Thermal Characterization of Crosslinked Polymeric Microspheres Bearing Thiol Groups Studied by TG/FTIR/DSC under Non-Oxidative Conditions.

This paper presents the thermal behavior of polymer microspheres based on glycidyl methacrylate (GMA) and crosslinking agents benzene-1,4-diylbis(2-methylprop-2-enoate) (1,4DMB) and trimethylolpropane trimethacrylate (TRIM) before and after functionalization with thioglycolic acid (TGA). The thermal stability of the polymers was determined using thermogravimetric analysis and differential scanning calorimetry under non-oxidizing conditions. The evolved gases were detected by FTIR and NMR spectroscopy, and the chemical structure of solid residues after preheating was assessed by FTIR/ATR spectroscopy. The post-functionalized microspheres showed higher thermal stability (within 270-290 °C) than the initial copolymers (within 240-250 °C). In this paper, examples of decomposition patterns of polymer microspheres before and after functionalization are presented. The decomposition of the initial microspheres starts with the emission of GMA monomers, acrolein, carbon dioxide, and the formation of unsaturated bonds in the solid residue. In the case of functionalized microspheres, degradation involves the transesterification of ester groups with the -SH groups, resulting in the emission of carbonyl sulfide, acrolein and carbon dioxide. Furthermore, lactone groups are created in the solid residue. The degradation of the functionalized copolymers is a complex process due to their crosslinked structure, rendering the identification of all the degradation products unattainable.

Study on the Biodegradation of Poly(Butylene Succinate)/Wheat Bran Biocomposites.

This paper presents the results of a study investigating the biodegradation of poly(butylene succinate) (PBS)/wheat bran (WB) biocomposites. Injection mouldings were subjected to biodegradation in compost-filled bioreactors under controlled humidity and temperature conditions. The effects of composting time (14, 42 and 70 days) and WB mass content (10%, 30% and 50% wt.) on the structural and thermal properties of the samples were investigated. Measurements were made by infrared spectral analysis, scanning electron microscopy, differential scanning calorimetry, thermogravimetric analysis, and gel permeation chromatography. Results demonstrated that both the thermal and structural properties of the samples depended greatly on the biodegradation time. Specifically, their crystallinity degree increased significantly while molecular mass sharply decreased with biodegradation time, whereas their thermal resistance only showed a slight increase. This resulted from enzymatic hydrolysis that led to the breakdown of ester bonds in polymer chains. It was also found that a higher WB content led to a higher mass loss in the biocomposite samples during biodegradation and affected their post-biodegradation properties. A higher bran content increased the degree of crystallinity of the biocomposite samples but reduced their thermal resistance and molecular mass.

Preparation and Spectroscopic, Thermal, and Mechanical Characterization of Biocomposites of Poly(butylene succinate) and Onion Peels or Durum Wheat Bran.

The utilization of plant based fillers: onion peels (OP) and durum wheat bran (WB) to obtain sustainable biocomposite materials with poly(butylene succinate) (PBS) is presented in this paper. The biocomposites were first obtained in pellet form by extrusion method and then injection moldings were made from the pellets. Two kinds of biocomposites were fabricated containing 15% and 30% wt. of OP or WB. Additionally, pure PBS moldings were prepared for comparative purposes. The effect of the filler type and its amount on the chemical structure, density, thermal, and thermo-mechanical properties of the fabricated composite samples was studied. Fourier-transform infrared spectroscopy results showed that the composite preparation method had no effect on the chemical structure of composite components, but weak interactions such as hydrogen bonding between OP or WB and PBS was observed. The addition of OP or WB to the composite with PBS reduced its thermal stability in comparison with pure PBS, all studied composites start to degrade below 290 °C. Additionally, the mechanical properties of the composites are worse than PBS, as the impact strength dropped by about 70%. The deterioration of tensile strength was in the range 20-47%, and the elongation at maximum load of the composites was in the range 9.22-3.42%, whereas for pure PBS it was 16.75%. On the other hand, the crystallinity degree increased from 63% for pure PBS to 79% for composite with 30% wt. of WB. The Young's modulus increased to 160% for composition with 30% wt. of OP. Additionally, the hardness of the composites was slightly higher than PBS and was in the range 38.2-48.7 MPa. Despite the reduction in thermal stability and some mechanical properties, the studied composites show promise for everyday object production.

Flammability of Polymer Compositions Filled with Wheat Bran.

The article presents the results of flammability tests on polymer compositions with wheat bran (WB) as the applied filler, and polyethylene (PE) or poly(butylene succinate) (PBS) as the matrix material. Tests were conducted using samples of compositions containing 10, 30 and 50%wt wheat bran. The test samples were manufactured by injection moulding from compositions previously produced by extrusion pelleting. For comparative purposes, samples made only of the plastics used for the composition matrix were also examined. Flammability tests were carried out in accordance with the recommendations of EN 60695-11-10 Part 11-10 with horizontal and vertical positioning of the sample, using a universal flammability-test-stand. During the flammability tests, changes in the temperature field in the area of the burning sample were also recorded, using a thermal imaging camera. Sample residues after flammability tests were also examined with infrared spectroscopy (FTIR) to assess their thermal destruction. The results of the study showed a significant increase in flammability with bran content for both PE and PBS matrix compositions. Clear differences were also found in the combustion behaviour of the matrix materials alone. Both the burning rate and maximum flame temperature were lower in favour of PBS. PBS compositions with wheat bran also showed lower flammability, compared with their PE matrix counterparts.

Crosslinked 4-Vinylpyridine Monodisperse Functional Microspheres for Sorption of Ibuprofen and Ketoprofen.

Nowadays, ibuprofen and ketoprofen are widely used over-the-counter medications to treat inflammation, fever, or pain. Their high consumption and improper disposal cause them to get into the environment and often pollute surface water. In this study, the new polymeric porous microspheres based on 4-vinylpyridine (4VP) are presented as effective sorbents for ibuprofen and ketoprofen preconcentration and removal. The porous microspheres were obtained via seed swelling polymerization with the use of two types of methacrylate crosslinkers, i.e., trimethylolpropane trimethacrylate (TRIM) and 1,4-dimethacryloiloxybenzene (14DMB). Additionally, as a reference sorbent, a copolymer of styrene and divinylbenzene was obtained. Porous structure investigations showed that the microspheres possess a specific surface area of about 100 m2/g, but noticeable differences were observed in their internal topography depending on the type of crosslinker used. Moreover, the porous structure of dry and swollen microspheres differs significantly. Swollen copolymers reveal the presence of micropores. The 4VP microspheres are characterized by high thermal stability; their initial decomposition temperature is about 300 °C. The performance of the 4VP copolymers as sorbents in aqueous solutions of drugs was evaluated in static and dynamic modes at three pH values of 3, 7, and 11. The highest sorption efficiency was obtained for ibuprofen and ketoprofen in pH 3. Both 4VP copolymers indicate the high sorption capacity in a static sorption as follows: towards ketoprofen of about 40 mg/g whereas towards ibuprofen of about 90 mg/g and 75 mg/g on copolymer crosslinked with trimethylolpropane trimethacrylate and 1,4-dimethacryloiloxybenzene, respectively. The recovery of ibuprofen and ketoprofen after dynamic sorption experiments was higher than 90%.

Artificial Ageing, Chemical Resistance, and Biodegradation of Biocomposites from Poly(Butylene Succinate) and Wheat Bran.

The results of comprehensive studies on accelerated (artificial) ageing and biodegradation of polymer biocomposites on PBS matrix filled with raw wheat bran (WB) are presented in this paper. These polymer biocomposites are intended for the manufacture of goods, in particular disposable packaging and disposable utensils, which decompose naturally under the influence of biological agents. The effects of wheat bran content within the range of 10-50 wt.% and extruder screw speed of 50-200 min-1 during the production of biocomposite pellets on the resistance of the products to physical, chemical, and biological factors were evaluated. The research included the determination of the effect of artificial ageing on the changes of structural and thermal properties by infrared spectra (FTIR), differential scanning calorimetry (DSC), and thermogravimetric analysis (TG). They showed structural changes-disruption of chains within the ester bond, which occurred in the composition with 50% bran content as early as after 250 h of accelerated ageing. An increase in the degree of crystallinity with ageing was also found to be as high as 48% in the composition with 10% bran content. The temperature taken at the beginning of weight loss of the compositions studied was also lowered, even by 30 °C at the highest bran content. The changes of mechanical properties of biocomposite samples were also investigated. These include: hardness, surface roughness, transverse shrinkage, weight loss, and optical properties: colour and gloss. The ageing hardness of the biocomposite increased by up to 12%, and the surface roughness (Ra) increased by as much as 2.4 µm at the highest bran content. It was also found that ageing causes significant colour changes of the biocomposition (ΔE = 7.8 already at 10% bran content), and that the ageing-induced weight loss of the biocomposition of 0.31-0.59% is lower than that of the samples produced from PBS alone (1.06%). On the other hand, the transverse shrinkage of moldings as a result of ageing turned out to be relatively small, at 0.05%-0.35%. The chemical resistance of biocomposites to NaOH and HCl as well as absorption of polar and non-polar liquids (oil and water) were also determined. Biodegradation studies were carried out under controlled conditions in compost and weight loss of the tested compositions was determined. The weight of samples made from PBS alone after 70 days of composting decreased only by 4.5%, while the biocomposition with 10% bran content decreased by 15.1%, and with 50% bran, by as much as 68.3%. The measurements carried out showed a significant influence of the content of the applied lignocellulosic fillers (LCF) in the form of raw wheat bran (WB) on the examined properties of the biocompositions and the course of their artificial ageing and biodegradation. Within the range under study, the screw speed of the extruder during the production of biocomposite pellets did not show any significant influence on most of the studied properties of the injection mouldings produced from it.

Analysis of Selected Properties of Injection Moulded Sustainable Biocomposites from Poly(butylene succinate) and Wheat Bran.

The paper presents a procedure of the manufacturing and complex analysis of the properties of injection mouldings made of polymeric composites based on the poly(butylene succinate) (PBS) matrix with the addition of a natural filler in the form of wheat bran (WB). The scope of the research included measurements of processing shrinkage and density, analysis of the chemical structure, measurements of the thermal and thermo-mechanical properties (Differential Scanning Calorimetry (DSC) and Thermogravimetric Analysis (TG), Heat Deflection Temperature (HDT), and Vicat Softening Temperature (VST)), and measurements of the mechanical properties (hardness, impact strength, and static tensile test). The measurements were performed using design of experiment (DOE) methods, which made it possible to determine the investigated relationships in the form of polynomials and response surfaces. The mass content of the filler and the extruder screw speed during the production of the biocomposite granulate, which was used for the injection moulding of the test samples, constituted the variable factors adopted in the DOE. The study showed significant differences in the processing, thermal, and mechanical properties studied for individual systems of the DOE.

Efficiency of Twin-Screw Extrusion of Biodegradable Poly (Butylene Succinate)-Wheat Bran Blend.

Unmodified poly (butylene succinate) (PBS) is characterized by very good processability; however, after the incorporation of various fillers of plant origin, its processing becomes much more complicated and its properties are significantly affected. Detailed studies of the processing aspects of PBS/wheat bran (WB) biocomposition are lacking, despite the addition of WB having a significant impact on both the production efficiency and the properties of end products. This research paper presents test results of the co-rotating twin-screw extrusion processing of a biodegradable polymer blend, the matrix of which was PBS, with WB as the filler. In undertaking this task, we examined the impact of extruder screw rotational speed and WB content on the characteristics of extrusion processing, as well as on certain thermal, physical, structural and processing properties of the obtained blend. The WB introduced to the blend was in the form of a selected fraction with particles smaller than 0.2 mm. The measurements were conducted using the Design of Experiment (DOE) methods, which enabled establishing the studied relationships in the form of polynomials and response surfaces. The determined extrusion process characteristics covered the impact of screw rotational speed and WB content on the mass flow rate of the processed blend and its pressure, the screw drive torque and specific energy consumption. The studies of the obtained polymer blend included determining the impact of the aforementioned variable factors on the melt flow rate (MFR) index, chemical structure (FTIR), thermal properties (differential scanning calorimetry (DSC), thermogravimetry (TG), derivative thermogravimetry (DTG)), p-v-T relationships, microstructure, density and moisture absorbance. Analysis of variance (ANOVA) was used to assess the effect of individual variable factors. The results of this work are presented, inter alia, using Pareto charts of standardized effects, which illustrate the influence of individual terms of the determined regression equations on the studied quantity.

Biodegradable and Drug-Eluting Inorganic Composites Based on Mesoporous Zinc Oxide for Urinary Stent Applications.

Conventional technologies for ureteral stent fabrication suffer from major inconveniences such as the development of encrustations and bacteria biofilm formation. These drawbacks typically lead to the failure of the device, significant patient discomfort and an additional surgery to remove and replace the stent in the worst cases. This work focuses on the preparation of a new nanocomposite material able to show drug elution properties, biodegradation and eventually potential antibacterial activity. Poly(2-hydroxyethyl methacrylate) or the crosslinked poly(2-hydroxyethyl methacrylate)-co-poly(acrylic acid) hydrogels were prepared by the radical polymerization method and combined with a biodegradable and antibacterial filling agent, i.e., flower-like Zinc Oxide (ZnO) micropowders obtained via the hydrothermal route. The physico-chemical analyses revealed the correct incorporation of ZnO within the hydrogel matrix and its highly mesoporous structure and surface area, ideal for drug incorporation. Two different anti-inflammatory drugs (Ibuprofen and Diclofenac) were loaded within each composite and the release profile was monitored up to two weeks in artificial urine (AU) and even at different pH values in AU to simulate pathological conditions. The addition of mesoporous ZnO micropowders to the hydrogel did not negatively affect the drug loading properties of the hydrogel and it was successfully allowed to mitigate undesirable burst-release effects. Furthermore, the sustained release of the drugs over time was observed at neutral pH, with kinetic constants (k) as low as 0.05 h-1. By exploiting the pH-tunable swelling properties of the hydrogel, an even more sustained release was achieved in acidic and alkaline conditions especially at short release times, with a further reduction of burst effects (k ≈ 0.01-0.02 h-1). The nanocomposite system herein proposed represents a new material formulation for preparing innovative drug eluting stents with intrinsic antibacterial properties.

Analysis of Selected Properties of Biocomposites Based on Polyethylene with a Natural Origin Filler.

The study investigates the effect of the content and size of wheat bran grains on selected properties of a lignocellulosic biocomposite on a polyethylene matrix. The biocomposite samples were made by injection method of low-density polyethylene with 5%, 10% and 15% by weight of wheat bran. Three bran fractions with grain sizes <0.4 mm, 0.4-0.6 mm and 0.6-0.8 mm were used. The properties of the mouldings (after primary shrinkage) were examined after their 2.5-year natural aging period. Processing properties, such as MFR (mass flow rate) and processing shrinkage, were determined. Selected physical, mechanical and structural properties of the produced biocomposite samples were tested. The results allowed the determination of the influence of both the content of bran and the size of its grains on such properties of the biocomposite as: color, gloss, processing shrinkage, tensile strength, MFR mass flow rate, chemical structure (FTIR), thermal properties (DSC, TG), p-v-T relationship. The tests did not show any deterioration of the mechanical characteristics of the tested composites after natural aging.

Influence of the Design Solutions of Extruder Screw Mixing Tip on Selected Properties of Wheat Bran-Polyethylene Biocomposite.

The study investigated the impact of the extruder screw design solution-the intensive mixing tip used-on the course of the extrusion process and the properties of the obtained biocomposite extrudate. A lignocellulosic wheat bran biocomposite based on a low-density polyethylene matrix was extruded. Three mixing tips of the screw were used interchangeably: apineapple tip, a cut rings tip, and a Maddock tip. The experimental tests carried out included the production of an extrudate with a mass content of bran altered within the range from 10% to 50%. Processing properties such as the melt flow rate (MFR) and mass flow rate of the extruded biocomposite were determined. Selected physical, mechanical, and structural properties of the biocomposite extrudate obtained with the use of the three tested mixing tips at five bran contents were tested.

Influence of the Conditions of Corotating Twin-Screw Extrusion for Talc-Filled Polypropylene on Selected Properties of the Extrudate.

The aim of the study was to determine the effect of the application of processing screws with a modified test segment in a corotating twin-screw extruder on selected properties of talc-filled polypropylene extrudate. The test segment was built of trilobe kneading elements and its design modifications refered to changing the distance between the kneading elements and the angle of positions of kneading elements that are relative to each other. The performed tests included the production of extrudate with various degrees of talc-filling using five design solutions of the test segment and then measurements of selected properties, such as tensile strength, elongation at maximum tensile stress, and melt flow rate. Structural studies using scanning electron microscope (SEM) and differential scanning calorimetry (DSC) were also carried out. The study includes not only the description of experimental results but also the determination of empirical models describing the dependence of the properties of the obtained extrudate on the conditions of the extrusion process and the design features of the test segment.

Polymer-amino-functionalized silica composites for the sustained-release multiparticulate system.

This study presents an interesting and promising strategy for producing an oral multiparticulate formulation of the sustained-release of diclofenac sodium (DS) consisting of subunits closed inside hard gelatin capsules (each capsule contains ~50mg of diclofenac sodium). The subunits in the form of beads were produced through the encapsulation of diclofenac sodium dispersed within a nondisintegrating polymer carrier by a silica gel functionalized with the 3-aminopropyl groups. The hybrid silica gel, which plays the role of enteric coating, was fabricated by the gelation of the liquid silica precursors mixture (i.e. tetraethoxysilane (TEOS) and (3-aminopropyl)triethoxysilane (APTES)) in the vapor phase of ammonia. The conducted studies reveal that the introduction of the hybrid silica gel into the solid DS dispersion facilitates prolonged release in the neutral environment of the intestine. Since the ability of the multiparticulate formulation to control the release of the drug depends on the properties of its subunits, studies involving the low temperature N2 sorption, DSC analysis together with spectroscopic techniques (XRD, SEM, 29Si MAS NMR) were conducted.

Vapour-phase method in the synthesis of polymer-ibuprofen sodium-silica gel composites.

The study discusses the synthesis of polymer-silica composites comprising water soluble drug (ibuprofen sodium, IBS). The polymers selected for this study were poly(TRIM) and poly(HEMA-co-TRIM) produced in the form of permanently porous beads via the suspension-emulsion polymerization method. The acid and base set ternary composites were prepared by the saturation of the solid dispersions of drug (poly(TRIM)-IBS and/or poly(HEMA-co-TRIM)-IBS) with TEOS, and followed by their exposition to the vapour mixture of water and ammonia, or water and hydrochloric acid, at autogenous pressure. The conducted analyses reveal that the internal structure and total porosity of the resulting composites strongly depend on the catalyst which was used for silica precursor gelation. The parameters characterizing the porosity of both of the acid set composites are much lower than the parameters of the base set composites. Moreover, the basic catalyst supplied in the vapour phase does not affect the ibuprofen sodium molecules, whereas the acid one causes transformation of the ibuprofen sodium into the sodium chloride and a derivative of propanoic acid, which is poorly water soluble. The release profiles of ibuprofen sodium from composites demonstrate that there are differences in the rate and efficiency of drug desorption from them. They are mainly affected by the chemical character of the polymeric carrier but are also associated with the restricted swelling of the composites in the buffer solution after precipitation of silica gel.

Effect of some parameters on the synthesis and the physico-chemical properties of new amphiphilic starch-g-copolymers.

The detailed studies on the graft copolymerization of phenyl methacrylate onto gelatinized potato starch in water using potassium persulfate as radical initiator were presented. The different reaction parameters such as effect of initiator concentration, starch to monomer ratio, reaction temperature and reaction time were studied in terms of grafting efficiency, grafting percent and percent homopolymer formation. It was found that grafting process of aromatic methacrylate monomer onto potato starch backbone allowed obtaining new amphiphilic copolymers with different physicochemical properties as compared to non-modified starch. The influence of the copolymer structure on the swelling behavior in polar and non-polar solvents, moisture absorbance, gelatinization properties, acid and base resistance, surface morphology and thermal properties was discussed.

Synthesis and characterization of nanostructural polymer-silica composite: positron annihilation lifetime spectroscopy study.

The swelling of poly(TRIM) spherical particles in TEOS is assessed as a potential way for obtaining polymer-silica nanocomposite materials. Silica deposition was achieved by simply stirring of swollen polymer particles in acidic hydrochloric-water solution. This procedure leads to spherical composite particles with dispersed silica gel within the polymer matrix. The resulting material exhibits the same morphology as the initial polymer. Nanocomposite particles are silica rich (about 17 wt.%). Characterization of the nanocomposites was performed using scanning electron microscopy, FT-IR spectroscopy, (29)Si CP MAS NMR spectroscopy and thermogravimetry. Moreover, the use of positron annihilation lifetime spectroscopy PALS to characterize the structural properties of the nanocomposites is presented. This technique gave more realistic pieces of information about the pore structure of the investigated samples in contrast to nitrogen adsorption studies.