Cross-Linking Characteristics, Morphology, Dynamics, and Mechanical and Thermal Properties of Polychloroprene/Polybutadiene/Nano-Zinc (CR/BR/nZn) Compositions with Reduced Fire Hazard.

The properties of unconventional blends of crystallizable and thermo-cross-linkable polychloroprene (CR) with polybutadiene (BR) were investigated in this study. The compositions were prepared using the method of reactive processing and cross-linking in the presence of nano-sized zinc (nZn). The purpose of the research was to assess the efficacy of nano-zinc as a curing agent of polychloroprene and polybutadiene (CR/BR) composites and to obtain rubber goods characterized by increased flame resistance. The blends were filled with nano-silica (aerosil) and fillers of natural origin (chalcedonite or silitin). The cross-linking process was characterized by determining the kinetics curves, the equilibrium swelling, and the Mooney-Rivlin elasticity constants. The morphology of the vulcanizate surface was specified by scanning electron microscopy (SEM). The dynamic and mechanical properties, flammability, and toxicity of gaseous substances involved in thermal decomposition were determined. Mass changes and thermal effects were studied using simultaneous thermal analysis (STA). It was confirmed that nano-zinc is an efficient curing agent for the polychloroprene and polybutadiene compositions, with a satisfactory degree of cross-linking (αc = 0.10, CRI = 4.11 min-1), good mechanical strength (TSb = 5 MPa), satisfactory tear resistance (Ts = 2.9 N/mm), and very high flame resistance (OI = 30%, HRRmax = 283 kW/m2). Filled products could be used as non-combustible materials, confirming the low fire hazard (1/tflashover = 3.5-6.4 kW/m2∙s). The most effective filler of the tested composites was nano-sized silica.

Effect of Hybrid Filler, Carbon Black-Lignocellulose, on Fire Hazard Reduction, including PAHs and PCDDs/Fs of Natural Rubber Composites.

The smoke emitted during thermal decomposition of elastomeric composites contains a significant number of carcinogenic and mutagenic compounds from the group of polycyclic aromatic hydrocarbons, PAHs, as well as polychlorinated dibenzo-p-dioxins and furans, PCDDs/Fs. By replacing carbon black with a specific amount of lignocellulose filler, we noticeably reduced the fire hazard caused by elastomeric composites. The lignocellulose filler reduced the parameters associated with the flammability of the tested composites, decreased the smoke emission, and limited the toxicity of gaseous decomposition products expressed as a toximetric indicator and the sum of PAHs and PCDDs/Fs. The natural filler also reduced emission of gases that constitute the basis for determination of the value of the toximetric indicator WLC50SM. The flammability and optical density of the smoke were determined in accordance with the applicable European standards, with the use of a cone calorimeter and a chamber for smoke optical density tests. PCDD/F and PAH were determined using the GCMS-MS technique. The toximetric indicator was determined using the FB-FTIR method (fluidised bed reactor and the infrared spectrum analysis).

The Morphology, Mechanical and Dynamic Properties, Fire Hazard and Toxicity of Chloroprene and Butadiene Rubber Composites Cross-Linked with Zinc.

This paper presents the influence of zinc on the cross-linking process, mechanical and dynamic properties, morphologies and balance of thermal degradation of blends containing chloroprene rubber (CR) and butadiene rubber (BR). The novel aspect of this research is a comprehensive approach presenting a new curing agent for the CR/BR blends to increase their cross-linking density and final properties, including non-flammability and low fire hazard. This is due to the need to find an alternative to zinc oxide, which is the standard curing agent for chloroprene rubber. The regulations of the European Union enforce a significant limitation on the use of this compound in elastomer technology, due to its harmful effect on aquatic organisms. In this paper, the CR/BR composites were cured with zinc and filled with natural silica fillers (sillitin or chalcedonite) or synthetic silica filler (aerosil). The investigation focused on the morphology characterization of the obtained compounds, their cross-linking degree, swelling, mechanical and dynamic properties, fire hazard and toxicity. The structure of cured CR/BR blends was characterized via scanning electron microscopy (SEM). The fire resistance studies were performed using cone calorimetry or oxygen index methods, whereas toxicity tests were performed with the use of the FB-FTIR (fluidized bed reactor coupled with FTIR analyzer) method. The results showed that obtained CR/BR products were characterized by satisfactory final properties. The properties determined by the oxygen index and cone calorimetry methods, including the behaviors of the tested CR/BR vulcanizates in fire conditions, showed that the produced compounds were characterized by a low fire hazard and can be classified as non-combustible rubber products. However, the toxicity of the decomposition products, determined at 450, 550 and 750 °C, was very high.

An assessment of an ion exchange resin system for the removal and recovery of Ni, Hg, and Cr from wet flue gas desulphurization wastewater-a pilot study.

The paper presents the results of a pilot-scale study investigating the efficiency of an ion exchange resin system in the removal of Ni, Hg, and Cr from flue gas desulphurisation wastewater, in the presence of competitive metals such as Ca, Mg, Al, Fe, and Mn. The core part of the ion exchange installation consisted of two columns that were filled with ion exchange resin with iminodiacetic functional groups (Purolite S930) and one column filled with resin with isothiouronium functional groups (Purolite S920). The results showed that Ni, Hg, and Cr were almost completely removed from the wastewater with nearly 100% efficiency. Purolite S930 almost totally removed Ni, reducing its content from 89.3 ± 35 µg dm-3 to below 0.1 µg dm-3, while Purolite S920 reduced the remaining Cr content from 2.2 ± 0.6 µg dm-3 and most of the Hg content, from 23.5 ± 6.6 µg dm-3 to below 0.1 µg dm-3. The competitive metals Ca, Mg, Mn, and Al showed low affinity to the studied ion exchange resins. The study also assessed speciation of ion forms and sorption mechanisms. Breakthrough curve analysis was also carried out, which revealed that the selectivity sequence of iminodiacetic resin was Ni > Cr > Hg > Fe > Al > Mn > Ca, Mg. Elution studies were performed on S930 resins that allowed the separation of two streams: one containing mostly Ni and Fe which can be subjected to Ni recovery and the other containing mostly Cr and Hg which can be separated.

Modeling of the Kinetics of Polyoxymethylene Decomposition under Oxidative and Non-Oxidative Conditions.

Research on the thermal and thermo-oxidative degradation of polyacetals allows for the development of effective methods of utilization of the waste of these polymers towards the recovery of monomers. For this purpose, in addition to qualitative analysis, it is necessary to understand the mechanisms of chemical reactions accompanying the decomposition process under the influence of temperature. Therefore, in this article, with the experimental results from the thermal analysis of the POM homopolymer of three various stages of life-POM-P-unprocessed sample; POM-R-recycled sample, and POM-O-sample waste-we took steps to determine the basic kinetic parameters using two well-known and commonly used kinetic models: Friedman and Ozawa-Flynn-Wall (OFW). Knowing the values of the course of changes in apparent activation energy as a function of partial mass loss, theoretical curves were fitted to the experimental data. The applied calculation models turned out to be consistent in terms of the nature of the curve changes and similar in terms of Ea in the entire range of mass loss. Both kinetic models showed a very similar course of the Ea curves. The samples that decompose under oxidative conditions obtained the best fit for the reaction of nth order with autocatalysis by product B model and the samples that decompose under inert conditions for the n-dimensional nucleation according to the Avrami-Erofeev model.

The Presence of Selected Elements in the Microscopic Image of Pine Needles as an Effect of Cement and Lime Pressure within the Region of Biale Zaglebie (Central Europe).

In this study, we present the results of microscopic observations of pine needles Pinus sylvestris L. collected in the area of cement-lime pressure in the south-western part of the Swietokrzyskie Mountains in the region of Biale Zaglebie. Images of scanning electron microscopy (SEM) confirm the presence of particles with a size of about 2 to 20 µm on the surface of the needles. Analysis using X-ray energy dispersion spectroscopy (EDS) allowed, in turn, to identify lead, iron, aluminium, calcium, and silicon in particles deposited in the surface layer of assimilation organs and dispersed in the surface layer of vegetation tissue within cell structures. Chemical composition, size and shape of particles of foreign bodies on the needles' surface allow them to be identified as cement-lime dust coming from production plants located in the Biale Zaglebie. Negative influence on the condition and liveliness of Scots pine in the study area is manifested by images on which stomata is sealed, which limits the possibility of gas exchange.

Recovery and Characterization Studies of Post-Production Alloy Waste from the Automotive Industry.

Superalloys provide high corrosion resistance and are widely used as high-performance materials in aerospace, automotive, chemical, and other industries. Herein, the investigation into the characteristics and properties of alloy waste; Inconel 625, Inconel 718, and Titanium Grade 5, from the automotive industry, was introduced as a result of a recovery in various processes. For this reason, the following procedures were carried as follows; the washing process to remove oil from the swarf was evaluated using several commercial agents and for the process of thermal disposal of processing fluids, a temperature of 900 °C was used in a muffle furnace without air access. The presented studies show that the commercially available series of washing agents did not modify the composition of the surface. However, the high temperatures during the calcination of oil residues are affecting the elemental composition of the alloys. According to the results of the analyses, it is not possible to remove 100% of the oil residues from alloy waste using washing agents based on light organic fractions; however, the effectiveness of this method reaches 99%. In this report, accurate SEM-EDS analyses show changes that occur on the surface after machining and removal of processing fluids. The NMR and GC/MS investigations indicate contaminants as a mixture of aliphatic and cycloaliphatic hydrocarbons with carbon numbers from C8-C30.

Impact of Calcium Oxide on Hygienization and Self-Heating Prevention of Biologically Contaminated Polymer Materials.

During the storage of spent polymer materials derived from municipal solid waste, which contain biodegradable impurities, an intense growth of microorganisms takes place. The aerobic metabolism of microorganisms may cause these materials to combust spontaneously and to become a real epidemiological risk for humans. The aim of the research is to determine the optimal addition of calcium oxide (CaO), which effectively reduces the number of selected microorganism groups populating the analyzed materials, in which spent polymers represent a significant fraction: refuse-derived fuel (RDF) and an undersize fraction of municipal solid waste (UFMSW). The main novelty of the experiments is to assess the benefits of using the commonly available and cheap filler (CaO), to hygienize the material and to reduce the fire hazard arising from its storage. During the mixing of spent polymer materials with pulverized CaO (mass shares: 1, 2, and 5% CaO), temperature changes were monitored using thermography. Moisture content (MC), pH, respiration activity (AT4) and bacterial count were determined before and after the experiment. During the addition of CaO (especially when the content was at 5%) to the UFMSW, higher maximum temperatures were obtained than in the case of RDF analyses, which may be the result of a high percentage of the biodegradable fraction and higher MC of the UFMSW. In all cases the waste temperature did not increase again after 3 min. CaO used in the experiment effectively limited the number of microorganisms. The addition of 5% of CaO has showed the strongest antimicrobial properties, and it can be recommended for hygienization of the analyzed materials and for the reduction of the risk of self-heating during their storage in windrows.

Dataset on flue gas composition during combustion in the fluidised bed reactor. Polyethylene combustion.

The dataset presented in this article is the supplementary data for the research article titled "The combustion of polyolefins in the inert and catalytic fluidised beds", in which polyethylene combustion in the cenosphere fluidised bed were investigated. The use of cenospheres as a bed material made it possible to free sink of PE particles in the bed and rule out its combustion in freeboard. It also lead to elimination of soot formation. The quantitative and qualitative analysis of flue gases were performed by Fourier Transform Infrared Spectroscopy (FTIR, Gasmet DX-4000). This data article provides detailed information on changes in product concentration at intervals of a few seconds.

Application of Earth Pigments in Cycloolefin Copolymer: Protection against Combustion and Accelerated Aging in the Full Sunlight Spectrum.

In this paper, we assess various natural earth pigments as potential colorants and stabilizers for ethylene-norbornene copolymer composites. Several cycloolefin copolymer (COC) composites colored with 2 wt% of a selected pigment were prepared using a two-step mixing method. The aging resistance of the polymer composites was investigated in terms of changes to their mechanical properties, following accelerated aging in the full sunlight spectrum (100, 200, 300, 400, and 500 h). Fourier-transform infrared spectroscopy (FTIR), surface energy measurements, and spectrophotometry were used to assess the color changes, surface defects, and morphology of the composites. Thermogravimetric analysis (TGA) was used to study their thermal stability. The combustion characteristics of the prepared COC composites were evaluated based on the microcombustion calorimetry test (MCC). The application of earth pigments resulted in interesting color changes and a significant improvement in the aging resistance of the COC-filled samples, as evidenced by higher aging factor values and lower carbonyl index parameters compared to the reference (COC). The best results were observed for hematite (HM), gold ochre (GO), and red ochre (RO). In addition, the application of earth pigments, especially iron ochre (IO) and red ochre (RO), in COC contributed to a significant reduction in the heat release rate (HRR) values, indicating improved flame retardancy. This research opens the possibility of producing colorful COC composites with enhanced photostability and reduced flammability for use in polymer applications.

Adsorption of Cadmium, Manganese and Lead Ions from Aqueous Solutions Using Spent Coffee Grounds and Biochar Produced by Its Pyrolysis in the Fluidized Bed Reactor.

The adsorption process of cadmium ions (Cd), manganese ions (Mn) and lead ions (Pb) onto the spent coffee grounds (SCG) and activated spent coffee grounds (biochar, A-SCG) was investigated. The SCG activation was carried out in the pyrolysis process in a fluidized bed reactor. scanning electron microscope (SEM) with energy dispersive X-ray spectroscopy (EDX), Fourier-transform infrared spectroscopy (FTIR), Brunauer-Emmett-Teller (BET) measurements and CHN analysis were used in order to define the differences between biomaterials. In the study the different mass of materials (0.2-0.5 g) and constant heavy metal volume and concentration (20 cm3/100 ppm) were investigated on the adsorption process. In order to describe the sorption parameters the Langmuir, Freundlich and Temkin isotherms were used. The maximum adsorption for biochar reached 22.3 mg/g for Pb ions, 19.6 mg/g for Mn ions and 19.4 mg/g for Cd ions which were noticeably higher than the results obtained for spent coffee grounds which reached 13.6 mg/g for Pb ions, 13.0 mg/g for Mn ions and 11.0 mg/g for Cd ions. Metal ion adsorption on both SCG and A-SCG was best described by the Langmuir model, thus chemisorption was a dominant type of adsorption. Studying the kinetics of the sorption process, one can see that the process is of a chemical nature according to the best fit of the pseudo-second rate order model. The obtained results show that the chosen sorbents can be used for the removal of cadmium, manganese and lead compounds from aqueous solutions with high efficiency.

Dataset on flue gas composition during pyrolysis of polyoxymethylene in a fluidised bed with the possibility of incorporating CO2.

The dataset presented in this article is the supplementary data for the research article titled "The pyrolysis and combustion of polyoxymethylene in a fluidised bed with the possibility of incorporating CO2" [1], in which possible paths of polyoxymethylene conversion in the fluidised bed made from cenospheres and by means of various fluidising gases (air, N2, CO2) were tested. The use of CO2 as fluidising gas was particularly interesting because above 600°C its incorporation into process products (i.e. CO-rich flue gas) was observed. The gaseous products were detected using Fourier Transform Infrared Spectroscopy (FTIR, Gasmet DX-4000) at intervals of a few seconds. The data on the concentration changes over time will allow to evaluate and verificate of new kinetic models of polyoxymethylene degradation with the possibility of incorporating CO2.

Synthesis and Performance of TiO2/Fly Ash Cenospheres as a Catalytic Film in a Novel Type of Periodic Air-Sparged Photocatalytic Reactor.

The results of a photocatalytic process performed in a new type of inclined, three-phase fluidised bed reactor with a periodic photocatalyst film are presented. These phases were fly ash cenospheres coated with TiO2, an aqueous solution of methylene blue and an air stream passing from the bottom of the photoreactor. The cenospheres have a density lower than water and could thus form a catalytic film on a top irradiated window. The formed surface film is stable but is easy to break and be reproduced in a cyclic air-sparged process. Mixing was performed in either a cyclic or a continuous manner. From an operational point of view, the best variant of mixing was a 10 s air-sparge/10 s break with a 50% duty cycle, because it provided the same discolouration efficiency and reduced energy demand by 50% in comparison with the continuous mixing. Due to film formation, the proposed catalytic reactor enables a substantial reduction in the energy required for mixing while maintaining the desired degree of discolouration.

Dataset on flue gas composition during combustion in the fluidised bed reactor. Glycerol combustion.

The dataset presented in this article is the supplementary data for the research article by Zukowski and Berkowicz (doi:10.1016/j.combustflame.2019.05.024) [1], in which for the first time the inert and catalytic cenospheres were used as the fluidised bed material, giving the possibility to burn liquids inside the fluidised bed without the need for using specialised dosing systems. The instantaneous concentrations of the gaseous products during the combustion of glycerol samples were detected using Fourier Transform Infrared Spectroscopy (FTIR, Gasmet DX-4000). The accurate composition at the outlet of the reactor makes it possible to evaluate and verify new kinetic models of the glycerol combustion in the fluidised bed. It also will be helpful in creating new simplified models. The data presented here is essential for the evaluation of CFD combustion models which have to include accurate kinetic data.

Characterization of Ethylene-propylene Composites Filled with Perlite and Vermiculite Minerals: Mechanical, Barrier, and Flammability Properties.

Perlite and vermiculite are naturally occurring minerals, commonly used by industry to obtain highly thermoisolative and/or non-flammable materials. However, there has been little research into the preparation and application of rubber compounds containing these inexpensive mineral fillers. Here, we show the benefits of perlite and vermiculite minerals as fillers for ethylene-propylene rubber (EPM) composites. To obtain more uniform dispersion and improved compatibility between the minerals and the elastomer matrix, 1-allyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (AMIMTFSI) and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BMIMTFSI) imidazolium ionic liquids (ILs) were added. The mineral fillers were found to be attractive semi-reinforcing fillers, which also act as flame retardants in the elastomer composites. Furthermore, a higher content of vermiculite mineral significantly reduced the air permeability of the composites. The incorporation of ionic liquids into the EPM-filled systems had a considerable effect on the torque increment, crosslink density, and more importantly the flammability of the studied compounds. The application of 2.5 parts per hundred parts of rubber (phr) BMIMTFSI, in particular, reduced the flammability of the EPM composite, as the maximum heat release rate (HRRmax) decreased from 189.7 kW/m2 to 170.2 kW/m2.

Impact of Basalt Filler and Ceramizable Additives on the Toxicity of Gaseous Products Emitted from Thermal Decomposition of Silicone Rubber Composites.

The article illustrates the impact of basalt filler in the form of flakes and fibres on the toxicity of gaseous products that formed during the thermal decomposition of silicone rubber composites. The values of specific emissions of gases were determined with the help of the IR spectroscopy and further applied to calculate the toxicometric index. The presented method of measuring the concentrations of gaseous products resulting from thermal decomposition consists in the application of a fluidised bed reactor, which makes it possible to conduct the decomposition of a sample at a precisely assumed temperature value and imitate the conditions of a real fire. At a temperature lower than 700 °C, the gases resulting from the thermal decomposition of composites are particularly toxic due to the presence of significant concentrations of formaldehyde that does not undergo oxidation to more stable inorganic products. At a temperature of 600 °C the toxicity of gases for the samples with ceramizable additives and without them was similar. In the first case, there appeared to be a positive synergistic effect of mineral and basalt additives, and the basalt additives themselves increased the toxicity of gases. At higher temperatures of decomposition, the exponentially increasing rate of the oxidation reaction in the gaseous phase results in the lack of significant differences between the toxicity of gases for the samples with and without basalt additives. The toxicometric index value at temperatures of 700 °C and 800 °C was by one or two orders of magnitude higher, respectively, than the one that was observed in the temperature range of 500-600 °C, as inorganic components appear in the place of formaldehyde.

Impact of Basalt Filler on Thermal and Mechanical Properties, as Well as Fire Hazard, of Silicone Rubber Composites, Including Ceramizable Composites.

This article illustrates the impact of basalt filler, both in the form of basalt flakes and basalt fibers, on thermal and mechanical properties, as well as on the fire hazard, of silicone rubber (SR) composites, including ceramizable composites. In addition to basalt filler, ceramizable composites contain mineral fillers in their composition in the form of silica and calcium carbonate, inorganic fluxes such as zinc borate and glass frit, and melamine cyanurate as a flame retardant. The obtained composites were analyzed from the point of view of their morphology, rheological and thermal properties, flammability, and mechanical properties before and after the ceramization process. The obtained research results indicate that the basalt filler has an unambiguous impact on the improvement of thermal properties and the reduction of flammability in the analyzed composites. The results of morphological analyses of ceramizable composites before and after the process of their ceramization indicate a definite impact of the basalt filler on the structure of the formed ceramic layer. An increase in its homogeneity exerts a direct impact on the improvement of its mechanical parameters.

Premixed LPG + Air Combustion in a Bubbling FBC with Variable Content of Solid Particles in the Bubbles.

This paper presents the results of studies on the combustion of gaseous LPG in a bubbling fluidized bed. Relationships between the temperature, the bed mass and the location of the combustion zone and the NOx and CO concentrations in exhaust gases are described. The concentrations of both gases increase with rising temperature and then quickly decline. It has been shown that despite the increase in average bed temperature the drop in the emission of nitrogen oxides is connected with lower temperatures inside the exploding bubbles. These temperatures strongly depend on the quantity of solid contained in them. The paper also presents the results of modeling the combustion process in a fuel-air bubble. The modeling carried out has shown that above the temperature at which bubble self-ignition becomes possible inside the bed, with further bed temperature rise there is an increase in the solids content inside the bubbles at the moment of explosion. As a result, the maximum temperature inside the bubbles falls and the emission of nitrogen oxides is reduced. In turn, the emission of CO is linked to the propagation of combustion between bubbles when self-ignition cannot take place inside them. Graphical AbstractComparison of experimental and calculated NOx concentration, as a function of the fluidised bed temperature Highlights1.A gaseous fuel burns in a bubbling fluidized bed2.The combustion is intermittent and takes place inside bubbles, the combustion process starts in the toroidal part of the bubble3.The NO concentration is linked to the bubble temperature, not to the bed temperature4.The solids inside a bubble affect its thermal capacity5.Consequently NO concentration falls with rising bed temperature.

Effect of POSS Particles and Synergism Action of POSS and Poly-(Melamine Phosphate) on the Thermal Properties and Flame Retardance of Silicone Rubber Composites.

This article presents flame retardant compounds for silicone rubber (SR) in the form of polyhedral oligomeric silsequioxanes (POSS), containing both isobutyl groups and amino-propyl (AM-POSS) or chloro-propyl group (HA-POSS) or vinyl groups (OL-POSS). Silsequioxanes were incorporated into the silicone rubber matrix in a quantity of 3 and 6 parts by wt by the method of reactive stirring with the use of a laboratory mixing mill. Based on the analyses performed by TG (Thermogravimetry) FTIR (Fourier Transform Infrared Spectroscopy), conical calorimeter, and SEM-EDX (Scanning Electron Microscopy and Energy Dispersive X-ray Spectroscopy) methods, the thermal degradation mechanism of non-cross-linked and cross-linked silicone rubber has been elucidated. The effects of POSS, and POSS in a synergic system with melamine polyphosphate (MPP), on the thermal properties and flammability of silicone rubber composites were presented. Based on the test results obtained, a mechanism of flame retardant action POSS and POSS-MPP has been proposed. It has been shown that POSS, especially with MPP, considerably increases the thermal stability and decreases the flammability of the SR rubber composites under investigation.

Thermal treatment of electronic waste in a fluidised bed and chemical digestion of solid products.

The article presents the results of e-waste thermal treatment in a fluidised bed reactor and solid products digestion under acidic conditions. During the processes, measurements of carbon monoxide, carbon dioxide, volatile organic compounds, nitrogen oxides, sulphur dioxide, hydrogen chloride, hydrogen bromide, hydrogen cyanide, ammonia, phenol, aliphatic and aromatic hydrocarbons, hydrogen fluoride and phosgene were carried out. Several digestion tests of the solid residue in sulphuric acid (VI) at 25 °C-65 °C, for 55 min-24 h were conducted. In each case, the dilution method was used, i.e. preliminary digestion in concentrated sulphuric acid (VI) (95%) for 40 min, and then dilution to expected concentrations (30%-50%). Most preferred results were obtained using sulphuric acid (VI) with a target concentration of 40% at 65 °C, where the leaching degrees were 76.56% for copper, 71.67% for iron, 91.89% for zinc and 97.40% for tin. The time necessary to effectively carry out the digestion process was 220 min.