Simultaneous rheology and cure kinetics dictate thermal post-curing of thermoset composite resins for material extrusion.

Thermoset composites are excellent candidates for material extrusion because they shear thin during extrusion but retain their shape once deposited via a yield stress. However, thermal post-curing is often required to solidify these materials, which can destabilize printed parts. Elevated temperatures can decrease the rheological properties responsible for stabilizing the printed structure before crosslinking solidifies the material. These properties, namely the storage modulus and yield stress, must therefore be characterized as a function of temperature and extent of reaction for various filler loadings. This work utilizes rheo-Raman spectroscopy to measure the storage modulus and dynamic yield stress as a function of temperature and conversion in epoxy-amine resins with fumed silica mass fractions up to 10 %. Both rheological properties are sensitive to conversion and particle loading, but only the dynamic yield stress is reduced by elevated temperatures early in the cure. Notably, the dynamic yield stress increases with conversion well before the chemical gel point. These findings motivate a two-step cure protocol that starts at a low temperature to mitigate the drop in dynamic yield stress, then ramps up to a high temperature when the dynamic yield stress is no longer at risk of decreasing to rapidly drive conversion to near completion. The results suggests that structural stability can be improved without resorting to increasing filler content, which limits control over the final properties, laying the groundwork for future studies to evaluate the stability improvements provided by the multi-step curing schedules.

Complicating cure: How Australian criminal law shapes imagined post-hepatitis C futures.

In recent years, highly tolerable and effective drugs have emerged promising a radical new 'post-hepatitis C' world. Optimism about medical cure potentially overlooks discrimination and stigma associated with hepatitis C and injecting drug use. Legal frameworks are especially relevant to hepatitis futures, since the law has the potential to reinforce or alleviate stigma and discrimination. This article explores how hepatitis C figures in Australian criminal law and with what potential effects. Drawing on Bruno Latour's work on legal veridiction, Alison Kafer's work on futurity and disability and case law data collected for a major study on hepatitis C and post-cure lives, we explore how the criminal law handles hepatitis C in the age of cure. We find that law complicates cure, constituting hepatitis C as disabling despite the advent of effective cures. The law steadfastly maintains its own approach to disease, disability and illness, untouched by medical and scientific developments, in ways that might complicate straightforwardly linear imaginaries of cure, transformation and progress of the kind that dominate biomedicine. We explore the implications of these tensions between law and medicine.

Understanding the Effect of Thermal Treatment on the Physico-Mechanical Properties of Light-Cured Composites for use in Indirect Restorations.

OBJECTIVES: To study the potential benefits of a post-cure thermal treatment on key physico-mechanical properties of light-cured resin-based composites for use in indirect restorations, a CAD/CAM composite block being used as control. MATERIAL AND METHODS: Six commercial composites were light-cured before being thermally treated in a furnace at 90°C during 15 minutes (CAD/CAM composite used as a control). The properties measured with or without thermal treatment were: degree of conversion, flexural strength, elastic modulus, Vickers microHardness, organic mass content and eluted and absorbed mass before and after storage in ethanol. The data were analysed using one-way ANOVA, and Weibull distributions. RESULTS: A general increase in the properties measured was observed for all materials after thermal treatment, except a general decrease in mass elution and absorption (most statistically significant: p⟨0.05). Weibull analysis showed a tendency (p⟩0.05) of increased reliability of the flexural strength after thermal treatment for all materials. CONCLUSION: The present data revealed clear physico-mechanical improvements after thermal treatment of light-cured composites. Such method could hence be beneficially used to produce indirect restorations as compared to stratifying and light-curing the same composites in situ. However, most properties of the control CAD/CAM composite were higher, but CAD/CAM technologies aren't available everywhere.

Effect of Post-Cure on the Static and Viscoelastic Properties of a Polyester Resin.

This work intends to study the effect of the curing parameters on the mechanical properties of a polyester resin without a complete curing reaction process. For this purpose, cures at room temperature, 40 °C, and 60 °C, and post-cures at 40 °C and 60 °C, with different exposure times, were considered. Three-point bending tests were performed to assess the bending properties and both stress relaxation and creep behavior. The degree of crosslinking was estimated by evaluating the C = C ester bond, by Fourier infrared spectroscopy and complemented with the thermal characterization made by differential scanning calorimetry. The results showed that higher curing temperatures are preferable to methods involving curing and post-curing, which can be confirmed by the higher degree of conversion of unsaturated ester bonds at 60 °C. Compared to the resin cured at room temperature, the bending strength increased by 36.5% at 40 °C and 88.6% at 60 °C. A similar effect was observed for bending stiffness. In terms of stress relaxation and creep strain, the lowest values were obtained for samples cured at 60 °C.

Characterizing surface viscoelastic integrity of ultra-fast photo-polymerized composites: Methods development.

OBJECTIVE: Resin-Composites are now available designed for polymerization using 3 s of intense light irradiation. The aim was to develop an experimental method to probe their surface viscoelastic integrity immediately following such rapid photo-cure via macroscopic surface indentation under constant stress as a function of time. METHODS: Two bulk-fill composites (Ivoclar AG) were studied: Tetric PowerFill (PFill) and PowerFlow (PFlow). Split molds were used to fabricate cylindrical {4 mm (dia) × 4 mm} paste specimens, irradiated at 23 °C at 0 mm from the top surface with a BluephasePowerCure LED-LCU, with 3 s or 5 s modes, emitting 3 and 2 W/cm2, respectively. Post-irradiation specimens were immediately transferred to an apparatus equipped with a flat-ended indentor of 1.5 mm diameter. 14 MPa compressive stress at the indentor tip was applied centrally in < 2 min and maintained constant for 2 h. Indentation (I) magnitudes were recorded in real-time (t), with I(t) data re-expressed as % indentation relative to the 4 mm specimen height. After 2 h, the indentor was unloaded and indentation recovery was monitored for a further 2 h. Parallel sets of measurements were made where indentation was delayed for 24 h. Further measurements were made with more conventional composites: EvoCeram Bulk Fill (ECeram) and Tetric EvoFlow Bulk Fill (EFlow). These were irradiated for 20 s at 1.2 W/cm2. Kinetic data were curve-fitted to exponential growth functions and key parameters analyzed by ANOVA and post-hoc tests (α = 0.05). RESULTS: I(t) plots looked initially similar to bulk creep/recovery: rapid deformation plus viscoelastic response; then, upon unloading: rapid (elastic) recovery followed by partial viscoelastic recovery. However, unlike multiply irradiated and stored bulk-creep specimens, the present specimens were exposed to only 3 or 5 s "occlusal" irradiation; generating "hard" surfaces. Subsequently, during the 2 h indentation, the polymer matrix network continued to harden and consolidate. Upon initial loading, I(t) reached 2-3% indentation, depending upon the formulation. Upon unloading at 2 h, elastic recovery was only ca. 1 %. Delayed loading for 24 h, generated I(t) plots of significantly reduced magnitude. Most importantly, however, the I(t) plots for ECeram and EFlow, after 20 s irradiation, showed I(t) magnitudes quite comparable to the PFill and PFlow rapid-cure composites. SIGNIFICANCE: Macroscopic indentation creep has been shown to be a workable procedure that can be applied to rapid-cure materials to assess their immediate surface integrity and developing viscoelastic characteristics. The applied stress of 14 MPa was relatively severe and the indentation/recovery profiles of PowerFill materials with only 3 or 5 s irradiation demonstrated comparability with their established 20 s cure siblings, evidencing the suitability of the PowerCure system for clinical application.

Understanding and Improving Mechanical Properties in 3D printed Parts Using a Dual-Cure Acrylate-Based Resin for Stereolithography.

Application of 3D printed structures via stereolithography (SLA) is limited by imprecise dimensional control and inferior mechanical properties. These challenges is attributed to poor understanding ofpolymerization behavior during the printing process and inadequate post-processing methods. The former via a modified version of Jacob's working curve equation that incorporates the resin's sub-linear response to irradiation intensity is addressed by the authors. This new model provides a more accurate approach to select 3D printing parameters given a desired z-resolution and conversion profile along the depth of the printed part. The authors use this improved model to motivate a novel material design that can be post-processed to be indistinguishable from the polymer at 100% conversion. This approach employs a dual initiating system in which photo-initiated printing is followed by a thermal post-cure to achieve uniform conversion. The authors show that this approach enables fast printing times (10 s per layer), exceptional horizontal resolution (1-10 microns), precise control over vertical resolution, and decreased surface corrugations on a 10's of microns scale. The techniques described herein use an acrylate-based SLA resin, but the approach can be extended to other monomer systems to simultaneously achieve predictable properties and dimensions that are critical for application of additive manufacturing in load-bearing applications.

Revealing the Mechanical Properties of Emulsion Polymer Isocyanate Film in Humid Environments.

Knowledge of the mechanical behaviors of polymer film in humid environments is of great significance for predicting the long-term performance of emulsion polymer isocyanate (EPI) as a high-performance wood adhesive. A tri-copolymer latex was cross-linked by the general polymeric methylene diisocyanate (p-MDI) and aqueous emulsified isocyanate (EMDI) at different loadings for preparing EPI. Furthermore, a series of uniaxial tension tests under different relative humidity (RH) were carried out on cured EPI samples before and after post-curing treatment, and the corresponding chemical structure, as well as the microstructure of polymers, was investigated in detail. In addition, a constitutive equation was formulated to calculate the viscoelastic characteristics of the adhesive layer. The results indicate that the EPI films reveal various kinds of intrinsic deformation as RH increases, and the tensile rupture stress and stiffness would obviously decrease, even at cross-linker weight ratios of up to 20%. Furthermore, the moisture resistance could be markedly improved by increasing the isocyanate content and post-cure. Importantly, EMDI-cross-linked film not only exhibits much better mechanical properties than that containing p-MDI at 0⁻80% RH, but is also more sensitive to post-cure. Finally, the derived viscoelastic model could efficiently track moisture-dependent stress-strain curves of EPI films, and the obtained relaxation time further reveals the influence mechanism of isocyanate and post-cure on the mechanical response of the cured polymer under moist conditions.

Post-cure depth of cure of bulk fill dental resin-composites.

OBJECTIVES: To determine the post-cure depth of cure of bulk fill resin composites through using Vickers hardness profiles (VHN). METHODS: Five bulk fill composite materials were examined: Tetric EvoCeram(®) Bulk Fill, X-tra base, Venus(®) Bulk Fill, Filtek™ Bulk Fill, SonicFill™. Three specimens of each material type were prepared in stainless steel molds which contained a slot of dimensions (15 mm × 4 mm × 2 mm), and a top plate. The molds were irradiated from one end. All specimens were stored at 37°C for 24h, before measurement. The Vickers hardness was measured as a function of depth of material, at 0.3mm intervals. Data were analysed by one-way ANOVA using Tukey post hoc tests (α=0.05). RESULTS: The maximum VHN ranged from 37.8 to 77.4, whilst the VHN at 80% of max.VHN ranged from 30.4 to 61.9. The depth corresponding to 80% of max.VHN, ranged from 4.14 to 5.03 mm. One-way ANOVA showed statistically significant differences between materials for all parameters tested. SonicFill exhibited the highest VHN (p<0.001) while Venus Bulk Fill the lowest (p≤0.001). SonicFill and Tetric EvoCeram Bulk Fill had the greatest depth of cure (5.03 and 4.47 mm, respectively) and was significant's different from X-tra base, Venus Bulk Fill and Filtek Bulk Fill (p≤0.016). Linear regression confirmed a positive regression between max.VHN and filler loading (r(2)=0.94). SIGNIFICANCE: Bulk fill resin composites can be cured to an acceptable post-cure depth, according to the manufacturers' claims. SonicFill and Tetric EvoCeram Bulk Fill had the greatest depth of cure among the composites examined.

Avaliação das propriedades mecânicas de resinas compostas fotoativáveis submetidas a ativação complementar / Evaluation of the mechanical properties of light-cure composite resins submitted to post-cure

Objective: This study evaluated the flexural strength and Vickers hardness of a direct restorative composite resin (Filtek P-60TM), submitted or not to the post-cure, and a laboratory composite resin (ArtglassTM). Methods: The flexural strength tests followed the ISO 4049:1988 regulations, and the Vickers microhardness tests the ASTM E-384:1999 regulations. The Filtek P-60TM com-posite resin was cure activated as follows: Group I - conventional light cure; Group II - conventional li-ght cure followed by post-cure with dry heat; Group III - conventional light cure followed by post-cure in a stroboscopic light unit; Group IV - ArtglassTM composite resin was light cured in a stroboscopic unit. After cure activation procedures, the samples were kept in deionized water at 37 ± 1 oC for 24h and protected from light. Results were submitted to Anova and Duncan?s test and revealed an increase in flexural strength and Vickers microhardness test after Filtek P-60TM post-cure. Results and Conclusion: It is possible to conclude that the Vickers microhardness values for Filtek P-60TM samples were superior to the ArtglassTM composite resin values; and that the flexural resistance values for Filtek P-60TM submitted to post-cure were superior to the ArtglassTM resin values.