The limitations in the transport of oxygen, nutrients, and metabolic waste products pose a challenge to the development of bioengineered bone of clinically relevant size. This paper reports the design and characterization of hierarchical macro/microporous scaffolds made of poly(lacticco-glycolic) acid and nanohydroxyapatite (PLGA/nHA). These scaffolds were produced by combining additive manufacturing (AM) and thermally induced phase separation (TIPS) techniques. Macrochannels with diameters of ~300 μm, ~380 μm, and ~460 μm were generated by embedding porous 3D-plotted polyethylene glycol (PEG) inside PLGA/nHA/1,4-dioxane or PLGA/1,4-dioxane solutions, followed by PEG extraction using deionized (DI) water. We have used an I-optimal design of experiments (DoE) and the response surface analysis (JMP® software) to relate three responses (scaffold thickness, porosity, and modulus) to the four experimental factors affecting the scaffold macro/microstructures (e.g., PEG strand diameter, PLGA concentration, nHA content, and TIPS temperature). Our results indicated that a PEG strand diameter of ~380 μm, a PLGA concentration of ~10% w/v, a nHA content of ~10% w/w, and a TIPS temperature around −10°C could generate scaffolds with a porosity of ~90% and a modulus exceeding 4 MPa. This paper presents the steps for the I-optimal design of these scaffolds and reports on their macro/microstructures, characterized using scanning electron microscopy (SEM) and micro-computed tomography (micro-CT).

Sulfur trioxide (SO3) additions, up to 3.0 mass%, were systematically investigated for effects on the physical properties of sodium borosilicate glass melted in air, with a sulfur‐free composition of 50SiO2–10Al2O3–12B2O3–21Na2O–7CaO (mass%). Solubility measurements, using electron microscopy chemical analysis, determined the maximum loading to be ~1.2 mass% SO3. It was found that measured sulfur (here as sulfate) additions up to 1.18 mass% increased the glass transition temperature by 3%, thermal diffusivity by 11%, heat capacity by 10%, and thermal conductivity by 20%, and decreased the mass density by 1%. Structural analysis, performed with Raman spectroscopy, indicated that the borosilicate network polymerized with sulfur additions up to 3.0 mass%, presumably due to Na2O being required to charge compensate the ionic SO42- additions, thus becoming unavailable to form non‐bridging oxygen in the silicate network. It is postulated that this increased cross‐linking of the borosilicate backbone led to a structure with higher dimensionality and average bond energy. This increased the mean free paths and vibration frequency of the phonons, which resulted in the observed increase in thermal properties.

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