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Charles E. Hoyle - One of the best experts on this subject based on the ideXlab platform.

  • Enthalpy Relaxation of Photopolymerized Multilayered Thiol-ene Films
    Journal of Applied Polymer Science, 2012
    Co-Authors: Junghwan Shin, Sergei Nazarenko, Charles E. Hoyle
    Abstract:

    Multilayered thiol-ene network films with two and three different components were fabricated by spin coating and photopolymerization. The distinctive glass transition temperatures of each layer component were observed at corresponding glass transition regions of each bulk sample. Sub-Tg aging of 10-, 21-, and 32-layered thiol-ene films was investigated in terms of Enthalpy Relaxation. Enthalpy Relaxation of each layer component occurred independently and presented the characteristic time and temperature dependency. Overlapped unsymmetrical bell-shaped Enthalpy Relaxation distribution having peak maximum at Tg-10°C of each layer component was observed, resulting in broad distribution of Enthalpy Relaxation over wide temperature range. In addition, Enthalpy Relaxation of each layer component in the multilayered thiol-ene films was significantly accelerated comparing to that of bulk thiol-ene samples. Dynamic mechanical thermal properties of multilayered thiol-ene films also showed two and three separated glass transition temperature. However, for 32-layered thiol-ene film consisting of three different layer components, glass transition and damping region are overlapped and the width is extended more than 100°C. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013

  • Effects of Chemical Modification of Thiol-Ene Networks on Enthalpy Relaxation
    Macromolecules, 2009
    Co-Authors: Junghwan Shin, Sergei Nazarenko, Charles E. Hoyle
    Abstract:

    The highly uniform and dense network structure of photopolymerized thiol−enes was chemically modified, and the Enthalpy Relaxation of the networks was measured. n-Alkyl acrylate and hydroxyl acrylate groups were incorporated into thiol−ene networks using a phosphine-catalyzed Michael addition reaction. The effect of flexible alkyl side chains and hydrogen bonding on sub-Tg Relaxation was evaluated without sacrificing network uniformity. Overall both the rate and extent of Enthalpy Relaxation decreased as a function of the flexible n-alkyl chain length, while hydrogen bonding resulted in enhanced Enthalpy Relaxation. A trithiol−triene−triacrylate ternary system was investigated by correlating Enthalpy Relaxation and network uniformity. A multifunctional acrylate (TMPTA), being capable of homopolymerization as well as thiol−acrylate copolymerization, was incorporated into a thiol−ene network structure, thereby decreasing the network uniformity and significantly affecting the Enthalpy Relaxation behavior. In...

  • Physical and chemical modifications of thiol-ene networks to control activation energy of Enthalpy Relaxation
    Polymer, 2009
    Co-Authors: Junghwan Shin, Sergei Nazarenko, J. Paige Phillips, Charles E. Hoyle
    Abstract:

    Abstract Gold nanoparticles and multi-functional acrylate (TMPTA) were incorporated into a photopolymerized thiol-ene (TMPMP–APE) network as a physical and chemical approach to intentionally control sub-Tg aging. The degree of the restriction effect was evaluated by differential cooling rate measurements allowing the quantification of the apparent activation energy for Enthalpy Relaxation (Δh*) upon sub-Tg aging. Incorporation of gold nanoparticles (0.01 to 1 wt%) into the TMPMP–APE network increased Tg and decreased ΔCp at Tg due to molecular mobility restrictions. The extent of Enthalpy Relaxation and apparent activation energy for Enthalpy Relaxation (Δh*) clearly indicated the significant restrictive effect of the gold nanoparticles on the molecular mobility in the thiol-ene network. A TMPMP–APE–TMPTA ternary system was investigated in order to correlate Δh* and network uniformity as a chemical approach. TMPTA, being capable of homopolymerization as well as TMPMP–TMPTA copolymerization, was incorporated into a TMPMP–APE network structure, thereby decreasing the network uniformity and significantly affecting the sub-Tg aging. The extent of Enthalpy Relaxation decreased and the distribution was drastically broadened as a function of TMPTA content due to molecular mobility restrictions, which were also quantified by measuring values for the apparent Enthalpy Relaxation activation energy (Δh*).

  • Enthalpy Relaxation of Photopolymerized Thiol−Ene Networks: Structural Effects
    Macromolecules, 2008
    Co-Authors: Junghwan Shin, Sergei Nazarenko, Charles E. Hoyle
    Abstract:

    Physical aging behavior of photopolymerized thiol−ene networks was investigated by measuring the extent of Enthalpy Relaxation in terms of network density and molecular structure. The homogeneous network structure of the thiol−enes, having narrow glass transition temperature ranges, showed characteristic temperature and time dependency relationships for Enthalpy Relaxation. All thiol−ene films annealed at different temperatures (Ta) for 1 h according to the isochronal method showed maximum Enthalpy Relaxation peaks at approximately Tg − 10 °C by DSC. The extent of Enthalpy Relaxation as a function of annealing time (ta) was obtained by the isothermal aging method. Correlations between the extent of Enthalpy Relaxation and the heat capacity difference at Tg were made and related to thiol−ene chemical group rigidity and network linking density. Pendulum hardness values for a selected thiol−ene film showed a clear change in hardness upon aging, indicating sub-Tg mechanical Relaxation, consistent with the rel...

  • Enthalpy Relaxation of photopolymerized thiol ene networks structural effects
    Macromolecules, 2008
    Co-Authors: Junghwan Shin, Sergei Nazarenko, Charles E. Hoyle
    Abstract:

    Physical aging behavior of photopolymerized thiol−ene networks was investigated by measuring the extent of Enthalpy Relaxation in terms of network density and molecular structure. The homogeneous network structure of the thiol−enes, having narrow glass transition temperature ranges, showed characteristic temperature and time dependency relationships for Enthalpy Relaxation. All thiol−ene films annealed at different temperatures (Ta) for 1 h according to the isochronal method showed maximum Enthalpy Relaxation peaks at approximately Tg − 10 °C by DSC. The extent of Enthalpy Relaxation as a function of annealing time (ta) was obtained by the isothermal aging method. Correlations between the extent of Enthalpy Relaxation and the heat capacity difference at Tg were made and related to thiol−ene chemical group rigidity and network linking density. Pendulum hardness values for a selected thiol−ene film showed a clear change in hardness upon aging, indicating sub-Tg mechanical Relaxation, consistent with the rel...

Junghwan Shin - One of the best experts on this subject based on the ideXlab platform.

  • Enthalpy Relaxation of Photopolymerized Multilayered Thiol-ene Films
    Journal of Applied Polymer Science, 2012
    Co-Authors: Junghwan Shin, Sergei Nazarenko, Charles E. Hoyle
    Abstract:

    Multilayered thiol-ene network films with two and three different components were fabricated by spin coating and photopolymerization. The distinctive glass transition temperatures of each layer component were observed at corresponding glass transition regions of each bulk sample. Sub-Tg aging of 10-, 21-, and 32-layered thiol-ene films was investigated in terms of Enthalpy Relaxation. Enthalpy Relaxation of each layer component occurred independently and presented the characteristic time and temperature dependency. Overlapped unsymmetrical bell-shaped Enthalpy Relaxation distribution having peak maximum at Tg-10°C of each layer component was observed, resulting in broad distribution of Enthalpy Relaxation over wide temperature range. In addition, Enthalpy Relaxation of each layer component in the multilayered thiol-ene films was significantly accelerated comparing to that of bulk thiol-ene samples. Dynamic mechanical thermal properties of multilayered thiol-ene films also showed two and three separated glass transition temperature. However, for 32-layered thiol-ene film consisting of three different layer components, glass transition and damping region are overlapped and the width is extended more than 100°C. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013

  • Effects of Chemical Modification of Thiol-Ene Networks on Enthalpy Relaxation
    Macromolecules, 2009
    Co-Authors: Junghwan Shin, Sergei Nazarenko, Charles E. Hoyle
    Abstract:

    The highly uniform and dense network structure of photopolymerized thiol−enes was chemically modified, and the Enthalpy Relaxation of the networks was measured. n-Alkyl acrylate and hydroxyl acrylate groups were incorporated into thiol−ene networks using a phosphine-catalyzed Michael addition reaction. The effect of flexible alkyl side chains and hydrogen bonding on sub-Tg Relaxation was evaluated without sacrificing network uniformity. Overall both the rate and extent of Enthalpy Relaxation decreased as a function of the flexible n-alkyl chain length, while hydrogen bonding resulted in enhanced Enthalpy Relaxation. A trithiol−triene−triacrylate ternary system was investigated by correlating Enthalpy Relaxation and network uniformity. A multifunctional acrylate (TMPTA), being capable of homopolymerization as well as thiol−acrylate copolymerization, was incorporated into a thiol−ene network structure, thereby decreasing the network uniformity and significantly affecting the Enthalpy Relaxation behavior. In...

  • Physical and chemical modifications of thiol-ene networks to control activation energy of Enthalpy Relaxation
    Polymer, 2009
    Co-Authors: Junghwan Shin, Sergei Nazarenko, J. Paige Phillips, Charles E. Hoyle
    Abstract:

    Abstract Gold nanoparticles and multi-functional acrylate (TMPTA) were incorporated into a photopolymerized thiol-ene (TMPMP–APE) network as a physical and chemical approach to intentionally control sub-Tg aging. The degree of the restriction effect was evaluated by differential cooling rate measurements allowing the quantification of the apparent activation energy for Enthalpy Relaxation (Δh*) upon sub-Tg aging. Incorporation of gold nanoparticles (0.01 to 1 wt%) into the TMPMP–APE network increased Tg and decreased ΔCp at Tg due to molecular mobility restrictions. The extent of Enthalpy Relaxation and apparent activation energy for Enthalpy Relaxation (Δh*) clearly indicated the significant restrictive effect of the gold nanoparticles on the molecular mobility in the thiol-ene network. A TMPMP–APE–TMPTA ternary system was investigated in order to correlate Δh* and network uniformity as a chemical approach. TMPTA, being capable of homopolymerization as well as TMPMP–TMPTA copolymerization, was incorporated into a TMPMP–APE network structure, thereby decreasing the network uniformity and significantly affecting the sub-Tg aging. The extent of Enthalpy Relaxation decreased and the distribution was drastically broadened as a function of TMPTA content due to molecular mobility restrictions, which were also quantified by measuring values for the apparent Enthalpy Relaxation activation energy (Δh*).

  • Enthalpy Relaxation of Photopolymerized Thiol−Ene Networks: Structural Effects
    Macromolecules, 2008
    Co-Authors: Junghwan Shin, Sergei Nazarenko, Charles E. Hoyle
    Abstract:

    Physical aging behavior of photopolymerized thiol−ene networks was investigated by measuring the extent of Enthalpy Relaxation in terms of network density and molecular structure. The homogeneous network structure of the thiol−enes, having narrow glass transition temperature ranges, showed characteristic temperature and time dependency relationships for Enthalpy Relaxation. All thiol−ene films annealed at different temperatures (Ta) for 1 h according to the isochronal method showed maximum Enthalpy Relaxation peaks at approximately Tg − 10 °C by DSC. The extent of Enthalpy Relaxation as a function of annealing time (ta) was obtained by the isothermal aging method. Correlations between the extent of Enthalpy Relaxation and the heat capacity difference at Tg were made and related to thiol−ene chemical group rigidity and network linking density. Pendulum hardness values for a selected thiol−ene film showed a clear change in hardness upon aging, indicating sub-Tg mechanical Relaxation, consistent with the rel...

  • Enthalpy Relaxation of photopolymerized thiol ene networks structural effects
    Macromolecules, 2008
    Co-Authors: Junghwan Shin, Sergei Nazarenko, Charles E. Hoyle
    Abstract:

    Physical aging behavior of photopolymerized thiol−ene networks was investigated by measuring the extent of Enthalpy Relaxation in terms of network density and molecular structure. The homogeneous network structure of the thiol−enes, having narrow glass transition temperature ranges, showed characteristic temperature and time dependency relationships for Enthalpy Relaxation. All thiol−ene films annealed at different temperatures (Ta) for 1 h according to the isochronal method showed maximum Enthalpy Relaxation peaks at approximately Tg − 10 °C by DSC. The extent of Enthalpy Relaxation as a function of annealing time (ta) was obtained by the isothermal aging method. Correlations between the extent of Enthalpy Relaxation and the heat capacity difference at Tg were made and related to thiol−ene chemical group rigidity and network linking density. Pendulum hardness values for a selected thiol−ene film showed a clear change in hardness upon aging, indicating sub-Tg mechanical Relaxation, consistent with the rel...

Valentyn Maidannyk - One of the best experts on this subject based on the ideXlab platform.

  • physical properties of maltodextrin de 10 water sorption water plasticization and Enthalpy Relaxation
    Journal of Food Engineering, 2016
    Co-Authors: Bambang Nurhadi, Yrjo H Roos, Valentyn Maidannyk
    Abstract:

    Maltodextrins are hydrolysis products of starch. The present research aimed to study physical properties of maltodextrins (water sorption, water plasticization behavior and Enthalpy Relaxation) and highlighting their functions as food components. The GAB and GT equation were fitted successfully to water sorption and water plasticization data of maltodextrin DE 10. The critical water content and critical water activity values at 25 °C were 14 g water/100 g dry solid and 0.68 aw, respectively. The Kohlrausch–Williams–Watt (KWW model) and extended Adam-Gibbs model fitted well the Enthalpy Relaxation kinetics data. The non-exponential parameter, β value of maltodextrin DE 10 was within in the range of 0.15–0.93 and its value was dependent on the water activity. At 25 °C, Maltodextrin with aw <0.43 was stable glassy as indicated by very long Enthalpy Relaxation time. The KWW model gave a more accurate fit than the extended Adam-Gibbs model. Arrhenius model fitted well to Enthalpy Relaxation data and gave a free activation energy (Ea) of 459.5 kJ/mol.

  • Physical properties of maltodextrin DE 10: Water sorption, water plasticization and Enthalpy Relaxation
    Journal of Food Engineering, 2016
    Co-Authors: Bambang Nurhadi, Yrjo H Roos, Valentyn Maidannyk
    Abstract:

    Maltodextrins are hydrolysis products of starch. The present research aimed to study physical properties of maltodextrins (water sorption, water plasticization behavior and Enthalpy Relaxation) and highlighting their functions as food components. The GAB and GT equation were fitted successfully to water sorption and water plasticization data of maltodextrin DE 10. The critical water content and critical water activity values at 25 °C were 14 g water/100 g dry solid and 0.68 aw, respectively. The Kohlrausch–Williams–Watt (KWW model) and extended Adam-Gibbs model fitted well the Enthalpy Relaxation kinetics data. The non-exponential parameter, β value of maltodextrin DE 10 was within in the range of 0.15–0.93 and its value was dependent on the water activity. At 25 °C, Maltodextrin with aw

Jean-marc Pelletier - One of the best experts on this subject based on the ideXlab platform.

  • Enthalpy Relaxation in Cu46Zr45Al7Y2 and Zr55Cu30Ni5Al10 bulk metallic glasses by differential scanning calorimetry (DSC)
    Intermetallics, 2011
    Co-Authors: J.c. Qiao, Jean-marc Pelletier
    Abstract:

    Abstract Structural Relaxation process in Cu46Zr45Al7Y2 and Zr55Cu30Ni5Al10 bulk metallic glasses during annealing below the glass transition temperature Tg was investigated by differential scanning calorimetry (DSC). The features of Enthalpy Relaxation are sensitive to both annealing temperature and annealing time. For a given annealing time ta, the results indicated that the Relaxation time ta decreases with increasing the annealing temperature Ta, in good agreement with results relative to other bulk metallic glasses. Additionally, the Enthalpy Relaxation behaviour of the bulk metallic glasses appears independent on the cooling rate used before the physical aging experiments, i.e. on the initial as-cast state. The recovered Enthalpy evolution of the bulk metallic glasses is well described by the Kohlrausch–Williams–Watts (KWW) exponential Relaxation function as ΔH(Ta) = ΔHeq{1 − exp[−(ta/τ)β]}. Kohlrausch exponent β and Enthalpy Relaxation time τ are sensitive to the composition of the bulk metallic glasses. Finally, the influence of different heating treatment processes on the Enthalpy Relaxation in the bulk metallic glasses is presented and shows that this phenomenon is mainly reversible. The structural Relaxation behaviour is interpreted by free volume model and quasi-point defects model. Kinetic fragility parameters m in Cu46Zr45Al7Y2 and Zr55Cu30Ni5Al10 bulk metallic glasses are 72 and 69, respectively, indicating therefore that these alloys are intermediate glasses. Crystallization process was also investigated by DSC experiments. According to the Kissinger model, corresponding activation energy is 3.18 eV in Cu46Zr45Al7Y2, and 3.19 eV in Zr55Cu30Ni5Al10, respectively.

  • Enthalpy Relaxation in Cu46Zr45Al7Y 2 and Zr55Cu30Ni5Al10 bulk metallic glasses by differential scanning calorimetry (DSC)
    Intermetallics, 2011
    Co-Authors: J.c. Qiao, Jean-marc Pelletier
    Abstract:

    Structural Relaxation process in Cu46Zr45Al 7Y2 and Zr55Cu30Ni 5Al10 bulk metallic glasses during annealing below the glass transition temperature Tg was investigated by differential scanning calorimetry (DSC). The features of Enthalpy Relaxation are sensitive to both annealing temperature and annealing time. For a given annealing time ta, the results indicated that the Relaxation time ta decreases with increasing the annealing temperature Ta, in good agreement with results relative to other bulk metallic glasses. Additionally, the Enthalpy Relaxation behaviour of the bulk metallic glasses appears independent on the cooling rate used before the physical aging experiments, i.e. on the initial as-cast state. The recovered Enthalpy evolution of the bulk metallic glasses is well described by the Kohlrausch-Williams-Watts (KWW) exponential Relaxation function as ΔH(Ta) = ΔH eq1 - exp[-(ta/τ)β]. Kohlrausch exponent β and Enthalpy Relaxation time τ are sensitive to the composition of the bulk metallic glasses. Finally, the influence of different heating treatment processes on the Enthalpy Relaxation in the bulk metallic glasses is presented and shows that this phenomenon is mainly reversible. The structural Relaxation behaviour is interpreted by free volume model and quasi-point defects model. Kinetic fragility parameters m in Cu 46Zr45Al7Y2 and Zr 55Cu30Ni5Al10 bulk metallic glasses are 72 and 69, respectively, indicating therefore that these alloys are intermediate glasses. Crystallization process was also investigated by DSC experiments. According to the Kissinger model, corresponding activation energy is 3.18 eV in Cu46Zr45Al7Y2, and 3.19 eV in Zr55Cu30Ni5Al10, respectively. © 2010 Elsevier Ltd. All rights reserved.

Sergei Nazarenko - One of the best experts on this subject based on the ideXlab platform.

  • Enthalpy Relaxation of Photopolymerized Multilayered Thiol-ene Films
    Journal of Applied Polymer Science, 2012
    Co-Authors: Junghwan Shin, Sergei Nazarenko, Charles E. Hoyle
    Abstract:

    Multilayered thiol-ene network films with two and three different components were fabricated by spin coating and photopolymerization. The distinctive glass transition temperatures of each layer component were observed at corresponding glass transition regions of each bulk sample. Sub-Tg aging of 10-, 21-, and 32-layered thiol-ene films was investigated in terms of Enthalpy Relaxation. Enthalpy Relaxation of each layer component occurred independently and presented the characteristic time and temperature dependency. Overlapped unsymmetrical bell-shaped Enthalpy Relaxation distribution having peak maximum at Tg-10°C of each layer component was observed, resulting in broad distribution of Enthalpy Relaxation over wide temperature range. In addition, Enthalpy Relaxation of each layer component in the multilayered thiol-ene films was significantly accelerated comparing to that of bulk thiol-ene samples. Dynamic mechanical thermal properties of multilayered thiol-ene films also showed two and three separated glass transition temperature. However, for 32-layered thiol-ene film consisting of three different layer components, glass transition and damping region are overlapped and the width is extended more than 100°C. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013

  • Effects of Chemical Modification of Thiol-Ene Networks on Enthalpy Relaxation
    Macromolecules, 2009
    Co-Authors: Junghwan Shin, Sergei Nazarenko, Charles E. Hoyle
    Abstract:

    The highly uniform and dense network structure of photopolymerized thiol−enes was chemically modified, and the Enthalpy Relaxation of the networks was measured. n-Alkyl acrylate and hydroxyl acrylate groups were incorporated into thiol−ene networks using a phosphine-catalyzed Michael addition reaction. The effect of flexible alkyl side chains and hydrogen bonding on sub-Tg Relaxation was evaluated without sacrificing network uniformity. Overall both the rate and extent of Enthalpy Relaxation decreased as a function of the flexible n-alkyl chain length, while hydrogen bonding resulted in enhanced Enthalpy Relaxation. A trithiol−triene−triacrylate ternary system was investigated by correlating Enthalpy Relaxation and network uniformity. A multifunctional acrylate (TMPTA), being capable of homopolymerization as well as thiol−acrylate copolymerization, was incorporated into a thiol−ene network structure, thereby decreasing the network uniformity and significantly affecting the Enthalpy Relaxation behavior. In...

  • Physical and chemical modifications of thiol-ene networks to control activation energy of Enthalpy Relaxation
    Polymer, 2009
    Co-Authors: Junghwan Shin, Sergei Nazarenko, J. Paige Phillips, Charles E. Hoyle
    Abstract:

    Abstract Gold nanoparticles and multi-functional acrylate (TMPTA) were incorporated into a photopolymerized thiol-ene (TMPMP–APE) network as a physical and chemical approach to intentionally control sub-Tg aging. The degree of the restriction effect was evaluated by differential cooling rate measurements allowing the quantification of the apparent activation energy for Enthalpy Relaxation (Δh*) upon sub-Tg aging. Incorporation of gold nanoparticles (0.01 to 1 wt%) into the TMPMP–APE network increased Tg and decreased ΔCp at Tg due to molecular mobility restrictions. The extent of Enthalpy Relaxation and apparent activation energy for Enthalpy Relaxation (Δh*) clearly indicated the significant restrictive effect of the gold nanoparticles on the molecular mobility in the thiol-ene network. A TMPMP–APE–TMPTA ternary system was investigated in order to correlate Δh* and network uniformity as a chemical approach. TMPTA, being capable of homopolymerization as well as TMPMP–TMPTA copolymerization, was incorporated into a TMPMP–APE network structure, thereby decreasing the network uniformity and significantly affecting the sub-Tg aging. The extent of Enthalpy Relaxation decreased and the distribution was drastically broadened as a function of TMPTA content due to molecular mobility restrictions, which were also quantified by measuring values for the apparent Enthalpy Relaxation activation energy (Δh*).

  • Enthalpy Relaxation of Photopolymerized Thiol−Ene Networks: Structural Effects
    Macromolecules, 2008
    Co-Authors: Junghwan Shin, Sergei Nazarenko, Charles E. Hoyle
    Abstract:

    Physical aging behavior of photopolymerized thiol−ene networks was investigated by measuring the extent of Enthalpy Relaxation in terms of network density and molecular structure. The homogeneous network structure of the thiol−enes, having narrow glass transition temperature ranges, showed characteristic temperature and time dependency relationships for Enthalpy Relaxation. All thiol−ene films annealed at different temperatures (Ta) for 1 h according to the isochronal method showed maximum Enthalpy Relaxation peaks at approximately Tg − 10 °C by DSC. The extent of Enthalpy Relaxation as a function of annealing time (ta) was obtained by the isothermal aging method. Correlations between the extent of Enthalpy Relaxation and the heat capacity difference at Tg were made and related to thiol−ene chemical group rigidity and network linking density. Pendulum hardness values for a selected thiol−ene film showed a clear change in hardness upon aging, indicating sub-Tg mechanical Relaxation, consistent with the rel...

  • Enthalpy Relaxation of photopolymerized thiol ene networks structural effects
    Macromolecules, 2008
    Co-Authors: Junghwan Shin, Sergei Nazarenko, Charles E. Hoyle
    Abstract:

    Physical aging behavior of photopolymerized thiol−ene networks was investigated by measuring the extent of Enthalpy Relaxation in terms of network density and molecular structure. The homogeneous network structure of the thiol−enes, having narrow glass transition temperature ranges, showed characteristic temperature and time dependency relationships for Enthalpy Relaxation. All thiol−ene films annealed at different temperatures (Ta) for 1 h according to the isochronal method showed maximum Enthalpy Relaxation peaks at approximately Tg − 10 °C by DSC. The extent of Enthalpy Relaxation as a function of annealing time (ta) was obtained by the isothermal aging method. Correlations between the extent of Enthalpy Relaxation and the heat capacity difference at Tg were made and related to thiol−ene chemical group rigidity and network linking density. Pendulum hardness values for a selected thiol−ene film showed a clear change in hardness upon aging, indicating sub-Tg mechanical Relaxation, consistent with the rel...