In this paper results of microstructural observations for series of CuZn39Pb2 alloys produced from qualified scraps are presented. The individual alloy melts were differentiated in terms of thermal parameters of continuous casting as well as refining methods and modifications. Structural observations performed by SEM and TEM revealed formation of different types of intermetallic phases including “hard particles”. EDS results show that “hard particles” are enrich in silicon, phosphorus, iron, chromium and nickel elements. Additionally, formation of Al-Fe-Si and Al-Cr in alloy melts was observed as well. It was found that quantity and morphology of intermetallic phases strongly depends upon the chemical composition of raw materials, process parameters, modifiers and refining procedure applied during casting. It was observed that refining process results in very effective refinement of intermetallic phases, whereas modifiers, particularly carbon-based, results in formation of large particles in the microstructure.
The article presents the results of research which describes antagonism between Pb-Zn in selected plant species from the area of Czestochowa – Mirow district (north-western part of the Czestochowa Upland). There were analyzed changes in the ratio of Pb/Zn in different organs of the tested plants as a function of the Zn content changes. The content of metals in the plants and the soil was determined using atomic absorption spectrophotometry AAS. In all organs of the plants there was observed antagonistic decrease of Pb uptake and accumulation, resulting from the increase in the concentration Zn. Antagonism between Zn and Pb in roots of the tested plants occurred at Zn content of 200–600 μg/g. In turn, antagonism in stems and flowers occurred at lower contents of zinc (100–180 μg/g). In leaves, antagonism between Pb and Zn occurred when Zn was present at the level of 300–800 μg/g. Ex definition of the analyses confirm the presence of antagonism of lead with regard to high levels of Zn. The study also confirmed that the degree of antagonism depends on the plant species.
From all the detonation parameters of explosives, “strength” – the capability to perform work is the most important for the user. The detonation of explosives in the blast hole is a quick and complicated process: first there is a detonation pressure causing the crushing of the rock in the vicinity of the explosive, then the pressure of the detonation products causes the cracking of the rock. The article presents the methods of determining the capability to perform work by explosives for civil use (dynamite and ANFO) used in the accredited Laboratory of Explosives and Electric Detonators Testing of the Experimental Mine “Barbara” of the Central Mining Institute – the lead block (Trauzl) method and the ballistic pendulum method. The aim of the research was to determine the relationship between the values of the capability to perform the work received in a ballistic pendulum method and a lead block method. As a result of the performed tests and the analysis of the results, the α-Pb coefficient was determined, which can be used to convert the value of the capability to perform work on the ballistic pendulum to the corresponding value of the capability to perform work in the lead block. At present, the Central Mining Institute is the only Notified Body of the European Union in the scope of Directive 2014/28 /EU, which has a station for smelting lead blocks and equipment and for determining the capability to perform work by explosives in lead blocks – this method was abandoned in other research units for testing with a ballistic pendulum and/or underwater test.
Cd and Pb concentrations were measured in water, sediment and plant organs collected from selective sites located along the Bogdanka river (Poznań, Poland) in the 2012 growing season. The aim of the investigations was to monitor changes in heavy metal (HM) concentrations in different media over the periods, as well as to evaluate potential of two littoral plants, Phragmites australis and Typha angustifolia, for phytoremediation under natural conditions. Investigations revealed differences in HM concentrations in water and sediments. Higher values were observed in sediments than in water. The decrease in concentrations of both HMs in sediments was noted in two of the three selected water reservoirs during growing seasons, which suggests the possibility of their adsorption and accumulation by aquatic plants. Both investigated plant species accumulated ample amount of Cd and Pb in underground and aboveground plant tissues, however T. angustifolia revealed higher Cd translocation potential than P. australis. The latter revealed higher Pb accumulation in two lakes. Moreover, the translocation ratio was usually higher in spring, especially for Pb, in both plant species. Increasing level of pollution load index in sediment along the Bogdanka watercourse indicates accumulation of measured HMs.
The purpose of the investigation was to assess the suitability of sewage sludge, brown coal and a mix of sewage sludge and brown coal to be used for fertilizing a light soil with an increased content of lead (I0 ) and slightly contaminated with cadmium (II0 ). The subject of tests were soil and plant samples taken from a pot experiment conducted during the years 2007-2009. The tests determined the effect of the type of fertilization on the pH and sorption properties of the soil, the contents of heavy metals in the soil and in the plants, and the volume of crops. The fertilization types applied had an effect of slightly increasing the soil pH. The application of sewage sludge, brown coal and the mix of sewage sludge with brown coal to the soil resulted in an improvement of the sorption properties of the soil. In the soil treated with sewage sludge and the mix of sewage sludge with brown coal, an increase in the contents of Cd, Zn and Pb was found. This increase was, however, small and did not change the degree of soil contamination with heavy metals. In the above-ground parts of plants fertilized with brown coal the concentration of heavy metals was lower than in biomass from plants cultivated on the control combination. The application of sewage sludge and the mix of sewage sludge with brown coal generally resulted also in a reduction of metal contents in the above-ground parts of the plants. This was the effect of enriching the soil with an organic substance that improves the sorption properties. From among the fertilization combinations tested, the application of either sewage sludge or the mix of sewage sludge with brown coal had the most favourable effect on the crop volume. It resulted in a twofold increase in the yield compared to the control combination.
In this article, we review the research state of the bullwhip effect in supply chains with stochastic lead times. We analyze problems arising in a supply chain when lead times are not deterministic. Using real data from a supply chain, we confirm that lead times are stochastic and can be modeled by a sequence of independent identically distributed random variables. This underlines the need to further study supply chains with stochastic lead times and model the behavior of such chains.
This work reports on cadmium and lead contaminations in the edible snail Helix pomatia harvested in Poland. One hundred and 24 samples of Helix pomatia meat collected from seven provinces (voivodeships) of Poland were analyzed for their trace metal levels by graphite furnace atomic absorption spectrometry (GFAAS). The research was conducted in 2 stages. The 1st stage analyzed snail meat prior to any further technological treatment (raw meat). In the 2nd stage, the trace element levels were measured in meat subjected to technological treatment (processed meat). The trace element contents in raw meat samples ranged from 0.06 mg kg-1 to 0.22 mg kg-1 for Cd and from 0.06 mg kg-1 to 0.18 mg kg-1 for Pb. The analyses revealed an increase in the cad- mium content from 0.12 mg kg-1 to 0.18 mg kg-1 in thermally treated snail meat and no changes in lead concentration during the two-stage heat treatment. Regulation (EC) 1881/2006 does not specify the Cd and Pb residue limits in meat of terrestrial edible snails. The limits are set for in- vertebrate aquatic organisms meat (i.e. shellfish, mollusc, cephalopod) and range from 0.5 mg/kg to 1.5 mg/kg of tissue fresh weight for Pb and from 0.5 mg kg -1 to 1 mg kg-1 for Cd (EU Commis- sion 2006). The results demonstrate that the land snail Helix pomatia has a tendency to bioaccu- mulate trace elements, and the cooking process is likely to affect (increase) the Cd content in the snail meat.
The paper describes the studies of ternary SnZn9Al1.5 lead-free alloy from the viewpoint of its mechanical behavior as well as microstructure examined by the light and scanning electron microscopy. The authors focused their attention specifically on the fatigue parameters determined by the original modified low-cycle fatigue method (MLCF), which in a quick and economically justified way allows determination of a number of mechanical parameters based on the measurement data coming from one test sample only. The effect of the addition of 1.5% Al to the binary eutectic SnZn9 alloy on its microstructure and the obtained level of mechanical parameters was analyzed. The phases and intermetallic compounds occurring in the alloy were identified based on the chemical analysis carried out in micro-areas by the SEM/EDS technique. It was shown that the addition of 1.5% Al to the binary eutectic SnZn9 alloy resulted in a more favorable microstructure and consequently had a positive effect on the mechanical parameters of the alloy. Based on the conducted research, it was recommended to use a combinatorial method based on the phase quanta theory to quickly evaluate the microstructure and the original MLCF method to determine a number of mechanical parameters.
Lead-free alloys containing various amounts of zinc (4.5%, 9%, 13%) and constant copper addition (1%) were discussed. The results of microstructure examinations carried out by light microscopy (qualitative and quantitative) and by SEM were presented. In the light microscopy, a combinatorial method was used for the quantitative evaluation of microstructure. In general, this method is based on the phase quanta theory according to which every microstructure can be treated as an arrangement of phases/structural components in the matrix material. Based on this method, selected geometrical parameters of the alloy microstructure were determined. SEM examinations were based on chemical analyses carried out in microregions by EDS technique. The aim of the analyses was to identify the intermetallic phases/compounds occurring in the examined alloys. In fatigue testing, a modified low cycle fatigue test method (MLCF) was used. Its undeniable advantage is the fact that each time, using one sample only, several mechanical parameters can be estimated. As a result of structure examinations, the effect of alloying elements on the formation of intermetallic phases and compounds identified in the examined lead-free alloys was determined. In turn, the results of mechanical tests showed the effect of intermetallic phases identified in the examined alloys on their fatigue life. Some concepts and advantages of the use of the combinatorial and MLCF methods in materials research were also presented.
The results of studies presented in this article are an example of the research activity of the authors related to lead-free alloys. The studies covered binary SnZn90 and SnZn95 lead-free alloys, including their microstructure and complex mechanical characteristics. The microstructure was examined by both light microscopy (LM) and scanning electron microscopy (SEM). The identification of alloy chemical composition in micro-areas was performed by SEM/EDS method. As regards light microscopy, the assessment was of both qualitative and quantitative character. The determination of the geometrical parameters of microstructure was based on an original combinatorial method using phase quantum theory. Comprehensive characterization of mechanical behavior with a focus on fatigue life of alloys was performed by means of the original modified low cycle fatigue method (MLCF) adapted to the actually available test machine. The article discusses the fatigue life of binary SnZn90 and SnZn95 alloys in terms of their microstructure. Additionally, the benefits resulting from the use of the combinatorial method in microstructure examinations and MLCF test in the quick estimation of several mechanical parameters have been underlined.
The study includes the results of research conducted on selected lead-free binary solder alloys designed for operation at high temperatures. The results of qualitative and quantitative metallographic examinations of SnZn alloys with various Zn content are presented. The quantitative microstructure analysis was carried out using a combinatorial method based on phase quanta theory, per which any microstructure can be treated as an array of elements disposed in the matrix material. Fatigue tests were also performed using the capabilities of a modified version of the LCF method hereinafter referred to in short as MLCF, which is particularly useful in the estimation of mechanical parameters when there are difficulties in obtaining many samples normally required for the LCF test. The fatigue life of alloys was analyzed in the context of their microstructure. It has been shown that the mechanical properties are improved with the Zn content increasing in the alloy. However, the best properties were obtained in the alloy with a chemical composition close to the eutectic system, when the Zn-rich precipitates showed the most preferred morphological characteristics. At higher content of Zn, a strong structural notch was formed in the alloy because of the formation in the microstructure of a large amount of the needle-like Zn-rich precipitates deteriorating the mechanical characteristics. Thus, the results obtained during previous own studies, which in the field of mechanical testing were based on static tensile test only, have been confirmed. It is interesting to note that during fatigue testing, both significant strengthening and weakening of the examined material can be expected. The results of fatigue tests performed on SnZn alloys have proved that in this case the material was softened.
The article presents the study results of Sn-Zn lead-free solders with the various Zn content. The results concern the hypoeutectic, eutectic and hypereutectic alloys containing respectively 4.5% Zn, 9% Zn and 13.5% Zn. Moreover, these alloys contain the constant Ag (1%) addition. The aim of the study was to determine the microstructural conditionings of their fatigue life. In particular it was focused on answer the question what meaning can be assigned to the Ag addition in the chemical composition of binary Sn-Zn alloys. The research includes a qualitative and quantitative assessments of the alloy microstructures, that have been carried out in the field of light microscopy (LM). In order to determine some geometrical parameters of the microstructure of alloys the combinatorial method based on the phase quanta theory was applied. Moreover, for the identification necessities the chemical analyses in the micro-areas by SEM/EDS technics were also performed. Based on the SEM/EDS results the phases and intermetallic compounds existing in the examined lead-free solders were identified. The mechanical characteristics were determined by means of the modified low cycle test (MLCF). Based on this method and on the results obtained every time from only one sample the dozen of essential mechanical parameters were evaluated. The research results were the basis of analyzes concerning the effects of microstructural geometrical parameters of lead-free alloys studied on their fatigue life at ambient temperature.
The article describes the influence of anomalous values and local variability on the structure of variability and the estimation of deposit parameters. The research was carried out using statistical and geostatistical methods based on the Pb accumulation index in the shale series in part of the Cu-Ag ore deposit, LGCD (Lubin-Głogów Copper District). The authors recommend the use of a geostatistical tool, the so-called semivariogram cloud to determine the anomalous values. Anomalous values determined by the geostatistical method and removed from the dataset have resulted in a significant reduction of the relative variability of data, which is still very large in the case of the analyzed parameter or parameters with similar statistical features such as extreme variability and strongly asymmetric distribution. Calculations of the resources of this element can be treated only as estimates and formally classified to category D. The hypothetical assumption of the absence of sampling errors, resulting in a decrease in the magnitude of local variation, leads to a certain reduction of the median error of resource estimates. However, they are still high (> 35%). This is due to the large natural variability of the accumulation index of Pb on the local observation scale. The current method for collecting samples from mine workings of the Cu-Ag deposits in the Lubin-Głogów Copper District (LGCD), aimed at the proper assessment of copper resources, the Cu content, and at estimating the quality of copper output, makes it impossible to achieve an accuracy of estimates of Pb resources similar to that obtained for the main metal. Theoretically, this effect can be achieved by a strong concentration of the sample collection points and thanks to a multiple increase in the samples weight; this, however, is unrealistic for both economic and organizational reasons. It is therefore to be expected that the assessment of Pb resources and other accompanying elements of similar statistical features (e.g. As), located in parts of the deposit where mining activities are to be carried out, will be subject to significant errors.
As part of the presented work, tests were carried out to check the possibility of replacing of conventional reducers used in the lead pyrometallurgical processes by cheaper, but equally effective substitutes. For research of lead oxide reduction, the following fine-grained carbonaceous materials were used, ie anthracite dust and coal flotation concentrate, as well as traditional used coke breeze for comparison. The obtained test results indicate a similar ability to reduce the lead oxide of all studied carbonaceous materials.
The phytoextraction is a process that uses living plants for cleaning up the heavy metals from contaminated soil. The cadmium and lead contamination of soils results from the application of sludge or urban composts, fertilizers, pesticides, motorization, metallurgy, and different technological processes. In industrial terrain the content of cadmium and lead in soils has increased in the recent years. This study was undertaken to evaluate the potential of Amaranthus caudatus L. ‘Atropurpureus’ and Ricinus communis L. ‘Sanguineus Apache’ for phytoextraction of cadmium and lead. Two species of ornament plants, i.e. Amaranthus caudatus L. ‘Atropurpureus’ and Ricinus communis L. ‘Sanguineus Apache’, were planted in drainless containers in a substrate artificially polluted with cadmium and lead in order to evaluate their suitability for phytoremediation of soils or substrates contaminated with these metals. Cadmium was applied at increasing rates of 0, 1, 5 and 10 mg Cd∙dm-3 in the form of cadmium sulfate 3CdSO4∙8H2O, while lead was used at 0, 100, 500 and 1000 mg Pb∙dm-3 in the form of lead acetate (CH3COO)2Pb∙3H2O. The applied doses of cadmium and lead in the experiment reflected different degrees of soil pollution. After five months of growth it was found that Amaranthus caudatus L. accumulated the biggest concentrations of cadmium and lead in leaves and the lowest concentrations in inflorescences. Ricinus communis L. accumulated the highest concentrations of cadmium in stems, while the lowest concentrations in inflorescences, whereas the biggest concentration of lead was accumulated in inflorescences and the least lead was accumulated in leaves. The biggest reduction of cadmium and lead concentrations after the completion of the experiment was found in substrates, in which Amaranthus caudatus L. was grown. The tested species of ornamental plants may be used in the phytoextraction of cadmium and lead from soils contaminated.
The article presents the results of plasma vitrification of solid remnants from thermal waste treatment with and without the addition of a carbonate fraction obtained from lead-zinc ore flotation. The substrates used in the research were slags and ashes from medical waste treatment, incineration of municipal waste, sewage sludge as well as hazardous and industrial wastes. The plasma treatment resulted in acquiring products of different quality depending on the processed substrate. Most of the obtained products were of vitreous and homogenic build. Treatment of remnants from incineration of hazardous and industrial wastes resulted in obtaining heterogeneous and rough surfaced products. A 20% share of the carbonate fraction enabled the obtaining of a vitrified product with a glassy surface and fracture. Hardness of the obtained products was rated in Mohs scale and ranged from 6 to 6,5. Leaching tests showed a decrease in heavy metal concentration in the leachates from vitrificates with the addition of carbonate fraction compared to the ones with it.
Laboratory and field experiments have been conducted to study mobility of chromium and lead in floodplain sediments. The main goal of the research was to verify a hypothesis whether changes of chromium and lead concentration could be used to estimate the relative age of floodplain deposits. The basis for undertaking such research was the presence of weaving industry centers in the Obra River valley between the 16th and the 19th century and using Cr and Pb compounds in paint recipes. The Cr and Pb contents were also analyzed in three vertical profiles unaffected by the field experiments. The age of organic sediments in each of the profiles was determined using the radiocarbon analysis. The results of the laboratory experiments have shown that the highest contents of the elements were noted in the surface layer of the sediments placed in the column. However, the contents decreased during the last phase of the experiments and both vertical and horizontal migration of both elements was observed. A more intensive mobility was observed in the field test. Its cause could be the changes of the groundwater level, floodplain inundation and pH conditions in alluvial deposits. Such processes may have influenced migration of the compounds originating from the weaving industry production; Cr and Pb contents detected in the profiles unaffected by the field experiment were too small to be used for relative dating of alluvial deposits. Moreover, the alluvial deposits with increased contents of the studied elements may be older than the period of the weaving industry development. Cr and Pb mobility was especially intensive in the profiles situated within the near bed zone of the floodplain due to regular inundation, and the activity of erosion and accumulation processes entraining the studied elements back to transport in the river bed.
In the work five ceramic compounds based on the (K0.44Na0.52Li0.04)NbO3 (KNLN) material modified with oxides: Cr2O3, ZnO, Sb2O3 or Fe2O3 (in an amount of 0.5 mol.%) were obtained. The KNLN-type composition powder was prepared by solid phase synthesis from a mixture of simple oxides and carbonates, while compacted of the ceramic samples was conducted by free sintering methods. In the work the effect of the used admixture on the electrophysical properties of the KNLN ceramics was presented. The XRD, EDS tests, the SEM measurements of the morphology ceramic samples, dielectric properties and DC electric conductivity were conducted. The research showed that the used admixtures introduced into the base of KNLN-type composition improve the microstructure of the ceramic samples and improve their sinterability. In the case of the dielectric measurements, it was observed a decrease in the maximum dielectric permittivity at the TC for dopred KNLN-type samples. The addition of an admixture of chromium, zinc, antimony or iron in an amount of 0.5 mol.% to the base composition (K0.44Na0.52Li0.04)NbO3 practically does not change the phase transition temperature. The diminution in the density value of doped KNLN ceramics was attributed to the alkali elements volatilization.
The adsorption of lead ions onto a zeolite bearing tuff (stilbite) from synthetic acid aqueous solution and acid mine drainage taken from Sasa mine, Macedonia, is elaborated in this paper. The results present that adsorption occurs effi ciently in both of cases. The physical and chemical properties of the used natural material, zeolite bearing tuff, are characterized by X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy. The concentration of metal ions in solution before and after treatment is obtained by AES-ICP. The effectivity of zeolite bearing tuff is determined through a series of experiments under batch conditions from single ion solutions, whereby the main parameters are the effects of initial pH of solution, mass of adsorbent, initial metal concentration in solution, contacting time and competing cations. The maximum capacity of zeolite bearing tuff for removal of lead ions from solution is determined by equilibrium studies. The experimental obtained data are fi tted with Freundlich and Langmuir adsorption models. The experimental data are better fi tted with Langmuir adsorption isotherm. Zeolite bearing tuff is effective adsorbent for treating acid mine drainage. The results showed that 99% of lead ions are removed from acid mine drainage, i.e. the concentration of lead ions from 0.329 mg/dm3 decrease to 0.002 mg/dm3 . The pH value of acid mine drainage from 3.90 after treatment with zeolite bearing tuff increases to 5.36.
The ecological factor is very important in shaping properties of alloys. It leads to a limitation or elimination, from the surroundings, of harmful elements from the heavy metals group. The so-called eco-brasses group comprises common lead-free brasses containing 10 to 40% of zinc and arsenic brasses of a high dezincification resistance. Among standardized alloys, CW511L alloy ( acc. to EN standard) or MS-60 alloy (acc. to DIN) can be mentioned. Investigations were performed on two different kinds of metal charges: ingots cast by gravity and the ones obtained in the semi-continuous casting technology with using crystallizers. The casting quality was analysed on the basis of the microstructure images and mechanical properties. The investigations also concerned increasing the corrosion resistance of lead-free alloys. This resistance was determined by the dezincification tendency of alloys after the introduction of alloying additions, i.e. aluminium, arsenic and tin. The investigations focused on the fact that not only alloying additions but also the production methods of charge materials are essential for the quality of produced castings. The introduced additions of aluminium and tin in amounts: 0÷1.2 wt% decreased the dezincification tendency, while arsenic, already in the amount of 0.033 wt%, significantly stopped corrosion, limiting the dezincification process of lead-free CuZn37 brass. At higher arsenic contents, corrosion occurs only within the thin surface layer of the casting (20 μ).
The research focuses on assessing the metal content, mainly copper, lead, iron and also silver in metallurgical slag samples from the area where historical metallurgical industry functioned. In the smelter located in Mogiła, near Krakow (southern Poland), whose operation is confirmed in sources from 1469, copper was probably refined as well as silver was separated from copper. Based on the change of chemical and soil phase content and also taking cartographic and historical data into account, considering the restrictions resulting from the modern land use the area was determined whose geochemical mapping can point to the location of the 15th century Jan Thurzo’s smelter in Mogiła near Krakow. Moreover, using the same approach with the samples of this kind here as with hazardous waste, an attempt has been made to assess their impact on the environment. Thereby, taking the geoenvironmental conditions into account, potential impact of the industrial activity has been assessed, which probably left large scale changes in the substratum, manifested in the structure, chemical content and soil phase changes. Discovering areas which are contaminated above the standard value can help to identify historical human activities, and finding the context in artefacts allows to treat geochemical anomalies as a geochronological marker. For this purpose the best are bed sediments, at present buried in the ground, of historical ditches draining the area of the supposed smelter. Correlating their qualities with analogical research of archeologically identified slags and other waste material allows for reconstructing the anthropopressure stages and the evaluation of their effects. The operation of Jan Thurzo’s smelter is significant for the history of mining and metallurgy of Poland and Central and Eastern Europe.