Characterization of PLA Sheets Prepared by Stretching under Different Conditions: Influence of Reprocessing and Establishing Optimal Conditions.

Polylactide (PLA) is one of the most commonly used biomaterials nowadays, with many recognized benefits, particularly in the packaging and single-use products industries. However, little research has been conducted on its stretching behavior. This work investigates the optimal conditions of biaxial stretching of injection-molded PLA samples produced under different processing conditions (pressure, drying, and pre-processing by extrusion, to simulate a recycling step). The injection-molded samples were characterized to determine their mechanical, thermal and thermo-mechanical behavior, water absorption, thermal behavior, and crystallization kinetics. The extruded samples showed reduced thermal stability, lower viscosity, decreased mechanical properties, and higher crystallization rates due to thermal degradation. However, the stretched samples provided similar properties regardless of the materials pre-processing. Regarding the assessment of the biaxial stretching process, processing at lower temperatures provides the films with a higher yield and breaking strength, while the time and strain rates have little influence on such properties. It was then determined that 82 °C is the optimal temperature for stretching the PLA samples. An increase in the stretch ratio provided a higher elastic modulus and higher values of opacity due to an increased crystallinity induced by stress during the process. Films as thin as 50 µm can be obtained by biaxially stretching injection-molded preforms, producing a deformation over 150% and acquiring good mechanical properties: about 90 MPa for the yield and a breaking strength and elastic modulus of 4000 MPa.

Recent Developments in Inorganic Composites in Rotational Molding.

Rotational molding allows for obtaining hollow parts with good aesthetics and properties, having as main drawbacks the lack of pressure and the long cycle times, which limit the range of materials. Different fillers have been introduced in rotomolding to obtain composite materials assessed. This review has shown that glass fibers or particles are the most common material among them, although carbon fibers or clays have also been studied. In general terms, 10% loadings provide an increase in mechanical properties; higher loadings usually lead to a decrease in processability or final properties. When the filler consists of a micro- or nano-material, such as clay or graphene, lower loadings are proposed, generally not exceeding 3%. The use of fillers of an inorganic nature to obtain composites has not been as explored as the incorporation of lignocellulosic materials and even less if referring to waste materials or side streams from industrial processes. So, there is a broad field for assessing the processing and properties of rotomolded composites containing inorganic waste materials, including the study of the relationship between the ratio of filler/reinforcement and the final properties and also their preprocessing (dry blending vs. melting compounding).

Using in vitro bioassays to guide the development of safer bio-based polymers for use in food packaging.

Petroleum-based polymers traditionally used for plastic packaging production have been shown to leach dangerous chemicals such as bisphenol-A (BPA). Bio-based polymers are potentially safer alternatives, and many can be sustainably sourced from waste streams in the food industry. This study assesses bio-based polymers undergoing food packaging development for migration of endocrine disrupting leachates at the level of estrogen, androgen and progestagen nuclear receptor transcriptional activity. Reporter gene assays were coupled with migration testing, performed using standardised test conditions for storage and temperature. Test samples include nine bio-based polymers and four inorganic waste additives mixed with a traditional petroleum-based polymer, polypropylene. Thermoplastic starch material, polybutylene succinate, polycaprolactone, polybutylene adipate terephthalate (PBAT), two polylactic acid (PLA)/PBAT blends, polyhydroxybutyrate (PHB) and eggshell/polypropylene (10:90) presented no significant reduction in metabolic activity or hormonal activity under any test condition. Polypropylene (PP) presented no hormonal activity. Metabolic activity was reduced in the estrogen responsive cell line after 10 days migration testing of eggshell/polypropylene (0.1:99.9) in MeOH at 40°C, and PP in MeOH and dH20. Estrogenic agonist activity was observed after 10 days in poultry litter ash/polypropylene (10:90) in MeOH at 20°C and 40°C, poultry feather based polymer in MeOH and dH2O at 40°C, and eggshell/polypropylene (40:60) and PLA in dH2O at 40°C. Activity was within a range of 0.26-0.50 ng 17ß-estradiol equivalents per ml, equating to an estrogenic potency of 3-∼2800 times less than the estrogenic leachate BPA. Poultry litter ash/polypropylene (10:90) in MeOH for 10 days presented estrogenic activity at 20°C and 40°C within the above range and anti-androgenic activity at 40°C. Progestagenic activity was not observed for any of the compounds under any test condition. Interestingly, lower concentrations of eggshell or PP may eliminate eggshell estrogenicity and PP toxicity. Alternatively eggshell may bind and eliminate the toxic elements of PP. Similarly, PLA estrogenic activity was removed in both PLA/PBAT blends. This study demonstrates the benefits of bioassay guidance in the development of safer and sustainable packaging alternatives to petroleum-based plastics. Manipulating the types of additives and their formulations alongside toxicological testing may further improve safety aspects.

Development of three-dimensional printing polymer-ceramic scaffolds with enhanced compressive properties and tuneable resorption.

In this study, bone tissue engineered scaffolds fabricated via powder-based 3D printing from hydroxyapatite (HA) and calcium sulphate (CaSO4) powders were investigated. The combination of using a fast resorbing CaSO4 based powder and the relatively slower HA powder represents a promising prospect for tuning the bioresorption of 3D printed (3DP) scaffolds. These properties could then be tailored to coincide with tissue growth rate for different surgical procedures. The manufactured scaffolds were infiltrated with poly(ε­caprolactone) (PCL). The PCL infiltrated the inter-particle spacing within the 3DP structures due to the nature of a loosely-packed powder bed and also covered the surface of ceramic-based scaffolds. Consequently, the average compressive strength, compressive modulus and toughness increased by 314%, 465% and 867%, respectively. The resorption behaviour of the 3DP scaffolds was characterised in vitro using a high-throughput system that mimicked the physiological environment and dynamic flow conditions relevant to the human body. A rapid release of CaSO4 between Day 0 and 28 was commensurate with a reduction in scaffold mass and compressive properties, as well as an increase in medium absorption. In spite of this, HA particles, connected by PCL fibrils, remained within the microstructure after 56 days resorption under dynamic conditions. Consequently, a high level of structural integrity was maintained within the 3DP scaffold. This study presented a porous PCL-HA-CaSO4 3DP structure with the potential to encourage new tissue growth during the initial stages of implantation and also offering sufficient structural and mechanical support during the bone healing phase.

Effects of poly (ε-caprolactone) coating on the properties of three-dimensional printed porous structures.

Powder-based inkjet three-dimensional printing (3DP) to fabricate pre-designed 3D structures has drawn increasing attention. However there are intrinsic limitations associated with 3DP technology due to the weak bonding within the printed structure, which significantly compromises its mechanical integrity. In this study, calcium sulphate ceramic structures demonstrating a porous architecture were manufactured using 3DP technology and subsequently post-processed with a poly (ε-caprolactone) (PCL) coating. PCL concentration, immersion time, and number of coating layers were the principal parameters investigated and improvement in compressive properties was the measure of success. Interparticle spacing within the 3DP structures were successfully filled with PCL material. Consequently the compressive properties, wettability, morphology, and in vitro resorption behaviour of 3DP components were significantly augmented. The average compressive strength, Young׳s modulus, and toughness increased 217%, 250%, and 315%, following PCL coating. Addition of a PCL surface coating provided long-term structural support to the host ceramic material, extending the resorption period from less than 7 days to a minimum of 56 days. This study has demonstrated that application of a PCL coating onto a ceramic 3DP structure was a highly effective approach to addressing some of the limitations of 3DP manufacturing and allows this advanced technology to be potentially used in a wider range of applications.

Extent and mechanism of phase separation during the extrusion of calcium phosphate pastes.

The aim of this study was to increase understanding of the mechanism and dominant drivers influencing phase separation during ram extrusion of calcium phosphate (CaP) paste for orthopaedic applications. The liquid content of extrudate was determined, and the flow of liquid and powder phases within the syringe barrel during extrusion were observed, subject to various extrusion parameters. Increasing the initial liquid-to-powder mass ratio, LPR, (0.4-0.45), plunger rate (5-20 mm/min), and tapering the barrel exit (45°-90°) significantly reduced the extent of phase separation. Phase separation values ranged from (6.22 ± 0.69 to 18.94 ± 0.69 %). However altering needle geometry had no significant effect on phase separation. From powder tracing and liquid content determination, static zones of powder and a non-uniform liquid distribution was observed within the barrel. Measurements of extrudate and paste LPR within the barrel indicated that extrudate LPR remained constant during extrusion, while LPR of paste within the barrel decreased steadily. These observations indicate the mechanism of phase separation was located within the syringe barrel. Therefore phase separation can be attributed to either; (1) the liquid being forced downstream by an increase in pore pressure as a result of powder consolidation due to the pressure exerted by the plunger or (2) the liquid being drawn from paste within the barrel, due to suction, driven by dilation of the solids matrix at the barrel exit. Differentiating between these two mechanisms is difficult; however results obtained suggest that suction is the dominant phase separation mechanism occurring during extrusion of CaP paste.

Review of patents on microneedle applicators.

Transdermal drug delivery offers certain advantages over conventional oral or parenteral administration. However, transdermal delivery is not available to many promising therapeutic agents, especially high molecular weight hydrophilic compounds. This is due to the excellent barrier property of the superficial skin layer, the stratum corneum (SC). Only drugs with very specific physicochemical properties (molecular weight < 500 Da, adequate lipophilicity, and low melting point) can be successfully administered transdermally. Of the several active approaches used to enhance the transport of drugs through the SC, the use of microneedles (MNs) has recently been shown to be very promising and has attracted considerable attention by researchers from both industry and academia. MNs, when used to puncture skin, will by-pass the SC and create transient aqueous transport pathways of micron dimensions and enhance the transdermal permeability. However, for effective performance of these MNs in drug delivery applications, irrespective of the type, material, height and density, it is imperative that they penetrate into the skin with the greatest possible accuracy and reproducibility. Due to the inherent elasticity and irregular surface topography of the skin, it remains a major challenge to the reproducibility of MN penetration. Therefore, in order to achieve uniform and reproducible MN penetration into skin, an external source of assistance could be very useful. Accordingly, this review deals with various innovative applicator designs developed by industry and research centres in the context of effective application of MN arrays for transdermal drug delivery, as disclosed in the recent patent literature.

Hydroxyapatite bone substitutes developed via replication of natural marine sponges.

The application of synthetic cancellous bone has been shown to be highly successful when its architecture mimics that of the naturally interconnected trabeculae bone it aims to replace. The following investigation demonstrates the potential use of marine sponges as precursors in the production of ceramic based tissue engineered bone scaffolds. Three species of natural sponge, Dalmata Fina (Spongia officinalis Linnaeus, Adriatic Sea), Fina Silk (Spongia zimocca, Mediterranean) and Elephant Ear (Spongia agaricina, Caribbean) were selected for replication. A high solid content (80 %wt), low viscosity (126 mPas) hydroxyapatite slurry was developed, infiltrated into each sponge species and subsequently sintered, producing a scaffold structure that replicated pore architecture and interconnectivity of the precursor sponge. The most promising of the ceramic tissue engineered bone scaffolds developed, Spongia agaricina replicas, demonstrated an overall porosity of 56-61% with 83% of the pores ranging between 100 and 500 microm (average pore size 349 microm) and an interconnectivity of 99.92%.