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By A. H. Daane, A. S. Wilson

The U-Cr system is of the simple eutectic type with some solid solubility of chromium in r and ß uranium. The eutectic occurs at 20 atomic pet Cr and melts at 859°C. The maximum solubility of chromium in y uranium is 4 atomic pet at the eutectic temperature, and in ß uranium the solubility is estimated to be 1 atomic pet. y-ß and ß-a transformations were found to occur at 737°estimatedt° and 612°C respectively. DURING 1944 and 1945, the U-Cr constitution diagram was studied in this laboratory as a part of a research program on uranium metallurgy in the Manhattan Project, and the work was described in a Manhattan Project report issued in December 1945. This paper is based on that report, which has been declassified. Prior to this study, it had been shown by other Manhattan Project workers that the low Cr-U alloys could be quenched to retain the form of uranium. Experimental The uranium used in this work was massive metal prepared in this laboratory and contained less than 0.1 pct of other elements. The chromium was 200 mesh powder obtained from the A. D. McKay Co. and was found on analysis to be 99.5 pct Cr with 0.3 pct Fe the major impurity. Alloys, weighing 400 to 600 g, were prepared by induction heating the components to 1700°C in slip-cast ZrO, crucibles in a vacuum of 3x103 mm Hg. TO prevent too violent agitation of the melt by the induction field with subsequent crucible breakage and sample loss, the ZrO2 crucible was placed in a graphite crucible, which was surrounded by a layer of powdered carbon insulation 2 to 3 cm thick. Polished vertical sections of the alloys were examined microscopically to confirm their homogeneity. Heating and cooling curves were taken on the alloys by reheating them in ZrO, crucibles to 1200°C and inserting a mullite-protected chromel-alumel thermocouple into the melt by means of a slip seal in the vacuum head of the furnace. A recording potentiometer traced the curves which had a slope of from 3" to 6" per min. Samples of the alloys were prepared for metallo-graphic examination by conventional mechanical polishing techniques followed by an electrolytic polish in an ethylene glycol-phosphoric acid-ethyl alcohol bath. The structure of the alloys was brought out clearly by this procedure so that no further etching was required. Samples for chemical analysis were taken from drillings from the top, center, and bottom sections of the alloys. The uranium was determined by titra-tion with Ce(SO1)2, while the chromium was titrated with FeSO,; the uranium and chromium totaled at least 99.6 pct in all of the alloys prepared. X-ray samples were prepared by filing bulk specimens in a helium-filled glove box and annealing the resulting powder in a zirconium-gettered helium atmosphere. A 114.6 mm diam Debye-Scherrer camera and a Weyland nonsymmetrical self-focusing camera were used with filtered copper radiation to obtain the powder X-ray diffraction data. Results The data obtained in this study have been combined to construct the constitution diagram of the U-Cr system shown in Fig. 1 where the arrests observed in cooling curves are indicated by dots. The liquidus arrest was quite distinct in thermal data taken on alloys in the range 0 to 20 atomic pct Cr. The eutectic arrest was not observed in studies on the 2.5 and 4.5 pct Cr samples but appeared in the 7.5 pct samples, which suggested some solubility of chromium in y uranium. On quenching from 859 °C, the 2.5 pct sample showed but one phase while the 4.5 pct sample contained a small amount of the eutectic along the grain boundaries; see Figs. 2 and 3. From this the maximum solubility of chromium in r uranium has been set at 4 pct. X-ray studies on these samples showed that the r phase was not retained at room temperature by quenching, but in each case a pattern was observed .which has been identified with the ß phase of uranium. Thermal data show the y-ß transformation of uranium lowered to 737°C as a consequence of this solubility. On quenching from the ß range (660°C), precipitation of chromium in the primary uranium is observed in the 2.5 and 4.5 pct Cr samples (see Figs. 4 and 5),

Jan 1, 1956

By R. W. D. Clarke, J. C. Folinsbee

INTRODUCTION This paper deals with a procedure for planning the mining of an orebody for which cross-sections, plans, grade of ore, and a geological estimate of the ore reserve have been prepared. The procedure begins with the preliminary selection of a mining method or methods on which an engineering evaluation will be carried out. The engineering evaluation is described in three parts: Conceptual Studies Engineering Studies Detailed Design An overall planning model is presented, plus an expanded model for the Engineering Study Throughout the discussion of the planning procedure, reference is made to three bulk mining methods, including block caving, sublevel caving, and longhole sublevel stoping, including a summary of the main characteristics of each of these mining methods. The planning model is designed for a longhole sublevel stoping method, but with modification, will apply to other methods. PRELIMINARY SELECTION OF A MINING METHOD To experienced mining engineers, identification of the nominal mining method for a given orebody normally involves a large measure of judgement. The geological data is reviewed to determine the configuration of the orebody, including size, shape, dip, grade, and metal distribution. Geotechnical data is considered, including the competence of the ore and host rock, faults, fracture patterns, groundwater, and the potential for in situ stresses. Geographical data, including the natural and societal conditions, are evaluated for their effect upon the mining method, and finally, economic data, basically defined as the value of the ore in the ground, but more specifically, including grade of mineable ore, distribution of ore grade throughout the orebody, and metallurgical recovery, will have a bearing on the nominal method selected. Preliminary evaluation of these factors will result in the elimination of the obviously inappropriate mining methods, leaving some method or methods for further, more detailed study. Since ore does not occur in simple geometric shapes, the method selected for more detailed study will require some variation to the standard. A few key factors will bear heavily on the selection and provide a basis for the most realistic choice. Geological Data The configuration of an orebody defined by the horizontal and vertical dimensions, the dip and strike, and the possibility of repetitive occurrences will have the major influence on the selection of the mining method. For bulk mining methods, the dip of the orebody should be steep, or the orebody must be thick so that gravity can be utilized to deliver fragmented ore to a central gathering area. Geotechnical Data The geotechnical data will be studied in greater detail when the nominal mining method has been selected and the engineering evaluation is undertaken. However, some basic initial information must be available. The structural strength of the ore and host rock, including the effect on it of faulting, fracturing, and insitu stresses, must be known. Data from exploration drilling and examination of drill core will assist in the preliminary assessment of these factors. Highly fractured ground may suggest a caving method of mining for certain orebody configurations, whereas highly competent or strong ore might indicate that for a similar configuration, longhole sublevel stoping will more likely succeed. Data obtained on groundwater from exploration drilling will be considered to determine if it can be controlled, or if it will represent a long term major expense or a hazard for which no control is possible.

Jan 1, 1981

By Albert Stazicker

AT Climax the warehouse department operates as an independent unit similar to the mine and mill departments. It has the responsibility of receiving, checking, unloading, and storing all material and supplies delivered to the plant. In addition, the transportation of all supplies comes under the direction of the warehouse so that prompt delivery of supplies to all departments is one of its major functions. The transportation division operates heavy and light trucks, trailers, two large tractors, and two snowplows. In addition to delivering supplies it is also responsible for snow removal from the roads, hauling of sand and gravel for concrete and domestic coal to employees. and all miscellaneous work involving the use of tractors or trucks.

Jan 1, 1946

By M. L. Lissberger

entirely suitable for certain uses and even possess advantages over present solders at high temperatures, but they are certainly not suitable for all uses. However, it is conceivable that their use in many places will effect a material conservation of tin. It will probably be wiser to use cadmium in solders where good results have been obtained than in brass where this element will be a source of possible trouble. F. F. Colcord,* New York, N. Y.-—The cadmium-lead solder has a higher conductivity than the lead-tin alloy, which ought to make it advantageous in the manufacture of electrical machinery. In the case of solder for tin-can work, one of the high officials of the American Can Co. said that he fully intended to .give it a good trial, and I do not believe they are going to reach hasty conclusions and run the risk of poisoning the public. Solder, Its Use and Abuse Milton L. LissbeRgeR,† New York, N. Y.—Solder is a mechanical mixture of tin and lead, a fact which is susceptible of very simple demonstration. A bar of solder of a grade even as low as 30 per cent. tin and 70 per cent. lead, passed through a buffing machine, will show a surface practically identical with that of a bar of second-quality or reclaimed tin. The buffings, on chemical analysis, will prove to be almost pure lead. According to the best practice, solder is made in the following manner. Virgin pig lead is first melted, and when it is thoroughly liquefied, virgin pig tin is added, together with a small amount of flux; the latter is for the purpose of bringing to the surface the so-called "liver," consisting of impurities that may have remained in either the lead or the tin as a result of incomplete refining. The combined material, when completely liquid, is thoroughly stirred for some hours, and is then cast into small pigs. Just before casting, and continuously during this operation, the molten metal yields dross, consisting largely of the oxides of lead and tin; this should be carefully skimmed off. After the pigs have cooled, they are taken to a smaller kettle, re-melted, and cast into the desired shape for use; or if wires, ribbons, etc., are to be made, the solder is cast into slugs suitable for extrusion and rolling. During this second operation, the skimming of dross should be even more carefully done than at first. Hand mixing has proved to be the only reliable method for the production of the best quality of solder, irrespective of its percentages of lead and tin. The best quality of solder is not necessarily that which contains the highest percentage of tin, but rather is that composition which performs best on the required piece of work. In order to produce

Jan 1, 1919

By John M. Hartman

(Read at the Wilkes-Barre Meeting, May, 1877.) Two systems are used for heating air in blast-furnace operations I. The double surface system, in which a cast-iron pipe is heated on the outer surface, and, at the same time, heats the blast from its inner surface. This is simple in operation and gives a continuous effect, but is limited by 1100° F. as a maximum temperature of the blast. II. The single surface system, by which large surfaces of fire-brick are heated, and air passed over the heated surface, absorbing the heat and carrying it on to the furnace. This system is more complex than the double surface, as it involves the reversing of the air and gas every hour and a half. The single surface system has two advantages: 1. The blast can be heated to a temperature of 1800° F. 2. The stoves are indestructible. From recent experience it has been found that 1300° F. to 1400° F. is the best average temperature for economy of coal for safe work¬ing. This is equivalent to a saving of 12 to 2 cwt. of coal per ton, of iron over the extreme limit of cast-iron stoves. Independently of this, it is a strong point in favor of this system that the blast can be raised to a temperature of 1800° F. within an hour when the hearth is getting cold. All furnacemen know the value of a hot hearth for quality and quantity of iron. Cooling of a hearth occurs from leaky tuyeres, scaffolds, or heavy burden. When there is not sufficient coal at the tuyeres to seize on the oxy¬gen of the entering air and convert it at once to carbonic oxide, there will not be enough heat to liquefy the cinder. Black cinder and poor iron are the results. The remedy is additional heat from the blast. If the stoves will give 1800° in place of 1100°, it is obvious that the furnaces will get around sooner, and without waiting for a change of burden at the tunnel head to bring extra coal to the hearth. The heat absorption caused by a leaky tuyere will chill the hearth and drive the zone of fusion higher up in the furnace. This loss must be supplied, and the calories lost to the hearth must be regained before good iron can be made. Take another case : A furnace carefully burdened on No. 1 iron, during a spell of damp weather, goes on to No. 2 or No. 3. Heat is lost to the furnace through absorption by the moisture, and less burden must be carried in order to get back on No. 1. When the

Jan 1, 1878

By John M. Hartman

TWO systems are used for heating air in blast-furnace operations: I. The double surface system, in which a cast-iron pipe is heated on the outer surface, and, at the same time, heats the blast from its inner surface. This is simple in operation and gives a continuous effect, but is limited by 1100" F. as a maximum temperature of the blast. 11. The single surface system, by which large surfaces of fire-brick are heated, and air passed over the heated surface, absorbing the heat and carrying it on to the furnace. This system is more comylex than the double surface, as it invoives the reversing of the air and gas every hour and a half. The single surface system has two advantages: 1. The blast can be heated to a temperature of 1800° F. 2. The stoves are indestructible. From recent experience it has been found that 1300" F. to 1400' F. is the best average temperature for economy of coal for safe working. This is equivalent to a saving of 11/2 to 2 cwt. of coal per ton of iron over the extreme limit of cast-iron stoves. Independently of this, it is a strong point in favor of this system that the blast can be raised to a temperature of 1800° F. within an hour when the hearth is getting cold. All furnacemen know the ralue of a hot hearth for quality and quantity of iron. Cooling of a hearth occurs from leaky tuyeres, scaffolds, or heavy burden. When there is not sufficient coal at the tuyeres to seize on the oxygen of the entering air and convert it at once to carbonic oxide, there will not be enough heat to liquefy the cinder. Black cinder and poor iron are the results. The remedy is additional heat from the blast. If the stoves will give 1800" in place of 1100°, it is obvions that the furnaces will get around sooner, and without waiting for a change of burden at the tunnel head to bring extra coal to the hearth. The heat absorption caused by a leaky tuyere will chill the hearth and drive the zone of fusion higher up in the furnace. This loss must be supplied, and the calorics lost to the hearth must be regained before good iron can be made. Take another case: A furnace carefully burdened on No. 1 iron, during a spell of damp weather, goes on to No. 2 or No. 3. Heat is lost to the furnace through absorption by the moisture, and less burden must be carried in order to get back on No. 1. When the

Jan 1, 1879

By Wm. R. Dotson

Forty years ago the atom was split and the Age of Fission dawned. Uranium was the element used in this earth-shaking accomplishment. Thitherto almost unknown to the man in the street, uranium soon became widely and persistently sought. And the quest for this unique material is not likely to diminish during this century. To find is one thing; to own is another. Who owns uranium in the ground? Where no mineral rights in the land have been severed by devise, grant, reservation or lease, the uranium belongs to the fee simple owner of the land. But where there has been a conveyance or reservation of all or part of the "minerals", determining WHAT a substance is has been the traditional way of determining WHO owns it. What, then, is this element called uranium? The 1907 edition of Watts Dictionary of Chemistry calls it "a lustrous, hard, silver-white metal". Of nature's three prime divisions it falls within the embrace of the mineral kingdom - substances neither animal nor vegetable. In its natural state uranium always is combined with other elements or substances in the form of an ore mineral. May we, then, put to rest any doubt or question as to the nature of uranium and classify it for all purposes, including that of ownership, as mineral? Not quite! That self-same logic would find oil and gas primly ensconced in the animal or vegetable kingdom. Technically, oil and gas are not minerals but legally they have been classified as such. Why? The Supreme Court of Tennessee sought the answer in 1897 in the case of Murray v. Allard, 43 S.W. 355. After citing authorities pro and con, and while admitting their origin to be "decomposition of marine or vegetable organises" that court firmly concluded that since they were obtained by a form of mining, oil and gas were minerals. From the above example two elementary truths emerge. First, for purposes of ownership, uranium is and will be whatever the courts say it is. Secondly, the courts historically and currently favor a practical rather than technical test to determine the "mineral" character of a substance. So now we turn to the jurisprudence for enlightenment and definition. EARLY CASES ALLOT URANIUM TO MINERAL OWNERS Two early cases involving the ownership of uranium followed what had been well-settled mineral within the meaning of the conveyances involved, confirming ownership in the mineral owners. In 1956 the U. S. District Court for New Mexico in the case of New Mexico and Arizona Land Company v. Elkins, 137 F. Supp. 767, appeal dism'd 239 F.2d 645 (10th Cir. 1956), found that a 1946 deed reservation of "all oil, gas and minerals underlying or appurtenant to said lands" included uranium and thorium. The court reasoned that uranium and thorium, being minerals within the scientific, geological and practical meaning of the term, would certainly constitute minerals within the purview of the reservation. While agreeing that uranium and thorium were "minerals", defendants argued that at the tine of execution of the conveyance it could not have been the intention of the parties to reserve them because they had no commercial value in the locality and were, in fact, not known to there exist until their later discovery in 1950. The court re¬jected, as a matter of law, this "lack of knowledge" theory citing the Supreme Court of Kentucky holding in Maynard v. McHenry, 113 S.W. 2d 13, that: "The mere fact that a particular mineral has not been discovered in the vicinity of the land conveyed or is unknown at the time the deed is executed rules of construction and held that uranium was a does not alter the rule . . ." that a grant or exception of "mineral" in a deed includes all mineral substances which can be taken from the land unless restrictive language is used indicating that the parties contemplated something less general than all substances legally cognizable as minerals. Further, argued the defendants, the only feasible mining procedure for such substances was open pit or strip mining, which would destroy the value of the land for grazing or agriculture. Finding that the language of the reservation was clear and unambiguous, the court would not permit the admission of extrinsic evidence as to mining procedures required. Elkins is the first uranium case construing the granting clause involved. In 1958 the Texas Court of Civil Appeals at San Antonio, in Cain v. Neuman, 316 S.W. 2d 915, no writ, held that a 1918 lease conveying "all of the oil, gas, coal and other minerals in and under" the land involved covered uranium. The lease provided a royalty of 1/10th on "other minerals." "We find no Texas precedent which discusses uranium," said the court, "but the usual arguments that uranium is not embraced within a lease are that the ejusden generis rule excludes uranium from the meaning of the lease

Jan 1, 1979

By Clarence Zener

THEORETICAL considerations by one of the authors have led1 to the prediction that the dynamic internal friction of annealed metals has a broad maximum at a certain grain size. This prediction they have veri-fied2 for alpha brass. In the present paper the theory is extended to include the precise manner in which the internal friction varies with grain size on either side of the maximum. New experimental data are pre¬sented to test this extended theory. The physical basis for the type of internal friction that is being investi-gated lies in the interplay between stress and temperature. Just as local fluctuations in temperature give rise to local fluctuations in stress, so like-wise fluctuations in stress give rise to fluctuations in temperature. But temperature gradients give rise to necessarily irreversible thermal cur-rents, and hence to internal friction. The theory for this type of internal friction has been developed quantitatively,3 and has been experimentally verified,4,5 for the particularly simple case of the transverse thermal cur-rents accompanying transverse vibrations. Of more fundamental impor-tance are the intercrystalline thermal currents accompanying all types of vibration. The variation in stress across grain boundaries arises from the elastic anisotropy and at least partial random orientation of the individual crystallites. An exact quantitative treatment of the internal friction due to these thermal currents is of course out of the question. However, much information can be obtained from general arguments.1,6 Thus when the frequency of vibration f is low, or when the grain size d is small, adja-cent grains remain nearly in thermal equilibrium, and vibration proceeds isothermally with little internal friction. Again, when the frequency is high, or the grain size large, the heat flow per cycle is small, the vibration proceeds adiabatically with little internal friction. The internal friction will become a maximum in the transition region. The degree of adiabatic-

Jan 1, 1940

By W. E. Bergman, P. G. Carpenter, H. B. Fisher

The conditions under which barium carbonate can be used to remove sulfates from drilling muds are limited The amount of sulfate remaining in solution in the system after treatment with barium carbonate is shown to be a function of the concentration of the carbonate and barium ions and the concentration of other electrolytes. Barium hydroxide may advantageously replace barium carbonate when the contamination is not entirely due to anhydrite (calcium in the system is then stoichiometrically less than sulfate) or when the carbonate concentration is high. The effect of substances such as quebracho, phosphates, and chromates, which form complexes or precipitates with barium, is discussed. INTRODUCTION As the complexity of the operations in drilling for oil has increased, more attention has of necessity been directed to the problems pertaining to the maintenance of good drilling mud properties. As a result, chemical treatment of muds has become an important factor in recent years. Some of these treatments have been designed to eliminate the deleterious effects of contaminants in aqueous mud systems by precipitation or other means. The most common of substances encountered during drilling include sodium chloride, cement, and calcium sulfate while various other contaminants: usually in small amounts, may be introduced from the water, clays, and other materials used in preparation of the mud. In certain cases, for example where continued salt-water flow is encountered or massive anhydrite is drilled, special muds may be used so that the physical properties of the mud will remain satisfactory for drilling. In other cases, it is desirable to remove the contaminants so that soluble electrolytes in the system are maintained at low values. For sulfate contamination, the conlmon practice in the field is to add barium carbonate to precipitate the sulfate as barium sulfate Ordinarily such a procedure gives satisfactory results. There have been important instances, however, where addition of barium carbonate was not effective in removal of soluble sulfates from drilling muds. and it is to these cases that the present paper is directed. While it is generally known that barium carbonate is not always effective in removing soluble sulfates from drilling muds, certain inconsistencies appear in the literature as to the limitations of its use, and little explanation for the limitations are given. Varnell and Kimbrel state that "the treatment (with barium carbonate for removal of sulfate) is simple and consists in maintaining a pH of 9 with caustic soda and quebracho." They caution that concentrations of quebracho greater than 1 lb./bbl. may inhibit the reaction. In another publication', a pH of 10.5 is considered "the maximum desirable," and the indication is that as much as 2.5 lb. quebracho per barrel may be present in the particular mud under discussion. Lancaster and Mitchell5 state that appreciable amounts of phosphates in the mud will inhibit the reaction with barium carbonate and that the phosphate treatment should be discontinued at least 24 hours before addition of the carbonate. Experimental work was initiated to ascertain the factors involved in using barium carbonate for the removal of sulfate contamination in drilling muds. While the experimental data herein reported are limited, they focus attention on the pertinent factors which must be considered for successful treatment. These factors are discussed from a practical and a theoretical view, the latter being supported by equilibrium data found in the literature. Further, it will be appreciated that the factors involved in this specific study will be closely analogous to those in certain of the other chemical treatments which involve a precipitation of the soluble contaminant. A thorough comprehension of these factors should result in a more fruitful application of this type of chemical reaction to the treatment of drilling muds. EXPERIMENTAL A. Reagents Two muds were used during this investigation. For one series of tests, bentonite suspensions were prepared by dilution of a stock suspension containing 8 per cent by weight of bentonite (Aquagel). For another series, a 6.4 per cent ben-tonitic mud weighted to 9.7 lb./gal. with barium sulfate (Mag-cobar) was used. Distilled water was used in all preparations. The quebracho (72% tannin extract) was obtained from the Thompson-Hayward Co. of Tulsa and contained 11.4 per cent moisture (105 C.). All other materials were reagent grade, and concentrations were corrected for water of crystallization, if any. All concentrations are expressed in pounds per barrel (42 gallons). B. Technique The systems — either mud or water — were contaminated with either sodium or calcium sulfate after treatment with the desired amounts of sodium hydroxide and quebracbo. For treatments with barium carbonate an approximately 3-fold excess (5 lb./bbl.) was used over that computed to be required to precipitate all the sulfate as barium sulfate. Barium hydroxide was used in concentrations of 2 lb./bbl. — about

Jan 1, 1949

By P. G. Carpenter, H. B. Fisher, W. E. Bergman

The conditions under which barium carbonate can be used to remove sulfates from drilling muds are limited The amount of sulfate remaining in solution in the system after treatment with barium carbonate is shown to be a function of the concentration of the carbonate and barium ions and the concentration of other electrolytes. Barium hydroxide may advantageously replace barium carbonate when the contamination is not entirely due to anhydrite (calcium in the system is then stoichiometrically less than sulfate) or when the carbonate concentration is high. The effect of substances such as quebracho, phosphates, and chromates, which form complexes or precipitates with barium, is discussed. INTRODUCTION As the complexity of the operations in drilling for oil has increased, more attention has of necessity been directed to the problems pertaining to the maintenance of good drilling mud properties. As a result, chemical treatment of muds has become an important factor in recent years. Some of these treatments have been designed to eliminate the deleterious effects of contaminants in aqueous mud systems by precipitation or other means. The most common of substances encountered during drilling include sodium chloride, cement, and calcium sulfate while various other contaminants: usually in small amounts, may be introduced from the water, clays, and other materials used in preparation of the mud. In certain cases, for example where continued salt-water flow is encountered or massive anhydrite is drilled, special muds may be used so that the physical properties of the mud will remain satisfactory for drilling. In other cases, it is desirable to remove the contaminants so that soluble electrolytes in the system are maintained at low values. For sulfate contamination, the conlmon practice in the field is to add barium carbonate to precipitate the sulfate as barium sulfate Ordinarily such a procedure gives satisfactory results. There have been important instances, however, where addition of barium carbonate was not effective in removal of soluble sulfates from drilling muds. and it is to these cases that the present paper is directed. While it is generally known that barium carbonate is not always effective in removing soluble sulfates from drilling muds, certain inconsistencies appear in the literature as to the limitations of its use, and little explanation for the limitations are given. Varnell and Kimbrel state that "the treatment (with barium carbonate for removal of sulfate) is simple and consists in maintaining a pH of 9 with caustic soda and quebracho." They caution that concentrations of quebracho greater than 1 lb./bbl. may inhibit the reaction. In another publication', a pH of 10.5 is considered "the maximum desirable," and the indication is that as much as 2.5 lb. quebracho per barrel may be present in the particular mud under discussion. Lancaster and Mitchell5 state that appreciable amounts of phosphates in the mud will inhibit the reaction with barium carbonate and that the phosphate treatment should be discontinued at least 24 hours before addition of the carbonate. Experimental work was initiated to ascertain the factors involved in using barium carbonate for the removal of sulfate contamination in drilling muds. While the experimental data herein reported are limited, they focus attention on the pertinent factors which must be considered for successful treatment. These factors are discussed from a practical and a theoretical view, the latter being supported by equilibrium data found in the literature. Further, it will be appreciated that the factors involved in this specific study will be closely analogous to those in certain of the other chemical treatments which involve a precipitation of the soluble contaminant. A thorough comprehension of these factors should result in a more fruitful application of this type of chemical reaction to the treatment of drilling muds. EXPERIMENTAL A. Reagents Two muds were used during this investigation. For one series of tests, bentonite suspensions were prepared by dilution of a stock suspension containing 8 per cent by weight of bentonite (Aquagel). For another series, a 6.4 per cent ben-tonitic mud weighted to 9.7 lb./gal. with barium sulfate (Mag-cobar) was used. Distilled water was used in all preparations. The quebracho (72% tannin extract) was obtained from the Thompson-Hayward Co. of Tulsa and contained 11.4 per cent moisture (105 C.). All other materials were reagent grade, and concentrations were corrected for water of crystallization, if any. All concentrations are expressed in pounds per barrel (42 gallons). B. Technique The systems — either mud or water — were contaminated with either sodium or calcium sulfate after treatment with the desired amounts of sodium hydroxide and quebracbo. For treatments with barium carbonate an approximately 3-fold excess (5 lb./bbl.) was used over that computed to be required to precipitate all the sulfate as barium sulfate. Barium hydroxide was used in concentrations of 2 lb./bbl. — about

Jan 1, 1949

By Jeffrey L. Thompson, Kenneth A. Gutschick, Robert C. Freas, Robert S. Boynton

Lime, the "versatile chemical," is, generally speaking, a calcined or burned form of limestone commonly known as quicklime, calcium oxide or calcia, or, when water is added, calcium hydroxide or slaked lime. Almost 40 different lime products are available, a fact which has contributed to the rather loose use of the term lime as well as to much confusion and misunderstanding. The term is frequently, albeit erroneously, used to denote almost any kind of calcareous material or finely ground form of limestone or dolomite. Lime is usually made from high-calcium or high-magnesium limestone, generally having a minimum of 97% combined carbonate content. Normally, high-calcium limes contain less than 5% MgO. When the lime is produced from a high-magnesium limestone, the product is referred to as dolomitic lime. Calcination, or the production of lime, has its origins in the earliest days of alchemy, with the general reaction class having been identified in an Arabic text printed in 1000 A.D. It was much later, however, in the mid-1700s to the mid-1800s before this basic reaction became understood from a scientific perspective. The production of lime has been so basic and simple that its underlying scientific principles have over the years received only intermittent investigation. Rather, much of the thought and inquiry has been directed toward the development of kilns. Thus, it has only been in the last 15 to 20 years that lime has received any concentrated scientific investigation relative to the thermodynamics and kinetics of the calcination and hydration reactions. Calcination refers to a broad class of reactions, of which the lime/limestone reaction is just one, wherein a substance is heated to less than its melting point, resulting in a weight gain or weight loss. In the calcination of limestone to produce lime, the basic chemical reaction is as follows: [CaCO3 (limestone) + heat (1000° to 1300°C)= 100 CaO (quicklime) + CO2 T 5644 or CaCO3 • MgCO3 (limestone) 10084 + heat (900°C to 1200°C) CaO • MgO (quicklime) + 2CO2 T 56 4088] While there is nearly universal agreement about the equilibrium conditions related to the limestone/lime reaction above, there have been numerous and varied calcination models developed for the reaction. Recent investigations have resulted in the development of the model shown in Fig. 1. From this model it can be seen that calcination is a function of both temperature and CO2 pressure. It does not, however, provide any indication of the rate at which the reaction takes place. Calcination is strongly time variant with different limestones. In a very broad sense this relates to the fact that the calcination reaction starts on the exterior surface of the limestone and then proceeds toward the center. As the calcination reaction takes place, the CO2 released at the reaction interface must make its way through the lime to the exterior surface. Therefore, because calcination is limited by gas diffusion to the surface of the partially calcined limestone, natural impurities in the stone, differences in crystallinity, grain boundary chemistry, density variations, and imperfections in the atomic lattice all play a significant role in

Jan 1, 1983

By J. C. Savins

The practical analysis of the hydrodynamics of the wellbore has long been a subject of interest to engineers. This paper presents a simplified solution to the problem of computing the pressure drop for the flow of drilling mud in the annulus of the wellbore. This solution is, however, an exact and rigorous solution under the assumptions which have been imposed. These assumptions are that the drilling fluid is a Bingham plastic fluid* and that the annulus is formed by two concentric, stationary, cylindrical pipes. It is further assumed that the fluid is incompressible and that its motion is isothermal and in a steady state. This problem under the same assumptions has been attacked by previous authors. Beck, Nuss and Dunn' proposed that the equation for the flow of a Bingham plastic fluid in a cylindrical pipe could be applied to an annulus if the pipe radius were replaced in the equation by the hydraulic radius. This equation, known as the Buckingham-Reiner equation' (see Appendix 1), was also used in an approximate form. Van Olphen pointed out that even for a simple or Newtonian- fluid the pipe equation (Poiseuille's law) could not be converted to the Lamb equation escriptive of flow in an annulus (see Appendix 1) by using the hydraulic radius. Van Olphen further attempted to give a solution for the annular flow of a Bingham plastic fluid by introducing approximations similar to those which have been used in the case of the Buckingham-Reiner equation. Other attempts to provide approximate or exact solutions have been made by Grodde' and by Mori and Ototakeq. The present authors some years ago in unpublished work derived the correct expressions relating the pressure drop and flow rate for this problem. It was found that the solution consisted of two simultaneous equations, one of which contained a logarithmic term. Thus, obtaining numerical results for any particular case of interest involves very tedious trial-and-error computations. Very recently Laird presented the correct derivation of the two equations which are given in full detail in Appendix 1. In order to reduce the amount of calculation time which would be involved in providing a complete tabular or graphical solution to the problem, a high-speed electronic digital computer has been utilized. For this purpose the two simultaneous equations were transformed into more compact expressions by introducing reduced variables. These expressions are given in the following theoretical section. A similar procedure in this problem has been developed by Fredrickson and Bird1" Their tabular results, however, are very incomplete in the range of practical interest for problems of wellbore hydrodynamics. We have furthermore been able to express our graphical results in terms of convenient and familiar dimensionless groups. THEORETICAL DEVELOPMENT Use of Reduced Variables In terms of reduced variables the two simultaneous equations just discussed take the following form, The reduced variables q, x, a and z are defined in terms of the various measured quantities, where Q is volumetric flow rate, AP/L is pressure gradient, Dl is OD of inner pipe, D, is ID of outer pipe, is plastic viscosity, and is yield point. Thus, we have a dimensionless volume flux, a dimensionless reciprocal pressure gradient, and the ratio of the pipe diameters Before introducing the fourth reduced variable, z, it is of interest to consider the physical significance of the parameter x. As may 'be seen from the velocity profile of Fig. 1 the Bingham plastic fluid has the interesting property that a portion of the stream flows at a uniform velocity without shearing action. This section of the stream is situated approximately in the center of the conduit and is known as the "plug flow" region. Its existence is due to the fact that the shearing stresses within the region do not exceed the yield point, which is one of the two flow properties characterizing the fluid. The parameter x then turns out to be the ratio of the

By P. Somasundaran, D. W. Fuerstenau

The length of the collector is found to influence the flotation of the mineral even at incipient conditions, which are below the concentration at which interaction at the solid-liquid interface begins to take place to form hemi-micelles. To study this dependence, concentration for incipient flotation of quartz was determined as a function of pH with collectors of various chain lengths. The observed effect of chain length on flotation is ascribed to that of collector adsorbed on the bubble surface. In previous studies, it was shown that at low concentrations the alkyl collector ions adsorb at the solid-liquid interface as individuals.''2 At higher concentrations, the collector ions adsorbed at the solid-liquid interface associate with each other to form two-dimensional aggregates called hemi-micelles. Above the hemi-micelle concentration, the length of the hydrocarbon chain is extremely important since the hydrocarbons are in effect removed from water during the association, making the energetic conditions more favorable for adsorption at the interface. Because of this enhanced adsorption, one observes a very rapid increase in flotation associated with the hemi-micelle formation at the solid-liquid interface. However, a dependence of flotation on the chain length at concentrations below that required for hemi-micelle association was also observed,' and this cannot be explained by the above mechanism which postulated hydrocarbon chain interactions only at the solid-liquid interface. This prompted an investigation into other possible reactions of the hydrocarbon chains and an examination of the conditions at the bubble surface involved in the flotation system and how these observations might explain the reactions at the solid-gas interface which cause the particle-bubble attachment required for flotation. To obtain more information on chain length effects, flotation, under incipient conditions, was tested by vacuum flotation techniques. The collector-concen-tration-pH relationships for flotation of quartz with alkyl ammonium acetate collectors was delineated by observing the pH at which quartz particles begin to float to the liquid surface. By investigating flotation as a function of pH, it was also possible to study the effect of neutral molecules on incipient flotation conditions, since the aminium ions hydrolyze to amine molecules at higher pH values. EXPERIMENTAL WORK Brazilian quartz specimens were crushed and sized, and the 270 x 400 mesh fraction was used for flotation studies. The samples were leached with concentrated hydrochloric acid until no coloration of the acid occurred. The leached material was washed free of chloride ions and stored in distilled water. The vacuum flotation technique developed by Schuhmann and prakash3 was used to determine the critical pH-concentration curves. This method, which can be used to delineate conditions for incipient flotation, is fairly simple and rapid. About 0.5 gm of 270 x 400 mesh quartz was placed in a 100 ml graduated cylinder which was then filled to the 100 ml mark with the collector solution made from high-purity alkyl ammonium acetate salts. The water used for the test was conductivity water saturated with air that had been passed through a cleansing train consisting of Drierite, Ascarite, a water wash bottle, and a trap. After the pH was adjusted, the cylinder was then conditioned for thirty minutes. In the tests where an acid pH was desired, sufficient acid was added before the collector solution to avoid any effect due to slow desorption of collector from the quartz surface. After conditioning, vacuum was applied to the system and the flotation or nonflotation of the quartz was noted. The pH at which the quartz particles began to float to the liquid-gas interface was taken as the critical PH. Critical pH curves were thus determined for different concentrations of the various collectors. Hallimond tube flotation data were taken from the authors' previous publication1 for correlation with that from the vacuum flotation. RESULTS AND DISCUSSION The results of vacuum flotation studies for determining critical pH-concentration curves, i.e., curves which delineate conditions for incipient flotation, are shown in Fig. I. In generaI, all the curves exhibit an upper and lower pH limit between which flotation will

Jan 1, 1969

By Craig S. Hartley

An approximate expression is obtained for the energy of a closed dislocation loop in equi1ibriu)n with a constant net stress. The result obtained is valid for loops in isotropic or anisotropzc materials provided that they are suJficiently large that the energy per unit length of a segment of the loop can be approximated by that of an infinite straight dislocation tangent to the loop. It is shown that this approximation leads to very close agreement with a more rigorous calculation of the elastic energy of a circular glide loop. The Gibbs-Wulff Form, GWF, of a dislocation is the closed planar loop which has the smallest elastic self-energy of all possible loops having the same Burgers vector and enclosing a fixed area, A.' The energy of such a loop is related to the net resolved shear stress* required to expand the loop and to the stress required to activate a Frank-Read source.223 In the following sectiorls the problem of determining the form of the GWF is discussed and an approximate method for calculating its elastic self-energy is presented. It is demonstrated that the approximations employed lead to no serious errors when applied to a calculation of the elastic energy of a circular glide loop. This method is then used to obtain a closed form expression for the energy of GWFs in isotropic and anisotropic materials. THEORY Burton, Frank, and cabrera4 have proved that the relationship of the equilibrium shape of a two-dimensional array of atoms under the influence of the Gibbs free energy associated with unit length of its boundary, G(O), is that the polar plot of G(0) vs 0 is proportional to the pedal of the GWF.* The angle 0 is measured "The pedal of the polar graph ofG(0) vs0 is the envelope of tangents to the eraph.relative to some crystallographic reference direction. The difficulty in applying this result to a closed dislocation loop arises from the self-interaction of the loop. For a dislocation the energy analogous to G(0) is a function of the total configurati~n.~ Consequently the relation which determines the GWF is an integro-differential equation rather than the simple differen- tial equation which results when G(8) is a function of 0 alone. Mitchell and smialek3 and Brown~ have used the self-stress concept introduced by ~rown' to calculate the shapes of dislocations in equilibrium with an applied stress. In this approach the glide force on an element of the dislocation loop due to the interaction of the element with the rest of the loop is equated to the glide force exerted by the local applied stress. The shape of the loop is then adjusted so that the two forces above are equal at all points on the loop. It is possible to calculate the energies of such loops by noting that, for equilibrium with an applied stress, the energy is equal to pijbiAj (summation convention) where bi is the Burgers vector, p.. is the local net stress tensor, and Ai is a vector directed perpendicular to the plane of thd loop with magnitude equal to the area of the loop. Also Brown' has calculated the energy of a hypothetical polygonal GWF using the above technique and anisotropic elasticity. However, his indicated solution for the energy in the general case of an arbitrary GWF is only slightly less involved than an iterative solution of the integrodifferential equation referred to earlier. In the present work the approximation employed by DeWit and Koehler' is used to calculate the energy of a closed loop in equilibrium with an applied stress. That is, the energy of a loop segment, ds, is approximated by the product of ds and the energy per unit length of an infinite, straight dislocation in a cylinder coaxial with the tangent to the loop at the angular position of the segment. This is known as the "line tension" approximation. The inner cutoff radius of the elastic solution defines the core radius, while the outer cutoff radius is determined by some characteristic dimension of the loop. Actually, both of these radii vary with the edge-screw character of the segment. The effective core radius changes because of the orientation dependence of the Peierls width of a dislocation,8 and the outer radius should be the radial distance from the circumference of the loop to the center of symmetry of the area enclosed by the loop.g However, since the energy varies logarithmically with the ratio of these radii while depending directly on the effective elastic constants, only the effect of the latter is considered. This approximation also neglects the self-interaction of the loop segments. For small loops this will doubtless be extremely important, but for large glide loops produced by plastic deformation the self-interaction is not nearly so important in determining the energy of the loop. This point is illustrated by the following calculation of the energy of a circular loop. Consider a circular loop of radius R which lies in the XI - x, plane of an infinite isotropic continuum and whose Burgers vector makes an angle $ with xs. The first-order solution for the elastic self-energy is:'

Jan 1, 1970

By Z. F. Danes

Combination of gravity data and density logs makes it possible to determine the structural relief. Under a wide class of geologic conditions, the solution is unique, or limited to a single parametric system of solutions. As a useful byproduct, the method yields a new way to construct derivative maps, continue the field up or down, subtract regional anomalies, and perform smoothing. In the past, the problem of interpreting gravity anomalies in terms of structural geology was solved along two main lines: 1) A body of a certain shape and density contrast was assumed and the corresponding gravity anomaly calculated, analytically for simple bodies, graphically and/or numerically for more complex ones; then the computed anomaly was compared with the observed one, and the assumed shape corrected according to the differences between the two. 2) The anomaly is assumed to come from a warped interface between two media of different density; the relief of the warping is assumed small compared to the depth of burial, so that the structure can be approximated by a flat horizontal surface of variable density distribution. The first method is a standard technique, described in every text book on applied geophysics, and is well applicable, for bodies with predominant vertical dimension. The second one, probably first used by Tsuboi and Fuchida,' is mathematically more elegant. It applies to the fashionable field of integral transforms (Bullard and Cooper, 2 Tomoda and Aki, 3 Dean 4) and is useful mainly in cases when the vertical relief of the structures is comparatively small. 30th methods, tacitly or openly, assume a density discontinuity across the boundary of the two media, while within each medium the density is constant. However, the recent invention of the gamma-gamma

Jan 1, 1962

By C. R. Dodson, W. T. Cardwell

This paper presents the results of a theoretical and experimental study of the effect of preperforated liners on well productivity. The analysis concerns the rectangular type of slot, either machine or torch cut, which is common in California. Muskatla treated this problem recently in a mathematical analysis of the flow of oil or gas from natural reservoirs into both gun-perforated and slotted liners. This paper presents additional and simplified analytical considerations and conclusions for the slotted liner, the solutions being applicable in the laboratory as well as in the field. An application of the analytical methods to permeability measurements on mounted core samples is given, to show the effects of sealing wax or other obstructions on the end faces of the cores. Results Fig. I 'Ompares the results of some theoretical calculations with the results of electrical analogy experiments performed in the Standard Oil Company of California's Production Technology Laboratory at La Habra, California. Fig. I indicates that the flux into short, "three-dimensional slots" of the relative dimensions encountered in practice is approximately equal to that into full-length, "two-dimensional slots" having the same open fraction of pipe. (The same numbers of slot rows, and the same radius ratio are also implied.) It can be seen from physical considerations that the closeness of this approximation must improve as the ratio of the external radius to the internal radius increases. Therefore, it is possible to calculate the flow into a slotted liner using a simple modification of the Darcy equation: where N is .the number of slot rows and O is the open fraction of the pipe. Fig. 2 shows the results of calculations . using Eq. 28. The most remarkable features of Fig. 2 are the high flux values for very small open fractions of pipe. For instance, with six slot rows and a radius ratio of 500, 74 per cent of the open-hole flux may be obtained with only o.I per cent of pipe Open. Fig. 2 shows that for a given open frac tion of pipe, the flux is greater, the greater

Jan 1, 1945

By D. Turnbull, J. H. Hollomon

THERE is a large body of evidence'" indicating that solidification during the liquid-solid transition is usually induced by heterogeneities present in the liquid. By dispersing liquid metals into small droplets, the impurities responsible for catalyzing solidification are isolated within a small number of these droplets. The effect of the foreign body therefore is restricted to a single drop by this technique. Thus upon cooling below the melting temperature, solidification is initiated by homogeneous nucleation in the majority of the droplets that do not contain impurities. In the case of solidification of liquid metals, the activation energy for nucleation is so great that its rate changes by orders of magnitude for a change in temperature of only several degrees centigrade.' Effectively homogeneous nucleation occurs at a critical temperature upon continuous cooling. Thus by microscopic observation of single particles during cooling, a temperature at which the rate of homogeneous nucleation becomes sensible can be determined.3 since at the temperatures at which nucleation occurs in the absence of impurities the rate of crystal growth is extremely rapid, the temperature at which the entire particle solidifies is very nearly the temperature at which the nucleation of the solidification occurs. Thus for liquids that freeze at high temperatures the onset of nucleation can be established by simply observing the temperature at which the marked heat evolution and increase in brightness of the particle occur. For liquids that freeze at lower temperatures the onset of nucleation can be determined by a rumpling and change in shape of the particle resulting from its solidification. The microscopic technique for observing the solidification of small particles has already been described." In earlier papers the nucleation of solidification of pure metals 5,6 and of alloy systems7 showing complete liquid and solid solubility have been described. In the present paper, the observations are extended to a simple eutectic system (Pb-Sn) where the possibility of the formation of two solid phases exists. Metals for the investigation were obtained from the American Smelting and Refining Co. in the form of pure lead and pure tin, 99.8 and 99.9 pct purity, respectively. An ingot of each of the pure metals was made into shot by heating the metals at a temperature about 50 °C in excess of the melting point and pouring the liquid slowly into a container of water at 15°C. Samples of the shotted pure metals were weighed out to make alloys containing 5, 10, 15, 20, 25, 30, 40, 50, 60, 70, 80, and 90 atomic pct Pb. Samples of each alloy were then melted in separate beakers. Each melt was poured through a pyrex funnel into a cylindrical mold (% in. ID). The casting solidified in 10 to 20 sec. The inside of the mold as well as the funnel through which the metal was poured were coated with graphite to eliminate adherence of the metal. Analyses were performed on some of the compositions and are given in Table I. The compositions also were checked for these samples and for those that were not analyzed by determining the spread between the liquidus and the solidus upon melting the small metal particles. These measurements agreed as well with the nominal compositions as the analyses listed above. Results The results of the supercooling experiments for the several alloys are summarized in Table II and plotted on the constitution diagram in Fig. 1. Data for the pure lead and pure tin were taken from earlier investigations. The values for the maximum supercooling of the several alloys are the average of several determinations on a number of drops of each alloy. The maximum value in any determination was within about 2 pct of the average. For the alloys containing from 20 to 60 atomic pct Sn, inclusive, two marked changes of the surface structure were observed upon cooling. At the higher temperature, after the first appearance of the solid phase it continued to grow slowly at a constant temperature and then stopped. At the lower temperature the alteration of surface structure was abrupt. For the alloys containing from 70 to 95 atomic pct Sn, inclusive, an abrupt change in surface structure was observed at a single critical temperature.

Jan 1, 1952

In the past few years the hydraulic aspects of rotary drilling have received considerable attention. It is generally recognized that accurate prediction of circulating pressures is desirable, particularly in those areas where a delicate pressure balance is necessary to prevent both blowouts and lost circulation. For calculation purposes the standard hydraulic equations for the pipeline flow of Newtonian fluids have been altered to facilitate similar calculations for non-Newtonian or plastic fluids.'.' This latter classification includes most colloidal types of drilling muds. Two properties: plastic viscosity, un, and Bingharn yield value, Y,, are commonly used to define the flow characteristics of a plastic fluid. These are commonly obtained with multispeed viscosimeters such as the Fann V-G meter.3 Normally these measurements are obtained at some surface temperature, and are not corrected to circulating temperatures for calculation purposes. This may result in considerable error, particularly in the laminar flow calculations which comnlonly apply to the drill pipe-borehole annulus. The purpose of this study was to investigate the effect of temperature on the flow properties of some water-base muds. A laboratory model Fann V-G meter was used for measurement of viscosities, yield values and gel strengths. An aluminum water jacket with O-ring seals was machined to fit around the mud cup of the Fann meter. All mud samples were prepared by thorough mixing in a Hobart mixer. Viscosity and gel strength measurements were made with the Fann meter using standard procedures. Flow properties of muds were studied at 80, 120, 160 and 180°F. The compositions of the test samples are given in Table 1. The typical effect of temperature on the flow properties of these drilling muds is illustrated by Fig. 1. It was found that plastic viscosity and apparent viscosity decreased with an increase of temperature. However, the curves were not linear, and did not appear to follow any definite trends or patterns. Yield point data showed much more scattering.' Since a usable method for predicting drilling mud flow behavior with temperature was desired, an attempt was made to find a simple relationship between these variables. The basic approach used by Havenaars for predicting the same effect on turbulent viscosity resulted in Fig. 2, which shows that

By S. Sumski, M. B. Panish, R. T. Lynch

The liquidus isotherms in the gallium-rich corner of the Ga-Al-P phase diagram have been determined from 1000" to 1200°C and at I100°C the corresponding solidus isotherm was obtained. A simple thermody-namic treatment which permits calculation of the solidus and liquidus isotherms is discussed. A technique which was previously used for the growth of GaxAl1-xAs was used for the preparation of solution epitaxial layers of GaxAl1-xP and ALP. An approximate value of 2.49 i 0.05 ev for the band gap of Alp at 300°K was obtained and the ternary phase data were used to estimate a value of 36 kcal per mole for the heat of formation 0f Alp at that temperature. The Gap-A1P crystalline solid solution is one in which there exists the possibility of obtaining crystals with selected energy gaps, within the limits imposed by the energy gaps of Gap and Alp. Such crystals are of considerable interest because of their potential value for optoelectronic and other solid-state devices. Furthermore, it has been amply demonstrated for GaAs and GaP,'-7 that device, or bulk materials grown from gallium solution generally have more efficient radiative recombination than materials prepared in other ways. This presumably due to the lower gallium vacancy concentration in such material.= Small crystals of GaXAl1-xP and A1P have been grown from solution,8-10 and A1P has been grown from the vapor," but neither have previously been grown by liquid epitaxy. In this paper we present the ternary liquidus-solidus phase diagram of the Ga-A1-P system in the region of primary interest for solution epitaxy, and discuss the thermodynamic implications of that phase diagram with particular reference to the liquidus and solidus isotherms in the gallium-rich corner of the GaxAl1-xP primary phase field and to the A1-P system. Several measurements of the absorption edge of GaxAl1-xP crystals have been made and the width of the forbidden gap of A1P has been estimated from these measurements. EXPERIMENTAL The differential thermal analysis technique used to determine the liquidus isotherms and the optical measurements used in this work are similar to those described previously12 for the Ga-Al-As system, ex- thermocouples in the thermopile for added sensitivity. The materials used were semiconductor grade Ga, Gap, and Al+ The composition and temperature range at which DTA studies could be done was quite restricted. The upper temperature was limited by the chrome l-alumel thermopile to about 1200°C, and the highest aluminum concentration to about 5 at. pct by low sensitivity caused by the reduced solubility of Gap with increasing aluminum concentration in the liquid. DTA studies were not possible at 1000°C and below because of the low sensitivity caused by low solubility of Gap in the Ga-A1-P system. The cooling rate for these studies was about 1°C per min. No heating studies were done because of limited sensitivity. Supercooling probably does occur, but our experience with other 111-V systems indicates that it is no greater than about 10 to 15.c. Solid solubilities were determined by analyzing epitaxial layers of GaxAl1-xP grown from the liquid, with an electron beam microprobe. The layers were grown on Gap seeds by a tipping technique in which the layer is grown over a short-temperature range (20" to 50°C) on the seed from a solution of known composition. The tipping technique reported by Nelsson1 for GaAs could not be used, particularly for solutions containing appreciable amounts of aluminum, because of the formation of an A1203 scum on the liquid surface. A system was therefore designed, which would effectively remove the oxides mechanically, so that uniform wetting and crystal growth could occur. This tipping technique has already been described in detail." The best control over the composition of the re-grown layer was obtained when the tipping was done at a temperature which corresponded to the temperature of first formation of solid for the solution being used. Generally, therefore, a solution was prepared by adding the amounts of Ga, Gap, and A1 required to yield a solution which would be completely liquid above the tipping temperature with solid precipitating below that temperature. For most of the work reported here, the 1100°C isotherm of the ternary was used. It was generally necessary to heat the solution to 50" to l00. C above the tipping temperature to dissolve all of the Gap in a reasonable length of time. The epitaxially grown layers were used both for optical transmission measurements to aid in the estimation of the way in which the absorption edge changed with aluminum concentration, and for the electron beam microprobe analyses to provide data for the determination of the solid solubility isotherm. RESULTS AND DISCUSSION Liquidus Isotherms in the Ga-A1-P Ternary Phase Diagram: Thermodynamic properties of the system. The only thermal effect studied in this work was that

Jan 1, 1970

By Milton Lissberger

MILTON L. LISSBERGER, ? New York, N. Y.-Solder is a mechanical mixture of tin and lead, a fact which is susceptible of very simple demonstration. A bar of solder of a grade even as low as 30 per cent. tin and 70 per cent. lead, passed through a buffing machine, will show a surface practically identical with that of a bar of second-quality or reclaimed tin. The buffings, on chemical analysis, will prove to be almost pure lead. According to the best practice, solder is made in the following manner. Virgin pig lead is first melted, and when it is thoroughly liquefied, virgin pig tin is added, together with a small amount of flux; the latter is for the purpose of bringing to the surface the so-called "liver," consisting of impurities that may have remained in either the lead or the tin as a result of incomplete refining. The combined material, when completely liquid, is thoroughly stirred for some hours, and is then cast into small pigs. Just before casting, and continuously during this operation, the molten metal yields dross, consisting largely of the oxides of lead and tin; this should be carefully skimmed off. After the pigs have cooled, they are taken to a smaller kettle, remelted, and cast into the desired shape for use; or if wires, ribbons, etc., are to be made, the solder is cast into slugs suitable for extrusion and rolling. During this second operation, the skimming of dross should be even more carefully done than at first. Hand mixing has proved to be the only reliable method for the production of the best quality of solder, irrespective of its percentages of lead and tin. The best quality of solder is not necessarily that which contains the highest percentage of tin, but rather is that composition which performs best on the required piece of work. In order to produce

Jan 12, 1918