Enhancing Sustainability and Antifungal Properties of Biodegradable Composites: Caffeine-Treated Wood as a Filler for Polylactide.

This study investigates the suitability of using caffeine-treated and untreated black cherry (Prunus serotina Ehrh.) wood as a polylactide filler. Composites containing 10%, 20%, and 30% filler were investigated in terms of increasing the nucleating ability of polylactide, as well as enhancing its resistance to microorganisms. Differential scanning calorimetry studies showed that the addition of caffeine-treated wood significantly altered the crystallization behavior of the polymer matrix, increasing its crystallization temperature and degree of crystallinity. Polarized light microscopic observations revealed that only the caffeine-treated wood induced the formation of transcrystalline structures in the polylactide. Incorporation of the modified filler into the matrix was also responsible for changes in the thermal stability and decreased hydrophilicity of the material. Most importantly, the use of black cherry wood treated with caffeine imparted antifungal properties to the polylactide-based composite, effectively reducing growth of Fusarium oxysporum, Fusarium culmorum, Alternaria alternata, and Trichoderma viride. For the first time, it was reported that treatment of wood with a caffeine compound of natural origin alters the supermolecular structure, nucleating abilities, and imparts antifungal properties of polylactide/wood composites, providing promising insights into the structure-properties relationship of such composites.

Structure and Properties of Polylactide Composites with TiO2-Lignin Hybrid Fillers.

The research presented in this article focuses on the use of inorganic-organic material, based on titanium dioxide and lignin, as a filler for polylactide (PLA) biocomposites. To date, no research has been conducted to understand the impact of hybrid fillers consisting of TiO2 and lignin on the supermolecular structure and crystallization abilities of polylactide. Polymer composites containing 1, 3 or 5 wt.% of hybrid filler or TiO2 were assessed in terms of their structure, morphology, and thermal properties. Mechanical properties, including tensile testing, bending, impact strength, and hardness, were discussed. The hybrid filler is characterized by a very good electrokinetic stability at pH greater than 3-4. The addition of all fillers led to a small decrease in the glass transition temperature but, most importantly, the addition of 1% of the hybrid filler to the PLA matrix increased the degree of crystallinity of the material by up to 20%. Microscopic studies revealed differences in the crystallization behavior and nucleation ability of fillers. The use of hybrid filler resulted in higher nucleation density and shorter induction time than in unfilled PLA or PLA with only TiO2. The introduction of small amounts of hybrid filler also affected the mechanical properties of the composites, causing an increase in bending strength and hardness. This information may be useful from a technological process standpoint and may also help to increase the range of applicability of biobased materials.

Photopolymer-Based Composite with Substance Release Capability Manufactured Additively with DLP Method.

In this study, caffeine-loaded photoresin composites with homogeneous structures, suitable for additive manufacturing of transdermal microneedle systems, were obtained. The properties of the composites with varying caffeine concentrations (0.1-0.4% w/w) were investigated for carbon-carbon double bond conversion using Fourier Transform Infrared Spectroscopy, surface wettability and mechanical properties using a static tensile test and nanoindentation, and caffeine release in ethanol using UV-Vis. The caffeine concentration did not affect the final degree of double bond conversion, which was confirmed in tensile tests, where the strength and Young's modulus of caffeine-loaded samples had comparable values to control ones. Samples with 0.1 and 0.2% caffeine content showed an increase in nanohardness and reduced elastic modulus of 50 MPa and 1.5 MPa, respectively. The good wettability of the samples with water and the increase in surface energy is a favorable aspect for the dedicated application of the obtained composite materials. The amount of caffeine released into the ethanol solution at 1, 3 and 7 days reached a maximum value of 81%, was higher for the lower concentration of caffeine in the sample and increased over time. The conducted research may enhance the potential application of composite materials obtained through the digital light processing method in additive manufacturing.

Nanocellulose-Based Polymer Composites Functionalized with New Gemini Ionic Liquids.

The manuscript discusses the application of dimeric imidazolium ionic liquids with an aliphatic linker of different lengths, constituting a new class of compounds called gemini, for the modification of renewable materials. This innovative functionalization with the use of ionic liquids made it possible to obtain polymer composite nanomaterials with renewable fillers, which will reduce the consumption of petroleum-based raw materials and also be directly related to the reduction of energy intensity. Renewable filler in the form of nanocellulose modified with ionic liquids, as well as polymer composites with such filler obtained by extrusion and injection molding techniques, were subjected to detailed characterization using techniques like: X-ray diffraction (XRD), Fourier transform spectroscopy (FTIR), dispersion studies (DLS), morphological analysis (SEM), differential scanning calorimetry (DSC), hot-stage polarized light microscopy and characterization of mechanical properties. The use of innovative dimeric ionic liquids proved to be an effective method to carry out efficient functionalization of cellulose. This provided a stable space structure between polysaccharide particles, limiting aggregate formation. It was shown that chemical modification with ionic liquids has a significant effect on the nucleation activity of cellulose fillers and the formation of the supermolecular structure of the polymer matrix, which consequently allowed to obtain polymer composites with excellent strength characteristics and increased flexibility, which will allow to increase their application potential. Innovative ionic liquids have contributed to obtaining green nanomaterials with excellent functional properties, which have not been described in the literature so far.

Bioactive Propolis-Silane System as Antifungal Agent in Lignocellulosic-Polymer Composites.

Polymer composites with renewable lignocellulosic fillers, despite their many advantages, are susceptible to biodegradation, which is a major limitation in terms of external applications. The work uses an innovative hybrid propolis-silane modifier in order to simultaneously increase the resistance to fungal attack, as well as to ensure good interfacial adhesion of the filler-polymer matrix. Polypropylene composites with 30% pine wood content were obtained by extrusion and pressing. The samples were exposed to the fungi: white-rot fungus Coriolus versicolor, brown-rot fungus Coniophora puteana, and soft-rot fungus Chaetomium globosum for 8 weeks. Additionally, biological tests of samples that had been previously exposed to UV radiation were carried out, which allowed the determination of the influence of both factors on the surface destruction of composite materials. The X-ray diffraction, attenuated total reflectance-Fourier transform infrared spectroscopy, and mycological studies showed a significant effect of the modification of the lignocellulose filler with propolis on increasing the resistance to fungi. Such composites were characterized by no changes in the supermolecular structure and slight changes in the intensity of the bands characteristic of polysaccharides and lignin. In the case of systems containing pine wood that had not been modified with propolis, significant changes in the crystalline structure of polymer composites were noted, indicating the progress of decay processes. Moreover, the modification of the propolis-silane hybrid system wood resulted in the inhibition of photo- and biodegradation of WPC materials, as evidenced only by a slight deterioration in selected strength parameters. The applied innovative modifying system can therefore act as both an effective and ecological UV stabilizer, as well as an antifungal agent.

Evaluation of the Hydrolysis Efficiency of Bacterial Cellulose Gel Film after the Liquid Hot Water and Steam Explosion Pretreatments.

The influence of bacterial cellulose gel film pretreatment methods on the efficiency of enzymatic hydrolysis was investigated. An increase in the efficiency of enzymatic hydrolysis due to liquid hot water pretreatment or steam explosion was shown. The glucose yield of 88% was obtained from raw, non-purified, bacterial cellulose treated at 130 °C. The results confirm the potential of bacterial cellulose gel film as a source for liquid biofuel production.

Multifunctional Polyurethane Composites with Coffee Grounds and Wood Sawdust.

Currently, the fundamental activity that will allow for the development of an economy with closed circulation is the management of food waste and production waste for the preparation of biocomposites. The use of waste materials of natural origin allows for the creation of innovative composites with improved physicochemical and functional properties. The present investigation concerns the use of coffee grounds (2.5-20 wt.%) and oak sawdust (2.5-20 wt.%) as effective fillers of rigid polyurethane foam. Innovative composite materials, previously indebted in the literature, were subjected to the necessary analyses to determine the application abilities: processing times, free density, water absorption, dimensional stability, mechanical properties (compressive strength), thermal conductivity, morphology, and flame resistance. The results with respect to the mechanical tests turned out to be the key. Increasing the number of coffee additives has a positive effect on the compressive strength. The addition of this filler in the range of 5-15 wt.% increased the compressive strength of the composites, 136-139 kPa, compared to the reference sample, 127 kPa. The key parameter analysed was thermal conductivity. The results obtained were in range of the requirements, that is, 0.022-0.024 W/m·K for all used amounts of fillers 2.5-20 wt.%. This is extremely important since these materials are used for insulation purposes. The results of the burning-behaviour test have confirmed that the addition of renewable materials does not negatively affect the fire resistance of the received foams; the results were obtained analogously to those obtained from the reference sample without the addition of fillers. The height of the flame did not exceed 17 cm, while the flame decay time was 17 s for the reference sample and the composite with coffee grounds and 18 s for the composite with oak sawdust. In this work, the practical application of bioorganic waste as an innovative filler for the insulation of flooded polyurethane foam is described for the first time. The introduction of fillers of natural origin into the polymer matrix is a promising method to improve the physicochemical and functional properties of rigid polyurethane foams. Composites modified with coffee grounds and sawdust are interesting from a technological, ecological, and economic point of view, significantly increasing the range of use of foam in various industries.

Highly Insulative PEG-Grafted Cellulose Polyurethane Foams-From Synthesis to Application Properties.

In this paper, native cellulose I was subjected to alkaline treatment. As a result, cellulose I was transformed to cellulose II and some nanometric particles were formed. Both polymorphic forms of cellulose were modified with poly(ethylene glycol) (PEG) and then used as fillers for polyurethane. Composites were prepared in a one-step process. Cellulosic fillers were characterized in terms of their chemical (Fourier transformation infrared spectroscopy) and supermolecular structure (X-ray diffraction), as well as their particle size. Investigation of composite polyurethane included measurements of density, characteristic processing times of foam formation, compression strength, dimensional stability, water absorption, and thermal conductivity. Much focus was put on the application aspect of the produced insulation polyurethane foams. It was shown that modification of cellulosic filler with poly(ethylene glycol) has a positive influence on formation of polyurethane composites-if modified filler was used, the values of compression strength and density increased, while water sorption and thermal conductivity decreased. Moreover, it was proven that the introduction of cellulosic fillers into the polyurethane matrix does not deteriorate the strength or thermal properties of the foams, and that composites with such fillers have good application potential.

Nanocellulose Production Using Ionic Liquids with Enzymatic Pretreatment.

Nanocellulose has gained increasing attention during the past decade, which is related to its unique properties and wide application. In this paper, nanocellulose samples were produced via hydrolysis with ionic liquids (1-ethyl-3-methylimidazole acetate (EmimOAc) and 1-allyl-3-methylimidazolium chloride (AmimCl)) from microcrystalline celluloses (Avicel and Whatman) subjected to enzymatic pretreatment. The obtained material was characterized using Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), dynamic light scattering (DLS), scanning electron microscopy (SEM), and thermogravimetric analysis (TG). The results showed that the nanocellulose had a regular and spherical structure with diameters of 30-40 nm and exhibited lower crystallinity and thermal stability than the material obtained after hydrolysis with Trichoderma reesei enzymes. However, the enzyme-pretreated Avicel had a particle size of about 200 nm and a cellulose II structure. A two-step process involving enzyme pretreatment and hydrolysis with ionic liquids resulted in the production of nanocellulose. Moreover, the particle size of nanocellulose and its structure depend on the ionic liquid used.

Chemical and Structural Characterization of Maize Stover Fractions in Aspect of Its Possible Applications.

In the last decade, an increasingly common method of maize stover management is to use it for energy generation, including anaerobic digestion for biogas production. Therefore, the aim of this study was to provide a chemical and structural characterization of maize stover fractions and, based on these parameters, to evaluate the potential application of these fractions, including for biogas production. In the study, maize stover fractions, including cobs, husks, leaves and stalks, were used. The biomass samples were characterized by infrared spectroscopy (FTIR), X-ray diffraction and analysis of elemental composition. Among all maize stover fractions, stalks showed the highest C:N ratio, degree of crystallinity and cellulose and lignin contents. The high crystallinity index of stalks (38%) is associated with their high cellulose content (44.87%). FTIR analysis showed that the spectrum of maize stalks is characterized by the highest intensity of bands at 1512 cm-1 and 1384 cm-1, which are the characteristic bands of lignin and cellulose. Obtained results indicate that the maize stover fraction has an influence on the chemical and structural parameters. Moreover, presented results indicate that stalks are characterized by the most favorable chemical parameters for biogas production.

Production of Nanocellulose by Enzymatic Treatment for Application in Polymer Composites.

In the last few years, the scientific community around the world has devoted a lot of attention to the search for the best methods of obtaining nanocellulose. In this work, nanocellulose was obtained in enzymatic reactions with strictly defined dispersion and structural parameters in order to use it as a filler for polymers. The controlled enzymatic hydrolysis of the polysaccharide was carried out in the presence of cellulolytic enzymes from microscopic fungi-Trichoderma reesei and Aspergillus sp. It has been shown that the efficiency of bioconversion of cellulose material depends on the type of enzymes used. The use of a complex of cellulases obtained from a fungus of the genus Trichoderma turned out to be an effective method of obtaining cellulose of nanometric dimensions with a very low polydispersity. The effect of cellulose enzymatic reactions was assessed using the technique of high-performance liquid chromatography coupled with a refractometric detector, X-ray diffraction, dynamic light scattering and Fourier transform infrared spectroscopy. In the second stage, polypropylene composites with nanometric cellulose were obtained by extrusion and injection. It was found by means of X-ray diffraction, hot stage optical microscopy and differential scanning calorimetry that nanocellulose had a significant effect on the supermolecular structure, nucleation activity and the course of phase transitions of the obtained polymer nanocomposites. Moreover, the obtained nanocomposites are characterized by very good strength properties. This paper describes for the first time that the obtained cellulose nanofillers with defined parameters can be used for the production of polymer composites with a strictly defined polymorphic structure, which in turn may influence future decision making about obtaining materials with controllable properties, e.g., high flexibility, enabling the thermoforming process of packaging.

Propolis and Organosilanes as Innovative Hybrid Modifiers in Wood-Based Polymer Composites.

The article presents characteristics of wood/polypropylene composites, where the wood was treated with propolis extract (EEP) and innovative propolis-silane formulations. Special interest in propolis for wood impregnation is due to its antimicrobial properties. One propolis-silane formulation (EEP-TEOS/VTMOS) consisted of EEP, tetraethyl orthosilicate (TEOS), and vinyltrimethoxysilane (VTMOS), while the other (EEP-TEOS/OTEOS) contained EEP, tetraethyl orthosilicate (TEOS), and octyltriethoxysilane (OTEOS). The treated wood fillers were characterized by Fourier transform infrared spectroscopy (FTIR), atomic absorption spectrometry (AAS), and X-ray diffraction (XRD), while the composites were investigated using differential scanning calorimetry (DSC), X-ray diffraction (XRD), and optical microscopy. The wood treated with EEP and propolis-silane formulations showed resistance against moulds, including Aspergillus niger, Chaetomium globosum, and Trichoderma viride. The chemical analyses confirmed presence of silanes and constituents of propolis in wood structure. In addition, treatment of wood with the propolis-silane formulations produced significant changes in nucleating abilities of wood in the polypropylene matrix, which was confirmed by an increase in crystallization temperature and crystal conversion, as well as a decrease in half-time of crystallization parameters compared to the untreated polymer matrix. In all the composites, the formation of a transcrystalline layer was observed, with the greatest rate recorded for the composite with the filler treated with EEP-TEOS/OTEOS. Moreover, impregnation of wood with propolis-silane formulations resulted in a considerable improvement of strength properties in the produced composites. A dependence was found between changes in the polymorphic structures of the polypropylene matrix and strength properties of composite materials. It needs to be stressed that to date literature sources have not reported on treatment of wood fillers using bifunctional modifiers providing a simultaneous effect of compatibility in the polymer-filler system or any protective effect against fungi.

Preparation of Nanocellulose Using Ionic Liquids: 1-Propyl-3-Methylimidazolium Chloride and 1-Ethyl-3-Methylimidazolium Chloride.

Cellulose nanocrystals were prepared using ionic liquids (ILs), 1-ethyl-3-methylimidazolium chloride [EMIM][Cl] and 1-propyl-3-methylimidazolium chloride [PMIM][Cl], from microcrystalline cellulose. The resultant samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), dynamic light scattering (DLS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The XRD results showed that nanocellulose obtained by treatment with both ILs preserved basic cellulose I structure, but crystallinity index of samples (except for Sigmacell treated with [EMIM][Cl]) was lower in comparison to the starting microcrystalline cellulose. The DLS results indicated noticeably smaller particle sizes of prepared cellulose for material treated with [PMIM][Cl] compared to cellulose samples hydrolyzed with [EMIM][Cl], which were prone to agglomeration. The obtained nanocellulose had a rod-like structure that was confirmed by electron microscopy analyses. Moreover, the results described in this paper indicate that cation type of ILs influences particle size and morphology of cellulose after treatment with ionic liquids.

Functional MgO-Lignin Hybrids and Their Application as Fillers for Polypropylene Composites.

Inorganic-organic hybrids are a group of materials that have recently become the subject of intense scientific research. They exhibit some of the specific properties of both highly durable inorganic materials (e.g., titanium dioxide, zinc) and organic products with divergent physicochemical traits (e.g., lignin, chitin). This combination results in improved physicochemical, thermal or mechanical properties. Hybrids with defined characteristics can be used as fillers for polymer composites. In this study, three types of filler with different MgO/lignin ratio were used as fillers for polypropylene (PP). The effectiveness of MgO-lignin binding was confirmed using Fourier transform infrared spectroscopy. The fillers were also tested in terms of thermal stability, dispersive-morphological properties as well as porous structure. Polymer composites containing 3 wt.% of each filler were subjected to wide angle X-ray diffraction tests, differential scanning calorimetry and microscopic studies to define their structure, morphology and thermal properties. Additionally, tensile tests of the composites were performed. It was established that the composition of the filler has a significant influence on the crystallization of polypropylene-either spherulites or transcrystalline layers were formed. The value of Young's modulus and tensile strength remained unaffected by filler type. However, composites with hybrid fillers exhibited lower elongation at break than unfilled polypropylene.

Cilostazol-loaded electrospun three-dimensional systems for potential cardiovascular application: Effect of fibers hydrophilization on drug release, and cytocompatibility.

Currently marketed drug-eluting stents are non-selective in their anti-restenotic action. New active substance introduction to polymeric stents and vascular grafts can promote early re-endothelialization, crucial in preventing implant restenosis. Additionally, managing material hydrophobicity by blending synthetic polymers limits adverse effects on bulk properties and controls active substance release. However, the influence of hydrophilic synthetic polymer on human cells in the cardiovascular system remains to be determined. In this report, effects of both poly(ε-caprolactone) (PCL) fibers hydrophilization with Pluronic P123 (P123) and cilostazol (CIL) loading were studied. Physicochemical and mechanical properties of electrospun tubular structures produced from PCL and PCL/P123 fibers with and without CIL were investigated and compared. Release profiles studies and in vitro cell proliferation assays of electrospun materials were conducted. It was found that P123 located near the surface of electrospun fibers increased the rate of CIL release. PCL formulation sustained human umbilical vein endothelial cells (HUVEC) growth for 48 h. Despite improved hydrophilicity, PCL/P123 formulations were found to reduce HUVEC viability. Both PCL and PCL/P123 materials reduced primary aortic smooth muscle cells (PASM) viability after 48 h. In PCL formulations containing CIL, drug release caused a decrease in PASM viability. P123 blending with PCL was found to be as a useful pre-fabrication technique for modulating surface hydrophobicity of electrospun materials and the release profile of incorporated active substance. The cytotoxicity of P123 was evaluated to improve the design of drug-loaded vascular grafts for cardiovascular applications.

Thermal and Mechanical Properties of Silica⁻Lignin/Polylactide Composites Subjected to Biodegradation.

In this paper, silica⁻lignin hybrid materials were used as fillers for a polylactide (PLA) matrix. In order to simulate biodegradation, PLA/hybrid filler composite films were kept in soil of neutral pH for six months. Differential scanning calorimetry (DSC) allowed analysis of nonisothermal crystallization behavior of composites, thermal analysis provided information about their thermal stability, and scanning electron microscopy (SEM) was applied to define morphology of films. The influence of biodegradation was also investigated in terms of changes in mechanical properties and color of samples. It was found that application of silica⁻lignin hybrids as fillers for PLA matrix may be interesting not only in terms of increasing thermal stability, but also controlled biodegradation. To the best knowledge of the authors, this is the first publication regarding biodegradation of PLA composites loaded with silica⁻lignin hybrid fillers.

The Influence of Processing and the Polymorphism of Lignocellulosic Fillers on the Structure and Properties of Composite Materials-A Review.

Cellulose is the most important and the most abundant plant natural polymer. It shows a number of interesting properties including those making it attractive as a filler of composite materials with a thermoplastic polymer matrix. Production of such composite materials, meeting the standards of green technology, has increased from 0.36 million tons in 2007 to 2.33 million tons in 2012. It is predicted that by 2020 their production will reach 3.45 million tons. Production of biocomposites with lignocellulosic components poses many problems that should be addressed. This paper is a review of the lignocellulosic materials currently used as polymer fillers. First, the many factors determining the macroscopic properties of such composites are described, with particular attention paid to the poor interphase adhesion between the polymer matrix and a lignocellulosic filler and to the effects of cellulose occurrence in polymorphic varieties. The phenomenon of cellulose polymorphism is very important from the point of view of controlling the nucleation abilities of the lignocellulosic filler and hence the mechanical properties of composites. Macroscopic properties of green composites depend also on the parameters of processing which determine the magnitude and range of shearing forces. The influence of shearing forces appearing upon processing the supermolecular structure of the polymer matrix is also discussed. An important problem from the viewpoint of ecology is the possibility of composite recycling which should be taken into account at the design stage. The methods for recycling of the composites made of thermoplastic polymers filled with renewable lignocellulosic materials are presented and discussed. This paper is a review prepared on the basis of currently available literature which describes the many aspects of the problems related to the possibility of using lignocellulosic components for production of composites with polymers.