A Dyciandiamine-Based Methacrylate-Epoxy Dual-Cure Blend-System for Stereolithography

In this research, an epoxy-based dual-cure system is developed and characterized for SLA additive manufacturing. Dual-cure systems consist of UV-curable acrylates and thermal active components. The second curing step offers an additional degree of freedom to design specific material properties. In this study, a blend of varying concentrations of an epoxy/curing agent mix, respectively, DGEBA, DICY and photocurable methacrylate, was used to create a material that is printable in the SLA process into a UV-cured or green part and subsequently thermally cured to achieve superior thermal and mechanical properties. Calorimetric measurements were performed to determine the reactivity of the thermal reaction at different concentrations of epoxy. The fully cured specimens were tested in mechanical and dynamic mechanical measurements, and the results showed a significant improvement in tensile stress and glass transition temperature with rising epoxy concentrations. Fractured surfaces from tensile testing were investigated to further characterize the failure of tested samples, and thermal degradation was determined in TGA measurements, which showed no significant changes with an increasing epoxy concentration.

Structure and Thermodynamics of Silicon Oxycarbide Polymer-Derived Ceramics with and without Mixed-Bonding

Silicon oxycarbides synthesized through a conventional polymeric route show characteristic nanodomains that consist of sp2 hybridized carbon, tetrahedrally coordinated SiO4, and tetrahedrally coordinated silicon with carbon substitution for oxygen, called “mixed bonds.” Here we synthesize two preceramic polymers possessing both phenyl substituents as unique organic groups. In one precursor, the phenyl group is directly bonded to silicon, resulting in a SiOC polymer-derived ceramic (PDC) with mixed bonding. In the other precursor, the phenyl group is bonded to the silicon through Si-O-C bridges, which results in a SiOC PDC without mixed bonding. Radial breathing-like mode bands in the Raman spectra reveal that SiOC PDCs contain carbon nanoscrolls with spiral-like rolled-up geometry and open edges at the ends of their structure. Calorimetric measurements of the heat of dissolution in a molten salt solvent show that the SiOC PDCs with mixed bonding have negative enthalpies of formation with respect to crystalline components (silicon carbide, cristobalite, and graphite) and are more thermodynamically stable than those without. The heats of formation from crystalline SiO2, SiC, and C of SiOC PDCs without mixed bonding are close to zero and depend on the pyrolysis temperature. Solid state MAS NMR confirms the presence or absence of mixed bonding and further shows that, without mixed bonding, terminal hydroxyls are bound to some of the Si-O tetrahedra. This study indicates that mixed bonding, along with additional factors, such as the presence of terminal hydroxyl groups, contributes to the thermodynamic stability of SiOC PDCs.

The Influence of Temperature on the Hydration Rate of Cements Based on Calorimetric Measurements

The study presents results of calorimetric tests of three different cements. Two Ordinary Portland cements, CEM I 52.5 R and CEM I 42.5 R, and one Blastfurnace cement, CEM III/A 42.5 N LH/HSR/NA, were analysed. The analysis has shown that the empirical formulas derived based on the results can successfully replace the Arrhenius formula in determination of the hydration rate in relation to curing temperature. It was proven that the hydration rate in relation to the curing temperature changes with the progression of hydration. The study introduces an En coefficient which determines the influence of curing temperature on generation of heat. Results of the study have shown that the value of En is not constant and changes with the progression of hydration process. Proposed method of numerical modelling of the total heat generated and generation rate based on obtained results allows for the calculation of those two parameters for any curing conditions.