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By A. M. Richardson

The significance of a massive sandstone unit in the immediate roof to longwall support weighting is well known. If the unit lies in the main roof above the zone of caving, its influence becomes more difficult to calculate using traditional methods. Much of the reserves at Cyprus Plateau's new, multi-seam Willow Creek Mine are located in the A Seam. The massive Kenilworth Sandstone is typically situated 21.3 m (70 ft) above the A Seam in the main roof and is on average 14.6-m (48-ft) thick, ranging to 29.0-m (95-ft) thick. This paper describes the application of distinct-element modeling to determination of the appropriate yield capacity for supports at Willow Creek. The modeling was determined to be useful for understanding support loading mechanisms and as an aid to engineering judgment in selecting supports.

Jan 1, 1996

By David G. Dixon, Ahmad Ghahremaninezhad, Edouard Asselin

"Atmospheric leaching of chalcopyrite in sulfuric acid solutions is a slow process due to the mineral’s passivation. We have investigated the nature of the passive film in this work. Electrochemical reduction and oxidation of chalcopyrite over the potential range of -0.5 to 1.2 VSHE were investigated in 0.5 M sulfuric acid solution (pH 0.3) at 25 ºC by multicyclic voltammetry and open circuit potential measurement. The influence of scan limits on the evolution of current peaks was studied with both stationary and rotating electrodes. It was observed that the anodic oxidation of chalcopyrite begins at potentials above 0.6 VSHE, most likely by preferential dissolution of iron atoms over copper atoms. The selective electro-dissolution process results in formation of a metal-deficient sulfide passive film (i.e. Cu1- xFe1-yS2, y > x). The passive film dissolves at 0.9 VSHE. Elemental sulfur is one of the products of chalcopyrite dissolution above 1.0 VSHE. Cathodic reactions within the potential region of 0.1 to 0.6 VSHE and anodic reactions at potentials lower that 0.5 VSHE are associated with at least one soluble species from solution. The soluble species involved in the cathodic reactions are likely ferric and cupric, while the soluble species involved in the anodic reactions is likely H2Saq."

Jan 1, 2014

In considering the preparation of any paper concerning bearing metals, one feels a certain amount of diffidence in venturing into a field which has been capably explored at great length and in great detail during recent years. Many excellent articles have appeared in technical literature, dealing with the general theory of bearings and of bearing metals, the properties of white metals of the tin-base and lead-base types, and of the recently developed lead-bronzes.The justification for this further excursion into the field lies in the fact that it treats a branch of the bearing metal family which has so far received very little attention, and that of a somewhat sketchy nature, in published papers.The author's object is to give some outline of the history, development, present status and possibilities of the cadmium-base bearing metal alloys, particularly those in which copper is the main alloying element.GENERAL CONSIDERATIONS.It is desirable that attention should first of all be given to the general theory, constitution, and necessary attributes of bearing metals, in order that some of the problems met with during the development work may be better appreciated.Despite some evidence to the contrary, it is fairly generally maintained that an alloy for bearing metal use should be of a heterogeneous nature. It should consist of particles of a hard constituent uniformly distributed through a softer matrix.The basic idea is that the hard constituent should actually bear the load and resist wear, while the matrix imparts the necessary ductility and allows the bearing to align itself on the shaft in service.

Jan 1, 1934

By T. Holmes

Investigations reveal that the throughput difference between a perfect production day and the average is often on the order of 40%, and that bulk solids handling system deficiencies are the largest (>50%) class of lost opportunities. Root causes for underperformance of elements in material handling systems can often be traced back to the detailed design and even study-stage oversights. To reduce or eliminate bulk solids handling problems in an existing system requires an analysis of troublesome handling equipment – for example, a concentrate transfer chute that experiences plugging, poor flow to the furnace, unacceptable dust generation, and spillage. These problems often lead to significant maintenance costs related to downtime and personnel time. Understanding the cause and cost of flow issues is the first step in troubleshooting the problem. Next, measuring the material’s flow properties is critical to providing design data required to develop a comprehensive scientific solution. In the case of a new installation, the design data is required to properly design the system right first time and prevent flow problems from occurring so that the new equipment works correctly from start-up. This paper highlights the cost of material handling problems and discusses the best approach to evaluate material handling system deficiencies. A case study is given of how Anglo American's operation in Barro Alto Brazil enjoyed a 5-month payback from a bulk solid transfer chute debottleneck project. INTRODUCTION When operating a plant or designing a greenfield or brownfield operation, the intent is to have perfect production days (PPD) each and every day. Money is made by moving material through the plant in a controlled manner to produce the desired product. Mining operations and copper concentration processes are at the most basic level a practice in bulk solids handling (BSH). Unfortunately, many of the project planning steps are overlooked, particularly related to BSH. Investigations reveal that the throughput difference between a PPD and the actual average is often on the order of 40%, and that BSH system deficiencies are the largest (>50%) class of lost opportunities (Wellwood, 2017). Root causes for underperformance of elements in material handling systems can often be traced back to the detailed design and even study-stage oversights. BSH issues are essentially baked into the fabricated plant and left to operations to accept the deficiencies and deal with them for the life of the mine. These deficiencies then become part of the normal operation of the mine and plant.

Jan 1, 2019

By Larry DeGraff

With the increase of new mine development in the past several years, many coal mines have decided to self- perform the design and construction for their slope development projects. The development process of determining the proper configuration is challenging, and a major economical consideration. Greenbrier Smokeless Minerals engineering staff and consultants, along with DSI/American Commercial, developed a support configuration that was best suited for their slope. The developmental process took into consideration the length of slope, depth of slope at the high-wall transition, economics of a single or multiple entries, waterproofing, stresses on the steel supports and lagging during the backfilling operation. This paper describes the developmental concept of using a single entry, side by side configuration, using steel ?Banjo String? supports with steel plank lagging, to develop a long term permanent installation in a cut and cover application.

Jan 1, 2009

he Wyalong goldfields were discovered in September, 1893, Messrs. Neeld and Sons, owners of the principal mine, being the pioneer prospectors. During the earliest days of the field the ore was sent to Barmedman, a distance of eighteen miles, for treatment at a battery there. The field rapidly increased in importance, and it was not long before a public battery was established on the spot. After some considerable quantity of ore was treated by this process, it became apparent that battery treatment was quite unsuitable for the richer ores, involving, as it did, considerable loss in the tailings. Recognition of this fact led to the erection, in 1895, of plants by the Wyalong Chlorination and Cyanide Works, owned by Mr. Walter Sully, for treatment by their processes; followed, at a later date, by Messrs. Neeld and Sons Chlorination Works. The Wyalong Chlorination and Cyanide Works, after a delay of twelve months in the erection of their plants, have since catered continuously up to the present time for the requirements of the field.Their plant consists of a No. 3 Gates' rock·breaker, a revolving dryer, a No. 5 Krupp mill, revolving roasting furnace with finishing hearth, two chlorination vats of 20 tons capacity each, "nine cyanide vats of 30 to 100 tons capacity, two Wheeler pans and three chlorine generators. The ores are purchased outright on assay at a fixed scale of charges, and treated by the owner of the works on his own account.

Jan 1, 1903

By Gabsoo Kim, Rulin Yang, Dave Kay

Blast vibration data, such as PPV are usually scattered. In many cases, plots of PPV versus the charge weight scaled distance are so scattered that useful trends from different blast designs cannot be identified. The scattering of the data may be attributed to the inaccuracy of the PPV measurement, the definition of the scaled distance from a multiple-hole production blast, and the measurement of distances and charge weights. The error from vibration measurements is one of the major contributors to the scattering of the plots. If accurate monitoring is conducted, improved design options may be identified. This paper documents two case examples that compare different vibration sensor couplings. The first case shows mounting accelerometers at spots that protrude from the ground, compared with the sensors that were mounted on a flat ground surface. The second case compares data from loose-sand buried geophone with that from sensors coupled to the ground using concrete blocks.

Jan 1, 2014

Radioisotope x-ray methods for the on-stream determination of copper, lead, and zinc in mineral product slurries were developed, and were successfully tested at the plant of Cobar Mines Pty. Ltd.The tests were made in three stages. Measurements to determine the precision of analysis were made initially on briquettes of the mineral products. The effect of slurry solids content variations was then determined by measurements on the mineral products in a recirculating slurry loop. The radioisotope analyser was finally tested in a series of on-stream measurements in the plant.Copper, lead, and zinc in flotation feed and in copper concentrate were determined to a precision ranging between 1·4 and 15 per cent of the mean element concentration in the slurry solids. These precisions are within limits required for plant control purposes at Cobar.

Jan 1, 1971

By Bernard S. Borie

THE U-A1 binary system has been studied by Kaufmann and Gordon.' They have shown that three intermetallic compounds occur in the system: UAl², UAl², and a third compound tentatively identified as UA15. UA1³ is simple cubic, a, = 4.26A. Its unit cell contains one formula weight, and it is iso-morphous with AuCu³. UA1² is face-centered cubic, a, = 7.72A, with eight formula weights per unit cell. Rundle and Wilson have shown that it is iso-morphous with Cu²Mg.² A Debye-Scherrer pattern of the Al-rich compound indicated a more complex structure than either UA1² or UA1³. The following is a report of an investigation of the crystal structure of this compound and a determination of its stoi-chiometric formula. A melt of uranium (99.9 pct pure) and aluminum (99.9 pct pure) was prepared which contained about 25 pct U by weight. It was cooled from 950" to 650°C at a rate of 500" per hr and then taken from the furnace and air cooled. An X-ray diffraction pattern of the ingot showed only lines of aluminum and the Al-rich compound. Filings from the ingot were reacted with a solution of sodium hydroxide, producing a fine black powder, the diffraction pattern of which showed no traces of aluminum. A comparison of the Debye-Scherrer pattern of our sample with the data published by Kaufmann and Gordon1 showed that it is identical with the Al-rich phase which they reported. Single crystals were obtained by cooling the melt more slowly (about 50°C per hr). After reaction with sodium hydroxide, the crystals appeared as small black needles attached to the ingot surface. Cell Size, Space Group, and Uranium Positions A series of Weissenberg photographs for rotation about two of the crystallographic axes, taken with copper radiation filtered through nickel foil, revealed an orthorhombic cell of dimensions: a = 4.41 ± 0.02A b = 6.27 ± 0.02A c = 13.71 ± 0.03A Reflections of the type hkl were observed only if: h + k + I = 2n, of the type hkO only if: h = 2n and k = 2n, of the type h01 only if: h + 1 = 2n, and of the type Okl only if: k + 1=2n. Hence, the cell is body-centered with an 001 glide plane. The evidence for the existence of the glide plane is the observed extinction of 23 possible re- flections of the type hkO with at least one index odd. There are only two space groups consistent with these data: C"" — I2ma and D28 2h — Imma.³ he possible sets of atomic positions for these space groups are: 12ma: (0 0 0; ½ ½ ½) + 4: (a) x 0 %; x % % (b) x ¼ z; x ¾ Z 8: (c) x y z; x y z; x, ½ + y, Z x, M - y, z Imma: (0 0 0; ½ ½ ½) + 4: (a) 0 0 0; 0 ½ 0 (b) 0 0 ½; 0 ½ ½ (c) ¼ ¼ ¼; ¾ ¼ ¼ (d) ¼ ¾ ¾ ; ¾ ¾ % (e) 0 ¾ Z; 0 ¾ z 8: (f) x 0 0; x 0 0; x 1/2 0; x ½ 0 (g) ¼ Y ¼; ¾ Y ¾; ¾ y ¼; 1 y ¼ (h) 0 y z; 0; ;; 0, ½ + y, z; 0, l/2 - Y, Z (i) x 1/4 z; x ¾ z; ¼ z; x ¾ z 16: (j) xy z; x y z; x y z; x y z; x, ½ + y, Z; x,½ - y, z; x, ½ - y, z; 11 1, + y,Z Though density measurements on different samples were found to vary somewhat, they were all within the range 5.7 * 0.3 g per cu cm. If it is assumed that the unit cell contains four formula weights of UAl,, it is 6.5 g per cu cm. If there were as many as eight uranium atoms per unit cell, the

Jan 1, 1952

The market for titanium feedstocks (ilmenite, rutile,synthetic rutile and slag) is driven primarily by offtake from the titanium dioxide (TiO2) pigment industry. The pigment sector depends on the performance of the global economy. Titanium sponge is the first stage of titanium metal manufacture. It constitutes a minor component (3 percent) of overall demand for titanium feed-stocks. Production and consumption TiO2 pigment consumption in 2004 was estimated to be 4.63 Mt (5.1 million st), up 7.6 percent from 2003. It was driven by strong demand in most regions. In the United States, apparent TiO2 pigment consumption rebounded by 5.4 percent (highest growth rate since 1997) to an estimated 1.12 Mt (1.23 million st), following the decrease in demand during 2003. Chinese TiO2 pigment consumption continued its strong upward trend, increasing by 10 percent to 598 kt (659,000 st) in 2004.

Jan 1, 2005

By Steve Kral

Reducing the cost per ton and increasing productivity are key factors in a mine’s profitability. Mining companies can do little about commodity prices. So to keep a mine operating at a profit, management must reduce costs and improve worker and equipment productivity in every facet of a mining operation. From mining to crushing to processing, mine management is constantly seeking new methods and technologies to improve the way it mines minerals. And it is willing to borrow techniques used by other operators.

Jan 1, 2002

By Wencheng Gao

An attractive way to beneficiate magnesium chloride and aluminum chloride is to prepare Mg-Al spinel, an excellent refractory material. Mg4Al2(OH)14?3H2O, the precursor of spinel, can be prepared using a co-precipitate method from aqueous MgCl2-AlCl3 solutions. The co-precipitation process of magnesium-aluminum from acidified chloride solutions by using NaOH or NH4OH as base neutralization agent was studied. Co-precipitation was conducted from different mixed solutions ? at initial CAl=0.0625M and Mg/Al molar ratio from 0.5 to 10, the temperature range from 30 to 90 °C. The effect of other parameters, including base type, method of base addition, base addition rate, aging time, background electrolyte and concentration were also investigated. The co-precipitation process was monitored by potentionmetric(pH) measurements. The experimental pH curves were characterized by two platforms separated by a steep jump in pH at Mg/Al molar ratio 0.5~6. The first platform was centered at about a pH of 3.8 and the pH of second platform was varied with different conditions. When the Mg/Al molar ratio was up to 6~10, the first platform in pH was almost disappeared. Furthermore, the shapes of pH curves were also affected by base type, base addition rate and method of base addition. Experimental results showed that the first platform in pH was connected with Al precipitation, and the second platform was involved with Mg. The final co-precipitates were characterized by XRD, TGA-DTA, particle size analysis, SEM and TEM. We found both Mg/Al molar ratio and temperature proved to be the key parameters controlling the formation of Mg4Al2(OH)14?3H2O phase. At solution Mg/Al ratio=0.5~4, the main precipitate phase was Bayerite (Al(OH)3) admixed with Mg4Al2(OH)14?3H2O; at Mg/Al ratio=4~6, the main phase was Mg4Al2(OH)14?3H2O admixed with some Mg(OH)2; while from Mg/Al ratio=6~10, the systems were mixtures of Mg(OH)2 and Mg4Al2(OH)14?3H2O.

Oct 1, 2011

By J Parr, P Ashworth, S Johns, C Yeats, A Littleboy

The ocean floor is increasingly being discussed in terms of its resource potential. New discoveries, improved knowledge and access to unexplored areas of the deep sea and continental shelf are some factors contributing to a renewed interest in the seafloor exploration and mining industry. The industry has been referred to as the ænext minerals frontierÆ. To date, much of the research has focused on proving economic and technical viability of the industry, with environmental issues addressed locally. However, there is limited research internationally, and none known in Australia that considers the social viability of the industry, addressing issues such as regulatory contexts, international precedence and public acceptability. Does the nascent seafloor exploration and mining industry have a social license to operate? Does it have support amongst the wider community? If not, why not? The Wealth from Oceans National Research Flagship explored these questions by scoping the social issues that would surround an expansion. Two desktop studies provide insight into the current level of activity in seafloor exploration and mining, recent developments and the regulatory regimes on which the industry is based. One study focused on the situation in Australia, while the other was internationally focused. A series of workshops were held with key stakeholders from government agencies, industry and other interested parties, such as environmental groups and the fisheries industry. These workshops identified and explored the different stakeholdersÆ perceptions of the benefits, concerns, opportunities and key questions associated with an expansion of the seafloor mining industry. The desktop studies revealed that Australia is one of only a few countries with legislation specific to seafloor exploration and mining. Nevertheless, barriers to licence approval exist because of lack of precedent in applying this legislation. Consequently, the decision process can be vulnerable to political issues and subjective judgements. The outcomes from the stakeholder workshops suggest this inconsistency may be influenced by the high levels of concern and uncertainty over environmental impacts. Uncertainty over environmental impacts can influence the acceptability of an environmental impact assessment (EIA) and also mean the perception of risk is variable. Overall, this research suggests that the future of the seafloor exploration and mining industry will be highly dependent on AustraliaÆs ability to:improve the knowledge-base underpinning the regulatory regime,generate open and transparent communications between stakeholders, andimprove the understanding of policy and regulatory processes.

Jan 1, 2008

By Tassos Grammatikopoulos, Gary Pearse, Massoud Aghamirian, Charlotte Forstner, Stephen Mackie

"SGS Minerals Services (Lakefield, Ontario site) has conducted a number of developmental and pilot programs that examined methods for the beneficiation, extraction and recovery of lithium from a variety of spodumene containing hard rock sources. An overview of the beneficiation programs is presented separately by Aghamirian, Mohns, Grammatikopoulos, Imeson & Pearse (2011). The focus of this discussion will be the hydrometallurgical steps involved in producing a high grade lithium carbonate (Li2CO3) sample from the spodumene concentrate. SGS has applied the standard Li2CO3 hydrometallurgical flow sheet to a number of spodumene concentrates and has determined that all of these samples respond in a similar manner to the process and produce a final product having a Li2CO3 grade of >99.5%. The standard process is sufficiently robust to accommodate the observed variability in the concentrates that have been tested. Advantage of one spodumene deposit over another will thus be gained through process optimization and innovation. Optimization at the beneficiation stage and at the hydrometallurgical stage must be considered. Some aspects of the process optimization of the hydrometallurgical flow sheet will be presented.INTRODUCTION The current activity in the exploration, development, and mining of lithium based minerals is due in large part to the key role that this metal plays in the rechargeable battery industry (U.S. Geological Survey, 2011). Lithium battery technologies are widely applied in a range of portable electronic consumer products. The expanding development and production of hybrid and fully electric vehicles has contributed to the increased interest in finding and developing new lithium sources in order to meet the expected demand from the lithium battery industry. Lithium may be sourced from continental brines (sub-surface salars), hard rock minerals (pegmatite, spodumene), hectorite clay deposits, geothermal brines and oilfield brines. Currently the majority of the lithium products are produced from Li brines. The four major lithium producing countries are Chile, Australia, China, and Argentina (U.S. Geological Survey, 2009; Roskill, 2009). These countries accounted for 97.6% of the total lithium produced in 2010."

Jan 1, 2012

Variations in delay timing can have a marked influence on blasting effectiveness and, hence, on total production costs. In single-row bench blasts, delay firing is invariably more effective than simultaneous initiation. In single-row delayed blasts, there is an optimum inter-hole delay above and below which inferior blasting results are obtained. This optimum delay is equal to the time required for each charge to just effectively detach its quota of the burden. The inter-hole delay should seldom be less than 4 ms.m-l of burden.In multi-row blasts in which holes in a given effective row are fired on the same delay, the entire burden on any effective row should be detached from the rock mass just before charges in the next effeotive row detonate. Delays shorter than this give inferior blasting results and an increased likelihood of environmental and slope stability problems. If the inter-row delay is too long, cut-offs can occur, especially where the delay unit is located outside the blasthole. For a surface delay system, the optimum inter-row delay usually varies between 4 ms.m-l and 8 ms.m-l of effective burden. The number of rows that can be fired effectively with surface delay systems (in a single blast) is limited by the threat of cut-offs. Greater interrow delays and a larger number of rows per blast can be fired to advantage with down-the-hole delay systems.There are practical limits to the timing accuracy of all available delay systems. The existence of delay time variability should be recognized and duly considered in the design of blasts.The relationship between delay timing and blasting vibrations is not discussed.

Jan 1, 1977

By Firth B. A

The flotation of fine coal (minus 0.5 mm) often requires the addition of an insoluble hydrocarbon collector to apparently promote the adhesion of coal particles to air bubbles. A series of experiments was conducted using a radiotracer and narrow size fractions of clean coal to determine the effect of particle size distribution, collector addition rate, desliming of feed and emuIisification of collector on the distribution of collector between the different size fractions. The concentration of collector per gram of each size fraction was found to be approximately proportional to (average particle size)-2 except if the collector was emulsified prior to addition, the dependence altered to approximately (average particle size)-1. Mechanistic consequences are discussed.

Jan 1, 1982

By Milson de Andrade Júnior

A Central Termoelétrica número 2 (CTE#2) possui três caldeiras de alta pressão que utilizam principalmente os combustíveis residuais dos processos siderúrgicos, com destaque para o gás de alto-forno (GAF), o qual está disponível em grande volume e com baixo custo. Como o GAF possui baixo valor calorífico, ele é enriquecido em duas misturadoras com gás de aciaria (GLD) e na ausência ou limitação deste, com gás natural (GN). A partir de 2014, devido a problemas com o gasômetro de GLD, passou-se a utilizar o GN com frequência para fazer o enriquecimento do GAF, o que gerava significativo impacto no custo do vapor devido o alto custo do GN. O sistema de injeção de GN nas misturadoras era controlado de forma manual e praticamente não acompanhava as variações no poder calorífico (PCI) do GAF. Percebeu-se que seria possível implementar um sistema de controle para as injeções que levasse em consideração o PCI do GAF, reduzindo o consumo de GN quando o PCI estivesse mais alto e aumentando o consumo quando o PCI estivesse mais baixo. Após a implementação deste sistema houve uma significativa redução no consumo médio de gás natural para enriquecimento do gás de alto-forno na CTE#2.

Aug 17, 2017

By Tony Mazzo

It has often been said by consulting engineers that foundation contractors are in the business of taking risks. One would agree that the mere fact a foundation project can be budgeted, planned, engineered and executed solely on the reliability of eight test borings made at a proposed site having an area of approximately 19,000 square feet, is a risky proposition, in and of itself. Now imagine that this site is actually one half of a city block located in an urban setting in an old, congested, historical neighborhood, surrounded by narrow city streets and historic landmark buildings. And suppose that the required depth of excavation for the construction of the new building on this site is approximately 35 feet and the natural groundwater table is at a depth below existing grade of only 25 feet. Given the difficult site conditions outlined above, one could certainly add the words "challenging" and "complicated" to the inherent word "risky" when describing the construction techniques involved to undertake a foundation project of this magnitude. This case study will discuss in detail how the excavation, sheeting, dewatering and underpinning work was accomplished as well as the problems overcome along the way.

Jan 1, 2003

By Paul G. Marinos, Vassilis Marinos, Evert Hoek

The Geological Strength Index (GSI) is a system of rock mass characterization that has been developed in engineering rock mechanics to meet the need for reliable input data related to rock mass properties required as input for numerical analysis or closed-form solutions for designing tunnels, slopes, or foundations in rocks. The geological character of the rock material, together with the visual assessment of the mass it forms, is used as a direct input for the selection of parameters for predicting rock mass strength and deformability. This approach enables a rock mass to be considered as a mechanical continuum without losing the influence that geology has on its mechanical properties. It also provides a field method for characterizing difficult-to-describe rock masses. Recommendations on the use of GSI are given and, in addition, cases where the GSI is not applicable are discussed.

Jan 5, 2007

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