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By Y. C. Liu, G. A. Alers

measurements of the anisotropy in Young's modulus produced in copper by rolling 95 pct reduction in thickness below room temperature have been carried out in order to study the dependence of the texture on rolling temperature. The results clearly show the transition from a copper-type texture to a brass-type texture as the temperature of rolling is lowered. The intermediate textures observed can be described very well as a simple mixture of the two terminal textures. These results cormbined with other texture measurements make possible afresh review of the experimental facts velating to rolling textures in fee metals and, as a consequence, a critical examination of the current theories is presented. PREVIOUS experiments have shown that the transition from the copper- to the brass-type rolling texture is clearly displayed and can be quantitatively analyzed by measurements of the anisotropy of Young's modulus.' Application of this method to the Cu-Zn alloy system showed that the description of the texture transition as a gradual rotation of the grains from the orientation characteristic of the copper texture to the {110}(112) texture of brass2 was inconsistent with the data. Instead, the data suggested that the texture within the transition region could be described as a simple mixture of the two terminal textures.5 Unfortunately, it was difficult to establish this point conclusively because of the inadequacy of corrections for the composition dependence of the single-crystal elastic constants. Since a rigorous establishment of the nature of this texture transition is essential to our understanding of the formation of rolling textures in fee metals, it is clearly important to undertake an investigation in which the composition dependence of the elastic constants would not enter. A suitable composition-independent texture transition is provided by the well-established variation in the rolling texture of copper with rolling temperature. This temperature-dependent texture transformation has been studied by smallman' in several fee alloys and by Müller5 and others"' in copper. They observed that the texture characteristic of copper rolled at room temperature changed to a brass-type texture when the rolling temperature was lowered to 77°K. Although it is not possible to decide unequivocally from the published pole figures whether or not the 77°K rolling texture of copper is entirely of the brass type,' this complication does not affect the main purpose of the present investigation. In addition to establishing the nature of the texture within the transition region, the modulus data should also provide a determination of the temperature at which the transition occurs as well as the temperature range over which the transition extends. This information when combined with the modulus data on Cu-Zn alloys would then provide a considerable body of new information on textures in fee metals. Since these modulus results and the data obtained from pole-figure studies must be internally consistent, it is appropriate to compile a brief summary of the experimental observations based on all available methods rather than on the pole-figure data alone as has been done in the past. The primary purpose of such a summary would be to yield a more precise definition of the experimental facts on the rolling textures of fee metals, and thus greatly facilitate our evaluation of various proposed theories in this field. The final section of this paper is devoted to this compilation of consistent, experimental facts and their application to the various theories. EXPERIMENTAL PROCEDURE Two 18-lb ingots of cathode copper of 99.99 pct purity were induction-melted under a nitrogen atmosphere in a graphite crucible and chill-cast into a steel mold. The ingots were repeatedly cold-rolled and annealed (I hr at 500°C) into slabs about 1 1/8 in. thick. Blocks 3 1/4 in. wide, 2 1/4 in. long, and 1.000 in. thick were machined from each slab. The rolling schedule used was the same as in the previous investigation1 and the final thickness of the sheet was 0.050 in. with a rolling reduction of thickness of 95 pct instead of 97.5 pct as in the previous work.' The compositions and temperatures of the cold baths used for the low-temperature rolling were as shown in Table I. After each pass the rolled strip was immediately immersed in the cold bath for about 1 min or until the bubbling of the bath had subsided. The modulus data were taken within 2 hr after the rolled strip was warmed to room temperature for the first time, so that effects due to recrystallization were minimized. The modulus specimens were in the shape of flat bars, 3 in. long, 4 in. wide, and 0.050 in. thick, cut with their long dimensions oriented at 15-deg intervals between the rolling direction and the transverse direction. The values of Young's modulus were deduced from measurements of the frequency at which these long narrow bars were set into longitudinal, resonant vibration as previously described.9 To excite the mechanical vibrations in the specimen, an electromagnetic drive similar to that employed by Thompson and lass" was used. The maximum in the amplitude of

Jan 1, 1968

By Martin Rubenstein

CdS crystals have been grown from a number of metallic solvents such as bismuth, tin, lead, and cadmium. Etching studies have shown that plastic deformation occurs if the crystals are not removed from the solvent prior to the solidification of the solvent, on cooling. The deformed crystals show a umique exciton fluorescence as a function of edge dislocation density. If one grows the CdS in the eutectic alloy of the above four metals (commonly called Wood's metal) the crystals can be removed from the solvent with hot water and no plastic deformation occurs. In this paper, the liquidus solubility measurements of CdS, as a function of temperature, are presented. The data were obtained using a high -temperature filtration technique. CADMIUM-SULFIDE crystals have been grown from a number of metallic solvents1 such as cadmium, bismuth, tin, and lead. Liquidus solubilities of CdS in cadmium,2 bismuth,3 and tin4 have already been measured. Crystals of CdS, in all four metals, have been grown by solution growth: 1) by cooling a saturated solution and 2) by a solution transport method.1'"1 CdS crystals grown in these four solvents have a few characteristics in common: 1) 1.8°K photolumines-cent emission consisted mainly of the radiative recombination of the bound exciton commonly known as I,, 2) slip lines which could easily be seen by the naked eye, and 3) edge dislocation densities in the order of l05 per cu cm.1 It was decided that these slip lines and the high edge dislocation densities were caused by a plastic deformation of the CdS crystals. It was felt that this plastic deformation did not occur during the growth of the crystals nor during the cooling of the solution, but did occur when the solvent which was in contact with the crystals froze. If these assumptions were valid, the slip lines and the high number of dislocations could be reduced or eliminated by removing the crystals from the solvent before the solvent froze. Since crystals of CdS had already been grown separately in such solvents as bismuth, lead, tin, and cadmium, it was felt that crystals could be grown in a eutectic mixture of these four metals. In this work a eutectic (or near eutectic) mixture of bismuth, lead, tin and cadmium in the proportion 50, 26.5, 13.5, and 10 wt pct, respectively, was used to grow CdS crystals. Such a mixture has a melting point of about 70°C and is close in composition to the alloy commonly known as Wood's metals. If the crystals could be grown from this mixture of solvents, and if hot water (>75°C) could be used to separate the crystals of CdS from the metallic solvent, it was hoped that CdS crystals could be grown with little or no plastic deformation which had been ob- served when crystals were grown from these solvents uncombined. CdS crystals were grown from this low melting eutectic mixture of bismuth, lead, tin, and cadmium using the solvent transport method. CdS powder and the appropriate amount of metals were sealed in a quartz tube under a pressure of about 5 X 10-6 torr. This ampule was then placed in a vertical position in a furnace. The temperature was raised to about 900°C. The furnace was designed so that the top of the liquid column within the ampule was between 10° to 40°C higher than the bottom of the liquid column. These temperatures were measured on the outside of the quartz ampule. The ampule was maintained at temperature for 7 to 14 days (depending on the temperature at which transport was taking place) and then the furnace temperature was lowered until the temperature was about 125°C. The ampule was then removed from the furnace, placed in water maintained at about 90°C, and opened in this 90°C environment. The crystals could then be removed from this two-phase liquid (Wood's metal and water) by mechanically picking them out. Alternatively, the crystals could be quantitatively removed by adding an excess of mercury to the mixture of metals, crystals, and hot water. The hot solution of metals and the hot water could be evacuated using a small diameter tube connected to a vacuum. Small amounts of mercury and water could be removed by heating the crystals in vacuum. Crystals prepared using this technique showed no evidence of slip. However, some of these crystals did show edge dislocation densities as high as l04 per cu cm. Some few selected crystals showed no dislocations. Single crystals of CdS were grown as large as 5 by 5 by 0.5 mm. The ampules for the growth of these crystals were 13 mm O.D., 11 mm I.D., 150 mm! LIQUIDUS SOLUBILITY MEASUREMENTS The CdS starting materials was G.E. 118-8-2 powder which was fired in H2S at 1000°C, and then a vapor transport technique5 was applied to produce a "sound" mass of CdS. The Wood's metal was prepared by weighing out bismuth, lead, tin, and cadmium in the proportions of 50, 26.5, 13.5, and 10 wt pct, respectively. The bismuth, cadmium, and lead were from the American Smelting and Refining Co. (ASARCO) and all had purities of 99.999+ pct. The tin was 99.9999 pct spectroscopic grade from the Vulcan Materials Co. The appropriate mixture was placed in a quartz tube, evacuated to a pressure of 5 X 10-6 torr, melted to a liquid, cooled to room temperature under this same vacuum. This ingot was then placed in another quartz tube, evacuated to 5 x l0-6 torr, and sealed off under vacuum. The ampule was then horizontally placed in a furnace. The temperature was raised to 600°C, and over a period of several hours the ampule was vigorously shaken several times. The ampule was then removed from the furnace, and the metallic liquid was

Jan 1, 1970

By Ottar Dragge, C. Danielsson, Bo Kalling

THE desulphurizing of pig iron has been accomplished with a number of different additions. The oldest and still most commonly used agent is soda, the extensive use of which commenced about 1925, when it was used principally for cupola furnace iron. More recent experience' seems to show that better results can be obtained with sodium hydroxide. The well-known desulphurizing properties of lime have also been exploited in different technical processes. Another material with even more powerful effect is calcium carbide.' The desulphurizing ability of manganese, when added to the ladle in sufficient quantity, should also be mentioned in this connection. During recent years increasing attention has been paid to the desulphurizing properties of metallic magnesium." An addition of a suitable alloy of magnesium is now in use purely for the purpose of sulphur elimination. Of the desulphurizing agents mentioned, lime is by far the cheapest, provided that the reaction can be brought about rapidly and completely. Therefore, a method that makes full use of the desulphurizing ability of lime may be able to compete with other processes. A method developed at the Dom-narfvet Iron and Steel Works (Sweden) will be described, which enables pig iron to be rapidly desulphurized to very low sulphur contents by using a burnt lime powder. as the desulphurizing agent. Lime in Older Processes In cases where lime has been used for the desul-phurization of pig iron, it has generally not been used alone, but mixed with other substances such as fluorspar, to obtain the formation of a molten slag during the process. This method has been tried by Tigerschiold,' who treated the iron with a lime-fluorspar mixture, the stirring of the iron being brought about inductively with low frequency alternating current. Very good results were obtained. A process of this type has also been suggested by R. P. Heuer, U. S. A. The principles of this method, which has been tested in Great Britain by Newell. Lanener. and Parsons." re that a mixture of lime and fluoispar is added to the hot metal in the ladle, while a powerful stream of nitrogen gas is blown into the bath to produce the required intermixing. The results of the tests were unsatisfactory, however. A similar process has been developed at The Steel Co. of Canada, according to a statement by H. M. Griffith.' Here the tests were carried out in a carbon-lined ladle provided with carbon tuyeres in the side wall for blowing nitrogen into the bath. The addition consisted of about 20 lb of a mixture of burnt lime and fluorspar per ton of pig iron. Good results appear to have been achieved. The sulphur content of the pig iron is stated to have been reduced from 0.025 to 0.050 pct down to 0.006 pct. Various methods of desulphurizing pig iron have been tried using lime powder without fluxing material for fusing. Eichholz and Behrendt7 have experimented with blowing a powdered limeicoke mixture with air into the ladle. Their results were, however, not conclusive and the experiments do not appear to have been continued. Similar experiments have been carried out at Domnarfvet, using nitrogen instead of air in order to avoid oxidation. But these attempts were not particularly successful. It appears to be difficult to achieve the required agitation by this means. The strong cooling effect of the gas on the iron is also a serious drawback. A method in many respects similar to that tried at Domnarfvet was tried by Eulenberg and Krus at the end of the 1930's. Here again desulphurization was carried out with lime alone, brought into contact with the molten iron in a rotary furnace. The temperature was kept at the required level, 1400" to 1500°C, by the introduction of a pulverized coal burner in one end of the furnace. The speed of rotating was not given. A paper by Bading and Krus states that, in one of the first experiments, the sulphur content in 56 tons of pig iron was brought down from 0.186 to 0.035 pct in 117 min, but that a considerable shortening of the time would be possible. According to later reports by Eichholz and Behrendt,' it should be possible by this process to achieve a desulphurization speed of 0.35 pct S per hr for a consumption of 6 to 10 pct limestone and 2 to 3 pct coke, as fuel exclusively. The final sulphur content is, however, not stated. Domnarfvet Method After a number of different procedures had been investigated, the tests at Domnarfvet were directed to desulphurization with lime in a rotary furnace. Before going into the practical details of the method, the theoretical aspects will be discussed briefly. If the pig iron does not contain alloying elements other than carbon, the reaction can be expressed most simply by the usual equation: FeS + CaO + C = Fe + CaS + CO [I] 4H,. ~ 34,000 cal That this reaction can be carried through to a very complete desulphurization of pig iron has been shown by OelsenD in a discussion in connection with the Eulenberg and Krus' method. He mentions two laboratory tests, in one of which the sulphur content in the pig iron at 1400°C was reduced from 0.540 to 0.006 pct after treating with 3.35 pct lime. The pig iron had a low manganese content, but other analysis is th. given. Mention also should be made of the recently published investigations by Fischer and Cohnen'" dealing with the influence of the carbon content of the iron on desulphurization with lime, although in this case fluorspar was added also. The tests show that efficient desulphurization is possible with lime in the steel bath, provided that the carbon content is sufficiently high. The temperature employed in these tests was considerably higher (1620") than that normal for treatment of pig iron. The author concludes that the product S% X C% - 0.011 at the temperature in question.

Jan 1, 1952

By R. D. Taylor, Jim Douglas Jr., H. H. Rachford Jr., P. M. Dyke

A major obstacle to the use of wetting agents in .secondary recovery by water flooding is the adsorption of the agents on the sand. As a result of adsorption, the surfactant always lags behind the floodwater front. Consideration of the chromatographic theory of adsorption indicates that the detergents will not lag as much if used in very high concentrations. An investigation was made of the possibility of using high concentrations economically by flowing slugs of wetting agents followed by normal flood water. The experiments consisted of adsorption studies on Alundum powder and Berea sandstone. Flow rests on a 12-in. Alundum core and 22-in. Berea core were used to determine rate of detergent movement. The results of the flow experiments indicate that the relative rate of surfactant advance is, indeed, sensitive to the concentration of the agent. A 10 per cent slug moved with a rate that war 78 to 95 per cent as fast as the rate of advance of the flood water. By contrast, one with 25 ppm (the number of parts of commercial detergent in a million parts of water on a weight basis) concentration moved less than one-fourth as fast as the flood water, and calculations indicate that in very long porous systems the rate of movement of the lower concentrations will be a small fraction of the rate of advance of the flood front. The results. of the adsorption studies were utilized to calculate the rate of advance of the detergent when only the initial concentration was known. The calculated rates showed substantial agreement with the experimental flow tests in the high concentration ranges. The adsorption results were also used to estimate the cost of the materials for a slug-type surfactant flood in the field. In addition to the faster rates of movement, the concentrated detergent slugs removed much more oil than the dilute solutions. However, the effectiveness of the slug process depends on many variables. The quantity of oil removed is increased markedly by increasing the flooding rate. The efficiency is also influenced by the type of crude, type of reservoir rock and initial water saturation. Therefore, a careful analysis of each reservoir system is required before the economic value of the process can be determined. INTRODUCTION It is well known that the displacement of oil by invading water during water flooding is far from complete. It is generally agreed that the unrecovered oil is retained in the porous medium by the capillary forces which may be relatively large compared to the forces generated by the flowing water. Therefore, it was logical that some early workers should turn to surface-active materials to reduce the capillary forces to facilitate the release of oil. As early as 1927,' a patent was granted for the use of surface-active materials in water flooding. In 1932, when soap solutions were passed through Bradford and Venango sands, it was reported that the results were inconclusive, erratic and that "further investigation is needed to determine exactly the function of the solution and to obtain a clearer insight into the phenomena involved."' Some of the modern scientific reports conclude with a similar statement,' showing that the lack of agreement on the mechanism of oil removal by wetting agents is still very widespread even though several comprehensive studies have been reported.'." Although there is a lack of agreement as to the general effectiveness of the detergents for water flooding, most investigators do agree that all of the common detergents are strongly adsorbed onto the solid surfaces of the reservoir. In the early calculations it appeared that all additives would be lost before reaching much of the formation area which contained the additional oil to be removed. Experiments indicated that if the usual small waterflood concentrations of wetting agents were used, the rate of advance of detergent through the formation would be only a small fraction of the rate of advance of the flood front. Indeed, some investigators4 felt that the use of wetting agents would never be economically feasible because of their adsorption. For example, DunningG estimated that the wetting agent in concentrations of 25 ppm, would advance only 0.05 times as fast as the flood front. Ojeda, et al,' found that a surfactant in a concentration of 10 ppm moved less than 0.01 times as fast as the flood front. It is significant, however, that both investigators found that increased concentrations of wetting agents moved faster, relative to the flood front, than solutions at the lower concentrations. Ojeda showed that an extrapolation of his data indicated a relative rate of 0.5 at 1 per cent concentration, while Dunning6 estimated a relative rate of 0.46 for a 1 per cent concentration. It was obvious that these concentrations could not be used for continuous injection because the cost of the injected detergent would far exceed the value of additional oil produced. Traditionally, detergents are used in very low concentrations for they show good

By R. A. Flinn, R. D. Pehlke, D. R. Glass, P. O. Hays

Knowledge of the depth of penetralion of an oxygen jet into the bath of the oxygen converter and of the correlation of penetration with driuing pressuve, lance heighl, and nozzle throat area is vital to the understanding of converter operation. If the penetration is too shallow, then severe and hazardous slopping takes place. On the other hand, if the jel penetrates entirely Lhvough lhe bath for an apprcciublc period of time, bottom damage occurs. In addilion to measurement of the penetralion of the jel, knou~ledge of the circulatory movement in the bath is also of interest in order to evaluale various theories oj-concerter operating behavior which have been published. In this investigation, experimental converters were buill of IOU- , 300-, and 4000-lb capacity. Four independent methods were used to determine penelralion: the onset of bottom marking, a nitrogen bubbler probe, observation througlt an optical syslew built into the oxygen lance, and direcl viewing of the jet issuing from the bottom of the vessel. Good correlation zuas obtained, and empirical relalions for pvedicling perletration were found. These relations were conjzrmed by bottom marking tests in 55- and 110-ton vessels. Within the operaling conditions employed in these tests, the depth to which a single oxygen jet penetrated zuas found lo vary according to the relatiorl ThE technical literature is replete with data concerning the successful use of the basic oxygen furnace or converter in steelmaking. Experimental data are lacking, however, on the vital factors of the depth of penetration of the jet into the bath and the induced circulation. Commercial operating conditions usually have been the result of cut and try experiments in lance manipulation until satisfactory results were obtained. There have been, however, two hotly argued opposing theories concerning desirable depth of penetration and these are exemplified by the Schwarz and Miles patents1,2 on one hand and the Suess patent3 on the other. The Schwarz patent teaches that the jet, issuing from the nozzle at supersonic speed, penetrates deeply "so that the reactions between the iron and the oxygen and between the oxygen and the rest of the smelting components take place in the center of the bath". Specific operating suggestions are given by Miles.2 By contrast, the Suess patent calls for surface Circulalion was investigated by lour methods: by direct observation in 200-lb open baths, by the use of graphite rudders in the 300- and 4000-lb converlers, by direct observalion through an oplical system in the lance, and by various models al room temperature. All were in excellent agreement and indicated that the motion of the bath ulas up at the center, radially outluavd at the surface, and down at the sides. Experi-ments in small and in commercial vessels indicate that it is essential to operate with a jet penetration of approximately 50 pct of the bath depth. Surface blowing results in low oxygen eficienty and in hazardous conditions which may render the process inopeuable. RejYactory dartzage al the bottom of the vessel is only encountered when the jet penetrates to the bottom, and this can be avoided by properly applying the penetration formula. The application of this en/pirical formula in commercial peraations is best when limited to combinations of lance size, pressure, and height which are typically encounteved in the use of a single-hole lance. blowing so that "...the oxygen jet does not penetrate deeply into the molten metal bath and is confined to an impingement area at the central portion of the bath surface". These references are given merely to illustrate the basic differences between the two schools of thought and to point out the need for measurement of penetration for the sake of the operator. For example, it is shown later that inefficient and even dangerous conditions can arise if improper blowing conditions are used. Differences are also evident between the two schools of thought as to the mixing, circulation, and agitation which is to be accomplished by the jet. The Schwarz patent states that "surface contact is not sufficient in most cases to bring about quick reaction, the same as the blowing of the gas over the bath surface or the mere blowing of the gas onto the bath surface". The patent goes on to call for active mixing. In contrast the claims of the Suess patent call for "discharging a stream of oxygen ... to an extent to avoid material agitation of the bath by the oxygen stream". In this patent the circulation is said to be downward in the center and up at the sides of the vessel. A number of investigators4-12 have explored penetration and circulation in transparent models. In general, it is agreed in these tests that the circulation is upward at the center (along the sides of the jet cavity),

Jan 1, 1968

By C. A. Stickels

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

Jan 1, 1967

THERE have been two important accomplishments of the Truman administration; the Hoover Commission report on inefficiency and waste in government and the report of the Paley Commission on the natural resources of the United States. Both reports are in the interest of the American people and should transcend the boundaries of political parties. Both reports are starting points for the formulation of policies which must be continuously revised to meet changing conditions. Regardless of the outcome of the election the principles embodied in these two great documents must be kept alive. The Paley report is right in our own bailiwick of mineral raw materials and it behooves us to study it carefully as our responsibility to posterity. To those in the mining industry who have limited their field of observation to moving rock or to metal prices it may come as a surprise that our production of such staples as copper, lead, and zinc has fallen behind increased requirements to the point that substantial tonnages must be imported. Iron ore is next on the list and everybody knows that such metals as tin, tungsten, chromium, manganese, nickel, and cobalt are imported almost exclusively. The crisis in raw materials pointed up by the Paley report has been reported annually by Elmer Pehrson and others to small gatherings at the Mineral Economics Division sessions at the Annual Meeting for as long as we can remember. In September 1949, the United Nations Economic and Social Council held an international resource conference at Lake Success which disclosed these same grave conclusions: - Consumption of raw materials is multiplying at an alarming rate, faster than discoveries or replacements are being made. - Production has been wasteful and utilization lavishly beyond enginee¬ing and practical requirements. - Industrialized nations are depleted and many raw materials consumed by industry are not found in the industrialized countries. - Nations formerly exporters of raw materials are increasingly building their own consuming industries. - Political forces in the world are limiting access to raw materials. The Paley Commission selecting the quarter century, 1950 to 1975, to project raw material requirements for the United States, pointed out obstacles to meeting these requirements, and made recommendations for procurement. It is not important that we disagree that cobalt consumption will reach 344 pct of present, or fluorspar 187 pct when iron and ferroalloys are only expected to increase 75 pct. What is important it that the fabulous appetite of the United States for mineral raw materials has consumed more since World War I than was consumed by the entire world in all recorded history prior to 1914. And, unless the people of the United States are satisfied to remain at their present standard of living (which is unthinkable) this consumption is correctly plotted by the Paley Commission as continuing to expand. If the U. S. is to continue on a course of progress, it must procure raw materials wherever it can at the lowest possible cost. Natural resources are clearly an area in which the broadest cooperation between industry and government must exist to achieve efficient exploitation, economic consumption, and expansion of sources of supply. The message of the Paley report requires action comparable to that of the North Atlantic Pact. Its implication is as significant as military preparedness. It is a world problem. It is a mining engineering problem. Don't let it die!

Jan 1, 1952

By R. T. Southin

Cast ingots of 99.99 pct purity A1 and aluminum/copper alloys containing up to 2 pct Cu have been found to contain four zones rather than the three previously accepted, i.e., chill, colummar, and equiaxed zones. The fourth zone consists of a coarse dendritic layer across the top surface of the ingot which is open to the atmosphere. It is also found that the grains in the equiaxed region have a "cornet" shape, with a head which is coarsely dendritic and a tail which grew with the same structure as the columnar grains. Experiments using mechanical barriers, and others involving the elimination of the surface dendrile layer, have indicated that nucleation of the equiaxed zone is caused by the showering of dendritic particles from this surface dendrite layer. These particles are the dendritic heads found in the comet grains. A mechanism of nucleation and growth of these comet grains is put forward. Experiments with a number of other metals and alloys suggests that these conclusions may apply generally to ingots cast without the addition of nucleating agents, and solidified under normal conditions. THE macrostructure of cast ingots may contain the following three zones: i) a peripheral zone of fine equiaxed grains, commonly called the chill zone; ii) a zone of columnar grains extending inwards from the chill zone; iii) a central zone of equiaxed grains; these are normally larger than the chill grains. All three zones are not necessarily present in any particular ingot since their existence and magnitude depend upon the casting conditions and composition of the cast material. The mode of formation of zones i and ii is fairly well understood. However, the cause of the central equiaxed zone remains a matter of conjecture. Previous theories put forward to explain the mechanism of nucleation in the equiaxed zone have been examined by Chalmers1 and Winegard.2 At the time when the present work was carried out the most re -cent hypothesis was that due to Chalmers,1 who recognized more fully than previous workers that conditions in this zone during solidification were not conducive to nucleation. In his hypothesis, he suggested that nuclei were formed near the mould wall during the very early stages of solidification, and that they can drift into the central zone by convective motion. This was supported by evidence from experiments using mechanical barriers to stop the drift of nuclei. A similar hypothesis had previously been put forward by Genders.3 More recently, Jackson et al. 4 have observed that dendrite arms in organic compounds can melt off during solidification. They have postulated that this occurs in metals and alloys, and that the dendrite arms which have been freed from the main dendrite act as nuclei for the equiaxed zone. In the present work, critical metallographic examination has shown that there is a fourth zone in the macrostructure of cast ingots which is a dendritic layer over the top surface of the ingot. It is also shown that there is a relationship between this zone and nucleation of the equiaxed zone. EXPERIMENTAL DETAILS The alloys examined were prepared from super -purity aluminum of 99.99 pct min purity (spectro-graphically detected impurities of Cu, Fe, Si, and Mg) and copper of 99.98 pct min purity (spectrographically detected impurities of Si, Zn, As, Fe, Pb, Bi, Ni, Sn, Mn, Ag, Cr, and Al). Three compositions of ingots were examined, containing 0.0, 0.1, and 2 pct Cu, respectively. The alloys were melted in an alumina-lined salamander crucible using a medium-frequency electric induction furnace; when the appropriate casting temperature was reached, the alloys were cast without degassing or fluxing treatment. The mould used was made of electrode graphite and had the following dimensions: external diameter 6 in., height 9 in., with a mould cavity 8 in. deep and a diameter tapering from 5 in. at the top to 4 in. at the bottom. Casting temperatures used were generally in the order of 70" to 90°C above the liquidus and the mould was at room temperature before casting. Inserts kere placed in the mould cavity in some experiments. These consisted of either an 18-g stainless-steel tube of 2 in. diam held axially in the mould i in. off the bottom and extending 1 in. out of the top of the mould or a "trap-door" barrier of stainless-steel gauze of 24-mesh held horizontally in the mould 31/2 in. down from the top. The construction of this insert is shown in Fig. 1. All inserts were preheated prior to casting to prevent chilling. RESULTS The macrostructures of ingots of the three compositions are described, in terms of the three generally recognized zones, in Table I, and illustrated in Figs. 2(a) to (c). The most interesting observation in this table is that relating to the shape of the equiaxed grains, which were not in fact equiaxed but of almost tear-drop shape. Closer examination of these grains showed that each consisted of a head which had a coarse dendritic structure and a tail which always grew in the opposite direction to heat flow, and which had the same structure as that of the columnar material of the ingot concerned; i.e., in the pure aluminum and 0.1 pct Cu alloy it was cellular and in the 2 pct Cu alloy it was cellular-dendritic. Identification of original cast grains was greatly hampered in the super-purity aluminum ingots, and to a lesser degree in the 0.1 pct Cu alloy,

Jan 1, 1968

By W. A. Backofen, D. L. Holt

Push-pull fatigue tests have been carried out at 4.2°K, 77oK, and room temperature on two poly crystalline materials of widely different stacking-fault energy (?): pure copper (? - 70 ergs per sq cm) and the Cu-8 wt pct A1 alloy (? - 2.8 ergs per sq cm). Constant stress-amplilude was imposed and measurement was made of the plastic-strain amplitude (ep) at saturation. Lives extended from 104 to 106 cycles. Designating lives at the various temperatures by NRT, N77, and N4.2. the ratios N77/NNT and N4.2/N77 ranged from 3.5 to 18 under the condition of common Ep . Metallo-graphic examination revealed different crack morphology in Cu-8 Al fatigued at room temperature, and at 77" and 4.2oK. At room temperature, cracks lay in or near grain and lain boundavies; at 77o and 4.2oK. cvacks were transcrystalline. Tests on single crystals of Cu-8 A1 showed that such a change in the cracking mode in polycrystallitle material accounted for a factor of- about 3.25 in N77/NRT . The longer life at lower tewperatztre (conslant cp) has heels attributed to two deuelopinents: a reduced production of the dislocation tangles and subgrain boundaries which serve as paths of rapid cracking, and suppression of oxygen chetni-sorption at the crack tip It was concluded that in both materials the luller accounted for an extension of the life at 4.2oK beyond that at room temperature by a factor of 15. XV ECENT experiments on the fatigue of Cu-A1 alloys in the so-called high-cycle range (greater than lo4 cycles) have emphasized the importance of stacking-fault energy (y) as a quantity affecting crack propagation rate and fatigue life.1,2 It was found in comparisons at essentially fixed plastic-strain amplitude that crack growth rate decreased by a factor of about 5 over the composition range from copper (? - 70 ergs per sq cm) to Cu-8 wt pct Al (? - 2.8 ergs per sq cm). The argument was made that, when stacking-fault energy is high, cross slip and climb are favored, so that dislocation tangles and/or subgrain boundaries form more readily under cyclic loading. Since the boundaries and tangles act as paths of rapid crack propagation ,3, 4 life is shortened as a result. However, when stacking-fault energy is reduced (as by alloying), cross slip and climb become more difficult, with the result that substructure formation is retarded and growth rate is also reduced. A purpose of the present work was to investigate the substructure effect in relation to temperature. As temperature is lowered, ? is varied only slightly (if at all), but decreased thermal activation can interfere with cross slip and climb. Thus substructure formation could be curtailed and life increased. Fatigue life in the high-cycle range is also known to be strongly influenced by environment. Working with copper, Wadsworth and Hutchings observed that life in a vacuum of 10-8 mm Hg exceeded life in air by a factor of 20.5 They isolated oxygen as the agent that furthered cracking. While the details are still unclear, a requirement in any mechanism of oxygen-accelerated cracking is that there be chemisorption at the crack tip. That could prevent welding on the compression half cycle,= interfere with reversal of slip,1, 6 or aid in breaking metal-metal bonds at the crack tip.5'7 In the work being reported here, temperature was lowered by immersion in liquid nitrogen and helium, which also served to reduce both the oxygen concentration and chemisorption rate. A possible effect upon life, i.e., a lengthening, had to be recognized. Several researchers have determined fatigue lives at low temperatures presenting their results in the form of stress amplitude (S) vs cycles in life (N) curves.8-11 Such curves reflect, primarily, the fact that metal is strengthened by lowering temperature; effects of substructure and changing environment tend to be masked. The difficulty can be overcome by comparisons based on identical plastic-strain amplitudes, and in the present work the dependence of life on both plastic strain and stress amplitude was established. EXPERIMENTAL Materials. The principal materials were polycrystal-line copper (? - 70 ergs per sq cm)" and the Cu-8 wt pct Al alloy (? - 2.8 ergs per sq cm),I3 the latter being near the limit of solubility of aluminum in copper and having, therefore, the lowest stacking-fault energy in the CU-Al system. Specimens were machined from 0.118-in.-diam cold-swaged rods of high-purity (99.999 pct) copper and the Cu-8 Al alloy, the latter produced initially in a graphite boat by induction vacuum melting a mixture of 99.999 pct Cu and 99.99 pct Al. The machined specimens were annealed to produce mean grain diameters of about 0.070 mm in copper and 0.190 mm in the alloy. Specimen dimensions are given in Fig. 1. Values of the tensile yield stress, ultimate strength, uniform strain (determined by the Considgre construction), and reduction of area, for both materials at 4.2oK, 77oK, and room temperature, are listed in Table I. The tensile apparatus in which these results were obtained has already been described.14 Apparatus. Specimens were fatigued in push-pull with a machine that is illustrated schematically in Fig. 2. The specimen is first soldered into the top grip (1) with Woods metal, and the grip is then screwed into the inner tube (2) which is connected to the drive rod of the Goodmans vibration genera-

Jan 1, 1968

By I. R. Kramer

The effect of the specimen diameter, d, on the flow stress, cra of polycrystalline aluminunz (99.997) was studied. The increase in the flow stress could be accountedfor by the increase in the surface layer stress, with decreasing specimen diameter. Both , and a, were found to be proportional to For the smaller-dianzeter specimen (< 0.033 in.) at strains less than aboul 0.1, the work hardening of the surface layer was greater than that associated with the bulk of the specimen. At higher strains the work hardening due to the bulk appears to be independent of the specimen diameter. THE increase in the strength of metals with decreasing diameter is well-known; however, an adequate explanation for the cause of the size effect is still lacking. The earliest systematic investigation of size effect appears to be that of Onol who reported that for aluminum monocrystals the resistance to slip at low strains increased as the specimen diameter decreased. A change in the stress-strain curve beyond 0.001 strain was not found. However, Suzuki et a1 .&apos; reported for monocrystals of a brass and copper having diameters in the range of 2 to 0.12 mm that the entire stress-strain curve was raised as the specimen diameter was decreased. The effect of size was most apparent when the diameter of the specimen was less than 0.5 mm. In the discussion of this paper Honey-combe reported a size effect in copper crystals as large as % in. diam. These results are in agreement with those of paterson3 and Garstone et al.4 While the majority of the investigations on size effects was conducted in terms of the variation in the diameter of the specimen, several investigators studied the influence of the specimen geometry. For example, Wu and smoluchowski 5 reported that in aluminum monocrystals the slip system was a function of the specimen dimension in the slip direction. King-man and Green 6 studied the influence of size on the compressive stress-strain relationship of aluminum monocrystals when the ratio of length to diameter was constant. Their specimen diameters ranged from to & in. For specimens oriented for single slip the critical resolved shear stress for the smaller-size specimens increased with decreasing diameter. No effect was observed in the large-size specimens. Specimens having an orientation near the corners of the stereographic triangle did not exhibit a size effect. Apparently, the increase in strength with decrease in the diameter of the specimen is a general phenomenon and has been observed in a brass |T and cadmium as well as in aluminum and copper.&apos; In a series of investigations (for example Ref. lo), it was shown that during deformation a surface layer was formed which imposes a back stress, a,, on the moving dislocations. It is reasonable to predict that this surface layer stress, as, should be a function of the specimen diameter and could possibly account for the flow stress size effect. In fact, experimental evidence will be presented to show that this is the case; i.e., the increase in flow stress with decreasing size is equal to the increase in the surface layer stress, as, with size. In addition, data will be presented on the variation with size of and a* where is the back stress associated with the generation of dislocation obstacles in the bulk of the specimen and a* is the net effective stress acting on the mobile dislocations. A limited investigation was carried out on gold specimens to determine the influence of an oxide film. EXPERIMENTAL PROCEDURE The aluminum specimens were prepared from -in. bar stock (99.997 pct purity). The 0.350- and 0.150-in.-diam specimens were machined directly from the bars while the specimens having a diameter of 0.033, 0.020, and 0.015 in. were prepared by swaging and drawing to 0.04 in. and electropolishing almost to final size. The specimens were prepared with a 2-in. gage length. The specimens were annealed in vacuum (-10-4 Torr) at 350°C for 8 hr. The grain diameter of the specimens in the various specimen diameter groups was 0.08 ± 0.02 mm. Gold specimens of two diameters, 0.14 and 0.03 in., were prepared in a similar way and annealed at 650°C for 8 hr. The grain diameter of the gold specimens was 0.2 mm. After annealing the specimens were electrochemically polished to the final size and tested in an Instron tensile machine at a strain rate, E&apos;, of 10- 3 per min. While it was possible to determine the surface layer stress, a,, in the larger-size specimens by measuring the difference, Aa, between the stress before unloading the specimens and the initial flow stress after removal of the surface layer as outlined in detail in Ref. 10, this method is not applicable for small wires because of the difficulty in obtaining a sufficiently accurate measure of the diameter. The values at the various strains were therefore determined by measuring after the specimen had been annealed at 35°C for 4 hr. It has previously been shown" that the two methods give the same results for a provided that the annealing temperature is low enough to affect only the surface layer and not the dislocation barriers in the bulk of the specimen. For the gold specimens a treatment at 150°C for 16 hr was found to be satisfactory for the determination of by the low-temperature annealing method. EXPERIMENTAL RESULTS Determination of a,, and a,. The stress-strain curves for the various diameter aluminum specimens, plotted in terms of the logarithms of the true stress, and true strain, are given in Fig. 1. These curves represent the average data taken from at least ten specimens at each size. Over the range of strains investigated the curves follow the empirical equation

Jan 1, 1968

By W. O. Philbrook, K. M. Goldman, G. Derge

T. Rosenqvist—The most interesting point in this paper is the observed transfer of iron into the slag in the initial stage of the desulphurization process, after which the iron again is reduced to the metallic state. The authors interpret this observation as showing that the sulphur enters the slag as an iron-sulphur compound which subsequently is decomposed by the slag. The present writer has previously suggested the following equation for the desulphurization process: S + O2- ? S2- + O For equilibrium in the blast furnace the oxygen potential is defined by equilibrium with graphite and CO of 1 atm pressure: C + O ? CO [2] During the desulphurization process the reactions proceed in the direction of the arrows. If one assumes eq 2 to be significantly slower than eq 1, the transfer of sulphur into the slag, in accordance with eq 1, will build up a local oxygen potential at the metal-slag interface very much higher than that corresponding to the value defined by eq 2. This is possible because the equilibrium oxygen potential in eq 1 is high as long as the sulphur content in the slag is low. This oxygen potential will again be able to oxidize some iron: Fe + O ? Fe2+ + O2- and an increase in the iron content of the slag will be observed. Adding up eqs 1 and 3 one obtains: S + Fe ? S2- + Fe2+ The net effect is thus in harmony with the experimental observation but is obtained without assuming any close ties between the sulphur and iron atoms during the process. Furthermore, it follows from eqs 1 and 2 that when the sulphur content in the slag increases, and equilibrium with C and CO is finally approached, the local oxygen potential at the metal-slag interface will decrease, and the iron in the slag will be reduced back into its metallic state. C. E. Sims-—The data and conclusions presented in this paper are thoroughly convincing in establishing the mechanism of sulphur transfer from iron to slag as in a blast furnace. The evolution of gaseous CO in step 3 of the reactions given on p. 1112 makes the process virtually irreversible. Assuming that the process is similar in slag-metal systems other than in the blast furnace, it is readily seen why free CaO and re-ducing conditions so greatly favor desulphurization. On the other hand, the very effective desulphurization obtained in oxidizing slags when strongly basic, must be attributed to the relatively high stability of CaS as compared to FeS. The ease and simplicity with which the reactions of classic chemistry agree with the experimental data and explain the mechanism is noteworthy. The concept of molecules of FeS, soluble in both phases (metallic iron is not soluble in the slag), migrating from the iron to the slag and there reacting with CaO, which is soluble only in the slag phase, is clear and uncomplicated. This is likewise true for step 3. Those who would deny the existence of molecules or molecular-type combinations in liquid iron, must strain to provide a mechanism so lucid. In the absence of molecules, the Fe and S exhibit a remarkable collusion. L. S. Darken—The investigation and interpretation of rate phenomena in the range of steelmaking temperatures is a difficult task. Most of the laboratory investigations of steelmaking reactions have been concerned with equilibrium. Having determined the equilibrium, our attention naturally focuses next on the mechanism and rate of approach to equilibrium. The authors seem to have contributed substantially to our understanding of these factors for the case of sulphur transfer. I should like to ask the authors whether they consider that the sulphur transfer reaction is diffusion controlled as many high-temperature reactions seem to be. If so, it would seem reasonable to suppose that the slow diffusion step of the process is the transfer across a pseudo-static layer or film similar to that considered in heat flow problems. As the diffusivity and fluidity are smaller for the slag than for the metal, it may tentatively be assumed that the sulphur gradient exists in a thin layer in the slag adjacent to the slag-metal interface and that the metal and the main mass of slag are each maintained uniform by convection. On this basis the amount of sulphur transferred across unit area per unit time is D p (?S%)/100 ?1, where D is the diffusivity, p the density, (?S%) the difference in percent sulphur on the two sides of the layer, and ?l is the layer thickness. At the beginning of the experiment the main body of the slag and hence one side of the layer contains no sulphur; therefore (?S%) may be replaced by (S%), the sulphur content of the slag at the slag-metal interface, which in turn is equal to L[S%] where [S%] is the sulphur content of the metal and L is the distribution coefficient. The rate of transfer thus becomes DpL[S%]/100 ?l, which the authors designate K[S%]. Equating these two quantities and setting D = 10-6 cm2 per sec, p = 3 g per cm3, L = 40, and K = lo-+ g cm-2 sec-1, it is found that ?l, the film thickness, is about 0.01 cm—a value of the order of magnitude of that found in heat transfer problems in liquids. The uncertainty of the numerical values used leaves much to be desired, but at least it can be said that this calculation tends to support the proposed model involving diffusion through a film. Although this does not seem to affect the general argument, I should like to call attention to the fact that the diffusivity3 of sulphur in hot metal is found (on conversion of units) to be about 10-4 cm2 per sec rather than 104 cm2 per sec as stated by the authors. The three equations written by the authors to express the steps in the overall process of sulphur transfer may alternatively be written ionically as only two Fe + S = Fe++ + S-- Fe++ + O-- + C (graphite or metal) = CO (gas) + Fe where the underscore is used to designate the metallic phase; ionic species are slag constituents. After the authors have so neatly demonstrated that iron and sulphur transfer together (at least initially), this fact seems almost self evident; from eq 4 it is seen that if sulphur acquires a negative charge during transfer

Jan 1, 1951

By F. A. Crossley

The titanium-rich end of the Ti-A1 system has been investigated up to 35 at. pct A1 (23 wt pet). One conzpound Ti3Al was found to occur between primary a and TiAl. It is ordered hcp with DO19 structure, it has virtually no solid-solubility range, and it has a closed maximum at about 875°C. OIL either side of the compound are a +Ti3Al two-phase fields. The limiting a1uminum solubility in primary a at the titanium-rich end is indicated to be 7.5 at. pct A1 (4.4 wt pet) at 550°C and about 6.8 at. pct Al fl wt pct) at 500°C. Quenching alloys from above the a + Ti3Al two-phase field produces the following structures with respect to alloy composition: Up to 13 at. pct A1 (7.8 wt pet), a solid solution; from 15 to 18 at. pct A1 (9 to 11 wt pct), shear transformation product or martensite; from 19 to approximately 30 at. pct (11 to 19 wt pet), submicro-scopic coherent Ti3Al in an a malvix. The twin hcp phase fields reported in the literature are the result of nonequilibrium corzdztions. Ti-A1 alloys, once partitioned by dwelling- in the a + ß phase field during either hot working or heat treatment, are extremely difjicult to homogenize at temperatures below 1000°C. Such partitioned alloys exhibit the characteristics or symptoms of two-phase materials, and may be said to suffer the "twin-phase syndrome". THE earliest investigations of the Ti-A1 system by Ogden et al.1 and Bumps et al.2 reported wide solubility of the primary solid solutions. Aluminum was reported soluble in the low-temperature allomorph to the extent of 37 at. pct (25 wt pct), and the first intermediate phase was reportedly TiA1. Somewhat later Kornilov et al.3 reported a similar diagram with phase boundaries displaced towards lower aluminum contents and higher temperatures. Beginning about this time (1956) reports in the literature made it very clear that one or more intermediate phases occurred at lower aluminum contents than TiAl.4-17 These reports included five major investigations of the titanium-rich end of the Ti-A1 diagram.4,12,14,16,17 Three of these diagrams show two two-phase fields below 37 at. pct Al, while two of them show a single two-phase field. The existence of the phase Ti3A1 is firmly established and is included in each of the diagrams, except one—that of Sato and Huang.12 The new phases are reportedly hcp and differ from primary a only slightly when disordered, and when ordered the "a" parameter is approximately one,4,12,15 two, 6-10,13,14 or four14 times that for primary a. Beyond this, however, the diagrams are remarkable for their lack of agreement. Two tacit assumptions are usually made in phase-diagram determinations of metal systems. These are: 1) equilibrium anneals bring the alloy to equilibrium or to indistinguishable closeness to it, and 2) equilibrium conditions established at elevated temperatures are either "frozen" by rapid quenching for evaluation at room temperature, or quench-transformation products are recognized as such. In the current investigation evidence was obtained that over substantial composition ranges neither of these two conditions was met in any of the more recent major investigations. I) MATERIALS, METHODS, AND TECHNIQUES The alloys of this investigation were prepared by nonc on sum able electrode arc melting. Materials used in the preparation of the alloys are summarized in Table I. The investigative tools employed were: optical and electron microscopy, differential thermal analysis (DTA), disatometry, X-ray diffraction, electron diffraction, and resistometry. Alloys for microscopic and X-ray investigations were prepared as 15-g melts. Alloys containing from 7 through 11 at. pct A1 were hot-rolled out of a furnace at 900°C, from 12 through 15 at. pct out of a furnace at 1000°C, and from 16 through 18 at. pct out of a furnace at 1125°C. Alloys containing more than 18 at. pct A1 could not be hot-rolled. The ingots were covered with Markal coating prior to hot rolling to minimize atmospheric contamination. After hot rolling, alloys containing up to 15 at. pct A1 were ground and pickled to remove 7 mils from each surface; alloys containing 16 and 18 at. pct A1 were skinned to a

Jan 1, 1967

By J. C. Williams, M. J. Blackburn

Several of the decomposition processes that can occur in supersaturated phases in a Ti:11.6 wt pct Mo and a Ti:20 wt pct V alloy have been studied by transmission electron microscopy. The deformation induced "marternsitic phase" in the Ti:Mo alloy has been found to have a bcc or bct structure rather than the previously reported hexagonal structure. The morphology of&apos; the transformed region is a rather complex asserrlblage of twins, twinning occurring in one or more systems; this internal twinning has been found to occur on (112). The w phase is formed in both alloys on aging and is present in the Ti:Mo alloy after quenching. The structure of this phase has been confirmed as hexagonal in both systems, however, differences in morphology and stability are found between the two alloys. Thus in the Ti-Mo alloy the w phase has an ellipsoidal morphology with the major axis lying parallel to <111>ß or [0001]w while in the Ti-V alloy the phase forms as cubes, the cube faces lying parallel to {100}ß or {2021}w Some observations on the particle sizes, volume fraction, and composition of the w phase in the Ti-Mo alloy are listed. The mode of formation of The a phase from the (ß + w) structures is also different in the two alloys. In the Ti-Mo alloy the a phase is formed by either a cellular reaction or by the growth of isolated needles, whereas in the Ti-V alloy the a phase is nucleated at an w:ß interface and grow to consume the w phase. Some of the difjerences in behavior of the w phase are attributed to the mismatch between it and the solute enriched ß matrix in which it forms. MaNY transition elements tend to stabilize the bcc or ß-phase when added to titanium. In general two types of phase diagrams are produced, either a ß-stabilized (ß-isomorphous) system, e.g., Ti:Mo, -Ti:V, Ti:Nb, or a ß-eutectoid system, e.g., Ti:Cr, Ti:Fe, Ti:Mn. In previous papers&apos;-4 the phase transformations in the a-phase and (a + ß)-phase alloys have been described and this work has been extended to ß-stabilized systems. Specifically, transformations in the alloys Ti:20 wt pct V and Ti:11.6 wt pct Mo have been studied; in both of these alloys the ß phase is retained at room temperature when quenched from the ß-phase field. A number of phase transformations can occur in such metastable ß phases and the two alloys were chosen to include most of the transformations reported for ß-stabilized systems. We list these possible phase transformations below. Ti:11.6 Mo quenched from >780°C to retain the ß phase: a) The w phase can form on quenching.5 b) Martensite can be produced by subzero cooling or deformation. Two martensite habit planes have been reported in Ti:Mo alloys; (334)ß and (344)ß=6 c) On aging at temperatures <-550° C the w phase is formed before the a-phase.5,7 d) On aging at temperatures >550°C the a phase is formed.7 e) The martensite can be tempered. It has been reported that the a phase rather than the ß phase is precipitated during tempering.&apos; Ti:20V quenched from >660°C to retain the ß phase:9 a) At aging temperatures <260°C separation into two bcc phases occurs. b) The w-phase is produced prior to the a phase on aging at temperatures <-400°C. c) At temperatures 2400°C the a phase is formed directly. T-T-T diagrams describing the temperature and time regimes for the formation of these phases have been published7,9 for a Ti:12 pct Mo and a Ti:20 pct V alloy. We have attempted to investigate these transformations using transmission electron microscopy, however thin foils undergo a spontaneous transformation in all conditions except the equilibrium (a + ß) structure. This transformation has been reported previ0usly10,11 and we will comment on its morphology and nature in the various sections of experimental results. EXPERIMENTAL The compositions in wt pct of the two alloys investigated were: Ti:11.6 Mo, 0.100 02, 0.006 N2, 0.0015 H2 Ti:20V, 0.0574 O2, 0.0111 N2, 0.005 H2 These alloys were cold-rolled to 0.020 in. thick sheet. Specimens were heat treated in vacuum or in inert gas at temperatures >500°C and in a circulating air furnace at temperatures <500°C. Thin foils were prepared using standard techniques, described in detail previously." Dark field micrographs were obtained using high resolution technique. RESULTS Martensitic Transformation in Ti:11.6 pct Mo. Detailed study of the deformation induced martensite is not possible due to a spontaneous transformation which occurs near the edge of thin foils as shown in Fig. 1. Similar transformations have been observed in iron-" and copper-base13 alloys as well as other titanium alloys, but some observations specific to the Ti:1l.6 Mo alloy are listed below. a) The boundaries of these transformed regions are glissile and move under the influence of the electron beam during examination. b) Selected area diffraction indicates the transformed regions have the same structure as the matrix, being separated by tilt boundaries. The misori-

Jan 1, 1969

By Eugene S. Meieran

The effects of methods of crystal growing, wafer sawing, polishing, routine handling, diffusion, and epitaxial growth on the defects in GaAs are reviewed and studied using reflection and transmission X-ray topographic techniques. In general, it was found that boat-grown crystals exhibited fewer defects than Czochralski crystals, although all crystals showed large numbers of precipitates visible when examined in the electron microscope. Mechanical surface treatments such as sawing and mechanical polishing introduce damage to a depth of about 5 µ, most of which can be removed by suitable chemical or chem-mechanical polishing. In addition, defects can be introduced through routine handling of wafers, for example with metallic tweezers. These defects can be quite severe, and have been observed 20 µ below the wafer surface. Defects can also be introduced through diffusion and epitaxial growth. These defects, which include precipitates, growth pyramids, stacking faults, dislocations, and so forth, can be detrimental to device fabrication. It is shown that wafers or films which appear defect-free optically can contain defects visible in the X-ray topographs. WHILE the use of GaAs in the semiconductor industry has increased very rapidly in the last few years, due mainly to the recent development of many important GaAs devices,1,2 the major limit to the production of commercial quantities of many GaAs devices remains a severe lack of suitable materials technology. This lack is apparent in two critical areas. First, production quantities of high-quality GaAs crystals, reproducibly doped and precipitate-free, simply are not available commercially, although some reasonable quality material is available on a limited first-come, first-serve basis. Second, in comparison to silicon technology, little is known about the effects of processing variables on the defects either present in as-grown GaAs or introduced through processing and handling of wafers. These areas are now receiving some attention from semiconductor device manufacturers, who are studying defects in GaAs in order to better understand how either to prevent their occurrence or to cope with their existence. Most investigations of the defects in GaAs have been made by optical microscopy3-5 or transmission electron microscopy techniques.&apos;-&apos; Recently, however, the imaging techniques of X-ray topography, electron mi-croprobe analysis, and scanning electron microscopy are being applied to the study of GaAs.9-14 In the case of X-ray topography, a one-to-one image is obtained that must be photographically enlarged. In compensa- tion, the defects within entire wafers may be imaged by simple scanning (Lang technique15) if the wafer is reasonably perfect, or by using the scan oscillation technique developed by Schwuttke16 if the wafer is warped or distorted. The purpose of this paper is to both review and extend the general application of X-ray topographic techniques to GaAs. Emphasis will be placed on the effects of growth and process variables on the quality and perfection of both bulk and epitaxial GaAs. Reference to optical or electron microscopy results will be made when useful. Since the effects on defects of a wide variety of processing variables such as crystal growing, sawing, polishing, diffusion, and epitaxial growth will be somewhat superficially reviewed, a fairly extensive bibliography of the most important recent results in these areas is included. However, for completeness, important defects will be illustrated here, although such defects have been previously shown by others. While this paper is concerned with defects rather than with the physics of X-ray scattering, the mechanisms of contrast formation in the topographs will of necessity be briefly mentioned. EXPERIMENTAL GaAs crystals, both boat-grown18 and Czochralski-grown,&apos;8 containing a variety of dopants of various concentrations, were purchased from outside vendors. Wafers were sliced from the crystals using a Hamco ID saw and were mechanically polished using 1 µ diamond paste. Chem-mechanical polishing was done in bromine-methanol as described by Sullivan and Kolb.18 Chemical polishing was done using a modified sulfuric-peroxide solution, 11 parts H2SO4, 1 part 30 pct H2O2, 1 part DI water.5 Zinc diffusion was carried out in a closed tube, using a 10 pct Zn-In source at 825°C for 1 hr. Oxide masking techniques were used to select the area to be diffused. Epitaxial wafers were either purchased or prepared here. All epitaxial runs prepared here were carried out using a Ga-GaAs-AsC13 source in a closed tube at a substrate temperature of 750°C. Wafers were chem-mechanically polished and gas-etched prior to deposition. The X-ray topographs were taken on a Krystallos Lang camera, operating in the transmission scanning geometry (Lang technique15) or in the reflection scanning geometry (modified Berg-Barrett technique20,21). MoKa, radiation was used for all transmission topographs using a Jarrell-Ash 100-µ spot focus. CuKal radiation was used for all reflection topographs using a General Electric CA-7 1-mm spot focus X- ray tube. Topographs were printed from an intermediate contrast inversion film, so the contrast shown in all figures here is the same as that of the original 50-µ-thick emulsion L4 Iiford nuclear plate used to record the topograph.

Jan 1, 1969

Marius R. Campbell, Washington, D. C. (Communication to the Secretary): Having spent considerable time in a systematic study of this field,&apos;both as regards the details of its structure and stratigraphy and the broader question of its relation to the Appalachian basin, I wish to add a word concerning the correlations made by Mr. Hodge in his paper. From A commercial standpoint, the question of correlation, even along the strike, is of little or no importance, for the variability is such that each opening should be tested individually, regardless of the horizon at which it appears; but these correlations assume an entirely different aspect when their scientific bearing is considered; they then become of vital importance, and, before being accepted, should be subjected to the most rigid scrutiny and severe tests. Mr. Hedge states positively that the Imboden seam of coal is equivalent to the Elkhorn coal of Pike and Letcher counties, Kentucky. In the writer&apos;s opinion, such equivalency is, at the utmost, only a possibility. This correlation has been generally adopted by the geologists of the Kentucky Geological Survey, but the writer has been unable to find on what grounds they base the statement. The evidence of identity seems to be in the character of the coal, as both seams furnish fine coking coal; also, in the similarity of the interval between them aid the " Bee Rock," or top of the great conglomerate. It is probably an easy matter to determine the thickness of this interval on Elkhorn creek, and we will assume that the measure of 300 to 350 feet is correct. In the Big Stone Gap field, the question of measuring the interval between the Imboden and the " Bee Rock " is exceedingly difficult. The line of outcrop of this mass of strata is along the northern base of Stone mountain, and, in the uprising of the great arch, the strata on its flanks have been thrown into many minor folds, and, in places, have been broken by local faults. This complicated structure, together with the absence of ally well-marked stratum, renders it exceedingly difficult to obtain a correct measure of the intervening sandstones and shales. The interval of 300 to 350 feet, assigned by Mr. Hodge, is mani-

Jan 1, 1893

By Victor A. Phillips

A series of strips of a Ni-12.7 at. pct A1 alloy were Prepared containing cubical y&apos;(NisAl) precipitates with edge lengths from 60 to 500A. A particle-free solution-tveated strip was included for cornparison. They weve cold-rolled 95 pct and the effects of particle size on the isochronal (1/2 hr) annealing behavior between 300° and 950°C studied (by hardness and light and electron microscopy). It ulas inferred that the particles deformed with the lnatvix becoming lamellae which remained coherent. Comparison with published data fov pure nickel showed that aluminum greatly re-tavded softening and recrystallization, but it made little difference whether or not particles were present. The presence of pakticles led to a heterogeneous distribution of precipitates after annealing at 700" to 750°C. Recovery was not detected. Recrystallization occurred by the growth of new grains into unrecrys-tallized material. In a previous study by the author,&apos; the growth of Ll2-type ordered yl(Ni3Al) precipitates was followed in Ni-12.7 at. pct A1 alloy as a function of aging at 600" and 700°C. The particles were showo to be cubical in shape in all sizes from 50 to 3000A and remained coherent. This work was used as a guide in preparing the starting structures for the present study of the effect of these particles on the annealing behavior of heavily cold-rolled strip. Another question of present interest was whether dislocation and particle hardening were additive, since the structures before rolling ranged from solution-treated to peak-aged to overaged. Also, precipitation might occur on annealing after cold-rolling. Reference may be made to other papers2"5 for previous work in this relatively unexplored field and only some recent work will be mentioned her:. phillips2 studied the effect of deformable 0 to 590A-diam cobalt particles on a Cu-3.23 pct Co alloy rolled 95 pct and found that the particles, which rolled out into thin lamellae, impeded softening and recrystallization. Tanner and servi3 likewise studied the annealing of cold-swaged Cu-2 pct Co alloy containing 150A-diam particles and found impeding effects. Haessner et a1.,4 on the other hand, found that incoherent 2-p-diam non-deformable particles of B4C (0.04 vol pct) tended to increase the rate of recrystallization of copper rolled up to 95 pct reduction. They attributed this to the formation of new grains at the particle interfaces. Humphreys and artin&apos; found that nondeformable silica particles in copper rolled to 30 pct reduction accelerated recrystallization if the particle spacing was large and retarded it if the spacing was smaller. Haessner et a1 4 also studied a rolled Ni-Cr-A1 alloy; however, the particles of y&apos;(Ni3Al)-type precipitate were not put in before rolling, but separated during the isothermal annealing at 750°C. No previous work appears to have been carried out on the effect of y&apos; (Ni3A1) particles on the annealing of Ni-A1 alloy. Hornbogen and ICreye7 redetermined the solubility c of aluminum in nickel as a function of temperature T and showed that it was given by c = 32.6 exp(-1940/RT). This relation gives aluminum solubilities of 15.1, 14.2, 12.0, and 10.7 at. pct at 1000°, 900°, 700°, and 600°C, respectively. The phase precipitated from the nickel-rich solid solution is fcc y1 (Ni3A1) which has a Cu3Au -type ordered structure8 and remains ordered up to 1000°C.B EXPERIMENTAL PROCEDURE The alloy used was identical with that used before. Chemical analysis showed 6.27 wt pct (12.71 at. pct) Al, the principle impurities being 0.065 pct Fe, 0.022 pct Co, 0.020 pct Cu, and 0.004 pct C. Bar stock of 1 in. diam was cold-swaged to % in. diam, cold-rolled to 0.300-in.-thick strip, and annealed at 900°C in dry hydrogen. It was cold-rolled to 0.100-in. thickness and solution-treated for 1 hr at 1000°C while sealed in a quartz tube in argon, quenching in iced brine with the aid of a device to snap off the nose of the tube. Lineal analysis gave an average grain size of 0.055 mm. Pieces of strip were aged at 700°C in vacuo for 30 min, 51/4 hr, and 1 week to produce nominal average particle widths of 60, 150, and 500A, respectively, as known from the previous work.&apos; The average diamond pyramid hardness was determined. The heat-treated strips were rolled from 0.100 to 0.005 in., a reduction of 95 pct, and the rolled strips stored at about -5°C. Small pieces were annealed within 1 week for 30 min at temperatures from 300° to 950° ±2°C in a horizontal vacuum furnace. Strips were withdrawn into a cooling zone, giving an estimated initial cooling rate from 950°C of about 50°C per sec. Average diamond pyramid hardnesses were determined on a lightly electropolished spot on the surface of each strip using 300-g load. Each point on the softening curves represents a separate annealed specimen. Sections containing the rolling direction were examined by optical metallography. Selected specimens were electrothinned to the center plane&apos; and examined by transmission at 100 kv in a Siemens Elmiskop I electron microscope. It is well-known that changes in the structure tend to occur when a deformed strip is electrothinned below a thickness of a few hundred angstroms, although this is less serious with a material such as nickel which has a high melting point, and also is apt to be less serious when particles are present. Observations were nevertheless confined to thicker regions of the foils with estimated thicknesses over 1000A. No changes were observed due to beam exposure.

Jan 1, 1968

By R. G. Davies, P. Beardmore, T. L. Johnston

The flow stress of a series of Ni-Cr-A1 alloys consisting of a dispersion of y&apos; (based on Ni3Al) in a rnatrix of nickel-base solid solution y has been measured at temperatures up to 950°C as a fwzction of the volume fraction of y&apos;. At high temperatures the flow stress is controlled by the amount of Y&apos; in the alloy, i.e., the higher the volume fraction of y&apos;, the greater is the flow stress. This simple relationship is not obeyed at low temperatures in so far as a peak in the flow stress-volume fraction relation occurs at about 25 pct y&apos;. The variation in the mechanical properlies of these alloys as a function of both temperature and volume fraction of y&apos; has been correlated with changes in distribution of both the dislocations and y&apos;. The results are interpreted on the basis that at low temperatures the y matrix is strengthened significantly bv the presence of a hyperfine y&apos; precipitate due to decomposition on cooling; at high temperatures the y matrix is a single phase of low strength. It is clearly recognized that the high temperature strength of most nickel-base superalloys depends upon a dispersion of the ordered fcc phase y&apos;, based on Ni3A1, in a fcc solid solution matrix y based on nickel. Although the volume fraction of y&apos; varies widely from about 0.2 in Nimonic 80A to about 0.6 in Mar-M200, all such nickel-base alloys manifest an unusual insensi-tivity of the flow stress with respect to temperature. In Mar-M200 for example, the 0.2 pct flow stress remains essentially constant from room temperature to 750°C. The conclusion has been drawn1 that the characteristically low temperature dependence of the flow stress of y-y&apos; nickel-base alloys is obtained when the state of dispersion of y&apos; is such that dislocations are forced to cut through the y&apos; particles at the onset of yielding. When the spacing between the y&apos; particles is so large that the flow stress is controlled by dislocation bowing between particles, then the initial flow stress decreases progressively with an increase in temperature at a rate determined by changes in elastic properties. The same conclusion is inherent in the detailed, mechanistic model of the deformation process in commercial superalloys which has been developed by Copley and ear&apos; in which the temperature independent flow stress is attributed primarily to the contribution of the antiphase boundary energy created in the y&apos; particles during deformation. In this theory the temperature insensitivity of the flow stress is a reflection of the constant antiphase boundary energy as a function of temperature. An important microstructural parameter that is relevant to the explanations that have been suggested&apos; to account for the temperature insensitivity of the flow stress is the volume fraction of y&apos;. To vary the latter to any significant extent in a given commercial alloy is clearly difficult. However, it is possible in a relatively simple Ni-Al-Cr ternary system which manifests analogous microstructures in terms of the distribution of y&apos; in y and contains specific alloys which have flow properties that depend on temperature in a manner quite similar to their more complex commercial counterparts. Hornbogen et . have studied precipitation phenomena and deformation mechanisms in such alloys but only where the y&apos; volume fraction was small (less than 0.2) and the y&apos; particle size varied from less than 100A up to a maximum of -1000A. In the present study, a series of alloys was prepared in which the volume percent of y&apos; at 900°C was varied from 0 to 100 pct with the y&apos; particle size (of the order 0.5 p) comparable to the sizes obtained in commercial superalloys. Particular attention has been given to the relationship between variations in the volume fraction and distribution of y&apos; and the temperature dependence of the flow stress EXPERIMENTAL TECHNIQUES The Ni-Cr-Al system was selected because it is well characterized, bears a close relationship to commercial alloys, and offers the advantage of an extra degree of freedom over a binary system. In the present investigation, a series of alloys across the tie line between NisA1 and Ni3Cr (Ni3Cr is not an in-termetallic compound, the nomenclature is only used to designate the composition) were vacuum cast. The pseudobinary6 and the composition of the alloys used are shown in Fig. 1. It is important to note that the compositions of the y phase and the y&apos; phase in the two-phase alloys was always the same. Alloy compositions were selected from the binary diagram, Fig. 1, in order that aging at 900°C would produce from 0 (100 pct y) to 100 pct y&apos; by volume percent. (The size of the y&apos; particles produced during the equilibrium aging treatment increased as the volume fraction of y&apos; increased, ranging from about 0.2 p at low volume fractions up to about 0.8 p at the highest volume fraction.) The y&apos; phase is based on the inter-metallic compound Ni,A1 which has the fcc LIZ type superlattice structure, and chromium substitutes for aluminum in the structure. The y phase is a disordered fcc solid solution. The alloys were heat treated at 1150°C for 2 hr, air cooled to room temperature, and finally annealed for 16 hr at 900°C. The rods were then centerless ground to 0.25 in. diam and cut into compression samples 0.5 in. long. The compression tests were made on an In-stron machine at a strain rate of 7 x 10"4 sec-&apos;. A rapid heating radiant heat furnace was used which minimized the heating and temperature stabilization time to 10 min for the highest testing temperature. All the tests were stopped after 5 pct plastic strain.

Jan 1, 1970

By H. J. Ramey

The wellbore acts as a storage tank during drawdown and build-up testing and causes the sand-face flow rate to approach the constant surface flow rate as a function of time. This effect is compounded if non-Darcy flow (turbulent flow) exists near a gas wellbore. Non-Darcy flow can be interpreted as a flow-rate dependent skin effect. A method for determining the non-Darcy flow constant using this concept and the usual skin effect equation is described. Field tests of this method have identified several cases where non-Darcy flow was severe enough that gas wells in a fractured region appeared to be moderately damaged. The combination of wellbore storage and non-Darcy flow can result in erroneous estimates of formation flow capacity for short-time gas well tests. Fortunately, the presence of the wellbore storage eflect permits a new analysis which can provide a reasonable estimate of formation flow capacity and the non-Darcy flow constant from a single short-time test. The basis of the Gladfelter, Tracy and Wilsey correction for wellbore storage in pressure build-up was investigated. Results led to extension of the method to drawdown testing. If non-Darcy flow is not important, the method can be used to correct short-time gas well drawdown or build-up data. A method for estimation of the duration of wellbore storage effects was developed. INTRODUCTION In 1953, van Everdingen and Hurst generalized results published in their previous paper3 concerning wellbore storage effects to include a "skin effect", or a region of altered permeability adjacent to the wellbore. Later, Gladfelter. Tracy and Wilsey4 presented a method for correcting observed oilwell pressure build-up data for wellbore storage in the presence of a skin effect. The method depended upon measuring the change in the fluid storage in the wellbore by measuring the rise in liquid level. To the author&apos;s knowledge, application of the Gladfelter, Tracy and Wilsey storage correction to gas-well build-up has not been discussed in the literature. It is, however, a rather obvious application. Gas storage in the wellbore is a conlpressibility effect and can be estimated easily from the measured wellbore pressure as a function of time. Several approaches to the wellbore storage problem have been suggested. As summarized by Matthews, it is possible to minimize annulus storage volume by using a packer, and to obtain a near sand-face shut-in by use of down-hole tubing plug devices. Matthews and Perrine have suggested criteiia for determining the time when storage effects become negligible. In 1962, Swift and Kiel&apos; presented a method for determination of the effect of non-Darcy flow (often called turbulent flow) upon gas-well behavior. This paper provided a theoretical basis for peculiar gas-well behavior described previously by Smith. Recently, Carter, Miller and Riley observed disagreement among flow capacity k,,h data determined from gas-well drawdown tests conducted at different flow rates for short periods of time (less than six hours flowing time). In the original preprint of their paper, Carter et al. proposed that the discrepancy in flow capacity was possibly a result of wellbore storage effects. Results of an analytical study of unloading of the wellbore and non-Darcy flow were recorded by carter.14 In the final text of their paper, Carter et al.!&apos; stated that they no longer believed wellbore storage was the reason for discrepancy in their kgh estimates. In view of the preceding, this study was performed to establish the importance of non-Darcy flow and well-bore storage for gas-well testing. In the course of the study. a reinspection of the previous work by van Everdingen&apos; and Hurst&apos; was made, and the basis for the Gladfelter, Tracy and Wilsey&apos; wellbore storage correction was investigated and extended to flow testing. WELLBORE STORAGE THEORY As has been shown by Aronofsky and Jenkins,11-12 Matthews," and others, flow of gas can often be approximated by an equivalent liquid flow system. The following developnlent will use liquid flow nomenclature to simplify the presentation. Application to gas-well cases will be illustrated later. First, we will use the van Everdingen-HursP treatment of wellbore storage in transient flow to establish (1) the duration of wellbore storage effects, and (2) a method to correct flow data for wellbore storage. DURATION OF WELLHORE STORAGE EFFECTS When an oil well is opened to flow. the bottom-hole pressure drops and causes a resulting drop in the liquid level in the annulus. If V. represents the annular volume in cu ft/ft of depth, and p represents the average density of the fluid in the wellbore, the volume of fluid at reservoir conditions produced from the annulus per unit bottom-hole pressure drop is approximately: res bbl-- (V, cu ft/ft) (144 sqin./sq ft) psi -(5.615 cu ft/bbl)(pIb/cuft) ........(I)

Jan 1, 1966

By K. A. Slagle, D. K. Smith

weight obtained. Additives used in conjunction with salt in these slurries have included silica flour, calcium ligno-sulfonate and cellulose retarders, granular lost-circulation materials, bentonite and selected low-water-loss additives that are not significantly deteriorated by the presence of the chloride ion. In some other areas of South Texas, the salt-saturated slurries have been used quite extensively for improvement of the flow properties of slurries and attainment of better circulation characteristics at lower displacement rates. Concurrently with this property, the protection of shales and shaly sands is also realized, as well as useful retardation of the slurry. Resultant superior cementing jobs have been indicated by both communication tests and acoustic logs for bonding to pipe and formation.&apos; In one section of Louisiana, a major oil company has been using salt-saturated API Class A cement with calcium lignosulfonate retarder for cementing through the Miocene at 9,000 to 10,000 ft. This is another of the situations where interbedding of sands and shales exists, creating difficulty in maintaining formation competency when a fresh-water slurry contacts the clay minerals of the formation. Further work has also been done in the shaly Miocene formation at 13,000 to 15,000 ft where fairly close water or gas contacts are encountered. Indications thus far are that better segregation of these various fluids is obtained by use of the saturated salt slurries because of their improved formation bonding characteristics. In addition to the properties of salt in this situation, attainment of turbulent flow at minimum displacement rates has also been accomplished by use of an additive to help provide exceptional dispersion and viscosity reduction of the slurry. Another oil company was encountering considerable expense in completing wells in Southwestern Louisiana due to extensive block squeeze requirements for effective separation of zones. A very effective mud program was being used to minimize washout in the shale sections and, apparently, a nearly gauge-size hole was being obtained. However, primary cementing results with fresh-water slurries were generally poor. On a few occasions when slurry was actually circulated to the surface, large pieces of shale formation were brought out of the hole with the slurry, indicating a severely water-sensitive, sloughing formation. Inhibition of shale heaving was being accomvlished in the drilling program, and immediately indone ipon circulation of the fresh-water slurry even though it contained a low-fluid-loss additive to reduce filtrate damage in the sands. The subsequent change to salt-saturated slurry yielded 11 successful primary cement jobs out of 12, compared to the previous success ratio of practically zero. Since these were deep, high-temperature wells in the range of 13,000 ft with high-pressure zones necessitating 17.5-lb/gal fluid densities, the slurry used was API Class E cement, silica flour, weight material, retarder, salt saturation (which also reduced the amount of weight material) and maintenance of low fluid loss by use of a salt-compatible additive. Other salt slurries have been used to a limited extent in this same general area for similar problems at depths ranging from 5,000 to 17,000 ft. In the shallower wells, the cement has usually been API Class A where the salt functions as a retarder, and in the deeper wells API Class E cement is used with the additional salt advantage being its increased slurry weight and inability to dissolve salt stringers. A considerable number of squeeze jobs have also been done on older wells using the salt-saturated slurries with very good results. MID-CONTINENT In North Texas, salt-water slurries have been used for cementing the Woodbine sand, Strawn sand, KMA sand and Pettit lime. Shales surrounding these formations have created the same difficulty in obtaining separation of producing zones that has been the problem in other areas. Depths in this area range from 3,400 ft for the Strawn to 7,400 ft for the Woodbine, and concentration of salt has varied accordingly. In the deeper wells, where retardation is desired, saturated salt-water cement is used; for the shallower wells, in order to provide shorter waiting-on-cement times, the amount of salt has been 18 per cent by weight of the mixing water. Results have been excellent with no reported failures on any of the salt cement jobs; where acoustic bond logs have indicated indifferent bonds previously, they are indicating very good bonding for the salt slurries. In Oklahoma various shales of Pennsylvanian age exhibit a high degree of sloughing in the presence of fresh water, causing severe washouts above and below sand formations which it is desired to isolate. This situation exists to some degree in practically all parts of Oklahoma and includes formations of other ages such as the Wood-ford shale. For the past few years, salt-saturated cements and displacement rates as high as practical have been used as a remedy for this problem, with very good results. The Layton and Bartlesville formations are two examples of shaly sands where saturated slurries have been helpful. In one area where five wells were drilled through this type of problem shale without obtaining a satisfactory primary cement job, a change was made to salt-saturated cement preceded by a suitable chemical wash for the drilling mud involved. Acoustic bond logging indicated excellent bonding, and final completion bore out this result by being trouble-free. This type of slurry has also been used extensively on squeeze jobs where shales have been heaving around the producing formations. Predominantly, the basic slurry has been either API Class A cement or a pozzolan cement—although, as deeper wells are being drilled, the use of salt in Class E cement is also increasing. Salt cement in West Texas has been used primarily to help prevent channeling through the shales around the Delaware sand, Queens dolomite and Hope lime. Many of the shaly and dirty sands of this area are sensitive to the filtrate from a fresh-water cement. Salt at 16 to 18 per cent by weight of mixing water has been added to centent, and has been effective in controlling formation damage and communication between zones in these formations. Use of these lower salt concentrations is dictated in this area by the relatively low formation temperatures where retardation of the slurry would create unduly long waiting-on-cement times. Also, quite a bit of cementing has been done in this area using salt concentrations in the accelerating range— that is, 2 to 5 per cent by weight of water. Specifically, these concentrations have been used in coiljunction with high percentages of gel to overcome the retarding effect of the calcium lignosulfonate dispersant, although there are probably several shales where these concentrations could provide some degree of formation stability. On several occasions, the salt has also been used to lower the critical velocity or rate for turbulence with the slurry, particularly in the pozzolan cements. On wells in the Hope lime, it has usually been necessary to squeeze the shale above and below the lime to get a water-free completion. Use of salt-saturated slurries has largely eliminated this

By H. W. Mossman

Three aspects of magnetite smelting are discussed. The first is the working out of equilibrium conditions for eliminating sulfur. The second is the influence of magnetite solubility on the difficulty of tapping the reverb matte. The third is an approximation of the equilibrium conditions in the reverb gases which govern whether magnetite is mode or reduced in the reverb slag by these gases and by any iron sulfide in the slag. MAGNETITE has had a varied history in the Hurley Smelter since its start in 1939. Magnetite determinations on the smelter products are made regularly only on the monthly composite samples. Variations on the monthly averages are shown in Table I. Magnetite which drops from the slag and matte in the reverb has some slight bottom buildup which comes and goes, but no substantial accumulation from this source has been found at the end of a normal nine months&apos; furnace campaign. However, there has been some low grade magnetite bearing material mixed with considerable A1,0,, which has slid down from the bottom of the sloping flue between the reverberatory furnace and the waste heat boilers. This accretion has required drilling and blasting near the skimming end of the furnace. The magnetite has interfered with tapping at times. When the smelter was first started, tapping trouble from magnetite was extremely severe. Increasing the reverberatory furnace temperature by putting in an air preheater and a Dutch oven has helped greatly, although there still is occasional tapping trouble. When the present series of physical chemistry articles on copper smelting started coming out in 1950, they were read with interest, but no immediate application was seen for them. Results of some laboratory work in 1952 aroused a much stronger interest in this physical chemistry. A series of melts was made on some converter slags, which had magnetite in very large grain sizes, with the object of reducing the grain sizes in the slag, as it was known that it was easier to handle in the reverb in that condition. Anything done in the tests greatly reduced the grain sizes—even in the controls, where nothing was done except melt the slag and cast it. There was more magnetite in the slags after the tests than before, and with wide variations. There were no obvious reasons lor much of what happened in these tests. Much of the base material published in English in this field was made available for study. Recalculations were made on many of the type problems, and part of the data was reduced to local temperatures and compositions. Explanations were found for what happened in the 1952 series of tests on converter slags, and the same principles turned out to be a description of much of what magnetite does in the reverb. This article is to present the results of that study, from the viewpoint of applying the technical material in definite numerical form to the operating conditions in both the converters and the reverberatory furnaces at the Hurley smelter. Table I. Magnetite Variations on Monthly Averages, 1939 to 1955 Pet Magnetite Lowest Highest Average Converter slag 13.6 43.3 25.4 Roverb slaa 2.7 20.9 8.7 Matte 28 15.9 98 In general it was found that magnetite is made or reduced in both the converters and the rever-beratory furnace, depending on variations of temperature, matte composition, and reverb gas composition occurring in ordinary plant operation. Within reasonable limits, the field conditions for formation or reduction can be predicted, and probably can be set up and maintained. Converter conditions affecting magnetite formation can be put into numerical values better than for the reverb from purely technical calculations. The converter can be operated so as to keep the magnetite in the slag down to between 12 and 14 pct and still give satisfactory life for the converter brick. This depends upon having converter flux available which will make a slag with a good separation without raising the temperature too high. In the Hurley reverb and others with similar conditions, it is likely that a compromise of conditions will give a reasonably good control of combustion and still keep the magnetite from building up on the bottom. This discussion consists of three main parts. The first is the working out of the equilibrium conditions in the converter for determining in which direction the reaction 3 Fe,,O, (s) + FeS (1) F? 10 FeO (1) + SO, will go under actual converter operating conditions. The second deals with the influence of the solubility of magnetite in the slag and matte in the reverb on the difficulty of tapping matte. The third is an approximation of the equilibrium conditions in the

Jan 1, 1957