Multifunctional Block Copolymers, Acting as Recycling Aids, by Atom Transfer Radical Polymerization.

Block copolymers utilizing oligomeric poly(pentylene-co-hexylene carbonate)diol modified with 2,4-diisocyanatotoluene and further with 2-bromo-N-(3-hydroxypropyl)-2-methylpropanamide were synthesized and utilized as Activators ReGenerated by Electron Transfer Atom Transfer Radical Polymerization macroinitiators to obtain a first generation of multifunctional recycling additives with poly(glycidyl methacrylate-co-butyl methacrylate-co-methyl methacrylate) side chains, which could act as chain extenders. Then, chosen additive was reacted with a radical scavenger, 3,5-ditertbutyl-4-hydroxybenzoic acid (DHBA), to obtain a second generation of reactive additives. Those copolymers had different numbers of epoxy groups per polymer chain, and different number of epoxides opened with DHBA, hence showed a range of properties, and were utilized as reactive modifiers for polylactide (PLA) extrusion melting. The first-generation modifiers caused an increase in PLA's blends relative melt viscosity, stabilized material properties, and enhanced impact strength, while the second-generation modifiers with more than 8 % of epoxide ring opened showed worse properties. However, they managed to suppress the UV degradation of PLA blend plates.

Cytotoxic Properties of Polyurethane Foams for Biomedical Applications as a Function of Isocyanate Index.

Polyurethane foams are widely used in biomedical applications due to their desirable mechanical properties and biocompatibility. However, the cytotoxicity of its raw materials can limit their use in certain applications. In this study, a group of open-cell polyurethane foams were investigated for their cytotoxic properties as a function of the isocyanate index, a critical parameter in the synthesis of polyurethanes. The foams were synthesized using a variety of isocyanate indices and characterized for their chemical structure and cytotoxicity. This study indicates that the isocyanate index highly influences the chemical structure of polyurethane foams, also causing changes in cytotoxicity. These findings have important implications for designing and using polyurethane foams as composite matrices in biomedical applications, as careful consideration of the isocyanate index is necessary to ensure biocompatibility.

Structural Hierarchy of PA6 Macromolecules after Hydrostatic Extrusion.

This article presents the influence of severe plastic deformation by hydrostatic extrusion (HE) on the thermal and structural properties of polyamide 6 (PA6). During the hydrostatic extrusion process, a fibrous structure oriented along the extrusion direction is formed, which was visualized during microscopic observations. The degree of crystallinity was analyzed by differential scanning calorimetry (DSC). Wide-angle X-ray scattering diffraction (WAXS) analysis was used to partially characterize the PA6 structure after the HE process. The contents of various forms of the crystalline phase in PA6 samples before and after the HE process were analyzed in fragments of spectroscopy in infrared (FTIR). The favorable properties of PA6 after the HE process were obtained after deformation under conditions generating an adiabatic temperature higher than the glass transition temperature and lower than the temperature of the onset of melting of the crystalline phase. Thermal analysis using DSC allowed us to conclude that in the PA6 after the HE process generating deformations in the range of 0.68-1.56, the proportion of the crystalline phase α increases in PA6. As the deformation increases in the HE process, the crystalline phase proportion increases by 12% compared to the initial material (before HE). The glass transition temperature of PA6 is ca. 50.6 °C, reduced for the sample after the HE process at a small deformation of 0.68 (PA6_0.68) to ca. 44.2 °C. For other samples, Tg is ca. 53.2-53.5 °C. As a result of the analysis of WAXS diffractograms of PA6 samples after various deformations in the HE process, the presence of typical peaks of phases α1 and α2 and γ was observed. The results of the FTIR spectroscopic analysis confirm these observations that as the deformation increases, the proportion of the crystalline phase α increases.

Effect of Different Amine Catalysts on the Thermomechanical and Cytotoxic Properties of 'Visco'-Type Polyurethane Foam for Biomedical Applications.

Components for manufacturing polyurethane foams can adversely affect the human body, particularly if they are in contact with it for long periods. In applications where the foam is not placed directly into the body, the study of the product's effects is often neglected. In the case of human skin, distinguishing the increasingly frequent problems of skin atopy, more attention should be paid to this. This paper presents the influence of the different catalytic systems on cytotoxic and thermomechanical properties in polyurethane foams. Among others, foams were produced with the most popular catalysts on the market, DABCO and a metal-organic tin catalyst. The foams were characterized by thermomechanical properties and were subjected to a cytotoxicity test against human keratinocytes. In biocompatibility tests with skin cells, the results were highly variable. VAB 2 with a catalytic system consisting of commercial Diethanolamine and Addocat®105 performed the best. However, with such a catalytic system, the mechanical properties have worsened.

Spent Coffee as a Composite Filler for Wastewater Treatment.

Currently composites play an important role in all aspects of engineering and technology, with constantly growing applications. Recently, more attention was focused on natural fillers due to their suitability as reinforcement materials in thermo-plastic matrices which improve the mechanical properties of these polymers. Biofillers are used due to their low cost, high strength rigidity, non-toxicity, biodegradability, and availability. Currently, spent coffee grounds (SCG) are attracting more attention as a natural filler since high amounts of SCG are generated every day (food waste of coffee processing). This study allowed us to determine the long-term effect of activated sludge microorganisms with known technical and technological parameters on the mechanical properties of composites with spent coffee grounds filler. The fittings consisted of high-density poly-ethylene (PE-HD), which was used as the matrix, and a filler based on spent coffee grounds (SCG), which was used as a modifier. It was established that the composition of the composite and its residence time in the bioreactor directly influenced the contact angle value. The shift of the contact angle value is associated with the formation of the biofilm on the tested materials. An increase in the contact angle was observed in the case of all samples tested in the bioreactor, with the lowest values equal to approx. 76.4° for sample A (PE-HD) and higher values of approx. 90° for the remaining composite samples with a coffee grounds filler. The research confirmed that the increased ratio of coffee grounds in the composite results in the increased diversity and abundance of microorganisms. The highest number and the greatest diversity of microorganisms were observed in the case of the composite with 40% coffee grounds after more than a year of exposure in the bioreactor, while the composite with 30% SCG was second. Ciliates (Ciliata), especially the sessile forms belonging to the Epistylis genus, were the most common and the most numerous group of microorganisms in the activated sludge and in the biofilm observed on the samples after immersion in the bioreactor. The conducted research confirms that the use of polymer composite mouldings with a filler in the form of spent coffee grounds as a carrier allows the efficient increase in the population of microorganisms in the bioreactor.

The Effect of Mixing Pressure in a High-Pressure Machine on Morphological and Physical Properties of Free-Rising Rigid Polyurethane Foams-A Case Study.

This article presents the results of testing foam blocks made with a high-pressure foaming machine under industrial conditions. Foam blocks were made at pressures in the range of 110-170 bar with substrate temperatures allowed by machine suppliers. The foaming process parameters of each block were evaluated. The structure of the foams in the outer and central parts of the blocks was characterized using FTIR spectroscopic analysis and microscopic observations using SEM. The changes in apparent density, strength properties and brittleness of the foams were evaluated. The properties of the blocks made at different mixing pressures varied depending on the pressure at which the substrates were mixed and the location in the block. The biggest differences that were observed were the friability of the foams taken from different locations in the blocks by up to about 30%; the apparent density differed by about 8% and the compressive strength by about 5%.

Grafted Lactic Acid Oligomers on Lignocellulosic Filler towards Biocomposites.

Lactic acid oligomers (OLAs) were in situ synthesized from lactic acid (LAc) and grafted onto chokeberry pomace (CP) particleboards by direct condensation. Biocomposites of poly (lactic acid) (PLA) and modified/unmodified CP particles containing different size fractions were obtained using a mini-extruder. To confirm the results of the grafting process, the FTIR spectra of filler particles were obtained. Performing 1HNMR spectroscopy allowed us to determine the chemical structure of synthesized OLAs. The thermal degradation of modified CP and biocomposites were studied using TGA, and the thermal characteristics of biocomposites were investigated using DSC. In order to analyse the adhesion between filler particles and PLA in biocomposites, SEM images of brittle fracture surfaces were registered. The mechanical properties of biocomposites were studied using a tensile testing machine. FTIR and 1HNMR analysis confirmed the successful grafting process of OLAs. The modified filler particles exhibited a better connection with hydrophobic PLA matrix alongside improved mechanical properties than the biocomposites with unmodified filler particles. Moreover, a DSC analysis of the biocomposites with modified CP showed a reduction in glass temperature on average by 9 °C compared to neat PLA. It confirms the plasticizing effect of grafted and ungrafted OLAs. The results are promising, and can contribute to increasing the use of agri-food lignocellulosic residue in manufacturing biodegradable packaging.

Mechanical Reinforcement of Polyamide 6 by Cold Hydrostatic Extrusion.

This paper presents the effect of severe plastic deformation obtained using the cold hydrostatic extrusion (HE) method on the mechanical and structural properties of polyamide 6 (PA6). As a result of the plastic strain, a significant increase in ultimate tensile strength and tensile modulus were observed. Tensile strength rose by almost 500%, up to the level of 508 MPa, whereas the tensile modulus rose by about 65%. Flexural modulus increase was also observed to 3230 MPa, i.e., by approx. 160%. As a result of high plastic deformation, the structure of the polyamide 6 changed significantly, as evidenced by its fibrous nature as presented in the results of the scanning electron microscopy inspection (SEM). The surface quality of products investigated was tested using profilometry.

Composites of Poly(vinyl chloride) with Residual Hops after Supercritical Extraction in CO2.

The common applications of poly(vinyl chloride) (PVC) in many industries mean that the topic of recycling and disposal of post-consumer waste is still very important. One of the methods of reducing the negative impact of PVC waste on the natural environment is to use technological or post-consumer waste of this polymer to produce new composite materials with favorable utility properties, with the addition of natural fillers, among which agro-waste, including hop residue, is deserving of special attention. In this study, the effect of the addition of residual hops (H) on the mechanical and physicochemical properties of poly(vinyl chloride) was investigated. PVC blends containing 10, 20 and 30 wt % of hop residue were mixed in an extruder, while the specimens were obtained by the injection molding method. It was observed that the addition of H increased their thermostability, as shown by a Congo red test. Furthermore, thermogravimetric analysis showed that the degradation rate of PVC/H composites in the first and second stages of decomposition was lower in comparison with unmodified PVC. In turn, composite density, impact strength and tensile strength decreased significantly with an increasing concentration of filler in the PVC matrix. At the same time, their Young's modulus, flexural modulus and Rockwell hardness increased. Flame resistance tests showed that with an increasing residual hop content, the limiting oxygen index (LOI) decreased by 9.0; 11.8 and 13.6%, respectively, compared to unfilled PVC (LOI = 37.4%). In addition, the maximum heat release rate (pHRR) decreased with an increasing filler content by about 16, 24 and 31%, respectively. Overall, these composites were characterized by a good burning resistance and had a flammability rating of V0 according to the UL94 test.

Polyurethane Composite Foams Synthesized Using Bio-Polyols and Cellulose Filler.

Rigid polyurethane foams were obtained using two types of renewable raw materials: bio-polyols and a cellulose filler (ARBOCEL® P 4000 X, JRS Rettenmaier, Rosenberg, Germany). A polyurethane system containing 40 wt.% of rapeseed oil-based polyols was modified with the cellulose filler in amounts of 1, 2, and 3 php (per hundred polyols). The cellulose was incorporated into the polyol premix as filler dispersion in a petrochemical polyol made using calenders. The cellulose filler was examined in terms of the degree of crystallinity using the powder X-ray diffraction PXRD -and the presence of bonds by means of the fourier transform infrared spectroscopy FT-IR. It was found that the addition of the cellulose filler increased the number of cells in the foams in both cross-sections-parallel and perpendicular to the direction of the foam growth-while reducing the sizes of those cells. Additionally, the foams had closed cell contents of more than 90% and initial thermal conductivity coefficients of 24.8 mW/m∙K. The insulation materials were dimensionally stable, especially at temperatures close to 0 °C, which qualifies them for use as insulation at low temperatures.

Poly(vinyl chloride) Composites with Raspberry Pomace Filler.

This study examined, the effect of chemically extracted raspberry pomace on the thermal stability, mechanical properties, flammability, chemical structure and processing of poly(vinyl chloride). It was observed that the pomace in this study was used to extract naphtha, thereby permitting the removal of bio-oil as a factor preventing the obtaining of homogeneous composites. Furthermore, adding 20% raspberry pomace filler after extraction extended the thermal stability time for the composites by about 30%. It was observed that composite density, impact strength, and tensile strength values decreased significantly with increasing concentrations of filler in the PVC matrix. At the same time, their modulus of elasticity and Shore hardness increased. All tested composites were characterized by a good burning resistance with a flammability rating of V0 according to the UL94 test. Adding 20 to 40% of a natural filler to the PVC matrix made it possible to obtain composites for the production of flame resistant elements that emitted less hydrogen chloride under fire conditions while ensuring good rigidity.

Viscoelastic Polyurethane Foams for Use in Seals of Respiratory Protective Devices.

A key factor in effective protection against airborne hazards, i.e., biological and nonbiological aerosols, vapors, and gases, is a good face fit of respiratory protective devices (RPDs). Equally important is the comfort of use, which may encourage or discourage users from donning RPDs. The objective of the work was to develop viscoelastic polyurethane foams for use in RPD seals. The obtained foams were characterized using scanning electron microscopy, infrared spectroscopy, thermogravimetry, and differential scanning calorimetry. Measurements also involved gel fraction, apparent density, air permeability, elastic recovery time, compression set, rebound resilience, and sweat uptake. The results were discussed in the context of modifications to the foam formulation: the isocyanate index (INCO) in the range of 0.6-0.9 and the blowing agent content in the range of 1.2-3.0 php. FTIR analysis revealed a higher level of urea groups with increasing water content in the formulation. Higher INCO and water content levels also led to lower onset temperatures of thermal degradation and higher glass-transition temperatures of the soft phase. A decrease in apparent density and an increase in mean pore sizes of the foams with increasing INCO and water content levels was observed. Functional parameters (air permeability, elastic recovery time, compression set, rebound resilience, and sweat uptake) were also found to be satisfactory at lower INCO and water content levels.

Vegetable Fillers and Rapeseed Oil-Based Polyol as Natural Raw Materials for the Production of Rigid Polyurethane Foams.

The reported study concerns the introduction of renewable raw materials into the formulation of rigid polyurethane foams in the quest for the sustainable development of polymer composites. In this study, rigid polyurethane foam composites were prepared using 75 wt.% of rapeseed oil-based polyol and 15 parts per hundred parts of polyol (php) of natural fillers such as chokeberry pomace, raspberry seeds, as well as hazelnut and walnut shells. The influence of the used raw materials on the foaming process, structure, and properties of foams was investigated using a FOAMAT analyzer and a wide selection of characterization techniques. The introduction of renewable raw materials limited reactivity of the system, which reduced maximum temperature of the foaming process. Moreover, foams prepared using renewable raw materials were characterized by a more regular cell structure, a higher share of closed cells, lower apparent density, lower compressive strength and glass transition temperature, low friability (<2%), low water absorption (<1%), high dimensional stability (<±0.5%) and increased thermal stability. The proper selection and preparation of the renewable raw materials and the rational development of the polyurethane recipe composition allow for the preparation of environmentally-friendly foam products with beneficial application properties considering the demands of the circular economy in the synthesis of rigid foams.

Effects of Various Types of Expandable Graphite and Blackcurrant Pomace on the Properties of Viscoelastic Polyurethane Foams.

We investigated the effect of the type and amount of expandable graphite (EG) and blackcurrant pomace (BCP) on the flammability, thermal stability, mechanical properties, physical, and chemical structure of viscoelastic polyurethane foams (VEF). For this purpose, the polyurethane foams containing EG, BCP, and EG with BCP were obtained. The content of EG varied in the range of 3-15 per hundred polyols (php), while the BCP content was 30 php. Based on the obtained results, it was found that the additional introduction of BCPs into EG-containing composites allows for an additive effect in improving the functional properties of viscoelastic polyurethane foams. As a result, the composite containing 30 php of BCP and 15 php of EG with the largest particle size and expanded volume shows the largest change in the studied parameters (hardness (H) = 2.65 kPa (+16.2%), limiting oxygen index (LOI) = 26% (+44.4%), and peak heat release rate (pHRR) = 15.5 kW/m2 (-87.4%)). In addition, this composite was characterized by the highest char yield (m600 = 17.9% (+44.1%)). In turn, the change in mechanical properties is related to a change in the physical and chemical structure of the foams as indicated by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) analysis.

Effect of the Addition of Biobased Polyols on the Thermal Stability and Flame Retardancy of Polyurethane and Poly(urea)urethane Elastomers.

Due to the current trends in sustainable development and the reduction in the use of fossil fuels (Green Deal strategy and the circular economy), and thus, the increased interest of the polyurethane industry in polyols derived from renewable sources, it is important to study the impact of these polyols on the flammability of new bioelastomers. The goal of this study was to check the influence of biobased polyols, such as tall oil (TO)-based polyols, soybean oil (SO)-based polyol, and rapeseed oil (RO)-based polyol, on the reduction in the burning and fume emissions of polyurethane and poly(urea)urethane elastomers (EPURs and EPUURs). The thermal stability of these materials was tested using thermogravimetric analysis (TGA). In turn, the flame retardancy and smoke emissions were checked using a cone calorimetry test. The released gases were identified using TGA coupled with Fourier transform infrared (FT-IR) spectroscopy (TGA/FT-IR). Moreover, the morphological and structural characteristics of the char residues were characterized using FT-IR and scanning electron microscopy (SEM) with energy-dispersive spectroscopy (EDS). The obtained data were compared to the results received for elastomers produced with petroleum substrates. The addition of biobased polyols led to a reduction in the burning as a result of the formation of char, especially RO polyol. Moreover, the TO and RO polyols increased the thermal stability of the elastomers.

Viscoelastic Polyurethane Foam with Keratin and Flame-Retardant Additives.

Viscoelastic polyurethane (VEPUR) foams with increased thermal resistance are presented in this article. VEPUR foams were manufactured with the use of various types of flame retardant additives and keratin fibers. The structure of the modified foams was determined by spectrophotometric-(FTIR), thermal-(DSC), and thermogravimetric (TGA) analyses as well as by scanning electron microscopy (SEM). We also assessed the fire resistance, hardness, and comfort coefficient (SAG factor). It was found that the use of keratin filler and flame retardant additives changed the foams' structure and properties as well as their burning behavior. The highest fire resistance was achieved for foams containing keratin and expanding graphite, for which the reduction in heat release rate (HRR) compared to VEPUR foams reached 75%.

Composites of Open-Cell Viscoelastic Foams with Blackcurrant Pomace.

Taking into account the circular economy guidelines and results of life cycle analyses of various materials, it was proposed to use a blackcurrant pomace filler in the production process of viscoelastic polyurethane (PUR) foams intended for application as mattresses, pillows, or elements for orthopedics. Open-cell viscoelastic PUR foams containing 10-60 per hundred polyols (php) blackcurrant pomace were prepared. It was found that after introducing the filler to the PUR foam formulation, the speed of the first stage of the foaming process significantly decreases, the maximum temperature achieved during the synthesis drops (by 30 °C for the foam containing 40 php of filler compared to unfilled foam), and the maximum pressure achieved during the synthesis of foam containing 20 php is reduced by approximately 57% compared to the foam without filler. The growth time of the foams increases with increasing the amount of introduced filler; for the foam containing 60 php, the time is extended even by about 24%. The effect of the filler on the physical, morphological, mechanical, and functional performances of PUR foam composites has been analyzed. The use of 60 php as the filler reduced the hardness of the foams by approximately 30% and increased their comfort factor from 3 to 5.

Viscoelastic Polyurethane Foams for Use as Auxiliary Materials in Orthopedics.

One of the essential factors in prostheses is their fitting. To assemble a prosthesis with the residual limb, so-called liners are used. Liners used currently are criticized by users for their lack of comfort, causing excessive sweating and skin irritation. The objective of the work was to develop viscoelastic polyurethane foams for use in limb prostheses. As part of the work, foams were produced with different isocyanate indexes (0.6-0.9) and water content (1, 2 and 3 php). The produced foams were characterized by scanning electron microscopy, computer microtomography, infrared spectroscopy, thermogravimetry and differential scanning calorimetry. Measurements also included apparent density, recovery time, rebound elasticity, permanent deformation, compressive stress value and sweat absorption. The results were discussed in the context of modifying the foam recipe. The performance properties of the foams, such as recovery time, hardness, resilience and sweat absorption, indicate that foams that will be suitable for prosthetic applications are foams with a water content of 2 php produced with an isocyanate index of 0.8 and 0.9.

Viscoelastic Polyurethane Foams with Reduced Flammability and Cytotoxicity.

Consistent and proper use of respiratory protective devices (RPD) is one of the essential actions that can be taken to reduce the risk of exposure to airborne hazards, i.e., biological and nonbiological aerosols, vapours, and gases. Proper fit of the facepiece and comfort properties of RPDs play a crucial role in effective protection and acceptance of RPDs by workers. The objective of the present paper was to develop viscoelastic polyurethane foams for use in RPD seals characterised by proper elasticity, allowing for the enhancement of the device fit to the face and the capability of removing moisture from the skin in order to improve the comfort of RPD use. Moreover, it was pivotal to ensure the non-flammability of the foams, as well as a simultaneous reduction in their cytotoxicity. The obtained foams were characterised using scanning electron microscopy, infrared spectroscopy, thermogravimetry, and differential scanning calorimetry. Measurements also involved gel fraction, apparent density, compression set, rebound resilience, wettability, flammability, and cytotoxicity. The results are discussed in the context of the impact of modifications to the foam formulation (i.e., flame-retardant type and content) on the desired foam properties. The test results set directions for future works aimed to develop viscoelastic polyurethane foams that could be applied in the design of respiratory protective devices.

Composites of Semi-Rigid Polyurethane Foams with Keratin Fibers Derived from Poultry Feathers and Flame Retardant Additives.

Semi-rigid composites of polyurethane foams (SRPUF) modified with the addition of keratin flour from poultry feathers and flame retardant additives were manufactured. Ten percent by mass of keratin fibers was added to the foams as well as halogen-free flame retardant additives such as Fyrol PNX, expandable graphite, metal oxides, in amounts such that their total mass did not exceed 15%. Thermal and mechanical properties were tested. Water absorption, dimensional stability, apparent density and flammability of produced foams were determined. It was found that the use of keratin fibers and flame retardant additives changes the foam synthesis process, changes their structure and properties as well as their combustion process. The addition of the filler made of keratin fibers significantly limits the amount of smoke generated during foam burning. The most favorable reduction of heat and smoke release rate was observed for foams with the addition of 10% keratin fibers and 10% expandable graphite. Systems of reducing combustibility of polyurethane foams using keratin fillers are a new solution on a global scale.