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By P. Tim Johnson

Relentless increases in demand for nickel and vanadium for uses such as steelmaking, catalysts and battery materials, plus the growing financial and environmental costs of their primary extraction, have led to much interest in potential secondary sources of these metals. The presence of such metals in heavy fuel oils, bitumen and related materials offers both opportunities and challenges for potential extraction methods, especially with the growing production and importance of metal-rich fossil fuels around the world. For several decades, Tetronics’ DC plasma smelting technology has been used for the recovery of metals such as nickel and chromium from stainless steel melt dusts and other wastes in compact, environmentally-friendly and efficient plants. This paper explores the suitability of DC plasma smelting as part of a wider flowsheet with feed preparation and aluminothermic reduction techniques for smaller-scale extraction operations based on this important niche secondary source of these key metals.

By Stephen Chryssoulis, Stamen Dimov

Detection and quantification of precious metals (Au, Pd, Pt, and Rh) in spinels and silicate minerals is important for establishing the maximum attainable recovery by sulphide flotation. To achieve this goal subpart per billion (ppb) detection limits are required plus the ability to quantify results. Existing quantitative microbeam techniques (EPMA, PIXE, SIMS, TOFLIMS) have limits of detection in the O. l-200ppm range. Time-of-flight resonance ionization mass spectrometry (TOF-RIMS) is a microbeam analytical technique that allows for the identification and quantification of atomic species in very small quantities. It utilizes a tunable laser source for resonant excitation and ionization of a particular element of interest and has some unique features: elemental selectivity, linear response over a large dynamic range and very high sensitivity. The analysis consist of three steps: (i) the solid sample is vaporized by laser ablation to form a plume containing neutral atoms, (ii) the neutral atoms of a specific atomic element in the plume are resonantly excited and ionized by another tunable laser, and finally (iii) the ions created are mass analyzed in a time-of-flight mass spectrometer. A TOF-RIMS mass spectrometer was developed at AMTEL for trace element analysis of Au, Pd, and Rh in minerals. The spectrometer was calibrated using homogeneous CANMET and NIST reference samples covering three orders of magnitude in concentration. Attained minimum detection limits (MDL=2cr of the background) are in the low ppb range.

Jan 1, 1999

By Brajendra Mishra

Molten Salt electrolytic processes offer unique opportunities to extract and refine metals where gaseous or metallothermic reduction, hydro metallurgical extraction and aqueous electrolytic methods are thermodynamically constrained. Production of aluminum and magnesium by molten salt electrolysis are well known commercial processes. Several other reactive metals, such as lanthanides and actinides, as well as beryllium and calcium, make use of molten salt processing for extraction and refining. This presentation describes the science of molten salt chemistry and electrochemistry for winning and refining of several metals. In addition, recovery of metals from waste process salts by molten salt reduction as well as oxidation have been discussed. Material issues in design of molten salt reactors have been included. Various applications have been presented through case studies. Experimental data have been included to justify the suitability as well as limitations of these specific processes.

Jan 1, 2003

By Hojat Naderi

In this research assisted leaching of chalcopyrite using sodium peroxodisulfate was studied. Electrochemical techniques such as Tafel analysis and electrochemical impedance spectroscopy (EIS) were used to investigate the surface reactions of a chalcopyrite electrode in the presence and absence of Na2S2O8. According to the results, addition of sodium peroxodisulfate increases the current exchange of the corrosion process and prevents the formation of a passive layer on the surface of the electrode. EIS tests show the trans-passive dissolution of the passive layer on the chalcopyrite electrode in presence of Na2S2O8. Equivalent electrochemical circuits were modeled for Na2S2O8-free and -containing solutions and the model parameters were compared to determine the effect of S2O8 2− on chalcopyrite dissolution. Copper dissolution from pure chalcopyrite mineral and chalcopyrite concentrate was carried out using 15 g/L sulfuric acid solution with and without Na2S2O8. Simultaneous presence of 10 g/L ferric ion and 40 g/L peroxodisulfate salt results in about 40 and 18% of Cu extraction from chalcopyrite concentrate and pure chalcopyrite mineral, after 96 h, respectively.

By John J. J. Chen, Barry J. Welch

"As in many industrial processes, the detailed mechanisms involved must first be understood before being able to redesign, or to carry out improvements or optimisation of the process and equipment performance. In a great majority of metallurgical processes, visual observation and actual measurement of process variables are either very difficult or near impossible. Often, the cost and effort involved are prohibitive. Consequently, physical modelling is often used to provide some understanding of the process and for the validation of computer numerical models. In this paper, we summarise some of the work carried out at The University of Auckland on the modelling of the Hall-Héroult electrolytic cell, the in-line melt treatment process, and the steel casting tundish. IntroductionIn any industrial process, it is essential to understand the underlying mechanisms before any optimization or process improvement can be carried out. In many metallurgical operations, the processes are conducted at elevated temperature and under rather hostile environments. Consequently, it is often difficult, and sometimes impossible, to observe the actual processes occurring, or conduct measurements which are pertinent. In some situations, it is possible to formulate mathematical equations purported to describe the process, and obtain the solutions numerically. However, in this latter case, the validity of the simplifying assumptions made are often uncertain. Physical modelling may provide the necessary information for the validation of such numerical models. Furthermore, through an application of the principle of similitude, it is possible to apply data obtained from physical modelling to actual metallurgical processes. This paper will summarise some the work carried out at The University of Auckland on the physical modelling of gas-induced flow in the Hall-Héroult electrolytic cell, an in-line melt treatment unit, and the flow in a steel casting tundish.Gas-Induced Flows in a Hall-Héroult CellIn an aluminium cell, the effects due to electro-magnetic forces have been addressed and various design modifications such as magnetic shielding and the positioning of risers have been carried out to control or lninimise the effects of magnetic fields'. Consequently, the effects of gas-induced flows are now becoming significant providing the impetus for the study of the gas behaviour in the bath. Furthermore, the shape and size, and the rate of evacuation of the anodically generated gases affect the cell voltage affecting the energy efficiency; at the same time, the back-reaction between the anode gas and the metal produced is the predominant cause of the loss of current efficiency. Figure 1 shows a cross-section of a conventional cell in which the gas evolution occurs directly under the anodes, and the gas induced flow is confined mainly to the region occupied by the bath"

Jan 1, 1994

By Kimio Itagaki

The distribution ratios of Ag, Pb, As, Sb and Bi for the Cu2S-FeS or Ni3S2-FeS matte / FeOx SiO2, FeOx-SiO2-CaO or FeOx-CaO slag equilibration in a MgO crucible were determined experimentally at 1523~1573K under controlled partial pressures of S2 and O2 at given PSO2 of 10.1, 50.7 and 101.3 kPa (0.1, 0.5 and 1 atm) and be observed dependency of distribution ratio on the matte grade, SO2 pressure and slag basicity were analyzed on the basis of thermodynamics,

Jan 1, 2003

By Chuanfu Zhang, Liwei Liang, Yanxin Wu, Jinliang Wang

"According to the reaction shaft operation characteristics during the flash smelting process, 15 groups of slag samples containing high Fe3O4 were prepared by some chemical reagents, and then the slag viscosities were measured using a RTW-10 type synthetic test instrument for melt physical property by the rotating cylinder method. The effects of Fe/SiO2 ratio (mFe/mSiO2), Fe3O4 content (wFe3O4), Cu2o), MgO content (WMgO) and Cao content (wCaO) on the slag viscosity were also studied. Results show that slag viscosity is decreased with the increase of temperature, mFe/mSiO2, wCu2o, wMgO and wCao, and with the decrease of wFe3O4, under the range of slag contents: mFe/mSiO2 1.36~1.78, wFe3O4 17.83%~21.18%, wCu2o 3.51%~8.34%m wNgI 2.21%~6.57%m w/caI 6.22%~9.387% and temperature range if 1250 o/c~1450 oC. Only wFe3O4m and w/caO have great influence on the slag viscosity when temperatures as high as 1400 oC. Only wFe3O4 and wCaO have great influence on the slag viscosity when temperatures as high as 1400 oC or so. To form a freeze slag with higher viscosity inside the reaction shaft, wFe3O4 should be more than 20% and wCaO should be less then 6%.IntroductionSince its appearance in 1949, Outokumpu flash smelting technology has making continuous innovation and has become the most competitive intensified smelting technology [1], widely considered to be the standard clean smelting process [2]. At present, flash smelting technology is adopted to newly build or reconstruct most of the world's copper or nickel smelting enterprise [3]. Reaction shaft is the most important part of the flash smelting furnace. During the flash smelting process, reaction shaft must be able to withstand the following harsh conditions at the same time: 1) high temperature varying from 1400 °C to 1500 °C. 2) strong oxidative atmosphere containing 50% - 80% oxygen. 3) solid particles and melt with speed up to l00 m/s. 4) high acidic or basic slag with strong chemical corrosiveness. 5) smelting gas containing 50% - 80% SO2. 6) matte with strong dissolution."

Jan 1, 2012

By J. A. Innes

"""The oxygen, next uniting with the carbon, sent up an ever-increasing stream of sparks and a voluminous white flame. Then followed a succession of mild explosions, throwing molten slags and splashes of metal high up into the air, the apparatus becoming a veritable volcano in a state of active eruption.""IntroductionHenry Bessemer F.R.S(An autobiography, 1905)Thank you Mr Chairman for the opportunity to speak: at this, the opening session of your International Symposium on the subject of ""Injection in Pyrometallurgy"". Judging from the list of papers to be presented over the next three days, the Symposium promises to provide a most valuable addition to our existing knowledge base in what is now an extremely active area of R&D investigations. Whilst we have obviously come a long way since Sir Henry Bessemer's pioneering experiments of the mid-19th century, there is still much for us to learn.Most importantly, the Symposium offers a further opportunity to acknowledge the many significant technical contributions made in this field by the Organising Committee's special guest, Professor Howard Worner - one of this country's most respected research leaders.When first approached to give this talk I had two areas of concern. Firstly, I was not entirely clear just what injection metallurgy was meant to cover. How should the overall scope of this particular subject be defined?My second concern related to Howard Worner himself - a man for whom I have the highest personal regard and who, in fact, played a most influential role in respect of shaping my own career. Having already spoken about Howard's achievements on earlier occasions, I wondered what I could sensibly add.Notwithstanding these personal reservations, I am delighted to be here with you this morning. If my thoughts on the meaning and scope of injection metallurgy appear to be slightly off-course, and if Howard should perhaps recognise some repetition in my remarks, then I hope I can be forgiven."

Jan 1, 1996

By Xin Li, Hai-Xing Fang, Bing Xie, Hong-Yi Li

Chromium-containing vanadium slag (V-Cr slag) was obtained by an industrial smelting process of Hongge Ore, which is valuable vanadium-titanium magnetite to extract V and Cr in China. Sodium roasting thermodynamics of V-Cr slag in presence of oxygen were calculated to evaluate the reactivity of chemical compounds. Results showed that the oxidation of FeV2O4 was intensified in presence of Na2CO3 while the oxidation tendency of FeCr2O4 was far lower than that of FeV2O4. It was probably that reactions of impurities including Al2O3, SiO2 and Fe2O3 with Na2CO3 happened and the products can promote the oxidation of vanadium or chromium compounds in lower valence. Based on thermodynamic analysis, a two-step selective extraction process of vanadium and chromium was proposed. Extraction rate of vanadium was 88.6% while 7.0% for chromium in the first extraction step; extraction rate of 90.7% and 95.4% for vanadium and chromium, respectively, were obtained in the second step.

Jan 1, 2014

By José D. T. Capocchi

Viscosity of liquid lead, tin, and Pb-Sn alloys has been measured by the rotational viscometer method in the temperature range from 50 K above their respective liquidus temperature to 823 K. The results are accurate to within ±1.0 %. The variation of viscosity with temperature followed the Arrhenius-type equation µ = µo.exp(Q/RT). The composition dependence of the isothermal viscosity and the activation energy for viscous flow have not shown anomalous changes at the eutectic composition of the Pb-Sn system.

Jan 1, 2000

By B. C. Jena

Activities of carbon, cobalt and nickel were evaluated in the ternary systems iron-carbon-cobalt and iron-carbon-nickel for the temperature range 1300-1600°C for cobalt and 1300-1700°C for nickel. The carbon activities were determined from the knowledge of activities (1) in the binary system iron-carbon, (2) in the dilute ternary systems and (3) from the knowledge of carbon saturation data. The activities were mathematically expressed with the Taylor series expansion of Wagner's interaction parameter formalism modified to suit concentrated solutions. The cobalt and nickel activities were determined from the knowledge of carbon activities by applying the Gibbs-Schuhmann integration and from cobalt and nickel activities in the binary systems iron-cobalt and iron-nickel. Partial molar enthalpies of mixing were determined based on the temperature behaviour of the activity coefficients.

Jan 1, 1992

By L. M. Abrantes, A. P. Paiva

"A brief review of some innovative methods for the direct recovery of metals from loaded organic phases is presented; emphasis is given to electroreductive stripping and cementation, which are described and illustrated by examples: of current research. The recovery of silver using a two-phase electrolysis - by direct application of an electrical potential to a mixture of a metal loaded organic phase· containing Cyanex 471X, obtained by solvent extraction, and a stabilized sodium thiosulfate solution - is more extensively discussed. The overall efficiencies are analyzed and compared with data obtained by conventional stripping procedures. Some preliminary results achieved for the recovery of the precious metal using galvanic stripping, applied directly to similar organic solutions and involving zinc and iron powders as reducing agents, are also evaluated.Introductory ReviewThe application of hydrometallurgical methods to the recovery of metal values from ores and concentrates has been receiving a growing interest, either from researchers or from the mining industry [1].For the concentration / purification of the relatively low concentrated metallic solutions resulting from the leaching of those raw materials, solvent extraction (SX) is a well established technique [2]; the loaded organic solvent is then conventionally contacted with a suitable aqueous solution, the metal in its final form being usually recovered from this solution by electrowinning.As an efficient and / or selective stripping is sometimes difficult to achieve, depending on the specific characteristics of the system under consideration, some alternative procedures have been analyzed in order to overcome this problem. One of the chosen routes, mainly developed by Hirai and Komasawa, is to promote the reduction of the desired metal species in the organic phase, in such a way that the stripping stage becomes feasible; for the selective stripping of vanadium from a solvent containing a mixture of vanadium and molybdenum, the authors successfully used reductive [3], electro-reductive [4,5] and photo-reductive [6] techniques. The two latter methodologies have also been applied to the recovery of europium from a solvent containing europium, samarium and gadolinium [7,8].However, further processing is necessary to recover the metal in its solid state; therefore, methods causing the direct reduction of the metal species in the organic phase to their fmal metallic form would be of interest, as an intermediate step would be avoided"

Jan 1, 1997

By N. Kanari

Kinetics of the carbochlorination of Cr2O3 has been studied with C12+CO gas mixtures between 500 °C to 900 °C using thermogravimetric analysis. The apparent activation energy is about 100 kJ/mol. Mathematical fitting of the experimental data suggests that the shrinking sphere model is the most adequate to describe the carbochlorination mechanism of chromium oxide and that is controlled by the chemical reaction. In the temperature range of 550 "C to 800 OC, the reaction order is about 1.34 and is independent of temperature. Changing the C12+CO content from 15 pct to 100 pct increases the reaction rate and does not affect the reaction mechanism. Similarly, changing the ratio of C12/(Cl2+CO) from 0.125 to 0.857 do not modify the carbochlorination mechanism of Cr203. In these conditions, the reaction rate passes through a maximum when using a chlorinating gas mixture having a Cl2/(C12+CO) ratio of about 0.5.

Jan 1, 1998

By Anja Pfennig, Thomas Böllinghaus, Marcus Wolf

During CCS components are exposed to a corrosive environment and mechanical stress which results in corrosion fatigue and is inevitably followed by the lifetime reduction of these components. The lifetime reduction of the cyclically loaded high alloyed stainless injectionpipe steel AISI 420C (X46Cr13, 1.4034) constantly exposed to highly corrosive CO2- saturated hot thermal water is demonstrated in in-situ-laboratory experiments (T = 60 °C, brine: Stuttgart Aquifer, flow rate: 30 l/h, CO2) in an environment similar to the on-shore CCS-site in the Northern German Bassin. In-situ tension-compression experiments were established simultaneously along with electrochemical measurements using a newly designed corrosion chamber in a resonant testing machine at a frequency as low as 30 – 40 Hz. In addition technical CO2 was introduced into the closed system at a rate close to 9 L/h. S-N plots, micrographic analysis and surface analysis of the fracture surface are demonstrated. X46Cr13 (surface roughness Rz = 4) reached the maximum number of cycles (12.5 x 106) at stress amplitude of 173 MPa producing a low scatter range of 1:3.5. Hydroxide and siderite layers were found on pits and crack surfaces. No typical fatigue limit exists. Pit corrosion prior to crack initiation may be identified as failure cause.

Jan 1, 2016

By Cong Wang, Siyang Long, Pengcheng Zhang, Haibin Zuo

This paper introduced the research progress of microwave treatment on coal. The mechanics of microwave treatment mainly include thermal effects and non-thermal effects. Thermal effects, which lead to cracks and changes of pore structure, attribute to the selective heating of microwave. Non-thermal effects involve the removal of oxygen functional groups, improvement of coal rank and decomposition of minerals. Therefore, microwave treatment of coal has a lot of potential applications, mainly including drying, desulfurization, improvement of grindability, enhancement of coal-water slurry property and change the combustion and gasification properties.

Jan 1, 2016

By N. L. Piret

In copper smelting minimization of solid waste generation is receiving increased attention with more stringent environmental legislation and lower disposal space availability. Copper smelting slags generally being valorizable, solid waste generation is attributed to the presence in the feed of unvalorizable impurities which do not report to the slag and to the unavoidable formation of contaminated dilute acid solutions which need neutralization. As to unvalorizable impurities, solid waste minimization is achieved by rejecting them in the highest possible concentration. Dilute acid is mainly due to the formation of SO3 in the smelter gases and to the discard of decopperized bleed-off electrolyte. Its generation is substantially lowered by preventing SO3 formation, by converting the dilute acid to a valorizable product, e.g., by thermal decomposition for H2S04 recovery or by precipitation as chemical gypsum, and by suitable treatment of the bleed-off electrolyte for impurity removal. Industrial processes are evaluated and alternatives are discussed.

Jan 1, 1994

By W. H. (Bill) Jay

The destruction of cyanide creates a significant impost on the financial returns of gold mines. These losses increase substantially when ores containing cyanide-soluble copper are treated. Failure to remove or destroy free or WAD cyanide before it is discharged into tailings dams has, on a number of occasions, led to significant fish, bird and animal deaths. Thus, the retention of cyanide within the leach circuit and the recovery or removal of stable metal cyanide complexes needs to become standard practice for all gold mining operations. Furthermore, reducing cyanide purchases will minimise the quantity of cyanide transported to the mine site thereby reducing the opportunity for spillage of this chemical. Many different physical and chemical methods have been investigated for the removal of cyanide from process solutions. All cyanide destruction methods create a financial impost on the economic viability of the gold mine. To reduce these costs, the recycle of cyanide and the economic recovery of the metals solubilised by cyanide is of prime importance. The alternative methods currently in use, or under consideration for the treatment of copper cyanide, entail high reagent costs, produce the recovered metal in a contaminated form and require the safe handling of hydrogen cyanide. These processes will be briefly discussed within this report Environmental and financial benefits are enhanced by recent laboratory and pilot plant studies conducted by Oretek Limited. The Oretek CPC process for the recovery of copper and the recycle of cyanide from copper cyanide-containing solutions does not require pH adjustment to the alkaline cyanide leach conditions. Copper ions are coordinated to a water-soluble and/or an organic soluble polychelating agent under alkaline conditions and the cyanide ions are displaced Membrane separation, or phase separation of the polychelated copper from the cyanide ions enables the cyanide ions to be recycled and the copper to be directly electrowon from the polychelating polymer. The polychelating polymer is then recycled. Ion exchange resins and solvent extraction systems which may be incorporated into the above process will also be discussed in detail.

Jan 1, 1998

By H. Deveci

Bioleaching/biooxidation is essentially a dissolution process with the involvement of acidophilic bacteria acting as the "catalyst" to accelerate the dissolution of metals from sulfide minerals. The contribution of bacteria to the metal dissolution is closely controlled by the growth of bacteria, which is itself affected by the physico-chemical conditions within the bioleaching environment. There are a number of operating parameters controlling bioleaching processes, which are required to be maintained within a certain range in the leaching environment whereby the activity of bacteria with the resultant oxidation of sulfide minerals can be optimized. In this regard temperature, acidity, oxidizing conditions, availability of nutrients, oxygen and carbon dioxide, surface area and presence of toxic ions are of prime importance for control and optimization of bioleaching of sulfide ores/concentrates. Bioleaching processes are temperature and pH dependent with optimum metal dissolution occurring in a particular range where the bacterial strain is most active e.g. mesophiles at 35-40°C and pH 1.6-2.0. Provision of nutrient salts is required to maintain the optimnm growth and hence metal dissolution with the quantity of nutrients apparently being dependent on the availability of substrate i.e. head grade/pulp density of an ore/concentrate. Oxygen transfer is one of the most critical factors since the oxygen levels below 1-2 mgll may adversely affect the oxidizing activity of bacteria. Bioleaching rate tends to improve with increasing the surface area at low pulp densities but, in practice. the pulp density is limited to -20010 w/v. Increasing concentrations of ions such as cr may also adversely affect the oxidative activity of bacteria. Keywords: Bioleaching, Biooxidation, Acidophilic bacteria

Jan 1, 2003

By Joël P. T. Kapusta, Romeo U. Pagador, Noparut Wachgama, Chumnoom Khuankla

"Thai Copper Industries (TCI) is a custom copper smelter and refinery in Rayong, Thailand, with an annual capacity of 165,000 tons of cathodes. It employs the El Teniente Technology as the primary smelting reactor to produce white metal from copper concentrates. The white metal is further treated in Hoboken Siphon Converters to produce blister copper then refined in anode furnaces before being cast into anodes for electro-refining in the on-site tankhouse.Thai Copper Industries is the first copper smelter to install and successfully operate on a commercial scale with the Air Liquide Shrouded Injection (ALSI™) Technology in the Hokoben converters with sonic injection of oxygen enriched air and nitrogen for cooling of the injector tip areas. Following commissioning and the establishment of operating practices, the performance of the Hoboken converters with ALSI™ Technology produced outstanding results. The unique combination of an El Teniente and Hoboken siphon converters, both of which are bath smelting operations, offers very high blowing and oxygen efficiencies. As a consequence, reverts recycling was accelerated with minimal build up on the mouth, end-plates or even below the siphon that is typical in Hoboken converters.These outstanding results in the Hoboken Siphon Converters with ALSI™ Technology helped the TCI Plant reach a production of about 75% of its capacity within four months despite the fact that the TCI staff is quite young and its converter know-how and experience are not yet fully developed."

Jan 1, 2009

By Kimiaki Utsunomiya, Yasumasa Hattori, Yoshiaki Mori, Toyokazu Okubo

"The effect of various operating conditions on splashing behavior in a Peirce-Smith converter has been investigated with a 1/5.7 scale cold model. Dynamic similarity between the model and a commercial converter was attained by setting the modified Froude number in the model experiments in· the range for normal converter operation. It is known that for a given modified Froude number the dimensionless penetration length of gas into the liquid phase increases as the liquid density decreases. Moreover, penetration· length has a large effect on splashing behavior. Therefore, a heavy liquid, a mixture of water and lead concentrate was used as the liquid phase. It was concluded that the amount of splash dramatically decreases with a reduction in the buoyancy energy per, unit liquid mass and an increase in the horizontal distance between the tuyere tip and the edge of the mouth.IntroductionSubmerged gas injection is widely used in practice in ferrous and nonferrous pyrometallurgical operations to achieve large gas-liquid contact areas and good agitation of liquid for rapid chemical reaction. The common application in ·nonferrous industry is the Peirce-Smith converter with multi-tuyere for copper and nickel matte converting. This process has been used for over 100 years because of its effectiveness in mixing of the molten bath, as well as its merits of the engineering simplicity. However, the mechanisms which · determine the blowing performance is poorly understood, and the design and operating conditions of the Peirce-Smith converter varies widely from plant to plant, such as by diameter, length, mouth angle, tuyere position and level of molten matte. Smelters have continuously made an effort to increase converter productivity, implying maximum tuyere blowing rate. Above a certain critical blowing rate, splash of molten matte from the converter mouth becomes unacceptable because of dangerous ejection and accretion buildup around the converter mouth, which results in interference with effective hood sealing. In fact, a 1993 converter survey[!] reported that splash was a major limiting factor for blowing rate and 54% of responding plants from around the world regard it as a limiting condition[2]. In order to increase tuyere blowing rate a study of the effect of various operating conditions on splashing behavior is expected."

Jan 1, 2000