Scripting approach in hybrid organic–inorganic condensation simulation: the GPTMS proof-of-concept

Malý, Marek; Posocco, Paola; Fermeglia, Maurizio; Pricl, Sabrina

doi:10.1080/08927020802235706

Cited by 14 publications

(19 citation statements)

References 39 publications

(22 reference statements)

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“…In this respect, a comprehensive study of the epoxide opening versus silicon condensation reaction of 3‐glycidoxypropyltrimethoxysilane (GPTMS) as a function of pH value is still missing, despite initial efforts on this topic 20. To the best of our knowledge, studies on GPTMS reactivity on its own have been reported at very high pH values21–23 or at acidic pH values in the presence of Lewis acids such as boron trifluoride etherate,19b titanium chloride,24 or metal (alk)oxides 25–27.…”

Section: Introductionmentioning

confidence: 99%

Epoxide Opening versus Silica Condensation during Sol–Gel Hybrid Biomaterial Synthesis

Gabrielli

Russo

Poveda

et al. 2013

Chemistry A European J

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Hybrid organic-inorganic solids represent an important class of engineering materials, usually prepared by sol-gel processes by cross-reaction between organic and inorganic precursors. The choice of the two components and control of the reaction conditions (especially pH value) allow the synthesis of hybrid materials with novel properties and functionalities. 3-Glycidoxypropyltrimethoxysilane (GPTMS) is one of the most commonly used organic silanes for hybrid-material fabrication. Herein, the reactivity of GPTMS in water at different pH values (pH 2-11) was deeply investigated for the first time by solution-state multinuclear NMR spectroscopic and mass spectrometric analysis. The extent of the different and competing reactions that take place as a function of the pH value was elucidated. The NMR spectroscopic and mass spectrometric data clearly indicate that the pH value determines the kinetics of epoxide hydrolysis versus silicon condensation. Under slighly acidic conditions, the epoxy-ring hydrolysis is kinetically more favourable than the formation of the silica network. In contrast, under basic conditions, silicon condensation is the main reaction that takes place. Full characterisation of the formed intermediates was carried out by using NMR spectroscopic and mass spectrometric analysis. These results indicate that strict control of the pH values allows tuning of the reactivity of the organic and inorganic moities, thus laying the foundations for the design and synthesis of sol-gel hybrid biomaterials with tuneable properties.

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Section: Introductionmentioning

confidence: 99%

Epoxide Opening versus Silica Condensation during Sol–Gel Hybrid Biomaterial Synthesis

Gabrielli

Russo

Poveda

et al. 2013

Chemistry A European J

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“…Each resulting simulation box was relaxed and equilibrated at the corresponding initial density value at 300 K by 1 ns of MD simulations in the NVT ensemble. For the calculation of polymer density as a function of temperature and degree of cross-linking, an adapted version of our original methodology to generate atomistic models of cross-linked networks based on molecular mechanics/dynamics schemes was adopted (Maly et al, 2008). The calculation of polymer density at each condition was performed by applying the compression-decompression MD scheme proposed by Larsen (Larsen et al, 2011).…”

Section: Nano-scale Md/gcmc Modelsmentioning

confidence: 99%

“…Accordingly, instead of using empirical and unreliable expressions for the estimation of these quantities, here the nano-scale model is employed. In particular, molecular dynamics (MD) simulations are run to calculate the density of the networking polymer (Ferkl et al, 2017;Laurini et al, 2016;Maly et al, 2008) while Grand Canonical Monte Carlo (GCMC) are carried out to predict the different gases solubility as a function of temperature and degree of crosslinking (P Cosoli et al, 2008a(P Cosoli et al, , 2008bPaolo Cosoli et al, 2008;Pricl and Fermeglia, 2003). The final macro-scale CFD model predictions, calculated in turn by using results from the underpinning nano-scale models, are validated against experimental data for density and temperature time evolutions for different test cases.…”

Section: Introductionmentioning

confidence: 99%

Bridging the gap across scales: Coupling CFD and MD/GCMC in polyurethane foam simulation

Karimi

Marchisio

Laurini

et al. 2018

Chemical Engineering Science

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This work presents a multi-scale approach to reacting and expanding polyurethane (PU) foams modeling and simulation. The modeling strategy relies on two pillars: an atomistic model (molecular dynamics (MD)/Grand Canonical Monte Carlo (GCMC)) that provides liquid mixture density and reactant solubility and a continuum model (CFD) in which the expansion characteristics of the foam is modeled exploiting the results of the atomistic simulations. The resulting coupled model is validated for two different PU systems applied in four batches with chemical and physical blowing agents. The results demonstrate the efficacy and reliability of the developed model in the simulation of different PU foam properties such as apparent density and temperature evolutions.

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“…3-Glycidoxypropyltrimethoxysilane (GPTMS) is an interesting trialkoxysilane precursor for obtaining hybrid organicinorganic materials because it possesses functionality of both silicon alkoxide and an epoxy ring (Innocenzi et al, 2009;Robertson et al, 2003;Liu et al, 2004;Peng et al, 2005). The sol-gel process of GPTMS often leads to the formation of fully condensed structures of formula (RSiO 3/2 ) n or partially condensed structures of formula [RSiO 3/2Àx (OH) 2x ] m (where R is the 3-glycidoxypropyl group) (Maly et al, 2008), leading to several resulting networks. These can include three-dimensional networks of trifunctional monomers, 'ladder' structures, cake-like fragments, and a combination of linear, 'ladder' and cake-like fragments (Innocenzi et al, 2009;Maly et al, 2008;Boury & Corriu, 2003;Materě jka et al, 2001), depending on the polymerization conditions.…”

Section: Introductionmentioning

confidence: 99%

“…The sol-gel process of GPTMS often leads to the formation of fully condensed structures of formula (RSiO 3/2 ) n or partially condensed structures of formula [RSiO 3/2Àx (OH) 2x ] m (where R is the 3-glycidoxypropyl group) (Maly et al, 2008), leading to several resulting networks. These can include three-dimensional networks of trifunctional monomers, 'ladder' structures, cake-like fragments, and a combination of linear, 'ladder' and cake-like fragments (Innocenzi et al, 2009;Maly et al, 2008;Boury & Corriu, 2003;Materě jka et al, 2001), depending on the polymerization conditions. In addition, GPTMS has a cross-linking capacity through the epoxy group (Innocenzi et al, 2009;Robertson et al, 2003), which increases its potential for applications in a variety of areas like proton-conducting membranes, corrosion-and scratch-resistant coatings, and optical applications (Robertson et al, 2003).…”

Section: Introductionmentioning

confidence: 99%

Rod-like particles growing in sol–gel processing of 1:1 molar mixtures of 3-glycidoxypropyltrimethoxysilane and tetraethoxysilane

et al. 2017

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The growth kinetics and the structure of organic/silica hybrids prepared from acid hydrolysis of 1:1 molar mixtures of 3‐glycidoxypropyltrimethoxysilane and tetraethoxysilane were studied by small‐angle X‐ray scattering (SAXS) at 315, 325 and 335 K. The evolution of the SAXS intensity is compatible with the growth of silica‐rich domains by aggregation from a fixed number of primary particles. Two distinct growth regimes could be identified by analyzing the relation I(0) ∝ RgD between the intensity extrapolated to zero I(0), the radius of gyration Rg of the aggregates and the exponent D, which gives information on the geometry and the mechanism of growth of the aggregates. An initial period was attributed to the growth of rod‐like particles with approximately the same radius and variable length. At more advanced degrees of aggregation the process was controlled by the growth of larger aggregates with higher‐order dimensionality. A narrow distribution of cylinder lengths given by the Schulz function fitted the experimental SAXS data well during the most part of the initial regime of cylindrical particle growth. These particles were later found as rod‐like subunits of the larger aggregates grown at more advanced degrees of aggregation. Some condensation possibilities yielding the formation of structures compatible with those inferred from the present study are discussed.

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Scripting approach in hybrid organic–inorganic condensation simulation: the GPTMS proof-of-concept

Cited by 14 publications

References 39 publications

Epoxide Opening versus Silica Condensation during Sol–Gel Hybrid Biomaterial Synthesis

Epoxide Opening versus Silica Condensation during Sol–Gel Hybrid Biomaterial Synthesis

Bridging the gap across scales: Coupling CFD and MD/GCMC in polyurethane foam simulation

Rod-like particles growing in sol–gel processing of 1:1 molar mixtures of 3-glycidoxypropyltrimethoxysilane and tetraethoxysilane

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