Polycaprolactone (PCL) has been one of the most popular biomaterials in tissue engineering due to its relatively low melting temperature, excellent thermal stability, and cost-effectiveness. However, its low cell attraction, low elastic modulus, and long-term degradation time have limited its application in a wide range of scaffold studies. Dimethyl sulfone (DMSO₂) is a stable and non-hazardous organosulfur compound with low viscosity and high surface tension. PCL and DMSO₂ composites may overcome the limitations of PCL as a biomaterial and tailor the properties of biocomposites. In this study, PCL and DMSO₂ composites were investigated as a new bio-scaffold material to increase hydrophilicity and mechanical properties and tailor degradation properties in vitro. PCL and DMSO₂ were physically mixed with 10, 20, and 30 wt% of DMSO₂ to evaluate thermal, hydrophilicity, mechanical, and degradation properties of the composites. The water contact angle of the composites for hydrophilicity decreased by 15.5% compared to pure PCL. The experimental results showed that the mechanical and degradation properties of PCL and DMSO₂ were better than those of pure PCL, and the properties can be tuned by regulating DMSO2 concentration in the PCL matrix. The elastic modulus of the composite with 30 wt% of DMSO2 showed 532 MPa, and its degradation time was 18 times faster than that of PCL.

The significance of rheology in the context of bio three-dimensional (3D) printing lies in its impact on the printing behavior, which shapes material flow and the layer-by-layer stacking process. The objective of this study is to evaluate the rheological and printing behaviors of polycaprolactone (PCL) and dimethyl sulfone (DMSO₂) composites. The rheological properties were examined using a rotational rheometer, employing a frequency sweep test. Simultaneously, the printing behavior was investigated using a material extrusion 3D printer, encompassing varying printing temperatures and pressures. Across the temperature range of 120–140 °C, both PCL and PCL/DMSO₂ composites demonstrated liquid-like behavior, with a higher loss modulus than storage modulus. This behavior exhibited shear-thinning characteristics. The addition of DMSO₂ 10, 20, and 30 wt% into the PCL matrix reduced a zero-shear viscosity of 33, 46, and 74% compared to PCL, respectively. The materials exhibited extrusion velocities spanning from 0.0850 to 6.58 mm/s, with velocity being governed by the reciprocal of viscosity. A significant alteration in viscosity by temperature change directly led to a pronounced fluctuation in extrusion velocity. Extrusion velocities below 0.21 mm/s led to the production of unstable printed lines. The presence of distinct viscosities altered extrusion velocity, flow rate, and strut diameter. This phenomenon allowed the categorization of pore shape into three zones: irregular, normal, and no-pore zones. It underscored the importance of comprehending the rheological aspects of biomaterials in enhancing the overall quality of bio-scaffolds during the 3D printing process.

Polymer materials used in 3D printing exhibit degradation of material mechanical properties when exposed to thermal environments and thermal expansions can induce residual stresses in products or molds, which may result in dimensional instability and subsequent structural failures. In this study, based on linear thermo-viscoelastic principles, material degradation master curves, shift functions, and glass transition temperatures for four different polymers used for 3D printing techniques such as MultiJet Printing and Digital Lighting Process were measured by using a dynamic mechanical analyzer. Based on the single frequency test, the glass transition temperature was measured. In addition, dynamic measurements were carried out over a frequency range at isothermal condition and storage modulus vs. frequency curves were obtained. Then, the storage moduli curves measured at different temperatures were superposed into master curves using the frequency–temperature superposition principle and shift factors were calculated as a function of temperature. Subsequently, the complex moduli curves that were measured in the frequency were curve-fitted onto generalized Maxwell models by using the least squares method and the master curves of relaxation moduli at reference temperature were obtained. The effects of temperature, frequency, and time on dynamic moduli and relaxation behaviors of four polymers used for 3D printing were evaluated. Experimental results showed that Polymers C and D could be suitable to use at the service temperature above 100 ${}^{°}$C and Polymer C was highly crosslinked and showed low modulus reduction after about a year. The master relaxation curves obtained through this process can be utilized to predict the long-term performance of polymer molds made by 3D printing at a given environmental condition.

Bone tissue engineering shows potential for regenerating or replacing damaged bone tissues by utilizing biomaterials renowned for their biocompatibility and structural support capabilities. Among these biomaterials, polycaprolactone (PCL) and polylactic acid (PLA) have gained attention due to their biodegradability and versatile applications. However, challenges such as low degradation rates and poor mechanical properties limit their effectiveness. Dimethyl sulfone (DMSO₂) has emerged as a potential additive to address these limitations, offering benefits such as reduced viscosity, increased degradation time, and enhanced surface tension. In this study, we investigate tailored composites comprising PLA, PCL, and DMSO₂ to enhance mechanical properties and hydrophilicity. Through material characterization and mechanical testing, we found that the addition of DMSO₂ led to improvements in the yield strength, modulus, and hydrophilicity of the composites. PCL and DMSO₂ 10, 20, and 30 wt% were premixed, and 20 wt% PCL + 10, 20, and 30 wt% DMSO₂ were mixed with PLA. Specifically, PLA/PCL/DMSO₂ composites exhibited higher yield strengths and moduli compared to pure PLA, pure PCL, and PLA/PCL composites. Moreover, the hydrophilicity of the composites increased with DMSO₂ concentration, facilitating cell attachment. Fourier-transform infrared spectroscopy (FTIR) confirmed the presence of –COOH and –COH bands in PLA/PCL/DMSO₂ composites, indicating chemical interactions between DMSO₂ and the polymer matrix. Fractography analysis revealed enhanced interface adhesion in PLA/PCL/DMSO₂ composites due to the hydrogen bonding. Overall, this study demonstrates the potential of PLA/PCL/DMSO₂ composites in bone tissue engineering applications, offering improved mechanical properties and enhanced cell compatibility. The findings contribute to the advancement of biomaterials for additive manufacturing in tissue engineering and regenerative medicine.

Manganese (II) chloride tetrahydrate, classified as an inorganic phase-change material (PCM), can be used as a thermal energy storage material, saving and releasing thermal energy during its phase transitions. In this study, thermophysical properties, such as phase change temperatures, latent heat, and thermal conductivities, of four types of MnCl₂·4H₂O PCMs were investigated under single and dual phases (liquid-, solid-, and dual-phase PCMs) using differential scanning calorimetry (DSC) and a heat flow meter. PCMs with a liquid or dual phases exhibited superheating issues, and their melting temperatures were 7 to 10 °C higher than the reference melting temperatures. The PCMs had latent heats between 146 and 176 J/g in the temperature range of 23 to 45 °C under the endothermic process. Severe supercooling during the exothermic process was observed in all as-received specimens, but was mitigated in the homogenization-treated specimen, which sustained an increase in solidification temperature of about 15 °C compared with the as-received and treated PCMs. The diffusivities of PCMs were between 9.76 × 10⁻⁶ and 2.35 × 10⁻⁵ mm²/s. The diffusivities of the PCMs in the solid phase were higher than those in the liquid phase. During the initial holding time of the endothermic process, the PCM in the liquid phase could not be fully solidified due to an insufficient initial holding time and very low diffusivity, which caused superheating during the DSC measurement. Moreover, in the exothermic process, a fast cooling rate of 5 °C/min and low thermal diffusivity caused supercooling. In particular, the diffusivity of the liquid PCM was lower than those of the solid PCM and other PCMs, which caused extremely high supercooling during the DSC measurement. This paper provides the thermophysical properties of MnCl₂·4H₂O PCMs, which are not available in the literature. The homogeneity of PCMs in their initial states and their heating/cooling rates were identified, and constitute important factors for accurately measuring the thermophysical properties of PCMs.