Pyrolysis of poly-methyl methacrylate (PMMA) binder in thermoelectric green tapes made by the tape casting method

The pyrolysis of poly-methyl methacrylate (PMMA) binder in thermoelectric green tapes, are analysed through differential thermal analysis (DTA), thermogravimetric analysis (TGA). These analyses confirmed that the main mechanism of the PMMA binder decomposition is the depolymerization or the unzipping mechanism. The best pyrolysis procedure was found to be in air to a maximum temperature of 410°C with 1.30–2 h hold out time. Some small amount of binder residue was found to remain in tapes after the pyrolysis procedure. This was suspected to be due to an interaction between the thermoelectric powder and the PMMA binder. Despite this small residue, the thermoelectric tape was sintered successfully to almost 95% of its theoretical density, in vacuum at 1200°C after 4 h.     

Effects of CO Atmosphere on the Pyrolysis of a Typical Lignite

To reveal the effect mechanism of CO atmosphere on coal pyrolysis, a study on raw and demineralized lignite was carried out in a horizontal tube furnace under N₂ and CO/N₂ atmosphere. CO had a negligible effect on the char yield at low temperatures, whereas it enhances the char yield at temperatures higher than 550 °C. The release of tar was higher in the presence of CO above 450 °C because of more free radicals, which reduced low‐temperature crosslinking, and higher selectivity of hydroxyl groups to phenols in the CO‐containing atmosphere. The yields of CO₂ and H₂ increased, water and CO yields decreased under CO/N₂ atmosphere. Light hydrocarbon gases were not affected by changing the reaction atmosphere. The difference between product yields from raw and demineralized coal confirmed that the catalysis of inherent minerals had a great catalytic effect on the water‐gas shift reaction and Boudouard reaction.     

Fabrication of SiC-Whisker-Reinforced MoSi2 Composites by Tape Casting

In this paper, we describe a procedure for the processing of SiC-whisker-reinforced MoSi₂ composites via tape casting. Based on the characteristics of SiC whiskers and MoSi₂ powder in aqueous and nonaqueous solvents, a slip formulation (solvent, dispersant, binder, etc.) has been developed. The formulation developed allows for a uniform distribution of SiC whiskers in the matrix, easy separation of the tapes from the polymeric carrier, convenient control of both tape thickness and orientation of SiC whiskers, and a low binder burnout temperature. The latter is important for the prevention of the oxidation of MoSi₂ powder during the binder burnout in an oxidizing atmosphere.     

The influence of pyrolysis conditions on the subsequent gasification of lignocellulosic chars

Prune pit chars prepared by pyrolysis at heating rates of 1 and 15°C/min to 500, 700 and 900°C were subsequently gasified by exposure to CO₂ at 900°C for various lengths of time. Gasification rate was found to be dependent on the conditions during pyrolysis: slow heating below 500°C and prolonged exposure to high temperatures (~900°C) during pyrolysis in an inert atmosphere lead to lower rate gasification. Despite differences in gasification rate, the pore structure developed for a given mass loss due to the gasification reactions was apparently independent of the char preparation conditions. Pore volume in the gasified char (expressed on an absolute basis) passed through a maximum at 40–50% burnoff, apparently due to mass loss from the exterior of the particles.     

Low-temperature air oxidation of caking coals. 1. Effect on subsequent reactivity of chars produced

The effect of preoxidation of two highly caking coals in the temperature range 120–250 °C on weight loss during pyrolysis in a N₂ atmosphere up to 1000 °C and reactivity of the resultant chars in 0.1 MPa air at 470 °C has been investigated. Preoxidation markedly enhances char reactivity (by a factor of up to 40); the effect on char reactivity is more pronounced for lower levels of preoxidation. For a given level of preoxidation, the oxidation temperature and the presence of water vapour in the air used during preoxidation have essentially no effect on weight loss during pyrolysis and char reactivity. An increase in particle size of the caking coals reduces the rate of preoxidation as well as subsequent char reactivity. Preoxidation of caking coals sharply increases the surface area of the chars produced. Compared to heat treatment in a N₂ atmosphere, pyrolysis in H₂ of either the as-received or preoxidized coal results in a further increase in weight loss and a decrease in subsequent char reactivity.     

The volatilization behavior of chlorine in coal during its pyrolysis and CO2-gasification in a fluidized bed reactor

The volatilization behavior of chlorine in three Chinese bituminous coals during pyrolysis and CO₂-gasification in a fluidized bed reactor was investigated. The modes of occurrence of chlorine in raw coals and their char samples were determined using sequential chemical extraction method. The Cl volatility increases with increasing temperature. Below 600 °C the Cl volatility is different, depending on the coal type and the occurrence mode of Cl. Above 700 °C, the Cl volatilities for the three coals tested are all higher than 80%. About 41% of the chlorine in Lu-an coal and 73% of that in Yanzhou coal are organic forms, and most of them are covalently-bonded organic chlorine, which shows high volatile behavior even at low pyrolysis temperatures (below 500 °C), while the inorganic forms of chlorine in two coal samples are hardly volatilized even at low pyrolysis temperatures (below 400 °C). The restraining efficiency of addition of CaO on chlorine volatility is greatly dependent on pyrolysis temperature. The optimal restraining efficiency can be obtained at temperature range from 450 to 650 °C during pyrolysis of Lu-an coal. The volatile behavior of Cl is mainly dependent on temperature. Above 700 °C high volatility of Cl is obtained in both N₂ and CO₂ atmospheres.     

Novolac-Polydimethyl Siloxane networks through click chemistry: Thermal and Thermophysical characterization

Polydimethyl siloxane combs projecting from a novolac stem were synthesized using click reaction of azide-terminated polydimethylsiloxane (AZ-PDMS), and novolac propargyl ether (NPE) under ambient (30°C) conditions. Dynamic mechanical analyses (DMA) indicated the transition of soft segments at nearly −100°C and that of the hard segments in the range of 25°C-30°C. The hybrid novolac-siloxane networks have been found to possess an elongation at break of 100%–260%. Thermal degradation behavior of the networks of different crosslink densities was studied using TGA and pyrolysis GC-MS. Thermogravimetry revealed an anaerobic char residue of 23%–40% at 900°C. Further rise in temperature up to 1500°C has been observed to result in hardly 1% reduction in the char yield/ceramic residue, thus attributing to the presence of high char-yielding aromatic part. The ceramic residue obtained at 1500°C under argon atmosphere was analyzed using FTIR, Raman, and XRD. XRD studies implied formation of βSiC, and SiO₂. Morphology of the ceramics conformed to nanowires with diameters in the range of 20-100 nm. The nanowire consisted of mainly SiOC as attested by EDS analysis.     

Thermal studies on kraft black liquor

Kraft black liquor and lignin from the same batch were subjected to thermal analysis (DTA and TGA) under an inert atmosphere and also in an oxidising atmosphere to simulate conditions which might be encountered in the recovery furnace. Gasification studies were carried out by rapidly heating the sample under helium. Results showed that the thermal decomposition of black liquor can be divided into four characteristic steps: drying up to 200°C, pyrolysis between 200 and 550°C, inorganic sodium salt formation between 550 and 800°C and salt fusion between 800 and 1000°C. Gases evolved during gasification of black liquor are rich in flammable compounds while those from the lignin sample are rich in CO₂.     

Optimization of non-aqueous tape casting of high solid loading slurry for aluminum nitride ceramic substrates

Aluminum nitride (AlN) ceramic substrates have been fabricated using non-aqueous tape casting and pressureless densification under flowing N₂ atmosphere. Considering the economic and environmental impact, a new strategy of solvent and dispersant system was adopted to prepare AlN slurries with high solid loading. According to the viscosity characteristics of AlN slurries, dispersant content was adjusted to be 0.5 wt% of AlN powder in order to optimize the rheological behavior of AlN slurries. The addition contents of binder and plasticizer were both optimized as 5 wt% of AlN powders by combining the viscosity of slurries and tensile strength of green tapes. Green AlN tapes were fabricated with an optimized tape casting process such as dry temperature. The exclusion process of organic additives was investigated by employing thermogravimetric analysis. Flat and dense AlN ceramic substrates with a relative bulk density over 99.75 % were achieved after being sintered under 1800°C for 6 hours, which had a maximum size of 110 × 110 mm. The thermal conductivity of the AlN substrate could reach 145 Wm⁻¹K⁻¹.     

Value-added products from waste: Slow pyrolysis of used polyethylene-lined paper coffee cup waste

The objectives of this study were to examine how to recycle cup waste efficiently and effectively and to determine if cup waste can be converted into liquid, solid, and gas value-added products by slow pyrolysis. The characteristics and potential utilizations of the pyrolysis products were investigated. The study included the effects of temperature, heating rate, and different feedstocks. The yield of pyrolysis oil derived from cup waste increased from 42% at 400°C to 47% at 600°C, while the yield of char decreased from 26% at 400°C to approximately 20% at 600°C. Acetic acid and levoglucosan were identified as the main components of the pyrolysis oil. The char obtained at 500°C was physically activated at 900°C for 3 h with CO₂. The adsorption capacity of the activated char was investigated with model compounds, such as methyl orange, methylene blue, ibuprofen, and acetaminophen. The results showed that the adsorption capacity of the activated char was similar to that of commercial activated carbon produced from peat. The higher heating value of the produced gas stream calculated at 400°C was 19.59 MJ/Nm³. Also, conventional slow pyrolysis (CSP) and microwave-assisted pyrolysis (MAP) technologies were compared to determine the differences in terms of products yields, composition and characteristics of the pyrolysis oil, and their potential applications. The CSP yields higher liquid products than MAP. Also, the pyrolysis oil obtained from the CSP had significantly more levoglucosan and acetic acid compared to that of the MAP.     

Thermogravimetric characteristics and pyrolysis kinetics of Giheung Respia sewage sludge

Sewage sludge acquired from Giheung Respia treatment facility was characterized and converted into gas, bio-oil and char by pyrolysis. The rate of conversion as a function of temperature was obtained from differential thermogravimetric analysis (DTG) for different heating rates. The activation energy calculated from data selected conversions shows that the activation energy decreased with increasing conversion up to 10%, steadily increased from 10 to 70%, and substantially increased from 70 to 90%. Depending on the level of conversion, the values of activation energies varied between 181 and 659 kJ/mol. The gas product obtained in the experiment at 450 °C, 20 min mainly included CO₂ (30%), CO (23%) and CH₄ (17%). The product yields of gas, oil and char were systematically studied by changing the pyrolysis temperature and residence time.     

Active carbon from scrap tyres

The possibility of producing active carbon by activation at 850 °C of the char obtained from the pyrolysis (at 450 and 600 °C) of scrap tyres has been studied. The activated char showed good adsorbing characteristics, similar to those of typical commercial grades. The yield and the desired adsorbing capacity depend on the activation time. However, the ash content and friability are quite high; therefore the activated char is suitable for applications in powder form in which the ash does not cause problems.     

Role of organic additives on non-aqueous tape casting of SiAlON ceramics

Suspensions consisting of precursor α/β SiAlON forming powders, azeotropic solvent mixture of 60 MEK/40E, dispersant, binder, and plasticizer were optimized for tape casting by rheological measurements and tape properties. Sodium tripolyphosphate (STPP) was introduced as a dispersant for low temperature applications of α/β-SiAlONs. Optimum STPP amount was determined as 0.012 g/m² (of the particle surface) for stable α/β-SiAlON suspensions. Different amounts of binder/plasticizer mixtures were added to the slurries and the effects on rheological and green tape properties were investigated. Green tapes with dibutyl phthalate (DBP), and plasticizer mixture, poly(ethylene glycol) (PEG) and DBP, exhibited centered cracks with high plasticity, on the other hand, polyvinyl butral (PVB) and PEG showed no crack but low plasticity. Therefore, many different parameters were found to be effective on final tape properties. In addition, tapes were prepared with 6 vol% PVB + PEG, sintered at 1800 °C for 2 h and exhibited almost 97%TD in room temperature applications of α/β SiAlONs.     

CO2 gasification of wood charcoals derived from vacuum and atmospheric pyrolysis

The gasification of biomass derived char obtained via vacuum and atmospheric pyrolysis of Populus tremuloides has been studied in the ranges of 725–960°C and 0.1 to 6 MPa. CO₂ was used as the oxidizing gas. The results show that char reactivity is influenced by the preheating rates and that pressure effects are significant between 850°C and 950°C. A correlation based on the expression: df/dt = k₀{exp(-E/RT)}(1 - f)^af^βP^yCO₂ was used to fit the experimental data. In general, vacuum pyrolysis derived char showed a higher reactivity than atmospheric pyrolysis chars. An explanation based on a higher oxygen content of the vacuum pyrolysis char is suggested.     

Effects of Atmospheric Composition on the Molecular Structure of Synthesized Silicon Oxycarbides

The dependence of silicon oxycarbides' chemical composition and molecular structure on their reaction conditions was tested by varying the atmosphere under which pyrolysis was performed. To obtain the silicon oxycarbides, densely cross‐linked silicone resin particles with an averaged diameter of 2 μm were pyrolyzed in various atmospheres of H₂, Ar, and CO₂, in the temperature range 700°C–1100°C. The residual mass of resin after pyrolysis was almost constant at 700°C, although their apparent colors varied distinctly. The sample obtained from the H₂ atmosphere was white, whereas that obtained from the CO₂ atmosphere was dark brown. Fourier‐transform infrared (FT‐IR) spectra of the residues suggested that the Si–O–Si network evolution was accelerated in the CO₂ atmosphere. Beyond 800°C, the chemical compositions of the compounds obtained from a H₂ atmosphere increasingly approached near‐stoichiometric SiO₂–xSiC composition with increasing the pyrolysis temperature. Compounds from a CO₂ atmosphere approached a composition of SiO₂–xC with no free SiC as the pyrolysis temperature increased. In the products from an Ar atmosphere, SiO₂–xSiC–yC compositions were typically obtained. The observed effects of the pyrolysis atmosphere on the resulting chemical compositions were analyzed in terms of thermodynamic calculations. Electron spin resonance (ESR) spectra revealed broad and intense signals from products obtained from either Ar or CO₂. Estimating from the signal intensity, the residual spin concentrations were in the range 10¹⁸–10¹⁹ g^?1. Meanwhile, the spectra from the samples obtained in H₂ showed weak and sharp signals with estimated spin concentrations ranging from 10¹⁶–10¹⁷ g^?1. This signal attenuation may have been due to the hydrogen capping of dangling bond formed during pyrolysis.     

Liquefaction of cellulosic wastes: III. Production,characterization and evaluation of pyrolytic oils

Liquefaction of municipal solid wastes has been achieved in an atmosphere of hydrogen gas and in the presence of boric acid which catalyzes the pyrolysis reaction. Two petroleum distillates, namely gas oil and residual fuel oil, were used as carrier media of solid refuse. The yield of pyrolytic oil was studied as a function of different operational conditions (temperature, pressure of hydrogen, carrier oil medium and concentration of boric acid). Hydrocarbon constituents of the oil mixtures, produced by liquefaction of cellulosic wastes slurried in fuel oil, were investigated by means of gas chromatography. It was found that the oil mixture, obtained at optimum reaction conditions, showed pronounced occurrence of low hydrocarbons in the range C₃-C₁₅ as compared with the original fuel oil and the oil resulting from the pyrolysis of carrier oil without solid refuse. The residual pyrolytic char exhibited catalytic activity towards hydrocracking. It was suggested that the activity of char is due to the presence of transition metals as evidenced by an electron dispersion system (EDS). The hydrocracking activity of char seemed to be dependent on the operational conditions of the liquefaction. Multiple analytical parameters including API gravity, calorific value, total acid number and wt% of residue over 450°C were used to evaluate the oil mixtures produced as a petroleum crude oil. Carrier oils, particularly fuel oil, seemed to be highly modified in the course of the pyrolysis process. Also, the oil mixtures produced were distinguished from the original carrier oils by a considerably higher acidity due to association with oxygenated compounds which could be derived from cellulose macromolecules.     

The effect of steam on pyrolysis and char reactions behavior during rice straw gasification

Steam gasification of biomass can generate hydrogen-rich, medium heating value gas. We investigated pyrolysis and char reaction behavior during biomass gasification in detail to clarify the effect of steam presence. Rice straw was gasified in a laboratory scale, batch-type gasification reactor. Time-series data for the yields and compositions of gas, tar and char were examined under inert and steam atmosphere at the temperature range of 873-1173 K. Obtained experimental results were categorized into those of pyrolysis stage and char reaction stage. At the pyrolysis stage, low H₂, CO and aromatic tar yields were observed under steam atmosphere while total tar yield increased by steam. This result can be interpreted as the dominant, but incomplete steam reforming reactions of primary tar under steam atmosphere. During the char reaction stage, only H₂ and CO₂ were detected, which were originated from carbonization of char and char gasification with steam (C + H₂O→CO + H₂). It implies the catalytic effect of char on the water-gas shift reaction. Acceleration of char carbonization by steam was implied by faster hydrogen loss from solid residue.     

Mechanical Properties of Gd‐CeO2 Electrolyte for SOFC Prepared by Aqueous Tape Casting

Mechanical properties of gadolinium‐doped ceria (Ce_0.9Gd_0.1O_1.95, 10GDC) green tape prepared by aqueous‐based tape casting process were characterized by tensile test and shear punch test (SPT). SPT was found to be a useful method for characterizing mechanical properties of green tapes. Microstructures and mechanical properties such as flexural modulus, bending strength, and microhardness of tapes sintered at 1,300–1,500 °C have been evaluated. Indentation fracture toughness was also determined by the method of Palmqvist cracks at different applied loads for tapes sintered at 1,500 °C. Grain size measurements showed that excessive grain growth occurred during sintering despite using 10GDC nanopowders as the starting material. However, mechanical properties of sintered tapes improved by increasing sintering temperature and the results are comparable with those reported for 10GDC in literature.     

Thermal and catalytic pyrolysis of a synthetic mixture representative of packaging plastics residue

A synthetic mixture of real waste packaging plastics representative of the residue from a material recovery facility (plasmix) was submitted to thermal and catalytic pyrolysis. Preliminary thermogravimetry experiments coupled with Fourier transform infrared spectroscopy were performed to evaluate the effects of the catalysts on the polymers’ degradation temperatures and to determine the main compounds produced during pyrolysis. The thermal and catalytic experiments were conducted at 370°C, 450°C and 650°C using a bench scale reactor. The oil, gas, and char yields were analyzed and the compositions of the reaction products were compared. The primary aim of this study was to understand the effects of zeolitic hydrogen ultra stable zeolite Y (HUSY) and hydrogen zeolite socony mobil-5 (HZSM5) catalysts with high silica content on the pyrolysis process and the products’ quality. Thermogravimetry showed that HUSY significantly reduces the degradation temperature of all the polymers—particularly the polyolefines. HZSM5 had a significant effect on the degradation of polyethylene due to its smaller pore size. Mass balance showed that oil is always the main product of pyrolysis, regardless of the process conditions. However, all pyrolysis runs performed at 370°C were incomplete. The use of either zeolites resulted in a decrease in the heavy oil fraction and the prevention of wax formation. HUSY has the best performance in terms of the total monoaromatic yield (29 wt-% at 450°C), while HZSM5 promoted the production of gases (41 wt-% at 650°C). Plasmix is a potential input material for pyrolysis that is positively affected by the presence of the two tested zeolites. A more effective separation of polyethylene terephthalate during the selection process could lead to higher quality pyrolysis products.     

The effect of inorganic additives on the formation,composition, and combustion of cellulosic char

At temperature above 300°C the glycosyl units of cellulose are simultaneously depolymerized to a tar and decomposed to a char by evolution of H₂O, CO, and CO₂. When the glycosyl units are depleted, a stable char is formed containing about 30% aliphatic and 70% aromatic components. The aliphatic component is formed first, but on further heating is converted to polycyclic aromatic structures. The chars formed at lower temperatures are more combustible because the aliphatic component of the char is highly pyrophoric and is oxidized almost at the same temperature at which it is formed (～360°C). The aromatic component, however, is less reactive and is oxidized at ～520°C. Consequently, the chars formed at higher temperatures are less combustible. It has been shown that (NH₄)₂HPO₄, which is a well-known flame retardant and smoldering inhibitor, lowers the pyrolysis temperature and increases the char yield by accelerating the decomposition reactions. This affects the composition of the intermediate chars but the final products have about the same composition irrespective of additives. (NH₄)₂HPO₄ also lowers the rate of oxidation of the aromatic component and the corresponding heat release. NaCl, which is an enhancer of smoldering combustion, has a slight stabilizing effect on pyrolysis of cellulose. It lowers the oxidation temperature of the aromatic component and dramatically increases its rate. The corresponding heat release is also increased due to complete oxidation to CO₂. The rate of oxidation calculated from the dynamic thermal analysis data is more than tripled by NaCl and significantly reduced by (NH₄)₂HPO₄.