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By Roscoe C. Clark

A study of the effect of various corrosive waters on five different types of cements indicated that those cements containing less than 5 per cent tricalcium aluminate were the most resistant to corrosion. INTRODUCTION Oil field experience indicates that some formation waters are excessively corrosive to some cements. A study has been made to determine the most corrosive waters and the relative resistance of various types of cement to these corrosive waters. PROCEDURE This study of the corrosion of cement was limited to an evaluation of the effect of various corrosive waters on five different types of cements. A determination was made of the types of cements which offer the greatest resistance to corrosion and of the chemical contents of waters found to be the most destructive to cements. The laboratory tests were conducted by immersing small cylinders of 20 samples of set cement in various corrosive waters. The initial mixing of most of the cement slurries was done using Tulsa tap water as the mixing water; however, a few of the slurries were mixed using a sulfate water as the mixing water. When the 20 samples had been immersed for a period of nine months, they were removed from their corrosive baths, inspected and photographed. The field tests were conducted by placing ten cement specimens, each contained in a screen wire thimble, in the gas anchors of insert pumps in wells in six different fields. The specimens were observed whenever it was necessary to pull the pumps and were returned to the 1aboratory when deterioration had reached a serious state. EXPERIMENTAL RESULTS In both the field and laboratory tests the resistance of the different cements to corrosion was determined by the condition of the samples and the number of samples of each that were in good condition at the end of the immersion period. Table I lists the various cements tested in the order of their resistance to corrosion with the most resistant at the top and the least resistance at the bottom. An analysis of Table I reveals that the upper half of the table predominates in slow set and sulphate resisting cement.: (low 3CAO.A12O3 content) while in the lower half the port-land and high early strength cements are in the majority. Of the last two the high early strength cements appear to offer less resistance to sulfate water corrosion. An investigation of the composition of the cements listed in Table I indicated that as a general rule the cements containing less than five per cent tricalcium aluminate will exhibit the greatest resistance to corrosion. The destructive action of various corrosive waters was compared by listing the waters in the order of those containing the largest number of samples that failed completely. These ratings are presented in Table II with the most corrosive waters listed first and the least corrosive last. Figs. 1 and 2 show the end views of cement samples which had been immersed in the baths of five per cent MgSO, water and the five per cent Na2SO4 water respectively in the laboratory. These .pictures are representative of the results obtained and present a pictorial evaluation of the corrosive resistance of various types of cements.

Jan 1, 1950

By A. J. de Witte

It has been observed that upon invasion of a sand containing oil or gas and connate water by mud filtrate the hydrocarbons are more rapidly flushed by the filtrate than is the connate water.' In time, it appears that the following displacement pattern emerges: oil (or gas) is being swept ahead by connate water which, in turn, is pushed by invading fluid. Eventually the connate water may have "banked up" sufficiently to form a zone of appreciable thickness leading the invading front. In the extreme case, Fig. 1 shows how the situation will develop.' Immediately adjacent to the borehole (radius r) there is a zone, the invaded zone proper, where the connate water has been flushed out completely and which contains only residual oil or gas and mud filtrate. This zone (extending out to a radius ri) grades more or less abruptly into the next (thickness A), which contains only residual hydrocarbon and connate water. Beyond it, again more or less sharply bounded, extends the virgin formation with the original interstitial water saturation Sw. The various saturations are indicated in Fig. 1. The three zones generally will be marked by resistivity contrasts owing to their different fluid contents. As the connate water is usually more saline than the invading fluid, the second zone having a high connate water saturation forms a concentric cylindrical ring or annulus of low resistivity R, around the borehole.',' It will be referred to as the "low zone." Fig. 1 shows schematically the resistivity profile. It is clear that the phenomenon of a low zone could not occur in invaded water sands. The presence of a low zone, therefore, would be a qualitative indication of a hydrocarbon-bearing formation. Granted that the phenomenon is real, if it were pronounced enough to be detected, one might thereby have a means of locating oil or gas in the ground. This is the aim of the "displacement logging" method.' In any case, the presence of a low resistivity zone will affect the reading of electric logs. Using conventional log interpretation techniques, one must be aware of this and, if necessary, correct for it. Whether correction or detection should be the goal will depend primarily on the magnitude of the effect. The type of log which is likely to be affected most is the induction log. The current pattern of an induction log is concentric with the borehole. Any concentric ring of low resistivity, therefore, will tend to become crowded by current lines. This zone of maximum current density will obscure the relative contributions to the current conduction by other portions of a bed making, for instance, the contribution of the virgin formation less significant and thus detracting from the value or the induction log as an R, reading device. The present note is intended to ascertain the maximum possible effect of a low zone in the extreme case portrayed by Fig. 1 on three commercially available types of induction logs, sc., 5 FF 27, 5 FF 40 and 3 F 60. Type 5 FF 27 or 5 PF 40 is currently run in conjunction with a 16 in. normal and SP log. This combination is gradually replacing the regular electric survey (two normals and one lateral) as a standard log in many areas. On the basis of the scheme of Fig. 1 (sharp boundaries between successive zones), the thickness of the low zone may be computed for various amounts of infiltration measured by the ratio of invaded zone diameter to hole diameter D,/d. Referring to Fig. 1, we can set up a material balance for the water displaced from the invaded zone proper and the water present in the low zone. The volume of connate water displaced from invaded zone upon flushing by mud filtrate is: V1 = e p (r2 - r2) ? Sw . where c = bed thickness ? = porosity Su, = original connate water satu-ration. The volume of water finally accu-mulated in the low zone is: Vz = e p [(r1 -?)2 - r2 4] ? Sw . where SW1 = 1 — Sor = "water" saturation in the invaded and low zones both. The volume of water originally present in the low zone is:

Jan 1, 1958

By E. S. Machlin, W. R. Yankee

IN a previous study1 of the effect of heating com-mercial titanium in air on its subsequent friction coefficient against other metals, as well as itself, it was found that the friction coefficient markedly decreased from a value of about 0.7 to about 0.3. A tentative explanation was given that surfaces normally produced at room temperature are not contaminated sufficiently to prevent seizing or welding of the titanium to the softer mating metals. The latter tend to cleanse themselves during rubbing over the harder titanium. It was thought that the lack of a contaminant protective film on the titanium was due to the high solubility of titanium for oxygen and nitrogen and hence an inability to form a contaminant oxide or nitride. This explanation requires the ratio of the surface absorption rate to the diffusion rate to become much lower at room temperature than it is at high temperatures. In order to check the phenomenon further, commercial titanium specimens were nitrided or oxidized at 800°C for 20 hr in flows of prepurified N2 and 01, respectively, at about 1/2 in. H2O above atmospheric pressure. Friction runs were made in argon using a freshly cut copper hemisphere (cut in argon) on surfaces cut successively into the diffusion layers in the titanium (cut in argon) using the techniques described in a previous publication.' DPH values (100 gram load) were made as a function of depth into the diffusion layer using a Tukon tester. Also, micrographs were taken at separate cross sections to indicate the diffusion layers. The results obtained are presented in Figs. 1 and 2, which show the "static" friction coefficient vs hardness for the nitrided and oxidized specimens, respectively. A separate measurement of the friction coefficient of clean copper vs iodide titanium also was made. From results reported in the literature' giving the oxygen and nitrogen contents as functions of the hardness, cross plots were made showing the friction coefficients as functions of the amount of interstitial solute. These plots are given in Figs. 3 and 4. From micrographs of the diffusion layers and the phase diagrams, it was deduced that the data in Figs. l through 4 correspond to the single phase a region. The points observed on the compound regions have been excluded from the figures. It is apparent that nitrogen or oxygen in solution in the a titanium markedly affects the friction coefficient against a softer mating metal. Discussion of Results These results are extremely interesting from both a practical and theoretical viewpoint. The theoretical implications will be discussed first. According to Bowden, the friction coefficient should be given to a good approximation by the relation where a is the fraction of contact area that has welded, a is the shear strength of weaker component, and H is the hardness of softer component. Using this relation alone, it is difficult to understand the results because none of the terms should be affected by a variation in the oxygen or nitrogen content of the harder and stronger metal, titanium. Even if the ratio of S/H for titanium is used in Eq. 1, the ratio has been shown to be independent of oxy-gen or nitrogen content.' If a more rigorous equa-tion is used combining Eq. 1 and a result given pre-viously" for the case where welding is absent, then the relation obtained is µ = a S/H + (1-a) a W aß/H where a is constant and Waß is the work of adhesion between the two metals comprising the friction couple. This relation states that if a is less than 1/2 or so, variation in the work of adhesion Waß between copper and the titanium should affect the friction coefficient markedly. It is reasonable to expect that the work of adhesion will depend on the oxygen or nitrogen content of the titanium. Available data4 show that clean metals and oxides have much lower works of adhesion than the same metals against the

Jan 1, 1955

By P. K. Foh, C. G. Dunn

IN an investigation of the rolling and recrystalliz-ing textures obtained from single crystals of Si-Fe, Koh and Dunn included specimens in the (111) [lie] orientation.1,2 This note reports some additional results obtained on samples of this orientation set aside for further study. After, primary recrystallization longer annealing treatments at 980°C produced only normal grain growth; after 16 hr at 980°C the largest grains were approximately 0.010 to 0.020 in. in diam. The orientations of 13 of the larger grains were found by the transmission Laue method. The unidentified (110) poles of these grains have been added to the (110) pole figure obtained after primary recrystallization2 to give the plot shown in Fig. 1. When grain identifications are also included, such a plot reveals the following. Two orientations agree almost exactly with the peak pole ,density positions of component B of the primary recrystallization texture, one with component A, and one with component C. All the remaining orientations except one have (110) poles near weaker and unidentified pole density peaks. In fact, the correlation is good enough for an identification of eight components. Previously only components A, B, and C were certain. The results are perhaps even more informative when combined with the (110) pole figure of the cold-rolled crystal to give the plot shown in Fig. 2. Each of the 13 orientations is identified and uniquely determined by selecting two (110) poles per crystal, which are 90" apart. The plot shows that every grain of the 13, except grain 6, has a (110) pole in common with a (110) pole concentration of the cold-rolled crystal. The orientation relationship with the cold-rolled orientation may be expressed as approximately 25" rotations about <110> axes, which is in agreement with the results found for coarse-grained primary recrystallization.2 If primary recrystallization had occurred according to the <110> rule without preference, there would have been 12 components. Actually our limited data reveals nine of the possible 12. The integrated pole figure also shows preferences among them, since three are considerably stronger than the rest. In addition to the above direct information, the following conclusions may be drawn. Primary recrystallization of the (111) [110] cold-rolled crystal produces a limited number of weak and strong components with the larger than average primary grains from these components related to the cold-rolled crystal by 25° <110> relationships. In arriving at this conclusion of limited orientations the (111) [110] orientation has to be ruled out as a source of large primaries for two reasons. First, growth in this orientation was not observed, despite an expected high grain boundary mobility (due to its 25" <110> relationship with every component of the texture). Secondly, primary recrystallization usually produces grains in new orientations, particularly in a single orientation matrix; but (111) [110] is not new. Other orientations besides those of the <110> type may be considered unlikely, of course, because the <110> relationship holds quite well for primary recrystallization2 and should produce the large primaries. There are exceptions to this rule, but probably not enough to provide large

Jan 1, 1958

By R. H. King, D. R. Schricker, R. E. Cameron

Mine managers rely on their experience, section foreman&apos;s daily reports and occasional time studies to make important production, maintenance and forecasting decisions. This information is often subjective and imprecise, consumes expensive engineers time, is often biased and is restricted to short time periods. Managers need better information. Furthermore, if a recently purchased machine is being evaluated, a large increase (>10%) in productivity may be obvious, but small increases are usually masked by other variables. In today&apos;s highly competitive markets, cumulative small changes are important, especially since managers have already exhausted most available, obvious avenues of improvement. A technique to separate these charges from effects of other variables and to quantify the target effect is necessary. CSM researchers are addressing this need by developing an intelligent decision support system (IDSS). It provides key production and maintenance information to support management decisions by recognizing patterns in mining machine sensor data and representing knowledge about mine management, operations, layout and equipment. A continuous miner section at Western Fuels-Utah Inc.&apos;s Deserado Mine in Rangely, CO is the test facility for the research. Power transducers located in the sections load center provide kilowatt versus time data from continuous section equipment. The IDSS pattern recognition algorithms classify the kilowatt versus time patterns into individual machine operating modes. It produces an output similar to a typical industrial engineering time study but continuously, automatically and without an engineer in the section. It is relatively easy for a time-study engineer to identify the stop and end points of a cycle element and classify it by looking at the machine and glancing at a stop watch. The problem is that monitoring system hardware and software do not have these unique capabilities. Consequently, IDSS algorithms must automatically define the begin and end points of machine tasks and identify the task by recognizing patterns in kilowatt versus time data. However, many mines have file drawers of time-study type data that are not very useful. So, IDSS contains the knowledge representation subsystem (IDSS/KRS) to produce short reports containing only key information. This is difficult because mine environments continually change and information requirements differ for each management level. Consequently, IDSS/KRS must learn and adapt to new conditions in a dynamic mining environment. Western Fuels-Utah owns and operates the Deserado Mine, located about 19 km (12 miles) northeast of Rangely, CO (Upadhyay, 1988; King and Eros, 1988). One longwall and two continuous miner sections produce about 900 kt (1 million st) of coal annually for the Deseret Generation and Transmission Cooperative&apos;s 4000 MW power plant located near Bonanza, UT. Three mine monitoring systems control the underground mine, the preparation plant and the unit train load out. Pattern recognition IDSS/PRS produces a listing of begin and end times for each machine operating event as shown is Table 1.

Jan 1, 1991

By N. Brown, M. Herman

IT has been pointed out by Cottrell&apos; and Fisher that long-range order would produce superdis-locations, consisting of two partial dislocations separated by an out-of-phase region. The mutual repulsion of the partial dislocations is balanced by the surface tension of the out-of-phase domain boundary joining the dislocations (Fig. 1). The calculation of the equilibrium spacing of the dislocations has yet to be made. The argument uses the Bragg and Williams theory of long-range order." The metal under consideration is the A-B, body-centered type, such as ß brass. The slip system is taken to be [Ill], (110). Since nearest-neighbor interactions are considered, only the atoms position in the two (110) planes adjoining the slip plane have to be labeled. Corner sites are called a and a&apos; in the top and bottom (110) planes, respectively. Similarly ß and ß are the body-centered sites. Thus, a and ß and 0 and a sites are nearest neighbors. Assume that the bottom plane moves and the top plane is fixed during slip; the atoms in a and ß sites exchange sites but atoms in a and ß sites remain fixed. Fraction of A atoms in a sites, for example, is given by fa and fa. for the un-slipped and slipped condition, respectively. Similarly number of A atoms in the a sites is given by n, and n&apos;a for the unslipped and slipped condition, respectively. As the dislocation moves into the ordered region the change in number of A-A bonds is given by

Jan 1, 1957

By J. B. Darby, P. A. Beck

IN a previous publication,&apos; the 1200°C isothermal section of the Cr-Mo-CO system was surveyed. It was found that starting from the binary (Cr,Co)a, the u phase extends deep into the ternary system in the form of a narrow band, which, when extrapo-

Jan 1, 1956

By Roscoe C. Clark

In a previous technical note&apos; by Walter Rose, evidence is offered in support of the contention that "the possibility of describing oil recovery features in terms of capillary pressure phenomena has not been established entirely." It is not the purpose of this note to present further discussion of this possibility but rather to point out that the argument presented there does not appear to be generally valid. In the cited note&apos; reference is made to the experiments of Welge2 wherein it was shown that when water was displaced by oil from a core the pressure in the water phase was less than in the oil phase but that when this oil was then produced by water drive the pressure in the water phase was greater than in the oil phase. Rose has concluded from these observations that conditions of static equilibrium did not obtain since the fluid saturations were such that phase discontinuities seemed unlikely. The argument from which this conclusion was drawn is based on the contention that "the pressure is always greatest in the non-wetting phase at each static interstitial interface of contact with the wetting phase." This premise appears to have been reached from a consideration of capillary phenomena in cylindrical tubes, although it may a1so hold for other types of pore geometry, hut as will be shown below it does not hold for all pore shapes and hence is not generally applicable. Since the pore structure of porous media such as reservoir rocks i- in general so complex as to defy exact description. it is undoubtedly of great value to establish a model in terms of pore shapes of known geometry, provided of course that the limitations of the model are recognized. That the limitations of the capillary. or cylindrical, tube model have not always been fully recognized will be evident from the following discussion of a pore of different shape hut one which may a. logically he considered a.; the capillary tube. The pore space to be considered is that shown in Fig. 1, which may be thought of as the "hole in a doughnut."* Consider the interface, A-B-A&apos;, between two immiscible fluids, P, and P2, which interface meets the solid alone a line, A-C.A&apos;-C&apos;. The interface A-B-A&apos; is the surface of a spherical segmen† while the line of mutual contact be-

Jan 1, 1950

By C. C. Clark, J. R. Mihalisin, K. G. Carroll

OBSERVATIONS made in this paper were for the purpose of exploring the anomalous behavior of a particular heat of Type 310 stainless steel. The alloy, of nominal composition 25 pct Cr, 20 pct Ni, was observed to form a grain boundary precipitate at exceedingly high rates. A sheet of this metal, 0.060 in. thick, after cooling in air from 2000°F showed the presence of the grain boundary material, whereas none was found after water-quenching from the same temperature. X-ray techniques were applied without success and, in view of the ex-

Jan 1, 1958

By Emma Smith, R. W. Guard

INVESTIGATION of the nickel-rich end of the Ni-Zr system has been prompted by an interest in the effect of small amounts of zirconium in high temperature alloys. Hansenl presents a hypothetical diagram based on the work of Allibone and Sykes,2 who investigated the system up to 44 atomic pct (55 wt pct) Zr by metallographic means. Since the alloys they used were melted in Alundum crucibles they were probably contaminated with appreciable amounts of aluminum. They found two compounds which they called Ni3Zr and Ni4Zr. Hayes, Roberson, and Paasche3 identified a compound NiZr (50 atomic pct Zr) with a melting point of 1470°C. Such a high melting compound is not compatible with the observation of Allibone and Sykes2 hat a eutectic is formed near 50 atomic pct. The alloys containing up to 60 atomic pct Zr were melted in an inert atmosphere in a noncon-sumable electrode arc furnace. Analysis of most of the alloys indicated negligible loss of zirconium. The alloys were examined in the as-cast condition and also after annealing for 6 hr at 1175°C (or 1000°C for the alloys between 25 atomic pct and 45 atomic pct). Metallographic specimens were etched using mixtures of HF-HNO3-H2O or acetic acid- HN0,-H,O. The specimens for the solidus determinations were wrapped in molybdenum foil and sealed in evacuated quartz tubes. Specimens to be heated above 1300°C were enclosed in zirconia tubes inside the quartz to prevent reaction with molybdenum. The solidus determinations were carried out by heating the specimens at various temperatures for a few minutes and then examining the interior structure metallographically to determine at what temperature melting began. The 150 mesh powders for X-ray analysis were annealed in an evacuated quartz tube for 2 hr at 540 °C to remove cold work. Alloys with 22.5 atomic pct Zr and 44.4 atomic pct Zr required annealing at 700 °C for complete recovery. The grains of both of these alloys were soft and rather ductile. Both Debye-Scherrer film patterns and spectrometer traces were made for each alloy using filtered copper radiation. Results and Discussion The presence of a substantial amount of second phase in an alloy with 1.1 atomic pct Zr indicated that the solid solubility of zirconium in nickel is somewhat less than 1 atomic pct. The a0 value for the face-centered-cubic matrix in the same alloy was equal to that of pure nickel, so that the solubility must be very small. This observation is as expected from the large atom size difference. Annealed specimens of alloys with 15.0, 16.7, 22.5, 28.6, 44.4, and 59.4 atomic pct Zr showed. micro-structures that were essentially single phase. When

Jan 1, 1958

By R. B. Rosene, G. L. Foster, A. R. Hendrickson

he properties of some of the common fracturing oils, such as sand-falling rate, fluid loss and viscasity, are a function of the three major constituents of the oil. These are: asphaltic material, parafin waxes and a base oil. The base oil can be either high or low viscosity. Asphaltic material increases viscosity by thickening the oil, decreasing the rate of fall of sand through the oil. at temperatures up to 200" F. When large arnorrnts of parafin wax are present, much of the wax i.s not dissolved, but is present in the form of rnicroscopic crystals. 7&apos;his, of course is limited to temperatures below the melting points of waxe.s. As a result, parafin waxes clo not function primarily as thickener.7, but rother as bullting materials. The functiori of wax, without asphaltic material, in a low viscosity base oil is uniquely unlike that of wax with asphalt coexistent in the oil. The resulting difierence in wax crystal size governs the sand-falling rate to a large extent. An ideal type of fracturing oil is one containing neither asphalt nor waxes. In such cases, the viscosity and resulting low sand-falling rate are apparently due to soluble resin- ous hydrocarbons, which are compatible with formation oils. INTRODUCTION Since the introduction of hydraulic fracturing as a method of stimulating production from oil and gas wells, a variety of fluids have been employed to open the fractures and carry the propping agent. Such fluids include gels, emulsions, and oils. In the latter category, the use of refined oils has increased tremendously, and it is probably safe to assume that such oils represent more than one-half of the total fluid used in fracturing. The general acceptance of refined oils for fracturing can be accounted for on the basis of their relatively low cost and general applicability. To minimize transportation costs, such refined oils are generally obtained within the local areas of operation. As a result there are several kinds of oil used in different areas, with a wide variation in the basic composition. These types may vary from a fair grade of lubricating stock to a highly viscous cut-back asphalt. or road oil. Originally, little attention was paid to the composition of the oils used for fracturing, and any oil which would carry sand was considered satisfactory. Recently, however, service companies and well operators have become more concerned with the type of oils used for fracturing. With this in mind, the present work was undertaken to evaluate and compare many widely used fracturing oils to determine which constituents were most desirable for fracturing purposes. Some of the important properties of fracturing fluids are sand-falling rate, viscosity, and fluid loss. Other properties, that are actually of no less importance, include flash point, pour point, emulsifying tendencies with formation brines, and compatability with the formation oils. This discussion has been limited, however, to the first mentioned properties in order to give some idea of the general composition of the refined oils, how they function, and why. PROPERTIES OF FRACTURING OILS The properties of fracturing oils are a function of the three major constituents of the oil. These may be designated as: (1) asphaltic material, (2) paraffin waxes and (3) a base oil, which may be of either high or low viscosity. The asphaltic material clas-

Jan 1, 1956

By M. J. Sinnott, H. B. Probst

AN extensive survey of the factors which affect austenite grain growth has already been made.&apos; These factors are temperature, time at temperature, rate of heating, initial grain size, hot-working, alloy content, ofheating,initialand rate of cooling from the liquidus-solidus temperature. In the present work, a vacuum-melted temperature.electrolytic iron was used and the variables studies were temperature, time at temperature, and prior ferrite grain size. Other factors were maintained constant. The iron used in this study was vacuum-melted electrolytic iron of nominal composition of impurities of 0.07 wt pct. It was supplied as a ½ in. round cold-drawn bar. This iron was tested in three conditions: as-received, annealed 6 hr at 1200°F, and annealed 6 hr at 1600°F. Samples were ? in. disks cut from the bar. The prior anneals were carried out in vacuum and the isothermal treatments were carried out in vacuum-sealed Vycor tubing. The thermal etch technique was employed to determine the austenite grain size. Prior to sealing the test specimens, one surface of the sample was polished metallographically. This surface, after heating, was examined to determine the austenite grain size, since the austenite boundaries are revealed by thermal etching. This is essentially the only technique available for measuring the austenite grain size of low carbon steels or pure irons without altering the composition. It has been shown to yield results that are in agreement with other methods used for determining austenite grain sizes.&apos; The specimen size was quite large compared to the grain size measured, so inhibition of growth due to size effects is probably negligible. After vacuum sealing, each sample was placed into a furnace at temperature and at the completion of the run was quenched into a mercury bath. The growth temperatures used were 1700°, 1800°, 1900°, and 2000°F controlled to -~10"F. Growth times were varied from 10 to 240 hr. The long times were used in order to eliminate the nucleation and growth effects occurring during the initial transformation. Time was measured from the introduction of the capsule into the hot furnace to the time of quench. Grain-size measurements were made with the use of a grain-size eyepiece of a microscope. By determining the number of grains per square millimeter at X100 and taking the square root of the reciprocal of this number, the average linear dimension of the grains was determined. Figs. 1 and 2 are plots of these data as a function of time and temperature for the various conditions investigated. The variation of D, the linear dimension of the grains, was assumed to follow the equation3 D = A tn. The curves of Fig. 1 were obtained from the data by the use of the least-squares method of analysis. Fig. 1 is for the growth of the as-received stock and Fig. 2 is for growth after prior treatments. Differentiating the foregoing equation gives an expression for the rate of growth dD/dt = G = nAtn-1 = nD/t. Both D and G as functions of t are given in Table I. It should be noted that G is a function of time; the growth rate is rapid at early stages and decreases with increasing time. Since increasing temperature increases the growth rate, it has been common practice to use the empirical relationship G = Go e-Q/RT to relate temperature to growth rate. The growth rate customarily has been taken at constant values of D on the basis that the rate of growth is related to the boundary surface tension and this is measured by the curvature of the boundary. At constant D values, the growth rate is a function of time and temperature. The growth rate can be related however to temperature at constant time, and this has the advantage that under these conditions the growth rate is a function only of temperature. Obviously the Q values, activation energies, obtained for each assumption will not be the same and the question of which is the more correct is a moot one, since the assumed exponential relationship in either case has no particular theoretical significance. By plotting G, at constant grain size, vs 1/T, the activation energy over the temperature range of 1800" to 2000°F is found to vary from 30,000 cal per mol at the smaller grain sizes to 50,000 cal per mol at the larger grain sizes. The 1700°F data do not correlate with the data at higher temperatures. The activation energies for the 1200" and 1600°F prior annealed materials were calculated as 50,000 and 62,000 cal per mol, respectively, using the reciprocal time to a given grain size as a measure of the growth rate. Plotting G, at constant times, vs 1/T yields an activation energy of 12,300 cal per mol for the tem-

Jan 1, 1956

By B. C. Woodfine

WHEREAS it is generally assumed that the highest temperature at which temper brittle-ness takes place is about 625°C, 1,2,3 Jaffe, Buffum, and coworkers have referred in several recent papers45,6,7 to the occurrence of temper brittleness in an SAE 3140 steel at 650" and 675°C. Their re- sults show that a considerable increase in transition

Jan 1, 1955

By L. D. Jaffe, D. C. Buffum, F. L. Carr, M. Goldman

IN an earlier investigation by Jaffe and Buffum,&apos; a time-temperature transformation diagram for isothermal temper embrittlement of an SAE 3140 steel showed some suggestion of two overlapping "noses." These authors mentioned, as a possible explanation, that their specimens embrittled at 525°C were slightly softer than expected, perhaps because of some slight unknown variation in tempering treatment. Because a double nose would be of considerable importance in elucidating the mechanism of the temper brittleness reaction,&apos; it appeared worthwhile to redetermine the portion of the diagram near 525°C. The same heat of SAE 3140 steel was used as in the previous work, and experimental procedures were the same.&apos; Blanks were austenitized 1 hr at 900°C, water-quenched, tempered 1 hr at 675°C, and water-quenched. Groups were then embrittled isothermally at the temperatures and for the times shown in Table I, and water-quenched. For comparison, one series was tempered various times at 675°C, water-quenched, and given no further treatment. V-notched Charpy impact specimens machined from the blanks were tested over a range of temperatures. Energy absorption and percentage of fibrous fracture were plotted vs test temperature for each group, utilizing both the new data and those for the same treatment obtained in the earlier work,&apos; except that the earlier data at 525°C were discarded.* are given in Table I. After a small correction (-0.28°C/BHN) for the variation of hardness" from Rockwell C24, the transition temperatures were plotted against embrittling time for each embrittling temperature, using the data of Table I for the range of treatments covered there, and using previous dataL for other treatments. By cross-plotting, Fig. 1 was finally obtained. It appears from this figure that if there are two noses to the time-temperature-transformation diagram for isothermal temper embrittlement of SAE 3140 steel, the upper nose must lie above 575°C. As interest had been primarily in the region near 525°C, a thorough study of embrittlement above 575°C was not made. Fig. 1 shows that such a study is needed, especially since preliminary measurements at the tempering temperature of 675°C reveal much more rapid embrittlement than would be expected from the data at lower temperatures. The transition temperature increased, approximately, as the logarithm of the tempering time (about 81/2°C, after correction for hardness, for each doubling of the time).& Since three tensile specimens tempered 240 hr at 675°C and water-quenched had an average yield-tensile ratio of 0.844, with 70.7 pct reduction of area, it is assumed1 that the tempering temperature is not above Ae1. The omission of a quench-and-reheat operation below Ae1, for the groups tempered at 675°C, as compared to groups embrittled at lower temperatures, should not affect results." More detailed investigation of embrittlement above 575°C is now under way.

Jan 1, 1954

By D. J. Blickwede

WHEN iron is dipped in molten zinc at temperatures in the range 840" to 930°F, the two metals react to form layers of Fe-Zn compounds which adhere to the iron. At the galvanizing tem- perature, the successive layers are:&apos; y (Fe5Zn21), 61 (FeZn;), and 5 (FeZn13), in conformity with the Fe-Zn constitution diagram. There is no quantitative information in the literature on the rates of growth of the individual alloy layers over the temperature range 840° to 930°F. Rather all the past experiments have studied the loss in weight of iron as a function of galvanizing

Jan 1, 1954

By B. W. Levinger

THE lattice parameter of the ß form of pure titanium has been measured at elevated temperature.&apos;, &apos; No attempt was made, however, to correct the parameter obtained to room temperature. In the course of phase diagram studies at Armour Research Foundation and elsewhere, the variation of ß-phase lattice parameter with composition has been established in a number of binary and ternary systems involving titanium. It was possible to extrapolate in these instances to 100 pct Ti to find the apparent lattice parameter of ß titanium at room temperature. Table I lists the results thus obtained. The suggested value for the lattice parameter of ß titanium is the average of the extrapolated values 3.276 ±0.003 kX. This suggested value gives an interatomic distance in ± titanium of 2.837 kX and hence a Goldschmidt atomic diameter (coordination number 12) of 2.925 kX. The latter agrees closely with the value of 2.93 given by Hume-Rothery." From the data of Adenstedt and coworkers&apos; it was possible to determine by extrapolation the mean coefficient of linear expansion for /3 titanium in the range from room temperature to 1000°C. This value, 10.1x10-8 per degree C, compares with about 11x10-8 for a titanium in a similar range." It was thus possible to calculate the parameter at 900 °C. The value of 3.305 kX agrees well with 3.3065 given by Eppel-sheimer.&apos; The majority of values reported in the literature7-&apos;, &apos; were given as Angstroms. In at least one case, ref. 8, it was shown that they actually represented kX units. The source of this confusion appears to be that a large number of tables of X-ray emission spectra list wavelengths as Angstroms and give values in kX units. The accepted conversion factor for kX units to Angstroms (10.&apos; cm) is 1.00202. Thus the parameter of ß titanium suggested corresponds to 3.282A. References J. H. de Boer, W. G. Burgers, and J. D. Fast: Proc. Acad. Amsterdam (1936) 39, p. 515. 2D. S. Eppelsheimer and R. R. Penman: Nature (Dec. 2, 1950) 166, p. 960. 3 W. Hume-Rothery: The Structure of Metals and Alloys (1945) London. Inst. Metals. 4 H. K. Adenstedt, J. R. Pequignot, and J. M. Raymer: Trans. ASM (1952) 44, p. 990. 5 Gmelins Handbuch der Anorganischen Chemie. Titan, Verlag Chemie, Weinhein (1951). 8 P. Pietrokowsky and P. Duwez: Trans. AIME (1952) 194, p. 627; Journal of Metals (June 1952). 7 P. Duwez and J. L. Taylor: Trans. ASM (1952) 44. D. 495. 8 M. Hansen, E. L. Kamen, H. D. Kessler, and D. J. McPherson: Trans. AIME (1951) 191, p, 881; Journal of Metals (October 1951). 8 Unpublished Research, Armour Research Foundation.

Jan 1, 1954

By T. S. Liu, E. A. Peretti

A LITERATURE survey of the In-Sb system, which was made before a study of the binary diagram was undertaken, revealed that the intermediate phase InSb existed and that its crystal structure is face-centered cubic of the zinc blend type. In 1929 Goldschmidt&apos; determined the lattice constant for InSb and obtained a value of 6.452A. A more recent value, 6.461A was reported by Iandelli2 in 1941. The purity of the indium used was not very high, however. The indium used by Iandelli contained 2 pct Ge. In view of this fact it was decided to remeasure the lattice parameter using high-purity indium (99.97+ pct In) and spectrographically standardized antimony of the highest purity available (99.91 pct Sb). Specimens corresponding to the InSb composition were made by carefully weighing the ingredients on an analytical balance and heating them in vacuo in a quartz tube at 700°C. As melting losses were negligible, the alloys were not analyzed chemically, but the intended analysis was taken as being accu- rate. Powder samples were prepared by either filing or crushing of the brittle alloy, followed by screening at 325 mesh. The powders were then annealed at 400°C in evacuated capsules for about an hour. X-ray photograms were taken with a Debye and a back-reflection focusing camera, using characteristic cobalt K. radiation. Lattice parameters were calculated by Cohen&apos;s³ method. The results of a Debye pattern and of a back-reflection pattern at 25°C are given in Tables I and 11. The lattice parameter at 25 °C is 6.47602A.

Jan 1, 1952

By T. E. Watkins, M. D. Nelson

A method of determining the lime content of drilling muds proposed by Battle and Chaney* has been examined both in the Field Research Laboratories of Magnolia Petroleum Co. and in field drilling operations. This proposed analytical method is condensed as follows: Titrate one ml of mud and one ml of mud filtrate, each with 0.02 N H2SO4, to the end point with phenolphthalein. The volume of acid in ml required for the mud titration is recorded as Pm and that of the mud filtrate titration as Pf Calculation of the lb lime/bbl mud is accomplished by use of the formula, lb lime/bbl mud = 0.6 (Pm - 1.3Pf) - 0.6 The analytical procedure outlined by Battle and Chaney was found to be quite satisfactory when reasonable precautions are used in mud sampling technique. Calculation of lime concentration by the method proposed in the above publication, however, has given values that varied as much as 100 per cent from the known lime content, for muds of either high or low solids concentration. By use of a formula, lb lime/bbl mud = 0.26 (Pm-F1.Pf), based on chemical equivalents of acid required for titration, both laboratory and field data have been satisfactorily correlated with the known amounts of lime present in the muds. In this formula a correction, F1, or volume fraction of liquid in the mud, is made for the solid content of the mud. Pm and Pf * Paper on "Lime Base Muds," presented by J. L. Battle (Humble Oil and Refining Co., Houston, Tex., and P. E. Chaney (Sun Oil Co., Beaumont Tex.), at the 1949 Spring Meeting of the Southwestern District API Division of Production, Dallas, Tex. The analytical procedure has also had wide distribution in a trade journal, Kembreak, published by the Accuracy Rig and Tool Co., Houston, Tex, †Derivation of equation lb/bbl — grams/350 ml 1 ml 0,02 N acid = 0.000741 grams of lime 1 ml 0.02 N acid/ml lime suspension = 0.26 lb of lime bbl lb of lime/bbl = 0.26 (Pm -F1, Pf ) have the same significance as in the Battle and Chaney equation. Table I shows typical data employing both formulas in calculating the lime content of various lime muds. This suggested procedure ignores lime which is in solution in the mud. The solubility of lime in water, normally about 0.5 lb per bbl, is greatly decreased by the addition of caustic soda, and, in a lime mud, it is probable that the concentration of dissolved lime is of the order of 0.1 lb per bbl. Such an amount of lime can be ignored, since it is within the range of accuracy of the method.

Jan 1, 1950

By C. T. Wei, A. Kelly

USING a recently developed X-ray method, reported by Schulz,2 it is possible to make a rapid survey of the perfection of a single crystal at a particular surface. This technique has the advantage of allowing a large surface of a specimen to be examined by taking a single photograph and it compares well with other X-ray methods in regard to sensitivity of detection of small angle boundaries. During the course of a survey of the perfection of large crystals of aluminum produced by a number of methods, an examination has been made of a number of single crystals produced from the melt using a soft mold (levigated alumina)." Crystals grown by this method are known, from an X-ray study carried out by Noggle and Koehler,3 to contain regions where they are highly perfect. In the present work, it has been possible to obtain photographs showing directly the distribution of low angle boundaries at a particular surface of these crystals. single crystals were grown from the melt using the modified Bridgman method with a speed of furnace travel of -1 mm per min. These were about 1/10 in. thick, 1 in. wide, and several inches long. The metal was 99.99 pct pure aluminum supplied by the Aluminum co. of America. The crystals were examined by placing them at an angle of about 25° to the X-ray beam issuing from a fine focus X-ray tube of the type described by Ehrenberg and Spear4 and constructed by A. Kelly at the University of Illinois. A photographic film was placed SO as to record the X-ray reflection from the lattice planes most nearly parallel to the crystal surface. The size of the focal spot on the X-ray tube was between 25 and 40 u, and the distance from the X-ray tube focus to the specimen (approximately equal to the specimen to film distance) was -15 cm. White X-radiation was used from a tungsten target with not more than 35 kv in order to reduce the penetration of the X-rays into the specimen. Exposure times were approximately 1 hr with tube currents between 150 and 250 microamp. The type of photograph obtained from these crystals is illustrated in Fig. 1, which shows a number of overlapping reflections from the same crystal. The large uniform central reflection is traversed by sets of horizontal white and dark lines. These two sets run mainly parallel to one another. Lines of one color are wavy in nature and often branch and run together. Large areas of the crystal surface show no evidence of these lines whatsoever. The lines are interpreted as being due to low angle boundaries in the crystal, separating regions which are tilted with respect to one another. A white line is formed when the relative tilt forms a ridge at the interface and a black line is found when a valley is formed. In a number of cases, the lines stop and start within the area of the reflection and often run into the reflection from the edge, corresponding to a low angle boundary starting from the edge of the crystal. The prominent lines run roughly parallel to the direction of growth of the crystal although narrow bands can run in a direction perpendicular to this; see Fig. 2. Although they may change their appearance slightly, the lines tend to occur in the slightly,Same place in the X-ray image and to maintain their rough parallelism when the crystals are reduced in thickness by etching. Thus the low angle boundaries can occur at any depth within the crystal. The appearance of the lines is unaffected by subjecting the crystal to rapid temperature changes, such as plunging into liquid nitrogen or rapid quenching from 620°C. From the width of the lines on the x-ray reflection, values can be found for the angular misorienta-tion of the two parts of the crystal on either side of a boundary. The values found run from 1&apos; to 10&apos; of arc, but values of UP to 20&apos; have sometimes been found, e.g., the widest lines on Fig. 2. These mis-orientations are much less than those commonly found in crystals possessing a lineage structure. When a number of a and white lines occur, running in a roughly parallel direction across the image of a Crystal, the total misorientation corresponding to lines of one color is approximately equal to that corresponding to lines of the other color. The interpretation of the lines as due to low angle boundaries has been checked in a number of ways. Photographs taken with different specimen-to-film distances distinguish lines due to low angle boundaries from effects due to surface relief of the specimen. Normal Laue back-reflection photographs, taken with the beam irradiating an area of the surface showing a number of the lines, show white lines running through each Laue spot. Black lines are set to see by this method. X-ray photographs were also taken, using the set-up described by Lam-one et al.5 when the beam straddles regions giving rise to lines in the Schulz pattern, split reflections are observed within the Bragg spot. The misorienta-tions calculated from the separation of these reflections and that found from the widths of the lines on the schulz technique patterns show good agreement. An exposure was made with Lambot technique of an area of the crystal showing no evidence of low angle

Jan 1, 1956

By C. F. Austin

lined-cavity shaped charge is an explosive mass with a cavity at one end and the detonator at the opposite end. The cavity is lined with a dense material, such as metal, glass, or a ceramic. Such an explosive device can be a useful drilling tool. Lined-cavity shaped charges are constructed to do just one thing — create a high-velocity jet of liner particles that can bore a hole in a target. The liner must be smooth and symmetrical, and high-velocity, high-brisance explosive must be used rather than ordinary commercial dynamites. Since the depth of target penetration is related to jet length, a standoff distance should be provided to hold the charge a short distance from the target. This allows the jet to lengthen prior to target impact. The best results are obtained when the jet is perpendicular to the target surface. Charges can be positioned for firing by taping them to a stake or simply laying them on a flat surface at the proper distance and angle with respect to the target. EFFECTS ON THE TARGET When a jet strikes a rock target, the jet and target particles at the jet-target interface move outward radially with respect to the jet axis to create a tremendous compressive load on the target material immediately below the target surface. The result is a shallow crater formed by spalling at the point of target entry. After cratering ceases, the steadily deepening hole continues to form as a result of the jet&apos;s imparting radial motion to the target particles at the jet-target interface. These radially moving particles collide with one another and with the hole walls, the net motion of the spent jet particles and target particles being back out of the hole in an axial direction (the backblast). The backblast keeps the penetration free of debris during penetration, al- though loose surface rock often falls into the hole after penetration ceases. The sudden stress relief after penetration ceases sometimes results in minor hole-wall rebound, which can partially fill the hole. The hole bottom will taper as the jet velocity decreases, until the jet velocity is too low to maintain the backblast. At this point the remaining jet and the following slug material are simply packed into the hole bottom. HAZARDS INHERENT IN USE Air blast from the highly brisant explosives used in shaped charges can damage nearby structures

Jan 1, 1961