Sulfur and Peroxide Vulcanization of the Blends Based on Styrene-Butadiene Rubber, Ethylene-Propylene-Diene Monomer Rubber and Their Combinations.

Rubber blends based on styrene-butadiene rubber, ethylene-propylene-diene monomer rubber and a combination of both rubbers were cured with different sulfur and peroxide curing systems. In sulfur curing systems, two type of accelerators, namely tetramethylthiuram disulfide, N-cyclohexyl-2-benzothiazole sulfenamide, and combinations of both accelerators were used. In peroxide curing systems, dicumyl peroxide, and a combination of dicumyl peroxide with zinc diacrylate or zinc dimethacrylate, respectively, were applied. The work was aimed at investigating the effect of curing systems composition as well as the type of rubber or rubber combinations on the curing process, cross-link density and physical-mechanical properties of vulcanizates. The dynamic mechanical properties of the selected vulcanizates were examined too. The results revealed a correlation between the cross-link density and physical-mechanical properties. Similarly, there was a certain correlation between the cross-linking degree and glass transition temperature. The tensile strength of vulcanizates based on rubber combinations was higher when compared to that based on pure rubbers, which points out the fact that in rubber combinations, not only are the features of both elastomers combined, but improvement in the tensile characteristics can also be achieved. When compared to vulcanizates cured with dicumyl peroxide, materials cured with a sulfur system exhibited higher tensile strength. With the application of co-agents in peroxide vulcanization, the tensile strength overcame the tensile behavior of sulfur-cured vulcanizates.

Biodegradable Nanocomposites Based on Blends of Poly(Butylene Adipate-Co-Terephthalate) (PBAT) and Thermoplastic Starch Filled with Montmorillonite (MMT): Physico-Mechanical Properties.

Poly(butylene adipate-co-terephthalate) (PBAT) is widely used for production of biodegradable films due to its high elongation, excellent flexibility, and good processability properties. An effective way to develop more accessible PBAT-based bioplastics for wide application in packaging is blending of PBAT with thermoplastic starch (TPS) since PBAT is costly with prices approximately double or even triple the prices of traditional plastics like polyethylene. This study is focused on investigating the influence of TPS/PBAT blend ratio and montmorillonite (MMT) content on the physical and mechanical properties and molecular mobility of TPS-MMT/PBAT nanocomposites. Obtained TPS-MMT/PBAT nanocomposites through the melt blending process were characterized using tensile testing, dynamic mechanical thermal analysis (DMTA), and X-ray diffraction (XRD), as well as solid-state 1H and 13C NMR spectroscopy. Mechanical properties demonstrated that the addition of TPS to PBAT leads to a substantial decrease in the tensile strength as well as in the elongation at break, while Young's modulus is rising substantially, while the effect of the MMT addition is almost negligible on the tensile stress of the blends. DMTA results confirmed the formation of TPS domains in the PBAT matrix. With increasing TPS content, mobility of starch-rich regions of TPS domains slightly increases. However, molecular mobility in glycerol-rich regions of TPS domains in the blends was slightly restricted. Moreover, the data obtained from 13C CP/MAS NMR spectra indicated that the presence of TPS in the sample decreases the mobility of the PBAT chains, mainly those located at the TPS/PBAT interfaces.

Effects of glycerol content on structure and molecular motion in thermoplastic starch-based nanocomposites during long storage.

Thermoplastic starch-based nanocomposites with varying glycerol content and montmorillonite as a nanofiller were studied using dynamic-mechanical analysis (DMA), X-ray diffraction (XRD) and nuclear magnetic resonance (NMR) during one-year storage. DMA results showed that starch-rich and glycerol-rich domains were present in the samples and during storage for up to one year the content of the amorphous phase decreased and molecular mobility changed. 13C NMR and XRD measurements confirmed that ordered structures were formed during storage and its content was larger for samples with higher glycerol content and increased with the storage time. The data obtained from deconvolutions of 1H broad line NMR spectra indicate increased overall molecular mobility in the samples up to four months of storage, while after nine months the trends were opposite. Lower free water content compared to the total water content in the samples determined according to deconvoluted 1H MAS (magic-angle spinning) NMR spectra indicated that a part of water molecules was immobilized in the ordered structures.

Combined Sulfur and Peroxide Vulcanization of Filled and Unfilled EPDM-Based Rubber Compounds.

The sulfur curing system, peroxide curing system and their combinations were applied for the cross-linking of unfilled and carbon black-filled rubber formulations based on ethylene-propylenediene-monomer rubber. The results demonstrated that the type of curing system influenced the course and shape of curing isotherms. This resulted in the change of curing kinetics of rubber compounds. The cross-link density of materials cured with combined vulcanization systems was lower than that for vulcanizates cured with the peroxide or sulfur system. Good correlation between the cross-link density as well as the structure of the formed cross-links and physical-mechanical characteristics of the cured materials was established. Both filled and unfilled vulcanizates cured with combined vulcanization systems exhibited a higher tensile strength and elongation at break when compared to their equivalents vulcanized in the presence of the peroxide or sulfur curing system. It can be stated that by proper combination of vulcanization systems, it is possible to modify the tensile behavior of vulcanizates in a targeted manner. On the other side, dynamical-mechanical properties were found not be significantly influenced by the curing system composition.

Thermoplastic starch/bentonite clay nanocomposite reinforced with vitamin B2: Physicochemical characteristics and release behavior.

This study presents the development and characterization of a nanocomposite material, consisting of thermoplastic starch (TPS) reinforced with bentonite clay (BC) and encapsulated with vitamin B2 (VB). The research is motivated by the potential of TPS as a renewable and biodegradable substitute for petroleum-based materials in the biopolymer industry. The effects of VB on the physicochemical properties of TPS/BC films, including mechanical and thermal properties, water uptake, and weight loss in water, were investigated. In addition, the surface morphology and chemical composition of the TPS samples were analyzed using high-resolution SEM microscopy and EDS, providing insight into the structure-property relationship of the nanocomposites. The results showed that the addition of VB significantly increased the tensile strength and Young's modulus of TPS/BC films, with the highest values observed for nanocomposites containing 5 php of VB and 3 php of BC. Furthermore, the release of VB was controlled by the BC content, with higher BC content leading to lower VB release. These findings demonstrate the potential of TPS/BC/VB nanocomposites as environmentally friendly materials with improved mechanical properties and controlled release of VB, which can have significant applications in the biopolymer industry.

Influence of Air Humidity Level on the Structure and Mechanical Properties of Thermoplastic Starch-Montmorillonite Nanocomposite during Storage.

Thermoplastic starch (TPS) consisting of corn starch and glycerol as a plasticizer, and TPS-montmorillonite (MMT) nanocomposite were stored at room temperature in the air with relative humidities (RH) of 11, 55 and 85% for seven weeks. Mechanical testing and dynamic mechanical thermal analysis (DMTA) were performed to detect changes in their mechanical properties. Solid-state NMR spectroscopy monitoring the changes in molecular mobility in the samples provided an insight into relations between mechanical properties and local structure. The results of mechanical testing indicated that the addition of MMT results in the increase in the tensile strength and Young's modulus while elongation at break decreased, indicating the reinforcing effect of MMT. DMTA experiments revealed a decrease in glass transition temperature of starch-rich phase below room temperature for samples stored at higher RH (55 and 85%). This indicates that absorbed water molecules had additional plasticizing effect on starch resulting in higher mobility of starch chain segments. Recrystallization in these samples was deduced from the shape of cross-polarization magic-angle spinning 13C NMR spectra. The shape of broad-line 1H NMR spectra reflected changes in molecular mobility in the studied samples during seven weeks of storage and revealed that a high amount of water molecules impacts the starch intermolecular hydrogen bond density.

Application of Plasticizer Glycerol in Lignosulfonate-Filled Rubber Compounds Based on SBR and NBR.

The work deals with the application of biopolymer fillers in rubber formulations. Calcium lignosulfonate was incorporated into styrene-butadiene rubber and acrylonitrile-butadiene rubber in a constant amount of 30 phr. Glycerol in a concentration scale ranging from 5 to 20 phr was used as a plasticizer for rubber formulations. For the cross-linking of the compounds, a sulfur-based curing system was used. The study was focused on the investigation of glycerol in the curing process; the viscosity of rubber compounds; and the cross-link density, morphology, physical-mechanical, and dynamic mechanical properties of vulcanizates. The study revealed that the application of glycerol as a plasticizer resulted in a reduction in the rubber compounds' viscosity and contributed to the better dispersion and distribution of the filler within the rubber matrices. The mutual adhesion and compatibility between the filler and the rubber matrices were improved, which resulted in the significant enhancement of tensile characteristics. The main output of the work is the knowledge that the improvement of the physical-mechanical properties of biopolymer-filled vulcanizates can be easily obtained via the simple addition of a very cheap and environmentally friendly plasticizer into rubber compounds during their processing without additional treatments or procedures. The enhancement of the physical-mechanical properties of rubber compounds filled with biopolymers might contribute to the broadening of their potential applications. Moreover, the price of the final rubber articles could be reduced, and more pronounced ecological aspects could also be emphasized.

Effects of Peroxide and Sulfur Curing Systems on Physical and Mechanical Properties of Nitrile Rubber Composites: A Comparative Study.

This study compares the effect of sulfur and dicumyl peroxide (DCP) vulcanizing systems on the physical and mechanical properties of rubber compounds based on acrylonitrile butadiene rubber (NBR). NBR compounds cured by different amounts of DCP and NBR vulcanizates filled with various concentrations of carbon black (CB) and a constant amount of sulfur or DCP were prepared. The vulcanizates were characterized by tensile testing, dynamic mechanical thermal analysis (DMTA), and cross-link density determination. The tensile strength and Young's modulus were found to increase with the rising amount of DCP and CB, while elongation at break decreased. The samples vulcanized by the sulfur system and filled with CB show a substantial increase in tensile strength from 13.1 to 21.2 MPa. Higher storage modulus and glass transition temperature were observed with the increase in the amount of peroxide and filler, and consequently, the increase in cross-link density, indicating rigidity increase and lower molecular mobility. The changes in the physical and mechanical properties of the NBR vulcanizates were in correlation with the changes in solvent uptake and cross-link density.

Electrical Conductivity of Rubber Composites with Varying Crosslink Density under Cyclic Deformation.

Studies addressing electroconductive composites based on rubber have attracted great interest for many engineering applications. To contribute to obtaining useful materials with reproducible behavior, this study focused on understanding the mechanism of conductivity changes during mechanical deformation for rubber composites based on styrene-butadiene rubber (SBR) or ethylene-propylene-diene terpolymer (EPDM) vulcanized for various times. The composites were characterized by static electrical conductivity, tensile testing, dynamic mechanical thermal analysis (DMTA), and crosslink density measurements. The tensile strength and Young's modulus were found to increase significantly with rising vulcanization time. Higher static conductivity values of the composites were observed with the increase in vulcanization time. The most important aspect of this investigation consisted in the electrical current measurement online with recording the stress-strain curves, revealing the details of the uniaxial cyclic deformation effect on changes in the structure of conductive pathways indirectly. The electrical conductivity during five runs of repeated cyclic mechanical deformations for SBR composites increased permanently, although not linearly, whereas EPDM composites showed a slight increase or at least a nearly constant current, indicating healing of minor defects in the conductive pathways or the formation of new conductive pathways.

Modification of Hot-Melt Adhesives Based on Metallocene Poly(ethylene-propylene) Copolymer for High Adhesion to Polar Surfaces.

A procedure is described of grafting the acrylic acid onto an oxygen/ozone-activated metallocene poly(ethylene-co-propylene). Consequently, the grafted copolymer is applied as a component in a metallocene polyolefin-based hot-melt adhesive composition with increased adhesion. The surface properties and adhesion strength of the prepared hot-melt adhesive (HMA) were determined and used to account for the effect of grafting. The application of grafted polyolefin as one of the components of the HMA mixture provides significant increase in adhesive strength, and it also results in increased compatibility and negligible effects on the technological parameters of the final composition. The obtained results may have significant impact for the practical application of prepared HMA for book bonding.

Thermoplastic Starch-Based Composite Reinforced by Conductive Filler Networks: Physical Properties and Electrical Conductivity Changes during Cyclic Deformation.

Conductive polymer composites (CPC) from renewable resources exhibit many interesting characteristics due to their biodegradability and conductivity changes under mechanical, thermal, chemical, or electrical stress. This study is focused on investigating the physical properties of electroconductive thermoplastic starch (TPS)-based composites and changes in electroconductive paths during cyclic deformation. TPS-based composites filled with various carbon black (CB) contents were prepared through melt processing. The electrical conductivity and physicochemical properties of TPS-CB composites, including mechanical properties and rheological behavior, were evaluated. With increasing CB content, the tensile strength and Young's modulus were found to increase substantially. We found a percolation threshold for the CB loading of approximately 5.5 wt% based on the rheology and electrical conductivity. To observe the changing structure of the conductive CB paths during cyclic deformation, both the electrical conductivity and mechanical properties were recorded in parallel using online measurements. Moreover, the instant electrical conductivity measured online during mechanical deformation of the materials was taken as the parameter indirectly describing the structure of the conductive CB network. The electrical conductivity was found to increase during five runs of repeated cyclic mechanical deformations to constant deformation below strain at break, indicating good recovery of conductive paths and their new formation.

In situ dual crosslinking strategy to improve the physico-chemical properties of thermoplastic starch.

This study is focused on enhancing the stability of mechanical and chemical properties of thermoplastic starch (TPS) by dual crosslinking strategy through melt processing conditions. The dually crosslinked TPS was prepared by in situ reaction of starch, glycerol, and epichlorohydrin (ECH), resulting in both noncovalent and covalent bond formation. The TPS was characterized by tensile testing, dynamic mechanical analysis (DMTA), rheology, and solubility in water. A substantial increase in tensile strength, Young's modulus, insoluble portion, and stability in water for dually crosslinked TPS was observed in comparison with conventional TPS. The rheology results indicated that the ECH induced the formation of 3D networks and significantly limited the chain mobility of the melted TPS, resulting in an extended relaxation process, which was also verified by DMTA. The suggested strategy avoids any chemical modification pretreatment of starch for introducing covalent bonds into TPS before one-step mixing using the melt processing technique.

Changes of physical properties of PLA-based blends during early stage of biodegradation in compost.

Three biodegradable plastics materials, namely pure poly(l-lactide) (PLA), PLA with plasticizer triacetine (TAC) and the mixture PLA/polyhydroxybutyrate (PHB) and TAC were investigated concerning changes of physical properties due to biodegradation in compost at 58°C up to 16days. With rising time of degradation in compost, both number and weight molecular masses were decreasing progressively, but only marginal change of the polydispersity index was observed which indicates that biodegradation is not random process. FTIR spectroscopy revealed that in spite of the extensive decrease of molecular weight, no substantial change in chemical composition was found. The most significant modification of the spectra consisted in an appearing of the broad band in region 3100-3300cm-1, which was assigned to a formation of biofilm on the sample surfaces. This effect appeared for all three materials, however, it was much more pronounced for samples containing also triacetine. Measurement of changes in crystalline portion confirmed that amorphous phase degrades substantially faster compared to crystalline part. The plasticizer triacetine is disappearing also rather fast from the sample resulting besides other effect also in a temporary increase of Tg, which at the beginning grows almost to the value typical for PLA without plasticizer but later the Tg is decreasing due to substantial changes in molecular weight. Generally during composting, the samples keep shape for up to 8days, after that time the material disintegrates to rough powder.

A new route for chitosan immobilization onto polyethylene surface.

Low-density polyethylene (LDPE) belongs to commodity polymer materials applied in biomedical applications due to its favorable mechanical and chemical properties. The main disadvantage of LDPE in biomedical applications is low resistance to bacterial infections. An antibacterial modification of LDPE appears to be a solution to this problem. In this paper, the chitosan and chitosan/pectin multilayer was immobilized via polyacrylic acid (PAA) brushes grafted on the LDPE surface. The grafting was initiated by a low-temperature plasma treatment of the LDPE surface. Surface and adhesive properties of the samples prepared were investigated by surface analysis techniques. An antibacterial effect was confirmed by inhibition zone measurements of Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus). The chitosan treatment of LDPE led to the highest and most clear inhibition zones (35 mm(2) for E. coli and 275 mm(2) for S. aureus).

Anti-bacterial treatment of polyethylene by cold plasma for medical purposes.

Polyethylene (PE) is one of the most widely used polymers in many industrial applications. Biomedical uses seem to be attractive, with increasing interest. However, PE it prone to infections and its additional surface treatment is indispensable. An increase in resistance to infections can be achieved by treating PE surfaces with substances containing antibacterial groups such as triclosan (5-Chloro-2-(2,4-dichlorophenoxy)phenol) and chlorhexidine (1,1'-Hexamethylenebis[5-(4-chlorophenyl)biguanide]). This work has examined the impact of selected antibacterial substances immobilized on low-density polyethylene (LDPE) via polyacrylic acid (PAA) grafted on LDPE by low-temperature barrier discharge plasma. This LDPE surface treatment led to inhibition of Escherichia coli and Staphylococcus aureus adhesion; the first causes intestinal disease, peritonitis, mastitis, pneumonia, septicemia, the latter is the reason for wound and urinary tract infections.

An in vitro bacterial adhesion assessment of surface-modified medical-grade PVC.

Medical-grade polyvinyl chloride was surface modified by a multistep physicochemical approach to improve bacterial adhesion prevention properties. This was fulfilled via surface activation by diffuse coplanar surface barrier discharge plasma followed by radical graft copolymerization of acrylic acid through surface-initiated pathway to render a structured high density brush. Three known antibacterial agents, bronopol, benzalkonium chloride, and chlorhexidine, were then individually coated onto functionalized surface to induce biological properties. Various modern surface probe techniques were employed to explore the effects of the modification steps. In vitro bacterial adhesion and biofilm formation assay was performed. Escherichia coli strain was found to be more susceptible to modifications rather than Staphylococcus aureus as up to 85% reduction in adherence degree of the former was observed upon treating with above antibacterial agents, while only chlorhexidine could retard the adhesion of the latter by 50%. Also, plasma treated and graft copolymerized samples were remarkably effective to diminish the adherence of E. coli.

Structure modification of UHMWPE used for total joint replacements.

Modification of ultrahigh-molecular-weight polyethylene (UHMWPE) consisting of a combination of gamma irradiation and subsequent thermal treatment has been performed in order to investigate the resultant changes to its supramolecular structure. In the first step the polymer was irradiated by gamma rays at laboratory temperature under nitrogen. Five radiation doses (25, 50, 100, 150, and 200 kGy) were applied at two dose rates (0.25 and 2.5 kGy/h). In the second step the irradiated samples were thermally treated above the UHMWPE melting temperature. Insoluble fraction, crystallinity (fraction), and lamellar periodicity were determined as functions of dose and dose rate for irradiated samples before and after thermal treatment. Both modification steps were shown to produce substantial changes in the UHMWPE structure.