Nils Leone - Academia.edu (original) (raw)

Papers by Nils Leone

ACS Omega, 2019

In this work, we report on a novel hydrogenb o n d i n g c o m p o u n d , N , N ′-b i s (2-h y d... more In this work, we report on a novel hydrogenb o n d i n g c o m p o u n d , N , N ′-b i s (2-h y d r o x y e t h y l)terephthalamide (BHET), and its potential as additive in poly-L-lactide (PLA). Although the hydroxyl groups of BHET can participate in transesterification with the PLA matrix, we demonstrate through gel permeation chromatography that extrusion at 200°C does not result in a drastic decrease in molecular weight. When dissolved in the PLA matrix, BHET facilitates a plasticizing effect, indicated by a suppression in both melt viscosity and glass-transition temperature. Additionally, BHET can crystallize from the PLA melt during cooling, where the generated BHET crystals facilitate heterogeneous nucleation of the PLA matrix. In general, BHET crystallization is favored at high undercooling/superstaturation, as this yields BHET crystals with a high surface area-to-volume ratio. However, rapid cooling to temperatures below the glass-transition temperature prevents the crystallization of the BHET, effectively yielding samples where only the plasticizing effect of BHET is evident. A suppression in yield point is observed during mechanical analysis of samples with increasing BHET concentration, a characteristic feature for samples with decreasing glass-transition temperatures. In contrast, when allowed to crystallize during processing, BHET can be used to generate PLA crystals oriented along the flow direction, effectively enhancing the tensile modulus. Overall, the combined plasticizing and nucleating effect of BHET makes it a verstaile additive for controlled processing and performance of PLA.

Macromolecules, 2018

We report on the effect of an aliphatic oxalamide based nucleating agent (OXA3,6) on the melt and... more We report on the effect of an aliphatic oxalamide based nucleating agent (OXA3,6) on the melt and crystallization behavior of isotactic polypropylene (iPP) under defined shear conditions. Through polarized optical microscopy, we demonstrate that OXA3,6 self-assembles from the iPP melt into rhombic crystals whereas their size and distribution proved highly dependent on the employed cooling rates. The presence of 0.5 wt % of OXA3,6 in iPP results in a significant suppression in iPP melt viscosity, which could not be explained via molecular modeling. A possible cause for the drop in viscosity in the presence of OXA3,6 is attributed to the interaction (absorption) of high molecular weight iPP chains with the nucleating agent, thereby suppressing their contribution to the viscoelastic response of the melt. This proposed mechanism for the suppression in melt viscosity appears similar to that encountered by the homogeneous distribution of nanoparticles such as CNTs, graphene, and silica. Shear experiments, performed using a slit flow device combined with smallangle X-ray diffraction measurements, indicate that crystallization is significantly enhanced in the presence of OXA3,6 at relatively low shear rates despite its lowered sensitivity to shear. This enhancement in crystallization is attributed to the shear alignment of the rhombic OXA3,6 crystals that provide surface for iPP kebab growth upon cooling. Overall, the suppression in melt viscosity in combination with enhanced nucleation efficiency at low as well as high shear rates makes this self-assembling oxalamide based nucleating agent a promising candidate for fast processing.

Polymers, 2018

In this study, we report on the visco-elastic response during start-up and cessation of shear of ... more In this study, we report on the visco-elastic response during start-up and cessation of shear of a novel bio-based liquid crystal polymer. The ensuing morphological changes are analyzed at different length scales by in-situ polarized optical microscopy and wide-angle X-ray diffraction. Upon inception of shear, the polydomain texture is initially stretched, at larger strain break up processes become increasingly important, and eventually a steady state texture is obtained. The shear stress response showed good coherence between optical and rheo-X-ray data. The evolution of the orientation parameter coincides with the evolution of the texture: the order parameter increases as the texture stretches, drops slightly in the break up regime, and reaches a constant value in the plateau regime. The relaxation of the shear stress and the polydomain texture showed two distinct processes with different timescales: The first is fast contraction of the stretched domain texture; the second is the ...

ACS Sustainable Chemistry & Engineering, 2019

Macromolecules, 2019

We report on the role of temperature and shear on the melt behavior of iPP in the presence of the... more We report on the role of temperature and shear on the melt behavior of iPP in the presence of the organic compound N1,N1′-(propane-1,3-diyl)bis(N2-hexyloxalamide) (OXA3,6). It is demonstrated that OXA3,6 facilitates a viscosity suppression when it resides in the molten state. The viscosity suppression is attributed to the interaction of iPP chains/ subchains with molten OXA3,6 nanoclusters. The exact molecular mechanism has not been identified; nevertheless, a tentative explanation is proposed. The observed viscosity suppression appears similar to that encountered in polymer melts filled with solid nanoparticles, with the difference that the OXA3,6 compound reported in this study facilitates the viscosity suppression in the molten state. Upon cooling, as crystal growth of OXA3,6 progresses, the decrease in viscosity is suppressed. Retrospectively, segmental absorption of iPP chains on the surface of micrometer-sized OXA3,6 crystallites favors the formation of dangling arms, yielding OXA3,6 crystallites decorated with partially absorbed iPP chains. In other words, the resulting OXA3,6 particle morphology resembles that of a hairy particle or a starlike polymer chain. Such hairy particles effectively facilitate a viscosity enhancement, similar to branched polymer chains. This hypothesis and its implications for the shear behavior of iPP are discussed and supported using plate−plate rheometry and slit-flow experiments combined with smallangle X-ray scattering analysis.

RSC Advances, 2018

In this work, we report on the small scale polycondensation and consecutive analysis of novel pol... more In this work, we report on the small scale polycondensation and consecutive analysis of novel polyesters based on the potentially renewable 1,3-cyclopentanediol (CPdiol).

Industrial & Engineering Chemistry Research, 2016

In this study, the performance of three aliphatic oxalamide based compounds as nucleating agent (... more In this study, the performance of three aliphatic oxalamide based compounds as nucleating agent (NA) for isotactic polypropylene (iPP) has been evaluated. The NAs evaluated in this study contain two oxalamide motifs that are connected through linking spacers with 2, 3, or 4 methylene units in between the oxalamide groups, while containing flexible hexyl end-groups on the outside. It is demonstrated that the onset of crystallization in the presence of these NAs under quiescent conditions, generally observed around 120−125°C, is strongly dependent on both the crystallization conditions and NA concentration. Although these oxalamide compounds are only moderately effective under quiescent conditions, they show promise for use under industrially relevant processing conditions that require high cooling and shear rates: When the NA is forced to undergo shear-induced self-assembly and shearalignment during cooling, the onset of crystallization of the iPP phase is observed in SAXS at temperatures up to 140°C.

ACS Omega, 2019

In this work, we report on a novel hydrogenb o n d i n g c o m p o u n d , N , N ′-b i s (2-h y d... more In this work, we report on a novel hydrogenb o n d i n g c o m p o u n d , N , N ′-b i s (2-h y d r o x y e t h y l)terephthalamide (BHET), and its potential as additive in poly-L-lactide (PLA). Although the hydroxyl groups of BHET can participate in transesterification with the PLA matrix, we demonstrate through gel permeation chromatography that extrusion at 200°C does not result in a drastic decrease in molecular weight. When dissolved in the PLA matrix, BHET facilitates a plasticizing effect, indicated by a suppression in both melt viscosity and glass-transition temperature. Additionally, BHET can crystallize from the PLA melt during cooling, where the generated BHET crystals facilitate heterogeneous nucleation of the PLA matrix. In general, BHET crystallization is favored at high undercooling/superstaturation, as this yields BHET crystals with a high surface area-to-volume ratio. However, rapid cooling to temperatures below the glass-transition temperature prevents the crystallization of the BHET, effectively yielding samples where only the plasticizing effect of BHET is evident. A suppression in yield point is observed during mechanical analysis of samples with increasing BHET concentration, a characteristic feature for samples with decreasing glass-transition temperatures. In contrast, when allowed to crystallize during processing, BHET can be used to generate PLA crystals oriented along the flow direction, effectively enhancing the tensile modulus. Overall, the combined plasticizing and nucleating effect of BHET makes it a verstaile additive for controlled processing and performance of PLA.

Macromolecules, 2018

We report on the effect of an aliphatic oxalamide based nucleating agent (OXA3,6) on the melt and... more We report on the effect of an aliphatic oxalamide based nucleating agent (OXA3,6) on the melt and crystallization behavior of isotactic polypropylene (iPP) under defined shear conditions. Through polarized optical microscopy, we demonstrate that OXA3,6 self-assembles from the iPP melt into rhombic crystals whereas their size and distribution proved highly dependent on the employed cooling rates. The presence of 0.5 wt % of OXA3,6 in iPP results in a significant suppression in iPP melt viscosity, which could not be explained via molecular modeling. A possible cause for the drop in viscosity in the presence of OXA3,6 is attributed to the interaction (absorption) of high molecular weight iPP chains with the nucleating agent, thereby suppressing their contribution to the viscoelastic response of the melt. This proposed mechanism for the suppression in melt viscosity appears similar to that encountered by the homogeneous distribution of nanoparticles such as CNTs, graphene, and silica. Shear experiments, performed using a slit flow device combined with smallangle X-ray diffraction measurements, indicate that crystallization is significantly enhanced in the presence of OXA3,6 at relatively low shear rates despite its lowered sensitivity to shear. This enhancement in crystallization is attributed to the shear alignment of the rhombic OXA3,6 crystals that provide surface for iPP kebab growth upon cooling. Overall, the suppression in melt viscosity in combination with enhanced nucleation efficiency at low as well as high shear rates makes this self-assembling oxalamide based nucleating agent a promising candidate for fast processing.

Polymers, 2018

In this study, we report on the visco-elastic response during start-up and cessation of shear of ... more In this study, we report on the visco-elastic response during start-up and cessation of shear of a novel bio-based liquid crystal polymer. The ensuing morphological changes are analyzed at different length scales by in-situ polarized optical microscopy and wide-angle X-ray diffraction. Upon inception of shear, the polydomain texture is initially stretched, at larger strain break up processes become increasingly important, and eventually a steady state texture is obtained. The shear stress response showed good coherence between optical and rheo-X-ray data. The evolution of the orientation parameter coincides with the evolution of the texture: the order parameter increases as the texture stretches, drops slightly in the break up regime, and reaches a constant value in the plateau regime. The relaxation of the shear stress and the polydomain texture showed two distinct processes with different timescales: The first is fast contraction of the stretched domain texture; the second is the ...

ACS Sustainable Chemistry & Engineering, 2019

Macromolecules, 2019

We report on the role of temperature and shear on the melt behavior of iPP in the presence of the... more We report on the role of temperature and shear on the melt behavior of iPP in the presence of the organic compound N1,N1′-(propane-1,3-diyl)bis(N2-hexyloxalamide) (OXA3,6). It is demonstrated that OXA3,6 facilitates a viscosity suppression when it resides in the molten state. The viscosity suppression is attributed to the interaction of iPP chains/ subchains with molten OXA3,6 nanoclusters. The exact molecular mechanism has not been identified; nevertheless, a tentative explanation is proposed. The observed viscosity suppression appears similar to that encountered in polymer melts filled with solid nanoparticles, with the difference that the OXA3,6 compound reported in this study facilitates the viscosity suppression in the molten state. Upon cooling, as crystal growth of OXA3,6 progresses, the decrease in viscosity is suppressed. Retrospectively, segmental absorption of iPP chains on the surface of micrometer-sized OXA3,6 crystallites favors the formation of dangling arms, yielding OXA3,6 crystallites decorated with partially absorbed iPP chains. In other words, the resulting OXA3,6 particle morphology resembles that of a hairy particle or a starlike polymer chain. Such hairy particles effectively facilitate a viscosity enhancement, similar to branched polymer chains. This hypothesis and its implications for the shear behavior of iPP are discussed and supported using plate−plate rheometry and slit-flow experiments combined with smallangle X-ray scattering analysis.

RSC Advances, 2018

In this work, we report on the small scale polycondensation and consecutive analysis of novel pol... more In this work, we report on the small scale polycondensation and consecutive analysis of novel polyesters based on the potentially renewable 1,3-cyclopentanediol (CPdiol).

Industrial & Engineering Chemistry Research, 2016

In this study, the performance of three aliphatic oxalamide based compounds as nucleating agent (... more In this study, the performance of three aliphatic oxalamide based compounds as nucleating agent (NA) for isotactic polypropylene (iPP) has been evaluated. The NAs evaluated in this study contain two oxalamide motifs that are connected through linking spacers with 2, 3, or 4 methylene units in between the oxalamide groups, while containing flexible hexyl end-groups on the outside. It is demonstrated that the onset of crystallization in the presence of these NAs under quiescent conditions, generally observed around 120−125°C, is strongly dependent on both the crystallization conditions and NA concentration. Although these oxalamide compounds are only moderately effective under quiescent conditions, they show promise for use under industrially relevant processing conditions that require high cooling and shear rates: When the NA is forced to undergo shear-induced self-assembly and shearalignment during cooling, the onset of crystallization of the iPP phase is observed in SAXS at temperatures up to 140°C.