Valerio Brucato

Investigation of the cooling of hot walls by liquid water sprays

Abstract An experimental study was conducted for the heat transfer from hot walls to liquid water sprays. Four full cone, swirl spray nozzles were used at different upstream pressures, giving mass fluxes impinging on the wall, G, from 8 to 80 kg m−2 s−1, mean droplet velocities, U, from 13 to 28 m s−1 and mean droplet diameters, D, from 0.4 to 2.2 mm. A target consisting of two slabs of beryllium–copper alloy, each 4×5 cm in size and 1.1 mm thick, was electrically heated to about 300°C and then rapidly and symmetrically cooled by water sprays issuing from two identical nozzles. The midplane temperature was measured by a fast response, thin-foil thermocouple and the experimental data were regularized by Gaussian filtering. The inverse heat conduction problem was then solved by an approximation of the exact Stefan solution to yield the wall temperature Tw and the heat flux qw transferred to the spray at temperature Tf. As a result, cooling curves expressing the heat flux qw as a function of Tw−Tf were obtained. The single-phase heat transfer coefficient h and the maximum heat flux qc were found to depend upon the mass flux G and the droplet velocity U, while the droplet size D had a negligible independent influence. Simple correlations for h and qc were proposed.

Crystallization Behaviour at High Cooling Rates of Two Polypropylenes

Phase distribution of quenched samples of two isotactic polypropylenes, having different molecular weight distributions, was evaluated by a deconvolution procedure of WAXD spectra. The dependence on cooling rate of the two resins shows the low molecular weights rich polymer is characterized by a faster kinetics with an α-monoclinic to mesomorphic transition taking place at higher cooling rates.

Synthesis, characterization and foaming of PHEA–PLLA, a new graft copolymer for biomedical engineering

In this study a chemical grafting procedure was set up in order to link high molecular weight poly L-lactic acid (PLLA) chains to the hydrophilic α,β-poly(N-2-hydroxyethyl)-DL-aspartamide (PHEA) backbone. A graft copolymer named PHEA-g-PLLA (or simply PHEA-PLLA) was obtained bearing a degree of derivatization of 1.0 mol.% of PLLA as grafted chain. This new hybrid derivative offers both the opportune crystallinity necessary for the production of scaffolds trough a thermally induced phase separation (TIPS) technique and the proper chemical reactivity to perform further functionalizations with bio-effectors and drugs. PHEA-PLLA porous scaffolds for tissue engineering applications were successfully obtained via TIPS and characterized. Structures with an open porosity and a good level of interconnection were detected. As the applicability of the scaffold is mainly dependent on its pore size, preliminary studies about the mechanisms governing scaffolds pore diameter were carried out.

Morphology and thermal properties of foams prepared via thermally induced phase separation based on polylactic acid blends

Blends of poly-l-lactic acid with two different types of polylactic acid with different average molecular weights (50,000 and 175,000 g/mol, respectively) in different proportions (90/10, 80/20 and 70/30) were utilized in order to produce biodegradable and biocompatible scaffolds for soft tissue engineering applications. The scaffolds were produced via thermally induced phase separation starting from ternary systems where dioxane was the solvent and water the non-solvent. Morphology (average pore size and interconnection) was evaluated by scanning electron microscopy. Foams apparent density was also evaluated (porosity ranges from 87% to 92%). Moreover, a differential scanning calorimetry analysis was carried out on the as-obtained scaffold, so as to obtain information about their thermal properties (enthalpy of melting and crystallization). The results showed that is possible to prepare scaffolds of poly-l-lactic acid/polylactic acid via thermally induced phase separation with both polylactic acids and to tune their average pore size (from 40 to 70 µm) by changing some experimental parameters (e.g. demixing temperature). Moreover, the average molecular weight of the polylactic acid in the blend seems to influence the thermally induced phase separation process in terms of demixing temperatures, which resulted higher than pure poly-l-lactic acid for the blends containing the high molecular weight polylactic acid, and lower for the blends containing the low molecular weight polylactic acid. Finally, a decrease in the crystallinity of the foams when increasing polylactic acid content in poly-l-lactic acid/polylactic acid blends was observed, as witnessed by a drop in the enthalpy of melting and crystallization. The results confirm that the morphology and the mechanical properties of the scaffold can be tuned up, starting from poly-l-lactic acid and blending it in different proportions with polylactic acid with different molecular weights.

Measurement of cloud point temperature in polymer solutions

A temperature-controlled turbidity measurement apparatus for the characterization of polymer solutions has been instrumented and set up. The main features are the coupled temperature-light transmittance measurement and the accurate temperature control, achieved by means of peltier cells. The apparatus allows to measure cloud point temperatures by adopting different cooling protocols: low rate for quasi-equilibrium measurements and high rate for detect kinetic effects. A ternary polymeric solution was adopted as case study system showing that cooling rate affects the measured cloud point temperature.

PLLA scaffolds produced by thermally induced phase separation (TIPS) allow human chondrocyte growth and extracellular matrix formation dependent on pore size

Damage of hyaline cartilage species such as nasoseptal or joint cartilage requires proper reconstruction, which remains challenging due to the low intrinsic repair capacity of this tissue. Implantation of autologous chondrocytes in combination with a biomimetic biomaterial represents a promising strategy to support cartilage repair. The aim of this work was to assess the viability, attachment, morphology, extracellular matrix (ECM) production of human articular and nasoseptal chondrocytes cultured in vitro in porous poly(l-lactic) (PLLA) scaffolds of two selected pore sizes (100 and 200μm). The PLLA scaffolds with 100 and 200μm pore sizes were prepared via ternary thermally induced phase separation (TIPS) technique and analyzed using scanning electron microscopy (SEM). Articular and nasoseptal chondrocytes were seeded on the scaffold and cultures maintained for 7 and 14days. Live/dead staining, (immuno-)histology and gene expression analysis of type II, type I collagen, aggrecan and SOX9 were performed to assess scaffold cytocompatibility and chondrocyte phenotype. The majority of both chondrocyte types survived on both scaffolds for the whole culture period. Hematoxylin-eosin (HE), alcian blue (visualizing glycosaminoglycans) stainings, immunoreactivity and gene expression of ECM proteins and cartilage marker (type II, I collagen, aggrecan, SOX9) of the chondrocyte scaffold constructs indicated that the smaller pore dimensions promoted the differentiation of the chondrocytes compared with the larger pore size. The present work revealed that the scaffold pore size is an important factor influencing chondrocyte differentiation and indicated that the scaffolds with 100μm pores serve as a cytocompatible basis for further future modifications.

Galvanic deposition and characterization of brushite/hydroxyapatite coatings on 316L stainless steel

In this work, brushite and brushite/hydroxyapatite (BS, CaHPO4·H2O; HA, Ca10(PO4)6(OH)2) coatings were deposited on 316L stainless steel (316LSS) from a solution containing Ca(NO3)2·4H2O and NH4H2PO4 by a displacement reaction based on a galvanic contact, where zinc acts as sacrificial anode. Driving force for the cementation reaction arises from the difference in the electrochemical standard potentials of two different metallic materials (316LSS and Zn) immersed in an electrolyte, so forming a galvanic contact leading to the deposition of BS/HA on nobler metal. We found that temperature and deposition time affect coating features (morphology, structure, and composition). Deposits were characterized by means of several techniques. The morphology was investigated by scanning electron microscopy, the elemental composition was obtained by X-ray energy dispersive spectroscopy, whilst the structure was identified by Raman spectroscopy and X-ray diffraction. BS was deposited at all investigated temperatures covering the 316LSS surface. At low and moderate temperature, BS coatings were compact, uniform and with good crystalline degree. On BS layers, HA crystals were obtained at 50°C for all deposition times, while at 25°C, its presence was revealed only after long deposition time. Electrochemical studies show remarkable improvement in corrosion resistance.

Modulation of physical and biological properties of a composite PLLA and polyaspartamide derivative obtained via thermally induced phase separation (TIPS) technique

In the present study, blend of poly l-lactic acid (PLLA) with a graft copolymer based on α,β-poly(N-hydroxyethyl)-dl-aspartamide and PLA named PHEA-PLA, has been used to design porous scaffold by using Thermally Induced Phase Separation (TIPS) technique. Starting from a homogeneous ternary solution of polymers, dioxane and deionised water, PLLA/PHEA-PLA porous foams have been produced by varying the polymers concentration and de-mixing temperature in metastable region. Results have shown that scaffolds prepared with a polymer concentration of 4% and de-mixing temperature of 22.5°C are the best among those assessed, due to their optimal pore size and interconnection. SEM and DSC analysis have been carried out respectively to study scaffold morphology and the influence of PHEA-PLA on PLLA crystallization, while DMF extraction has been carried out in order to quantify PHEA-PLA into the final scaffolds. To evaluate scaffold biodegradability, a hydrolysis study has been performed until 56days by incubating systems in a media mimicking physiological environment (pH7.4). Results obtained have highlighted a progressive increase in weight loss with time in PLLA/PHEA-PLA scaffolds, conceivably due to the presence of PHEA-PLA and polymers interpenetration. Viability and adhesion of bovine chondrocytes seeded on the scaffolds have been studied by MTS test and SEM analysis. From results achieved it appears that the presence of PHEA-PLA increases cells affinity, allowing a faster adhesion and proliferation inside the scaffold.

Functional Activation of Osteoclast Commitment in Chronic Lymphocytic Leukaemia: A Possible Role for RANK/RANKL Pathway

Skeletal erosion has been found to represent an independent prognostic indicator in patients with advanced stages of chronic lymphocytic leukaemia (CLL). Whether this phenomenon also occurs in early CLL phases and its underlying mechanisms have yet to be fully elucidated. In this study, we prospectively enrolled 36 consecutive treatment-naïve patients to analyse skeletal structure and bone marrow distribution using a computational approach to PET/CT images. This evaluation was combined with the analysis of RANK/RANKL loop activation in the leukemic clone, given recent reports on its role in CLL progression. Bone erosion was particularly evident in long bone shafts, progressively increased from Binet stage A to Binet stage C, and was correlated with both local expansion of metabolically active bone marrow documented by FDG uptake and with the number of RANKL + cells present in the circulating blood. In immune-deficient NOD/Shi-scid, γcnull (NSG) mice, administration of CLL cells caused an appreciable compact bone erosion that was prevented by Denosumab. CLL cell proliferation in vitro correlated with RANK expression and was impaired by Denosumab-mediated disruption of the RANK/RANKL loop. This study suggests an interaction between CLL cells and stromal elements able to simultaneously impair bone structure and increase proliferating potential of leukemic clone.

In vitro degradation and bioactivity of composite poly-l-lactic (PLLA)/bioactive glass (BG) scaffolds: comparison of 45S5 and 1393BG compositions

AbstractThe objective of this study was to compare the effect of two bioglass (BG) compositions 45S5 and 1393 in poly-l-lactic composite scaffolds in terms of morphology, mechanical properties, biodegradation, water uptake and bioactivity. The scaffolds were produced via thermally induced phase separation starting from a ternary polymer solution (polymer/solvent/non-solvent). Furthermore, different BG to polymer ratios have been selected (1, 2.5, 5% wt/wt) to evaluate the effect of the amount of filler on the composite structure. Results show that the addition of 1393BG does not affect the scaffold morphology, whereas the 45S5BG at the highest amount tends to appreciably modify the scaffold architecture interacting with the phase separation process. Bioactivity tests confirmed the formation of a hydroxycarbonateapatite-layer in both types of BGs (detected via scanning electron microscopy, X-ray diffractometry and Fourier Transform Infrared Spectroscopy). Overall, the results showed that 1393BG composition affects the experimental preparation protocol to a minimal extent thus allowing a better control of the scaffold’s morphology compared to 45S5BG.