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X-ray analysis of polycrystalline powder samples has grown beyond its roots in the world of laboratory research and is now regarded as one of the most powerful industrial process-control tools in the field of building materials. This is the key to characterise the element and crystalline phase composition of the material. This is due largely to the development of industrial X-ray analytical systems such as PANalyticalÆs twin solution, which has transformed the advanced analytical techniques born in the laboratory into a robust, workmanlike and easy-to-use tool for todayÆs heavy industries. The increasing use of alternative fuels makes the Bogue method less reliable. Therefore, the real phase quantification by the Rietveld method is the only choice. Additional fine-tuning of the Rietveld method by using alternative methods guarantees the most accurate quantitative results. Moreover, the recent development of ultra high-speed X-ray detectors allows for æon the flyÆ quantitative X-ray diffraction analysis and a truly interactive process and quality control.

Jan 1, 2008

By George C. Carter

It was just a little over three years ago that the "Go" button was pushed to start operations on the blending piles at Oro Grande. As is usual with any new installation, there were problems that had to be solved. This paper will concern itself with those problems directly related to quality control. To obtain a consistent outgoing quality level at the most economical level for a finished product requires two main points: 1. Measurement of variations in the process, 2. A method of making a predictable change to adjust for variations. The manufacture of cement requires a relatively high degree of accuracy if a consistent outgoing quality level is to be maintained. The blending piles were our solution to this problem.

Jan 1, 1962

By Dipak Sengupta

This study analyzes the safety, technology, and economic impact of eliminating safety fuse from metal/nonmetal mines, based on operation and manufacturer experience over the past five to ten years. If safety fuse is eliminated, blasting accidents will decrease with no technical impact except for some limited, specific applications. The economic impact will be minor for large operations, but will be significant enough for small operations that some small operations will likely close rather than change. The majority of the mines would probably change over, with the extra cost absorbed by the market. Elimination of safety fuse would have obvious impact on the two manufacturers of safety fuse; one manufacturer already produces an alternative system, and will remain unaffected; the other will be affected if they do not change their production strategy. There will be a very minor effect on the mining industry as a whole due to abolishment of safety fuse from the standpoint of employment or production.

Jan 1, 1980

By Sean Dessureault

Information technology (IT) initiatives in the past have tended to be sold on their ability to maximize resource output and return on capital by using assets more effectively and efficiently. Many IT projects fail, not delivering return on their investment. This is known in the IT industry as the ?productivity paradox,? where increasing investments in IT do not result in comparable increases in productivity. Experiences and studies of most business sectors reveal that this paradox is rooted in the false assumption that more IT spending automatically results in financial benefit, whereas the true source of benefits is in how effectively IT is used. Most business sectors have accepted that the reengineering of processes is required to gain the full benefits promised of IT. A mining operation has organizational processes similar to most business sectors but unique operational processes. The lessons of changing business practice in more common business processes such as inventory control and customer-supplier relationships can be adequately transposed into a mine. The unique operational processes in mines, in turn require unique redesign efforts. Several enabling information technology opportunities have recently become available, such as more integrated mine production management systems and tactical manger training simulators. This paper reviews the latest IT products and ou lines the processes and kinds of change that will be required in order to benefit from these new investment options.

May 1, 2002

By Jr. F. M. Perkins.

Capillary forces play a controlling role in water-drive displacement processes both in laboratory experiments and in actual reservoirs, but their quantitative importance may be quite different in the two cases. Because of the importance of conducting laboratory experiments which are representative of field conditions, it is necessary to understand exactly the role of capillary forces in the displacement process. Though a number of experimental investigations related to this subject are contained in the literature, there appears to be a lack of information pertaining to unsteady-state experiments in water-wet media. This experimental study was conducted to obtain additional laboratory data to clarify further the role of capillary forces in both the macroscopic and microscopic flow of oil and water in porous materials. THEORETICAL CONSlDERATlONS The capillary pressure is defined as the difference in pressure between a continuous oil phase and a continuous water phase in a porous material.' The magnitude of this pressure difference depends on the interfacial curvature and the interfacial tension. The interfacial curvature is determined by the geometry of the pore spaces, the wettability of the rock surfaces, and the quantity of cach phase present. Capillary forces are involved in a water-drive displacement process in that they exert a controlling influence on the microscopic fluid distribution which in turn is reflected in the saturation or macroscopic flow behavior. Microscopic Fluid Distribution Because of the microscopic nature of the displacement of oil by water, it is necessary to consider the flow and the fluid distribution in individual pores. On this microscopic scale the capillary Forces, which act over a distance of one or two sand grain diameters, control the distribution of oil and water under static equilibrium conditions. When an external force is applied to the fluids, such as in a water-injection experiment, the applied forces tend to distort the oil-water interfaces. However, in most fine-grained, water-wet sands, the applied pressure difference across one or two grain diameters is usually several orders of magnitude less than the capillary pressure difference. These con-siderations lead to the theory' that even during flow the capillary forces continue to control the microscopic distribution of oil and water within the pores of a porous material for all practical reservoir and laboratory flow rates. This concept of capillary forces controlling the microscopic distribution of fluids has been substantially verified by other investigators3-7 who have found a lack of dependence of relative permeability and residual oil saturation on rate of fluid injection. Macroscopic Distribution The microscopic influence of capillary forces cannot be observed easily and only the effect on the macroscopic or average saturation can be detected. The saturation, of course, is really the point of interest. During a water flood, large differences in saturation at the flood front cause large capillary pressure gradients. This, in turn, causes water to advance ahead of the flood front thereby reducing the capillary pressure gradient in this region. The result is that in homogeneous porous media capillary pressure gradients tend to cause a diffuse displacement front. At low rates in laboratory columns, the front may extend over the entire column length. When the advancing water first reaches the outflow face of a core, the water, which is the wetting phase, cannot be produced because the pressure in the water just inside the core is lower than the pressure in the oil-filled space around the outflow face. This difference in pressure is equal to the capillary pressure for the water saturation existing at the outflow face. Water, therefore, accumulates at the outflow end of the core which causes a reduction in the capillary pressure. Because the capillary pressure does not vanish except at the residual oil saturation,7,8,9 water will not be produced until the residual oil saturation exists at the outflow face. This entire effect,"' which is called the "boundary effect", results in a region of relatively high water saturation near the outflow face. At low rates of injection in a short column, this region of high water saturation may extend over a considerable portion of the column. The influence of capillary forces on the macroscopic flow of oil and water have been described by Leverett.10 For unidirectional, viscous flow in the absence of gravity segregation, the expression in dimensionless form for the fraction of water in the flowing stream, f, is

Jan 1, 1958

By Todd S, Lam K, Hewitt A

A series of field experiments investigated the perfonnance of fine mesh curtain screens which were used to suppress coal dust in a transport roadway of a New South Wales colliery. Four types of screens were tested under dry and wet conditions. The screen materials consisted of flyscreen and garden "shadecloth" with single and double membranes of both materials. Personal dust samplers coupled to dust cyclones and filtration cassettes were used to collect the respirable and total components of dusts respectively. The procedure used for locating the samplers upstream and downstream of the screen was based on the roadway air velocity profiles. The number and configuration of the water sprays impinging onto these screens had significant influence on the results. The study showed that wet double layered flyscreen is the most effective of the four configurations tested.

Jan 1, 1991

By Guillermo Mariaca, Jorge Muñoz Reyer

As far as technology is concerned there has been no development in Bolivia during the year 1936, because the country, just emerging from the war with Paraguay, is only beginning to rebuild its economic foundations. Great steps, however, are being taken in order to secure a rapid and sound development of its oil resources, as follows: 1. The new Petroleum Law, which contemplates the problem of proration and conservation of natural resources, prohibiting the wasteful use of gas, and regulating the number of wells, their spacing and the permissible output per well, for each particular pool according to the conditions prevailing therein. 2. The creation of an official entity with the object of developing and exploiting a large petroliferous area. This entity has been called Yacimientos Petroliferos Fiscales Bolivianos (Y.P.F.B.), and the region assigned to it is all the sub-andean zone, which is approximately one hundred miles wide and borders the eastern part of the Oriental Andean range, from Argentine to Peru. It is said that drilling will be started immediately in various localities. At the present time a wide geological survey of part of the area is being made in order to find out which regions offer the best possibilities of commercial development. Y.P.F.B. has been authorized by the Government to draw up contracts with private companies for the exploitation of limited zones. Production The only company that has been producing in the country in 1936 is the Standard Oil Company of Bolivia, and only from two of its fields: Camiri and Sanandita. New wells were not drilled. During the first nine months of the year 12,762,958 liters (80,275 bbl.) was produced, 34,985 bbl. from the Camiri field and 45,290 bbl. from the Sanandita field. Reports for October, November and December are not yet available. The total for the year 1935 was 25,978,737 liters (163,388 bbl.).

Jan 1, 1937

By Bruno Lebon, Koulis Pericleous, Georgi Djambazov, Mayur Patel

"High speed compressible jets are used in a number of steel-making applications. In the case of the BOF, a compressible oxygen jet reacts with a carbon-rich iron bath to reduce carbon levels and produce steel. The intensity of the process is governed by the speed of the jet and by the size and shape of the depression created in the metal and slag by the force of the jet, i.e. by the corresponding free surface. This is a difficult CFD problem, since there are compressible and incompressible regions in the flow domain, which need to be handled differently in a finite-volume (FV) pressure-correction scheme. Also, standard turbulence models do not account for compressibility, or the large difference in density between the cold oxygen jet and the hot reacting surroundings. Corrections are introduced to the k-E model to remedy this deficiency and the results are validated against experimental data. The compressible/incompressible boundary is handled through a transition region, based on Mach number.IntroductionThe deformation of a free surface by a compressible high speed jet is of paramount engineering interest, particularly for understanding the physical processes within a Basic Oxygen Furnace (BOF). In a BOF, a supersonic oxygen jet impinges on a molten iron surface, thereby creating a cavity. Oxygen penetrates the bath and removes carbon, resulting in low carbon steel [1].The challenges in modelling such a process lie in coupling a solution domain with distinct compressible and incompressible regions and in dealing with large density differences between the modelled gas and liquid. The modelling of compressibility within the jet is crucial, since the correct velocity profile in the jet is required to determine the cavity depth with accuracy."

Jan 1, 2012

By Rudineli Demarque

Este artigo apresenta um estudo das características metalúrgicas, geométricas e microestruturais da soldagem TIG autógena aplicada em chapas de um aço AISI 304, o processo autógeno tipo cordão sobre chapa foi utilizado com a finalidade avaliar o comportamento deste aço quando submetido a ciclos térmicos distintos. A soldagem foi automatizada, na posição plana, e realizada com controle de velocidade com a finalidade de regular a energia adicionada ao material soldado. As variáveis de entrada foram a velocidade da tocha de soldagem TIG, e a corrente setada na máquina de solda. Foram avaliados os efeitos da variação da energia de soldagem sobre as características metalúrgicas do processo, sobre as características geométricas (penetração e largura) do cordão se solda, microestrutura, espaçamento dendrítico e microdureza da seção transversal da junta soldada. Os resultados indicaram uma forte influência sobre a geometria da junta soldadas, aumento de 28,5% na largura, 59,6% na profundidade e 44,6% na área, além de alterações microestruturais, aumento de 100% na quantidade de ferrita d, 12% na microdureza e 51,69% no espaçamento das dendritas no metal de solda, Além disso observaram-se ausência de defeitos nos passes isolados sobre as chapas.

Oct 30, 2017

In 1846 a bill was pending in Congress to reduce, or eliminate, the tariff on coal; the debate caused the same writer to visit the mines on the north side of the James River and to write a letter about them to the same paper.' Omitting the political arguments, his account follows: "July 13, 1846. "Early in the morning we rose, washed, combed, and ate a first-rate breakfast, and then went to the Tuckahoe, mined by Messrs. Sneed and Dietrock. Coal was first discovered here sixty years ago, and mined by Colonel Thomas Randolph, the proprietor of the land. They were worked by him for his smith-shops. Since which time they have been worked periodically, up to the war of 1812, when they were abandoned; and recommenced in 1837 under the management of Dr. W. T.- Scott. Subsequently a Company was formed called Tuckahoe Coal Mining Company, which purchased the whole track at a cost of $30,000. They commenced the sinking of a shaft and went as far as 412 feet, and then pitched the fat all into the fire by hauling off altogether in despair. In 1843 Major Sneed went to work at it, and succeeded. I may here remark that Major Sneed has been the pioneer in this business on the North side of the River, and has sunk more shafts than any other man who has pursued this vocation in Eastern Virginia. The difficulties and expense in sinking these shafts are sometimes immense. The coal on the outcrop or surface is not always a guide to where it may be found imbedded many hundred feet under earth and rock. "The Tuckahoe Pits are on the Eastern end of the coal field, within twelve hundred yards of the Canal, and about twelve miles from Richmond. They employ fifty hands and raise some three hundred thousand bushels of coal per year. It is highly bituminous and excellent for the manufacture of iron. The Tredegar and Belle Isle Rolling Mills are supplied with it. It must be good and of the right kind', or they would not use it. These pits are the only. ones on this side troubled-with gas-of course ventillation is necessary. There is not as much water in this Pit as I have found generally in many others, although they have extended their operations to a considerable distance under ground. I have observed in examining the coal mines, that, where they are sunk over four or five hundred feet, they are annoyed by gas, and where there is a less depth they are troubled with water. It is evident, therefore, that water, in the region of these coal fields, does not run through the earth to any extent, even five hundred feet deep, and the farther you go below that the greater the increase of gas. "We next visited William Cottrell's Pits, situated one mile and a half north of this. He employs some thirty hands, and raises from 4 to 500 bushels per day. "T. & R. Crouch's Pits are one hundred yards north of Cottrell's. This firm employ from 80 to 90 hands, and raise from 8 to 900 bushels per day. They are now

Jan 1, 1942

The planning, design and construction of a service tunnel, under a major arterial road between two hospitals are described. The multiple uses of the tunnel combine to provide a favourable cost-benefit ratio for the tunnel as part of a rationalisation of services between hospitals. The driven tunnel provides economic, program and approval advantages over that of a cut and cover construction. The cross sectional shape of the tunnel was determined during feasibility studies by the degree of weathering of the Silurian mud- stones, the shallow cover and the proposed excavation equipment as well as the functional requirements. The site investigations covering geotechnical, building, noise and level surveys provided input to the design documentation and construction phases. Monitoring of settlement levels and primary support stresses during early construction stages confirmed the adequacy of the proposed tunnelling methods and support to be used adjacent to the major building foundations. The 140 metre long tunnel was success- fully completed in April 1980 at a cost of $650,000.

Jan 1, 1981

By Luane Isquierdo Ferreira Holanda, Lucio Fabio Cassiano Nascimento, Luis Henrique Leme Louro, Sérgio Neves Monteiro, Alaelson Vieira Gomes, Édio Pereira Lima Júnior

In the present study,we used natural fibers malva (Urenalobata, Linn) in 0, 15 and 30 vol.% as reinforcement of epoxy matrix composites to ballistic application. Ballistic efficiency of these composites was assessed by measuring the energy absorbed and residual velocity after impact 9 mm FMJ ammunition projectile, aiming to compare with traditional materials, such as: aramid fabric Kevlar™ used in vests for personal protection. The results showed by visual analysis and scanning electron microscopy (SEM) that the main active failure mechanisms in composites were delamination layers and fiber rupture. In test groups can be seen that the absorbed energy and the residual velocity varies with the fiber percentage used. Compared to aramid there is both a gain in weight and cost of the ballistic armor, which makes the fiber malva a promising material applications involving personal protection against 9 mm caliber ammunition.

Mar 1, 2017

By Warner N. A

There is an inherent problem in producing simultaneously lead, zinc and copper as metals in a single polymetallic smelting furnace. It relates to the condensation of lead and zinc from the gas phase under vacuum conditions such that metals in bulk form, either solid or liquid, are obtained as products rather than a fume or dust containing both metallic and non-metallic components. To understand this phenomenon, it has been necessary to establish mathematical models with computer simulation to identify the process requirements for effecting the objective of maximum bulk metal production with minimum fog formation. The theoretical framework of simultaneous heat and mass transfer involved in condensation from gas mixtures containing a non-condensable gas has been extended to the high temperature and reduced pressure conditions. These apply to new technology for polymetallic smelting now being developed in a project currently funded jointly by the Commission of the European Communities and the Mineral Industry Research Organisation. Under the right conditions it is theoretically possible to condense out both lead and zinc with minimal fume formation, but in all practical cases it is anticipated that some circulating load for reversion back to the smelter will be needed.

Jan 1, 1989

By S. S. Huyett

The opportunity to cooperate with the Mining Department of the Pennsylvania State University in their Student-Trainee Program is accepted by The New Jersey Zinc Company who believes that the participation in this type of a program will lead to a larger supply of high calibre engineers in mining. Trainees compete with other employees to earn the cost of their education while gaining practical experience in the mining industry. The practical experience is arranged to complement the technical education through a variety of work assignments. Job opportunities for the trainee are related to the work requirements of the Company and to the performance of the trainee. Management must consider and deal with a good many problems uncommon with regular, full 'time employees. For a number of reasons this program is recommended to other companies as a means to encourage outstanding young men who are interested in a career in the mineral industry to obtain a professiona1 education.

Jan 1, 1963

By Moxon N. T, Berndt J. R

BHP-Utah Coal Limited's Peak Downs Mine is located in Cen- tral Queensland, approximately 200 km south west of Mackay. The annual raw coal production of the mine is over 8 million tpa, requiring the removal of about 40 million cubic metres of prime overburden. This is achieved through the use of five large draglines. The large depths of overburden (up to 55 metres) encountered over half the strike length of the mine enables cast blasting to be carried out in conjunction with draglines employ- ing the chopping method of digging. The objective of cast blast- ing is to use explosive energy to move as much material directly into spoil as possible. The additional costs of drilling and blast- ing are offset by reducing dragline rehandle. Two factors which are of primary importance to the design of cast blasts are initiation control and material velocity. High speed motion picture photography is a powerful diagnostic tool to quantify these aspects of blasting (Winzer, Montenyohl and Ritter, 1979; Chiappetta et al., 1983; Anon., 1983). The objec- tives of such analysis are to: 1. Determine the burden velocity, 2. Determine the time to initial movement (that is, the inter- val between a face hole firing and the initial movement of the burden), 3. Check the accuracy of the initiation sequence. BHP Central Research Laboratories (CRL) and Peak Downs Mine monitored a cast blast in the mine's Winchester Pit on 18 August, 1988. The objectives of this exercise were to: 1. Quantify current cast blast performance, providing a base case for comparison with modified blast design. 2. Compare two orientations of angled holes within the blast. 3. Assess the effectiveness of cast blasting utilising an air-deck. 4. Check blast timing with respect to burden movement times.

Jan 1, 1989

By C Muñoz, N Ortega, J Vergara, D Avilés

Mass blasts have been the subject of extensive studies because of their potential benefits in mining operations. However, it has not been possible to advance due to the paradigm that states that the blasts near the designed final wall or to critical structures have to be low tonnage. Another reason is the absence of specialised simulation programs to more precisely determine the influence of the energy released by blasting to the rock mass. There are some studies that demonstrate the possibility of massive blasting that maintain the design of the final slope (Farias and Santander, 2014). It should be noted that these studies develop the concept that the size of the blast should not increase the peak vibration in the rock mass.The study was carried out in partnership with Los Colorados Mining Company. Analysis, reconciliation and wall control for two types of blasts were performed:blasting production: approximately 850 000 t, with special wall control considerationsblasting of approximately 950 000 t over the entire width of the bench.Monitoring systems were used in the near field and far field using examination of holes in order to obtain information to assess the impact on the rock mass and then to compare these to conventional blasting combining production and contour blasting.The results show that for a large blasted volume, production and/or those generated from toe to crest on the bench did not produce more impact in the rock mass than the conventional blasting.The conclusions drawn from this study are:an improvement in the excavation rate of 7500 t/h that is higher than the maximum rates normally obtainedthe peak vibrations of the P wave generated by both blasts did not exceed the peak particle velocity criteria (Vergara and Muñoz, 2014)holes examination indicating no difference in their entire length, in pre- and post-blast reviewover US$2 000 000 savings generated in the year (estimated by the client) (Avilés, 2014).CITATION:Vergara, J, Muñoz, C, Ortega, N and Avilés, D, 2015. Benefits related to applications of a mass blast in open cut mining, in Proceedings 11th International Symposium on Rock Fragmentation by Blasting, pp 625–632 (The Australasian Institute of Mining and Metallurgy: Melbourne).

Aug 24, 2015

Hello, everyone. Way back in 1965, Devine and others at the US Bureau of Mines showed that a presplit fracture plane did not affect vibration levels transmitted across the plane (RI 6695).

Jan 1, 2010

By Gordon M. Miner

When I was originally invited to speak to this audience on the subject of the future supply of precious metals I was somewhat apprehensive and suggested that the Program Chairman select someone with more credentials. He declined and the results of our conversation gave me cause to reflect and recall the opportunities I have had over the years and how fortunate I have been to be associated with so many successful companies and knowledgeable people affiliated with the precious metals field. I discovered that since 1935, 1 have worked in or visited most of the gold and silver camps in the United States; have been a leaser of a gold mine in Mohave, California; have both lost and made money in the silver futures market; have worked for two of the greatest precious metals companies in the United States - Homestake Mining Company and Hecla Mining Company, have spent a considerable amount of time in precious metal related discussions with men like Don MacLaughlin, Paul Henshaw, Dick Stoehr, Abe Shoemaker, Bill Love, Phil Lindstrom, Simon Strauss, Herbert and Bunker Hunt and many others. It is those exposures and experiences that I draw onto discuss the subject at hand.

Jan 1, 1980

By M Flanagan, T Sua, B Wright, T Carroll, B Van Dijken

"BHP Billiton (BHPB) West Australian Iron Ore (WAIO) conducts an extensive geometallurgy (geomet) program for its iron ore deposits in the Pilbara. The geomet program provides accurate information to infrastructure engineers, resource geologists, mine planning engineers and the technical marketing team on the performance characteristics of iron ores. Performance metrics include production planning, such as lump/fine splits, processing capability such as the level of ultra-fine iron ore and ironmaking blast furnace properties including tumble index (TI) and reduction disintegration index (RDI). Prior to the introduction of the current geomet program in WAIO, basic geometallurgical information was provided at the deposit level, such as deposit lump percentage and head grade chemistry. As the business value of geometallurgy was realised during the growth period of WAIO, the geomet process was reviewed and formalised into five steps: geomet drill planning laboratory measurement data management algorithm development block estimation.The geomet laboratory process produces simulated iron ore products from drill core, which are then subjected to physical geometallurgy test work. With the large amount of geometallurgy data collected, extensive databases are utilised to collate and organise the data to improve its usability within the business. Algorithms are created from the data to predict important geomet variables and a block estimation method is used to estimate geometallurgical properties into resource models. The predicted geometallurgy data is regularly reviewed at the different steps against plant and shipping data to allow refinement of the geometallurgy algorithms. It is also recognised that geomet data can be used to optimise the operations in existing processing hubs for improved production rate. In addition, future geomet programs will focus on generating data from all available drill core programs, not just dedicated geomet drill holes, and will incorporate new types of data, such as hyper-spectral information, for improved geometallurgical estimation.CITATION:Wright, B, Carroll, T, Flanagan, M, Sua, T and Van Dijken, B, 2013. BHP Billiton West Australian iron ore geometallurgy - past, present and future, in Proceedings The Second AusIMM International Geometallurgy Conference (GeoMet) 2013, pp 105-110 (The Australasian Institute of Mining and Metallurgy: Melbourne)."

Sep 29, 2013

By J. Alfred Berger, O. M. Katz

The Zv-Hf-H ternary system was studied between 500° and 900°C at pressures less than 1 atm of hydrogen gas between 1 and 60 at. pct H. A new and unique microgravimentric apparatus was used. Cizanges of slope on pressure-hydrogen composition isothernis delineated phase boundaries. These boundaries separatecl the three regions, a, 0, and y—so designated to correspond to the regions of the Zr-H binary system—from the multiphased areas between them. A eutectoidal decomposition was found with the ß region phase or phases decornposing into a lamellar product on quenching to rool ter,zperatuve. Reproducible decomposition-pressure hysteresis occilrved lnainly at lower hydrogen cornpositions and at lower temperatures across multiplzase vegions between a and 0 and a and y. Tire effects of hqfniur7z on the hydriding charactevistics of zirconiurrz weYe as follows: 1) stabilization of the a and y vegions while destabilizing the 0 region; 2) a/?preciable elevation of the decomposition pressrkres in the multiphase region between the a and /3 field; 3) ~nouenzent of the eutectoid reaction to high te~nperatures; 4) reduction in the total qiiantity of hydrogen absorbed under one atmospheve of Hz p7-essure; and 5) introduction of a split deconzposilion at the eiitectoiclal poinl in pa?? of the ternavy. Assuru~ptions based on an ir-2terstitial vandonl-solulion rtioclel 0.f hydrogen in metals slzowed that the bindit~g energy between solute sites prednnzinatecl at low /i?!dvogen concentrations. However, at high hydrogen contents the entropy was the predorninatlt factor in determining the stability of the Zr-Hf-H al1o.s. This was interpreted to mean a scarcity of filrtlzer itltevslilinl solute sites caused by hydrogen-hydvogen intet-actions in the metal lattice. INTEREST in the reaction of hydrogen with metals has increased in the past few years for the following reasons: 1) the formation or use of high hydrogen potential environments in nuclear reactors; 2) the reaction of hydrogen with alloys in nuclear reactors with the accompanying deleterious effects on the mechanical and corrosion properties; 3) the theoretical implications of thermodynamic data on the theory and rules of alloy formation in the metal-hydrogen systems; 4) the use of hydrogen-containing fuels in rocket engines; 5) the need for a process of making fine metal powders of high-melting reactive metals; and 6) the beneficial impregnation of superconducting alloys with hydrogen. In nuclear pressurized-water reactors, the problem exists of limiting the hydrogen pickup of zirconium alloys which are utilized as fuel cladding, heat shields, and support members. In general, zirconium alloys have good mechanical and corrosion-resistant properties in high-temperature water. However, hydrogen is absorbed from the corrosion reaction between metal and water, greatly accelerating the formation of the corrosion product ZrOz as well as mechanically embrittling the underlying metal. In addition, recent observations1 at zirconium to hafnium welds showed that secondary elements in zirconium can have an appreciable, and somewhat unexpected, effect on hydrogen absorption. This paper lists the thermochemical data in the range 500" to 900°C for the equilibrium reaction of four high-purity Zr-Hf alloys with hydrogen. Phase boundaries and thermodynamic functions are determined while the structural data will be presented in a future paper. In general, the Zr-Hf-H system approximates the well-known, eutectoidal, Zr-H diagram2,3 with modifications introduced through the behavior of hafnium.4,5 The Hf-H system,' published while this work was in progress, provided a consistent trend with the Zr-Hf-H data. PREPARATION OF Zr-Hf ALLOYS Table I presents a complete flow chart of the preparation procedure. The zirconium and hafnium crystal bars were completely immersed in high-purity kerosene and slowly cut into thin wafers. Wafers were then cold-sheared into approximately 1-g pieces, thoroughly cleaned, weighed, and inserted into the furnace. The alloys, B-2, B-4, B-6, and B-8, were then nonconsumable arc-melted under 500 mm of purified argon. Additional purification of the argon was accomplished by melting a large titanium button each time an alloy was re-melted or a different alloy melted. Each alloy button, which weighed 25 g, was remelted four times in an approach to complete homogeneity. Material losses were less than 0.02 wt pct. Alloy buttons were alternately cold-rolled and vacuum-annealed into 10- and 20-mil sheets. Table I1 gives the composition of the four alloys used. Very little elemental segregation existed be-

Jan 1, 1965