Mechanical properties and fracture behaviors of C/C composites with PyC/TaC/PyC,PyC/SiC/TaC/PyC multi-interlayers

Carbon/carbon (C/C) composites with PyC/TaC/PyC or PyC/SiC/TaC/PyC multi-interlayers were prepared by isothermal chemical vapor infiltration, followed by Furan resin impregnation and carbonization. Microstructures, mechanical properties including flexural strength, ductile displacement, and fracture behaviors of composites were studied. Furthermore, composites were heat treated at 2000 °C to study the effects of heat treatment on mechanical properties and fracture behaviors. PyC/TaC/PyC and PyC/SiC/TaC/PyC multi-interlayers have been deposited uniformly in C/C composites. With the introduction of PyC/TaC/PyC multi-interlayers in C/C composites, the flexural strength decreases; however, the ductile displacement increases. The fracture behavior changes from brittleness (0% TaC) to pseudo-ductility (5% TaC) and high toughness (10% TaC). When PyC/SiC/TaC/PyC multi-interlayers are introduced in C/C composites, the flexural strength is improved remarkably from 270 MPa to 522 MPa, but the ductile displacement decreases obviously from 0.49 mm to 0.24 mm, and the fracture behavior becomes brittle again. After heat treatment at 2000 °C, the flexural strength decreases, but the ductile displacement increases and pseudo-ductility or high toughness can be obtained.     

Modelling physical properties of highly crystallized polyester reinforced with multiwalled carbon nanotubes

The effects of carbon nanotubes dispersion into thermoplastic polymers are complex and strongly dependent upon their aggregation state. A poly(ethylene terephthalate) (PET) matrix has been reinforced through addition of multiwalled carbon nanotubes (MWCNTs). Such an addition has generated an increase in flexural modulus and a decrease in flexural strength at room temperature, and an increase in both properties above the glass transition temperature (at 100 °C). These different behaviours, dictated by temperature, have been investigated through two different micromechanical models that have permitted to put forward hypothesis on failure mechanisms and to shed light on the role played by crystalline phase. The results of thermal analyses have shown that the heat capacity of PET nanocomposites varies according to the MWCNTs content as the flexural modulus. Such a similarity has suggested to modify the Halpin-Tsai equations (H-T), typically used to predict elastic properties of short fibres reinforced composites, in order to determine the relationships occurring between PET specific heat and aspect ratio of dispersed MWCNT. The analyses performed by means of either classical H-T (elastic modulus) or modified H-T (heat capacity) equations, provided very similar estimation of the MWCNT aspect ratios. In addition, a simple elaboration of the modified H-T equations permitted the calculation of rigid amorphous fraction (RAF) into PET. The obtained values were slightly higher than those evaluated by means of a procedure based on the loss tangent peak variation measured through dynamic mechanical experiments. The detected strength decrease at 25 °C have been attributed to crack propagation through a percolative path between crystalline coating layer of MWCNTs and PET (favoured by matrix brittleness), while at 100 °C the crack propagation is hampered by rubbery behaviour of the matrix.     

Application of Design of Experiment (DoE) for Parameters Optimization in Compression Moulding for Flax Reinforced Biocomposites

Lately, widespread research on polymer composites that consist of natural fiber as reinforcement have been widely discussed. In this work, an attempt on optimizing the hot press forming process parameters using Response Surface Methodology (RSM) have been made to improve the mechanical properties of the woven flax/PLA composites. Three independent process variables, including moulding temperature, time and pressure were studied. Through the Box Behnken approach, a set of experiment runs based on various combination of compression moulding via Minitab 16 were established. As a results the optimum value for the variables of compression moulding technique parameters were 200 °C, 3 min and 30 bar in order to yield 48.902 kJ/m^-2ofimpact strength.     

Synthesis of polyacrylamide-bound hydroquinone via a homolytic pathway: Application to the removal of heavy metals

Polyacrylamide (PAAm) was chemically modified with hydroquinone (HQ) via a homolytic route. A degree of modification of approximately 58% was obtained under optimal reaction conditions: time of 6 h, and [modifier]/[acrylamide] molar ratio of 5. PAAm and its modified form HQ–PAAm were characterized by UV–visible spectroscopy, FT–IR spectroscopy, ¹³C NMR spectroscopy, DSC, TGA, XRD, and SEM. A relatively lower molecular weight of the corresponding hydroquinone-functionalized form was measured. The glass transition temperature of the modified polymeric material was lower than that of the pristine one: 78.82 °C for HQ–PAAm versus 161.19 °C for PAAm. A study of Cu(II) adsorption by the cross-linked PAAm and HQ–PAAm resins was conducted by varying the following parameters: pH, time, temperature, ionic strength, sorbent mass, and initial Cu(II) concentration. The adsorption capacity of Pb(II) and Cd(II) by the different resins and their corresponding extents of desorption were estimated. The optimal conditions for metal ion uptake by polyacrylamide and its modified resin were: pH = 5.4, time = 120 min, temperature = 45 °C. The sorption extent by the modified resin was in the order Pb(II) > Cu(II) > Cd(II). The desorption of the experimented metallic ions from the resins exceeded 97%. A new way of cross-linking PAAm and its modified form is described herein.     

Structure characteristics contributing to flame retardancy in diazo modified novolac resins

The physical characteristics of two modified novolac resins (carbonyl phenyl azo novolac resin; CPAN and 4-(4-hydroxyphenyl azo) benzyl ester novolac resin; HPDEN) bearing nitrogen and aromatic functional groups by diazo-coupling or esterification in the branch structure of phenol novolac resin were examined. Presence of the modifiers raised the phenolic decomposition temperature (5% weight loss) from 300 °C (pure Phenolic) to 330 °C and 380 °C, while the char residue increased from 45% to 56% and 68%, respectively. The kinetics for thermal degradation energies (E_a) also rose from 151 kJ/mol K to 254 kJ/mol K (CPAN) and 273 kJ/mol K (HPDEN). The retarded decomposition kinetics is attributed both to the increase of crosslink densities and high aromatic content in the derivative resins. On the other hand, the diazo-coupling or phenyl diazenyl ester produces non-combustible gases (N₂, CO₂ and CO) during formation of aromatic char which dilute the ambient oxygen gas. Both the production of gases and the retarded kinetics due to cross-linking are definitive for the improved flame resistance.     

Influence of FCC catalyst steaming on HDPE pyrolysis product distribution

A commercial FCC catalyst based on a zeolite active phase has been used in the catalytic pyrolysis of HDPE. The experimental runs have been carried out in a conical spouted bed reactor provided with a feeding system for continuous operation. Different treatments have been applied to the catalyst to improve its behaviour. This paper deals with the optimization of catalyst steaming and pyrolysis temperature in order to maximize the production of diesel-oil fraction. The performance of the fresh catalyst has been firstly studied at 500 °C. This catalyst gives way to 52 wt% gas yield, 35 wt% light liquid fraction and a low yield of C₁₀⁺ fraction (13 wt%). After mild steaming (5 h at 760 °C) the results show a significant improvement in product distribution. Thus, gas yield decreases to 22 wt%, the yield of light liquid is similar to that of the fresh one (38 wt%), whereas the yield of the desired C₁₀⁺ fraction increases to 38 wt%. Nevertheless, the best results have been obtained when a severe steaming is applied to the catalyst (8 h at 816 °C) and pyrolysis temperature is reduced to 475 °C. There is a significant reduction in the gaseous fraction (8 wt%). The light liquid fraction has also been reduced to 22 wt%, but the yield of diesel fraction increases to 69 wt%. Moreover, the deactivation of the catalyst has also been studied under the optimum conditions.     

Properties of Calcium Phosphate Scaffolds Produced by Freeze-Casting

The pore structure of three-dimensional scaffolds applied in tissue engineering may influence the mechanical properties and cellular activity. As the optimal pore size is dependent on the specifics of the biomaterial or tissue engineering application, the ability to alter the pore size over a wide range is necessary for several scaffolds in order to meets the requirements of the applications. The aim of this study is to develop methodologies to produce calcium phosphate scaffolds with acceptable pore size and defined pore-channel interconnectivity. The pore size of calcium phosphate scaffolds is established during the freeze-drying fabrication process. In this process, material suspension is simply frozen and then dried by freeze-drier, which able to produce material with unique porous architectures, where the porosity is almost a direct replica of the frozen solvent crystals. There are two different method of freeze-casting carried out in order to study the effect of freezing temperature by which in the first method; sample being soaked with liquid nitrogen (-196 °C) for about 10 minutes before been place inside a freezer (-40 °C). In the second method, the sample was directly placed inside a freezer for casting at temperature of -40 ̊C. The results show that the pore size of the scaffolds decreased as the freezing temperature was reduced. Taken together, these results demonstrate that the methodologies applied in this study can be used to produce a range of calcium phosphate scaffolds exhibiting better compressive strength, approximately 665-875 KPa for 54-64.3% of porosity with mean pore size from 102-113 μm. The methods developed in this study provide a basis for the investigation on the effects of different freezing temperature in freeze-casting process on the porosity, morphology, and compressive properties of the calcium phosphate scaffolds.     

A new calcium trimellitate coordination polymer with a chain-like structure

The calcium trimellitate, Ca(H₂O)[(O₂C)₂–C₆H₃–CO₂H], was hydrothermally synthesized from a mixture of calcium hydroxide, 1,2,4-benzenetricarboxylic (or trimellitic) acid and water at 180 °C for 24 h (under autogenous pressure). Its crystal structure has been determined by single-crystal X-ray diffraction analysis using synchrotron radiation (station 9.8, SRS Daresbury, UK). It consists of infinite chains of calcium bicapped trigonal prismatic polyhedra connected to each other through the 1,2,4-benzenetricarboxylate ligand. The eight-fold coordinated calcium cation is bonded to one terminal water molecule, two carboxylate groups with a chelating conformation and three carboxylate groups in a monodentating mode. One of the monodentate carboxylate is terminal with the occurrence of protonated C–OH bonding.Triclinic space group P-1 with a = 6.9073(4) Å, b = 6.9917(4) Å, c = 10.3561(6) Å, α = 87.178(1)°, β = 83.233(1)°, γ = 69.576(1)°, V = 465.41(5) Å³.     

Thermal degradation and evolved gas analysis: A polymeric blend of urea formaldehyde (UF) and epoxy (DGEBA) resin

A polymeric blend has been prepared using urea formaldehyde (UF) and epoxy (DGEBA) resin in 1:1 mass ratio. The thermal degradation of UF/epoxy resin blend (UFE) was investigated by using thermogravimetric analyses (TGA), coupled with FTIR and MS. The results of TGA revealed that the pyrolysis process can be divided into three stages: drying process, fast thermal decomposition and cracking of the sample. There were no solid products except ash content for UFE during combustion at high temperature. The total mass loss during pyrolysis at 775 °C is found to be 97.32%, while 54.14% of the original mass was lost in the second stage between 225 °C and 400 °C. It is observed that the activation energy of the second stage degradation during combustion (6.23 × 10⁻⁴ J mol⁻¹) is more than that of pyrolysis (5.89 × 10⁻⁴ J mol⁻¹). The emissions of CO₂, CO, H₂O, HCN, HNCO, and NH₃ are identified during thermal degradation of UFE.     

Semivolatile and volatile compounds from the pyrolysis and combustion of polyvinyl chloride

Emissions evolved from the pyrolysis and combustion of polyvinyl chloride (PVC) were studied at four different temperatures (500, 700, 850 and 1000 °C) in a horizontal laboratory tubular quartz reactor in order to analyse the influence of both temperature and reaction atmosphere on the final products from thermal and oxidative reactions. It was observed that the CO₂/CO ratio increased with temperature. Methane was the only light hydrocarbon whose yield increased with temperature up to 1000 °C. Benzene was rather stable at high temperatures, but in general, combustion at temperatures above 500 °C was enough to destroy light hydrocarbons. Semivolatile hydrocarbons were collected in XAD-2 resin and more than 160 compounds were detected. Trends on polyaromatic hydrocarbon (PAH) yields showed that most had a maximum at 850 °C in pyrolysis, but naphthalene at 700 °C. Formation of chlorinated aromatics was detected. A detailed analysis of all isomers of chlorobenzenes and chlorophenols was performed. Both of them reached higher total yields in combustion runs, the first ones having a maximum at 700 °C and the latter at 500 °C. Pyrolysis and combustion runs at 850 °C were conducted to study the formation of polychlorodibenzo-p-dioxins (PCDDs) and polychlorodibenzofurans (PCDFs). There was more than 20-fold increase in total yields from pyrolysis to combustion, and PCDF yields represented in each case about 10 times PCDD yields.     

Oxygen selective ceramic hollow fiber membranes

Oxygen ion conducting Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ hollow fiber membranes with o.d. 1.15 mm and i.d. 0.71 mm were fabricated using a sequence of extrusion, gelation, coating and sintering steps. The starting ceramic powder was synthesized by combined EDTA–citrate complexing followed by thermal treatment at 900 °C. The powder was then dispersed in a polymer solution, and extruded through a spinerette. After gelation, an additional thin coating of the ceramic powder was applied on the fiber, and sintering was carried out at 1190 °C to obtain the final ceramic membrane. The fibers were characterized by SEM, and tested for air separation at ambient pressure and at temperatures between 700 and 950 °C. The maximum oxygen flux measured was 5.1 mL/min/cm² at 950 °C.     

Formation and characterization of magnetic barium ferrite hollow fibers with high specific surface area via sol–gel process

The magnetic barium ferrite (BaFe₁₂O₁₉) hollow fibers with a high specific surface area about 22–38 m² g^?1, diameters around 1 μm and a ratio of the hollow diameter to the fiber diameter estimated about 1/2–2/3 have been prepared by the gel-precursor transformation process. The precursor and resulting ferrite hollow fibers were analyzed by thermo-gravimetric and differential scanning calorimetry, infrared spectroscopy, scanning electron microscopy and X-ray diffraction. The specific surface area was measured by the Brunauer–Emmett–Teller method. The gel formed at pH 5.5 has a good spinnability. A pure barium ferrite phase is formed after calcined at 750 °C for 2 h and fabricated of nanograins about 38 nm with a hexagonal plate-like morphology, which are increased to about 72 nm with the calcination temperature increased up to 1050 °C. The barium ferrite hollow fibers obtained at 750 °C for 2 h have a specific surface area 38.1 m² g^?1 and average pore size 6.5 nm and then the specific surface area and average pore size show a reduction tendency with the calcination temperature increasing from 750 to 1050 °C owing to the particle growth and fiber densification. These barium ferrite hollow fibers exhibit typical hard-magnetic materials characteristics and the formation mechanism for hollow structures is discussed.     

Efficient synthesis of methyl carbamate via Hofmann rearrangement in the presence of TsNBr2

An efficient method has been developed for the synthesis of carbamates from the corresponding amides via the Hofmann rearrangement using N,N-dibromo-p-toluenesulfonamide (TsNBr₂) in the presence of DBU in methanol. The reaction goes into completion in 10–20 min at 65 °C to produce the corresponding carbamate in excellent yield.     

Utilization of Low-grade Iron Ore in Ammonia Decomposition

Due to its cleanliness, fast energy cycle, and convenience of energy conversion, hydrogen has been regarded as the new energy source. Conventional process to produce hydrogen yield large amount of CO as byproduct. Moreover, the hydrogen storage and transportation have become the drawbacks in hydrogen economy. Thus, there has been increased interest in the hydrogen transportation medium as alternatives from the conventional process to produce and transport hydrogen. Ammonia has drawn worldwide attention as the most reliable hydrogen transportation medium. Through the decomposition of ammonia, hydrogen and nitrogen gas were produces as the byproduct without any CO or CO₂ emission. In this experiment, the ore were introduced as the medium for ammonia decomposition. The ore were put into quartz tube reactor and were dehydrated at 400 °C for 1 hour, then hydrogen reduced for 2 hours before and undergone ammonia decomposition at 500-700 °C for 3 hours. The effects of temperature to the % conversion of ammonia decomposition were also studied. Ammonia decomposition at higher temperature gives higher conversion. As seen in the results, the NH₃ conversion decreased with increasing time and the value after 3 hours of reaction increased in the sequence of 500 °C<600 °C< 700 °C. During ammonia decomposition, nitriding of iron occurred. The relation between temperature and the nitriding potential, K_N is also investigated. The purpose of this study is to investigate the utilization of low-grade ore as medium for ammonia decomposition to produce hydrogen.     

Pyrolytic behavior of cellulose in presence of montmorillonite K10 as catalyst

Cellulose and cellulose/montmorillonite K10 mixtures of different ratio (9:1, 3:1, 1:1) were subjected to pyrolysis at temperatures from 350 to 500 °C with different heating rate (10 °C/min, 100 °C/s) to produce bio-oil and selected chemicals with high yield. The pyrolytic oil yield was in the range of 46–73.5 wt% depending on the temperature, the heating rate and the amount of catalyst. The non-catalytic fast pyrolysis at 500 °C gives the highest yield of bio-oil (84 wt%). The blending cellulose with increasing amount of montmorillonite K10 results in significant, linear decrease in bio-oil yield. The great influence of montmorillonite K10 amount on the distribution of bio-oil components was observed at 450 °C with a heating rate of 100 °C/s. The addition of catalyst to cellulose promotes the formation of 2-furfural (FF), various furan derivatives, levoglucosenone (LGO) and (1R,5S)-1-hydroxy-3,6-dioxabicyclo-[3.2.1]octan-2-one (LAC). Simultaneously, the share of levoglucosan (LG) in bio-oil decreases from 6.92 wt% and is less than 1 wt% when cellulose:MK10 (1:1, w/w) mixture at 450 °C is rapidly pyrolyzed. Additionally, several other compounds have been identified but in minor quantities. Their contributions in bio-oil also depend on the amount of catalyst.     

Kinetics of Calcium Oxalate Reduction in Taro (Colocasia Esculenta) Corm Chips during Treatments Using Baking Soda Solution

The oxalates content has caused limited utilizations of taro (Colocasia esculenta) as a food material. The insoluble oxalates, especially needle like calcium oxalate crystal may cause irritation, and swelling of mouth and throat. Removal of oxalates in food can be done by physical processes, such as soaking, boiling, and cooking or chemical process by converting them into soluble phases. The purpose of this research were to investigate the effects of baking soda concentration (0-10% w/w) and temperatures (70-97 °C) on the reduction of calcium oxalate content in the taro corm chips and to develop a kinetic model of that process during boiling in baking soda solution. The kinetic model development was done by considering the dissolution of calcium oxalate, chemical reaction and thermal degradation that take place during boiling. The experimental results showed that increasing of baking soda concentration and temperatures were found to increase the reduction of calcium oxalate in the taro corm chips. Based on the product's functional properties, the best condition for calcium oxalate reduction was soaking in 10% w/w baking soda solution for 2 hours followed by boiling at 90 °C for 60 minutes. The kinetic modeling concluded that the calcium oxalate reduction was found to follow a pseudo first order reaction. The modeling results showed that the model is able to represent the phenomena quite well with the apparent reduction rate constant, k = 15.77 Exp (21.239)/RT minute^-1.     

The electrochemical properties of thermophilic cytochrome P450 CYP119A2 at extremely high temperatures in poly(ethylene oxide)

The electrochemical measurements were carried out by using thermophilic cytochrome P450 CYP119A2 (P450st) modified with poly(ethylene oxide) (PEO) in PEO₂₀₀ as an electrochemical solvent. The PEO modified P450st gave clear reduction–oxidation peaks by cyclic voltammetry in oxygen-free PEO₂₀₀ up to 120 °C. The midpoint potential measured for the P450st was −120 mV vs. [Fe(CN)₆]⁴⁻/[Fe(CN)₆]³⁻ at 120 °C. The peak separation, ΔE, was 16 mV at 100 mV/s. The estimated electron transfer rate of PEO-P450st at 120 °C was 35.1 s⁻¹. The faster electron transfer reaction was achieved at higher temperatures. The electrochemical reduction of dioxygen was observed at 115 °C with the PEO-modified P450st system.     

Development of novel low-temperature SOFCs with co-ionic conducting SDC-carbonate composite electrolytes

A series of ceria-based composite materials consisting of samaria doped ceria (SDC) and binary carbonates(Li₂CO₃–Na₂CO₃) were examined as functional electrolytes for low-temperature solid oxide fuel cells (SOFCs). DTA and SEM techniques were applied to characterize the phase- and micro-structural properties of the composite materials. Conductivity measurements were carried on the composite electrolytes with a.c. impedance in air. A transition of ionic conductivity with temperature was occurred among all samples with different carbonate content, which related to the interface phase. Single cells based on the composite electrolytes, NiO as anode and lithiated NiO as cathode, were fabricated by a simple dry-pressing process and tested at 400–600 °C. The maximum output power at 600 °C increased with the carbonate content in the composite electrolytes, and reached the maximum at 25 wt.%, then decreased. Similar trend has also shown at 500 °C, but the maximum was obtained at 20wt.%. The best performances of 1085 mW cm⁻² at 600 °C and 690 mW cm⁻² at 500 °C were achieved for the composite electrolytes containing 25 and 20 wt.% carbonates, respectively. During fuel cell operation, it found that the SDC-carbonate composites are co-ionic (O²⁻/H⁺) conductors. At lower carbonate contents, both oxide–ion and proton conductions were significant, when the content increased to 20–35 wt.%, proton conduction dominated. The detailed conduction mechanism in these composites needs further investigation.     

Evaluation of the porous structure development of chars from pyrolysis of rice straw: Effects of pyrolysis temperature and heating rate

The effects of pyrolysis temperature and heating rate on the porous structure characteristics of rice straw chars were investigated. The pyrolysis was done at atmospheric pressure and at temperatures ranging from 600 to 1000 °C under low heating rate (LHR) and high heating rates (HHR) conditions. The chars were characterized by ultimate analysis, field emission scanning electron microscope (FESEM), helium density measurement and N₂ physisorption method. The results showed that temperature had obvious influence on the char porous characteristics. The char yield decreased by approximately 16% with increasing temperature from 600 to 1000 °C. The carbon structure shrinkage and pore narrowing occurred above 600 °C. The shrinkage of carbon skeleton increased by more than 22% with temperatures rising from 600 to 1000 °C. At HHR condition, progressive increases in porosity development with increasing pyrolysis temperature occurred, whereas a maximum porosity development appeared at 900 °C. The total surface area (S_total) and micropore surface area (S_micro) reached maximum values of 30.94 and 21.81 m²/g at 900 °C and decreased slightly at higher temperatures. The influence of heating rate on S_total and S_micro was less significant than that of pyrolysis temperature. The pore surface fractal dimension and average pore diameter showed a good linear relationship.     

Expedient one-pot organometallics-free synthesis of tris(2-pyridyl)phosphine from 2-bromopyridine and elemental phosphorus

2-Bromopyridine reacts with elemental phosphorus (red or white) in a superbasic KOH/DMSO(H₂O) suspension at 100 °C (for red phosphorus) and 75 °C (for white phosphorus) over 3 h to afford tris(2-pyridyl)phosphine in a 62% yield (from red phosphorus) and a 50% yield (from white phosphorus). Under microwave assistance, the reaction with red phosphorus takes just 20 min to produce tris(2-pyridyl)phosphine in 53% yield. A hitherto unknown complex, [Pd(PPy₃)₂Cl₂]·CH₂Cl₂, synthesized from tris(2-pyridyl)phosphine and PdCl₂, has the cis-configuration; this is unusual for bis(phosphino)palladium dichloride complexes.