scholarly journals Polymerization Kinetics of Cyanate Ester Confined to Hydrophilic Nanopores of Silica Colloidal Crystals with Different Surface-Grafted Groups

Polymers ◽  
2020 ◽  
Vol 12 (10) ◽  
pp. 2329
Author(s):  
Andrey Galukhin ◽  
Guzel Taimova ◽  
Roman Nosov ◽  
Tatsiana Liavitskaya ◽  
Sergey Vyazovkin
Keyword(s):  
Colloidal Crystals ◽  
Active Role ◽  
Reaction Model ◽  
Proton Donor ◽  
Cyanate Ester ◽  
Polymerization Process ◽  
Scanning Calorimetry ◽  
Significant Acceleration ◽  
Kinetics Of ◽  
Silica Colloidal Crystals

This study investigates the kinetics of confined polymerization of bisphenol E cyanate ester in the nanopores of the three types of silica colloidal crystals that differ in the concentration and acidity of the surface-grafted proton-donor groups. In all three types of pores, the polymerization has released less heat and demonstrated a very similar significant acceleration as compared to the bulk process. Isoconversional kinetic analysis of the differential scanning calorimetry measurements has revealed that the confinement causes not only a dramatic change in the Arrhenius parameters, but also in the reaction model of the polymerization process. The obtained results have been explained by the active role of the silica surface that can adsorb the residual phenols and immobilize intermediate iminocarbonate products by reaction of the monomer molecules with the surface silanols. The observed acceleration has been quantified by introducing a new isoconversional-isothermal acceleration factor Zα,T that affords comparing the process rates at respectively identical conversions and temperatures. In accord with this factor, the confined polymerization is 15–30 times faster than that in bulk.

scholarly journals Nonisothermal Cure Kinetics of Epoxy/Polyvinylpyrrolidone Functionalized Superparamagnetic Nano-Fe3O4 Composites: Effect of Zn and Mn Doping

2020 ◽  
Vol 4 (2) ◽  
pp. 55 ◽  
Author(s):  
Maryam Jouyandeh ◽  
Mohammad Reza Ganjali ◽  
Farzad Seidi ◽  
Huining Xiao ◽  
Mohammad Reza Saeb
Keyword(s):  
Superparamagnetic Iron Oxide ◽  
Cure Kinetics ◽  
Isoconversional Methods ◽  
Reaction Model ◽  
Partial Replacement ◽  
Scanning Calorimetry ◽  
Nano Fe3o4 ◽  
Kinetics Of ◽  
Mn Doped ◽  
Good Agreement

The effects of the bulk and surface modification of nanoparticles on the cure kinetics of low-filled epoxy nanocomposites containing electrochemically synthesized polyvinylpyrrolidone (PVP) functionalized superparamagnetic iron oxide (PVP-SPIO), Zn-doped PVP-SPIO (Zn-PVP-SPIO), and Mn-doped PVP-SPIO (Mn-PVP-SPIO) were studied using differential scanning calorimetry (DSC) and cure kinetics analyses. Integral and differential isoconversional methods were used to calculate the activation energies (Eα) and consequently propose the appropriate reaction model for the curing reaction under nonisothermal conditions. According to the alteration of Eα versus the fractional extent of conversion, the Eα trend was changed through the partial replacement of Fe2+ sites by the Zn2+ and Mn2+ cations in the general formula of MxFe3-xO4, due to smaller amounts of energy being required for curing by the incorporation of Zn-PVP-SPIO and Mn-PVP-SPIO nanoparticles into the epoxy resin. A good agreement was observed between the theoretical calculation and the observed calorimetric data for the model validation.

scholarly journals Effect of Temperature on the Mechanical Properties and Polymerization Kinetics of Polyamide-6 Composites

Polymers ◽  
2020 ◽  
Vol 12 (5) ◽  
pp. 1133 ◽  
Author(s):  
Mei-Xian Li ◽  
Dasom Lee ◽  
Gyu Hee Lee ◽  
Seung Mo Kim ◽  
Goichi Ben ◽  
...  
Keyword(s):  
Carbon Fiber ◽  
Model Fitting ◽  
Polyamide 6 ◽  
Reaction Model ◽  
Polymerization Kinetics ◽  
Thermoplastic Composites ◽  
Effect Of Temperature ◽  
Carbon Fiber Composites ◽  
Scanning Calorimetry ◽  
Kinetics Of

This work reports the preparation of carbon fiber reinforced thermoplastic composites via the in situ anionic ring opening polymerization of ε-caprolactam. Vacuum assisted resin transfer molding was used to fabricate polyamide-6/carbon fiber composites at different molding temperatures. As a result, the higher polymerization of ε-caprolactam was observed with the condition at 140 °C for satisfactory impregnation. Regarding molding temperature, the physical properties of polyamide-6/carbon fiber were observed that the bending and impact strengths at 140 °C were higher than those to at other molding temperatures. The polymerization kinetics of polyamide-6 was analyzed using differential scanning calorimetry by experimentally acquiring kinetic parameters according to model fitting approaches. Polymerization and crystallization, which occur simultaneously throughout the whole process, were separated using Gaussian and Maxwell–Boltzmann distributions to study polymerization kinetics. The result of the developed model was in good agreement with the experimental data for the presented first order autocatalytic reaction model.

Study of nickel-molybdenum catalysts for methanation of carbon monoxide

1980 ◽  
Vol 45 (3) ◽  
pp. 783-790 ◽  
Author(s):  
Petr Taras ◽  
Milan Pospíšil
Keyword(s):  
Carbon Monoxide ◽  
Catalytic Activity ◽  
Mixed Oxides ◽  
Minor Component ◽  
Fast Neutrons ◽  
Scanning Calorimetry ◽  
Low Concentrations ◽  
Γ Rays ◽  
Molybdenum Catalysts ◽  
Kinetics Of

Catalytic activity of nickel-molybdenum catalysts for methanation of carbon monoxide and hydrogen was studied by means of differential scanning calorimetry. The activity of NiMoOx systems exceeds that of carrier-free nickel if x < 2, and is conditioned by the oxidation degree of molybdenum, changing in dependence on the composition in the region Mo-MoO2. The activity of the catalysts is adversely affected by irradiation by fast neutrons, dose 28.1 Gy, or by γ rays using doses in the region 0.8-52 kGy. The system is most susceptible to irradiation in the region of low concentrations of the minor component (about 1 mol.%). The dependence of changes in catalytic activity of γ-irradiated samples on the dose exhibits a maximum in the range of 2-5 kGy. The changes in catalytic activity are stimulated by the change of reactivity of the starting mixed oxides, leading to different kinetics of their reduction and modification of their adsorption properties. The irradiation of the catalysts results in lowered concentration of the active centres for the methanation reaction.

scholarly journals PEG-POSS Star Molecules Blended in Polyurethane with Flexible Hard Segments: Morphology and Dynamics

Molecules ◽  
2020 ◽  
Vol 26 (1) ◽  
pp. 99
Author(s):  
Konstantinos N. Raftopoulos ◽  
Edyta Hebda ◽  
Anna Grzybowska ◽  
Panagiotis A. Klonos ◽  
Apostolos Kyritsis ◽  
...  
Keyword(s):  
Glass Transition ◽  
Star Polymer ◽  
Polymerization Process ◽  
Degree Of Crystallinity ◽  
Dielectric Relaxation Spectroscopy ◽  
Scanning Calorimetry ◽  
Similar System ◽  
Soft Phase ◽  
Hard Segments ◽  
Star Molecules

A star polymer with a polyhedral oligomeric silsesquioxanne (POSS) core and poly(ethylene glycol) (PEG) vertex groups is incorporated in a polyurethane with flexible hard segments in-situ during the polymerization process. The blends are studied in terms of morphology, molecular dynamics, and charge mobility. The methods utilized for this purpose are scanning electron and atomic force microscopies (SEM, AFM), X-ray diffraction (XRD), differential scanning calorimetry (DSC), and to a larger extent dielectric relaxation spectroscopy (DRS). It is found that POSS reduces the degree of crystallinity of the hard segments. Contrary to what was observed in a similar system with POSS pendent along the main chain, soft phase calorimetric glass transition temperature drops as a result of plasticization, and homogenization of the soft phase by the star molecules. The dynamic glass transition though, remains practically unaffected, and a hypothesis is formed to resolve the discrepancy, based on the assumption of different thermal and dielectric responses of slow and fast modes of the system. A relaxation α′, slower than the bulky segmental α and common in polyurethanes, appears here too. A detailed analysis of dielectric spectra provides some evidence that this relaxation has cooperative character. An additional relaxation g, which is not commonly observed, accompanies the Maxwell Wagner Sillars interfacial polarization process, and has dynamics similar to it. POSS is found to introduce conductivity and possibly alter its mechanism. The study points out that different architectures of incorporation of POSS in polyurethane affect its physical properties by different mechanisms.

scholarly journals Synthesis and Polymerization Kinetics of Rigid Tricyanate Ester

Polymers ◽  
2021 ◽  
Vol 13 (11) ◽  
pp. 1686
Author(s):  
Andrey Galukhin ◽  
Roman Nosov ◽  
Ilya Nikolaev ◽  
Elena Melnikova ◽  
Daut Islamov ◽  
...  
Keyword(s):  
Kinetic Analysis ◽  
Single Step ◽  
Polymerization Kinetics ◽  
Scanning Calorimetry ◽  
Modulated Differential Scanning Calorimetry ◽  
Diffusion Controlled ◽  
Polymerization Product ◽  
The One ◽  
Kinetics Of

A new rigid tricyanate ester consisting of seven conjugated aromatic units is synthesized, and its structure is confirmed by X-ray analysis. This ester undergoes thermally stimulated polymerization in a liquid state. Conventional and temperature-modulated differential scanning calorimetry techniques are employed to study the polymerization kinetics. A transition of polymerization from a kinetic- to a diffusion-controlled regime is detected. Kinetic analysis is performed by combining isoconversional and model-based computations. It demonstrates that polymerization in the kinetically controlled regime of the present monomer can be described as a quasi-single-step, auto-catalytic, process. The diffusion contribution is parameterized by the Fournier model. Kinetic analysis is complemented by characterization of thermal properties of the corresponding polymerization product by means of thermogravimetric and thermomechanical analyses. Overall, the obtained experimental results are consistent with our hypothesis about the relation between the rigidity and functionality of the cyanate ester monomer, on the one hand, and its reactivity and glass transition temperature of the corresponding polymer, on the other hand.

scholarly journals Isothermal Vulcanization and Non-Isothermal Degradation Kinetics of XNBR/Epoxy/XNBR-g-Halloysite Nanotubes (HNT) Nanocomposites

Materials ◽  
2021 ◽  
Vol 14 (11) ◽  
pp. 2872
Author(s):  
Seyed Mohamad Reza Paran ◽  
Ghasem Naderi ◽  
Elnaz Movahedifar ◽  
Maryam Jouyandeh ◽  
Krzysztof Formela ◽  
...  
Keyword(s):  
Thermal Stability ◽  
Degradation Kinetics ◽  
Halloysite Nanotubes ◽  
Butadiene Rubber ◽  
Order Model ◽  
Scanning Calorimetry ◽  
Theoretical Methods ◽  
Vulcanization Kinetics ◽  
Kinetics Of ◽  
Thermal Stability Of

The effect of several concentrations of carboxylated nitrile butadiene rubber (XNBR) functionalized halloysite nanotubes (XHNTs) on the vulcanization and degradation kinetics of XNBR/epoxy compounds were evaluated using experimental and theoretical methods. The isothermal vulcanization kinetics were studied at various temperatures by rheometry and differential scanning calorimetry (DSC). The results obtained indicated that the nth order model could not accurately predict the curing performance. However, the autocatalytic approach can be used to estimate the vulcanization reaction mechanism of XNBR/epoxy/XHNTs nanocomposites. The kinetic parameters related to the degradation of XNBR/epoxy/XHNTs nanocomposites were also assessed using thermogravimetric analysis (TGA). TGA measurements suggested that the grafted nanotubes strongly enhanced the thermal stability of the nanocomposite.

Effects of additives on the cure kinetics of vinyl ester pultrusion resins

2021 ◽  
pp. 002199832110015
Author(s):  
Alexander Vedernikov ◽  
Yaroslav Nasonov ◽  
Roman Korotkov ◽  
Sergey Gusev ◽  
Iskander Akhatov ◽  
...  
Keyword(s):  
Vinyl Ester ◽  
Mean Squared Error ◽  
Cure Kinetics ◽  
Zinc Stearate ◽  
Heating Rates ◽  
Scanning Calorimetry ◽  
Different Temperatures ◽  
Predicted Values ◽  
Kinetics Of ◽  
Final Degree

Pultrusion is a highly efficient composite manufacturing process. To accurately describe pultrusion, an appropriate model of resin cure kinetics is required. In this study, we investigated cure kinetics modeling of a vinyl ester pultrusion resin (Atlac 430) in the presence of aluminum hydroxide (Al(OH)3) and zinc stearate (Zn(C18H35O2)2) as processing additives. Herein, four different resin compositions were studied: neat resin composition, composition with Al(OH)3, composition comprising Zn(C18H35O2)2, and composition containing both Al(OH)3 and Zn(C18H35O2)2. To analyze each composition, we performed differential scanning calorimetry at the heating rates of 5, 7.5, and 10 K/min. To characterize the cure kinetics of Atlac 430, 16 kinetic models were tested, and their performances were compared. The model based on the [Formula: see text]th-order autocatalytic reaction demonstrated the best results, with a 4.5% mean squared error (MSE) between the experimental and predicted data. This study proposes a method to reduce the MSE resulting from the simultaneous melting of Zn(C18H35O2)2. We were able to reduce the MSE by approximately 34%. Numerical simulations conducted at different temperatures and pulling speeds demonstrated a significant influence of resin composition on the pultrusion of a flat laminate profile. Simulation results obtained for the 600 mm long die block at different die temperatures (115, 120, 125, and 130 °C) showed that for a resin with a final degree of cure exceeding 95% at the die exit, the maximum difference between the predicted values of pulling speed for a specified set of compositions may exceed 1.7 times.

The Formation of Cu3Si from Cu/a-Si Multilayers

1997 ◽  
Vol 481 ◽  
Author(s):  
R. R. Chromik ◽  
W. K. Neils ◽  
E. J. Cotts
Keyword(s):  
Diffusion Couples ◽  
X Ray Diffraction ◽  
Limited Growth ◽  
Scanning Calorimetry ◽  
Individual Layer ◽  
Diffusion Limited ◽  
Reaction Constant ◽  
Multilayered Composites ◽  
Reaction Constants ◽  
Kinetics Of

ABSTRACTThe kinetics of the formation of Cu3Si in Cu/a-Si diffusion couples have been investigated by means of differential scanning calorimetry and x-ray diffraction. Multilayered composites of average stoichiometry Cu3Si were prepared by sputter deposition with individual layer thicknesses varying in different samples between 2 and 100 nm. We observed diffusion limited growth of Cu3 Si upon annealing these diffusion couples below 500 K. Reaction constants were measured for a temperature range of 455 to 495 K for thicknesses of growing Cu3Si between 2.6 and 80 nm. The temperature dependence of the reaction constant, k2, was characterized as k2 = k0 exp(− Ea/kbT) with activation energy, Ea = 1.0 eV/atom and pre-factor, k0 = 1.9×10−3 cm2/s.

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