Giuseppe Storti

ETH Zurich, Zürich, Zurich, Switzerland

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Publications (211)411.97 Total impact

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    ABSTRACT: A new synthetic pathway for the polymerization of furan based polyesters is reported in this work. First, poly(butylene 2,5-furandicarboxylate) cyclic oligoesters (COEs) are chemically synthesized by semi-batch esterification. The structure of the COEs is confirmed by infrared spectroscopy, 1H, and 13C-NMR, while the molecular weight distribution of the COEs is determined by matrix-assisted laser desorption/ionization time of flight mass spectroscopy. The cyclic oligoesters are then successfully polymerized via ring-opening polymerization using tetrakis(2-ethylhexyl)-titanate as catalyst. Differential scanning calorimetry and 1H-NMR analysis unambiguously proves the formation of polymeric species. Both end-group analysis from 1H-NMR spectrum and calculation through Flory–Fox equation give comparable estimates of the number average molecular weight: 5.8 × 103 g mol−1 and 7.8 × 103 g mol−1, respectively.
    No preview · Article · Oct 2015 · Macromolecular Chemistry and Physics
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    ABSTRACT: In the present work the aggregation behavior of polymeric particles possessing different glass transition temperatures (i.e. different "softness") has been studied in order to shed light on the interplay between aggregation and coalescence. In particular, the time evolution of the clusters hydrodynamic and gyration radii as well as of their structure factor has been monitored. With the help of an ad hoc developed deterministic model, based on population balance equations, it was possible to establish a link between the experimentally obtained light scattering data and the predicted particle size distribution. The simplicity of the model, involving one single adjustable parameter based on the coalescence characteristic time, allowed to obtain a good accordance between simulations and experimental results with little computational effort.
    No preview · Article · Aug 2015 · Langmuir
  • Danilo Cuccato · Giuseppe Storti · Massimo Morbidelli
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    ABSTRACT: The free-radical copolymerization of acrylamide with the cationic monomer DMAEA-Q in aqueous medium is investigated with special attention to its composition behavior, which reveals to be affected by the electrostatic interactions between the charges in the system. The reaction kinetics is determined by in situ 1H NMR experiments, showing a peculiar dependence of the copolymer composition upon initial monomer and electrolyte concentrations. A kinetic model simulating the evolution of copolymer composition as a function of conversion is developed, accounting for the nonconventional features of the system. Namely, a description of the electrostatic interactions based on the DLVO theory is introduced to define a functional dependence of the rate coefficients on the ionic strength. Secondary reactions are also included due to the acrylic nature of both monomers. The proposed model is applied to estimate the corresponding reactivity ratios and proves to exhibit the correct functionality with respect to monomer concentration and ionic strength.
    No preview · Article · Jul 2015 · Macromolecules
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    ABSTRACT: A macroporous particulate support prepared previously by reactive gelation under shear and functionalized with poly(N-isopropylacrylamide), PNIPAM, brushes of variable length is applied for temperature-responsive chromatography, whereby temperature modulates hydrophobic interactions. Several different analytes, including small pharmaceuticals, peptides, proteins and monoclonal antibodies are employed. Contrary to the most commonly observed behavior in conventional chromatography, increasing retention is observed at elevated temperatures. Peak broadening is quantified using the peak standard deviation, which depends on both the polymer chain conformation and analyte adsorptivity. The favorable effect of grafted polymer thickness on retention becomes progressively less pronounced for thicker grafted PNIPAM layers. The effect of eluent composition on solute-sorbent interactions was investigated by introducing NaCl, methanol, dioxane and by varying the pH. Salt or organic solvent addition affects apart from the analytes solution properties, the hydrophobicity of the stationary phase itself. Frontal analyses performed at different temperatures to determine dynamic binding capacities, indicate small mass transfer resistances imposed by this novel packing material. Copyright © 2015 Elsevier B.V. All rights reserved.
    No preview · Article · Jun 2015 · Journal of Chromatography A
  • Tushar S. Bhatt · Giuseppe Storti · Renato Rota
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    ABSTRACT: A model for the detailed simulation of dual-reflux pressure swing adsorption process developed in the frame of the commercial software Aspen Adsim® is presented. For validation purposes, simulations were performed and model predictions were compared with published experimental results. At cyclic steady-state, model predictions were found to be in good agreement with reported experimental results in terms of (i) average ethane mole fraction in heavy product, (ii) average nitrogen mole fraction in light product, (iii) instantaneous heavy product composition profiles, and (iv) instantaneous column composition profiles. The predicted and experimental trends obtained by analyzing the effect of various operating parameters (light reflux flowrate, duration of feed/purge step, heavy product flowrate and mole fraction of heavy component in binary feed gas mixture) on process performance are also comparable. Overall, this simulation technique of dual-reflux pressure swing adsorption can serve as an effective tool for process design, cost reduction of laboratory and/or plant trails, and enhanced process understanding.
    No preview · Article · Jan 2015 · Chemical Engineering Science
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    ABSTRACT: The hydrolysis of lactic acid oligomers involves several different reactions, acid-catalyzed, base-catalyzed as well as non-catalyzed. In the present paper a pH-dependent kinetic model has been developed and its kinetic constants evaluated by fitting to experimental data of degrading lactic acid oligomers at 37 °C in aqueous solution at pH = 1, 2, 3.5, 5.7 and 7.4. The model was able to properly describe the experimental data with an average error of about 5%. The estimated values of the kinetic constants at the selected temperature are: kDα=4.44×10−3L2mol−2h−1L2mol−2h−1, kDβ=9.29×10−4L2mol−2h−1L2mol−2h−1 (acid-catalyzed), kRH=1.56×310kRH=1.56×103L2mol−2h−1L2mol−2h−1, kBB=2.88×610kBB=2.88×106Lmol−1h−1Lmol−1h−1 (base-catalyzed) and kW=2.49×10−5kW=2.49×10−5Lmol−1h−1Lmol−1h−1 (non-catalyzed).
    No preview · Article · Dec 2014 · Polymer Degradation and Stability

  • No preview · Conference Paper · Nov 2014
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    ABSTRACT: Reactive Gelation under Shear is a recently developed procedure towards rigid macroporous polymeric particles that does not require the use of any porogen. A comprehensive study of the effect of individual parameters on the resulting material characteristics is presented. Primary particles properties are found to be pivotal, namely the primary particles size, crosslinking degree and outer shell composition. Operating parameters also play a significant role; specifically, the effects of applied shear rate, salt feeding rate, swelling degree of primary particles, waiting time before post-polymerization and post-polymerization temperature are investigated. By varying the operating conditions, the size, internal structure, as well as porosity of the fabricated microclusters may be controlled. The pores are invariably micrometer-sized, with pore size distributions exhibiting adjustable maxima. Thanks to the sequential character of the procedure, different parameters may be tuned individually at different stages along the preparation route, allowing thus for high versatility in the control of different properties of the final material.
    No preview · Article · Oct 2014 · Langmuir
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    ABSTRACT: Ultrasonic measurement method based on the acoustic transit time method for determining the flow in hydropower application is common practice today. On the other hand Doppler profiler are in use for velocity measurement in natural open running water. Both measurement techniques operate in a similar frequency range and can capture beside the fluid or particle velocity, the influence of particles or other object in the water on the forward or backward scattered ultrasonic signal. The presentation gives an overview of the possible application of these methods for monitoring the water conditions and how they complement each another. In contrast to the need of a high accuracy for the measurement of the flow (+/-~0.5 to1.5%), the accuracy has not to be in the same range for monitoring purpose (+/-~10 to 20%). First the pro and cons of using ultrasonic for monitoring purposes are listed. Next the impurities in the water (particles, bubbles, cavitation bubbles) are characterized. These include size, size distribution, concentration, material properties and shape. Then the impact of the impurities on the received ultrasonic signals is described. In a next step the possible quantities that can be measured by an ultrasonic device are introduced. Emphasis is put on two different approaches for modelling the impact of the impurities on the ultrasonic signals. One is an empirical or black box approach, the other a physical model approach. With the physical model approach models are derived for the most important physical variables of a two phase water-particle mixture: attenuation, sound speed and far field function or scattering cross section. The models predict these physical variables dependent on the particle parameters which can be verified by measurements in a controlled environment. The problem arises when given for instance the measured attenuation, sound speed and far field function of a two phase flow, with the inversion of the models in order to estimate the underlying particle parameters. This inversion problem is ill-posed, which means there is no unique solution and the solution is sensitive to modelling and measurement errors. A priori information is needed and solutions have to be found in an iterative way. The use of multiple frequencies, the combination of measured forward scattered and backward scattered signals over a specified time-window and the measuring at different angles have the potential to improve the inversion problem. The black box modelling approach which is more in the focus of this overview, models the effects in an empirical way, by extracting characteristic signal parameters in a statistical way. For monitoring applications the classifier of different water conditions must be trained with training data. Training data are extracted signal parameters from situations where the water state is known. Typical classifiers are neural networks or decision trees which process the signal parameters in a nonlinear way. An example of a decision tree solution for detecting different cavitation states in two model test turbines is presented.
    Full-text · Conference Paper · Oct 2014
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    ABSTRACT: A process to prepare a polyester polymer composition comprising a polyester polymer having furanic units is disclosed. The process comprises the step of reacting a cyclic polyester oligomer in the presence of a catalyst in a ring-opening polymerization step under conditions of a reaction temperature and reaction time sufficient to yield a polyester polymer having furanic units. The invention further relates to a polyester polymer composition obtainable by said process, wherein the polyester polymer composition comprises a polyester polymer having furanic units and a cyclic polyester oligomer comprising either structure Y1 or Y2, preferably in a concentration of less than 5 wt %, more preferably less than 1, more preferably less than 0.5 in the composition. The present invention further relates also to the use of said polyester polymer composition in extrusion, injection molding, or blow molding.
    Full-text · Patent · Sep 2014
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    ABSTRACT: A process to prepare a cyclic polyester oligonner composition comprising a cyclic polyester oligomer having furanic units is disclosed. The process comprises the step of reacting a monomer component in the presence of an optional catalyst and/or optional organic base in a ring closing oligomerization step under conditions of a reaction temperature and reaction time sufficient to yield a cyclic polyester oligomer having furanic units. The invention further relates to a cyclic polyester oligomer composition obtainable by said process, wherein the cyclic polyester oligomer composition comprises a cyclic polyester oligomer of structure Y1 or Y2 having furanic units, wherein the composition contains less than 5 %, preferably 3, most preferably 1 weight % of linear oligomeric polyester species in the composition. The present invention further relates also to the use of said cyclic polyester oligomer composition in the production of a polyester polymer.
    Full-text · Patent · Sep 2014
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    ABSTRACT: A laboratory-scale dual-reflux pressure swing adsorption process unit comprised of two beds with intermediate feed position was built and tested for concentrating dilute gaseous feed of methane in nitrogen using Norit RB1 activated carbon. Experimental investigations revealed that the change in blowdown or pressurization step time, feed or purge step time, and heavy product flow rate did not have a significant effect on process performance (in terms of methane purity). However, the process performance was found to be quite sensitive to changes in light reflux flow rate. These experimental results were used to validate the predictions of a mathematical model developed in the frame of the commercial software Aspen Adsim, thus providing an effective tool to elucidate process behavior.
    No preview · Article · Aug 2014 · Industrial & Engineering Chemistry Research
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    Giacomo Cao · Giuseppe Storti · Maurizio Masi

    Preview · Article · Jun 2014 · Industrial & Engineering Chemistry Research
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    ABSTRACT: The predictions of four different models of crosslinking copolymerization,Kinetic Monte Carlo (KMC), statistic/kinetic Flory/Tobita (FT) model, and two kinetic approaches based on population balance equations (PBE) (solved with generating functions (GF) and numerical fractionation (MRNF), respectively), were compared. The approaches underlying more restrictive assumptions but asking for less computational effort, FT and MRNF, lead to very satisfactory predictions in terms of average properties (sol and gel fractions, degrees of polymerizations, crosslinking densities). On the other hand, fully detailed models (KMC) as well as more computationally demanding numerical solutions of the detailed PBE (GF) become necessary when the chain length distributions are required.The present paper compares the predictions of different modeling approaches on a bulk crosslinking copolymerization scheme. Models based on average properties match the predictions of more detailed models in terms of average predictions, but not for chain length distributions. As a result, guidelines for the most‐suitable usage of such models are provided.
    No preview · Article · Jun 2014 · Macromolecular Reaction Engineering
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    ABSTRACT: By combining elements from colloidal and polymer reaction engineering a new approach towards macroporous, mechanically robust polymer particles is presented, which does not require any porogenic additives. Specifically, aggregation and breakage in turbulent conditions of aggregates originating from fully destabilized primary latex particles is applied to produce compact, micrometer-sized clusters. Post-polymerization of monomer introduced initially to swell the primary particles is imparting mechanical rigidity and permanence to the internal structure. The resulting microclusters exhibit an internal porosity in the order of 70% and relatively broad pore size distribution, with exceptionally large pores, ranging from about 50 nm to 10 μm in diameter. These particulate microclusters, produced via reactive gelation under shear, are fractal objects with fractal dimension around 2.7, as opposed to the more open fractal structure of a monolith produced via stagnant reactive gelation, with fractal dimension of 1.9. Such macroporous particles are thought to be useful in applications requiring pores in the micrometer scale, e.g. in the chromatography of biomolecules or for packing beds perfusive to convective flow.
    No preview · Article · May 2014 · Langmuir
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    Ivan Kryven · Stefano Lazzari · Giuseppe Storti
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    ABSTRACT: A complex interplay between aggregation and coalescence occurs in many colloidal polymeric systems and determines the morphology of the final clusters of primary particles. To describe this process, a 2D population balance equation (PBE) based on cluster mass and fractal dimension is solved, employing a discretization method based on Gaussian basis functions. To prove the general reliability of the model and to show its potential, parametric simulations are performed employing both diffusion-limited-cluster aggregation (DLCA) and reaction-limited-cluster-aggregation (RLCA) kernels and different coalescence rates. It turns out that in both DLCA and RLCA regimes, a faster coalescence leads to smaller sized and more compact clusters, whereas a slow coalescence promotes the formation of highly reactive fractals, resulting in larger aggregates.
    Full-text · Article · Mar 2014 · Macromolecular Theory and Simulations
  • Alessandro Ghielmi · Danilo Cuccato · Giuseppe Storti
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    ABSTRACT: Radical desorption from polymer particles is a kinetic event peculiar to the emulsion polymerization process. A careful modeling of this phenomenon is highly valuable in order to achieve accurate predictions of polymerization rate and average properties of molecular weight. In this work, radical desorption is described accounting for an aspect fully neglected in previous modeling literature. Specifically, particle state dependent desorption coefficients are used instead of a single average coefficient, and the corresponding rate expressions are developed and applied to the solution of the well-known Smith–Ewart equations. Parametric model simulations show that the higher level of detail introduced in the description of radical desorption improves the accuracy of the predicted values of the average number of radicals per particle, especially in the cases of high desorption rate and slow reactions in the aqueous phase.
    No preview · Article · Jan 2014 · Industrial & Engineering Chemistry Research
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    ABSTRACT: The molecular weight distributions of poly(lactic acid) produced by ring-opening polymerization of l,l-lactide in bulk melt are measured and compared with the ones predicted using a kinetic model accounting for reversible catalyst activation, reversible propagation, reversible chain transfer to cocatalyst, and intermolecular transesterification. The same values of the model parameters as evaluated in previous works are used without any adjustment; i.e. the model is used in a fully predictive way. In order to calculate the complete molecular weight distribution, the model equations are solved through two different numerical methods, “direct integration” of the population balances at all values of chain length, and “fractionated moments”, where the chains are artificially classified into two different categories, depending upon the experienced reaction steps. The accuracy of the molecular weight distributions calculated in the latter case is evaluated by comparison with those computed by solving the model equations with the “direct integration” method. It is found that the “fractionated moments” method provides enough accuracy and much smaller computational effort, thus representing an optimal tool for most modeling applications. Finally, the model predictions are compared with the experimental molecular weight distributions measured experimentally in bulk melt at 130 °C and various initial concentrations of catalyst and cocatalyst. The generally good agreement verified between model and experiment after correcting for peak broadening represents a convincing confirmation of the model’s reliability.
    No preview · Article · Jan 2014 · Industrial & Engineering Chemistry Research
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    ABSTRACT: A model of free-radical cross-linking copolymerization in solution, based on Flory’s gelation theory and developed by Tobita and Hamielec [Macromolecules 1989, 22, 3098–3105] has been applied to the system acrylamide/N,N′-methylenebisacrylamide. The evaluation of missing rate constants was performed by comparing model predictions with experimental measurements of swelling ratios and literature data. This way, the interplay of cross-linking and intramolecular cyclization reactions, regulating the network formation and its properties, has been deepened. It turns out that the primary intramolecular cyclization is practically independent of the cross-linker amount employed, but it is affected by the total monomer concentration. For the latter dependency, an empirical correlation was proposed, which was tested in parametric simulations, showing its impact on the properties of hydrogels.
    No preview · Article · Jan 2014 · Industrial & Engineering Chemistry Research
  • Stefano Lazzari · Giuseppe Storti
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    ABSTRACT: In the present work, a kinetic model of crosslinking free-radical copolymerization based on multidimensional population balances and accounting for multiradicals is developed. The model is applied to the simulation of bulk copolymerization of methyl-methacrylate (MMA)/ethylene-glycol-dimethacrylate (EGDMA). A literature criterion proposed to elucidate the model type best suited for a given system (i.e., with or without MRs) is extended to the industrially relevant case of diffusion limited systems. Moreover, a master plot for the system under investigation is proposed: given the reaction recipe, the error on the gel point prediction employing the monoradical assumption is identified, thus allowing more conscious model selection.
    No preview · Article · Jan 2014 · Macromolecular Theory and Simulations

Publication Stats

4k Citations
411.97 Total Impact Points


  • 1999-2015
    • ETH Zurich
      • Institute for Chemical and Bioengineering
      Zürich, Zurich, Switzerland
  • 2011
    • Hochschule für Technik Zürich
      Zürich, Zurich, Switzerland
  • 1983-2011
    • Politecnico di Milano
      • Department of Chemistry, Materials and Chemical Engineering "Giulio Natta"
      Milano, Lombardy, Italy
  • 2006
    • Eawag: Das Wasserforschungs-Institut des ETH-Bereichs
      Duebendorf, Zurich, Switzerland
  • 2001
    • LTC
      Peshawar, Khyber Pakhtunkhwa, Pakistan
  • 1996-2000
    • Università degli studi di Cagliari
      • Department of Mechanical, Chemical and Material Engineering
      Cagliari, Sardinia, Italy
  • 1992-1996
    • University of Padova
      Padua, Veneto, Italy