Composite PCL Scaffold With 70% ß-TCP as Suitable Structure for Bone Replacement.

OBJECTIVES: The purpose of this work was to optimise printable polycaprolactone (PCL)/ß-tricalcium phosphate (ß-TCP) biomaterials with high percentages of ß-TCP endowed with balanced mechanical characteristics to resemble human cancellous bone, presumably improving osteogenesis. METHODS: PCL/ß-TCP scaffolds were obtained from customised filaments for fused deposition modelling (FDM) 3D printing with increasing amounts of ß-TCP. Samples mechanical features, surface topography and wettability were evaluated as well as cytocompatibility assays, cell adhesion and differentiation. RESULTS: The parameters of the newly fabricated materila were optimal for PCL/ß-TCP scaffold fabrication. Composite surfaces showed higher hydrophilicity compared with the controls, and their surface roughness sharply was higher, possibly due to the presence of ß-TCP. The Young's modulus of the composites was significantly higher than that of pristine PCL, indicating that the intrinsic strength of ß-TCP is beneficial for enhancing the elastic modulus of the composite biomaterials. All novel composite biomaterials supported greater cellular growth and stronger osteoblastic differentiation compared with the PCL control. CONCLUSIONS: This project highlights the possibility to fabricat, through an FDM solvent-free approach, PCL/ß-TCP scaffolds of up to 70 % concentrations of ß-TCP. overcoming the current lmit of 60 % stated in the literature. The combination of 3D printing and customised biomaterials allowed production of highly personalised scaffolds with optimal mechanical and biological features resembling the natural structure and the composition of bone. This underlines the promise of such structures for innovative approaches for bone and periodontal regeneration.

Aqueous Extracts from Hemp Seeds as a New Weapon against Staphylococcus epidermidis Biofilms.

This study investigated the antibiofilm activity of water-soluble extracts obtained under different pH conditions from Cannabis sativa seeds and from previously defatted seeds. The chemical composition of the extracts, determined through GC-MS and NMR, revealed complex mixtures of fatty acids, monosaccharides, amino acids and glycerol in ratios depending on extraction pH. In particular, the extract obtained at pH 7 from defatted seeds (Ex7d) contained a larger variety of sugars compared to the others. Saturated and unsaturated fatty acids were found in all of the analysed extracts, but linoleic acid (C18:2) was detected only in the extracts obtained at pH 7 and pH 10. The extracts did not show cytotoxicity to HaCaT cells and significantly inhibited the formation of Staphylococcus epidermidis biofilms. The exception was the extract obtained at pH 10, which appeared to be less active. Ex7d showed the highest antibiofilm activity, i.e., around 90%. Ex7d was further fractionated by HPLC, and the antibiofilm activity of all fractions was evaluated. The 2D-NMR analysis highlighted that the most active fraction was largely composed of glycerolipids. This evidence suggested that these molecules are probably responsible for the observed antibiofilm effect but does not exclude a possible synergistic contribution by the other components.

Tailoring the Magnetic and Electrical Properties of Epoxy Composites Containing Olive-Derived Biochar through Iron Modification.

The combination of conductive carbon together with magnetic particles is a consolidated strategy to produce cutting-edge fillers for the production of polymer composites able to shield against microwave radiation. In this work, we developed and characterized an iron-tailored biochar obtained from the pyrolysis of olive pruning which was added as filler for the preparation of epoxy composites. The biochar-based composites were obtained by keeping the filler concentration at 10 and 40 wt.%. An extensive characterization was carried out in order to assess the electrical and magnetic properties of the composites containing biochar and iron-tailored biochar. The highest DC electrical conductivity of 59 mS/m was observed in the 40 wt.% iron-tailored biochar-loaded composite, while the reduction of the filler loading led to a drastic reduction in conductivity: 60 µS/m in the 10 wt.%-loaded composite. Ferromagnetic behavior of composites containing iron-tailored biochar is visible in the emerging hysteretic behavior, with a magnetic signal increasing with the filler concentration. Finally, both the complex permittivity (ε') and the AC conductivity (σ) are enhanced by increasing the BC filler amount in the matrix, regardless of the presence of iron.

Mechanical and Biological Characterization of PMMA/Al2O3 Composites for Dental Implant Abutments.

The mechanical and biological behaviors of PMMA/Al2O3 composites incorporating 30 wt.%, 40 wt.%, and 50 wt.% of Al2O3 were thoroughly characterized as regards to their possible application in implant-supported prostheses. The Al2O3 particles accounted for an increase in the flexural modulus of PMMA. The highest value was recorded for the composite containing 40 wt.% Al2O3 (4.50 GPa), which was about 18% higher than that of its unfilled counterpart (3.86 GPa). The Al2O3 particles caused a decrease in the flexural strength of the composites, due to the presence of filler aggregates and voids, though it was still satisfactory for the intended application. The roughness (Ra) and water contact angle had the same trend, ranging from 1.94 µm and 77.2° for unfilled PMMA to 2.45 µm and 105.8° for the composite containing the highest alumina loading, respectively, hence influencing both the protein adsorption and cell adhesion. No cytotoxic effects were found, confirming that all the specimens are biocompatible and capable of sustaining cell growth and proliferation, without remarkable differences at 24 and 48 h. Finally, Al2O3 was able to cause strong cell responses (cell orientation), thus guiding the tissue formation in contact with the composite itself and not enhancing its osteoconductive properties, supporting the PMMA composite's usage in the envisaged application.

Effect of Hemp Hurd Biochar and Humic Acid on the Flame Retardant and Mechanical Properties of Ethylene Vinyl Acetate.

In this work, the combination of biochar produced through a pyrolytic process of hemp hurd with commercial humic acid as a potential biomass-based flame-retardant system for ethylene vinyl acetate copolymer is thoroughly investigated. To this aim, ethylene vinyl acetate composites containing hemp-derived biochar at two different concentrations (i.e., 20 and 40 wt.%) and 10 wt.% of humic acid were prepared. The presence of increasing biochar loadings in ethylene vinyl acetate accounted for an increasing thermal and thermo-oxidative stability of the copolymer; conversely, the acidic character of humic acid anticipated the degradation of the copolymer matrix, even in the presence of the biochar. Further, as assessed by forced-combustion tests, the incorporation of humic acid only in ethylene vinyl acetate slightly decreased both peaks of heat release rate (pkHRR) and total heat release (THR, by 16% and 5%, respectively), with no effect on the burning time. At variance, for the composites containing biochar, a strong decrease in pkHRR and THR values was observed, approaching -69 and -29%, respectively, in the presence of the highest filler loading, notwithstanding, for this latter, a significant increase in the burning time (by about 50 s). Finally, the presence of humic acid significantly lowered the Young's modulus, unlike biochar, for which the stiffness remarkably increased from 57 MPa (unfilled ethylene vinyl acetate) to 155 Mpa (for the composite containing 40 wt.% of the filler).

Influence of Mechanical Properties on the Piezoelectric Response of UV-Cured Composite Films Containing Different ZnO Morphologies.

ZnO flower-like (ZFL) and needle (ZLN) structures were synthesized and embedded into UV-curable acrylic resin (EB), with the aim to study the effect of filler loading on the piezoelectric properties of the resulting composite films. The composites showed uniform dispersion of fillers within the polymer matrix. However, by increasing the filler amount, the number of aggregates increased, and ZnO fillers appeared not to be perfectly embedded in polymer film, indicating poor interaction with acrylic resin. The filler content increase caused an increase in glass transition temperature (Tg) and a decrease in storage modulus in the glassy state. In particular, compared with pure UV-cured EB (Tg = 50 °C), 10 wt.% ZFL and ZLN presented Tg values of 68 and 77 °C, respectively. The piezoelectric response generated by the polymer composites was good when measured at 19 Hz as a function of the acceleration; the RMS output voltages achieved at 5 g were 4.94 and 1.85 mV for the composite films containing ZFL and ZLN, respectively, at their maximum loading levels (i.e., 20 wt.%). Further, the RMS output voltage increase was not proportional to the filler loading; this finding was attributable to the decrease in the storage modulus of the composites at high ZnO loading rather than the dispersion of filler or the number of particles on the surface.

Ethylene-Vinyl Acetate (EVA) Containing Waste Hemp-Derived Biochar Fibers: Mechanical, Electrical, Thermal and Tribological Behavior.

To reduce the use of carbon components sourced from fossil fuels, hemp fibers were pyrolyzed and utilized as filler to prepare EVA-based composites for automotive applications. The mechanical, tribological, electrical (DC and AC) and thermal properties of EVA/fiber biochar (HFB) composites containing different amounts of fibers (ranging from 5 to 40 wt.%) have been thoroughly studied. The morphological analysis highlighted an uneven dispersion of the filler within the polymer matrix, with poor interfacial adhesion. The presence of biochar fibers did not affect the thermal behavior of EVA (no significant changes of Tm, Tc and Tg were observed), notwithstanding a slight increase in the crystallinity degree, especially for EVA/HFB 90/10 and 80/20. Conversely, biochar fibers enhanced the thermo-oxidative stability of the composites, which increased with increasing the biochar content. EVA/HFB composites showed higher stiffness and lower ductility than neat EVA. In addition, high concentrations of fiber biochar allowed achieving higher thermal conductivity and microwave electrical conductivity. In particular, EVA/HFB 60/40 showed a thermal conductivity higher than that of neat EVA (respectively, 0.40 vs. 0.33 W·m-1 ·K-1); the same composite exhibited an up to twenty-fold increased microwave conductivity. Finally, the combination of stiffness, enhanced thermal conductivity and intrinsic lubricating features of the filler resulted in excellent wear resistance and friction reduction in comparison with unfilled EVA.

Recent Advances in Biochar Polymer Composites.

"Biochar" (BC) is the solid residue recovered from the thermal cracking of biomasses in an oxygen-poor atmosphere. Recently, BC has been increasingly explored as a sustainable, inexpensive, and viable alternative to traditional carbonaceous fillers for the development of polymer-based composites. In fact, BC exhibits high thermal stability, high surface area, and electrical conductivity; moreover, its main properties can be properly tuned by controlling the conditions of the production process. Due to its intriguing characteristics, BC is currently in competition with high-performing fillers in the formulation of multi-functional polymer-based composites, inducing both high mechanical and electrical properties. Moreover, BC can be derived from a huge variety of biomass sources, including post-consumer agricultural wastes, hence providing an interesting opportunity toward a "zero waste" circular bioeconomy. This work aims at providing a comprehensive overview of the main achievements obtained by combining BC with several thermoplastic and thermosetting matrices. In particular, the effect of the introduction of BC on the overall performance of different polymer matrices will be critically reviewed, highlighting the influence of differently synthesized BC on the final performance and behavior of the resulting composites. Lastly, a comparative perspective on BC with other carbonaceous fillers will be also provided.

Electron-Beam-Induced Grafting of Chitosan onto HDPE/ATZ Composites for Biomedical Applications.

The surface functionalisation of high-density polyethylene (HDPE) and HDPE/alumina-toughened zirconia (ATZ) surfaces with chitosan via electron-beam (EB) irradiation technique was exploited for preparing materials suitable for biomedical purposes. ATR-FTIR analysis and wettability measurements were employed for monitoring the surface changes after both irradiation and chitosan grafting reaction. Interestingly, the presence of ATZ loadings beyond 2 wt% influenced both the EB irradiation process and the chitosan functionalisation reaction, decreasing the oxidation of the surface and the chitosan grafting. The EB irradiation induced an increase in Young's modulus and a decrease in the elongation at the break of all analysed systems, whereas the tensile strength was not affected in a relevant way. Biological assays indicated that electrostatic interactions between the negative charges of the surface of cell membranes and the -NH3+ sites on chitosan chains promoted cell adhesion, while some oxidised species produced during the irradiation process are thought to cause a detrimental effect on the cell viability.

Bioactive films based on barley ß-glucans and ZnO for wound healing applications.

In this study, mixtures based on ß-glucans and proteins are extracted from barley, in mild (MA) and high (HA) alkaline conditions, and employed with zinc oxide (ZnO) to prepare bioactive films for wound healing. Composition of extracts and properties of resulting films depend on pH extraction conditions. MA based samples show weak physical interactions among mixture components, whereas in HA films the extent of these interactions is larger. Consequently, their chemico-physical properties are significantly different, as demonstrated by FT-IR, thermal, mechanical and morphological analyses. ZnO with its bound water molecules acts as a slight plasticizer in MA, as shown by the lower Tg and the decrease of elastic modulus. In HA, this effect is evidenced up to ZnO 1%, and above this concentration an increase of strength at break is observed. Finally, MA and HA films show intrinsic antimicrobial properties, enhanced by ZnO, which make them exploitable as wound dressings.

Study of the adhesive properties versus stability/aging of hernia repair meshes after deposition of RF activated plasma polymerized acrylic acid coating.

In order to confer adhesive properties to commercial polypropylene (PP) meshes, a surface plasma-induced deposition of poly-(acrylic acid) (PPAA) is performed. Once biomaterials were functionalized, different post-deposition treatments (i.e. water washing and/or thermal treatments) were investigated with the aim of monitoring the coating degradation (and therefore the loss of adhesion) after 3months of aging in both humid/oxidant (air) and inert (nitrogen) atmospheres. A wide physicochemical characterization was carried out in order to evaluate the functionalization effectiveness and the adhesive coating homogeneity by means of static water drop shape analysis and several spectroscopies (namely, FTIR, UV-Visible and X-ray Photoemission Spectroscopy). The modification of the adhesion properties after post-deposition treatments as well as aging under different storage atmospheres were investigated by means of Atomic Force Microscopy (AFM) used in Force/Distance (F/D) mode. This technique confirms itself as a powerful tool for unveiling the surface adhesion capacity as well as the homogeneity of the functional coatings along the fibers. Results obtained evidenced that post-deposition treatments are mandatory in order to remove all oligomers produced during the plasma-treatment, whereas aging tests evidenced that these devices can be simply stored in presence of air for at least three months without a meaningful degradation of the original properties.

Polylactic acid/zinc oxide biocomposite films for food packaging application.

Although PLA is much more expensive than polyolefins, such as PP and PE, there is a great interest to propose PLA based material as alternative films for food packaging being PLA derivable from natural source, compostable and biodegradable. For this purpose the research has the task to investigate and propose PLA materials with enhanced properties to be effectively and efficiently alternative to polyolefin films for food packaging application. In this contribution, biocomposite films of PLA with 1, 3 and 5wt% of ZnO have been investigated to determine mechanical, barrier and antimicrobial (against Escherichia coli) properties. It is found that the biocomposite films are characterized by a good dispersion of the ZnO particles in PLA matrix, although no previous treatment was performed on ZnO particles, such as silanization, to decrease its incompatibility with the polymer. The biocomposite films have shown good mechanical properties, decrease of permeability to CO2 and O2, and only a slight increase to water vapour. Particularly important is that, for the biocomposite with 5wt% of ZnO, the % Reduction for E. Coli test reached the value of 99.99 already after 24h.