References of "Sanctuary, Roland 50002979"
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See detailFractionation of cellulose nanocrystals: enhancing liquid crystal ordering without promoting gelation
Honorato Rios, Camila UL; Lehr, Claudius Moritz UL; Schütz, Christina UL et al

in NPG asia materials (2018)

Colloids of electrically charged nanorods can spontaneously develop a fluid yet ordered liquid crystal phase, but this ordering competes with a tendency to form a gel of percolating rods. The threshold ... [more ▼]

Colloids of electrically charged nanorods can spontaneously develop a fluid yet ordered liquid crystal phase, but this ordering competes with a tendency to form a gel of percolating rods. The threshold for ordering is reduced by increasing the rod aspect ratio, but the percolation threshold is also reduced with this change; hence, prediction of the outcome is nontrivial. Here, we show that by establishing the phase behavior of suspensions of cellulose nanocrystals(CNCs) fractionated according to length, an increased aspect ratio can strongly favor liquid crystallinity without necessarily influencing gelation. Gelation is instead triggered by increasing the counterion concentration until theCNCs lose colloidal stability, triggering linear aggregation, which promotes percolation regardless of the original rod aspect ratio. Our results shine new light on the competition between liquid crystal formation and gelation in nanoparticle suspensions and provide a path for enhanced control of CNC self-organization for applications in photonic crystal paper or advanced composites. [less ▲]

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See detailRelaxations in the metastable rotator phase of n-eicosane
Di Giambattista, Carlo UL; Sanctuary, Roland UL; Perigo, Elio Alberto UL et al

in The Journal of Chemical Physics (2015), 143

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See detailSlow dynamics in sheared DGEBA/SiO2 suspensions
Dannert, Rick UL; Sanctuary, Roland UL; Baller, Jörg UL

Presentation (2015, March)

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See detailMobility restrictions and glass transition behaviour of an epoxy resin under confinement
Djemour, A.; Sanctuary, Roland UL; Baller, Jörg UL

in Soft Matter (2015), 11(13), 2683-2690

Confinement can have a big influence on the dynamics of glass formers in the vicinity of the glass transition. Already 40 to 50 K above the glass transition temperature, thermal equilibration of glass ... [more ▼]

Confinement can have a big influence on the dynamics of glass formers in the vicinity of the glass transition. Already 40 to 50 K above the glass transition temperature, thermal equilibration of glass formers can be strongly influenced by the confining substrate. We investigate the linear thermal expansion and the specific heat capacity c(p) of an epoxy resin (diglycidyl ether of bisphenol A, DGEBA) in a temperature interval of 120 K around the glass transition temperature. The epoxy resin is filled into controlled pore glasses with pore diameters between 4 and 111 nm. Since DGEBA can form H-bonds with silica surfaces, we also investigate the influence of surface silanization of the porous substrates. In untreated substrates a core/shell structure of the epoxy resin can be identified. The glass transition behaviours of the bulk phase and that of the shell phase are different. In silanized substrates, the shell phase disappears. At a temperature well above the glass transition, a second transition is found for the bulk phase - both in the linear expansion data as well as in the specific heat capacity. The c(p) data do not allow excluding the glass transition of a third phase as being the cause for this transition, whereas the linear expansion data do so. The additional transition temperature is interpreted as a separation between two regimes: above this temperature, macroscopic flow of the bulk phase inside the porous structure is possible to balance the mismatch of thermal expansion coefficients between DGEBA and the substrate. Below the transition temperature, this degree of freedom is hindered by geometrical constraints of the porous substrates. Moreover, this second transition could also be found in the linear expansion data of the shell phase. [less ▲]

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See detailAnomalous glass transition behavior of SBR–Al2O3 nanocomposites at small filler concentrations
Sushko, Rymma UL; Filimon, Marlena UL; Dannert, Rick UL et al

in Nanotechnology (2014), 25(42), 425704

Elastomers filled with hard nanoparticles are of great technical importance for the rubber industry. In general, fillers improve mechanical properties of polymer materials, e.g. elastic moduli, tensile ... [more ▼]

Elastomers filled with hard nanoparticles are of great technical importance for the rubber industry. In general, fillers improve mechanical properties of polymer materials, e.g. elastic moduli, tensile strength etc. The smaller the size of the particles the larger is the interface where interactions between polymer molecules and fillers can generate new properties. Using temperature-modulated differential scanning calorimetry and dynamic mechanical analysis, we investigated the properties of pure styrene-butadiene rubber (SBR) and SBR/alumina nanoparticles. Beside a reinforcement effect seen in the complex elastic moduli, small amounts of nanoparticles of about 2 wt% interestingly lead to an acceleration of the relaxation modes responsible for the thermal glass transition. This leads to a minimum in the glass transition temperature as a function of nanoparticle content in the vicinity of this critical concentration. The frequency dependent elastic moduli are used to discuss the possible reduction of the entanglement of rubber molecules as one cause for this unexpected behavior. [less ▲]

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See detailComparative study of the effect of untreated, silanized and grafted alumina nanoparticles on thermal and dynamic mechanical properties of the styrene-butadiene rubber
Sushko, Rymma UL; Baller, Jörg UL; Filimon, Marlena UL et al

in AIP Conferences Proceedings (2014, May 15), 1599

Elastomers filled with hard nanoparticles are of great technical importance for the rubber industry. In general, fillers improve mechanical properties of polymer materials, e.g. elastic moduli, tensile ... [more ▼]

Elastomers filled with hard nanoparticles are of great technical importance for the rubber industry. In general, fillers improve mechanical properties of polymer materials, e.g. elastic moduli, tensile strength etc. The smaller the size of the particles the larger is the interface where interactions between polymer molecules and fillers can generate new properties. Using Temperature Modulated Differential Scanning Calorimetry (TMDSC) and Dynamic Mechanical Analysis (DMA), we investigated the properties of the pure styrene-butadiene rubber (SBR), SBR/ alumina nanoparticles, SBR/silanized alumina and SBR/alumina grafted to polymer chains. Beside a general reinforcement effect seen in the complex elastic moduli, the studies revealed that: i) small concentrations of nanoparticles (of 1.5-2 wt%) lead to a minimum in the glass transition temperature as a function of nanoparticle content; ii) for the grafted nanocomposites increasing the nanoparticle concentration beyond 4 wt% yields an increase of Tg by 4 K; iii) DMA mastercurves showed that in case of untreated and silanized alumina mechanical behaviour of the composite systems is rather near to the one of the SBR matrix, but the grafting of elastomer molecules to the silanized fillers induces a quasi-solid like response of the system in the low frequency regime. [less ▲]

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See detailAnomaly in thermal and mechanical properties of SBR/alumina nanocomposites
Sushko, Rymma UL; Baller, Jörg UL; Filimon, Marlena UL et al

Scientific Conference (2014, April 03)

Filling elastomers with nanoparticles generally leads to changes in the relaxation behavior of the matrix molecules. Using dynamic mechanical analysis (DMA) and temperature modulated calorimetry (TMDSC ... [more ▼]

Filling elastomers with nanoparticles generally leads to changes in the relaxation behavior of the matrix molecules. Using dynamic mechanical analysis (DMA) and temperature modulated calorimetry (TMDSC), we investigate the influence of different amounts of untreated, hydrophilic alumina nanoparticles on the properties of a model rubber system (SBR). Beside a reinforcement effect seen in the complex elastic moduli, small amounts of nanoparticles of about 2 wt% interestingly lead to an acceleration of the relaxation modes responsible for the thermal glass transition. This leads to a minimum in the glass transition temperature as a function of nanoparticle content in the vicinity of this critical concentration. The frequency dependent elastic moduli are used to discuss the possible reduction of the entanglement of rubber molecules as one cause for this unexpected behavior. [less ▲]

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See detailMolecular versus macroscopic perspective on the demixing transition of aqueous PNIPAM solutions by studying the dual character of the refractive index
Philipp, Martine UL; Aleksandrova, Ralitsa UL; Müller, Ulrich UL et al

in Soft Matter (2014), 10(37), 7297-7305

The phase separation of aqueous poly(N-isopropyl acrylamide) (PNIPAM) solutions is known to strongly affect their volume expansion behaviour and the elastic moduli, as the latter are strongly coupled to ... [more ▼]

The phase separation of aqueous poly(N-isopropyl acrylamide) (PNIPAM) solutions is known to strongly affect their volume expansion behaviour and the elastic moduli, as the latter are strongly coupled to the macroscopic order parameter. On the molecular scale, considerable changes in H-bonding and hydrophobic interactions, as well as in the structure govern the demixing process. However, the relationship between the molecular and macroscopic order parameters is unclear for such complex phase-separating solutions. We contribute to the clarification of this problem by relating optical to volumetric properties across the demixing transition of dilute to concentrated aqueous PNIPAM solutions. Far from the demixing temperature, the temperature dependence of the refractive index is predominantly determined by thermal expansion. In the course of phase separation, the refractive index is dominated by the anomalous behaviour of the specific refractivity, which reflects the spatio-temporally averaged changes in molecular interactions and the structural reorganization of the demixing solutions. Moreover, the presence of relaxation processes is studied by the complex expansion coefficient using the novel technique of temperature modulated optical refractometry. [less ▲]

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See detailPhase Instability and Molecular Kinetics Provoked by Repeated Crossing of the Demixing Transition of PNIPAM Solutions
Aleksandrova, Ralitsa UL; Philipp, Martine; Müller, Ulrich et al

in Langmuir (2014), 30

The demixing process of aqueous poly(N-isopropylacrylamide) (PNIPAM) solutions can occur either via a nucleation and growth process or via spinodal decomposition. The ensuing self-assembly, leading to ... [more ▼]

The demixing process of aqueous poly(N-isopropylacrylamide) (PNIPAM) solutions can occur either via a nucleation and growth process or via spinodal decomposition. The ensuing self-assembly, leading to heterogeneous morphologies within the PNIPAM solution, is codetermined by kinetic processes caused by molecular transport. By subjecting PNIPAM solutions to cyclic changes in temperature leading to repeated crossing of the demixing transition, we are able to assess the importance of kinetics as well as of overheating and supercooling of the phase transition within the metastable range delimited by the binodal and spinodal lines. First indications about the location of these stability limits for the low- and high-temperature phases, separated by about 1.6 K, could be gained by detailed kinetic studies of the refractive index. These investigations are made possible due to the novel technique of temperature-modulated optical refractometry. [less ▲]

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See detailStrain-induced low-frequency relaxation in colloidal DGEBA/SiO2 suspensions
Dannert, Rick UL; Sanctuary, Roland UL; Thomassey, M. et al

in Rheologica Acta (2014), 53(9), 715-723

Diglycidyl ether of bisphenol A (DGEBA) is widely exploited as an epoxy resin in adhesives and coatings. In this paper, it is used as an oligomer matrix for silica-filled nanocomposites. Rheological ... [more ▼]

Diglycidyl ether of bisphenol A (DGEBA) is widely exploited as an epoxy resin in adhesives and coatings. In this paper, it is used as an oligomer matrix for silica-filled nanocomposites. Rheological measurements show that the pure matrix obeys power-law relaxation dynamics in the vicinity of the dynamic glass transition of this low-molecular-weight glass former. In the filled systems, a low-frequency relaxation appears additionally to the structural alpha-process of the matrix. Considering the nanocomposites as Newtonian hard-sphere suspensions at low angular frequencies (or high temperatures), the modified terminal regime behavior of the matrix can be linked to strain-induced perturbations of the isotropic filler distributions. While in the low-frequency regime hydrodynamic stresses relax instantaneously, the Brownian stress relaxation is viscoelastic and can be evidenced by dynamic rheological measurements. At higher angular frequencies, the alpha-process of the matrix superimposes on the Brownian stress relaxation. In particular, we were able to depict the low-frequency anomaly for concentrated, semi-dilute, and even for dilute suspensions. [less ▲]

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See detailEffect of grafted alumina nanoparticles on thermal and dynamic mechanical properties of the styrene-butadiene rubber
Sushko, Rymma UL; Baller, Jörg UL; Filimon, Marlena UL et al

Poster (2013, September)

Elastomers filled with hard nanoparticles are of great technical importance for the rubber industry. In general, fillers improve mechanical properties of polymer materials, e.g. elastic moduli, tensile ... [more ▼]

Elastomers filled with hard nanoparticles are of great technical importance for the rubber industry. In general, fillers improve mechanical properties of polymer materials, e.g. elastic moduli, tensile strength etc. The smaller the size of the particles the larger is the interface where interactions between polymer molecules and fillers can generate new properties. The aim of this contribution is to study the influence of the fillers’ surface treatment on the thermal and mechanical behavior of nanocomposites made of styrene-butadiene rubber (SBR). Three types of nanocomposites are investigated : (i) SBR-unmodified alumina, (ii) SBR – silanized alumina and (iii) SBR – alumina grafted to polymer chains. The surface-modified alumina nanoparticles were prepared using the method described in [1]. The grafting of the SBR chains to the alumina nanoparticles was realized by means of the procedures described in [2] and [3]. Temperature Modulated Differential Scanning Calorimetry (TMDSC) and Dynamic Mechanical Analysis (DMA) are well appropriated tools to investigate the thermal and dynamic glass transition behavior of the different nanocomposites, which is expected to be very sensitive to interfacial interactions between the nanoparticles and matrix molecules. TMDSC experiments reveal that all of the nanocomposites undergo a single glass transition. Thus, interphases induced by interfacial interactions do not manifest themselves by an additional glass transition unless it is hidden by the one of the matrix. Moreover, TMDSC measurements reveal that in general the glass transition temperature Tg depends in a complex manner on the concentration and surface treatment of the nanoparticles. The most important change of Tg is observed for the grafted nanocomposites: increasing the nanoparticle weight concentration beyond 4% yields an increase of Tg by 4 K. The corresponding slowing down of the molecular dynamics goes along with a significant decrease of the relaxator strength. More generally the presented results prove that, at the same filler concentration, the number of degrees of freedom freezing at the glass transition in case of un-grafted systems is practically independent on the chemical nature of the particles surface whereas it changes when there exist covalent bonds between the polymer molecules and the nanoparticles. DMA was used to probe the rheological behaviour of the nanocomposites under oscillatory shear. Isothermal frequency sweeps performed at different temperatures yield the real (G’) and imaginary (G”) parts of the complex shear modulus. Linear response regime conditions were strictly respected. The temperature-frequency equivalence principle was exploited to construct mastercurves for G’ and G” at the reference temperature T=273 K. As usual in polymers, three different behaviors were observed: the dynamic glass transition at high frequencies, the entanglement plateau at intermediary frequencies and viscoelastic “flowing” at very low frequencies. It generally appears that the filling of the SBR matrix with nanoparticles leads to an increase of the storage modulus that is more prominent in the rubbery region than in the glassy segment. While, in the low frequency regime, untreated and silanized alumina yield a mechanical behaviour that is rather near to the one of the neat SBR matrix, the grafting of elastomer molecules to the silanized fillers obviously induces a quasi-solid like response of the system. References: 1. Y.-Ch. Yang, S.-B. Jeong, B.-G. Kim, P.-R. Yoon, Powder Technology, 191, 117–121, 2009. 2. E. Passaglia, F. Donati, Polymer, 48, 35-42, 2007. 3. A. Bhattacharya, B. Misra, Prog. Polym. Sci. 29, 767–814, 2004. [less ▲]

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