Degree Of Conversion Research Articles

Hydrogen production by the steam reforming of synthetic biogas in atmospheric-pressure microwave (915 MHz) plasma

This paper is a contribution to the development of microwave plasma-based technology aimed at efficient hydrogen (H2) production from a so-called synthetic biogas, considered a mixture of methane (CH4) and carbon dioxide (CO2), which can contain up to 70% CH4. In this work, we tested the performance of a waveguide-supplied metal cylinder-based microwave plasma source (MPS) operating at 915 MHz at atmospheric pressure as a tool for the efficient production of H2 in the steam reforming of the synthetic biogas. The test showed that the steam reforming of the synthetic biogas could be carried out under a wide range of working parameters without soot formation and extinction of the microwave discharge. We found that there is a minimal H2Osteam consumption rate for a given CH4 input volume content, which ensures stable operation of the MPS (no soot). The experiments did not show that increasing the amount of H2Osteam rate above the minimal value for a given CH4 input volume content results in an increase in the H2 production rate, energy yield, CH4 conversion degree, and H2 output concentration. To describe the MPS performance, which also takes into account a factor of the utilization of the CH4 feedstock, we introduced a new parameter, called an energy–CH4 feedstock consumption yield. The best results in terms of the H2 production rate, the energy yield, and the CH4 conversion degree were 239 g[H2]/h 36.8 g[H2]/kWh, and 74.3%, respectively. This shows that the application of the steam reforming, instead of the dry reforming, resulted in a 1.5-fold increase of the H2 production rate and the corresponding energy yield.

Techno-Economic Efficiency Estimation of Promising Integrated Oxyfuel Gasification Combined-Cycle Power Plants with Carbon Capture

The study concerns promising coal-fired power plants that can gain an advantage over traditional options in the context of decarbonization. The calculations show that combined-cycle plants with integrated coal gasification and carbon dioxide recirculation may have better technical and economic characteristics compared to existing gasification processes (one- and two-stage). The recirculation of carbon dioxide improves the efficiency of the gasification process (the combustible gases yield and the fuel carbon conversion degree) and reduces the energy costs of the flue gas cleaning and carbon capture unit, thereby improving the economic performance of the plant. The estimates show that the decrease in the efficiency of electricity production associated with the removal of carbon dioxide is approximately 8% for the recirculation of combustion products and 15–16% for traditional processes, and the increase in the cost of electricity is 20–25% versus 35–40%, respectively.

New dimethacrylate monomers based on phenolphthalein and resveratrol for the application of dental materials

Potential estrogenic effects and changes in fertility are some of the health problems associated with bisphenol A (BPA) derivatives used to produce some polymers, including dental materials that contain Bis-GMA. Those issues drove this study proposing the synthesis of methacrylate resveratrol and phenolphthalein monomers that, combined with diluent monomers, generate copolymers. Their key characteristics were determined and analyzed on the chemical structure-property perspective considering monomer planarity and flexibility based on molecular dynamic simulations. MethodsMethacrylate resveratrol ((E)-5-(4-(methacryloyloxy)styryl)-1,3-phenylenebis(2-methylacrylate)), EMPM) and methacrylate phenolphthalein ((3-oxo-1,3-dihydroisobenzofuran-1,1-diyl)bis(4,1-phenylene)bis(2-methylacrylate)), DIFPM) were synthesized through the reaction of precursors with methacryloyl chloride. After monomers purification and spectroscopic characterization (FTIR and NMR), the following copolymers were produced: DIFPM/TEGDMA and Bis-GMA/TEGDMA, EMPM/HEMA and Bis-GMA/HEMA. Microhardness, degree of conversion, water sorption and contact angle data were statistically analyzed through one-way ANOVA and Tukey's test (p ≤ 0.05). ResultsThe DIFPM molecular structure's reduced flexibility proved to be an important factor to inhibit TEGDMA cyclization. In turn, the EMPM molecule's high planarity modified the spatial organization of the HEMA copolymer, altering the water diffusion and, therefore, the water sorption when compared to Bis-GMA copolymers. ConclusionThe scientific findings contribute to better understand the effect of monomer chemical structures, molecular geometry, and planarity on some physicochemical properties of copolymers. Knowledge that can contribute to the design of new monomers to replace Bis-GMA.

Higher alcohols synthesis via Fischer–Tropsch reaction at hcp-Co@Co2C interface

The hcp-Co@Co2C catalysts were prepared by partial carbonization conversion of hcp-Co, which possessed rich Co-Co2C interface and strong synergy between hcp-Co and Co2C, compared with fcc-Co. The degree of carbonization conversion was easy to control, for ethyne was used as carbon source to dissociate on the surface of cobalt to form carbon species, and then carbonization conversion took place and hcp-Co@Co2C formed. The prepared hcp-Co@Co2C catalysts exhibited high selectivity of higher alcohols, compared with hcp-Co, owing to the rich interface and strong synergy between hcp-Co and Co2C.

Crystallization of SAPO-11 Molecular Sieves Prepared from Silicoaluminophosphate Gels Using Boehmites with Different Properties

In this article, we report the results of research the formation of silicoaluminophosphate gels under changing gel aging conditions and the influence of an aluminum source (boehmite), characterized by different properties. The samples of initial gels were characterized by XRF, X-ray diffraction, MAS NMR 27Al and 31P, and scanning electron microscopy (SEM). Products of crystallization were characterized by XRF, X-ray diffraction, MAS NMR 27Al and 31P, scanning electron microscopy (SEM), N2-physical adsorption, and IR spectroscopy with pyridine adsorption. It has been established that the chemical and phase composition of aging gels and the products of further crystallization is conditioned by the size of the crystals and the porous structure of boehmite. Methods of management the morphology and secondary porous structure of SAPO-11, including the hierarchical porous structure, are proposed based on the use of boehmits characterized by different properties and changing the aging conditions of the initial gels. SAPO-based catalyst with a hierarchical porous structure showed excellent catalytic performance in dimerization of α-methylstyrene with a high degree of conversion and selectivity for linear isomers.

Workflow for computational characterization of PDMS cross-linked systems

The aim of this work is to demonstrate a computational workflow for the generation of cross-linkable viscoelastic polymers and the determination of elastic and hyperelastic properties by means of all-atoms classical molecular dynamics simulations, using polydimethylsiloxane (PDMS) as an example. To improve the computational efficiency of the workflow, a phenomenological description of the cross-linking process is chosen instead of a quantum mechanical description of the cross-linking mechanism. The structures produced differ in their conversion degree of cross-linking (cdc) of 60, 70, and 80 percent and their quantity ratio between polymer chains and cross-linking units of 2 to 1 and 5 to 1. In order to exclude finite size effects of the molecular systems as much as possible, large systems of about 40,000 atoms are considered. Furthermore, for each possible configuration from the combination of cdc and the ratio of polymer chains to cross-linking units, six structures different from each other are used. Tensile and compression tests are performed to determine mechanical properties. A dependence of stresses in the deformation direction on strain rate is found for strain rates 107, 108, and 109 1/s. As the cdc increases, an increase in the stress values is observed in the tensile tests. To determine the viscoelastic material properties, relaxation tests are performed following the tensile tests. Thereby, the determined relaxed stresses after the tensile test rise with the increase of the cdc. Furthermore, no large stress deviations, .34 MPa maximum, between structures differing by chain to linker ratio are observed with the Ogden model. The computational workflow shows that classical all-atom molecular dynamics simulations can be a suitable method for structure generation and subsequent characterization of elastic and hyperelastic properties of cross-linked polymers.

A comparative evaluation of preheat treatment, postcure heat treatment, and combined heat treatment on degree of conversion of a bulk-fill composite: An in vitro study.

The aim of this study was to evaluate the effect on the degree of conversion of Tetric N-Ceram Bulk Fill Composite subjected to preheat treatment, postcure heat treatment, and combined heat treatment. A total of 90 samples were prepared from Tetric N-Ceram Bulk Fill using customized stainless steel molds and divided into six groups of 15 samples each based on the heat treatment. Group I (control group): no heat treatment, Group II: preheat treatment at 60°C, Group III: postcure heat treatment at 100°C, Group IV: postcure heat treatment at 200°C, Group V: combined preheat treatment at 60°C and postcure heat treatment at 100°C, and Group VI: combined preheat treatment at 60°C and postcure heat treatment at 200°C. The degree of conversion was analyzed using Raman spectrometer. Data were analyzed using analysis of variance followed by the Scheffé test using Statistical Package for the Social Sciences 20.0 version. The order of values of degree of conversion from maximum to minimum for the groups are as follows: Group VI (98.77 ± 0.52) > Group V (97.11 ± 0.78) > Group IV (95.00 ± 0.86) > Group III (93.00 ± 1.22) > Group II (86.88 ± 1.36) > Group I (76.55 ± 1.42). The statistical analysis revealed a statistically significant difference between the groups (P < 0.05). Combined heat treatment samples showed better values of degree of conversion.

Impact of silanization of different bioactive glasses in simplified adhesives on degree of conversion, dentin bonding and collagen remineralization.

To analyze simplified adhesive containing pure or silanized bioglass 45S5 (with calcium) or Sr-45S5 (strontium-substituted) fillers applied on dentin and to evaluate the microtensile bond strength (µTBS), interface nanoleakage, degree of conversion of adhesive, collagen degradation and remineralization. Ambar Universal adhesive (FGM) was doped with 10wt% bioactive glasses to form following groups: Control (no bioglass), 45S5 (conventional bioglass 45S5), Sr-45S5 (Sr-substituted bioglass 45S5), Sil-45S5 (silanized bioglass 45S5) and Sil-Sr-45S5 (silanized bioglass Sr-45S5). Adhesives were applied after dentin acid-etching using phosphoric acid at extracted human molars. Resin-dentin sticks were obtained and tested for µTBS, nanoleakage at 24h or 6 months. Degree of conversion was measured using micro-Raman spectroscopy. Dentin remineralization was assessed by FTIR after 6-month storage in PBS. Hydroxyproline (HYP) release was surveyed by UV-Vis spectroscopy. Statistical analysis was performed using ANOVA and Tukey's test (p<0.05). Regarding µTBS, Sr-45S5 and 45S5 presented higher and stable results (p>0.05). Control (p=0.018) and Sil-Sr-45S5 (p<0.001) showed µTBS reduction after 6-month aging. Sil-Sr-45S5 showed higher HYP release than that obtained in the 45S5 group. Sil-45S5 showed mineral deposition and increase in µTBS (p=0.028) after 6-months. All experimental adhesives exhibited higher degree of conversion compared to Control group, except for 45S5. All adhesives created gap-free interfaces, with very low silver impregnation, except for Sil-Sr-45S5. The incorporation of silanized 45S5 bioglass into the universal adhesive was advantageous in terms of dentin remineralization, bonding performance and adhesive polymerization. Conversely, Sil-Sr-45S5 compromised the µTBS, interface nanoleakage and had a negative impact on HYP outcomes.

In vitro evaluation of a silane containing self-adhesive resin luting agent.

To investigate the setting characteristics, wettability and bonding capacity with a lithium disilicate ceramic of a silane containing self-adhesive resin luting agent (Panavia SA Universal-PU). The degree of conversion (DC %) and extent of acid neutralization (SY %) of PU were measured on dual- (DC) and self-cured (SC) specimens after 10, 30 and 60 min storage by ATR-FTIR spectroscopy, whereas the presence of silanols was traced by curve-fitting the 60 min spectra, using the silane-free analog (Panavia SA Plus-PS) as a control. The role of a dedicated adhesive (Clearfil Universal Bond Quick-CU) in assisting the early DC % in PU-SC was investigated on 10 min-stored specimens. The water contact angles on polished and HF acid-etched lithium disilicate surfaces (IPS e.max Press), were assessed before and after silanization by unset PU or a silane primer (Ultradent Silane-SL). Finally, the shear strength of PU-DC specimens bonded to the acid-etched ceramic surfaces was determined before and after SL treatment. The DC % was higher in DC than SC (PU, PS; all time intervals), in PU-SC than PS-SC (30, 60 min) and in the CU assisted PU-SC group. The SY % was lower in DC than SC (PU, PS) and higher in PS-SC than PU-SC groups. Silanols were found only in unset PU and PU-DC groups. SL treatment provided higher water contact angles on polished and acid-etched ceramic surfaces and higher shear bond strength on acid-etched ceramic surfaces than PU (p < 0.05 for all comparisons). Although the degree of conversion of the silane containing luting agent was improved in the self-curing mode, especially in the adhesive assisted group, it was still inferior to light-curing. Acid-neutralization and presence of silanols were affected by the setting modes. The use of a silane primer enhanced the hydrophobicity and bond strength of the silane containing luting agent with the etched ceramic substrate.

Effect of shelf-storage temperature on degree of conversion and microhardness of composite restorative materials

BackgroundThe pre-cure temperature is considered an important parameter that affects the polymerization kinetics and the properties of composite restoration. As dissension exists about the effect of storing composite restorative materials in refrigerator, this study aimed to assess the effect of shelf-storage temperature on degree of conversion (DC) and microhardness of three composite restorative materials with different matrix systems.MethodsThree commercially-available composite restorative materials were used in this study; an Ormocer-based composite (Admira Fusion, Voco GmbH), a nanoceramic composite, (Ceram.X SphereTEC One, Dentsply Sirona GmbH), and a nanohybrid composite (Tetric N-Ceram, Ivoclar Vivadent AG). Regarding DC and microhardness tests, 60 disc-shaped composite specimens for each test were randomly divided into 3 groups (n = 20) according to the restorative material used. Each group was divided into 2 subgroups (n = 10) according to the composite storage temperature; stored at room temperature or stored in the refrigerator at 4°–5 °C. DC was evaluated using a Fourier-transform infrared spectrometer coupled to an attenuated total reflectance accessory. Microhardness was evaluated using micro-Vickers hardness tester under a load of 50 g with a dwell time of 10 s. The results were analyzed by ANOVA, post-hoc LSD, and independent t-tests at a significance level of p < 0.05.ResultsRegarding DC test all groups showed statistically significant differences at both storage temperature. The Ormocer-based composite had the highest mean values. There was a statistically significant difference between all room-stored groups and their corresponding groups stored at refrigerator (p < 0.05). For microhardness test, all groups exhibited also statistically significant differences at both storage temperatures with the Ormocer-based composite having the highest mean values. A statistically significant difference between both room-stored and refrigerator-stored groups has been observed also (p < 0.05).ConclusionsRefrigeration of resin-composite might have a deleterious effect on DC and microhardness of the tested composite restorative materials with different matrix systems. Moreover, the differences in the formulations of composite matrix have a potential impact on DC and microhardness.

Cytotoxicity and reactive oxygen species production induced by different co-monomer eluted from nanohybrid dental composites

BackgroundSafety issues for dental restorative composites are critical to material selection, but, limited information is available to dental practitioners. This study aimed to compare the chemical and biological characteristics of three nanohybrid dental composites by assessing filler particle analysis, monomer degree of conversion (DC), the composition of eluates, and cytotoxicity and reactive oxygen species (ROS) production in fibroblasts.MethodsThree nanohybrid composites (TN, Tetric N-Ceram; CX, Ceram X Sphere Tec One; and DN, DenFil NX) were used. The size distribution and morphology of the filler particles were analysed using scanning electron microscopy (n = 5). The DC was measured via micro-Raman spectroscopy (n = 5). For the component analysis, methanol eluates from the light-polymerised composites were evaluated by gas chromatography/mass spectrometry (n = 3). The eluates were prepared from the polymerised composites after 24 h in a cell culture medium. A live/dead assay (n = 9) and Water-Soluble Tetrazolium-1 assay (n = 9) were performed and compared with negative and positive controls. The ROS in composites were compared with NC. Statistical significance in differences was assessed using a t-test and ANOVA (α = 0.05).ResultsMorphological variations in different-sized fillers were observed in the composites. The DC values were not significantly different among the composites. The amounts of 2-hydroxyethyl methacrylate (HEMA) were higher in TN than DN (p = 0.0022) and triethylene glycol dimethacrylate (TEGDMA) in CX was higher than in others (p < 0.0001). The lowest cell viability was shown in CX (p < 0.0001) and the highest ROS formation was detected in TN (p < 0.0001).ConclusionsThree nanohybrid dental composites exhibited various compositions of filler sizes and resin components, resulting in different levels of cytotoxicity and ROS production. Chemical compositions of dental composites can be considered with their biological impact on safety issues in the intraoral use of dental restorative composites. CX with the highest TEGDMA showed the highest cytotoxicity induced by ROS accumulation. DN with lower TEGDMA and HEMA presented the highest cell viability.

Synthesis, characterization, photo-polymerization, hydrolytic stability, and etching behavior of new self-etch adhesive monomers

Considering the poor hydrolytic stability of the most methacrylate-based functional monomers of self-etch dental adhesives in acidic and aqueous conditions, in this study allyl-based photo-polymerizable self-etch monomers was synthesized in order to improve the hydrolytic stability.The new self-etch monomers based on phosphonic acid functional groups were synthesized through a two-step procedure. First, phosphoric anhydride, poly-phosphoric acid, and polyethylene glycol were reacted to produce phosphate ester precursor (P-PEG-P). Next, allyl 2, 3-epoxypropyl ether was reacted with P-PEG-P to synthesize allyl self-etch monomer. Glycidyl methacrylate was also reacted with P-PEG-P to synthesize a methacrylate self-etch analogue monomer. The monomers were characterized using FTIR and 1H-NMR spectroscopy. The viscosities of monomers were measured using a rheometer. The degree photopolymerization conversion of monomers was measured using FTIR spectroscopy. The pH assay was performed by a digital pH-meter. The etching behavior of the monomers on human teeth was studied using scanning electron microscopy (SEM). Thermo-gravimetric analysis (TGA) was performed to evaluate the possible interaction of the monomers with tricalcium phosphate (TCP). The solubility of synthesized monomers was examined in ethanol, acetone, and water. The hydrolytic stability of cured resins in artificial saliva during 4 months was also surveyed.The synthesis of new self-etching monomers was successfully confirmed by spectroscopy analyses. The results represented appropriate viscosity of self-etching monomers around 1 (Pa s). The resin containing methacrylate monomer exhibited its degree of conversion is more than that of allyl monomer (p < 0.05). The allyl and methacrylate self-etch monomers exhibited pH values of 1.2 and 1.3, respectively. SEM micrograph verified that the synthesized monomers were able to suitable etching of the enamel human premolar teeth. The data obtained from TGA tests revealed that thermal stability of (TCP) containing monomers is enhanced. Also, the monomers exhibited an excellent solubility in polar solvents, but when they are mixed with TCP, they are not, anymore, dissolved in these solvents. Furthermore, the allyl monomer showed higher hydrolytic stability than the methacrylate monomer.The new photo-polymerizable acidic monomer based on allyl functionality showed enhanced hydrolytic stability compared to methacrylate-based monomer. It may be considered as a promising monomer for self-etch dental adhesives.

Effect of Surface Polishing on Physical Properties of an Occlusal Splint Material for Additive Manufacturing under Protection Gas Post-Curing Condition.

The aim of this study was to evaluate the effect of surface polishing as well as the post-curing atmospheres (air and nitrogen gas) on the physical properties of an occlusal splint material for additive manufacturing. Flexural strength, flexural modulus, Vickers hardness number (VHN), degree of carbon double bond conversion (DC), water sorption (WSP), and water solubility (WSL) were evaluated. Surface polishing significantly affected the evaluated properties. Regardless of the post-curing atmosphere, flexural strength, flexural modulus, VHN, and DC showed significantly higher values for the polished specimens when compared with the unpolished ones, while WSP and WSL were significantly lower for the polished specimens. Unpolished specimens post-cured at nitrogen gas showed significantly higher VHN and DC values. However, the effect of the post-curing at a nitrogen gas atmosphere was non-significant in polished specimens. The current results suggested that surface polishing plays a role in the physical properties of the evaluated occlusal splint material and can enhance all the evaluated properties regardless of the post-curing atmosphere. Meanwhile, the post-curing at a nitrogen gas atmosphere can enhance the VHN and DC but its effect is confined only to the surface layers, which can be removed during surface polishing.

A universal adhesive containing copper nanoparticles improves the bonding and mechanical properties of resin cement–root dentin interface: an in vitro study

The aim of this study was to evaluate the anti-MMP activity of two concentrations of copper nanoparticles (CuNp) and the effect of their addition to a universal adhesive system on resin cement-radicular dentin in situ degree of conversion (DC), elastic modulus (EM), nanoleakage (NL), and push-out bond strength (PBS). Anti-MMP activity was evaluated for several MMPs. Seventy-two roots of endodontically prepared human lower premolars were randomly divided into six groups according to CuNp concentration (0% [control], 0.1%, 0.2%) and adhesive strategy (etch-and-rinse [ER] and self-etch [SE]). Fiber posts were cemented, DC was measured using micro-Raman spectroscopy, the EM of the hybrid layer and adhesive layer was measured using a nano-indenter, the NL was evaluated by scanning electron microscopy, and PBS was tested at 0.5 mm/min. Data were analyzed by two-way ANOVA and Tukey’s test (α = 0.05). CuNp demonstrated anti-MMP activity (p < 0.01). CuNp containing-adhesives showed significant increased DC (p = 0.01), increased EM in the hybrid layer and adhesive layer (p = 0.001), decreased NL values (p = 0.001), and increased PBS (p = 0.0001). Adhesive strategy was not statistically significant (p > 0.47). Usually, a significant difference among root thirds was observed, except for DC and NL when CuNp 0.2% was evaluated. This is the first in vitro study showing that the incorporation of CuNp in an adhesive is an achievable alternative that can provide anti-MMP activity and improve the mechanical and bonding properties to root canal dentin.

Changes in Strength Parameters of Composite Cements as Affected by Storage Temperature—A Review of the Literature

Fixed restorations are now among the most common restorations in modern dental prosthodontics. The current view in prosthodontics of maximum preparation economy is causing an increased interest in the mechanical properties of cements. Among the most important properties of materials used for indirect cementation are mechanical properties, i.e., hardness and compressive strength. These properties can change as a result of changes in physical factors. The purpose of this study was to analyze the available literature on the effect of conditioning temperature of cements used for cementation of indirect fixed restorations on the durability of their bonding to dental tissues and their mechanical and physical properties. The following databases were used: Mendeley, PubMed, ResearchGate, National Library of Medicine, and Google Scholar. Analysis of the available literature was carried out according to the Prisma diagram program. Forty-eight articles were selected, which were the following types of studies: clinical reports, research article, and review articles. Some studies indicated that mechanical properties, such as flexural strength, polymerization shrinkage, and conversion factor, did not change after heating the composite material. According to some researchers, preheating the composite material increased its conversion degree, which consequently led to an increase in hardness and fracture toughness, an increase in flexural strength and an increase in elastic modulus, and an increase in abrasion resistance. Studies on changes in the mechanical and physical properties of composite materials, as well as composite cements, have not always provided clear answers, as there are still no laboratory and clinical studies that fully confirm the benefits of heating composite cements. Conducting studies evaluating the effect of elevated storage temperature on the strength parameters of cements, in conjunction with the type of material and its composition, could provide answers to many clinical questions that are still unresolved. If the benefits of heating cements were unequivocally confirmed in laboratory studies, this could open up many possibilities for improving the retention of fixed prosthetic restorations.

Degree of conversion of light-polymerized composite resin in implant prosthesis screw access opening.

The mechanical and physical properties of implant screw access opening deteriorate if composite resin is not polymerized properly. Therefore, this study aimed to analyze the effect of using composite resin in implant access opening on the degree of conversion (DC). Two prosthetic materials (Co-Cr and zirconia), two types of composite resin (low and high viscosity), two light-cured resin depths (2 and 3mm), and two polymerization methods (max-mode 10s and mid-mode 20s: 16 and 22J/cm2 , respectively) were considered (n=192). The DC of the polymerized composite resin was measured through Fourier-transform infrared spectroscopy. The top and bottom surfaces of the polymerized composite resin body were observed through scanning electron microscopy. Multiple linear regression analysis and analysis of variance were used to identify significant differences in DC (α=0.05). The DC was lower when the low-viscosity composite resin (β=-0.431), light-polymerized resin depth of 2mm (β=-0.430), zirconia prosthesis (β=-0.191), and mid-mode polymerization method (β=-0.164) were used. The resin type, depth of resin to be light-cured, prosthesis material, and polymerization method had an effect on the DC. Low-viscosity composite resin should be polymerized at a low irradiance and long polymerization time (such that the light-cured resin depth does not exceed 2mm) to ensure proper composite resin polymerization in implant screw access opening.

Synthesis of amphiphilic molecular brushes by solution radical copolymerization of oligoethylene glycol and oligopropylene glycol methacrylates

The regularities of radical copolymerization of methoxyoligo(ethylene glycol)methacrylate (MOEGM) with an ethoxylation degree of 11 and methoxyoligo(propylene glycol)methacrylate (MOPGM) with a propoxylation degree of 6 or 10 in toluene solutions were determined. The copolymers formed at low degrees of conversion are enriched with ethoxylated ether units in both pairs of monomers. The relative activities of the comonomers determined by the Fineman-Ross methods are in the range of 1.36–1.88 (MOEGM) and 0.56–0.92 (MOPGM). It has been established that the activity of MOPGM decreases with an increase in the length of the oligopropylene glycol chain.

Blue Laser for Polymerization of Bulk-Fill Composites: Influence on Polymerization Kinetics.

The objective of this study was to compare the polymerization kinetics of bulk-fill resin composites cured with a LED-curing device and a diode laser (449 nm). Three bulk-fill composites were light-cured with constant radiation exposure at 10 J/cm2 by varying radiant exitance and curing time. The following three light-curing protocols were used: (I) 3300 mW/cm2 for 3 s; (II) 2000 mW/cm2 for 5 s; and (III) 1000 mW/cm2 for 10 s. The degree of conversion (DC) was monitored in real time at a data acquisition rate of 2 spectra/s over a 5-min period and again after seven days using Fourier transform infrared spectroscopy. DC amounted to 30.9-61.7% at 4-mm depth after 5 min. DC values of two sculptable composites were significantly higher with the laser, regardless of the curing protocol used, but not for the flowable composite. The maximum polymerization rate (2.0-22.1%/s) was less affected by the type of curing device for one of the composites, while the other two composites achieved significantly higher values when cured with the laser. Laser curing generally increased the DC and the maximum polymerization rate while it shortened the onset of the maximum reaction rate. New handheld laser devices with adjustable power have the potential to be used as a photopolymerization light source for new generations of bulk-fill composites.

Environmental characteristics of thermal utilization of waste with external and internal supply of thermal energy

THE PURPOSE. Identification of optimal regimes for autothermal and allothermic methods of gasification of plant biomass in terms of energy parameters of generator gases, as well as determination of environmental indicators during subsequent combustion of generator gases to obtain thermal energy.METHODS. When modeling gasification processes, a nonstoichiometric model was used, based on the assumption that a chemically reacting multicomponent mixture is in a state of thermodynamic and chemical equilibrium, which corresponds to the minimum value of the isobaric-isothermal potential. When modeling the combustion of generator gas in a mixture with air, a kinetic model of a perfectly mixed flow reactor was used and the detailed mechanism of chemical interaction for the C-H-O-N-S reacting system was taken into account. The calorific value of generator gas obtained by steam gasification and external supply of thermal energy is significantly higher than the calorific value of gas obtained by internal supply of thermal energy. However, the values of the energy potential and thermochemical efficiency are very close for both types of gasification.RESULTS. For plant biomass with a given averaged elemental composition, gasification conditions are determined that increase the degree of conversion of initial materials into generator gas. In particular, for the autothermal gasification method, the maximum calculated values of the energy potential of dry ash-free generator gas and thermochemical efficiency were obtained at an excess air coefficient α ≈ 0.32. For the allothermic gasification method, the maximum calculated values of the energy potential of the generator gas and the thermochemical efficiency correspond to the gasification temperature range T ≈ 1050 -1100 K and the mass fraction of the supplied steam gH2O ≈ 0.217. To ensure these conditions, it will be necessary to supply thermal energy through combustion of ≈ 37 wt. % generator gas. Generator gas produced by the allothermic method has higher energy performance, and the negative impact on the environment during its subsequent combustion is characterized by lower specific CO and CO2 emissions in terms of a ton of reference fuel.

Kinetics of the used cooking oil transesterification in the presence of slaked lime and the triethanolamine:menthol deep eutectic solvent

AbstractThe biodiesel production from the used cooking oils from the frying of different food items (French fries, chicken breasts, or pork steaks) and methanol in the presence of slaked lime as a catalyst and the triethanolamine:menthol (1:2 mol/mol) deep eutectic solvent as a cosolvent was studied. This deep eutectic solvent accelerated the transesterification reaction. The transesterification reaction involves only the chemical reaction controlled region from its beginning and follows the pseudo‐first‐order reaction rate law. A good agreement between the model and the experimental data was confirmed by a low mean relative percent deviation between the predicted and observed values of triacylglycerol conversion degree (&lt;3.5%). The highest apparent reaction rate constant of 0.421 min−1 was achieved with the used cooking oil from frying pork steaks at 60°C. The activation energy increases in the following order of the used cooking oils from frying the food items:French fries (23.1 kJ/mol) chicken breasts (30.7 kJ/mol) pork steaks (41.6 kJ/mol). A methyl esters content higher than 97.5% was achieved within 40 min of the transesterification of the used cooking oils over slaked lime combined with the triethanolamine:menthol deep eutectic solvent.