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By Blake M. Loring, Robert A. Colton

MeltiXg procedures for most metals and alloys usually include some provision for the control of oxygen, since this element frequently has some undesirable effect on the properties of the metal or alloy concerned. In the melting of the various bronzes, this is especially true, since oxygen can be introduced into the melt in a number of ways, most of which are difficult to control. In making bronzes from virgin materials, oxygen is usually present in the commercial grades of copper used; electrolytic fire-refined copper ingots usually contain from 0.02 to 0.05 per cent oxygen. When ingot metal or scrap bronze is used in the charge, oxides are almost always present to some degree. Under certain melting conditions and in certain types of melting equipment the atmosphere over the metal may be highly oxidizing. This, of course, may be desirable in the melting practice used, but is certain to introduce appreciable amounts of oxygen into the melt, and that may not be entirely desirable. From the foundry viewpoint oxygen may have several harmful effects on bronzes. The formation of excessive amounts of oxides may produce drossy metal, which, in turn, means dirty castings and a potentially high rejection rate. It is claimed, too, that oxides in the metal may combine with hydrogen to form steam and thereby produce porosity in certain of the bronzes. The presence of certain refractory oxides, such as SnOz, may be undesirable from the viewpoint of making machining difficult, or as possible stress-raisers in the metal matrix. It is often said that excessive oxide present in the liquid metal makes the metal run sluggishly. Since it appears impractical to try to control the amount of oxygen introduced into the metal beyond taking the economical limit of precaution about charging dirty scrap, it would seem' that control of the oxygen content of the liquid metal offers the most promising approach to this problem. This might be done by using slags, or covers, or by the use of some element or compound added to the melt to remove oxygen preferentially. Most aspects of this problem have been considered and considerable work has been done along these lines. A reconsideration of the problem is indicated, however, by the controversial nature of the evidence at hand, especially on the possibility of using a chemical deoxidizer to control the oxygen content of bronzes. Choice of Deoxidizer The choice of the chemical agent selected as a deoxidizer would naturally depend first on the alloy in which it is to ~he used: in this particular case the alloy is Navy gun metal. In Table. I are listed a group of elements that might be considered as deoxidizers for bronze, with some of their properties that should be considered in

Jan 1, 1946

By C. S. Giggins, F. S. Pettit

The oxidation properties of Ni-Cr alloys with fine grains, coarse grains, and deformed surface layers have been studied at temperatures of 900" and 1100°C in 0.1 atm of oxygen. The oxidation rates of alloys containing between 10 and 30 wt pct Cr have been found to be dependent upon the grain size of the alloy. Finegrained alloys had smaller oxidation rates than coarsegvained alloys because of the selective oxidation of chromium at alloy grain boundaries. In this compositional range alloys with deformed surface layers behaved similar to fine-grained alloys due to recrys-tallization of the deformed surface layer. In the preceding paper1 it was found that during the oxidation of Ni-Cr alloys, the volume fraction of precipitated Cr2O3 could be greater at alloy grain boundaries than at other areas of the alloy surface. In the case of alloys with chromium concentrations equal to or greater than 30 pct,* the volume fraction of Cr2O3 *AIL compositions are given as weight percent unless specified otherwise. precipitated at grain boundaries and within grains on the alloy surface both exceeded the critical amount required for lateral growth of the Cr2O3 particles and the surfaces of these alloys were completely covered with a continuous, external layer of Cr203 during oxidation. However, in the case of alloys with chromium concentrations between approximately 5 to 30 pct, the volume fraction of precipitated Cr2O3 exceeded the critical value required for external scale formation only at grain boundaries.but not within the interior of the grains. Consequently, the surfaces of these alloys had external scales of Cr3O3 over the grain boundaries but internal Cr2O3 subscales with external scales of NiO away from the grain boundaries. Under these latter conditions, it was found that chromium could diffuse laterally in the alloy from those areas covered with an external layer of Cr2O3, i.e., grain boundaries, to areas where the Cr2O3 was present as a subscale. This diffusion of chromium resulted in an increase in the volume fraction of Cr2O3 precipitated in the sub-scale zone and continuous layers of Cr2O3 could be formed at the subscale front in these regions. For the alloys used in the previous studies,' continuous layers of Cr2O3 were formed on Ni-20Cr alloys in the subscale regions after approximately 30 hr of oxidation at 900°C. For shorter periods of oxidation, the Cr2O3 layer was semicontinuous with the continuous portion at the subscale front emanating from points where the Cr2O3 had been formed as an external scale over alloy grain boundaries. Some lateral growth of a Cr2O3 layer in the subscale region was observed on Ni-15Cr and even Ni-10Cr alloys but this layer was never continuous after 30 hr of oxidation. These results indicate that the selective oxidation of chromium in Ni-Cr alloys with chromium contents between 5 to 30 pct may be dependent upon the grain size of the alloy. Fine-grained specimens in this compositional range should have a larger fraction of the surface covered with external Cr2O3 than coarsegrained specimens and the subscale areas required to be sealed via lateral diffusion of chromium should be smaller. It is therefore to be expected that a continuous layer of Cr2O3 can be formed on alloys in this compositional range after short periods of oxidation providing the alloy grain-size is sufficiently small. bo studieS2,3 have established that the oxidation behavior of alloys can be significantly influenced by pretreatments which produce mechanically deformed surfaces. It has been found that deformed surfaces usually promote the selective oxidation of elements in alloys and it is believed that these effects are due to rapid diffusion of elements in the deformed layer. In view of the previous results,' which showed that alloy grain boundaries may play an important role in the selective oxidation of chromium in Ni-Cr alloys, deformed surfaces may promote the selective oxidation of elements in alloys as a result of the numerous grain boundaries formed on the alloy surfaces via recrys-tallization during heating to the oxidation temperature. The purpose of the present studies was to determine the effect of alloy grain size and surface deformation on the selective oxidation of chromium in Ni-Cr alloys at temperatures of 900" and 1100°C in 0.1 atm of oxygen. EXPERIMENTAL The average grain diameter of the alloys used in the previous studies1 was not less than 0.04 mm and alloys with compositions between 5 and 30 pct chromium had average grain diameters between 0.04 and 0.14 mm. Since the oxidation kinetics were already available for these relatively coarse-grained alloys, it was desirable to use these same alloys in the present studies. The surfaces of the alloys listed in Table I of the previous paper were deformed by using a Model F S.S. White Industrial Airbrasive Unit, which delivered a controlled mixture of 25 µ Al2O3 particles in a stream of dry air at high velocity against the surface of a specimen. The amount of surface deformation produced by this treatment was not determined but a re-crystallized layer about 15 µ thick was formed upon annealing deformed specimens. The grain size at the surface of the specimens was reduced to an average grain diameter of 0.01 mm by annealing the deformed specimens, i.e., grit-blasted,

Jan 1, 1970

By Blake M. Loring, Robert A. Colton

MeltiXg procedures for most metals and alloys usually include some provision for the control of oxygen, since this element frequently has some undesirable effect on the properties of the metal or alloy concerned. In the melting of the various bronzes, this is especially true, since oxygen can be introduced into the melt in a number of ways, most of which are difficult to control. In making bronzes from virgin materials, oxygen is usually present in the commercial grades of copper used; electrolytic fire-refined copper ingots usually contain from 0.02 to 0.05 per cent oxygen. When ingot metal or scrap bronze is used in the charge, oxides are almost always present to some degree. Under certain melting conditions and in certain types of melting equipment the atmosphere over the metal may be highly oxidizing. This, of course, may be desirable in the melting practice used, but is certain to introduce appreciable amounts of oxygen into the melt, and that may not be entirely desirable. From the foundry viewpoint oxygen may have several harmful effects on bronzes. The formation of excessive amounts of oxides may produce drossy metal, which, in turn, means dirty castings and a potentially high rejection rate. It is claimed, too, that oxides in the metal may combine with hydrogen to form steam and thereby produce porosity in certain of the bronzes. The presence of certain refractory oxides, such as SnOz, may be undesirable from the viewpoint of making machining difficult, or as possible stress-raisers in the metal matrix. It is often said that excessive oxide present in the liquid metal makes the metal run sluggishly. Since it appears impractical to try to control the amount of oxygen introduced into the metal beyond taking the economical limit of precaution about charging dirty scrap, it would seem' that control of the oxygen content of the liquid metal offers the most promising approach to this problem. This might be done by using slags, or covers, or by the use of some element or compound added to the melt to remove oxygen preferentially. Most aspects of this problem have been considered and considerable work has been done along these lines. A reconsideration of the problem is indicated, however, by the controversial nature of the evidence at hand, especially on the possibility of using a chemical deoxidizer to control the oxygen content of bronzes. Choice of Deoxidizer The choice of the chemical agent selected as a deoxidizer would naturally depend first on the alloy in which it is to ~he used: in this particular case the alloy is Navy gun metal. In Table. I are listed a group of elements that might be considered as deoxidizers for bronze, with some of their properties that should be considered in

Jan 1, 1946

By P. M. Kelly, E. P. Butler

The stability of a 70/30 Mn-Cu alloy aged to peak damping has been investigated using electron microscopy, X-ray diffraction, and torsional pendulum measurements. Storage at room temperature or at 100" C causes a reduction in damping capacity. This is shown to be due to the formation of subdomains which "lock" the main domain structure and so hinder their movement. After storage the damping capacity can be restored by a retransformation treatment, which generates structures identical to those found in newly aged specimens. Plastic deformation by rolling also causes a decrease in damping capacity. In this case the damping capacity can only be restored by retransformation if the amount of deformation is less than about 5 pct. THE general metallography and structure of these high damping capacity alloys has been discussed in Part I of this work.1 Part II deals with some of the variables that affect the damping capacity. In particular, the stability of the damping capacity of a 70/30 alloy aged for 2 hr at 425° C and quenched has been investigated. The temperature sensitivity of the damping capacity of a 70/30 alloy aged for 2 hr at 450° C has been reported by Birchon.2 The damping capacity begins to decrease with increasing temperature, and is very low above the M, temperature of 125°C. The cubic — tetragonal transformation is completely reversible and there is no apparent thermal hysteresis associated with the change in damping capacity. Another important effect was first reported by Dean and his coworkers.3 They noticed a decrease in the damping capacity with time for specimens of a quenched tetragonal alloy. More recently workers at the Admiralty Materials Laboratory 4 have studied the stability of an aged 70/30 alloy. They found that the damping capacity decreased to half its original value after about 1000 hr at room temperature. EXPERIMENTAL The techniques used for electron microscopy and X-ray diffraction have been described in Part I. The damping capacity was measured by means of a torsional pendulum, using rectangular specimens, 3 by 0.3 mm with a 6 cm gage length. The specific damping capacity, S.D.C., was calculated as a percent amplitude decay in free vibrations over 10 cycles, starting at an amplitude which corresponded to a 700 psi surface shear stress. Because of the stress dependence of the damping,' the values obtained were about a third those reported for a 5000 psi surface shear stress.' RESULTS a) Effect of Aging Temperature. The effect of aging temperature on the damping capacity is shown in Fig. 1. The damping capacity reaches a peak of 12 pct after aging at 400° to 425°C) then begins to decrease as the volume fraction of a Mn increases. At higher aging temperatures the structure becomes cubic again with a low damping capacity. b) Stability of the Aged Structure. The damping capacity of the aged alloy decreases with time at room temperature. This process could be accelerated by storing at 100°C, when about 100 hr were required for the damping to fall to half its original value. The results of room temperature and 100°C storage, for times up to 1000 hr, are shown in Fig. 2. The damping capacity starts to decrease after about 24 hr at 18° C and 1 to 2 hr at 100°C. It was found, however, that the damping could be almost completely restored by retransformation. The specimens were held at a temperature above the M, for a short time, 250° C for 5 min, and then quenched. The values of damping capacity for specimens that were aged, stored, and then retransformed are shown by the full points in Fig. 2. X-ray measurements of the c/a ratio and hardness readings on the specimens did

Jan 1, 1969

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

In an earlier paper1 measurements of contact angles due to the effect of xanthates on mineral surfaces were reported. The solutions in which these measurements were made differed widely from those of modern flotation circuits. It is intended, however, by introducing, one at a time, the other principal reagents of flotation, to approach gradually the solution composition of flotation liquors. The work now described is an attempt to determine the effect of one of the most important of these reagents—namely, sodium cyanide—on the establishment of air-mineral contact. The work has been carried out for the following companies: Broken Hill South, North Broken Hill, Zinc Corporation, Electrolytic Zinc of Australasia, Mount Lyell Mining and Railway, and Burma Corporation. Since the effect of cyanide is inseparably connected with the alkalinity, the results cited below deal with the mutual effects of alkalis and cyanide. Alkalis alone exert a significant effect on the air-mineral contact but comparatively large amounts are required. Since the addition of a small amount of cyanide greatly decreases the degree of alkalinity necessary for the suppression of contact at surfaces of any of the minerals experimented with (except galena) and since alkalis are rarely used alone in practice, little attention has been paid to cyanide-free solutions. It was shown in the previous paper that, excluding the dixanthogen effect, whenever contact was practicable at all in an ethyl xanthate solution the angle of contact was 60". There is, therefore, less necessity to measure equilibrium contact angles; in fact, the experiments herein described have generally been conducted with a view to determining whether contact is possible and not to measuring the actual value of the contact angle. The separations which have generally to be effected in dealing with complex sulfide ores are: (1) galena from sphalerite, pyrite, etc.; (2) sphalerite from pyrite and/or gangue minerals; (3) copper minerals from pyrite and gangue minerals; (4) pyrite from gangue minerals; (5) chal-

Jan 1, 1935

By H. D. Hoskold

It was not for the purpose of asserting any superior knowledge or authority, but simply of clearing up, in greater detail, some points casually mentioned in Mr. Scott's able paper, that the writer entered, some two years ago, into the discussion which that paper initiated. In such matters there is always room for differences of judgment, as well as for additional data, which may modify or complete the conclusions even of the best authorities. Those who are immersed in the duties of practical administration or work in the field, and who, being remote from the great scientific national libraries, are obliged to rely on their private collections, and to supplement them by their recollections of earlier studies, labor under special disadvantages in such a discussion; and it must be to the scientific and engineering world a matter for gratitude that Mr. Lyman has been willing to give the benefit of his advantages in this respect. Mr. Lyman would, however, doubtless at once disclaim the conclusion that his masterly summary constitutes " the last word " on this subject, and welcome further evidence, comment and criticism, such as the various contributors may continue to offer. This, therefore, is the motive, and must be the excuse, of the introduction by the writer of the following observations. The Miners' Dial.—Many years since, the writer employed a miners' dial, older in type than Fig. 12,* but without any attached spirit-level, made by Thomas Jones, a pupil of the great Ramsden. Jones was one of the old London makers and opticians, and enjoyed great reputation for accuracy in the con-

Jan 1, 1902

By F. H. Wilson

Copper base alloys containing various amounts of aluminum and silicon are of considerable commercial interest. In particular the alloy containing 7 pct aluminum and 2 pet silicon shows an attractive combination of high strength with excellent, machinability. Since there is no evidence ill the literature that this ternary system has been studied since the recognition by Smith1 and Anderson2 in 1939 of the kappa phase of the binary copper-silicon system, the determination of the equilibrium phase relationships in the copper corner of the ternary diagram has been undertaken to provide a fundamental basis for understanding the behavior of these alloys. Phase boundaries have been determined by the micrographic examination of quenched samples while points on the liquidus surface have been obtained by thermal analysis. The results, of sufficient precision to serve their major purpose of providing a guide for the control of the manufacture of alloys in the region covered, are presented in a series of both isothermal and vertical sections of the diagram. Alloys StVdied For a rough survey of the copper corner of this ternary system the compositions listed in Table I (Series A) were employed. The results of examinations of these alloys indicated that the compositions listed in Table 2 (Series B) would further clarify regions of greater complexity. All alloys were prepared as 1200 g heats, the copper being melted under charcoal, and then first silicon and then aluminum were added. An excess of 0.05 pet silicon was allowed to cover deoxidation losses. Two small bars 5/8 by 1 1/4 by 5 1/4 in. were cast using Durville type casting equipment. Ailalyses were made on all alloys using material which was hot-rolled at 800 or 850°C and annealed 17 hr at 650°C. All analyses were found to be within 0.05 pet of the nominal composition. Since the precision of analysis is not much better than this, the points of both isothermal sections and vertical sections at fixed aluminum and silicon contents have been plotted at the compositions indicated by the nominal composition.

Jan 1, 1949

By H. S. Martin

The Phosphate Recovery Corporation operates three flotation plants, Nos. 1 and 2 concentrators about three miles northeast of Mulberry, Florida, and No. 3 plant at Wales, Tennessee. These plants represent the first commercial phosphate flotation operation and are also believed to be the largest nonmetallic flotation operation in the world at the present time. The details of this paper will be confined to plant No. 2, this being the newest and largest concentrator in Florida, and the flow sheet being practically the same as at plant No. 1. The No. 3 plant has been operated but a short time and has been shut down since December, 1932, on account of the decrease in phosphate rock production. The phosphate washers usually are located centrally on a known deposit so that about two hundred acres of ground can be mined economically to each washer location. The washers are moved to new areas when the distance becomes too great for economical pumping. The flotation plants are built either adjacent to a washer, so that current debris may be utilized, or on the site of a former washer where there is sufficient accumulated debris available for mining, and the flotation plants must also be moved from time to time. Most of the water used in the Florida flotation plants is recovered after passing through a circulating system where most of the fine suspended matter is settled out, but some make-up water is obtained from deep wells near the plant. Power is obtained from the Tampa Electric Co. through the distribution facilities of the International Agricultural Corporation. Flotation concentrate is hauled from the plant by trolley over the International Agricultural Corporation's trolley system, to the drying plant at Prairie, one mile northwest of Mulberry. Ore Treated In the pebble phosphate district of Florida, the phosphate mineral, or collophane, is usually found in horizontal beds of varying thickness

Jan 1, 1935

By Z. E. Arlin, R. D. Lynn

A deep well injection system is used by The Anaconda Co. for the disposal of uranium mill tailing water near Grants, N. M. A 2511-ft hole was cored and tested through Triassic, Permian, and Pennsylvanian (?) sediments and bottomed in Precambrian granite gneiss. The disposal well was plugged back to 1830 ft and completed in 563 ft of sandstones in the Yeso formation. The reservoir sandstones contain water similar to the injected waste water, and are isolated from overlying fresh-water aquifers by an evaporite barrier zone. Mill tailing water is decanted, filtered, and introduced into the well by gravity at an average rate of 400 gpm. The reservoir has a life expectancy of 10 years. The Anaconda Co. began uranium milling operations near Grants, N. M. in 1953 with a small mill that processed limestone ores. A larger second mill was built in 1955 to treat sandstone ores. In 1956 it became apparent that a large tailing pond would be required to contain the increased discharge of mill waste water. Research was begun on supplementary methods of disposal by which a minimal pond size could be maintained to avert excessive seepage losses. An intensive sampling program was begun to monitor the fresh-water wells in the area. The original limestone mill ceased operation in 1959. The present mill treats sandstone ores by sulfuric acid leach and a resin-in-pulp ion exchange recovery circuit that uses chloride elution. Process waste water is discharged to a tailing pond where, after evaporation losses, an annual average of about 400 gpm are available for injection into the disposal well. The waste water is a mildly acid solution that contains large amounts of manganese, iron, and the sulfate and chloride salts of sodium, calcium, and magnesium. It is a low-level radioactive fluid that contains small amounts of Uranium-natural, Thorium-230, and Radium-226. The average chemical and radioactive analyses of the waste water injected into the disposal well are shown in Column B of Table I. Disposal of the excess mill waste water by deep well injection was investigated after extensive research had proved that alternate methods were not satisfactory. A study of the regional geology and hydrology indicated that a disposal well was feasible, and a test well to basement rock was planned. Tentative plans for the test well and the results of the geologic and hydrologic studies were submitted to the New Mexico Dept. of Public Health, the New Mexico State Engineer's Office, the U.S. Atomic

Jan 1, 1962

By Charles S. Barrett, Frederick N. Rhines, Robert F. Mehl

The solid solutions which aluminum forms with copper, and with magnesium and silicon, are not extensive, and accordingly could not be expected to form Widmanstatten figures profusely nor with great ease. A study of the Widmanstatten figures in these systems seemed desirable, however, because of the interest which these alloys bear towards age-hardening theories resulting from the necessary relationship between the age-hardening phenomena and the atomic processes leading to the formation of Widmanstatten figures.' Alloys of Aluminum with Copper The most accurate determination of the solid solubi1it.y of copper in aluminum seems to be that by Dix and Richardsoq2 whose results are represented in Fig. 1. According to this work, aluminum dissolves 5.6 weight per cent of copper at 548", and less than one per cent at room temperature. Judging from the constitutional diagram, this solid solu-lion on cooling tends to precipitate the compound CuA12, and this conclusion has been confirmed experimentally by Schmid and Wassermann.

Jan 1, 1932

By P. J. Ehret

By and large, I agree with many of the precepts discussed in the Saperstein paper. I believe there is much more that can be done on the local level to involve both government and planning in the mine permit review process. Admittedly, much can be done to improve discussion between the state regulatory authority, local authorities, and mine operators. However, I strongly disagree, as suggested in the paper's conclusion, that such a system, as outlined in Saperstein's paper, could result in a reduction of review time or a lowering in the cost of permitting. The implementation of such a system by its very nature would only add a new level of bureaucracy to an already cumbersome process. This system, in my opinion, would only add to the cost of permitting and the time necessary to obtain a permit. Admittedly, it would achieve the result of adding local influence into the permitting process, but at what off-setting cost? It has been my professional first-hand experience and observation in the permitting and lands unsuitable processes to note that under the present system, local governments that do feel they have a stake in local mines and actively advocate their position (not simply comment), have had significant input into the conduct of mining and reclamation plans in their areas. Mining companies that mine in these areas are aware of local interests and attitudes, and do consider them in their plans. Simply put, local governments that want to get involved and want to play significant roles can and do. Those that do not advocate a position or have no input to offer do not. Although the present system is not as direct in effect in regard to local control as Saperstein's, it does work. It does so without the red tape that would result from developing miniature regulatory authorities in every county in which mining occurs. Although local input is important, there are many more sections of the Surface Mining Control and Reclamation Act (SMCRA) than Sections 508(a)(8) and 522(a)(3)(A) that also are important. It appears Saperstein's paper may overindulge these sections. An additional specific comment is made in regard to the statement that while local areas benefit from mining (wages, salaries, and purchases), they also endure environmental deterioration caused by mining affects. It is believed that the whole purpose for which SMCRA and its resulting regulations were enacted and developed was so mining would not be permitted if significant environmental deterioration could occur. Therefore, it could be argued that this point under current law is moot.

Jan 1, 1985

By Laurence Pellier

Electron microscopical studies were made of the effect of sensitization at 1200oF on a Type-.104 stainless steel with high carbon and low nitrogen and oxygen contents, after solution annealing and after cold working. The loci of the carbide precipitates in the early stages of sensitization were followed in dry stripped plastic replicas. Some observations were made by direct electron transmission on thinned films. Intragranular dislocations showed a high degree of stability through the annealing necessary to produce sensitization. I HE present work was undertaken to determine the effect of sensitization, at 1200°F, for 1/2 hr, on the electron microstructure of a Type-304 stainless steel with high carbon, and low nitrogen and oxygen contents, after solution annealing and after cold working. Many electron microscopical studies of sensitization of 18-8 stainless steels have already been made. Most of them utilized extraction replicas, from which the morphology and composition of the precipitated carbides could be established.'-" ry stripped replicas were seldom used for such studies, although it was demonstrated that they are applicable, in general, to EurveYs of the general microstructure of many alloys' and, in particular, to the observation of precipitated carbides in austenitic stainless steels.3

Jan 1, 1963

By M. Mills, M. W. Clegg

This Paper Presents an approximate analytical solution to the problem of the pressure distributions arising from the production of a compressible liquid in a partially penetrating well. The limits of validity of the approximation are discussed and it is shown that the basic approximation is the same as that used in previous numerical of the problem. The variation in pressure at the production well with time for different penetration ratios is investigated and is shown to agree with previous work. The solutiOns are used to assess the effects of partial penetration at large distances from the well and at the wellbore itself. In the latter case the effects of anisotropy are also studied for constant, but unequal, horizontal and vertical permeabilities. It is 'uggested that measurements of the Pressure drawdown below the producing interval in a well should give some indication of a thickness-vertical permeability product for the formation; this would chmacterize the effectiveness of the formation below the producing interval. INTRODUCTION In many oil and gas reservoirs the producing wells are completed as partially penetrating wells; that is, only a portion of the pay zone is perforated. This may be done for a variety of reasons, but the most common one is to prevent or delay the intrusion of unwanted fluids into the wellbore. This paper studies the effects of partial penetration on the pressure distribution resulting from the production of a compressible liquid at a constant rate. To simplify the mathematical analysis the case of a single well located in an infinite reservoir of constant thickness is considered, and it is assumed that this well is perforated over an interval adjacent to the upper (or lower) impermeable boundary of the formation. A well producing from an arbitrary interval within the bulk of the formation could be treated in a similar way, but this action would merely add to the complexities of the solution and contribute little to the appreciation of the over-all effects of partial penetration. In a recently published paper by Odeh,10 the more general problem of producing from an arbitrary interval within the pay zone was studied for the quasi-steady state flow of a compressible liquid, This is the case in which there is a a potential at the outer boundary and a constant flux across the same boundary. This contrasts with the problem studied here, which is concerned with the nonsteady-state behavior in an infinite reservoir. The exact solution of the partial penetration problem presents great analytical problems because the boundary conditions that solutions of the partial differential equations must satisfy are mixed; i.e., on one of the boundaries the pressure is specified on one portion and the flux on the other. This difficulty occurs at the wellbore, for the flux over the nonproductive section of the well is zero, and the potential over the perforated interval must be constant. In the case of constant rate production from the well, this uniform potential is time dependent and unknown, and the additional condition that where hl is the thickness of the perforated interval, must also b'e satisfied. This problem may be overcome in the case of constant rate production by making the assumption that the flux into the well is uniform over the entire perforated interval, so that on the wellbore the flux is specified over the total formation thickness. This approximation naturally leads to an error in the solution since the potential (pressure) will not

Jan 1, 1970

By K. C. Strebig, C. W. Schultz, A. A. Selim

The effect of some organic additives in diamond drilling of quartzite was investigated in the laboratory. The drill was designed to measure the rate of penetration, the thrust, and the torque and to record each as a function of the distance drilled. A statistical plan was followed throughout the investigation and an equation representing the bit performance was derived from the mathematical theory of reliability. The drilling torque was found to increase with the use of additives while the sliding coefficient of friction and the wear coefficient decreased. The energy per unit volume consumed was found to increase with the use of additives. A hypothesis explaining the effects achieved with the additives is given. INTRODUCTION For some time researchers have attempted to increase drilling efficiency by adding certain agents to the flushing medium. Much of this interest is the result of the observations of Rehbinder, Shreiner and Zhigach1 They postulated that "...in processes for the mechanical destruction of solids, a region of increased crack formation is created in the deformed layers adjoining that surface of destruction, forming the predestmction zone. The surrounding medium (for example, a liquid) which wets a given solid will penetrate the embryo microcracks of the predestruc-tion zone. Increasing the molecular affinity of this liquid for the surface of the solid considerably facilitates the deformation and destruction by softening the solid in the zone of increased crack formation. In this manner, the hardness or strength of the deformed body is decreased by the influence of the penetration of the liquid into the predestraction zone." This is known as the "Rehbinder effect". Rehbinder's work has prompted many investigators to examine the effect of additives on the mechanical destruction of rocks. Engelmann, Terichow and Selim reported that the maximum penetration of the rock by a diamond point in a solution environment was at the isoelectric point of the solution.* Robinson reported that his results did not appear to support the theory of Rehbinder.3 Joris and .McLaren suggested that additives with surface tension lower than water will be more efficient in cooling the diamonds.4 Their effectiveness in removing the fine cuttings from the face of the bit will also improve the efficiency of the system. They reported an improvement in impregnated bit life and penetration rates with the use of soluble oil additives. In contrast, Long and Agnew, drilling with surface set bits, reported that lubricating agents increase bit temperature and wear.5 A significant change was reported6 in the mechanical properties of rock with polar additives. It was concluded that this change in the mechanical properties of the rock in the presence of the additive is due to the rock hydrophilic properties. Ethylene glycol, glycerine and anionic detergent were selected for this investigation because their surface tension is lower than that of water. The surface tension of these additives for the concentrations studied was 42 to 75 percent of the surface tension of water. A low surface tension additive would wet the surface of the diamonds more easily and hence would be more effective in cooling the diamonds. Another characteristic of these low surface tension additives is their effectiveness in removing the cuttings and preventing the flocculation of the formed particles in the drilling process. This article summarizes the results of an investigation performed at the laboratories of USBM, Twin Cities Mining Research Center. The objective of the investigation was to study the over-all effects of some organic additives on the performance of diamond impregnated bits in atmospheric drilling conditions only and not in downhole pressured conditions.

Jan 1, 1970

By J. H. Moran, E. E. Finklea

The pressure build-up technique is a recognized method of determining permeability from conventional drillstem tests. In this paper an effort is made to extend such techniques to the interpretation of data obtained from the wireline formation tester. Such a study is necessary because of the differences, for this case, in the magnitude of the flow parameters (rate of flow, amount of recovered fluids) and in the flow geometry (flow through a perforation vs flow across the face of the wellbore, etc.) involved in the solution of the equations of flow for compressible fluids. The perforation is replaced by a spherical hole, and the effect of the borehole is neglected, so that the flow can be considered to be radial in a spherical co-ordinate system. Arguments are presented to justify this idealization. Assuming single-phase flow, general relations between pressure and flow rate are developed for a homogeneous medium. The study is then extended to permeable beds of finite thickness. It is shown that the early stages of pressure build-up tend towards spherical flow, while the later stages tend towards cylindrical flow. The thinner the bed, the more quickly flow approaches the cylindrical model. The prevalence of thin beds in practical work makes this analysis quite important. Cases involving permeability anisotropy are treated. INTRODUCTION From wireline formation tester operation, two types of data are obtained: (1) the nature and amount of recovered fluids, and (2) the pressure history recorded during the test. A number of papers have been written dealing with the interpretation of formation production on the basis of the recovered fluids.'.' In general, the methods described have been quite accurate for both high- and low-permeability formations. The present paper will deal with an analysis of the pressures observed. An analysis of the pressure build-up curves obtained in hard-rock country has already been attempted on the basis of the formula proposed by Hor-ner. Although this approach has met with success in many instances, some questions have been raised as to its validity. It is the aim of the present study to place the analysis of pressure build-up in the formation tester on a firmer basis, from which more detailed methods of interpretation can evolve. Because of the great differences between the operation of the wireline formation tester and the conventional drillstem test, modifications are necessary in the interpretation. The major difference relates to the flow geometry. Once the flow geometry has been established other features such as multiphase flow, skin effect, afterflow, etc., well described in the literature, can be introduced. It will be assumed that the mechanical operation of the formation tester is already known to the reader.6 t will suffice here merely to state that the tester provides the means for taking a relatively small sample of the fluid immediately adjacent to the borehole, and for recording the subsequent pressure response. In comparison with conventional drillstem tests, the time required for a satisfactory pressure build-up response is much shorter, because of the relatively small quantity of fluid withdrawn by the wireline tester. This feature is highly desirable in the case of low-permeability formations. For an analysis of the pressure response within the formation, three simple flow geometries are considered— linear, cylindrical and spherical. The spherical and cylindrical flow geometries are most pertinent to the formation tester; therefore, they will receive the major emphasis. Since the configuration of the borehole and the perforation made by the tester complicate the flow geometry, it is necessary to allow for them in the drawdown response. However, because of the volume of formations contributing to the pressure-response, the details of the perforation shape are unimportant in the build-up period. Since relatively small amounts of fluid are withdrawn from the formation, in contrast to a conventional drill-stem test, a study of the "depth of investigation" and the significance of drawdown as well as build-up data will be included. Because the "depth of investigation" will be shown to be rather large, the effect on the build-up curves of the finite thickness of the permeable bed is considered. It is this consideration that leads to the importance of cylindrical flow geometry. Also included is a discussion of permeability anisotropy and its effect on the interpretation of the tester results. The pressure curves recorded by the formation tester will follow two general patterns, depending upon whether the formation is of high or low permeability. Fig. I (a and b) schematically illustrates these two responses. In Fig. 1(a), the high pressure recorded during fill-up of the tool is essentially the pressure differential across the choke in the system. In Fig. l(b), the flow rate is

By H. E. Cline

A criterion for stability of a lamellar structure in two-phase alloys ulas derived froflr perturbation analysis of the steady-state solutions for eutectic growth. Both the mass and thermal diffusion were considered with boundary conditions for coupled lamellar growth. The concept of an effective liquidus slope was introduced. Excellent agreement was found with the experiments of Mollard and Flemings and the theory predicted a range of compositions on one side of the eulectic composition in which stable growth may occur with zero temperature gradient. The lamellar structure was found to be more stable than predicted by simple constitutional supercooling. The effect of impurity additions was also considered. DIRECTIONALLY solidified eutectic alloys may have a structure consisting of parallel plates or rods. It is important to know the range of composition and growth conditions that produce this ideal composite structure. Breakdown of the planar solid-liquid interface during growth may lead to a dendritic or cellular structure as in single-phase alloys. In the case of single-phase alloys, the concept of constitutional supercooling1 may explain breakdown, but in two-phase alloys the concept is no longer valid because the melting point is not given by the liquidus of one phase. Both phases must be considered in the mass and thermal diffusion problem. In the following theory a boundary condition at the solid-liquid interface was determined by using the steady-state equations of Jackson and ~unt' to relate the average temperature and composition of the liquid at the interface. Then a sinusoidal perturbation in the shape of the interface was introduced to test for stability as in the analysis of Mullins and ~ekerka.~ The wavelength of the important perturbation was assumed to be much larger than the lamellar spacing, h, and the perturbation was assumed not to change the lamellar spacing, A. Both the mass and thermal diffusion equation were used with averaged quantities at the boundary to determine whether the perturbation grows or shrinks in time. A stability criterion was determined by considering the case in which the perturbation remains stationary. An example of Pb-Sn alloys was used to illustrate the validity of this theory. I) THEORY A) Temperature at the Interface. The temperature of the interface in coupled two-phase growth is close to the eutectic temperature TE even for alloys off eutectic composition. It is assumed that the interface is in local equilibrium and one expects the temperature at the intersection of the liquid phase and the solid phases a and 0 to be near the eutectic temperature. The interface is undercooled because of curvature and the deviation of the composition in the liquid from the eutectic composition. The average interface temperature Ti for steady-state growth of a lamellar eutectic with a plane interface was determined by Jackson and Hunt' as given in their Eq. [17c]. Instead of using the ratio of the lamellar widths hp/h, as a parameter, the volume fraction of the 0 phase, +, will be used as it simplifies the algebra. The average interface temperature using this notation becomes: The average temperature of the interface depends on the volume fraction of the 0 phase, +, which may be related to the composition of the solid or the bulk composition of the liquid Co by: where C, and Cp are the average compositions of the solid phases. In steady-state growth, the composition of the solid is equal to the composition in the liquid far from the interface. The variation of the average interface temperature with composition is illustrated in Fig. 1 for the case of Pb-Sn alloys with a 10"4 cm lamellar spacing as calculated from Eqs. [I] and [2]. The interface temperature goes through a maximum at a composition near but not exactly at the eutectic composition. There is no reason why the composition corresponding to the maximum temperature should be equal to the eutectic

Jan 1, 1969

By Dale Nix

DuRing the past year approximately 400 depth pressures have been recorded in the Yates field. Of these, 315 were "shut-in depth pressures," observed for the purpose of adjusting well potentials without making open-flow tests. The "shut-in depth pressures" were distributed one to each well and determined under as nearly uniform conditions as possible. Therefore, there is a scarcity of data applicable to production problems, other than the adjusting of well potentials. A few of the data obtained have been used in an attempt to solve some of the producing problems. These applications, however, merely indicate partial solutions and their review herein is to emphasize the variety of problems to which depth-pressure data can be applied, rather than to present conclusive solutions. Very little had been accomplished in the development of instruments to determine pressures within the well bore, when it was decided to obtain such information in the Yates field. Through the combined efforts of the Yates Engineering Committee and several producing companies, three methods of determining pressures in the well bore were soon developed: (1) the "compressor" method, (2) the "volume chamber" method, (3) the "depth-pressure recorder" method. "Compressor" Method.—A small volume compressor is used to inject gas into the tubing. The rate of injection is low so that the frictional losses will be reduced to a minimum. During the test, the pressures at the top of the tubing and casing are observed on recording pressure gages. .As the compressed gas depresses the fluid in the tubing, the pressure on the casing decreases while the tubing pressure increases. The tubing pressure becomes a maximum when the fluid level reaches the bottom of the tubing; and the casing pressure usually rises quickly as the gas breaks around the bottom of the tubing. The sum of the maximum pressure recorded at the top of the tubing and the pressure exerted by the weight of the compressed gas column is equal to the depth pressure at the bottom of the tubing. The procedure can be reversed;

Jan 1, 1932

By Anton Sawatzky, Erich Vogt

By means of mathematical solutions to the appropriate diffusion equations, we describe the kinetics of the thermal diffusion of hydrogen in Zircaloy-2 for the various temperatures and concentrations encountered in a heavy water moderated reactor. When the hydrogen concentration is below terminal solid solubility only the a Phase is present. Redistributions are then described in terms of the characteristic functions of the difhsion equation. For higher concentrations both the a and 6 phases are present. We assume the two phases to be always in equilibrium. For moderately small hydrogen concentrations exact solutions of the two-phase equation approach the the approximate solutions derived by Sawatzky and for all concentrations the exact solutions exhibit the qualitative features of his result: the two-phase concentration increases with time, everywhere; in the absence of a hydrogen current at the hot end of the sample an a-phase region always exists there; the interface of the a + 6 , a-phase boundary moves toward the cold md of the sample and the hydrogen concentration is discontinuous at the interface. Simultaneous solulions of the a and a + 6 hydrogen distributims and of the concomitant interface motion are obtained and compared to the observations of Sawatzky and Markowitz. The kinetics of the hydrogen diffusion process are shown to lead to m apparent heat of transport of the a phase which is lower than the actual value (even for samples with long anneals) thus resolving at least partially the disparity between experimental measurements of this quantity. A number of recent papers1"4 have reported measurements on the diffusion and redistribution of hydrogen in Zircaloy-2 under temperature and concentration gradients. These studies were instigated by problems arising from increasing use of Zircaloy-2 as a fuel element cladding material in pressurized-water power-reactors. The Zircaloy-2 picks up hydrogen during the operation of the reactor: the consequent precipitation of zirconium hydride in the Zircaloy-2 has pronounced effects on its mechanical properties. The Purpose of the present Paper is to describe the kinetics of the thermal diffusion of hydrogen in Zircaloy-2 for the various hydrogen concentrations and temperatures likely to be encountered in reactors. When the hydrogen in the Zircaloy-2 is entirely in the solid solution phase (a phase), the differential equation for thermal diffusion is well known and the redistribution can be described by standard mathematical methods some of which are given in Section 11 below. The treatment of the a + 6 (hydride) region differs from the earlier treatment of sawatzky3 by taking into account several modifications of the two-phase diffusion equations as suggested to us by Markowitz4 and Kidson.5 Even with the modifications the results obtained in our more complete treatment are substantially the same as those found by Sawatzky. As we show, the difference between the results of sawatzky3 and kIarkowitz4 is largely due to the difference in the geometry of their experiments. In the next section we derive the modified two-phase equation for arbitrary geometry. The exact solution of this equation is given in Section III for linear and cylindrical geometry. It is shown that Sawatzky's approximate solution is quite accurate for almost all the temperatures and hydrogen concentrations which are actually encountered. In Sawatzky's approximate theory the hydrogen concentration everywhere in the two-phase region increases continuously. As his paper pointed out, this result, together with hydrogen conservation, implies that in a sample with no hydrogen current flowing into the hot end a two-phase region is always accompanied by a single-phase region at the hot end of the sample. The net hydrogen gain in the two-phase region is supplied by the decrease of hydrogen in the single-phase region and by the movement of the (a, a + 6) boundary toward the cold end of the sample. Hydrogen conservation at the (a, a + 6) boundary leads to a discontinuity in the concentration and its derivative there. In Section IV it is shown how these qualitative features of the thermal diffusion kinetics arise from the simultaneous solution of the a-phase differential equation and a + 6 phase equation. Methods derived by us previously for the solution of the redistribution in both phases and the accompanying motion of the boundary are used to obtain approximate solutions valid for large times. The solutions account well for the observed redistributions of Sawatzky and Markowitz. It is shown how the continuing motion of the (a, a + 6) boundary leads to measured values of the heat of transport lower than the actual value, even for specimens with relatively long anneals.

Jan 1, 1963

By Robert W. Hunt

HAVING devoted considerable time to the investigation of the Clapp-Griffiths converter and the metal produced in it, it may perhaps be of interest to the Institute to learn the conclusions which I have formed. Of course, it is well known that the stationary converter of small size is the very oldest type of vessel used in the pneumatic process. Hence it will be only necessary to call your attention to the points which are special features of the Clapp-Griffiths. This converter has a slag tap-hole, situated at such a height in relation to the metal under treatment that, when the cinder is formed and boils up as the blow progresses, it can run off and thus be removed from contact with the iron, and will also be out of the way when the decarbonized metal is tapped into the casting ladle and the manganiferous alloy added. The manner of shutting off the blast, when the process is completed and the metal is being tapped, is another distinctive feature. The tuyeres are situated around the sides of the vessel, and enter the interior some little distance above the bottom; they are provided with plugs through the centers of which there are small openings. When the blow is completed, these plugs are forced forward into the outer orifices of the tuyeres, thus shutting off the blast, excepting the small quantity' entering through the passages named. While this is sufficient to keep the metal from running into the tuyeres, it reduces to the minimum the action of the blast while the metal is being tapped. Of course, this is of great importance, as in an ordinary stationary converter any delay in getting open the tap-hole means overblowing, and even while the first part of the charge is running out the oxidation is in frill force. Duplicate or movable bottoms are used, thus more than doubling the possible output of the plant. The pressure of' blast is quite light, never ex-

Jan 1, 1885

By H. C. Gatos, A. D. Kurtz

WITH the growing interest in the mechanism of self-diffusion of metals, the study of accurate and convenient methods for determining self-diffu-sion coefficients appears highly desirable. It was with this objective in mind that the present investigation was undertaken. Gatos and Azzam1 employed an autoradiographic technique for measuring self-diffusion coefficients of gold. This method involved sectioning of the specimen through the diffusion zone and recording the radioactivity directly on a photographic film. Because of the very short range of the emitted ß rays in gold, the activity recorded on the film was essentially the true surface activity. With proper choice of the sectioning angle, sufficient resolution could be obtained and the entire concentration-distance curve recorded in one measurement. For the boundary conditions of the experiment, where an infinitesimally thin layer of radioactive material diffuses in positive and negative directions into the end faces of a rod of infinite length, the solution of the diffusion equation is C/Cn = 1/v4pDt exp (-x2/4Dt) where C is the concentration of diffusing element (photographic density in this case), C,, is the constant (depending upon amount of radioactive material), x is the diffusion distance, D is the diffusion coefficient, and t is the time. Thus, by plotting the logarithm of the concentration vs the square of the diffusion distance, a straight line results and the slope contains the diffusion coefficient. In this manner, the self-diffusion coefficient of gold can be obtained as a function of temperature. In the present investigation the results reported by Gatos and Azzam1 have been verified, and the autoradiographic technique has been further developed and applied for the determination of the self-diffusion coefficient of gold at a number of temperatures. Furthermore, the energy of activation for the self-diffusion of gold has been conveniently determined. . Experimental Techniques Preparation of Specimens: The inert gold of high purity was received in the form of a rod from which cylinders were cut and machined to a diameter of 0.500 in. The specimens were annealed to a suitably large grain size and the faces were surface ground prior to the deposition of the radioactive layer. The radioactive isotope Au198 was chosen. It was produced in the Brookhaven pile by means of the reaction Au197 + n ? Au108. It decays by ß emission (0.96 mev) to Hg108 with the subsequent emission of a y ray (0.41 mev). 70Au 108 ? 80Hg 108 + -1e°. The half life of the Au108 is 2.7 days so that a strict time schedule had to be maintained in order to secure sufficient activity until the end of the experiments. For this reason, initial activities as high as 10,000 millicuries per gram were used. The gold arrived in the form of foil and was evaporated onto one face of each gold specimen cylinder to a thickness of about 100A. A sandwich-type specimen was formed by welding two such cylinders together. Evaporation of Gold: The gold was evaporated under vacuum from heated tantalum strips which were bent in such a way as to limit the solid angle through which the gold was allowed to vaporize, thus insuring a more efficient utilization of the gold. The specimens rested on flat brass rings which had an inner diameter of 0.475 in. The entire specimen-holding assembly could be manipulated from outside the vacuum system by means of a magnet which attracted a slug of soft iron attached to the assembly. By evaporating inert gold on glass slides under conditions identical to those employed for the radioactive gold, it was found that the thickness of the films was about 100A. Welding: The welding was performed by hot pressing in a stainless steel cylinder. The inside of the cylinder was threaded and fitted for two plugs. The specimens to be welded were placed in the middle of the cylinder and two pressing disks, one at each end, were inserted to avoid shearing stresses as the plugs were tightened. Mica disks were placed between the pressing disks and the specimens to prevent them from welding. The plugs were then tightened with a hand wrench and the entire unit was placed in an argon stream for about an hour to remove the oxygen. The unit was then inserted in the center of an argon atmosphere furnace maintained at about 700°C and left there for about an hour. Because of the difference in the temperature coefficient of expansion of the two metals, as the temperature rose. the pressure on the specimen-rollple increased and a weld resulted Welding was generally satisfactory under the conditions described.

Jan 1, 1955