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By H. P. Allen

THE Achotla mill of the Cia. Minera de Pe[n]oles is of special interest in that it is one of the few still employing the chloridization process. The ore milled comes from the Suriana mine and consists of both oxide and sulphide, from neither of which can the gold or silver be extracted by a simple cyanide treatment. The mill was built in 1927, after several years of study in the development of the process1, and operated from December of that year until October 1930. Operations were resumed in February 1935, and have been continuous since, treating approximately 5000 tons per month, while the mine is getting up to full tonnage of 6500 tons per month. Transportation Of Supplies The property is in Guerrero, Mexico, some 175 km. by airline southwest of Mexico City. The mill site is at Temisco (Fig. I), 8 km. from the Balsas River and 4.8 km. by aerial tram from the mine. At Temisco are the general office, shops, warehouses and laboratory serving both mine and mill. Here sufficient water is available either from a small creek running through the property or from the Balsas River, also convenient and ample storage space for the tailings. With the exception of the mine timber and a few native building materials which may be obtained locally, all supplies for both mine and mill are brought down the Balsas River from Balsas, the terminal of a Mexican National Railway line out of Mexico City. The method of transportation on the river is interesting. Rapids with very fast water are numerous, prohibiting the use of mechanically propelled boats. Those used resemble large, flat-bottomed rowboats some 22 ft. long by 8 ft. wide (Fig. 2). They are manned by two oarsmen sitting in the bow, each handling one large oar, and usually another man in the stern who, with his oar, assists in steering the boat, especially when the rapids are run. From 3 to 7 tons of freight are carried on each boat, depending upon the stage of the water, which governs also the time

Jan 1, 1937

By D. I. Bardos, Paul A. Beck

The 1100°c isothermal, sections of the V-Fe-Si, V-Co-Si, and V-Ni-Si systems were studied at silicon contents between 0 and 40 at. pct. The single-phase fields in the 30 and 50 at. pct Mn sections of the 1100°C tetrahedron of the V-'Wn-Fe-Si system were also determined. The direction of extension of the elongated O, R, D, and a-Mn Phase fields suggests that the stability of these phases is determined largely by the electron concentration. The peculiar shape of the above ternary a phase fields, as well as of the a phase fields in the V-;Mn-Si and Cr-MTZ-Si systems is accounted for on the assumption that in manganese-(iron-, coball-, nickel-) rich alloys silicon atoms do not exclude d electrons , while in alloys low in the above components they do. This assumption also leads to the expected electronconcentrations for q and ß-Mn phases formed by transition metals with aluminurn. In earlier work it was shown that in ternary alloy systems of transition elements the a a and certain other phases with complex structure, such as the p and R phases,3 form elongated phase fields extending in a direction corresponding to a constant electron concentration. Recently similar behavior was observed in manganese-rich ternary ß-Mn solid solutions with another transition element and with silicon, germanium, or tin,4 confirming earlier indications3 that ß-Mn is also an electron phase. The alloying behavior of silicon in these manganese-rich alloys sug- gested that the four outside electrons of silicon participate in the bonding and that the predominantly d-like bonding electrons are not excluded from the silicon sites. Presumably, some of the normally unoccupied 3d states associated with the silicon atoms are in these alloys lowered to the Fermi level;4 thus silicon behaves as if it, too, were a transition element. The manganese-rich boundary of the a phase in the V-Mn-Si system,4 as well as in the Cr-Mn-Si sys-tem,4,5 extends approximately parallel to the ß-Mn phase boundary, corresponding to the transition ele-mentlike behavior of silicon described above. However, at lower manganese contents (i.e., in the high-vanadium or -chromium region) the a phase field in both ternary systems mentioned extends in a direction roughly perpendicular to that of its manganese-rich boundary, a phenomenon that is apparently inconsistent with the behavior of silicon in the manganese-rich alloys. A similar, although somewhat less pronounced, extension of the a phase occurs also in the high-vanadium (low-iron) region of the V-Fe-Si system at 1175C, but reportedly not in the V-Co-Si or V-Ni-Si systems at the same temperature.5 The present work was undertaken to investigate in more detail the extension of the a phase (as well as of other electron phases that may be present) in the last three systems and to elucidate this phenomenon, which has not been satisfactorily explained previously. EXPERIMENTAL PROCEDURES Most of the alloys were melted in an arc furnace, using a water-cooled copper crucible under helium atmosphere. The transition metals were of better than 99.9 pct purity and the silicon used was 99.98 pct pure. Alloys containing less than 20 pct V were induction-melted in recrystallized alumina crucibles under argon atmosphere.

Jan 1, 1967

By J. F. Breedis

The morphology and crystallography of marten -site formed during quenclzing were examined by transmission electron microscopy in alloys whose compositions lie between Fe-19 wt pct Cr-11 wt pet Ni and Fe-33 wt pet Ni. Depending upon composition, four types of transformation products were observed in this portion of the Fe-Cr-Ni system. Three of these products are denoted as lath, plate, and surface martensite. The hcp structure found in association with martensite it? certain higlz-clzromium stairzless steels does not influence the transformation crystallogyaphy and cannot he Considered to act as a transitional structure in the transformation from austenite to martensite. DISTINCT changes in the characteristics of mar-tensitic transformations are produced by the partial replacement of nickel by chromium in austenitic iron alloys. Large, discrete martensite plates form in Fe-30 pct Ni, while aggregates of small crystals form in sheets parallel with (111)A austenite planes in stainless steels containing in the vicinity of 18 pct Cr and 8 pct Ni. These transformation structures are termed plate and lath martensite, respectively. In addition, an hcp structure (E) has been observed in certain high-chromium stainless steels in association with martensite. It has been suggested that the E structure acts as an intermediate step in the nucleation of martensitel-' and influences the morphology and crystallography of the final transformation product. However, this structure may be the consequence of the deformation of austenite arising from the shape distortion accompanying the transformation to bcc martensite.' An hcp stacking of atoms is produced in an fcc lattice by the introduction of an intrinsic stacking fault on alternate (111)A planes. At present, the arguments behind each explanation for the E structure are based on circumstantial evidence. This investigation seeks to determine the importance of the hcp structure to the martensitic transformation, and to examine the crystallography and morphology of the structures produced in bulk samples by quenching in alloys whose compositions lie between Fe-19 wt pct Cr-11 wt pct Ni and Fe-33 wt pct Ni. These aspects of the martensitic transformations occurring in these alloys have been studied by electron metallography and selected-area diffraction of foils examined in transmission in the electron microscope. EXPERIMENTAL METHODS The alloys have been prepared from thoroughly mixed powders of pure iron (99.6+ pct, 0.06 max pct C, 0.15 max pct N), chromium (99.9+ pct), and nickel (99.9+ pct). After sintering in an Ar-H2 atmosphere, the mixtures were melted by induction heating in recrystallized alumina boats under purified argon. The ingots were cold-rolled to 0.4-mm sheets (100 pct reduction in thickness) after the removal of at least 1.5 mm from their surfaces by grinding. Three-millimeter discs were punched from the cold-rolled sheet and annealed at 1150°C for approximately 24 hr in evacuated quartz capsules. The average grain size was 40 µ Thin foils for examination in transmission in the electron microscope were prepared from discs quenched to liquid-nitrogen temperature. A depression was first jet-machined into the center of a disc and a thin area (less than approximately 3000A in thickness) was produced at the base of the depression by electropolishing. Electron-microscope studies utilized the RCA EMU-3 and the Philips EM-100B microscopes operating at 100 kv. X-ray examination of the polycrystalline alloys was performed either in a diffractometer or in a

Jan 1, 1964

By David R. Maneval, W. E. Foreman, J. Richard Lucas

INTRODUCTION The objective of this chapter is to inform the industry, as well as the public, of the challenges in dealing with the problems associated with the contamination of air and water from coal preparation plants. The need for an informed industry is most important. It is hoped that some contribution may be given to a more efficient and economical approach to the problems of plant waste contaminants at individual plants. The problem has many facets, and consideration to specific area should begin early before any significant problems develop at a given plant. It is then possible to have a reasoned approach before the pressures of an emergency environment force hasty and incomplete solutions. It will be necessary to anticipate these problems in the design of new preparation plants and advance consideration should be given to all the problems concerned with contaminants. The first part of the chapter will concern itself mainly with the contamination aspects of fine-coal cleaning and "black-water" disposal. Also attention will be given to the nature and formation of water from coal-mine drainage systems and the treatment of these waters for industrial use. Some attention will be devoted to the cost of installing and operating the various beneficiation systems for the removal of suspended solids. The second part of the chapter will analyze the problems of air contaminants from coal preparation plants. The nature and the effects of these contaminants and their potential for air pollution will be examined. One of the most critical is the measurement and analysis of these contaminants. As a result of identifying and determining the extent of the problem, better control can be planned. One of the most serious contaminants in air involves the element sulfur, and its elimination as a source of air pollution is one of the most challenging areas in coal preparation today. The last part of the chapter will emphasize the long-range problem of refuse disposal and control. Minimum operating and maintenance costs are functions of the proper selection and geometry of refuse disposal areas. Disposal procedures are varied but must be rigidly pursued or difficulties will result. Maintenance of refuse areas, including monitoring of burning refuse, is critical. It should be recognized that fine-solid refuse disposal systems must be carefully designed to minimize contamination. WATER CONTAMINANTS FROM PREPARATION PLANTS Pollution Aspects of Fine-Coal Cleaning and "Black-Water" Disposal The effluents from coal washeries and waters draining from plant-site surfaces inevitably contain fine coal and coal refuse materials in suspen-

Jan 1, 1968

By Immo H. Redeker

Through close cooperation with geophysical and geological test work by Texas Gulf Sulphur Co. in Beaufort County, the Asheville Minerals Research Laboratory assisted in the evaluation of North Carolina's most valuable mineral resource, the Pungo River phosphate deposit. After a core evaluation study, the flotation process for the concentration of North Carolina phosphate was demonstrated in a 500-lb per hr pilot plant in Asheville. Tonnage samples of phosphate concentrate were produced for customer evaluation in the United States, Europe, and the Far East. Plans for a larger pilot plant to be erected at the plant site at Lee Creek were prepared for TGS. The larger pilot plant was operated by TGS in conjunction with a test dredging operation which led to the adoption of a dragline dry mining method to move 90,000 tpd of material for the production of 10,000 tpd of phosphate concentrate in the all-flotation phosphate concentrator. Calcining, dry grinding, and byproduct studies complimented the construction of one of the world's largest and most modern fertilizer raw-feed complexes on the eastern North Carolina seaboard.

Jan 1, 1972

By I. A. Goddard

INTRODUCTION This paper deals with the development of the sublevel open stoping (SLOS) method in lead orebodies at the Isa Mine of Mount Isa Mines Limited, during the last ten years. Open stoping in different forms has been used at the Isa Mine for many years. Prior to the period under review, stopes were small, pillars were not always recovered, and scrapers extracted the ore. By the end of the sixties, the use of load-haul-dump units was becoming more widespread. Wagner ST5's were the mucking units for the lead cut and fill stopes. Some of the open stopes in 5 orebody above 13 level had 100 kW slushers, but the more southerly stopes were the sites for the introduction of diesel front-end loaders for extraction. In the early seventies, new methods were used in the block of six stopes in 2 and 5 orebodies between 8 level and 13 level and a trial stoping project was undertaken in 7 orebody between 11 level and 13 level to determine possible stope dimensions for the extraction of the Racecourse orebodies below 13 level. By the mid-19701s, stoping was well underway in 5, 7 and 8 orebodies between 13 level and 15 level, using the 'triplet' system, incorporating cemented hydraulic fill to allow greater pillar recovery. As the eighties were entered, development of the Racecourse orebodies below 15 level commenced, as did preparations for 1 orebody in the upper levels of the north end of the mine. In both cases, the pillar recovery method has been changed to reduce the amount of cemented fill required for pillar recovery. GEOLOGY Most of the lead orebodies at Isa Mine lie chiefly to the north of the central shaft complex. They are bedded sulphide deposits in a host rock called Urquhart Shale, which dips at roughly 650 to the west. The main minerals are galena and sphalerite, with the silver mineral, freibergite, being contained in the galena. To the hangingwall of the sequence are the Black Star orebodies (1, 2 and 5) which are relatively wide, pyritic and with low to above average grade lead. The Racecourse orebodies (6 to 16) lie to the footwall, and have a large variation in width, low to high grade lead, and gradation in the lead to zinc ratio from north to south. Stope outlines are often determined by economic or engineering considerations rather than geological. The published extraction reserves are 56 million tonnes of primary ore, containing 150 grams of silver per tonne, 6.4% lead and 6.5% zinc. Traditionally, it has been regarded as lead ore, although the dominant revenue earner varies from time to time. In the Black Star orebodies, the ore and hangingwalls are more competent and open stoping has long been used. The major Racecourse orebodies which have been open stoped are 7 and 8 orebodies. This has been where the orebodies are wider (to the south) and where hangingwall conditions allow. This latter aspect has been greatly influenced by the presence of 'silica dolomite1. This tough, relatively homogeneous, non-bedded rock is, in fact, the host rock for the copper mineralisation at Mount Isa, and provides a competent hangingwall for some of the lead stopes. While the shale's bedding and jointing has a major influence on the ground conditions, there is a major fault system which causes local problems. The principal virgin stress direction is perpendicular to the bedding, but the local stress situation is complicated because of shielding by filled stopes in the hangingwall copper orebodies and because of the interaction between orebodies being extracted to the footwall. Most development on strike is mined with a 'shanty-back’, with the back being as close to normal to the bedding as possible. This is near parallel to most jointing and the principal stress direction. Figure 1 is a plan view of 14 level north, which provides a representative horizontal section through the orebodies. A typical cross section is shown in Figure 2. The narrow, parallel footwall orebodies can be seen to differ from the wider hangingwall orebodies.

Jan 1, 1981

By R. W. Bartlett

The rates of oxidation of tungsten have been determined at temperatures between 1320" and 3170°C and oxygen pressures to 1 amn using a surface -recession measurement technique. Above approximately 2000°C and 10-6 atm the rate is independent of temperature and can be calculated from gas collision theory assuming a constant reaction probability, e, of 0.06. Oxygen molecules react at surface sites where oxygen atoms have previously chemisorbed. This provides a direct pressure dependence at low pressures but at high pressures tungsten oxide molecule s form an adjacent gas boundary layer which lowers the PO2 at the tungsten surface. A correction for this effect using free-convection theory fits the rate data over the entire oxygen-pressure range from 10-8 to 1 atrn as well as data using O2-A mixtures. Below 10-6 atrn and above 2000°C, e decreases with increasing temperature because of desorption of oxygen atoms. Below 2000°C the rate decreases with decreasing temperature at all oxygen pressures following an apparent activation energy of 42 kcal per mole and depending on (Po2)n with n varying between 0.55 and 0.80. MOST of the previous tungsten oxidation studies have employed gravimetric methods and have been limited to temperatures below 1000°C where the weight loss associated with evaporation of tungsten oxides is negligible compared with the weight gain from oxidation.' At higher temperatures, oxygen-consumption rates have been determined from pressure measurements, usually at constant flow rates, by Langmuir,2 Eisinger,3 Becker, Becker, and Brandes,4 and Anderson.5 The sensitivity of this method decreases with increasing pressure and, with the exception of Langmuir's work, these investigations were confined to pressures below 10-6 atm. Above approximately 1300°C, depending on the oxygen pressure, the rate of oxide evaporation is greater than the oxide-formation rate and the recession of the tungsten surface can be measured optically without interference from an oxide layer. This was first done by Perkins and crooks6 who heated tungsten rods in air pressures from 1 to 40 torr at temperatures between 1300" and 3000°C. The present investigation of the oxidation kinetics of tungsten at high temperatures emphasizes oxygen pressures from 10-6 to 1 atm. This is the range of interest for earth atmosphere re-entry applications of tungsten for which little data were previously available. APPARATUS The apparatus is a modification of the type used by Perkins and crooks.' Ground tungsten seal rods, 6 in. long by 0.125 in. diam, were mounted vertically between two water-cooled electrodes, one fixed and the other having free vertical travel. The movable counter-weighted electrode is prevented from undergoing horizontal displacement by three sets of runners mounted at 120-deg intervals. Electrical contact is made by means of a water-cooled mercury pool. A 24-in. vacuum bell jar having a volume of approximately 267 liters was used as the reaction chamber with the sample holder mounted in the middle of the chamber. Power was supplied from an 800-amp dc variable power supply. Temperature readings were made by means of a Latronics automatic two-color recording pyrometer. With this instrument, corrections for emissivity are not necessary provided the spectral emissivi-ties at two closely spaced wavelengths are equal. Supporting measurements were made with a micro-optical pyrometer corrected for emissivity of bare tungsten and window absorptivity. The micro-optical pyrometer was calibrated against a National Bureau of Standards calibrated tungsten lamp and both pyrometers were periodically checked against the melting points of tungsten and molybdenum using the oxidation apparatus. Above 10-6 atm, pressures were measured with an Alphatron gage calibrated against a McCleod gage. At 10-6 atm, a hot-filament ionization gage was employed. A magnified image of the self-illuminated tungsten rod was formed using a 360-mm objective lens mounted outside the bell jar. When the experiment exceeded 1 hr, the image was focused on a ground-glass plate about 10 ft from the tungsten rod at about X8 and the recession of the thickness of this image was monitored with a Gaertner cathe-tometer. When faster rates were encountered, a 35-mm time-lapse cinecamera with a telephoto lens and bellows extension was substituted for the ground-glass plate and cathetometer. Diameter recession rates were determined from the photograph image projected on the screen of an analytical film reader. EXPERIMENTAL PROCEDURE After installing the rod in the apparatus and cleaning it with acetone, the system was evacuated to 5 1 x 10-5 torr. Before oxygen was introduced,

Jan 1, 1964

By Billy L. Crowder, John M. Fairfield

The implantation of B+ , P+, and As&apos; into silicon has been studied with the purpose of making shallow p-n junctions. The influence of such parameters as 1) ion energy, 2) target orientation and temperature, 3) total dose, and 4) annealing schedule was investigated. An energy range of 70 to 300 kev was used for boron and phosphorus implants and up to 500 kev for arsenic. It is found that the experimental projected range agrees well with theory and that shallow junction depths can be made reproducibly. ION implantation has received much attention recently as a technique for doping semiconductors. Specifically, it has the potential of supplementing or replacing the diffusion process as a method for making p-n junctions. In a few specific cases it has been used successfully to make semiconductor junction devices. Potential advantages of ion implantation doping over diffusion techniques are: 1) It affords greater control of shallow junction depths (< 0.2 µ) while maintaining high peak concentrations. This is particularly important for high-speed switching devices, since lower junction capacitances and resistances can be achieved. 2) More precise registration of small planar structures can be realized if proper masking procedures are employed. This advantage is especially useful in the design of high-density integrated circuits. It has been used to advantage in FET fabrication since the edge of the source or drain can be aligned precisely at the edge of the gate electrode.&apos; 3) Ion implanatation permits lower temperatures than diffusion techniques. This factor alleviates the problem of compatibility of diffusivities often encountered when designing multiple-junction structures. Also, the lower temperatures create fewer thermal defects and dislocations, which may account for the high efficiency of some ion-implanted solar cells.2 4) Impurity profiles can be more easily tailored to resemble ideal distributions. Successful exploitation of the potential advantages of ion implantation techniques will depend on increased knowledge and understanding of the subject. The factors likely to be influential in determining impurity distribution profiles in ion-implanted single-crystal targets have been reviewed by J. F. Gibbons.3 In addition to the mass and energy of the implanted ion, the total dose, target orientation, and target temperature are important parameters. The annealing temperature required for removing lattice damage and incorporating the implanted species on an electrically active site is very important. This paper describes an investigation of some of these factors. Implants of boron, phosphorus, and arsenic into silicon have been studied. Energy ranges of 50 to 300 kev were used for boron and phosphorus and up to 500 kev for arsenic. In addition to the implantation energy, the effects of total dose, target temperature, and post implant anneal have been investigated. EXPERIMENTAL PROCEDURE The implantation targets were silicon wafers cut from Czochralski-grown crystals, lapped, and chemically polished. The orientations were (111), (110). and (100) with misorientations of up to 7 deg from the principal axis. For this study, accurate target alignment (i.e., within 0.1 deg) was not available and quoted misorientation values should be regarded as approximate . The implantation equipment consisted of an ion source, a 300-kev linear accelerator tube, an electromagnetic separator, and the associated target supporting and beam focusing assemblies. The ion source was a simple oscillating electron type source,4 which has been described elsewhere.5 The gaseous compounds BF3, PF5, and AsH3 were used as ion sources for B+, P+, As+, and AS+&apos;. Analyzed current levels of up to 20 pamp could be obtained; however, for this investigation target current levels of 1-3 µ amp were usually employed. The analyzed ion beam was collimated through a double slit (1.4 x 0.4 cm) and swept perpendicularly to the long axis of the slit such that an area of about 2 sq cm on each target was covered. Dosages of around 1015 cm-2 were normally employed, but smaller amounts were also used for comparison. A uniform flux density over the bombarded area was assured by the continuous use of profile monitors similar to those described by Wegner and Feigenbaum.6 Post-implant annealing was accomplished in an argon atmosphere in a temperature range of 600" to 950°C. It was not part of the purpose of this investigation to study the annealing kinetics; however, some isochronal and isothermal anneal experiments were conducted to determine the time and temperature necessary to render a reasonably high portion of the implanted ions electrically active (i.e., higher than 50 pct). Post-implant anneal temperatures of around 900° and 600°C were required for boron, and arsenic and phosphorus implants, respectively. Arsenic and phosphorus implants increased in conductivity rather abruptly at the proper anneal temperature of the isochronal curve, but boron increased more gradually over a wider range. Isothermal anneal curves were reasonably flat after 10 min, so an anneal time of 1/2 hr was used for the experimental results described below. The profiling techniques were: 1) neutron activation analysis, 2) differential sheet resistance,7 and 3) junction staining.8 The differential sheet resistance technique is commonly employed in this type of study. Its principal disadvantage is the uncertainty of the ef-

Jan 1, 1970

By D. Weinstein

Yieldilzg in annealed arc-cast molybdenunz in torsion was studied as a function of strain rate and tem-perature. The temperature dependence of the yield point for different strain rates was used to calculate a heat of activation for the yield point. The heat of activation was not a constant but was approximately a linear function of the stress at yield. It is proposed that the rate effect in yielding is determined in part by a site place-change of C (or other interstitial atom) in the metal. THE low-temperature embrittlement phenomenon in metals and alloys has been known to exist for a long time. Although a transition from ductile to brit-tle behavior has been observed in some close-packed hexagonal metals1 and a face-centered cubic alloy, the most common class of metals exhibiting this be-havior has a body-centered cubic lattice structure. For example, a ductile to brittle transition has been observed in iron,3 molybdenum,4 chromium,5 colum-bium,6 and tungsten.7 In the present investigation, molybdenum specimens were tested in torsion over a wide range of temperatures at three widely separated strain rates, and the temperature for onset of embrittlement was determined. Characteristic of body-centered cubic metals and closely associated with plastic deformation is the appearance of a sharp upper and lower yield point. Theoretical explanation of the yield point in iron and low-carbon steel is due to Cottrell,8 who attributes the phenomenon to the pinning of dislocations by the formation of impurity atmospheres around the dislocations. These atmospheres tend to lock the dislocations and make them more difficult to move. The stress required to move a dislocation and thereby cause plastic deformation is greatly increased, and thus an upper yield point is observed. In addition, theoretical analysis,9 as well as experimental observations, show that the upper yield point is strongly a function of temperature. The upper yield point is observed to decrease with an increase in testing temperature, and above a certain temperature (-700° K in iron) it no longer appears. This is consistent with the concept that thermal vibrations will help free a dislocation from its atmosphere, so that the external stress required to free a dislocation from its pinning atmosphere decreases with increasing temperature. Furthermore, with increasing temperature the equilibrium concentration of impurity atoms around a dislocation decreases exponentially with the result that the dislocation is less firmly pinned. In Cottrell&apos;s theory of yield point a static model is visualized in which the pinning atmospheres, particularly interstitial atoms, are immobile, and the dislocations are anchored to stationary positions in the lattice. However, experiments1,7 show the upper yield point to be time-dependent or a function of the rate of straining, a high strain rate causing a high upper yield point. Present theory does not adequately account for the rate dependence of the yield point, and the exact function of the interstitial atom is not under stood. Nevertheless, observation of the temperature dependence and rate dependence strongly suggests that the upper yield point phenomenon is due to the interaction between dislocations and pinning atoms, and that a diffusion mechanism is important in determining the yield point.

Jan 1, 1962

By George C. Toland

In 1950 the phosphate fertilizer market warranted the design and construction of a new fertilizer plant by Cominco at Kimberley, B.C. The initial rated capacity of the plant was 70,000 tons per year of high- grade ammonium phosphate. The plant was placed on-stream in 1953. One of the major problems in operating the fertilizer plant was the disposal of the gypsum tailings slurry which was a by-product of phosphoric acid manufacture. The original weight of dry tailings produced by the mill was 500 tons per day. This quantity increased over the years until a projected 2200 tpd was selected for the pond design described in this paper. The original gypsum tailing area was located south of the fertilizer plant and adjacent to the St. Mary&apos;s River. By 1965 the original disposal area had proven inadequate and Cominco&apos;s engineering staff had selected a 500 acre disposal site to the east of the plant.

Jan 1, 1971

By C. E. Kemp, A. B. Dyes

Results of a field research project on the thermal recovery of oil by movement of a combustion front are presented. This field test was conducted in the South Belridge field, This The war paitern was a Southsing1e 2.5-acre five-spot pattern in the 700-ft deep Tulare sand. Results of this project indicate the technical feasibility of producing high viscosity, low-grallity crude oils by thermal means. It was demonstrated that heavy oils could be moved rapidly over considerable distances by thermal drive, and that high percentage recoveries of oil could be effected. The bulk of the oil recovery came after arrival of the burning front at a production well. However, rapid corrosion and high-temperature failure of conventional pipe and equipment both below and above surface occurred. Stainless steels gave more satisfectory performance under these conditions than did conventional steels. Oxygen was seldom observed in gas from wells ahead of the burning front, and it appears that the front was continuous throughout the life of the experiment. INTRODUCTION During late 1953 and early 1954, industry-wide attention was focused on the thermal recovery of oil by movement of a combustion front through an oil zone. Two separate Oklahoma field tests were described in publications by Kuhn and Koch, and Grant and Szasz. To obtain basic information needed for making engineering and economic appraisals of commercial recovery of heavy oil by this thermal recovery method, a new field research projecta3,4 was started May 31, 1955. Twelve oil companies contributed to this project with General Petroleum Corp. as operator. Since combustion recovery experiments* with heavy oils in other areas had been conducted in small patterns,"&apos; an important purpose of this test was to determine whether the process could be operated in a pattern of near-commercial well spacing. The south Belridge field, located 30 miles north of Taft, Calif., was chosen because its oil sands are similar to many heavy oil sands which typically have low primary recovery and leave a large amount of oil in place. such fields are not particularly suited for common secondary recovery methods. DESCRIPTION OF TEST SITE The test interval was a Tulare sand at a depth of about 700 ft. Nine test wells were drilled, cored and completed from Oct., 1955, through Jan., 1956. The initial pattern shown on the map, Fig. 1, consisted of an injection well (II)&apos;, four producing wells (1P-4P), and four observation wells (IT-4T). An old well (81) was also recompleted for use as an observation well. The area enclosed by the original four production wells was 2.5 acres; the distance from the injection well to each production well was 233 ft. During the combustion period, Well 5P was drilled to replace Well 2P, and Well 6P was drilled to replace Well 3P. The new wells were 25 ft beyond the old production wells along a diagonal from the injection well, and resulted in an increase in pattern area to 2.75 acres. Isopachs are shown in Fig. 1. The average thickness of the oil sand in the test pattern was 30 ft. Fig. 2 presents two cross sections through the test pattern. Oil sand is represented by white and claystone by gray. The dashed lines indicate layers of conglomerate grading to claystone. The sand thickness was fairly uniform throughout the test pattern except in the 1P area. The sand body dips gently from the northwest to southeast, about 3 degrees from horizontal. The sand is unconsoli-dated, and grades from very fine material to pebbles as large as 2 in. in diameter. Table 1 presents the average initial properties of the formation. The in-place porosity of 37 per cent was estimated from the porosity of coke-consolidated cores taken after combustion. Original core analyses data were adjusted to 37 per cent, giving pore volume saturations of 60 per cent oil, 37 per cent water, and 3 per

By Charles A. Ashburner

The Bradford Oil District lies in the northern part of McKean County, Pa., and the southern part of Cattaraugus County, N. Y. Although petroleum was first found in the producing sand in 1871, it was not until the early part of the year 1875 that a productive horizon was acknowledged to exist, even by those most largely interested in the production of the crude oil. It has been reported to me that the first well drilled in the valley of the Tuneangewant Creek (commonly called Tuna Creek) was drilled by F. E. Dean and brothers in 1865. This well was located on the Shepherd farm, near the present site of Custer City. One hundred and sixty feet of drive pipe was used, and the hole was drilled to the depth of 900 feet. The producing sand at Custer City is found about 1130 feet below the level of the railroad track. The Shepherd farm well was therefore abandoned over 200 feet above the top of the oil sand. The next well was drilled by the Dean brothers on the Clark farm at Tarport. Drilling was stopped at a depth of 605 feet, or over 400 feet above the top of the oil sand. In the year 1862 the old Bradford well, since known as the Barnsdall well, was drilled to a depth of 200 feet with a spring pole, and then abandoned. In the spring of 1866 the citizens of the village of Bradford concluded to club together and sink the Barnsdall well deeper. It was drilled to a total depth of 875 feet, or to within 150 feet of the Bradford producing sand. All of these wells were drilled with the expectation of finding the Venango County oil, and at

Jan 1, 1879

By Chas. A. Ashburner

THE Bradford Oil District lies in the northern part of McKean County, Pa., and the southern part of Cattaraugus County, N. Y. Although petroleum was first found in the producing sand in 1871, it was not until the early part of the year 1875 that a productive horizon was acknowledged to exist, even by those most largely interested in the production of the crude oil. It has been reported to me that the first well drilled in the valley of the Tuneangewant Creek (commonly called Tuna Creek) was drilled by F. E. Dean and brothers in 1865. This well was located on the Shepherd farm, near the present site of Custer City. One hundred and sixty feet of drive pipe was used, and the hole was drilled to the depth of 900 feet. The producing sand at Custer City is found about 1130 feet below the level of the railroad track. The Shepherd farm well was therefore abandoned over 200 feet above the top of the oil sand. The next well was drilled by the Dean brothers on the Clark farm at Tarport. Drilling was stopped at a depth of 605 feet, or over 400 feet above the top of the oil sand. In the year 1862 the old Bradford well, since known as the Barnsdall well, was drilled to a depth of 200 feet with a spring pole, and then abandoned. In the spring of 1866 the citizens of the village of Bradford concluded to club together and sink the Barnsdall well deeper. It was drilled to a total depth of 875 feet, or to within 150 feet of the Bradford producing sand. All of these wells were drilled with the expectation of finding the Venango County oil, and at

Jan 1, 1879

By C. R. Johnson, R. A. Greenkorn, R. E. Haring

Three confined five-spot miscible displacements at unity, favorable, and unfavorable mobility ratios were conducted in a shallow, water-saturated sandstone of Pennsylvan-ian age near Chandler, Okla. These studies, plus associated laboratory experiments, were designed to measure miscible displacement performance in a controlled natural system, using known scaling criteria to develop an approach to modeling the heterogeneous field system. We have concluded from these studies that: (I) displacement efficiency in the field is a pronounced function of mobility ratio, indicating that miscible fingering observed in simple laboratory models occurs in the field: (2) field displacements can be quantitatively predicted by scaled laboratory models if the degree and location of field permeability variations are preserved in the models: and (3) arbitrary simplifications of heterogeneity will not necessarily predict observed displacement efficiency, and the simpler the model, the more optimistic the prediction. INTRODUCTION Many processes to achieve miscible displacement of reservoir oil by injected fluids have been conceived and field tested by the oil industry. Among the better known are high-pressure gas, enriched gas, and LPG banks. The simplest form of miscible displacement—one fluid miscibly displacing another fluid of different viscosity but the same density—has been studied extensively in homogeneous laboratory models. Observations of unstable fingering have been made which explain the significant decrease in displacement efficiency as the mobility ratio (ratio of displacing fluid mobility to displaced fluid mobility) increases. General industry experience with field tests of miscible displacement projects, mostly LPG banks, has been premature solvent breakthrough and lower than predicted production rate increases. These results have been attributed to either unstable fingering, unusual or unexpected permeability stratification, or both. Miscible displacement data in a controlled natural system have never been reported, however. Also, it has not been shown that properly designed and constructed laboratory models quantitatively predict field-scale behavior. The purpose of the combined field and laboratory ex- periments reported in this paper is twofold. The first was to measure miscible displacement performance at different mobility ratios in natural rock approaching field size under precise, controlled conditions. The second purpose was to utilize known scaling criteria plus several approaches to heterogeneity to model the field. Comparison of model and actual field results should then determine whether or not the laboratory phenomena (manifested by miscible displacement efficiency) are exhibited in large, natural rock systems. We carried out our program by first locating a shallow, water-saturated reservoir whose rock properties were representative of oil-bearing reservoirs. Detailed reservoir description by core analysis and interference testing showed the field site to be heterogeneous. A sequence of controlled, aqueous-phase miscible displacements was conducted at unity, favorable and unfavorable mobility ratios. A central, confined pattern was used to obtain the displacement data. A laboratory program using sand-packed models was conducted to determine the modeling criteria necessary to simulate field behavior of miscible displacement in a heterogeneous system. SCALING THEORY The detailed derivations and descriptions of the scaling laws that apply to laboratory models of reservoirs are adequately described elsewhere, so the following discussion will be restricted to facets of importance in this study. For a displacement in which one liquid miscibly displaces another, the following dimensionless groups are required to have the same numerical value in the model as in the field: The model also must be geometrically similar to the field, be spatially oriented the same as the field (same dip angle), and have the same initial and boundary conditions as the field (same initial fluid saturations and same injection-production well arrangement). When these conditions are satisfied, the theory predicts that at dny dimensionless time (pore volumes of produced fluids) the dimen-sionless flow potential and dimensionless fluid concentrations will be identical at all dimensionless spatial locations within the model and the field. If this prediction is correct, then the local dimensionless velocities must be identical, thus the instantaneous fraction of displaced fluid produced and the cumulative recovery expressed as fraction of original fluids in place must be identical at all dimensionless times. The theory outlined above has been obtained by either dimensional analysis or inspectional analysis of differential

Jan 1, 1966

By Hans-Jürgen Schaller, Horst A. Brodowsky

Activity coefficients of boron in palladium were determined at concentrations up to PdB0.23 by reducing B2O3 between 870" and 1050°C in a controlled H2-H2stream and measuring the resulting weight gain. The deviations from ideal behavior closely resemble those of the system Pd-H and are interpreted in terms of three principles: 1) The solute atoms occupy octahedral interstitial positions. 2) They donate their valence electrons to the 4 d and 5s bands of palladium, raising its Fermi energy. 3) The lattice strain energy is lower for two nearesl -neighbor interstitial particles than for two farther separate ones. SOLID solutions of hydrogen in palladium are a useful subject for studying thermodynamic aspects of the formation of alloys and of nonstoichiometric systems.1-3 The activity of hydrogen is readily measurable to a high degree of accuracy,4&apos;5 even at low temperatures where the deviations from ideal behavior are more pronounced, and its simple structure facilitates an interpretation of these deviations in terms of a detailed model. Two effects are discussed to account for the non-ideal properties:3 An "electronic" effect, connected with the rise of the Fermi energy, as electrons of the interstitial hydrogen atoms enter the electron gas of the metal, and an "elastic" effect, due to an interaction of the regions of strain around each interstitial atom. The electronic effect is based on the idea that the lowest energy levels of the dissolved hydrogen atoms are higher than the Fermi energy, so that the electron will not occupy a localized state but enter into the electron band of the metal.6 The elastic effect is based on the observation that dissolved hydrogen distorts and expands the palladium lattice. The hypothesis is put forward that the elastic strain energy is lower for two adjacent dilatational centers than for two separate ones; i.e., they attract each other. The resulting pair interaction can be used to calculate an elastic contribution to the thermodynamic excess functions by means of one of the statistical methods. This model permitted a detailed description of the solution properties of hydrogen in palladium3 and in palladium alloys.798 An extension of the approach to describe the excess functions of substitutional palladium alloys is possible.9 In order to further test and refine the model, an investigation of other interstitial alloys was started. Palladium dissolves considerable amounts of boron in homogeneous solid solution.10 The palladium lattice expands linearly up to nB = 0.23 (nB = B/Pd atomic ratio), the highest concentration studied." The expan- sion, extrapolated for 1 mole of interstitial per mole of palladium, is 17 pct of the lattice constant of pure palladium vs 5.7 pct in the case of hydrogen.12 The fact that the lattice expands rather than contracts is a strong indication that interstitial positions are occupied. According to neutron diffraction experiments, hydrogen occupies the octahedral sites of the fcc lattice.13 Unfortunately, this direct evidence is not available for the Pb-B system, mainly because of the high-reaction cross section of boron with thermal neutrons. However, by way of analogy and on the grounds of the rather close similarities between the two systems to be reported here, it seems safe to attribute octahedral positions to the dissolved boron, too. At higher boron contents, compounds of stoichiomet-ric compositions are reported such as Pd3B, which has the structure of cementite,14 so that a close structural relationship seems to exist with the system r Fe-C. In their study of hydrogen absorption in Pb-B alloys, Sieverts and Briining noted that alloys with an atomic ratio of about nB = 0.16 are no longer homogeneous15 This observation was confirmed in an extensive X-ray investigation.11,16 The phase boundaries of two miscibility gaps were established. One two-phase region was stable below a transition temperature of about 315°C and extended from nB = 0.015 to 0.178. The other one extended from nB = 0.021 to 0.114 slightly above the transition temperature and had an apex at nB = 0.065 and 410°C. All phases involved have the fcc structure of pure palladium with lattice expansions proportional to their boron contents. The occurrence of miscibility gaps, i.e., the coexistence of dilute and concentrated phases, points to an energy of attraction between the dissolved particles, in the Pb-B system as well as in the Pd-H system. The filling up of the electron bands seems to be analogous, too, in the two systems, as indicated by the hydrogen absorption capacit15,17,18 and by the suscepti bility of Pd-B alloys.l8 In both types of experiments, boron acts as an electron donor. A chemical method was used to measure the activity of boron in palladium. Boron trioxide was reduced in a moist hydrogen stream: B2O3 + 3H2 = 2B + 3H3O [l] At known activities or partial pressures of boron trioxide, hydrogen, and water, the activity of boron could be calculated from the law of mass action. The equilibrium concentration of boron corresponding to this activity was determined as the weight gain of the sample. EXPERIMENTAL The samples consisted of small pieces of foil of 0.1 mm thickness and about 100 mg weight. The palladium was supplied by DEGUSSA, Germany, and stated to be

Jan 1, 1970

By M. D. Hassialis, C. G. Myer

THE nature of a collector-coated mineral surface has been the subject of some experimentation and much speculation. Various aspects of the problem have been isolated and studied; it is probable, however, that there exist aspects as yet unrecognized, which are needed for a complete description of the system. The recognized elements of the problem are: 1—The nature of the chemical units comprising the film and the nature of the forces holding these chemical units to the mineral surface; 2—The orientation of the chemical units at the surface; and 3—The disposition of the collector units at the mineral surface. This report touches upon all three aspects of the broad problem; it deals, however, with a new and heretofore unrecognized element—the mobility of the collector units in the two dimensions of the solid-liquid interface. Regardless of the viewpoint adopted as to whether the chemical units comprising the collector film are collector ions or molecules, held either by chemical or physical forces, the writers on flotation theory are in apparent agreement as to the orientation of the chemical units at the mineral surface. Wark and Cox&apos; showed that the contact angle at a stable collector-coated surface in a constant chemical environment is independent of the nature of the mineral and of any resurfacing agent; it depends solely upon the collector used. They showed further that the value of the contact angle increases with the number of carbon atoms in a homologous series of compounds. Taggart, Taylor, and Knoll2 postulated that the collector ion is oriented with the chemically reactive, polar end toward the mineral surface and the non-polar, hydrocarbon-like end toward the liquid phase. In support thereof they cited the abstraction of p-p1 dihydroxydiphenylthiourea and of glycol xanthate8 by galena without a concomitant increase in the contact angle above that of clean galena. It was argued that in these cases the water-repellent layer which normally would be presented to the liquid phase owing to the orientation of the collector ions is overlain by a layer of water-avid groups, the hydroxyl groups. Implicit is the analogous orientation exhibited by a monomolecular layer of an insoluble substance at an air-water interface. It should be pointed out that these facts also are consistent with the concept that the collector units be flat on the surface of the mineral and that the response of the surface to an air bubble is determined by the ratio of the area covered by water-avid groups to the area covered by water-repellent groups; the areas being weighted according to the relative watef-avidity or water-repellency of the groups involved. The disposition of the chemical units of the collector film at the mineral surface has not received the attention it merits. Taggart4 concluded from the observed stoichiometry of the ions entering and leaving a surface that the stoichiometry is obeyed in detail at the surface of the mineral. Thus, in the case of xanthate-coated galena, pairs of xanthate ions are attached to surface lead ions. In the case of chemisorption, Gaudin and Preller postulated an agreement between the atoms or ions of the substratum (the mineral surface) with those of the superstratum (collector film); in the case of the physical adsorption their position is not clear. In one place they state "the first type (physical adsorption) does not require any agreement between the atoms or ions of the substratum with that of the superstratum" and in another place that "It seems, in fact, as though some slight influence of the substratum is formed even in physical adsorption." The present work shows that in some cases of chemisorption the chemical units of the collector film are in constant surface-bound motion and may not be assigned to any site of the surface, hence there is no permanent association between the chemical units of the film and the atoms or ions of the solid. The physical property of the collector film that is of paramount importance is its surface energy. Although this property is not susceptible to direct experimental determination, the related contact angle is. Much of the knowledge of the properties of a collector film derives (by deductive and inductive reasoning) from the behavior of an air bubble thereat

Jan 1, 1952

By C. A. Stickels

A heat of electrolytic iron, to whzch alunzinutn and nitrogen had been added, was hot-rolled, cold-rolled 90 pct, and recrystallized at temperatures from 500" to 700°C. Primary recrystallization textures appear to arise from competitive growth of two types of nuclei: 1) those having orientations belonging to the "usual" primary recrystallization texture found in riming steel, and 2) those with the {111} (110) ovientation. Development of a (111}(1 10) component in the primary recrystallization texture occurs only over a certain interval of isothermal recrystallizatzon temperatures when the material is supersaturated with respect to the precipitation of AlN. Lowering the degree of supersaturation depresses the temperature interval in which a (111)(110) component occurs. An elongated, &apos;pancake-shaped" recrystallized pain structure and a marked delay in the start of recrystallization were found in all specimens which were supersaturated with respect to A1N precipitation after cold work, regardless of their recrystallization texture. ONE of the consequences of killing low-carbon steel with aluminum is a significant change in recrystallization behavior. About 15 years ago, Solter and eatttiel showed that this behavior was largely controlled by aluminum and nitrogen in the steel. If complete precipitation of A1N was prevented before cold rolling, an increased "recrystallization temperature" was observed in subsequent. annealing, and the recrystal-lized grains were not equiaxed. Leslie et a1.2 studied this phenomenon in some detail and clearly demonstrated the relationship between A1N precipitation, recrystallization kinetics, and the development of "pancake-shaped" grains. It has also been known for some time that aluminum-killed steels, processed to produce elongated "pancake" grains, develop a (11 I}( 110) primary recrystallization texture. This texture has not been found in iron or low-carbon rimming steel as a primary texture4j5 but has been observed following grain growth in electrolytic iron.5 The present work was undertaken to study in more detail the effect of A1N supersaturation on recrystallization textures in iron. LITERATURE REVIEW The deformation texture in heavily rolled iron has been studied in detail by Bennewitz.~ The texture consists primarily of a partial fiber texture about a (110) axis in the rolling direction, designated here as fiber texture A. It includes the range of orienta- tions (111)[110] - (001)[ 110] - (11l)[110]. A weak secondary texture also is present.6 This is a duplex partial fiber texture about two (110) fiber axes located 60 deg from the rolling direction and 30 deg from the sheet normal. The range of this texture, designated here as fiber texture B, about the [101} fiber axis is (112)[110] - near (545)[252] - (211:1[011] *The range given here follows Bennewit~.~ A few pole figures from re-crystallized material indicate a broader range than this.&apos; However, the components which are strongest in the recrystallization texture are in this range.&apos;________________________________________________________ Primary recrystallization textures in unkilled steels can be accounted for by growth of members of fiber texture B present in the deformed metal.5 However, while members of fiber texture B dominate the primary texture, other orientations survive primary recrystallization as well. In particular, some {111}(110) members of fiber texture A must also grow during primary recrystallization, because a well-defined {1ll)( 110) texture develops during subsequent grain growth at 700°C.5 The unusual recrystallization behavior of deformed supersaturated solid solutions has been attributed to: 1) retention of the solute in solution,&apos; 2) formation of coherent, preprecipitation solute clusters prior to and during re~r~stallization,~ and 3) formation of a precipitate prior to and concurrent with recrystallization.&apos;~-&apos;~ When aluminum is supersaturated with iron, the difference in grain boundary mobility between general high-angle boundaries and certain special coincidence site boundaries is apparently eliminated.&apos; In aluminum-killed steels, precipitation of A1N can take place at ordinary subcritical recrystallization temperatures. The rate of precipitation increases with increasing aluminum or nitrogen contents.2&apos;13 There is some doubt, however, as to whether true precipitates form during the time at temperature needed to complete recrystallization. Leslie ef a1.2 found that precipitation in one steel was complete after about 100 min at 700GC, or after about 1000 min at 650GC, as measured by chemical analysis for AlN. Aoki et a1.,13 using internal friction for dissolved nitrogen, showed that a large fraction of the dissolved nitrogen was removed from solution within a few minutes annealing time at temperatures from 400" to 800°C. However , the rate of formation of AlN, as detected bv chemical analvsis. was much slower than the apparent rate of nitrogen removal. Hasebe,&apos;~~ using carbon extraction replicas, has identified A1N precipitates by electron diffraction in a 0.2 C steel, solution-treated at 1300°C and annealed 2 hr at 700°C. Borchers and kim,I6 also using a replication technique, observed precipitates after annealing treatments as short as 2 min at 640°C. However, Leslie et a1.&apos; state that no A1N precipitate can be seen while recrystallization is being inhibited in aluminum-killed steel.

Jan 1, 1967

By Fred A. Anderson, George B. Wallace, Edward J. Slebir

Auburn Dam will be a thin, double-curvature concrete arch dam about 685 ft high. With a crest length of about 4000 ft, it will be the world&apos;s longest single-arch dam. The site is located on the North Fork of the American River about 40 miles northeast of Sacramento, Calif. Construction is scheduled to get under way in 1970. In planning for the design and construction of Auburn Dam (see artist&apos;s conception), the foundation material, with its various discontinuities, is being investigated and the structural characteristics of the rock mass evaluated. The investigation and testing programs will aid in defining the pertinent geologic features and their individual and cumulative influence on the foundation. The work includes geologic surface mapping, surface trenching, core drilling, geophysics, tunneling, excavating shafts and raises, performing in-situ tests, and conducting laboratory tests on core and block samples. Competent amphibolite is the predominant material in the foundation, but significant bodies of chloritic, talcose, and metasedimentary rocks, a strongly developed jointing pattern, faults, and shear zones also affect the deformability of the rock mass. A comprehensive rock mechanics program, closely coordinated with geologic investigations as well as the engineering studies, therefore is required The rock mechanics work is a combination of many analytical studies and experimental investigations. The experimental work includes laboratory tests on core samples from holes drilled for geological studies of the entire foundation and in-situ tests performed in selected areas. The laboratory testing program evaluates the general properties of all important rock types and aids in correlating many of the key structural features encountered within the foundation. To derive maximum benefit from the field tests, they are conducted in materials which represent a

Jan 1, 1970

By R. B. Campbell

One of the three power plants that will be in the Curecanti Unit of the Bureau of Reclamation&apos;s Colorado River Storage Project is the power plant at Morrow Point Dam. Presently under construction, the Morrow Point Power Plant is between Gunnison and Montrose on the Gunnison River in west-central Colorado. (Fig. 1). Morrow Point Dam will be a thin, double-curvature, concrete-arch dam, 465 ft high and will impound 120,000 acre-ft of water. Two 60,000-kw hydroelectric generators will be housed in an underground power plant in the left abutment just down- stream from the dam. The power-plant chamber will be an unlined opening 205.5 ft long, 57 ft wide and 65 to 134 ft high. The arch-type roof with a rise-to-span ratio of 1 to 4 will be supported with rock bolts and chain link fence. A description and discussion of the design considerations for the power-plant opening and rock bolt design are given by William H. Wolf, Gilbert L. Brown, and Ernest D. Morgan in "Morrow Point Under- ground Powerplant," ASCE Power Division Specialty Conference, Denver Colorado, August 18-20, 1965. The Morrow Point site is in a moderately active region of mild earth- quakes, as evidenced by recent earthquakes in 1960 and 1962. Therefore, the Bureau of Reclamation undertook an investigation of the effects on the underground power-plant chamber when subjected to an earthquake. The art of earthquake engineering has been directed primarily at developing methods of analyzing the nature of ground surface motions and designing surface structures to resist damage from vibrations impressed on the structure by the ground motions. The mechanism of straining an underground cavity by an earthquake

Jan 1, 1968

By H. H. Podgurski, H. E. Knechtel

Annealed Fe-Al alloys do not react readily to form AlN when held at 500ºC in NH3-H2 gas mixtures, but do so upon the introduction of dislocatims. Nuclea-tion of the nitride phase occurs on dislocation sites. In turn, the growth of the aluminum nitride particles causes the ferrite phase to yield plastically, generating more dislocations for the nucleation process. The nitride phase extracted from an Fe-2 pct A1 alloy nitrogenated at 500°C was identified as stoichio-metric aluminum nitride with a hexagonal crystal lattice. THIS investigation reveals the role that dislocations play in initiating and sustaining the nitriding reaction in Fe-A1 alloys. As early as 1931 the work of Meyer and Hobrock1 suggested that the initiation of the nitriding reaction could involve a nucleation controlled process. Recently Bohnenka2 depicted the gas-phase nitriding process below 600°C as one of mixed control limited by nitrogen penetration through the surface, by nitrogen diffusion, by aluminum diffusion, and by nucleation of the nitride phase, Fig. l(a). In our research in a comparable alloy (0.57 pct Al) at 575ºC, we have observed a nitrogenation which we feel is better described by Fig. l(b). In the case of a 2 pct-A1 alloy partially nitrided at 500°C we propose the profiles shown in Fig. l(c). For a complete and accurate description of the process, a concentration profile of the dislocation density in the test specimen would be needed. EXPERIMENTAL Nitrogenization was conducted between 500" and 575°C in a variety of NH3-H2 gas mixtures on three Fe-A1 alloys: 1) zone-refined iron + 0.16 i 0.2 pct Al—levita-tion melt, 2) zone-refined iron + 0.57 0.02 pct Al— levitation melt, 3) plastiron + 2 pct Al—melted by induction heating. To demonstrate the effect of dislocations on reactivity, both cold-worked and annealed samples were investigated. All nitrogenation rate studies were conducted gravimetrically with a gold-plated invar balance4 contained in a gas-flow system. To avoid contamination of the specimens in the reaction zone of the system, the reaction chamber was constructed of high-purity dense alumina. The activity of nitrogen was fixed by specific NH3-H2 gas mixtures whose compositions were continually monitored by calibrated thermal conductivity gages and checked by chemical analysis. Variations of ± 0.1 pct NH3 could easily be detected by both methods. Throughout this paper the activity of nitrogen is defined as PN3 /PH23/2 , where PNH3, and Ph2 are partial pressures in atmospheres. Electron transmission, density measurements, and chemical analyses were made on specimens before and after nitrogenating in order to reveal structural and chemical changes. Similar studies as well as X-ray diffraction studies were conducted on nitride extractions from the nitrogenated 2 pct-A1 alloy. These extractions were obtained by the use of an anhydrous bromine-methyl acetate solution which dissolves the iron and leaves the insoluble nitrides as a residue. Hardness profiles were obtained on cross-sections of partially nitrided specimens to demonstrate the extent of nitriding through the thickness of the specimens. RESULTS AND DISCUSSION The nitrogen activity in the NH3-H2, atmospheres was never allowed to reach a level capable of producing iron nitride (Fe4N). Hence, the term nitriding as used in this paper refers only to the formation of aluminum nitride whereas nitrogenation refers to the total uptake of nitrogen regardless of how it is distributed throughout the alloy. The weight increases observed during the initial stage of a nitrogenating treatment are due primarily to the solution of nitrogen in the ferrite phase, particularly when starting with annealed specimens. Because this initial nitrogenation rate in the case of the 0.57 pct A1 alloy, see Figs. 2 and 3(a), was most rapid the weight change that occurred thereafter might be attributed to the nitriding reaction with the exception of a small weight increment due to the irreversible pickup of oxygen by aluminum. The oxygen (<70 ppm) came from traces of H2O and 0, in the hydrogen and ammonia gases. On the basis of discrepancies between total weight increase and the increase in the nitrogen content of the sample as determined by chemical analysis, it was estimated and later established by activation analysis, that as much as 200 ppm of oxygen were taken up by a fully nitrided Fe-0.57 pct A1 specimen at 575°C. Most of the oxygen could have been picked up from the nitriding atmosphere on the surface of the samples during cooling to room temperature. Even 50 ppm of water in the gas phase will become oxidizing to iron before the sample has cooled to room temperature. The lack of reactivity* of these alloys in the annealed

Jan 1, 1970