other variables. Sized fractions of kaolin were used, supplied through the courtesy of S. C. Lyons of the Georgia Kaolin Co. Large batches were made by agitation in a flotation machine and in a glass jar equipped with a mixer. The settling vessels were 2, 4, and 6-in. diam glass cylinders of various heights. Pulp Dilution: The effects of pulp dilution on sedimentation behavior are shown in Figs. 3, 4, and 5. Fig. 3 shows data on pulps ranging from 2.44 to 16.7 pct solids initial pulp density, flocculated with Separan and charted in the traditional manner. At least two of the lines appear nearly straight in their early sections, but neither of the others does. Each of the curves in this figure includes a region labeled

Jan 1, 1960

By E. Lancaster-Jones

THE gravity magnitudes obtained by means of observations with the Eötvös balance in the field are necessarily resultant or total effects due to all abnormalities of mass distribution, including even the effects due to the ellipticity and rotational motion of the whole earth. Since the object of the survey is to isolate the effects which arise solely from some particular subterranean feature, and to deduce therefrom the configuration and extent of this feature, the first step is to eliminate from the observed effects all those due to "disturbing" (i. e., unwanted) features, whether above or below the surface of the ground. The disturbing features have different characteristics, according to their situation relative to the center of the balance and to the horizontal plane through the foot of the balance, or station point; this diversity was recognized by Eötvös, who divided the total effects into so-called Normal, Terrain, Topographical, Cartographical and Subterranean effects. This classification has been adhered to by most subsequent investigators, but the writer prefers to employ the term "three-dimensional," which really indicates the essential character of the class of effect known as "Subterranean," at any rate from the standpoint of the computer of effects. Before disturbing effects can be eliminated, the features must be measured up or surveyed, whether by topographical, mining, or boring methods, and then the effects of each feature calculated and subtracted from the total observed effects. After this the problem of interpreting the residual effects will itself necessitate the computation of the assumed feature, or even a series of trial features.

Jan 1, 1928

By William B. Plank

ENGINEERING educators and industries are worried about the engineering manpower shortage that is predicted as a result of the increasing demand for trained engineers not only by industry but by the armed services. This is in the face of a decreasing supply, as is shown by this and other studies. Not only has the number of entering freshmen been decreasing since 1947, because of a decrease in the number of high school graduates entering engineering, but the total number of high school graduates will continue to decrease until 1958 because of the lowered birth rate during the depression years.

Jan 8, 1951

By Fred Porter

Pollution problems from smelters may be unique in industry since the pollutants cover the wide range of SOx, particulates, carcinogens (arsenic), plus a number of heavy metals, the health implications of which are not clearly understood. In addition to this wide range of pollutants, many of the plants are extremely old; and fugitive emissions may, in fact, be the most significant air pollution problem. The Environmental Protection Agency, both in an in-house and contract effort, has assessed the quantity of pollutants emitted and evaluated the health impact. This paper will review the status of EPA's regulatory efforts in both new and existing smelters in light of these pollutant assessment studies.

Jan 1, 1976

By R. Stefanko

The use of strain gauges and compression pads for an underground bolt installation in a central Pennsylvania coal mine revealed that satisfactory anchorage could not be maintained in the shale stratum that constituted the immediate roof. Comprehensive laboratory tests resulted in a new shell designed with an increased area of contact and smaller surface serrations. Retightening of the bolt was also found to be beneficial for maintenance of high load values. Roof bolting in coal mines has progressed very rapidly in the last decade, and today this method of support is in general use. There are many theories concerning the functions of roof bolts, but the importance of beam building is indisputable. Proper tension in the bolts minimizes shearing along bedding planes and creates a thick, competent beam from individually weak layers. Bolting must be accomplished immediately upon exposure of the roof, and bolt tension must be maintained if roof failure is to be prevented. Seams are being mined today with roof bolt support where conventional timbering was not effective.' The widespread use of continuous mining equipment was made possible by roof bolts which permit long supported spans free of obstructions. Since adequate anchorage is the key to successful bolting, better methods for determining the efficiency of anchorage are continually being sought. Attempts have been made to measure bolt loads, thus assessing anchorage efficiency by employing sensing devices between the bolt head and roof. 3-s None of the techniques appears to be very accurate, and all have at least one serious deficiency. The greatest efforts are being directed toward the standardization of the pull test.6" Nevertheless, the author believes that the pull test is only one criterion for establishing the efficiency of anchorage and not necessarily the most important one. The conventional pull test involves the short-term application of forces, whereas the success of roof bolt installations is dependent upon the ability of anchorage to sustain relatively long-term forces. Therefore, it would appear that the time-dependent function of the anchor is the single most important parameter for the success of roof bolting in many types of rocks. UNDERGROUND TESTS Strain gauges and compression pads were employed to measure bolt loads in a central Pennsylvania coal mine.8 Bolting had been employed only sporadically in the shale top since dubious benefits were obtained with this type of support. Table I shows some typical results from this investigation. Anchorage losses were extremely variable among the bolts, but all showed a considerable degree of bleed-off. The tests indicated that anchorage efficiency was extremely low in this type of shale. The results confirmed that bolting under these conditions was practically worthless, and thus a waste of material and labor. Probably even more important, bolting constituted a hazard when reliance was placed upon it for support. Certainly the complete lack of confidence in roof bolting, which was apparent in the mine personnel, was justifiable since the bolts did not accomplish their purpose. PRELIMINARY LABORATORY BOLT TESTS The extreme losses in bolt tension that were detected in underground installations prompted a comprehensive study to assess the causes. However, preliminary studies were first made to determine the combined stresses in a roof bolt and to prove conclusively that the observed bleed-off phenomena were due to anchorage: slippage and not to some other physical manifestation. In all of the ensuing tests

Jan 1, 1962

By John Roberts

THE Federal income tax law permits as a deduction in determining net income "in the case of mines, . . . a reasonable allowance for depletion and for depreciation of improvements, according to the, peculiar conditions in each case, based upon cost, including cost of development not otherwise deducted: Provided, that in the case of such properties acquired prior to Mar. 1, 1913, the fair market value of the property (or the taxpayer's interest therein) on that date shall be taken in lieu of cost up to that date." The law provides for a reasonable allowance but the regulations provide for a definite method of computation that possesses more the virtue of simplicity than that of reasonableness. Article 210 of Regulations 45. reads: "When the cost or value as of Mar. 1, 1913, or within 30 days after the date of discovery of the property shall have been determined, and the number of mineral units in the property as of the date of acquisition or valuation shall have been estimated, the division of the former amount by the latter figure will give the unit value for purposes of depletion, and the depletion allowance for the taxable year may be computed by multiplying such unit value by the number of units of mineral extracted during the year." This is simple, but is it reasonable? The intent of the law is clearly that the cost of the ore in the ground shall be considered as part of the cost of the same ore when removed and sold. The regulations fail to carry out that intent, because of the unwarranted assumption that all the ore in the mine cost the same amount per ton. This is what gives the Treasury Department's method its simplicity, but at the same time robs it of its reasonableness because the assumption is contrary to fact.

Jan 1, 1921

By C. F. Jr. Nagel

THIS paper is written primarily for those who are familiar with the processes mentioned but who desire a further insight into some of the fundamental principles. It does not give a complete description of the various practices employed in the working of aluminum and its alloys, but presents a few illustrations of the essential respects in which aluminum differs from other common metals, and emphasizes the controlling factors of the processes under consideration. HEAT TREATING Certain aluminum alloys are capable of having their mechanical properties greatly altered by a heat-treatment process. The degree of this improvement may be illustrated by the typical properties of duralumin (Table 1). It is essential that the material be in the wrought condition in order to obtain maximum heat-treatment effects.

Jan 1, 1927

By E. T. Turkdogan, P. Grieveson

Experimental results are given for the rate 0.f solution of nitrogen in y iron in the temperature range 1000° to 1200°C. It is shown that, when purified reacting gas is used, the rate-controlling process is the diffusion of nitrogen into the iron. The difhsiuity of nitrogen in y iron is calculated from the results and the equation logD = —(8800/T) — 0.04 is recommended to represent the temperature dependence of the diffusivity. In some experiments using unpurified nitrogen, solution rates are found to be slower than those attributable to a solely solid-state diffusion process. Indications are that in the presence of impurities in the gas, e.g., H,O, chemisorption of nitrogen at the surface is hindered and becomes a rate-controlling process for the transfer of nitrogen across the gas -metal interface. ALTHOUGH the solubility of nitrogen in y iron at known nitrogen activities has been well-established,'-a the kinetics of the solution of nitrogen in iron are not known. The work of Darken, Smith, and Filer' indicates that at temperatures below about 1300°C the rate of solution of nitrogen in y iron is controlled by a chemical reaction at the metal surface, while at temperatures above about 1300°C the rate-controlling process is the diffusion of nitrogen in the metal. Fast and verrijps studied the denitro-genization of y iron using wet hydrogen at 950°C and their results clearly indicate that the rate of nitrogen removal is controlled by diffusion of nitrogen in the metal. In Part I of this series of papers, the kinetics of the solution of nitrogen in y iron are discussed in the light of the present experimental work. EXPERIMENTAL Apparatus. The reaction chamber consisted of a platinum wire-wound resistance furnace with a re-crystallized alumina reaction tube. The temoerature of the furnace, which was automatically controlled to approximately 1°C, was measured with a Pt/Pt-13 pct Rh thermocouple and a potentiometer. The temperature distribution in the working zone of the furnace was determined using a calibrated Pt/Pt-13 pct Rh thermocouple and the hot zone was found to be approximately 3 in. long with a temperature variation of * 3°C. A series of experiments was also carried out at 1000°C and pressures above atmospheric using a pressure vessel which was similar in construction to that described elsewhere.1° Materials. Ferrovac E grade iron used in all ex-

Jan 1, 1964

By Michael Hoch, Daniel B. Butrymowicz

The isothermal section of the Ta-Ti-Zr-0 system at 1500°C was investigated using X-ray diffraction and rrzetallographic techniques. Up to 71.4 at, pct 0 the system contains nine four -phase regions. Zsopleths at 10, 20, 30, 40, 50, and 60 at. pct 0 were constructed. The purpose of this investigation was to determine the general shape of the quaternary equilibrium phase diagram of tantalum, titanium, zirconium, and oxygen at 1500°C. The system was truncated at 66.7 at. pct 0 on the Ti-0 and Zr-0 binaries and at 71.4 at. pct 0 on the Ta-0 binary. The Ti-Zr-0 system was investigated in this laboratory.' The binary systems of interest have been compiled and discussed by Hansen and Anderk, chmidt, Hayes, Roberson, and asche, and Hoch and athur.' EQUIPMENT The Same equipment as that for the study of the Nb(Cb)-Ti-Zr-0 system was used.' The X-ray dif- fraction patterns were analyzed with the help of the ASTM card set7 and NBS circulars.' MATERIALS The tantalum powder (99 pct pure), the titanium powder (99.6 pct pure), the tantalum pentoxide, and the zirconium dioxide used in this study were purchased from the Fairmont Chemical Co., Newark, N.J. The zirconium powder (99.4 pct pure) was obtained from the Charles Hardy Co., Inc., New York. Reagent-grade titanium dioxide was purchased from the Matheson Co., Inc., Norwood, Ohio. The oxides were dried in air at 700°C for 24 hr before use. Though the materials used were not "hyper-pure", the impurities present do not affect the results (lattice parameters, phase boundaries), within the experimental accuracy. PROCEDURE The samples were heated by induction in a vacuum furnace, and examined metallographically and by X-ray diffraction at room temperature. The procedure was the same as that in the Nb(Cb)-Ti-Zr-O work,' EXPERIMENTAL RESULTS AND DISCUSSION OF DATA A four-component system can be represented by a tetrahedron at a single temperature and pressure

Jan 1, 1964

By Jacques Steininger, Robert E. England

Single crystals of ZnTe and ZnTe1-,Sex with x up to 0.13 have been grown from the elements by temperature gradient solution zoning using excess tellurium as a solvent. Best results have been obtained with charges with the compositions 45/55 at. pct Zn, Te, for ZnTe and increasing amounts of selenium for ZnTe1-xSex. The temperature in the molten zone was maintained at about 1070°C with a gradient of about 10°C per cm. Chemical analyses of quenched ZnTe ingots show tellurium concentrations in the molten zone as high as 70 pct with concentration differences across the zone of 1 to 2 at. pct Dark dots which are observed by transmitted light microscopy in as-grown crystals can be removed by annealing in zinc vapor at 900 C. INTEREST in wide band gap semiconductors has led to a new study of ZnTe and ZnTel-xSex crystal growth. ZnTe is the only II-VI compound with a wide band gap (2.3 ev) that can be made p type with low resistivity. Attempts to make it n type with low enough resistivity to be useful for p-n junctions have so far been unsuccessful.1 ZnSe has a band gap of 2.65 ev but can be made n type only. However, ZnTel-xSex solid solutions with x as low as 0.36 have been made both highly n and p type2 with a minimum band gap around 2.12 ev3 at room temperature and appear to hold the best promise for efficient injection electroluminescence in the visible. ZnTe has the lowest melting point of the zinc chal-cogenides (1295°C) and consequently attempts have been made to grow crystals from both the liquid and the vapor phase.4 Complicated apparatus is required for growth from stoichiometric melts because of the high vapor pressures of the elements at the melting point of ZnTe and because of the problem of quartz devitrification. Small crystals have thus been grown in high-pressure equipment by Fischer5 and by Narita et a1.6 with pressures of the order of 50 atm of argon to prevent excessive evaporation from the melt. Large crystals of ZnTe can be obtained by growth from the vapor phase4 but they often present numerous dislocations and inclusions. An improvement in the quality of vapor- grown ZnTe crystals was reported by Albers and Aten7 by equilibration of mixtures of small crystals with compositions lying on either side of the solid single-phase field at fixed temperature. The same technique was later applied by Aten8 to the growth of ZnTe1-xSex crystals with less than 1 pct inhomo-geneity. Because of the higher liquidus temperatures of the solid solutions and the high vapor pressure of selenium, previous attempts to grow ZnTel-xSex from the melt have been limited and unsuccessful.9 The phase diagram of the Zn- Te system is reproduced in Fig. 1, based on data from Kobayashi10 and Kulwicki.11 Carides and Fishher12 have reported lower liquidus temperatures on the tellurium-rich side, but their data would require confirmation. The liquidus temperature on the tellurium-rich side decreases rapidly with increasing tellurium concentration and the Te2 vapor pressure over the liquidus also decreases accordingly.'3 The decrease in liquidus temperature and vapor pressure therefore makes it possible to use conventional apparatus if there is a sufficient excess of tellurium in the melt. Single crystals of ZnTe have thus been grown by Kucza,14 in a modified Bridgman technique, from solutions containing up to 60 at. pct of Te by lowering unsupported quartz ampoules through a temperature gradient at about 1200°C. Under these conditions, the phase diagram indicates that the entire charge is initially molten. Crystal growth can therefore proceed by normal freezing and rejection of excess tellurium into the melt. The modified Bridgman technique has several major limitations. Because of the rejection of excess tellurium into the melt during freezing, the melt composition and the temperature at the growth interface vary continuously. They tend to follow the liquidus until the eutectic which is very close to pure tellurium (447°C, >99 pct Te). Since the solidus composition also varies with temperature,15 crystals grown by this method are inhomogeneous. They present small variations from stoichiometry which may affect their structure and physical properties. The simultaneous increase in tellurium content and decrease in melt temperature also combine to reduce the rate of diffusion of tellurium away from the growth interface, thereby causing constitutional supercooling and possibly dendritic growth. To minimize these effects, the initial melt composition is in practice kept relatively close to stoichiometry (less than 60 pct Te). This however limits the possibilities of operating at low temperatures and pressures. This paper describes a modified method of crystal growth by temperature gradient solution zoning (TGSZ) which is an adaptation of the temperature gradient zone-melting technique developed by pfann16 and of the traveling solvent method of Mlavsky and weinstein.I7 The TGSZ method now applied to the growth of ZnTe and ZnTel-xSex crystals is characterized by its very simple experimental arrangement and sample preparation technique. Unlike the modified Bridgman technique, there is no increase in the tellurium concentration in the melt and therefore it is possible to operate at lower temperatures and pressures. This method is also suitable for maintaining a constant temperature at the growth interface.

Jan 1, 1969