An Approach to Testing Antivandal Composite Materials as a Function of Their Thickness and Striker Shape-A Case Study.

Our research material comprised antivandal fire-retardant hybrid composites modified with inorganic and organic fillers intended for application in public transport vehicles. This paper presents an approach to studying their impact strength as a function of the composite thickness (3 to 6 mm) and striker shape (hemispherical, semicylindrical, wedge-shaped) used in the experimental stand. Group A composites, made of single fabric layers (n = 5), were thinner and their impact strength was lower by 73% than that for Group B composites made of double fabric layers. Study results show an almost threefold improvement in impact strength for a thickness increase of as little as 0.3 mm. Statistical analysis (the Shapiro-Wilk test, p > 0.05) did not show any significant differences in the quantitative evaluation of changes (n = 3) on the surface of the examined materials caused by impacts with strikers of different shapes. In turn, a linear correlation (Shapiro-Wilk test, W = 0.0857, p = 0.022) was found between impact strength and the thickness of the studied materials. It was observed that appropriate arrangement of fabrics and powder fillers can lead to a different distribution of forces and energy absorbed by the tested material. A lower impact strength was observed for the composite which had powder fillers in its composition, which caused the formation of microvoids in the structure of the material and thus led to a weakening in their strength properties. An effect of the placement of the glass fabric layer in the composite on the results was also observed. Moreover, SEM evaluation of the composites revealed their layered structure and the impregnation of woven fabrics with resin.

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.

Characterization of Thermoplastic Starch Plasticized with Ternary Urea-Polyols Deep Eutectic Solvent with Two Selected Fillers: Microcrystalline Cellulose and Montmorillonite.

The aim of the study was to prepare and characterize composite materials based on thermoplastic starch (TPS)/deep eutectic solvent (DES). Potato starch was plasticized with ternary DES: urea:glycerol:sorbitol and modified with the selected fillers: microcrystalline cellulose and sodium montmorillonite. Films were prepared via twin-screw extrusion and thermocompression of the extrudates. Then, the physicochemical properties of the TPS films were examined. The ternary DES effectively plasticized the polysaccharide leading to a highly amorphous structure of the TPS (confirmed via mechanical tests, DMTA and XRD analyses). An investigation of the behavior in water (swelling and dissolution degree) and water vapor transmission rate of the films was determined. The introduction of the two types of fillers resulted in higher tensile strength and better barrier properties of the composite TPS films. However, montmorillonite addition exhibited a higher impact than microcrystalline cellulose. Moreover, a cone calorimetry analysis of the TPS materials revealed that they showed better fire-retardant properties than TPS plasticized with a conventional plasticizer (glycerol).

Comprehensive Analysis of the Influence of Expanded Vermiculite on the Foaming Process and Selected Properties of Composite Rigid Polyurethane Foams.

This article presents the results of research on obtaining new polyurethane (PUR) foams modified with thermally expanded vermiculite. The filler was added in amount of 3 wt.% up to 15 wt.%. The additionally applied procedure of immersion the non-organic filler in H2O2 was performed to increase the exfoliation effect of thermally treated mineral and additional oxidation the surfaces. The effect of fillers on foaming process, cell structure, thermal insulation, apparent density, compressive strength, thermal properties, and flammability are assessed. The foaming process of PUR foams modified with vermiculite was comparable for all systems, regardless of the content of the filler. A slight increase in reactivity was observed, confirmed by a faster decrease in dielectric polarization for the system with modified vermiculite by H2O2. The modification of the reference system with the vermiculite increased the content of closed cells from 76% to 91% for the foams with the highest vermiculite content. Coefficient of thermal conductivity of reference foam and foams modified with vermiculite was in the range 24-26 mW/mK. The use of vermiculite up to 15 wt.% did not influence significantly on mechanical properties and flammability, which from an economic point of view is important because it is possible to reduce the cost of materials by introducing a cheap filler without deteriorating their properties.

Thermomechanical and Fire Properties of Polyethylene-Composite-Filled Ammonium Polyphosphate and Inorganic Fillers: An Evaluation of Their Modification Efficiency.

The development of new polymer compositions characterized by a reduced environmental impact while lowering the price for applications in large-scale production requires the search for solutions based on the reduction in the polymer content in composites' structure, as well as the use of fillers from sustainable sources. The study aimed to comprehensively evaluate introducing low-cost inorganic fillers, such as copper slag (CS), basalt powder (BP), and expanded vermiculite (VM), into the flame-retarded ammonium polyphosphate polyethylene composition (PE/APP). The addition of fillers (5-20 wt%) increased the stiffness and hardness of PE/APP, both at room and at elevated temperatures, which may increase the applicability range of the flame retardant polyethylene. The deterioration of composites' tensile strength and impact strength induced by the presence of inorganic fillers compared to the unmodified polymer is described in detail. The addition of BP, CS, and VM with the simultaneous participation of APP with a total share of 40 wt% caused only a 3.1, 4.6, and 3 MPa decrease in the tensile strength compared to the reference value of 23 MPa found for PE. In turn, the cone calorimeter measurements allowed for the observation of a synergistic effect between APP and VM, reducing the peak heat rate release (pHRR) by 60% compared to unmodified PE. Incorporating fillers with a similar thermal stability but differing particle size distribution and shape led to additional information on their effectiveness in changing the properties of polyethylene. Critical examinations of changes in the mechanical and thermomechanical properties related to the structure analysis enabled the definition of the potential application perspectives analyzed in terms of burning behavior in a cone calorimetry test. Adding inorganic fillers derived from waste significantly reduces the flammability of composites with a matrix of thermoplastic polymers while increasing their sustainability and lowering their price without considerably reducing their mechanical properties, which allows for assigning developed materials as a replacement for flame-retarded polyethylene in large-scale non-loaded parts.

Correction: Salasinska et al. Burning Behaviour of Rigid Polyurethane Foams with Histidine and Modified Graphene Oxide. Materials 2021, 14, 1184.

In the original article [...].

The Effect of Manufacture Process on Mechanical Properties and Burning Behavior of Epoxy-Based Hybrid Composites.

The production of hybrid layered composites allows comprehensive modification of their properties and adaptation to the final expectations. Different methods, such as hand lay-up, vacuum bagging, and resin infusion were applied to manufacture the hybrid composites. In turn, fabrics used for manufacturing composites were made of glass (G), aramid (A), carbon (C), basalt (B), and flax (F) fibers. Flexural, puncture impact behavior, and cone calorimetry tests were applied to establish the effect of the manufacturing method and the fabrics layout on the mechanical and fire behavior of epoxy-based laminates. The lowest flammability and smoke emission were noted for composites made by vacuum bagging (approximately 40% lower values of total smoke release compared with composites made by the hand lay-up method). It was demonstrated that multi-layer hybrid composites made by vacuum bagging might enhance the fire safety levels and simultaneously maintain high mechanical properties designed for, e.g., the railway and automotive industries.

Plasticized Poly(vinyl chloride) Modified with Developed Fire Retardant System Based on Nanoclay and L-histidinium Dihydrogen Phosphate-Phosphoric Acid.

The current work assessed the burning behavior of plasticized poly(vinyl chloride) (PVC-P) modified with a two-component composition, consisting of L-histidinium dihydrogen phosphate-phosphoric acid (LHP) and nanoclay (n). The thermal and thermodynamical properties of the PVC-P containing from 10 to 30 wt% of the fire retardant system (FRS) were determined by thermogravimetric analysis (TG) as well as by dynamic mechanical thermal analysis (DMTA). In contrast, fire behavior and smoke emission were studied with a cone calorimeter (CC) and smoke density chamber. The research was complemented by a microstructure analysis, using a scanning electron microscope, of the materials before and after burning CC tests. The effects were compared to those achieved for PVC-P, PVC-P with a commercially available fire retardant, the substrate used for the produced LHP, and the mixture of LHP and zinc borate, both of which contained the same share of nanoclay. Based on a notable improvement, especially in smoke suppression suggests that the n/LHP system may be a candidate fire retardant for decreasing the flammability of PVC-P.

Burning Behaviour of Rigid Polyurethane Foams with Histidine and Modified Graphene Oxide.

Since rigid polyurethane (PU) foams are one of the most effective thermal insulation materials with widespread application, it is an urgent requirement to improve its fire retardancy and reduce the smoke emission. The current work assessed the fire behavior of PU foam with non-halogen fire retardants system, containing histidine (H) and modified graphene oxide (GOA). For investigated system, three loadings (10, 20, and 30 wt.%) were used. The Fourier transform infrared spectroscopy (FT-IR), differential scanning calorimetry (DSC), thermogravimetric analysis, cone calorimetry (CC) and smoke density chamber tests as well as pre- and post-burning morphological evaluation using scanning electron microscope (SEM) were performed. Moreover, TGA combined with FT-IR was conducted to determine the substances, which could be evolved during the thermal decomposition of the PU with fire retardant system. The results indicated a reduction in heat release rate (HRR), maximum average rate of heat emission (MAHRE), the total heat release (THR) as well as the total smoke release (TSR), and maximum specific optical density (Dsmax) compared to the polyurethane with commercial fire retardant, namely ammonium polyphosphate (APP). A significantly improvement, especially in smoke suppression, suggested that HGOA system may be a candidate as a fire retardant to reduce the flammability of PU foams.

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.

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%.

Moisture Resistance, Thermal Stability and Fire Behavior of Unsaturated Polyester Resin Modified with L-histidinium Dihydrogen Phosphate-Phosphoric Acid.

In this paper, the fire behavior of unsaturated polyester resin (UP) modified with L-histidinium dihydrogen phosphate-phosphoric acid (LHP), being a novel intumescent fire retardant (IFR), was investigated. Thermal and thermomechanical properties of the UP with different amounts of LHP (from 10 to 30 wt. %) were determined by thermogravimetric analysis (TG) as well as dynamic mechanical thermal analysis (DMTA). Reaction to small flames was studied by horizontal burning (HB) test, while fire behavior and smoke emission were investigated with the cone calorimeter (CC) and smoke density chamber. Further, the analysis of volatile products was conducted (TGA/FT-IR). It was observed that the addition of LHP resulted in the formation of carbonaceous char inhibiting the thermal decomposition, burning rate and smoke emission. The most promising results were obtained for the UP containing 30 wt. % of LHP, for which the highest reduction in maximum values of heat release rate (200 kW/m2) and total smoke release (3535 m2/m2) compared to unmodified polymer (792 kW/m2 and 6895 m2/m2) were recorded. However, some important disadvantage with respect to water resistance was observed.

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.

Development and Characterization of "Green Open-Cell Polyurethane Foams" with Reduced Flammability.

This work presents the cell structure and selected properties of polyurethane (PUR) foams, based on two types of hydroxylated used cooking oil and additionally modified with three different flame retardants. Bio-polyols from municipal waste oil with different chemical structures were obtained by transesterification with triethanolamine (UCO_TEA) and diethylene glycol (UCO_DEG). Next, these bio-polyols were used to prepare open-cell polyurethane foams of very low apparent densities for thermal insulation applications. In order to obtain foams with reduced flammability, the PUR systems were modified with different amounts (10-30 parts per hundred polyol by weight-php) of flame retardants: TCPP (tris(1-chloro-2-propyl)phosphate), TEP (triethyl phosphate), and DMPP (dimethyl propylphosphonate). The flame retardants caused a decrease of the PUR formulations reactivity. The apparent densities of all the foams were comparable in the range 12-15 kg/m3. The lowest coefficients of thermal conductivity were measured for the open-cell PUR foams modified with DMPP. The lowest values of heat release rate were found for the foams based on the UCO_TEA and UCO_DEG bio-polyols that were modified with 30 php of DMPP.

Phosphorus-Containing Silsesquioxane Derivatives as Additive or Reactive Components of Epoxy Resins.

Two phosphorus-containing cage-like silsesquioxane derivatives were synthesized as reactive or additive flame retardants for epoxy resin. The silsesquioxanes were obtained via an epoxide ring-opening reaction using a 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPA). In one derivative containing in its structure 4 glycidoxypropyl and 4 phosphate groups, denoted as 4P4GS, only half of the epoxy rings was reacted with phosphate to obtain a reactive additive, while in the second derivative containing 8 phosphate groups, denoted as 8PS, all epoxy groups were converted, thus an additive modifier was obtained. The silsesquioxanes containing phosphorus atoms and the reactive phosphorus-free silsesquioxane derivative (octakis[(3-glycidoxypropyl)dimethylsiloxy]octasilsesquioxane (8GS)) were used to prepare hybrid materials based on epoxy resin. To compare the impact of the structure of silsesquioxane derivatives on the properties of hybrid materials, a number of samples containing 1, 5, and 10% of the modifiers making a series of epoxy materials containing additive or reactive modifiers, were obtained. The modified epoxies were studied using scanning electron microscopy and energy-dispersive X-ray spectroscopy (SEM-EDS), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), nanoindentation, water contact angle, and cone calorimetry tests to assess the effects of the modifier structure on the physicochemical properties of the investigated materials.

The Effect of Poly(Vinyl Chloride) Powder Addition on the Thermomechanical Properties of Epoxy Composites Reinforced with Basalt Fiber.

The aim of the article was to determine the effect of the poly(vinyl chloride) additive (PVC) on the thermomechanical and fire properties of epoxy composites reinforced with basalt fabric. Ten-layered composites with 2.5, 5 and 10 wt.% of PVC powder were fabricated using hand lay-up. The following features were evaluated for composites: structure (by scanning electron microscopy, SEM), thermomechanical properties (by dynamical thermomechanical analysis, DMTA), mechanical properties (in bending, tensile and interlaminar shear strength tests), hardness (using the Barcol method), thermal stability (by thermogravimetry, TGA) and fire behavior (using a cone calorimeter). It was found that the introduction of micron PVC powder into the epoxy matrix improved the thermomechanical properties of composites, such as storage module, and mechanical properties, such as flexural strength and modulus, as well as hardness.

Thermal Stability, Fire and Smoke Behaviour of Epoxy Composites Modified with Plant Waste Fillers.

The influence of plant fillers on the flammability and smoke emission of natural composites was investigated. Epoxy composites with 15, 25, and 35 wt % of walnut and hazelnut shell, as well as sunflower husk, were prepared and examined. The ground organic components were characterized by grain size distribution, thermogravimetric analysis (TGA) and microstructure observations (SEM). The composite materials were subjected to dynamic mechanical analysis (DMA) and structural evaluation with scanning electron microscopy. Cone calorimeter tests and TGA determined the influence of plant waste filler addition on thermal stability and flammability. Moreover, the semi-volatile and volatile compounds that evolved during the thermal decomposition of selected samples were identified using a steady state tube furnace and a gas chromatograph with a mass spectrometer. The intensity of the degradation reduced as a function of increasing filler content, while the yield of residue corresponded to the amount of lignin that is contained in the tested plants. Moreover, the incorporation of agricultural waste materials resulted in the formation of a char layer, which inhibits the burning process. The yield of char depended on the amount and type of the filler. The composites containing ground hazelnut shell formed swollen char that was shaped in multicellular layers, similar to intumescent fire retardants.