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By F. D. Patchen

Changes in the properties of partland cement upon the addition of fine-ground silica are discussed. Data were collected from formulations cured for periods up to 60 days at temperatures varying from 180" to 350°F. Compressive strengths, permeabilities and thickening times are compared. It is demonstrated that addition of find-ground silica in proper proportion results in a hydrated cement with superior properties above 230°F; i.e., early compressive strengths are higher and increase with additional curing, permeabilities are significantly lnrver and thickening times are increased. X-ray analysis of hydrated cement samples have been used to determine more fully the complex chemistry of these systems. Dicalcium silicate alpha-hydrate was found in all neat cements cured above 260°F. A 10 weight per cent silica addition produced a maximum amount of this phase. Xonotlite and tobermorite have been identified as hydration products at 320°F in systems containing 35 or more weight per cent silica. Formation of these components appears to be primarily responsible for the gain in strength and reduction of permeability observed after the addition of silica. INTRODUCTION For several years it has been recognized that loss of compressive strength occurs when portland cement is cured at a temperature above 250°F. This phenomenon has been called "strength retrogression". More recently it has been recognized that increased permeability usually is associated with decreased compressive strength at these temperatures. At curing temperatures above 300°F, these factors reach serious proportions. A compressive strength loss of 50 per cent between curing times of 24 hours and 14 days has been reported,' and permeabilities as high as 10 md have been measured in neat cements cured at 320°F for seven days.' Earlier investigators,' although unsuccessful in eliminating strength retrogression, stated ". . . .it appears possible that by the proper selection of additives for cement, strength loss with age at high temperatures can be either eliminated or considerably lessened". One solution suggested was the use of a pozzolanic material, hydrated lime, and a retarder. Menze15 in 1934 discovered that portland cement containing finely divided silica possessed high compressive strengths when the curing temperature was 350°F. The use of such a composition is now an established practice in the manufacture of steam-cured cement blocks. It is reasonable to assume that the same beneficial effect can be used advantageously in high-temperature oilwell cementing operations. Ludwig first mentioned the use of sand for this purpose. Later, a portland cement containing moderate additions of silica flour and retarded with CMHEC, a cellulose derivative. was recommended for high-temperature application." These formulations have been successfully employed in the field."'" This paper presents the results of a research program to test the efficacy of finely ground silica in increasing the compressive strength and reducing the permeability of oilwell cement compositions containing portland cement. Included also are X-ray diffraction patterns of powdered samples which have been used to determine some of the important chemical reactions occurring in these systems. LABORATORY PROCEDURES AND MATERIALS All compressive-strength test specimens were prepared and cured from a slurry in accordance with API RP 10B, with two modifications. A final curing pressure of 5,000 psi was maintained for a one- or three-day period; but, for further curing, pressures were reduced to the vapor pressure of water at the curing temperature. Also, the water content was varied in samples containing silica to maintain the slurry viscosity within a range of 5 to 15 poise as measured on a consistometer. Test specimens at 180°T were cured in a water bath at atmospheric pressure. At higher temperatures the specimens were cured in a steam-jacketed high-pressure curing vessel at 5,000 psi for a one- or three-day period. cubes cured for longer periods were removed from the pressure-curing vessel after 24 hours, sealed in small bombs containing water and placed in an aging oven.

By H. Becke, D. Stolnitz, D. Flatley, W. Kern

Extensive solid solubilities of CdTe (zincblende-type struckre) and InTe (B37 type) in each of the rock salt-type compounds, PbTe and SnTe, have been observed. Partial phase diagrams have been determined by thermal analysis and X-ray metallography. The limiting mol fraction. X,, of the solute in the rock salt-type a phase and the corresponding eutectic temperatures, T,, are: (PbTe)l-x(CdTe)x: X,- 0.2, T, =866°C; (PbTe),-,(lnTe),: X, - 0.35, T, = 646"C; (SnTe),-,(CdTe),:X,- 0.11, T, = 784 "C; (SnTe),-,(lnTe),: X,-0.53, T, = 630°C. The lattice parameters of the a phase decrease linearly with X, even in (PbTe),-,(CdTe),, where a, (CdTe) = 6.481A > %(PbTe) = 6.459A. This is taken as proof that the cadmium atom enters an octahedral interstice of the tellurium atom sublattice; i.e., the formation of the a phase entails the direct replacement of lead by cadmium. The a, us X curve extrapolates to 6.16A at X = 1, in agreement with the value predicted for an ionic crystal of CdTe; it is also consistent with the reported lattice parameter It is well-established that the compositions of intrinsic semiconducting and semimetallic compounds conform to normal valence rules.1"5 The apparent exceptions can be explained by taking account of anion-anion covalences, as in CdSb, or of multiple cation valences, as in In Te.'This empirical generalization is the basis of the chemical approach to semiconductors2 by which the properties of an intrinsic semiconductor are rationalized in terms of the ionic-covalent bonds necessary to saturate the valence-electron complement of the anion sublattice. A fundamental shortcoming of this approach is its disregard of long-range crystal interactions. It cannot, accordingly, deal with the phenomenon of charge conduction except through the use of ad hoc postulates. As an example, a crystal of CdTe would, in the valence-bond picture: be described in terms of electron pairs, each with the same discrete energy, localized between every cadmium and tellurium atom. This is, of course, contrary to the Pauli of the high-pressure rock-salt form of CdTe, corrected for decompression from 36 kbar. The free energy of formation of the a phase of pure CdTe at room temperature is calculated from the phase diagram to be +10 kcal per g-atom, in accmd with the value calculated from the transformation pressure. The standard enthalpy is +13 kcal per g-atom, and the standard entropy is +9 eu. The latter value implies the formation of extra classical particles, such as vacancies, interstitials, or nondegenerate charge carriers, but these alternatives are not consistent with the semiconducting properties and the densities of the a phase. The extrapolated values of the lattice parameters of (PbTe),-,(lnTe), and Spectively, for the rock salt-type modification of InTe. The corresponding interatomic separation is intermediate between monovalent and trivalent indium. The qualitative implications of the results are considered from the viewpoints of both valence-band theory and energy-band theory. principle, and is corrected by methods of molecular-orbital theory in which bonds are replaced by bands of molecular orbitals whose energies, E, depend upon a crystal-momentum vector, k.7 Each band is derived from a linear combination of atomic orbitals with two electrons required to saturate each molecular orbital in the band. In a crystal of N atoms containing z atoms in its primitive unit cell, there are 2 N/z states per band which lie in a region of k space bound by the Brillouin zone. In an intrinsic semiconductor, the bands can be grouped into valence bands which are normally filled and conduction bands which are normally empty. If the highest valence band and the lowest conduction band overlap anywhere within the Brillouin zone, the material is rendered semimetallic. The quantity defines the effective mass, m*, of an electron in a conduction band (or of a hole, i.e., an electron deficiency, in the valence band) and leads directly to the concept of charge mobility through the relation \x = et/m*, where e is the electron charge and t is the lattice relaxation time.

Jan 1, 1964

By William P. Blake

In view of the present exposition at Atlanta, and the timely meeting of the Institute in that city, and the expressed desire of the Council for contributions to the knowledge of the mineral resources of the Southern States, I may be permitted to offer some desultory notes upon the subject, chiefly in the form

Jan 1, 1896

By H. M. Otte

Certain choices for the shear elements of the inhomogeneous distortion in the phenomenological theory of martensite formation are examined for their agreement with crystallographic and X-ray data of iron alloys. The assumption that the shear elements must represent slip or twinning systems characteristic of bcc metals is found to covey all observations, even when a small uniform dilatation is taken into consideration. In bct martensite, (011) becomes a possible twinning or faulting plane, in addition to {112), and qualitatively similar X-ray line broadening is to be expected from both. The basic concept inherent in the current theoriesl-4 of the formation of martensite is that the interface between the parent (austenitic) and product (martensitic) phase is an invariant strain plane (i.e., one that is undistorted and unrotated). Experimental evidence that the interface is of such a nature is available in certain transformations2'5'6 but for the transformation in iron alloys direct observation has not proved enlightening. Internal strains resulting from the formation of the small martensite platelets within the parent austenite matrix7 make it difficult to produce the desired evidence. Indirect evidence, however, such as the continuity of scratches in passing from untrans-formed to a transformed region, strongly indicates that the habit plane in iron alloys is an invariant strain interface. The scatter in habit planes in a given specimen8 would suggest that internal stresses have a slight but definite influence. On the other hand, composition changes which affect the lattice parameter can alter the habit plane appreciably, and by an amount greater than the scatter.' The success of the theories depends on the choice made for the "inhomogeneous distortion" or "complementary shear'' in the analysis and also on the choice for the parameter 6 representing a small uniform dilatation. In the approach developed by Wechsler, Lieberman, and Read'," it is implicitly assumed that 6 is unity. In the case of iron alloys, all observations cannot be explained without varying either the inhomogeneous distortion or 6 . Bowles and Mackenzie3 considered only the effect of varying d. They found it difficult to reconcile the wide scatter of habit planes with the theory and were forced to the conclusion that it may also be necessary to consider variations or different choices of the inhomogeneous distortion. Wechsler and Read" considered a limited number of possible choices for the inhomogeneous distortion, but no variation in 6, though this could easily have been introduced if so desired. It is the purpose of the

Jan 1, 1961

By Mark A. Ammon

The two most widely used methods of measuring hardness are the Brinell and the scleroscope. In the Brinell method a hardened steel ball is pressed into the steel under a definite load and the area of the resulting depression is measured. The load in kg. per sq. mm. of the area of the depression is taken as a measure of the hardness. Within certain limits the hardness number so determined is independent of the load or the size of the ball. In the scleroscope method a small weight carrying a diamond point is dropped through a glass tube upon the steel and the amount of rebound is taken as proportional to the hard-' ness. In both methods the scale of hardness is an arbitrary one; however, they agree in a comparative may, that is, a steel showing 50 per cent. increase in hardness by the Brinell test mill show approximately 50 per cent. increase in hardness by the scleroscope test. Yet upon consideration of the two methods it appears that, upon a steel which has been carbonized, this should not be the case ; for the scleroscope method gives almost exclusively the surface-hardness, and the condition of the material below the surface has but a slight bearing upon the hardness number. The results given by the Brinell method should, however, be the exact opposite; for the depth of penetration 'of a ball pressed into the steel would be dependent to a large extent upon the condition of the material below the surface. This is particularly obvious when it is considered that the size of the ball ordinarily used in the Brinell method is 1 cm. (about 8 in.) in diameter under a load of 3,000 kg., while the diamond point of the scleroscope is in the neighborhood of 0.01 in. across, fitted in a hammer of about 0.5 oz. weight and dropping from a height of 10 inches.

Jan 1, 1913

By M. S. Burton, J. E. Ritter

The sessile-drop technique was employed to study the effect of atmosphere and alloy additions of titanium and chromium on the surface tension and contact angle of nickel on sapphire substrates at 1500oC. Shear tests were conducted on the solidified sessile drops. The liquid-gas surface tension of pure nickel on sapphire was found to be 1747 ergs per sq cm, with a contact angle of 109.6 deg. The surface tension and contact angle were not affected significantly by the four atmospheres, vacuum, impure argon, pure argon, and pure hydrogen. Small additions of titanium and chromium decreased the contact angle and for the same alloy content, contact angles were lower in pure argon than in pure hydrogen. On the basis of shear-test results , the most probable cause for adhesion in the Ni-Al2O system is the formation of NiO:Al2O3 spinel at the interface; in the titanium alloy-Al2O3 system adhesion is thought to be due to a mechanical interlocking effect; in the chromium alloy-Al2O3 system adhesion is believed to be the result of solid-solution formation involving Cr2O3 and Al2O3 at the interface. In the last few years there has been considerable interest in reinforcing metals with ceramic whiskers. It has been postulated that, by reinforcing nickel with sapphire whiskers, high-temperature strengths su- perior to those of the best current nickel alloys can be achieved.' To fabricate a whisker-metal composite having optimum density and strength, understanding of wettability and adherence in the system is of prime importance. Although there has been some previous research in this a a need for further studies has been cited4-8 to understand better the effects of impurities, alloys additions, and atmosphere on the wetting and bonding of metals to metal oxides. The purpose of this research was to investigate the factors involved in the wetting and adherence of nickel/nickel alloys to sapphire (single-crystal a Al2O3). Sessile-drop experiments were conducted in vacuum, impure argon, pure argon, and pure hydrogen, to determine the effect of atmosphere on the contact angle of the metals on sapphire, and the liquid-gas surface tension of pure nickel. The solidified sessile drops were sheared from the sapphire substrate to measure the bond strength between the metal and ceramic. The alloy additions chosen were titanium and chromium since both enhance the wetting of nickel on sapphire.2, 3c Also, titanium is commonly used when brazing metal-to-ceramic seals to improve adherence. Since chromium forms an oxide that is completely soluble in sapphire, it was thought that the oxide could serve as a transition phase to promote bonding between the Ni-Cr alloy and sapphire. I) EXPERIMENTAL APPARATUS AND PROCEDURE The sessile-drop apparatus was a horizontal furnace, with an induction-heated, cylindrical molybdenum susceptor in a water-cooled Pyrex chamber. This apparatus was patterned after that of Williams and Nielsen.7 A flat Pyrex window at each end of the furnace allowed temperature measurements to be made at one

Jan 1, 1968

Mr. Brown : .That part of the Standard Company's plant which has been added since the publication of Mr. Leggett's paper, and is described in mine, renders the single-phase, alternating system, which Mr. Hale has called " unelastic," much more elastic than it had been. The original plant at Bodie was substantially the same as the Telluride plant mentioned in his paper. The machines came from the same shops, and were practically the same; but while the Telluride Company has changed completely to a polyphase system, the Standard Company has retained its original plant, but has belted on a directcurrent generator at the receiving end, thereby converting the water-power into electricity, electricity into power, the power into electricity, and finally again electricity into power for use in the mines. This is a roundabout course, to be sure, but it shows that there are possibilities even in the out-of-date single-phase system. The only point perhaps, that deserves particular notice with respect to the hoist is the fact that the rheostat, or starting-resistance, was not built originally

Jan 1, 1897

By L. W. Kempf

DURING the recent development of aluminum alloys for free-cutting screw-machine rod, it became desirable to know something of the solubility of lead and bismuth in liquid aluminum and in some aluminum alloys. The literature is not particularly helpful in supplying this information. These portions, therefore, of the constitutional relationships of aluminum-ismuth and aluminum-lead alloys were investigated by thermal analysis and by chemical analysis of samples taken from aluminum-rich melts in equilibrium with precipitated lead or bismuth. The solubility of lead and bismuth in some liquid aluminum-copper alloys was also investi-gated. Some consideration was also given to the solubility of these elements in solid aluminum. Among the earliest investigators of the aluminum-lead and aluminum-bismuth systems was Wright,1 who reported that melts of aluminum and lead formed two layers indicating limited liquid solubility. Under his conditions, the aluminum-rich layer was reported to contain 1.91 per cent Pb and the lead-rich layer, 0.07 per cent Al. Subsequently, Pecheau2 found that in aluminum-rich alloy melts with more than 10 per cent Pb three layers were distinguishable. He reported that the middle layer contained from 3 to 10 per cent Pb. He also found that the melting point of aluminum appeared to be lowered slightly by the addition of lead. Gwyer3 investigated these alloys and found evidence of a slight lowering of the freezing point of aluminum by the addition of either lead or bismuth. He found no evidence of solid solubility in either case and made no attempt to determine the liquidus curves. Hansen and Blumen-thal4 reported that the addition of lead distinctly lowered the solidifica-tion point of aluminum. They also found that bismuth lowered the melting point of aluminum. Guillet5 reported almost complete mutual immiscibility for the aluminum-bismuth alloys in the liquid state. Bohner6 examined the effect of various concentrations of lead and bis-muth on the electrical conductivity of aluminum. He found decreases in conductivity on annealing at 500° C. as compared with the conductivity of the same alloys on annealing at 300° C.

Jan 1, 1938

By C. S. Roberts

THE advent of a sensitive X-ray method of analysis recently has allowed the determination of retained austenite in amounts as low as 0.3 pct.' As a result this phase has been found in quenched low carbon steels where its presence has not been generally suspected. In the course of a study of the tempering process,' retained austenite determinations were made by the X-ray method on a series of high purity Fe-C alloys and plain carbon steels. The chemical analyses of these materials and details of the hardening procedure are given in Table I. Results were obtained after quenching to 72°F (22°C) and — 321 °F (—196°C). Austenitizing temperatures were between 100" and 150°F above A, or Acm. All proeutec-toid cementite or ferrite was in solution. The combination of the results with those of Averbach, Castleman, and Cohen,' and earlier results of Esser

Jan 1, 1954

By R. R. Sayers

VENTILATION may be defined as the process by which vitiated air of an inclosed or partly inclosed space is continuously replaced by fresh air. Fresh air has been defined as invigorating pure air. Pure dry air at sea level contains the following gases:1 Analysis of Air at Sea Level PER CENT. Oxygen 20.94 Nitrogen 78.09 Carbon dioxide 0.03 Argon 0.94 Helium, krypton, neon, xenon, hydrogen, hydrogen peroxid, ammonia, ozone traces CARBON DIOXIDE LIMIT For many years carbon dioxide was used as an index of the purity of the air vitiated by the metabolism of people. It was, however, well known that the untoward effects produced on those exposed to such air was not due to the concentration of the carbon dioxide. It has been found that the untoward effects on the comfort and efficiency of those so exposed are due to the increased temperature and humidity. It has been found that men can breathe air containing many times the amount of carbon dioxide found in our worst ventilated theaters and assembly halls, which, according to Rosenau, do not contain above 0.5 per cent. carbon dioxide.

Jan 7, 1926

By V. S. Tuman

In the first part of this paper, an estimate is made of the magnitude and extent of the thermal stresses which result from mud circulation. Our study is made for the period of relaxation, i.e., when the drilling operations are terminated and mud circulation is discontinued. In the second part, we have shown how the thermal stress can affect the wave propagation. An example is worked out for a Carbondale sandstone (Illinois basin). It is concluded that, in extreme cases when differential temperature is about 100°F, the travel time will be affected by about 2 microsec/ft. For more refined permeability studies, such corrections would be desirable. MAGNITUDE AND EXTENT OF THERMAL STRESSES RESULTING FROM MUD CIRCULATION When geological beds are penetrated by boreholes, it is observed that the formation temperatures increase with depth; however, the temperature profile varies considerably from place to place. During drilling operations, mud pumped from a pit at atmospheric temperature absorbs heat from the lower beds. As a result, the drilling fluid returning to the surface is at a higher temperature than the surrounding beds. The temperature gradient in a well depends on the rate of mud circulation and other factors; normally, this temperature gradient is smaller than the natural gradient in the formations. (See Fig. 1.) The temperature difference between the mud column and the surrounding beds gives rise to therma1 stresses (which are also important in the phenomenon of fracturing), and it is expected that they will affect the transit time of the sonic front in velocity logging.1 It is evident chat beds near the surface will undergo various cycles and will have a complicated dynamical and thermal-stress history. A limestone bed which is just penetrated will act as a source of heat, warming up the cold mud pumped down a few minutes earlier from the surface pit. The same limestone bed a week later will act as a sink, absorbing heat from the drilling mud which has already warmed up sufficiently to be at a higher temperature than the bed in question. No doubt a large section of the hole will undergo a heat treatment, which will make the calculation of the exact magnitude of the thermal stresses very difficult. In the solution of wellbore thermal equation, it is assumed that the rock around the wellbore is elastic and isotropic, and that the system is radially symmetrical. A complete dynamical solution of the thermal stresses set up at different horizons during the drilling operations would require a comprehensive history of the mud circulation, the surface temperature of the pit and the number of hours in which mud was not circulated. CONDUCTION OF HEAT AND THERMAL EQUATION OF STATE

By C. M. Wayman, R. Bullough

The selection rules fir twinning in fcc, bcc, and hcp lattices as established in Part I are used to predict the positions, relative to the matrix (untwinned) reciprocal lattice, of reflections due to double diffraction from the twins. These doubly diffracted reciprocal lattice points, which often coincide with ordinary matrix reciprocal lattice points, are deduced from kinematical considerations. 1. INTRODUCTION. A Bragg diffracted beam under certain conditions may be rediffracted to produce a third beam i .e., the incident beam, the first diffracted beam, and the rediffracted beam). In such a case an initial incident beam is diffracted by a set of planes; the diffracted beam may then be rediffracted by a second set of crystallographically different planes. The initially diffracted beam acts as an incident beam for the second set of planes, thus resulting in a twice-diffracted beam. This twice-diffracted beam may be regarded as a singly diffracted beam from a set of lattice planes whose structure factor is zero. In order to find the reciprocal lattice point corresponding to the doubly diffracted beam, it is customary1,2 to combine vectorially the component reciprocal lattice vectors which head to the extra reflections. For example, hcp metals may exhibit the forbidden (0001) reflections.* As Fig. 1 shows, the (0001) reciprocal lattice point results from: (1010) + (1011) = (0001) Similarly, combination of the beams (1011) and (1010) gives rise to: (1011)- (1010) = (0001) As Pashley and stowell2 have pointed out, even if in fact the double diffraction points lie on the Ewald sphere, they may not actually represent observed doubly diffracted beams because the initially diffracted primary beam, i.e., the source, must also correspond to a reciprocal lattice point which lies on the sphere of reflection; however, the reciprocal lattice point corresponding to the planes causing the rediffraction need not lie on the sphere. A little consideration of the Ewald construction in Fig. 2 makes this argument clear. In Fig. 2 the incident beam is represented by the wave vector ko. This beam is initially diffracted by the lattice planes (hkl) which are represented by the reciprocal lattice vector r(hk1) The reciprocal lattice point (hkl) of course lies on the Ewald sphere in order that the Bragg condition be satisfied. The initially diffracted beam is represented by the wave vector kl. If now kl is rediffracted by a second set of planes (h'k'l') resulting in k2 the lattice point (h"k"l") must lie on the Ewald sphere if the double diffracted beam k2 is to be observed. It is clear that (h"k"l") is the vector sum of (hkl) and (h'k'l'), and that (h'k'l') need not in fact lie on the Ewald sphere. In the usual1,2 analysis the origin (000) of the reciprocal lattice is shifted to the point (hkl). However the translation (000)— (hkl) automatically shifts the point (h'k'l') to the Ewald sphere, i.e., (h'k'l')— (h"k"1"). It is to be seen that (hkl), the source reflection, must lie on the Ewald sphere; if it does not the translation (000) — (hkl) places the "new" origin off the sphere, not satisfying the Ewald construction and hence the Bragg condition. The point (h"k"1") of course must lie on the sphere if it corresponds to an observed doubly diffracted beam. It is to be noted that crystals having the hcp structure, as just discussed, are intrinsically capable (i.e., without lattice defects such as twins) of double diffraction, as contrasted to fcc and bcc crystals which are extrinsically capable (requiring lattice defects or reoriented lattice regions). The "allowed" bcc reciprocal lattice points (which comprise an fcc lattice) are (110), (2001, (211), (220), (310), (2221, (321), (4001, and so forth. The combination

Jan 1, 1967

By J. B. Mackintosh

The quantitative determination of copper, by means of electrodeposition, offers so many advantages, that it is to he preferred, when properly executed, to 611 other methods for ease and accuracy. The object of the present paper is to give the results of a number of experiments made during the past few months, and to indicate some sources of error, which must be avoided in order to attain the necessary accuracy. In 1867, C. Luckow, in competition for a prize offered by the directors of the Mansfield Copper Works, submitted the following

Jan 1, 1882

By John C. Smock

The fire-clays of New Jersey belong in two geological ages, the cretaceous and quaternary, or post-tertiary. Three very small deposits of plastic clays have been discovered within the limits of the Archæan rocks. These are not refractory and of little importance, excepting in a geological consideration. They have resulted from a decomposition of the feldspars of the rock in situ, and they have been classified as inferior kaolins.

Jan 1, 1879

By J. Bruce Wagner, Roger L. Levin

Integrated forms of two solutions of Fick's second law for the movement of a plane interface through a sample of wustite, and for diffusion into a semi-infinite slab of wustite, are shown to yield nearly identical values of the chemical diffusion coeffcients of cation vacancies in wustite, over the temperature range 900° to 1100°C. The chemical diffusion coefficients, the values of D obtained for the propagation of a concentration gradient through samples of undoped and doped wustite, are obtained from the equations It is becoming increasingly important in metallurgical practices to understand the role of the chemical diffusion coefficient, i.e., the diffusion coefficient of a species across a concentration gradient. During the first stages of sintering, one of the mechanisms by which the bonds between neighboring particles develop is by volume or bulk diffusion. This diffusion coefficient as deter- where ?m is the weight change at any time t, ?W is the total weight change at t =8, A is the area of the specimen, and AC is the total change in the cation concentration after the establishment of equilibrium, as determined by reduction experiments in different carbon monoxide -carbon dioxide mixtures within the limits of existence of the single-phase field. mined from the standard equations for volume diffusion during sintering is actually a chemical diffusion coefficient, and it has been observed to be many times larger than the self-diffusion coefficient as determined on the same materials by experiments using radioactive tracer techniques. Kuczyn-ski1 has noted that, if the controlling mechanism of sintering of A12O3 in an oxidizing atmosphere is the diffusion of oxygen, then this diffusion coefficient as measured from sintering rates is about 2.2 x 104 higher than the self-diffusion measurements obtained by tracer techniques. He has also reported the diffusion coefficient obtained from the rate of sintering of Fe2O3 powder to be about 10 6 times faster than the self-diffusion coefficient of

Jan 1, 1965

By O. J. Huber, P. D. Frost, H. A. Robinson

URANIUM is a (ß-stabilizing, eutectoid-forming element when alloyed with titanium. Udy and Boulger1 have reported that an alloy of 48.6 pet uranium in titanium retains ß-phase when quenched from the ß-region, while compositions of approximately 30 pet uranium transform to martensite during such quenching. Since the eutectoid reaction is rather sluggish, titanium-uranium alloys should be capable of being strengthened by the ß — a trans-

Jan 1, 1959

By D. J. Hawthorn

The widespread interest shown during the past year in the study of subsurface pressures warrants brief reference to its early development. Though it is impossible to set an exact date when constructive thinking on the subject first began, nevertheless, evidence is available that thought was given to the problem as far back as 16 or 1.7 years ago. There is record in one of the foreign journals of actual subsurface tests made by crude methods in one of the Rumanian fields in 1918 and 1919.' These tests were performed in conjunction with studies made on wells produced by bailing and, incidentally, the final outcome of the work led to the development of the so-called "duplex bailer" which is reputed to have trebled volumetric bailing efficiency. From this time on to 1927 a few scattered bottom-hole pressure determinations were made with makeshift instruments of one form or another, but probably not until 1927 was any great amount of concerted effort directed to the subject. At this fall meeting of the Petroleum Division four years ago was presented one of the first papers2 to appear in this country written for the express intent of advocating the value and importance of subsurface pressure determinations. It is thought to have been the first to present direct data on subsurface pressures obtained through the use of a specially designed recording instrument. As might be expected, the instrument had its limitations, but reasonably accurate results were obtained and, to say the least, it constituted a progressive step in the right direction. During the period from 1927 to 1931, many noteworthy improvements were made in the design and perfection of subsurface pressure instruments suitable to meet all conditions. Because of the magnitude of this task much credit is due the men who pioneered this work. They should feel a keen sense of satisfaction in the thought that their efforts have paved the way for the continuation of this most valuable study. At the present time more than a dozen companies are operating subsurface pressure instruments in the Mid-Continent field. Engineers in

Jan 1, 1933

By F. Kurata, A. F. Bertuzzi, P. C. Davis, T. L. Gore

The phase and volumetric properties of 10 very volatile mixtures are presented for temperatures from — 200°F to above the critical points. These mixtures consisted of natural gases and of mixtures of natural gases with methane and nitrogen. Existing correlations of compressibility factors have been extended to apply to these mixtures. Existing correlations of critical pressures and temperatures do not apply to these mixtures. Methods have been developed for estimating critical temperatures of these mixtures to ± 4°F and critical pressures to 2 5 per cent. These methods apply to other volatile and very volatile mixtures. The results of this work are particularly applicable to the separation of nitrogen from hydrocarbons by low-temperature distillation. INTRODUCTION Knowledge of the low-temperature phase and volumetric properties of natural gases and of other mixtures of the light hydrocarbons is becoming increasingly important as interest in low-temperature separation processes increases. Low-temperature distillation has been used to separate ethane and ethylene from natural gas and from refinery gases for petrochemical uses. Removal of nitrogen from natural gas by low-temperature distillation has been proposed 7,20 as a means of increasing the capacity of existing gas transmission lines and of improving the marketability of the gas. Further application of low-temperature separation processes has been retarded by lack of data on the phase and volumetric behavior of mixtures at low-temperatures and at high pressures. This paper presents the results of determination of the phase and volumetric properties of 10 very volatile mixtures at temperatures from - 200 °F to above the critical point. These mixtures consisted of natural gases with methane and nitrogen. Generalized methods are presented for estimating the critical temperatures, critical pressures, and the densities of such mixtures. EXPERIMENTAL APPARATUS AND PROCEDURES The apparatus and the experimental procedures have been described in an earlier paper13. The method consists of displacing the mixture from a reservoir which is maintained at constant temperature and pressure into an agitated glass equilibrium cell which is maintained at constant temperature. The liquid level within the glass equilibrium cell was visually observed, and the pressure was measured to within & 3 psi with a calibrated Bourdon gage. COMPOSITIONS OF MIXTURES STUDIED The compositions of the mixtures studied are summarized in Table 1. The measured properties included in Table 1 will be discussed later in this paper. The sources of these gases are described below: Gas "A-1'' was obtained from the Phillips Petroleum Co. Its composition was reported in connection with earlier work." The properties of this gas were reported in an earlier paper.13 Gases "A-2, A-3, A-4" were prepared by mixing nitrogen with gas "A-1." Gas "AB-1" was prepared by mixing methane with gas "A-1." The properties of this gas were reported in an earlier paper.'" Gases "AB-2" and "AB-3" were prepared by mixing nitrogen with gas "AB-1." Gas "B" was obtained by W. W. Bodle of J, F. Pritchard & Co. from the primary separator of a well in western Kansas. Gas "C" was obtained from a Cities Service Co. pipeline at Lawrence, Kans. Gas "D" was prepared by mixing gas "AB" with gas "C."

Jan 1, 1955

By Jack D. Webber

The successful use of oil well packers requires, in part: an understanding of the pressures which exist at the packer in various applications and an understanding of the characteristics of the various types of packers. It is with these pressures, the resultant forces, and the characteristics of packers. that this paper is primarily concerned. An oil well packer may be defined as a mechanical device for blocking the passage of fluids in an annular space. In the more usual case, the annular space is that between the tubing or drill pipe in a well and the casing, and packers which block such an annular space are broadly referred to as casing packers. In the other case. the annular space is that between the tubing or drill pipe and the walls of an open hole, and packers for blocking this space are generally called formation packers. While the hydraulics involved are essentially the same for casing and formation packers. a greater variety of conditions are encountered in the use of casing packers and only casing packers will be discussed. After a packer has been set and a pressure seal effected between tubing and casing, the packer is comparable to a piston in a cylinder. Pressures acting upon a piston result in forces which will move the piston unless some means is provided to prevent such movement. In the same manner, pressures acting upon a packer will move the packer unless there is present a sufficiently great restraining force. PACKER CLASSIFICATIONS Packers may be classified according to the pressure conditions under which they are capable of blocking the annular space between tubing and casing. Fig. 1 shows schematically two types of packers in common use. These packers are capable of blocking the annular space against the passage of fluids under a differential pressure of significant magnitude only when the pressure in the annular space above the packing element is greater than the pressure below. It may be seen that in Fig. l-a. slips with teeth which bite into the casing and prevent downward movement are provided. In Fig. 1-h. an anchor prevents downward movement. In each case, there i-only the tubing to prevent upward movement when differential pressures act to move the packers upwardly. Packers which hold only a significant differential pressure acting downwardly have been in use since the early days of the oil industry and will hereafter be referred to as conventional type packers. In many packer applications operating conditions will 1.crult in differential pressures across the packer which will at times act to move the packer upwardly, and at other times, act to move the packer downwardly. For these applications, designs are available which will block the annular space and resist movement in either direction. Fig. 2-a shows schematically a packer of this type which is designed to be run into a well and set, and removed when desired by merely pulling the tubing. It will be noted that two sets of slips are provided-— one set above the packing element to prevent upward movement, and another set below the packing element to prevent downward movement. This packer is built around a mandrel which is essentially a part of the tubing. and which is free to move longitudinally within certain limits through the set packer. Fig. 2-b shows schematically a permanent type packer which is capable of holding pressures from either direction. Here again, two sets of slips are provided to prevenl movement of the packer. This packer is designed to become virtuallv a part of the casing when set and it is made of drillable material so that it may be drilled out when its removal is desired. The seal nipple shown effects a pressure seal between the tubing and the packer. This seal nipple is a part of the the tubing, and the nipple and tubing may be withdrawn from the well without disturbing the packer. It should be noted that these figures are not representative of all available packers which are designed to hold pressures from both above and below. Packers which resist movement in either direction will hereafter be referred to as universal type packers. There is a third type of packer in general use and this type is designed to block the passage of fluids when the pressure below the packing element ii greater than that above. This type is provided with slips which prevent upward movement of the packer and is somewhat similar to a conventional type packer run upside-down. Packers designed to hold pressure only from below are made in a variety of designs and are usually owned and operated by service companies.

Jan 1, 1949

By Jack D. Webber

The successful use of oil well packers requires, in part: an understanding of the pressures which exist at the packer in various applications and an understanding of the characteristics of the various types of packers. It is with these pressures, the resultant forces, and the characteristics of packers. that this paper is primarily concerned. An oil well packer may be defined as a mechanical device for blocking the passage of fluids in an annular space. In the more usual case, the annular space is that between the tubing or drill pipe in a well and the casing, and packers which block such an annular space are broadly referred to as casing packers. In the other case. the annular space is that between the tubing or drill pipe and the walls of an open hole, and packers for blocking this space are generally called formation packers. While the hydraulics involved are essentially the same for casing and formation packers. a greater variety of conditions are encountered in the use of casing packers and only casing packers will be discussed. After a packer has been set and a pressure seal effected between tubing and casing, the packer is comparable to a piston in a cylinder. Pressures acting upon a piston result in forces which will move the piston unless some means is provided to prevent such movement. In the same manner, pressures acting upon a packer will move the packer unless there is present a sufficiently great restraining force. PACKER CLASSIFICATIONS Packers may be classified according to the pressure conditions under which they are capable of blocking the annular space between tubing and casing. Fig. 1 shows schematically two types of packers in common use. These packers are capable of blocking the annular space against the passage of fluids under a differential pressure of significant magnitude only when the pressure in the annular space above the packing element is greater than the pressure below. It may be seen that in Fig. l-a. slips with teeth which bite into the casing and prevent downward movement are provided. In Fig. 1-h. an anchor prevents downward movement. In each case, there i-only the tubing to prevent upward movement when differential pressures act to move the packers upwardly. Packers which hold only a significant differential pressure acting downwardly have been in use since the early days of the oil industry and will hereafter be referred to as conventional type packers. In many packer applications operating conditions will 1.crult in differential pressures across the packer which will at times act to move the packer upwardly, and at other times, act to move the packer downwardly. For these applications, designs are available which will block the annular space and resist movement in either direction. Fig. 2-a shows schematically a packer of this type which is designed to be run into a well and set, and removed when desired by merely pulling the tubing. It will be noted that two sets of slips are provided-— one set above the packing element to prevent upward movement, and another set below the packing element to prevent downward movement. This packer is built around a mandrel which is essentially a part of the tubing. and which is free to move longitudinally within certain limits through the set packer. Fig. 2-b shows schematically a permanent type packer which is capable of holding pressures from either direction. Here again, two sets of slips are provided to prevenl movement of the packer. This packer is designed to become virtuallv a part of the casing when set and it is made of drillable material so that it may be drilled out when its removal is desired. The seal nipple shown effects a pressure seal between the tubing and the packer. This seal nipple is a part of the the tubing, and the nipple and tubing may be withdrawn from the well without disturbing the packer. It should be noted that these figures are not representative of all available packers which are designed to hold pressures from both above and below. Packers which resist movement in either direction will hereafter be referred to as universal type packers. There is a third type of packer in general use and this type is designed to block the passage of fluids when the pressure below the packing element ii greater than that above. This type is provided with slips which prevent upward movement of the packer and is somewhat similar to a conventional type packer run upside-down. Packers designed to hold pressure only from below are made in a variety of designs and are usually owned and operated by service companies.

Jan 1, 1949