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By R. Floyd Farris

A method is presented for determining minimum waiting-on-cement time, which takes into account the differences that exist between types and brands of cements and such individual well conditions as depth, temperature, and pressure. The basis for the method was determined by laboratory tests. Being a laboratory development, several steps were required to prove its merit. The first step consisted of laboratory tests designed to determine the minimum cement strength required in wells. Basis was found for setting a minimum value of 8 Ib. per sq. in. tensile strength. Next, it was shown by laboratory tests that the time to 8 Ib. per sq. in. tensile strength may be expressed as a function of consistometer stirring time to loo "poises," the approximate relation being "the time to 8 Ib. per sq. in. tensile strength equals the time to I00 'poises' times three." Next, it was shown that the time of maximum temperature development in cement slurries, due to heat of hydration, is also related to consistometer stirring time to loo poises, but only by a factor of approximately two. It was shown also that the shut-in casing pressure will build up after cement is placed and register a maximum pressure at approximately the same time the slurry down the hole attains maximum temperature. From this and the relationships listed above, the general rule was established that minimum waiting-on-cement time (time to 8 Ib. per sq. in.) after casing cement jobs in any well is equal to the time when the shut-in casing pressure reaches a maximum, as measured from the initial mixing of cement, times a factor of 1.5. Cement plugs drilled in the field at the time prescribed by this formula were found to drill "firm to hard," thus confirming the laboratory tests. These tests prove that many of the present regulations for waiting on cement require a longer time than is absolutely necessary. Use of the method herein proposed offers the possibility of a saving of $1200 per well. Introduction The length of time allowed for cement to set after casing is determined either by state-wide rules, field rules, or self-imposed rules written into drilling contracts. In general, the time is dictated by experience and common practice. However, owing to differences in opinion and in experience of the various groups involved, waiting-on-cement time often varies from one area to the next. For example, an operator in an area where no rules exist may drill out of surface pipe at 24 to 36 hr., while another operator in another area may wait 48 hr. or more to comply with state or field rules, although the depth of the well, hole size, type of cement, and other data are identical. An even greater difference in practices will be found by making similar comparisons with respect to oil-string cement jobs. Differences in waiting-on-cement times of 36 to 48 hr. are common. Further complicating the picture is the rather common practice of allowing more waiting time for cement to set at the greater depths than is allowed at the shallow depths. This practice has existed for years in spite of the common knowl-edge1,2,3 that the temperature of the earth at the usual setting depths of surface

Jan 1, 1946

By P. E. Baker

Approximate solutions are presented for the heat-flow equations in a loss-free linear system with a moving source and with heat transfer by convection and conduction, representing in situ combustion in an oil reservoir. The rate of heat generation and the velocity vf of the source (flame front) are assumed constant. A cold front or convection front caused by the cooling effect of in-jected air develops behind the flame front and moves with velocity vc, which is determined by the thermal properties of the air and rock. Because of thermal conduction the fronts are not sharp; i.e., they do not represent temperature discontinuities. The following solutions apply after a sufficiently long time. where Q is heat generated per unit volume of formation, k is thermal conductivity, CF is volumetric heat capacity, a is thermal diffusivity, and subscripts 1 and 2 refer to values behind and ahead of the flame front, respectively. The parameter CF2 is contained in v . Te is initial reservoir temper- . C2 e ature and air-injection temperature. Other mathematically possible solutions are presented. The different solutions result from the use of different values for various physical parameters. The solution just presented is thought to be most commonly applicable. INTRODUCTION In this paper, approximate analytical expressions are derived for the temperature profile developed in the underground combustion method of oil recovery. A qualitative description of the process may be found in a paper by Tadema.1 The flame front is regarded as a moving source with a constant rate of heat generation. Heat transfer is by conduction and convection. Previous publications, of which a few are cited here, 2-5 have also attacked this problem and have presented solutions pertaining to different methods of approximating or idealizing the process studied. The present paper also treats an idealized case: linear flow is assumed for heat and fluids, and vaporization and condensation effects are neglected. The results obtained are similar to those derived by Bailey and Larkin,3 but are obtained by an entirely different procedure. The method used here should give considerably greater insight into the physics of the in situ combustion process. Four types of cases are considered, distinguished by thermal and fluid-flow properties of the system. A constant rate of heat generation and constant rate of flame-front advance are assumed. Flame-front temperature is determined for each case using a heat balance which involves the entire temperature profile. The applicability of the different solutions to real systems is discussed after they are all presented. Again, this is done for the purpose of understanding better the physics of the process. Consideration of the nonapplicable solutions and of the reasons for their not applying is significant. In a paper by Cooperman,4 the only case solved is one considered here as not applicable. Fluid flow, as such (pressures, saturations, oil recovery, etc.), is not treated. This subject has been covered in a paper by Wilson, et al.6 Also, we are not concerned with requirements for continuance of the process; we only attempt to determine the temperature history for cases where the process has continued for some time. PHYSICAL SYSTEM AND APPROACH TO PROBLEM A linear flow (heat and fluid) system is assumed and the x-axis is taken parallel to the flow direction. The combustion zone (flame front) is vertical,

By E. R. Buchanan, R. E. Reed-Hill, F. W. Caldwell

Poly crystalline zirconium tensile specimens containing a sizable fraction of grains unfavorably oriented for slip were deformed at 77°K to strains as high as 9 pct. The contributions of the various twinning modes to the observed strain were deter~nlned quantitatively using measured twin volume fractions and Schrnid orientation factors. The results indicate that at very small strains twinning can account for almost all of the observed strain. At higher strains slip becomes the dominant means of deformation. The most significant form of twinning was {1121}. PLASTIC deformation in polycrystalline aggregates is poorly understood even today. This is primarily because slip cannot be easily observed or studied in the interior of a metal. On the other hand, twinning can be discerned inside a specimen after deformation. Twinning studies can therefore often yield quantitative information about polycrystalline deformation not otherwise obtainable. This investigation uses the above aspect of twinning in determining the contributions of twinning to the strain during tensile deformation at a cryogenic temperature (77°K). Polycrystalline zirconium was used as the object of study. There are several reasons why this information should be of value. In contrast to many metals, both the strength and ductility of zirconium increase with a corresponding decrease in temperature. This may be related to the fact that twinning becomes more profuse and complex with decreasing temperature. Secondly, it has been discovered that certain room-temperature properties of zirconium can be greatly improved by about 1 pct prestrain at 77°K. These include an increase in tensile elongation in critical directions by over 50 pctl and a large mechanical hysteresis effect.2 Both effects are believed to be related to twins formed by prestraining: plastic twin-boundary movements accounting for the increased ductility, and anelastic twin-boundary movements for the internal friction. Thirdly, hexagonal metals which twin primarily on only the (1012) mode (such as beryllium, zinc, and magnesium), unlike zirconium, are very limited in ductility at cryogenic temperatures. Therefore, the significance of the various types of twinning in zirconium at cryogenic temperatures is of more than academic interest. Three twinning mechanism-s have beenobserved in quantity at WOK, {1012), {1121), and {1122). Each must be considered as a unique deformation mechanism because of their markedly different twinning shears and basically different angles between twinning and basal planes, as shown in Table I. It is therefore necessary to separately consider the role of each of these twins during plastic deformation at 77°K. Fortunately, each twin possesses unique morphological features which makes its identification possible on a properly prepared metallographic section. The use of the polarized microscope3 can also greatly aid in identification of the various forms of twins. EXPERIMENTAL PROCEDURE Arc-melted sponge zirconium plate, previously describedY4 was machined into 1/8 by 1 1/4 in. threaded-end, round tensile test specimens. These specimens were deformed to the desired strains in a liquid-nitrogen cryostat mounted in an Instron testing machine. The tensile axis was the transverse plate direction. This specimen direction resulted in large numbers of grains in orientations unfavorable for deformation by prism or basal slip. Deformed specimens were sectioned, mounted in epoxy cold-mount resin, ground on metallographic papers, electropolished, and anodized to provide surfaces sensitive to polarized light. Standard quantitative metallographic procedures5

Jan 1, 1965

By A. A. Bauer, H. A. Saller, F. A. Rough, J. R. Doig

among uranium alloy systems are the U-Zr, U-Ti,and U-Mo binary systems, in that an intermediate phase, of limited solubility range, exists in each system. These intermediate phase alloys offer a promising field of investigation, both as binary alloys and as ternary alloy combinations. While a limited amount of work has been done on the binary alloys, none has been done on ternary combinations of these alloys. As a possible prelude to more intensive investigation of these systems, a study of the phase relationships between the 6 phases of the U-Zr and U-Ti systems was undertaken. The solid-state portions of the binary constitutional diagrams for the U-Ti,1 Zr-Ti,2 and U-Zr3 systems are shown in Fig. 1. The solid to liquid transformations are not shown, as these transformations were not studied in the ternary system. The phase designations employed are based upon those shown in the uranium constitutional diagrams. The crystal structures of the various phases are given in Table I. Experimental Materials and Methods The ternary section presented is based upon the results of thermal, metallographic, and X-ray analyses of a series of alloys ranging in composition between the phases of the U-Zr and U-Ti systems (U-74 atomic pct Zr to U-35 atomic pct Ti). After preparation of the alloys, thermal data were obtained. On the basis of these data, specimens were heat treated and examined metallographically. Specimens were then selected from those heat treated for X-ray determination of the phases present in what were considered critical phase regions. Alloy and Specimen Preparation—Alloys for this investigation were prepared from selected as-reduced uranium and crystal-bar zirconium and titanium. For nominal compositions, see Table 11. Charges were arc melted from five to seven times under a helium atmosphere, finally being cast into wire-bar form for fabrication. A zirconium getter button was used to clean the furnace atmosphere prior to melting. The alloys were homogenized 20 hr at 900 °C and furnace cooled. A portion of each bar was then removed for thermal analysis; the remainder was saved for fabrication. Alloys 8 through 14 were placed in steel tubes along with zirconium getter chips and, after flushing with argon, the tubes were welded shut and rolled at 1500 °F to a 50 pct reduction in diam. The remaining alloys were annealed 24 hr at ll00°F to insure transformation of the ? phase to the 8-U2Ti phase and were then hot rolled from a salt bath. Attempts to roll alloys 6 and 7 at 1100 °F were unsuccessful. Following this, attempts were made to roll pieces of alloys 1 through 5, which had cracked rather severely during casting, at 1200 °F, but these efforts were also unsuccessful. These alloys were, therefore, further treated in their cast and homogenized condition. All alloys were pickled to remove oxide formed during rolling. Thermal data were obtained on these alloys by conventional differential thermal analysis at a heating rate of 30C per min, and by a high-speed heating method at rates of approximately 10°C per sec. For the latter method of analysis, a 36-gage Chromel-Alumel thermocouple is spot welded between two slivers of alloy, the sandwich being en-

Jan 1, 1958

By K. Torssell, U. Lindborg

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

Jan 1, 1969

By Pedro Bolsaitis, Paul M. Sullivan

The activities of zinc in liquid Zn-A1 alloys in the temperature range of 1000' to 1160°K were determined by means of the isopiestic technique. The results are in reasonable agreement with the previous values determined by the radioactive tracer dew point method. Slightly negative excess entropies of mixing were found. The measured activities suggest that the a function for these alloys is not a constant, as has frequently been assumed, but is better represented by two straight line segments of different slopes. THE thermodynamic data of Al-Z alloys have been the subject of investigation by many authors. However, in the recent compilation of such data by Hult-gren et al.,5 the conclusion is reached that none of the previous measurements are reliable or consistent with each other. Since then two new sets of measurements have been reported,2, 8 both laying claim to good accuracies, yet showing very significant disagreement in the measured activity coefficients of zinc in Zn-A1 alloys and in the magnitude and sign of the excess entropies of mixing. Information on the thermodynamics of the system is of particular interest for interpreting results of the Bureau of Mines research on refining of zinc by distillation of die cast scrap. The present study was undertaken as an independent check on the recent values obtained from dew point measurements 8 and electromotive force measurements.' The isopiestic method, first introduced by Herasy-menko,' was chosen because it is one of the few thermodynamic techniques which, in principle at least, is carried out under perfect equilibrium conditions. The disadvantage of the method is that data are obtained at various random compositions and temperatures, which makes the interpretation somewhat cumbersome. The random errors arising from temperature gradients and fluctuations appear to be comparable to those of other techniques, as evidenced by the magnitude of the estimated uncertainties in the calculated integral thermodynamic quantities. An advantage of the method is that each run provides a relatively large amount of data; thus, it is less time consuming than those methods where samples of each composition must be measured individually. EXPERIMENTAL PROCEDURE The activities of zinc in liquid Zn-A1 alloys were measured by the isopiestic method which uses the principle of the tendency toward equilibrium of a series of samples at various temperatures under an imposed vapor pressure of the more volatile component (i.e., zinc, in this case). The basic apparatus is shown in Fig. 1. The small graphite crucibles that contained the metal samples were 15 mm ID and 13 mm deep with approximately 3 mm wall thickness. Each crucible was notched at the top and bottom to allow easy passage of vapor from one to another. At the beginning of an experiment each crucible was weighed on an analytical balance. Zinc and aluminum of spectrographic purity (99.999 pct) were then weighed into the crucibles. The amounts of each metal added were such that initial compositions varied above and below equilibrium values. One crucible contained only pure zinc. After weighing, the crucibles were stacked with the pure zinc on the bottom (corresponding to the lowest temperature in the furnace) and richest aluminum alloys at the top. The entire stack of crucibles was then placed in the silica glass container "E" which was then sealed under vacuum. Sixteen to twenty calibrated Chromel-Alumel thermocouples were attached by wire along the length of the silica tube, one or more adjacent to each sample.

Jan 1, 1970

By L. G. Austin

If S (x) is the specific rate of breakage of size x and B (x, y) (see Table 1 for Nomenclature) is the cumulative breakage distribution function, the Herbst Fuerstenau2 assumption is that Inserting this assumption into first-order grinding equations it has been shown" that there are then simple analytical solutions to the grinding equations, as shown in Table 2. In this context "plug flow" is defined as all material passing through the mill in the same length of time, the residence time t. The term "n fully-mixed" means that the mill has a residence time distribution" which can be treated as if the mill were n equal fully mixed sections in series. In addition it has been shown that the assumption of Eq. 1 also leads to simple analytical solutions for closed-circuit, steady-state grinding with an ideal classifier at the mill exit returning oversize to the mill feed. The solutions are also given in Table 2, with µ as the ideal classifier cut size, C the circulation ratio, and Q (x) the size distribution of the circuit product. The specific surface area of these size distributions is where the density-shape factor k. is assumed to be constant with size. In practice, most methods of size analysis or area [ ] measurement have a finite lower limit, so that the integration is really performed from xm, to xm, For a realistic degree of grinding the value of So is dominated by the fine sizes because of the 1/x factor. Consider batch grinding of a feed of size y to y + dy. The batch grinding solution given in Table 2 is then [ ] The fresh surface area produced is the area of the fines plus the area of the original material remaining minus the area of the original material, [ ] Little error is introduced by neglecting the last term on the right-hand side since at t = 0 it is zero, and when t is significant the first term dominates because of the fine sizes produced. In addition, the form of P (x, t) for [ ] realistic values of S (x) 2t ax° is such that the major fraction of fresh surface produced is contained within the bottom 10% of weight of broken material, that is, for sizes for which P(x, t) < 0.1 (providing y is not near x.,). Thus for surface area purposes Eq. 3 can be approximated by [ ] becomes providing again that the feed sizes are coarse relative to xmi. Then the fresh area production is and W is the mass in the mill. The rate of surface production is WK, and the specific surface is Kt. From Table 2, the specific energy is mt/W so surface production per unit energy is [ ] Surface produced per unit energy input = KW/m (8) where m is the energy input of the mill. Clearly, identical reasoning applies to open-cycle, plug-flow grinding, with t replacing t, and Eq. 8 is obtained again. Considering open-cycle, fully mixed grinding, similar reasoning gives P(x) - t S(x) for surface area purposes, and

Jan 1, 1974

By R. T. DeHoff

Saltykov&apos;s meihod for the determination of the size distribution of spherical particles from measurements made on random plane sections is extended to particle shapes which are not equiaxed. The analysis permits the deterrrzination of the size distribution of aggregates of ellipsoidol particles provided all particles have tlze same shape. V ARIOUS solutions to the problem of the determination of the size distribution of spherical particles from measurements made on random plane sections have appeared in the literature since the original solution was first published by Scheill in 1934. Solutions have been offered utilizing measurements of the diameter1y2 or area3&apos;4 of circular sections that result when a test plane is passed through an aggregate of spherical particles, and the length of intercept5y6 that results when a test line is passed through the aggregate. To the best of the knowledge of the author, no method has been proposed which permits the determination of the size distribution of particles that are not equiaxed. The purpose of this paper is to develop a method which permits the determination of the size distribution for a specific class of particle shapes which cover awide range of axial ratios; namely, ellipsoids of revolution. In the interests of simplicity, it is necessary to limit consideration to aggregates of particles which are all similar in shape; that is, the ellipses which, by rotation about one of their axes, generate the particles, all have the same axial ratio. The size distribution, which is to be determined by the analysis, is arbitrary. It is also assumed that the section, or sections, upon which the measurements are made represent the average of all possible sections through the structure. This ideal condition can be approached as nearly as may be desired by observing a sufficient area of sections taken at random positions in a randomly oriented aggregate, and in random positions and orientations in an aggregate that has one or more axes of orientation. SIZE DISTRIBUTION FOR PROLATE ELLIPSOIDS Consider an aggregate of cigar shaped, geometrically similar particles (prolate ellipsoids), dispersed in an opaque matrix. Let the size of each particle be specified by the length of its minor axis, By Fig. 1, and the shape, q, be defined by the ratio of its minor to its major axis, B/A. Let the index, j, refer to dimensions of ellipsoids in a particular size class, and the index, i, to dimensions of an ellipse resulting from the intersection of a test plane and a particle. The size of such a section is specified by the length of its minor axis, b. Let the particles be arbitrarily divided into k size classes, and let the increment of size between each class be A, where A = &,$, B,,,being the minor axis of the ellipsoids in the largest size class. Since all sections are represented on the test plane, the minor axis of the largest of the sections observed, results from the intersection of the test plane with an ellipsoid in the largest size class at its center, and is therefore equal to Bmax Thus the increment, A = The final result will consist of the k numbers which represent the number of particles in each size class per unit volume of aggregate:

Jan 1, 1962

By ROBERT B. COONS

SELECTIVE SERVICE must meet three important demands for man power: (1) Activities concerned with production of war goods. (2) The armed forces. (3) Civilian activities and institutions the continuance of which are essential to maintaining the structure of our American democracy. In the above enumeration of demands I have placed everything, including most of our most prized possessions and activities, after the demand for men for war production and the armed forces. To establish an order between the latter two is difficult. For the time being, at least, the Selective Service policy is to make sure that we avoid the risk of "too little and too late." No soldier, sailor, or marine should be sent from these shores to risk his life without the assurance of having a gun, clothes, food, and medical supplies. Therefore, the premium is now being placed on man power for war production and in our process of selection no stone is left unturned to see that our agencies are fully informed of the needs of war production. Our procedures set up recourses for employers of war-production man power so that their activities need not be disrupted, at least not until they have had time to train replacements.

Jan 1, 1942

By Monte J. Pool, Rudolph Speiser, George R. St. Pierre, William T. Ebihara

Standard free energies of formation of WO,, W O W20058 and WO3from oxygen and the lower oxide or tungsten have been determined in the tempel-ature range of 700° to 1220°C. A tentative W-O phase diagmm is presented based on the evidence that the oxide phases, "W18O49" and "W20058", are unstable at l~atm total pressure, below 585° and 485°C:, respectively. A HE need for a complete quantitative treatment of the phase equilibria of the W-O system has been establishedby metallurgists during the past few years. In an attempt to improve the endurance of tungsten exposed to oxidizing atmospheres at high temperatures, many research groups have studied the kinetics of tungsten oxidation. The reverse process, the reduction of the tungsten oxides to metal, has also been investigated to some extent. Regardless of the particular interest, metal to oxide or oxide to metal, a knowledge of the phase equilibria of the W-O system is required to properly interpret all of the kinetic observations. It should be possible to state the stable phases of the W-O system at any given values of the chemical potential of oxygen and the temperature.

Jan 1, 1962

By Ralph H. Sweetser

N Greenup and Carter counties, in the northeastern part of Kentucky, are the remains of many old charcoal furnaces built and operated during the period from 1818 to 1892. They were all included in what was called the Hanging Rock district. In the summer of 1930 I visited ten of these old blast furnaces, as follows:

Jan 1, 1931

By Mark J. Klein

The creep of 043 was studied over the temperature range 1650" to 3200°F and over the stress range 3000 to 44,000 psi. The steady-state creep rate over this range of stress and temperature can be expressed by the equation where A is a constant, is the stress, and is -0.8 x 103 psi-&apos;. Over a narrow range of stress variations c0 a and for this proportionality n varies from 3 to 30 in accordance with the relation n = aB. Above about 2400° F, H, the apparent activation energy for creep, is 110,000 cal per mole, a value about equal to that estimated for self-diffusion in this alloy. Below 2400°F, H increases with decreasing temperature reaching a value of -125,000 cal per mole at 1700° F. In this temperature region, H appears to be a function of the interstitial concentration of the alloy. MOST of the detailed creep studies of dispersion strengthened metals have been concerned with metals having fcc structures. However, there are a number of important refractory alloys with bcc structures that derive part of their high temperature strength from an interstitial phase and whose creep behavior has not been well defined. This paper describes the creep behavior of the bcc alloy, D43, over the temperature range 1650" to 3200°F (0.4 to 0.7 Thm) and over the stress range 3000 to 44,000 psi. In addition to colum-bium, this alloy contains 10 pct W. 1 pct Zr, and sufficient carbon (-0.1 pct) to form a carbide dispersion throughout the matrix of the alloy. The effects of variations in temperature and stress on the steady-state creep rate of this alloy are presented in this paper. EXPERIMENTAL PROCEDURES Creep tests were made in a vacuum of 106 torr under constant tensile stress conditions using a Full-man-type lever arm.&apos; Creep specimens were machined from 0.020-in. D43 sheet (grain size -5 x l0-4 in.) processed in a duplex condition (solution annealed -2900°F, 40 pct reduction in area, aged 2600°F). The specimens were tested in this condition without further heat treatment. Specimen extensions over 1-in. gage lengths were continuously recorded using a high temperature strain gage extensometer. Differential temperature and stress measurements were used to determine temperature and stress dependencies of the creep rate. Activation energies were calculated from the changes in strain rate induced by abrupt shifts in the temperature during constant stress creep tests. The 100°F temperature shifts used in most of the activation energy determinations required 15 to 90 sec depending upon the temperature at which the shift was made. The dependence of strain rate on stress was determined by measuring the change in strain rate for incremental stress reductions during constant temperature tests. It has been shown that columbium-base alloys such as D43 are susceptible to contamination by gaseous interstitial elements during vacuum heat treatments.&apos; In this regard, it is unlikely that these alloys can be heat treated without some loss or gain of interstitial elements despite the precautions taken to control the heat treating environment. However, several factors suggest that changes in interstitial concentrations of the specimens during testing did not affect the results presented in this paper. First, the dependence of the creep rate on the stress or temperature determined during the course of a single creep test showed no variations with the duration of the test. A variation would be expected if a loss or gain in interstitial concentration during the course of the test affected results. In addition, precautions taken during this investigation to minimize interstitial contamination by wrapping the gage lengths of the specimens with various foils2 (Mo, Ta, W) did not produce a detectable change in the stress and temperature dependencies relative to the unwrapped specimens. The averages of duplicate analyses for carbon and oxygen in several specimens determined before and after creep testing are listed in Table I. The combined nitrogen and hydrogen concentrations which were ordinarily less than 50 ppm did not change in a detectable way with creep testing. The analyses show that only minor changes in carbon concentration occurred during creep testing except for specimen 4. This specimen which was tested at 3100°F lost a significant amount of its carbon concentration to the vacuum environment. Specimen 1 gained 100 ppm of O, while specimens 2, 3, and 4, which were tested at progressively higher temperatures, lost increasing portions of their initial oxygen concentrations during testing. RESULTS AND DISCUSSION The Temperature Dependence of the Creep Rate. The apparent activation energy for creep, H, was de-rived from creep curves similar to that shown in Fig. 1. Steady-state creep was rapidly attained at the beginning of the test and with each change in temperature. This behavior suggests that the alloy rapidly attains a stable structure with each shift in temperature or that the structure is constant throughout the test. Since the dispersion will tend to stabilize the structure, the latter is probably the case. The activation energy was found to be independent of the direction of the temperature shift and the magnitude of the shift (50" or 100°F). Although H was approximately independent of the strain, there was a tendency for it

Jan 1, 1970

By D. S. Gleason, D. E. Severson, D. R. Skidmore

Pittsburg and Midway Coal Co. has modified the German Pott-Broche process, on which patents date back to 1927, to produce on a bench scale liquid products by solution hydrogenation of coal. A continuing program of lignite solution-hydro gena-tion experiments is directed toward investigating coal solution reactions, determining favorable conditions for the solution refining of lignite by the Pott-Broche process, and investigating some of the uses for the de-ashed product obtained from lignite The German Pott-Broche process1" on which patents date back to 1927, has been modified by the Pittsburg and Midway Coal Co., a Gulf Oil subsidiary, to produce on a bench scale liquid products by solution -hydrogena-tion of coal." The objectives of the present effort are to investigate coal solution reactions, to determine favorable conditions for the solution refining of lignite by the Pott-Broche process, and to investigate some of the uses for the de-ashed product obtained from lignite. This paper is a summary of results to date in a continuing program of lignite solution-hydrogenation experiments. The coal solution reaction program has several principal aims. The first of these is to determine whether lignite can be successfully dissolved in solvents that might be practical for commercial development. The second object is to determine whether the solvents function after successive cycles of use, recovery, and reuse. It seems necessary to the economics of a potential commercial process that the solvent be recycled. Third, it is desired to learn something about the distribution of the ash constituents between cake and filtrate. The extent of ash removal is important. The nature and quantity of mineral matter passing through the filter may determine end-use marketability. For certain use applications, trace quantities of certain minerals can be objectionable, e.g., titanium and vanadium must be very low in electrode carbon for aluminum production. The Solution Reaction The coal solution Process involves an extremely complex system of chemical reactions. An initial solvent such as anthracene oil is a mixture of hundreds of different compounds with a boiling range of roughly 500" to 750°F at atmospheric pressure. The coal macro-molecule is broken down by thermal decomposition and solvent action into myriads of different compounds, some the same as those comprising the solvent. This similarity in structures opens up the possibility of production and subsequent recovery of solvent. Some solvent is inevitably lost by reaction. Regeneration of solvent was not a problem in the early German Pott-Broche plant. The coal refinery was an integral part of a petroleum refinery complex and replacement solvent was readily available. A coal refinery using lignite, however, might be isolated from other hydrocarbon processing facilities and the regenerability of solvent could be vital to the economic success of the venture. Several structural features of the solvent molecules have been cited as important to the coal solution process.&apos;. The first of these is aromaticity of the material, the second, ability to transfer hydrogen to another molecule, as for example the ability of tetralin to transfer hydrogen and be converted to naphthalene. Finally, the presence of hydroxyl groups on aromatic rings within the molecule, i.e., phenolic character, seems beneficial. Mixtures of pure compounds have been tried by various investigators. Mixtures of o-cresol, a phenolic substance, and tetralin were found to dissolve bituminous coal better than either substance alone.3 This maximum solubility was not found with lignite." Hydrogen contributes to the reaction by hydro-genolysis and by combining with free radicals and molecular "loose ends" to stabilize the compounds formed in coal depolymerization. High boiling point, and correspondingly high molecular weight, seems to be a property which improves solution potential for coal with a given type of compound.&apos; The maceral components of the coal appear to have an important bearing on its ease of solution. The fusain portion is quite inert to solvent action, but the an-thraxylon material dissolves quite readily.3 The hydrogenation reaction can be improved by the use of a catalyst; commercial hydrogenation catalysts having been found effective. Although cost is involved in the use of catalyst and catalyst recovery, the resulting saving in time and perhaps lowered temperature or pressure might justify their use in the solution refining process and decrease the total process costs. Apparatus and Procedure The coal solution runs were made in a 1-gal stainless steel stirred autoclave. The autoclave was provided with thermocouple wells and a transducer to permit continuous recording of temperature and pressure. The autoclave stirrer was magnetically driven, eliminating the leakage inherent with a rotating pressure seal. For runs in which a catalyst was used, the catalyst in the form of beads was placed in a wire mesh container mounted on the stirrer shaft. A control system programmed the heatup and reaction cycle. The permissible heating rate was 5°F per min because of the need to minimize thermal stress in the autoclave body. The temperature was raised at that rate until the reaction temperature was attained and then the temperature was held constant for the desired length of time. The maximum temperature seldom exceeded the average run temperature by more than 15°F.

Jan 1, 1971

By Thys B. Johnson

Traditional mine planning concepts are discussed and suggestions for improvement through use of the developed model are proposed. The approach developed in this paper allows optimal planning of the complete mining-concentrating-refining system over the entire planning horizon and permits the system to dictate how and when to process a block of material, i. e., a dynamic cutoff.

Jan 1, 1969

By Luther Wagoner

HAVING given in a former paper1 the results of assays of sea-water, bay-mud, dredgings from San Francisco bay, etc., and&apos; believing it might be interesting to extend the work to include&apos; some deep-sea dredgings, I procured from the Smithsonian Institution six samples taken by the U. S, steamer Albatross, and marked as follows

Jan 9, 1907

By C. Chu

A theoretical investigation has been made of the forward combustion process using a one-dimensional linear mathematical model, taking into consideration the effect of the vaporization-condensation which occurs on the leading edge of the heat wave. This work involves the solution of five coupled partial differential equations. Besides the vaporization-condensation phenomenon, these equations account for conduction, convection, combustion, heat loss, diffusion and bulk fluid flow. For the one-dimensional linear model studied, the vaporization-condensation phenomenon does not induce appreciable change in the temperature at the combustion front; and its primary effect is to create a steam plateau and to increase the length of the heated zone ahead of the combustion front. This effect becomes more pronounced at lower pressures, higher porosities or reduced gas saturations. The peak temperature and the temperature profile on the leading edge of the heat wave stabilize after a certain period. The length of the steam bank remains practically constant, although the length of the water bank increases as the heat wave advances. INTRODUCTION The existence of the vaporization-condensation phenomenon in the heat-wave process and the important role played by the phenomenon have been recognized by several investigators. Kuhn and Kochl stated that steam plateaus were frequently observed on the temperature records of their experiments. The steam plateaus were attributed primarily to the vaporization and subsequent condensation of the interstitial water existing in the oil sand. Szasz2 suggested that both lighter hydrocarbons and water are vaporized on the leading edge of the heat wave, carried forward in the gas stream, and then condensed to create banks of oil and water. Martin et al suggested that the vaporization-condensation phenomenon is one of the main mechanisms of the heat-wave process, along with thermal expansion and viscosity reduction. Wilson et al. reported the existence of a steam plateau several inches in length in their small-scale tube-run experiments. However, this important phenomenon has never been taken into consideration in the numerous theoretical analyses by various authors. 5 The purpose of this work was to study the thermal aspects of a linear heat wave, taking into consideration the vaporization-condensation on the leading edge of the wave, to determine the effect of this phenomenon on the temperature profile of the reservoir, and to investigate how this effect varies when other process variables are changed. THEORY We consider a reservoir of porous medium of cross-sectional area A, extending from x = 0 to x = L. This reservoir contains, aside from the solid matrix itself, a gas phase and a "combined liquid phase" which is a combination of two immiscible liquid phases — namely, an oil phase and a water phase. The oil present in the reservoir is assumed to consist of three fractions, a noncondensable gas, a nondistillable residuum, and a vaporizable oil fraction which may be present in both the gas phase and liquid phase. Before the heat-wave process begins, preheating has taken place and has imparted an initial temperature distribution T,(x) to the reservoir. At the start of the process, a stream of oxygen-bearing gas is introduced through the face at x = 0. This gas supports the combustion of the residual fuel and supplies the heat throughout the process. In order to develop a tractable system of equations, the model properties are postulated as follows: (1) the system is isotropic and homogeneous; (2) there is a uniform fuel content throughout the reservoir; (3) combustion takes place in a moving vertical planar region of infinitesimal thickness; (4) the temperatures of the fluids and the solid matrix are identical; (5) radiation is negligible; (6) the gas and liquid saturations are uniform throughout the reservoir and remain unchanged

Jan 1, 1965

By F. H. Buttner, E. R. Funk, H. Udin

A. P. Greenough (University College, swansea, Great Britain)—I have recently made some experiments on the deformation of silver wire at high temperature in an atmosphere of oxygen-free nitrogen. The observa-tions which 1 made confirm the main conclusion of this paper, that the most satisfactory mechanism so far suggested to explain the deformation which takes place

Jan 1, 1953

By N. V. Peterson, R. S. Mason

The violent explosion of Mount St. Helens in the state of Washington on May 18, 1980 showered volcanic ash over vast areas of the Northwest. It was another eruptive episode in a long history of similar occurrences in the region, which extends from Canada to California and reaches several hundred miles inland from the Pacific Ocean. Pumice, pumicite, and cinders are products of explosive volcanic eruptions. Pumice and pumicite are produced by the violent expansion of dissolved gases in a viscous silicic lava such as rhyolite or dacite. Scoria is the mafic counterpart of pumice. Pumice is a light-colored, cellular, almost frothy rock made up of glass-walled bubble casts. It may occur as coherent, massive blocks composed of highly vesicular glassy lava in either a flow or vent filling, or it may be more or less fragmented by violent eruption. Pumicite, the diminutive of pumice, has the same origin, chemical composition, and glassy structure, differing only in particle size. Particles less than 0.16 in. in diam are designated pumicite. Pumice usually is found relatively close to the vent from which it was expelled, while pumicite may be carried by winds for great distances before settling as an accumulation of fine-grained ash or tuffaceous sediment. Mount St. Helens lofted an estimated 5 billion cu yd of ash and pumicite. The volcano, unlike most of the High Cascade peaks, is composed largely of dacitic material with only minor amounts of andesite and basalt. Volcanic cinders are the reddish to black vesicular fragments which pile up during explosive eruptions of volcanoes of basaltic composition. Most cinder deposits occur as cones or mounds of stratified fragments ranging from a fraction of an inch to several inches in diameter. Individual cones or mounds may be several hundred feet in diameter and up to 500 ft high. Properties and Uses Low bulk density, good heat and sound insulating properties, and excellent abrasive capabilities make pumice and pumicite useful in industrial applications. Cinders, though less cellular and somewhat heavier, also have a variety of industrial uses. The main use of pumice and cinders continues to be in the construction industry as road-surfacing material, railroad ballast, and building block aggregate. Pumicite is used in sizable quantities as a pozzolanic additive to monolithic concrete where it increases workability, strength, and durability of the concrete and reduces the heat of hydration. Volcanic cinders generally are denser and more coarsely cellular than most pumice. Markets for cinders include aggregate for road construction and surfacing and use in lightweight concretes, particularly blocks. Some producers having access to both pumice and cinders offer a variety of blends of the two materials to block manufacturers. Table I lists the principal applications of industrial pumice. Tables 2 and 3 show US sales and uses of volcanic products. Most pumice deposits are unconsolidated and usually have a minimum of overburden. Mining is by open pit and can be easily carried out with conventional loading equipment. Sometimes air drying precedes hauling to a crushing and screening plant which yields the size product desired. Multiple bins at railroad hauling facilities permit blending if desired. Pumice for abrasive use may require more sophisticated processing by fine grinding and air classification before being bagged for market.

Jan 1, 1983

By S. Storchheim

MORE and more attention is being paid to the bonding of metals in their solid states. For a better understanding of this technique for joining metals and how it is affected by changes in temperature, pressure, and time at temperature and pressure, a detailed report concerning nickel to aluminum bonding has been published.&apos; In order to broaden the knowledge accrued, some additional work concerning solid state joining of aluminum to copper and aluminum to zirconium was performed. The investigation of the Al-Cu system was considerably more extensive than the investigation of the Al-Zr system. For the A1-Cu system, not only were tensile sudies made but intermetallic penetration rate investigations also were carried out. The effect of temperature on intermetallic penetration rate for the A1-Cu system was determined at 11 tsi pressure, held 2 min. Procedure Apparatus: The hot pressing technique was the means of solid state reaction used and required the equipment depicted in Fig. 1. The following procedure was involved: The two metals to be reacted were placed in an aquadag-lubricated 18-4-1 tool steel die, 16 in. high by 1.440 in. ID, between punches of 1.366 in. diam made of the same material. A thermocouple well was located in the die body 3½ in. down from the top of the die, while another well was located centrally in the bottom punch 8½ in. from the bottom of the die. This die assembly was located in three cylindrical ceramic heating furnaces placed in tandem. Each furnace was controlled individually by a Variac power transformer. In turn, the die and furnaces were placed in a water-cooled stainless steel pot which could be evacuated. A cover, which contained a centrally located Wilson seal with an 18-4-1 1 in. diam ram running through it, was bolted on the pot. After sealing, the pot was evacuated by a roughing pump to 200 microns pressure, after which a diffusion pump was used to bring the pressure down to 5 to 15 u. At this pressure, the furnaces were turned on. As soon as they started to heat, out-gassing of the entire unit raised the pressure to 30 to 400 p. By the time the specimens were at temperature ready to be pressed, approximately 4/2 hr, the vacuum pumps had re-established the 5 to 15 u pressure. Once the desired temperature was reached, the required pressure was applied for a predetermined length of time to the 1 in. ram, through to the top punch, and to the specimen. When the time for keeping the specimen under pressure had elapsed, the pressure was released, the energizing coil current turned off, and the assembly allowed to cool. After cooling, the die was removed from the pot and the specimen was ejected. Specimen Preparation: Two different types of specimens were made for this investigation. One was for subsequent tensile testing, while the other was for determination of intermetallic alloy zone penetration into the parent metals. Tensile Bars—Commercially rolled copper pieces in. thick or zirconium sheet pieces 1/32 in. thick and 1.366 in. diam were placed between commercial 2-S aluminum rod 1 in. thick and 1.366 in. diam. This sandwich in turn was slipped into a 2-S aluminum sleeve 1.438 in. OD and 1.370 in. ID. This sleeve lined the couple up and prevented the aquadag lubricant from getting in between either the A1-Cu or Al-Zr interfaces. Immediately prior to the specimen assembly, the copper or zirconium was abraded on the flat surfaces with 320 grit silicon carbide paper, producing clean smooth surfaces. The aluminum was chemically cleaned just before assembly by: l—degrease in acetone, 2—distilled water rinse, 3—immersion for 3 min in 5 pct NaOH at 70" to 80°C, 4—distilled water rinse, 5—immersion for 2 min in 50 pct HNO3 solution at room temperature, 6—distilled water rinse, and 7—drying in a blast of gas. After the A1-Cu sandwiches were hot pressed and ejected, the specimens were machined such that the aluminum sleeve was removed, and the remaining aluminum was then threaded; the bar so produced was tested later for tensile strength. In all the instances where Al-Cu couples were tested, the specimens broke during the test at the Cu-A1 interface and never within the aluminum or copper. The ultimate tensile strength values at times showed considerable scatter for a set of given reaction conditions. Because of this, as many as three to five specimens were made for a particular set of conditions. The trend of the average tensile strengths obtained was not as conclusive as was the trend of the maximum tensile strengths, the latter values being obtained under optimum reaction conditions. Therefore, the values of ultimate tensile strength given herein are maximums.

Jan 1, 1956

By S. Zelouf, G. Simkovich

THE role that impurities play as dopants in the movement of species in ionic and semiconductor crystals was first conclusively demonstrated by Koch and Wagner.&apos; At a later date Wagner demonstrated the effect of small amounts of alloying additions upon oxidation rates of pure metals, i.e., the effect of impurities as dopants in the scale being formed.&apos;

Jan 1, 1970