Mechanical and Rheological Evaluation of Polyester-Based Composites Containing Biochar.

The use of biodegradable polymers as matrices in composites gives a wide range of applications, especially in niche areas. The assessment of the effect of the filler content on the change of mechanical properties makes it possible to optimize the composition for specific needs. Biochar was used as a filler in the studied composites with two different biodegradable blends as a matrix. Poly(1,4-butylene adipate-co-1,4-butylene terephthalate)/polylactide/biochar (PBAT/PLA/BC) and polylactide/poly[(R)-3-hydroxybutyrate-co-4-hydroxybutyrate]/biochar (PLA/P(3HB-co-4HB)/BC) composites with 0, 10, 15, 20 and 30 wt% of biochar underwent mechanical tests. The test results revealed a change in the properties of the composites related to the filler content. The results of the tensile test showed that increasing the biochar content increased the tensile modulus values by up to 100% for composites with 30 wt% of biochar, compared to unfilled matrices, and decreased the elongation associated with the breaking of PBAT/PLA and PLA/P(3HB-co-4HB) matrix composites. The elongation values at break of PBAT/PLA and PLA/(3HB-co-4HB) composites with 30 wt% biochar were reduced by 50% and 65%, respectively, compared to the unfilled matrices. PLA/P(3HB-co-4HB) matrix composites, in contrast to PBAT/PLA/BC, showed a decrease in tensile strength with the increases in filler content from 35.6 MPa for unfilled matrix to 27.1 MPa for PLA/P(3HB-co-4HB)/BC30 composites. An increase in filler content increased the brittleness of the composites regardless of the matrix used, as determined under the Charpy impact-test. This phenomenon was observed for all tested PLA/P(3HB-co-4HB) composites, for which the impact strength decreased from 4.47 kJ/m2 for the matrix to 1.61 kJ/m2 for the composite containing 30 wt% biochar. PBAT/PLA-based composites with 10 wt% of biochar showed slightly lower impact strength compared to the unfilled matrix, but composites with 30 wt% biochar showed 30% lower impact strength than PBAT/PLA. The complex viscosity value increased with increased filler content. For all composites tested on both polyester matrices, the viscosity decreased with increasing angular frequency.

Analysis of Thermal Aging Influence on Selected Physical and Mechanical Characteristics of Polyaddition and Polycondensation Poly(dimethylsiloxane).

The aim of the study was to determine the effect of accelerated thermal aging on the properties of selected poly(dimethylsiloxanes) (PDMS) differing in viscosity and hardness. This was related to the potential application for specialist casting molds with complex geometry. Four polyaddition silicones and two polycondensation ones were selected. As part of the work, tensile strength, hardness, density, roughness, and Dynamic Mechanical Analysis (DMA) and Fourier Transform Infrared Spectroscopy (FTIR) were tested, which allowed us to determine the degree of degradation of the analyzed materials subjected to thermal aging at a temperature of 150 ± 2 °C. The aging temperature was conditioned by the parameters of the materials that can be cast into molds made of poly(dimethylsiloxanes) e.g., with polymer resins, for which the exothermic peak ranges from 100 to 200 °C depending on the volume. It was observed that the initial Shore A hardness value affects parameters such as tensile strength or the amount of value change (its increase or decrease) after thermal aging. It can also be concluded that for polyaddition PDMS, the viscosity of the material has an effect on the size of the relative elongation value after thermal aging.

Surface Modification of PHBV Fibrous Scaffold via Lithium Borohydride Reduction.

In this study, lithium borohydride (LiBH4) reduction was used to modify the surface chemistry of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) fibers. Although the most common reaction employed in the surface treatment of polyester materials is hydrolysis, it is not suitable for fiber modification of bacterial polyesters, which are highly resistant to this type of reaction. The use of LiBH4 allowed the formation of surface hydroxyl groups under very mild conditions, which was crucial for maintaining the fibers' integrity. The presence of these groups resulted in a noticeable improvement in the surface hydrophilicity of PHBV, as revealed by contact angle measurements. After the treatment with a LiBH4 solution, the electrospun PHBV fibrous mat had a significantly greater number of viable osteoblast-like cells (SaOS-2 cell line) than the untreated mat. Moreover, the results of the cell proliferation measurements correlated well with the observed cell morphology. The most flattened SaOS-2 cells were found on the surface that supported the best cell attachment. Most importantly, the results of our study indicated that the degree of surface modification could be controlled by changing the degradation time and concentration of the borohydride solution. This was of great importance since it allowed optimization of the surface properties to achieve the highest cell-proliferation capacity.

Influence of Herbal Fillers Addition on Selected Properties of Silicone Subjected to Accelerated Aging.

This work aims to assess the impact of the type and percentage of powdered herbs on selected properties of silicone-based composites. The matrix was an addition cross-linked platinum-cured polydimethylsiloxane. The fillers were powdered thyme and sage, which were introduced at 5, 10, and 15 wt.%. The introduced fillers differed in composition, morphology, and grain size. The grain morphology showed differences in the size and shape of the introduced fillers. The qualitative and quantitative assessment resulting from the incorporation was conducted based on tests of selected properties: density, wettability, rebound resilience, hardness, and tensile strength. The incorporation slightly affected the density and wettability of the silicone. Rebound resilience and hardness results differed depending on the filler type and fraction. However, tensile strength decreased, which may be due to the matrix's distribution of fillers and their chemical composition. Antibacterial activity evaluation against S. aureus proved the bacteriostatic properties of the composites. Accelerated aging in PBS solution further deteriorated the mechanical properties. FTIR and DSC have demonstrated the progressive aging of the materials. In addition, the results showed an overall minimal effect of fillers on the silicone chemical backbone and melting temperature. The developed materials can be used in applications that do not require high mechanical properties.

Chemo-Enzymatic Baeyer-Villiger Oxidation Facilitated with Lipases Immobilized in the Supported Ionic Liquid Phase.

A novel method for chemo-enzymatic Baeyer-Villiger oxidation of cyclic ketones in the presence of supported ionic liquid-like phase biocatalyst was designed. In this work, multi-walled carbon nanotubes were applied as a support for ionic liquids which were anchored to nanotubes covalently by amide or imine bonds. Next, lipases B from Candida antarctica, Candida rugosa, or Aspergillus oryzae were immobilized on the prepared materials. The biocatalysts were characterized using various techniques, like thermogravimetry, IR spectroscopy, XPS, elemental analysis, and SEM-EDS microscopy. In the proposed approach, a biocatalyst consisting of a lipase as an active phase allowed the generation of peracid in situ from the corresponding precursor and a green oxidant-hydrogen peroxide. The activity and stability of the obtained biocatalysts in the model oxidation of 2-adamantanone were demonstrated. High conversion of substrate (92%) was achieved under favorable conditions (toluene: n-octanoic acid ratio 1:1 = v:v, 35% aq. H2O2 2 eq., 0.080 g of biocatalyst per 1 mmol of ketone at 20 °C, reaction time 4 h) with four reaction cycles without a drop in its activity. Our 'properties-by-design' approach is distinguished by its short reaction time at low temperature and higher thermal stability in comparison with other biocatalysts presented in the literature reports.

Outperformance in Acrylation: Supported D-Glucose-Based Ionic Liquid Phase on MWCNTs for Immobilized Lipase B from Candida antarctica as Catalytic System.

This study presents a highly efficient method of a synthesis of n-butyl acrylate via esterification of acrylic acid and n-butanol in the presence of supported ionic liquid phase (SILP) biocatalyst consisting of the lipase B from Candida antarctica (CALB) and multi-walled carbon nanotubes (MWCNTs) modified by D-glucose-based ionic liquids. Favorable reaction conditions (acrylic acid: n-butanol molar ratio 1:2, cyclohexane as a solvent, biocatalyst 0.150 g per 1 mmol of acrylic acid, temperature 25 °C) allowed the achievement of a 99% yield of n-butyl acrylate in 24 h. Screening of various ionic liquids showed that the most promising result was obtained if N-(6-deoxy-1-O-methoxy-α-D-glucopyranosyl)-N,N,N-trimethylammonium bis-(trifluoromethylsulfonyl)imide ([N(CH3)3GlcOCH3][N(Tf)2]) was selected in order to modify the outer surface of MWCNTs. The final SILP biocatalyst-CNTs-[N(CH3)3GlcOCH3][N(Tf)2]-CALB contained 1.8 wt.% of IL and 4.2 wt.% of CALB. Application of the SILP biocatalyst led to the enhanced activity of CALB in comparison with the biocatalyst prepared via physical adsorption of CALB onto MWCNTs (CNTs-CALB), as well as with commercially available Novozyme 435. Thus, the crucial role of IL in the stabilization of biocatalysts was clearly demonstrated. In addition, a significant stability of the developed biocatalytic system was confirmed (three runs with a yield of ester over 90%).

(Bio)Degradable Polymeric Materials for Sustainable Future-Part 3: Degradation Studies of the PHA/Wood Flour-Based Composites and Preliminary Tests of Antimicrobial Activity.

The need for a cost reduction of the materials derived from (bio)degradable polymers forces research development into the formation of biocomposites with cheaper fillers. As additives can be made using the post-consumer wood, generated during wood products processing, re-use of recycled waste materials in the production of biocomposites can be an environmentally friendly way to minimalize and/or utilize the amount of the solid waste. Also, bioactive materials, which possess small amounts of antimicrobial additives belong to a very attractive packaging industry solution. This paper presents a study into the biodegradation, under laboratory composting conditions, of the composites that consist of poly[(R)-3-hydroxybutyrate-co-4-hydroxybutyrate)] and wood flour as a polymer matrix and natural filler, respectively. Thermogravimetric analysis, differential scanning calorimetry and scanning electron microscopy were used to evaluate the degradation progress of the obtained composites with different amounts of wood flour. The degradation products were characterized by multistage electrospray ionization mass spectrometry. Also, preliminary tests of the antimicrobial activity of selected materials with the addition of nisin were performed. The obtained results suggest that the different amount of filler has a significant influence on the degradation profile.

(Bio)degradable Polymeric Materials for Sustainable Future-Part 2: Degradation Studies of P(3HB-co-4HB)/Cork Composites in Different Environments.

The degree of degradation of pure poly(3-hydroxybutyrate-co-4-hydroxybutyrate) [P(3HB-co-4HB)] and its composites with cork incubated under industrial and laboratory composting conditions was investigated. The materials were parallelly incubated in distilled water at 70 °C as a reference experiment (abiotic condition). It was demonstrated that addition of the cork into polyester strongly affects the matrix crystallinity. It influences the composite degradation independently on the degradation environment. Moreover, the addition of the cork increases the thermal stability of the obtained composites; this was related to a smaller reduction in molar mass during processing. This phenomenon also had an influence on the composite degradation process. The obtained results suggest that the addition of cork as a natural filler in various mass ratios to the composites enables products with different life expectancies to be obtained.

Water-Tolerant Trifloaluminate Ionic Liquids: New and Unique Lewis Acidic Catalysts for the Synthesis of Chromane.

The first example of triflometallate ionic liquids, named in analogy to chlorometallate ionic liquids, is reported. Trifloaluminate ionic liquids, synthesized from 1-alkyl-3-methylimidazolium triflates and aluminum triflate, were characterized by multinuclear NMR spectroscopy and FT-IR spectroscopy, revealing the existence of oligonuclear, multiply-charged trifloaluminate anions, with multiple bridging triflate modes. Acceptor numbers were determined to quantify their Lewis acidity, rendering trifloaluminate ionic liquids as medium-strength Lewis acids (AN = ca. 65). Used as acidic catalysts in the cycloaddition of 2,4-dimethylphenol and isoprene (molar ratio 2:1) to prepare chromane, trifloaluminate systems outperformed literature systems, showing high activity (conversions 94-99%, selectivities 80-89%) and at low loadings (0.2 mol%) at 35°C. Using these new systems as supported ionic liquid phase (SILP) on multi-walled carbon nanotubes (ionic liquid loading 16 wt%) delivered a recyclable catalytic system, with activity enhanced with respect to the homogenous regime.

The impact of shape memory test on degradation profile of a bioresorbable polymer.

The semicrystalline poly(L-lactide) (PLLA) belongs to the materials with shape memory effect (SME) and as a bioresorbable and biocompatible polymer it have found many applications in medical and pharmaceutical field. Assessment of the SME impact on the polymer degradation profile plays crucial role in applications such as drug release systems or in regenerative medicine. Herein, the results of in vitro degradation studies of PLLA samples after SME full test cycle are presented. The samples were loaded and deformed in two manners: progressive and non-progressive. The performed experiments illustrate also influence of the material mechanical damages, caused e.g. during incorrect implantation of PLLA product, on hydrolytic degradation profile. Apparently, degradation profiles are significantly different for the material which was not subjected to the deformation and the deformed ones. The materials after deformation of 50% (in SME cycle) was characterized by non-reversible morphology changes. The effect was observed in deformed samples during the SME test which were carried out ten times.

Crystallinity as a tunable switch of poly(L-lactide) shape memory effects.

Materials with shape memory effect (SME) have already been widely used in the medical field. The interesting part of this group is represented by double function materials. The bioresorption and SME ability are common in polyesters implants. The first information about vascular stent made of bioresorbable polyester with SME was published in 2000. However, there are not many investigations about SME control of elements in the aspect of material processing. In the present work, the ability to control the shape memory (SM) of bioresorbable and semicrystalline poly(L-lactide) (PLLA) is investigated. The studies are based on the unexpected effect of material orientation which was demonstrated even at low percentage deformation in crystallized mould injected material. The presented studies revealed that the different degrees of crystallinity obtained during processing might be a useful switch to create a tailored SME for a specific application. The prepared samples of variable morphology revealed a possibility to control the value of material stress during permanent shape recovery. The degree of shape recovery of the prepared samples was also controlable. The highest stress value observed during permanent shape recovery reached 10MPa for the sample annealed 60min at 115°C even when the sample was only deformed in 8%. The other significant aspect of this work is to present the problem of slow crystallization of the material during and after processing (cooling rate) as well as the possibility of negative SME change during the shelf life of the fabric.

The novel semi-biodegradable interpenetrating polymer networks based on urethane-dimethacrylate and epoxy-polyester components as alternative biomaterials.

PURPOSE: This paper presents the pilot study aimed at the development of new full interpenetrating polymer networks based on urethane- dimethacrylate and biodegradable epoxy-polyester as the proposition of new biomaterials with gradually emerging porosity. METHODS: The urethane-dimethacrylate monomer was obtained from 4,4'-methylenebis(phenyl isocyanate) and tetraethylene glycol monomethacrylate. The redox-initiating system was employed for its radical polymerization. The epoxy-polyester was produced by oxidation of the polyester, synthesized from succinic anhydride and allyl glicydyl ether. It was cured in a step-growth process with biogenic, aliphatic amine - spermidine. The mixtures of both monomers with adequate curing agents were room temperature polymerized. The hardened materials were characterized for damping behavior and dynamic modulus, hardness, water sorption, the course of hydrolytic degradation as well as the morphology - before and during the degradation process. RESULTS: The cured materials revealed the nonporous, dense morphology. In the hydrolytic environment, the epoxy-polyester network degraded and the porous urethane-dimethacrylate scaffold remained. The epoxy-polyester appeared to prevent the urethane-dimethacrylate from attaining a high degree of conversion, even if the polymerization rate and the molecular mobility of the latter one are higher than those of the epoxy-polyester. The most homogeneous material with the best physico-mechanical properties was obtained when the urethane-dimethacrylate content was smaller than the epoxy-polyester content, respectively 25 and 50 wt%. CONCLUSIONS: The system presented in this work could be useful in tissue engineering, where at the beginning of the tissue regeneration process it would meet the implant mechanical properties and then would deliver its porosity, facilitating the tissue regeneration process.

Comparative Study of Structure-Property Relationships in Polymer Networks Based on Bis-GMA, TEGDMA and Various Urethane-Dimethacrylates.

The effect of various dimethacrylates on the structure and properties of homo- and copolymer networks was studied. The 2,2-bis-[4-(2-hydroxy-3- methacryloyloxypropoxy)phenyl]-propane) (Bis-GMA), triethylene glycol dimethacrylate (TEGDMA) and 1,6-bis-(methacryloyloxy-2-ethoxycarbonylamino)-2,4,4-trimethylhexane (HEMA/TMDI), all popular in dentistry, as well as five urethane-dimethacrylate (UDMA) alternatives of HEMA/TMDI were used as monomers. UDMAs were obtained from mono-, di- and tri(ethylene glycol) monomethacrylates and various commercial diisocyanates. The chemical structure, degree of conversion (DC) and scanning electron microscopy (SEM) fracture morphology were related to the mechanical properties of the polymers: flexural strength and modulus, hardness, as well as impact strength. Impact resistance was widely discussed, being lower than expected in the case of poly(UDMA)s. It was caused by the heterogeneous morphology of these polymers and only moderate strength of hydrogen bonds between urethane groups, which was not high enough to withstand high impact energy. Bis-GMA, despite having the highest polymer morphological heterogeneity, ensured fair impact resistance, due to having the strongest hydrogen bonds between hydroxyl groups. The TEGDMA homopolymer, despite being heterogeneous, produced the smoothest morphology, which resulted in the lowest brittleness. The UDMA monomer, having diethylene glycol monomethacrylate wings and the isophorone core, could be the most suitable HEMA/TMDI alternative. Its copolymer with Bis-GMA and TEGDMA had improved DC as well as all the mechanical properties.