Fire-Retardant Flexible Foamed Polyurethane (PU)-Based Composites: Armed and Charmed Ground Tire Rubber (GTR) Particles.

Inadequate fire resistance of polymers raises questions about their advanced applications. Flexible polyurethane (PU) foams have myriad applications but inherently suffer from very high flammability. Because of the dependency of the ultimate properties (mechanical and damping performance) of PU foams on their cellular structure, reinforcement of PU with additives brings about further concerns. Though they are highly flammable and known for their environmental consequences, rubber wastes are desired from a circularity standpoint, which can also improve the mechanical properties of PU foams. In this work, melamine cyanurate (MC), melamine polyphosphate (MPP), and ammonium polyphosphate (APP) are used as well-known flame retardants (FRs) to develop highly fire-retardant ground tire rubber (GTR) particles for flexible PU foams. Analysis of the burning behavior of the resulting PU/GTR composites revealed that the armed GTR particles endowed PU with reduced flammability expressed by over 30% increase in limiting oxygen index, 50% drop in peak heat release rate, as well as reduced smoke generation. The Flame Retardancy Index (FRI) was used to classify and label PU/GTR composites such that the amount of GTR was found to be more important than that of FR type. The wide range of FRI (0.94-7.56), taking Poor to Good performance labels, was indicative of the sensitivity of flame retardancy to the hybridization of FR with GTR components, a feature of practicality. The results are promising for fire protection requirements in buildings; however, the flammability reduction was achieved at the expense of mechanical and thermal insulation performance.

Solvent influence on the crystal structures of new cadmium tri-tert-butoxysilanethiolate complexes with 1,4-bis(3-aminopropyl)piperazine: luminescence and antifungal activity.

Monocrystals of dinuclear µ-1,4-bis(3-aminopropyl)piperazine-κ4N1,N1':N4,N4'-bis[bis(tri-tert-butoxysilanethiolato-κS)cadmium(II)], [Cd2(C12H27O3SSi)4(C10H24N4)] or [Cd2{SSi(OtBu)3}4(µ-BAPP)], 1, and polynuclear catena-poly[[bis(tri-tert-butoxysilanethiolato-κS)cadmium(II)]-µ-1,4-bis(3-aminopropyl)piperazine-κ2N1':N4'], [Cd(C12H27O3SSi)2(C10H24N4)]n or [Cd{SSi(OtBu)3}2(µ-BAPP)]n, 2, with 1,4-bis(3-aminopropyl)piperazine (BAPP) and tri-tert-butoxysilanethiolate ligands, were obtained from the same ratio of reactants, but with different solvents used for the crystallization processes. The structures and properties of both complexes were characterized using elemental analysis, X-ray diffraction and FT-IR, 1H NMR and luminescence spectroscopy. Applied density functional theory (DFT) computational methods and noncovalent interaction (NCI) analysis were used for geometry optimization and visualization of the interactions between the metallic centres and their surroundings. The X-ray analysis revealed four-coordinate CdII centres bound to two S atoms of the silanethiolate groups and two N atoms of the BAPP ligand; however, it chelates to tertiary and primary N atoms in 1, whilst in 2 it does not chelate and bonds only to RNH2. The photoluminescence properties of complexes 1 and 2 result from free-ligand emission and differ significantly from each other with respect to emission intensity. Additionally, antifungal activity was investigated against 18 isolates of fungi. Compound 1 strongly inhibited the growth of three dermatophytes: Epidermophyton floccosum, Microsporum canis and Trichophyton rubrum.

Cross-Linking, Morphology, and Physico-Mechanical Properties of GTR/SBS Blends: Dicumyl Peroxide vs. Sulfur System.

In this work, ground tire rubber and styrene-butadiene block copolymer (GTR/SBS) blends at the ratio of 50/50 wt%, with the application of four different SBS copolymer grades (linear and radial) and two types of cross-linking agent (a sulfur-based system and dicumyl peroxide), were prepared by melt compounding. The rheological and cross-linking behavior, physico-mechanical parameters (i.e., tensile properties, abrasion resistance, hardness, swelling degree, and density), thermal stability, and morphology of the prepared materials were characterized. The results showed that the selected SBS copolymers improved the processability of the GTR/SBS blends without any noticeable effects on their cross-linking behavior-which, in turn, was influenced by the type of cross-linking agent used. On the other hand, it was observed that the tensile strength, elongation at break, and abrasion resistance of the GTR/SBS blends cured with the sulfur system (6.1-8.4 MPa, 184-283%, and 235-303 mm3, respectively) were better than those cross-linked by dicumyl peroxide (4.0-7.8 MPa, 80-165%, and 351-414 mm3, respectively). Furthermore, it was found that the SBS copolymers improved the thermal stability of GTR, while the increasing viscosity of the used SBS copolymer also enhanced the interfacial adhesion between the GTR and SBS copolymers, as confirmed by microstructure evaluation.

Mater-Bi/Brewers' Spent Grain Biocomposites-Novel Approach to Plant-Based Waste Filler Treatment by Highly Efficient Thermomechanical and Chemical Methods.

Thermoplastic starch (TPS) is a homogenous material prepared from native starch and water or other plasticizers subjected to mixing at a temperature exceeding starch gelatinization temperature. It shows major drawbacks like high moisture sensitivity, poor mechanical properties, and thermal stability. To overcome these drawbacks without significant cost increase, TPS could be blended with bio-based or biodegradable polymers and filled with plant-based fillers, beneficially waste-based, like brewers' spent grain (BSG), the main brewing by-product. Filler modifications are often required to enhance the compatibility of such composites. Herein, we investigated the impact of BSG thermomechanical and chemical treatments on the structure, physical, thermal, and rheological performance of Mater-Bi-based composites. Thermomechanical modifications enhanced matrix thermal stability under oxidative conditions delaying degradation onset by 33 °C. Moreover, BSG enhanced the crystallization of the polybutylene adipate terephthalate (PBAT) fraction of Mater-Bi, potentially improving mechanical properties and shortening processing time. BSG chemical treatment with isophorone diisocyanate improved the processing properties of the composites, expressed by a 33% rise in melt flow index. Depending on the waste filler's selected treatment, processing, and rheological performance, thermal stability or interfacial adhesion of composites could be enhanced. Moreover, the appearance of the final materials could be adjusted by filler selection.

Green Polymer Nanocomposites for Skin Tissue Engineering.

Fabrication of an appropriate skin scaffold needs to meet several standards related to the mechanical and biological properties. Fully natural/green scaffolds with acceptable biodegradability, biocompatibility, and physiological properties quite often suffer from poor mechanical properties. Therefore, for appropriate skin tissue engineering and to mimic the real functions, we need to use synthetic polymers and/or additives as complements to green polymers. Green nanocomposites (either nanoscale natural macromolecules or biopolymers containing nanoparticles) are a class of scaffolds with acceptable biomedical properties window (drug delivery and cardiac, nerve, bone, cartilage as well as skin tissue engineering), enabling one to achieve the required level of skin regeneration and wound healing. In this review, we have collected, summarized, screened, analyzed, and interpreted the properties of green nanocomposites used in skin tissue engineering and wound dressing. We particularly emphasize the mechanical and biological properties that skin cells need to meet when seeded on the scaffold. In this regard, the latest state of the art studies directed at fabrication of skin tissue and bionanocomposites as well as their mechanistic features are discussed, whereas some unspoken complexities and challenges for future developments are highlighted.

Insights into the Thermo-Mechanical Treatment of Brewers' Spent Grain as a Potential Filler for Polymer Composites.

This paper investigated the impact of twin-screw extrusion parameters on the properties of brewers' spent grain. The chemical structure, antioxidant activity, particle size, and color properties, as well as the emission of volatile organic compounds during extrusion, were investigated. The main compounds detected in the air during modifications were terpenes and terpenoids, such as α-pinene, camphene, 3-carene, limonene, or terpinene. They could be considered as a potential threat to human health and the environment. Changes in the chemical structure, antioxidant activity, and color of materials after modification indicated the Maillard reactions during extrusion, which resulted in the generation of melanoidins, especially at higher temperatures. This should be considered an exciting feature of this treatment method because modified brewers' spent grain may improve the thermooxidative stability of polymer materials. Moreover, the impact of the brewers' spent grain particle size on color and browning index used to determine the melanoidins content was investigated. The presented results show that proper adjustment of extrusion parameters enables the preparation of brewers' spent grain with the desired appearance and chemical properties, which could maximize the efficiency of the modification process.

Reactive Sintering of Ground Tire Rubber (GTR) Modified by a Trans-Polyoctenamer Rubber and Curing Additives.

The proposed method of ground tire rubber (GTR) utilization involves the application of trans-polyoctenamer rubber (TOR), a commercially available waste rubber modifier. The idea was to investigate the influence of various curing additives (sulfur, N-cyclohexyl-2-benzothiazole sulfenamide (CBS), dibenzothiazole disulfide (MBTS) and di-(2-ethyl)hexylphosphorylpolysulfide (SDT)) on curing characteristics, physico-mechanical, thermal, acoustic properties as well as the morphology of modified GTR, in order to evaluate the possibility of reclaiming GTR and the co-cross-linking between applied components. The results showed that the presence of the modifier without the addition of curing additives hinders the physico-mechanical properties of revulcanized GTR. The addition of SDT, CBS, MBTS and sulfur change the melting kinetics of TOR, indicating partial degradation and/or co-cross-linking between components. In the studied conditions, the best mechanical properties were obtained by the samples cured with sulfur. The morphology analysis, combined with the physico-mechanical results, indicated that when the surface of the GTR is more developed, obtained by the addition of TOR, the properties of the GTR improve.

Novel tetrahedral cobalt(ii) silanethiolates: structures and magnetism.

Three heteroleptic complexes of Co(ii) tri-tert-butoxysilanethiolates have been synthesized with piperidine [Co{SSi(OtBu)3}2(ppd)2] 1, piperazine [Co{SSi(OtBu)3}2(NH3)]2(µ-ppz)·2CH3CN 2, and N-ethylimidazole [Co{SSi(OtBu)3}2(etim)2] 3. The complexes have been characterized by a single-crystal X-ray, revealing their tetrahedral geometry on Co(ii) coordinated by two nitrogen and two sulfur atoms. Complexes 1 and 3 are mononuclear, whereas 2 is binuclear. The spectral properties and thermal properties of 1-3 complexes were established by FTIR spectroscopy for solid samples and TGA. The magnetic properties of complexes 1, 2, and 3 have been investigated by static magnetic measurements and X-band EPR spectroscopy. These studies have shown that 1 and 3, regardless of the similarity in structure of CoN2S2 cores, demonstrate different types of local magnetic anisotropy. Magnetic investigations of 2 reveal the presence of weak antiferromagnetic intra-molecular Co(ii)-Co(ii) interactions that are strongly influenced by the local magnetic anisotropy of individual Co(ii) ions.

Preliminary Investigation on Auto-Thermal Extrusion of Ground Tire Rubber.

Ground tire rubber (GTR) was processed using an auto-thermal extrusion as a prerequisite to green reclaiming of waste rubbers. The reclaimed GTR underwent a series of tests: thermogravimetric analysis combined with Fourier-transform infrared spectroscopy (TGA-FTIR), scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), and static headspace and gas chromatography-mass spectrometry (SHS-GC-MS) in order to evaluate the impact of barrel heating conditions (with/without external barrel heating) on the reclaiming process of GTR. Moreover, samples were cured to assess the impact of reclaiming heating conditions on curing characteristics and physico-mechanical properties. Detailed analysis of the results indicated that the application of auto-thermal extrusion is a promising approach for the sustainable development of reclaiming technologies.