scholarly journals Kinetics of Resorcinol-Formaldehyde Condensation—Comparison of Common Experimental Techniques

Gels ◽  
2021 ◽  
Vol 8 (1) ◽  
pp. 8
Author(s):  
Eva Kinnertová ◽  
Václav Slovák ◽  
Roman Maršálek ◽  
Martin Mucha

Porous carbons, originated from resorcinol-formaldehyde (RF) gels, show high application potential. However, the kinetics and mechanism of RF condensation are still not well described. In this work, different methods (dynamic light scattering–DLS, Fourier transform infrared spectroscopy–FTIR, low field 1H nuclear magnetic resonance relaxometry–1H-NMR, and differential scanning calorimetry–DSC) were used to follow the isothermal RF condensation of mixtures varying in catalyst content (Na2CO3) and reactant concentration. The applicability and results obtained by the methods used differ significantly. The changes in functional groups can be followed by FTIR only at very early stages of the reaction. DLS enables the estimate of the growth of particles in reaction solution, but only before the solution becomes more viscous. Following the relaxation of 1H nuclei in water during RF condensation brings a different view on the system—this technique follows the properties of the present water that is gradually captured in polymeric gel. From this side, the process behaves similarly to the nucleation reaction, which is in contradiction to the n-order mechanism confirmed by other techniques. The widest range of applicability was found for DSC measurement of the freezing/melting behavior of the reaction mixture, which is possible to use without any limitations until full solidification. Furthermore, this approach enables us to follow the gradual formation and development of the gel through the intermediate undergoing glass transition.

2008 ◽  
Vol 1098 ◽  
Author(s):  
Saghar Sepehri ◽  
Betzaida Batalla Garcia ◽  
Guozhong Cao

AbstractThis study reports the effects of pore size of porous carbon scaffold on the dehydrogenation of ammoniaborane in the coherent carbon- ammoniaborane nanocomposites. Porous carbon scaffold is obtained from resorcinol formaldehyde derived carbon cryogels. The nanocomposites are made by simple soaking porous carbon scaffold in ammonia borane solution. Nitrogen sorption analysis and differential scanning calorimetry are used to investigate the structure and dehydrogenation of the nanocomposites. The results reveal that dehydrogenation temperature decreases in nanocomposites as compared to neat ammonia borane, and is lower in nanocomoposites with smaller pore sizes. These findings can be used to tune the dehydrogenation temperature to meet specific hydrogen storage applications. Also, dehydrogenation kinetics of nanocomposites is enhanced as compared to neat ammonia borane.


Polymers ◽  
2020 ◽  
Vol 12 (2) ◽  
pp. 364
Author(s):  
M. Jesús Fernández ◽  
M. Dolores Fernández

In clay/polymer nanocomposites, the crystallization behavior and kinetics of the polymer can be affected by the presence of clay, its content and the degree of miscibility between the clay and the polymer matrix. The effect of two different organomodified vermiculites on the non-isothermal cold crystallization and melting behavior of polylactide (PLA) was studied by differential scanning calorimetry (DSC). In the presence of vermiculites, the cold crystallization of PLA occurred earlier, particularly for the highest content of the most miscible organovermiculite with PLA. The cold crystallinity of PLA decreased at low heating rates, notably at high organoclay loadings, and increased at high heating rates, especially at low vermiculite contents. According to the crystallization half-time, crystallization rate coefficient (CRC), and crystallization rate parameter (CRP) approaches, the cold crystallization rate of PLA increased by incorporating vermiculites, with the effect being most noteworthy for the vermiculite showing better compatibility. The Mo model was successful in describing the non-isothermal cold crystallization kinetics of the PLA/vermiculite composites. The melting behavior was affected by the heating rate and the type and content of clay. The nucleating effect of the most compatible clay resulted in the less perfect crystallites. The activation energy was evaluated using the Kissinger and Takhor methods.


Polymers ◽  
2020 ◽  
Vol 12 (4) ◽  
pp. 791
Author(s):  
Fotis Christakopoulos ◽  
Enrico Troisi ◽  
Theo A. Tervoort

The melting behavior of nascent poly(tetrafluoroethylene) (PTFE) was investigated by way of differential scanning calorimetry (DSC). It is well known that the melting temperature of nascent PTFE is about 344 ∘ C, but reduces to 327 ∘ C for once molten material. In this study, the melting temperature of nascent PTFE crystals was found to strongly depend on heating rate, decreasing considerably for slow heating rates. In addition, during isothermal experiments in the temperature range of 327 ∘ C < T < 344 ∘ C, delayed melting of PTFE was observed, with complete melting only occurring after up to several hours. The melting kinetics of nascent PTFE were analyzed by means of the isoconversional methodology, and an apparent activation energy of melting, dependent on the conversion, was determined. The compensation effect was utilized in order to derive the pre-exponential factor of the kinetic model. The numerical reconstruction of the kinetic model was compared with literature models and an Avrami-Erofeev model was identified as best fit of the experimental data. The predictions of the kinetic model were in good agreement with the observed time-dependent melting of nascent PTFE during isothermal and constant heating-rate experiments.


1980 ◽  
Vol 45 (3) ◽  
pp. 783-790 ◽  
Author(s):  
Petr Taras ◽  
Milan Pospíšil

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.


1987 ◽  
Vol 52 (10) ◽  
pp. 2375-2382 ◽  
Author(s):  
Ľubica Adamčíková ◽  
Peter Ševčík

Glycerol causes chemical oscillations in Belousov-Zhabotinskii reaction in a closed system as well as in a reaction solution bubbled with nitrogen. Since the oxidation of glycerol with bromate ions does not proceed autocatalytically and bromine in the oxidation state 0 or +1 in the absence of light does not react with glycerol, hydrolysis of bromine is the probable source of bromide ions in the studied oscillation system.


Polymers ◽  
2021 ◽  
Vol 13 (11) ◽  
pp. 1686
Author(s):  
Andrey Galukhin ◽  
Roman Nosov ◽  
Ilya Nikolaev ◽  
Elena Melnikova ◽  
Daut Islamov ◽  
...  

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.


Materials ◽  
2021 ◽  
Vol 14 (11) ◽  
pp. 2872
Author(s):  
Seyed Mohamad Reza Paran ◽  
Ghasem Naderi ◽  
Elnaz Movahedifar ◽  
Maryam Jouyandeh ◽  
Krzysztof Formela ◽  
...  

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.


2021 ◽  
pp. 002199832110015
Author(s):  
Alexander Vedernikov ◽  
Yaroslav Nasonov ◽  
Roman Korotkov ◽  
Sergey Gusev ◽  
Iskander Akhatov ◽  
...  

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.


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