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The augmented demand for sustainable nanocomposites has paved the way to explore naturally derived materials. Nanocellulose, with its bountiful sources and inherent properties, ranks top in the list of biofillers with a perspective of reducing the carbon footprint. A systematic study is required to understand the reinforcing effect of various types of nanocellulose. In the present work, we selected three types of nanocellulose, i.e., cellulose nanocrystal (CNC), cellulose nanofiber (CNF) and microfibrillated cellulose (MFC), to investigate the effect of geometrical structure on the properties of unvulcanized natural rubber (NR). Incorporating these fillers improved the tensile strength and modulus of natural rubber films significantly through reinforcement via filler network structure. The reinforcing effect of CNF was found to be higher compared to CNC and MFC, where an increase of 3.85 MPa in tensile strength from the neat sample was obtained. More uniform dispersion was evident through transmission electron microscopy, atomic force microscopy and Raman imaging for CNF in the rubber matrix. The structural properties were determined using Raman spectra and X-ray diffraction. The rheological studies revealed a good interaction between filler and NR. The work presented comprehensively compares different types of nanocellulose as reinforcing filler in NR matrix, which will help the researchers select an ideal type for their specific application and, thus, the proper usage of renewable resources, leading to sustainability and a circular economy.

An environmentally friendly approach was studied for improving the fire retardancy of beech wood using a steam explosion process coupled with a phosphorylation reaction. Raw beech, steam-exploded, or bleached wood was subjected to phosphorylation employing etidronic acid (HEDP) and urea, and the resulting chemical composition and thermal behavior were analyzed using techniques such as elemental analysis, Fourier transform infrared spectroscopy, ionic chromatography, and pyrolysis combustion flow calorimetry. The thermal performance of beech wood underwent significant enhancements after the steam explosion treatment combined with soda impregnation. It resulted in a striking reduction in heat release rates (HRR), especially its peak (pHRR) and time-to-pHRR (TpHRR) values (from 139.5 W/g and 365 °C to 40 W/g and 247 °C) and an increase in residue from 10.5% to 41.3%. The results demonstrate that the process created a self-extinguishing and non-flammable material that exhibited noteworthy flame retardancy improvement.

Abstract The surge towards a sustainable future in the construction industry requires the use of bio‐based insulation materials as an alternative to conventional ones for improving energy efficiency in structures. In this article, the features of bio‐based insulation materials, including their thermal conductivities, moisture buffering value, fire performance, and life cycle evaluations are examined. It is clear from the review that pre‐ and post‐treatment of the bio‐based materials used for insulation materials optimize their properties. The life cycle analysis reveals a significant reduction in global warming potential (GWP) compared to conventional foams. In addition, it is envisaged that producing bio‐based insulation materials on a larger scale will further decrease the net GWP. The article, therefore, proposes the implementation of policies that will promote the commercialization of bio‐based insulation materials.

In 2019, we introduced Flame Retardancy Index (FRI) as a universal dimensionless index for the classification of flame-retardant polymer materials (Polymers, 2019, 11(3), 407). FRI simply takes the peak of Heat Release Rate (pHRR), Total Heat Release (THR), and Time-To-Ignition (ti) from cone calorimetry data and quantifies the flame retardancy performance of polymer composites with respect to the blank polymer (the reference sample) on a logarithmic scale, as of Poor (FRI ˂ 100), Good (100 ≤ FRI ˂ 101), or Excellent (FRI ≥ 101). Although initially applied to categorize thermoplastic composites, the versatility of FRI was later verified upon analyzing several sets of data collected from investigations/reports on thermoset composites. Over four years from the time FRI was introduced, we have adequate proof of FRI reliability for polymer materials ranking in terms of flame retardancy performance. Since the mission of FRI was to roughly classify flame-retardant polymer materials, its simplicity of usage and fast performance quantification were highly valued. Herein, we answered the question “does inclusion of additional cone calorimetry parameters, e.g., the time to pHRR (tp), affect the predictability of FRI?”. In this regard, we defined new variants to evaluate classification capability and variation interval of FRI. We also defined the Flammability Index (FI) based on Pyrolysis Combustion Flow Calorimetry (PCFC) data to invite specialists for analysis of the relationship between the FRI and FI, which may deepen our understanding of the flame retardancy mechanisms of the condensed and gas phases.

The increased use of plastics, particularly in terms of the use of polymers in electronics and electrical devices commonly used in homes, offices, schools, restaurants, and vehicles, has caused increased fire risks [...]

Ammonium polyphosphate (APP) was grafted onto the surface of exfoliated graphite nanoplatelet (GNP) to obtain a novel flame retardant, GNP-g-APP, and thereafter was incorporated into the ethylene vinyl acetate (EVA) to improve its flame retardancy. The chemical structures of the precursors and the target product were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and energy dispersive X-ray spectroscopy (EDS) techniques. FTIR spectra appeared at 1056 and 1103 cm−1 were attributed to POC asymmetric stretching bond, that conformed formation of GNP-g-APP. Thermal stability behaviour and flame retardancy performance of the samples were evaluated by TGA, UL-94, micro-calorimetry, and cone calorimetry. TGA measurements revealed the superiority of GNP-g-APP over GNP. The micro-calorimetry analyses indicated a sharp fall in both the total heat release (THR) and the peak of heat release rate (pHRR) of EVA containing 30 wt.% GNP-g-APP, evidenced by a thick char layer formed as barrier. Cone calorimetry confirmed flame-retardant effect of GNP-g-APP featured by a reduction in pHRR (−63 %) and THR (−31.6 %) due to the formation of a cohesive char layer. Although GNP addition sharply decreased the elongation at break of 70/30 (w/w) composites from 500% for neat EVA to 71%, a very promising value of 364% for EVA/GNP-g-APP sample preserved superior flexibility.

There have been several attempts to design innovative biomaterials as surface coatings to enhance the biological performance of biomedical implants. The objective of this study was to design multifunctional Cu/a-C:H thin coating depositing on the Ti-6Al-4V alloy (TC4) via magnetron sputtering in the presence of Ar and CH4 for applications in bone implants. Moreover, the impact of Cu amount and sp2/sp3 ratio on the interior stress, corrosion behavior, mechanical properties, and tribological performance and biocompatibility of the resulting biomaterial was discussed. X-ray photoelectron spectroscopy (XPS) revealed that the sp2/sp3 portion of the coating was enhanced for samples having higher Cu contents. The intensity of the interior stress of the Cu/a-C:H thin bio-films decreased by increase of Cu content as well as the sp2/sp3 ratio. By contrast, the values of Young's modulus, the H3/E2 ratio, and hardness exhibited no significant difference with enhancing Cu content and sp2/sp3 ratio. However, there was an optimum Cu content (36.8 wt.%) and sp2/sp3 ratio (4.7) that it is feasible to get Cu/a-C:H coating with higher hardness and tribological properties. Electrochemical impedance spectroscopy test results depicted significant improvement of Ti-6Al-4V alloy corrosion resistance by deposition of Cu/a-C:H thin coating at an optimum Ar/CH4 ratio. Furthermore, Cu/a-C:H thin coating with higher Cu contents showed better antibacterial properties and higher angiogenesis and osteogenesis activities. The coated samples inhibited the growth of bacteria as compared to the uncoated sample (p < 0.05). In addition, such coating composition can stimulate angiogenesis, osteogenesis and control host response, thereby increasing the success rate of implants. Moreover, Cu/a-C:H thin films encouraged development of blood vessels on the surface of titanium alloy when the density of grown blood vessels was increased with enhancing the Cu amount of the films. It is speculated that such coating can be a promising candidate for enhancing the osseointegration features.

Poly(3-hydroxybutyrate), PHB, has gathered a lot of attention for its promising properties—in particular its biobased nature and high biodegradability. Although PHB is prime candidate for the packaging industry, the applications are still limited by a narrow processing window and thermal degradation during melt processing. In this work, three novel additives based on ferulic acid esterified with butanediol, pentanediol, and glycerol (BDF, PDF, and GTF, respectively) were used as plasticizers and antioxidative additives to improve mechanical properties of PHB. Elongation at break up to 270% was obtained in presence of BDF and the processing window was improved nearly 10-fold. The Pawley method was used to identify the monoclinic space group P2 of the BDF. The estimated crystallite size (71 nm) agrees with a crystalline additive. With PHB70BDF30 blends, even higher elongations at break were obtained though dwindled with time. However, these properties could be recovered after thermal treatment. The high thermal stability of this additive leads to an increase in the fire retardancy property of the material, and the phenolic structure induced antioxidant properties to the samples as demonstrated by radical scavenging tests, further highlighting the possibilities of the PHB/additive blends for packaging applications.

In this work, GTR/thermoplastics blends (in ratio 50/50 and 75/25 wt.%) were prepared by melt-compounding in an internal mixer. During research, trans-polyoctenamer rubber (TOR), ethylene-vinyl acetate copolymer (EVA), ethylene-octene copolymer (EOC), and linear low-density polyethylene (LLDPE), were used in their thermoplastic phase. Microstructure and processing-performance property interrelationships of the studied materials were investigated by: atomic force microscopy (AFM), scanning electron microscopy (SEM), rubber process analyzer (RPA), Mooney viscometer, plastometer, gas chromatography with mass spectrometry, differential scanning calorimetry (DSC), tensile tests and swelling behavior. In blends of thermoplastics with a high content of GTR (50 and 75 wt.%), the thermoplastic modifier type had a significant impact on the processing behavior and microstructure of blends. In terms of the physico-mechanical properties, the GTR/thermoplastics ratio affected elongation at break, hardness, and density, while its effect on tensile strength was negligible. DSC analysis showed that thermoplastics, as modifiers of GTR, should be considered as binders and not plasticizers, as reflected in the almost constant glass-transition temperature of the blends. RPA measurements indicated higher values of G* and η* for GTR-rich blends. SEM showed a rubber-like interfacial break, while AFM confirmed interfacial contact between GTR and thermoplastics.

We synthesized pristine mica (Mica) and N-octadecyl-N’-octadecyl imidazolium iodide (IM) modified mica (Mica-IM), characterized it, and applied it at 0.1–5.0 wt.% loading to prepare epoxy nanocomposites. Dynamic differential scanning calorimetry (DSC) was carried out for the analysis of the cure potential and kinetics of epoxy/Mica and epoxy/Mica-IM curing reaction with amine curing agents at low loading of 0.1 wt.% to avoid particle aggregation. The dimensionless Cure Index (CI) was used for qualitative analysis of epoxy crosslinking in the presence of Mica and Mica-IM, while qualitative cure behavior and kinetics were studied by using isoconversional methods. The results indicated that both Mica and Mica-IM improved the curability of epoxy system from a Poor to Good state when varying the heating rate in the interval of 5–15 °C min−1. The isoconversional methods suggested a lower activation energy for epoxy nanocomposites with respect to the blank epoxy; thus, Mica and Mica-IM improved crosslinking of epoxy. The higher order of autocatalytic reaction for epoxy/Mica-IM was indicative of the role of liquid crystals in the epoxide ring opening. The glass transition temperature for nanocomposites containing Mica and Mica-IM was also lower than the neat epoxy. This means that nanoparticles participated the reaction because of being reactive, which decelerated segmental motion of the epoxy chains. The kinetics of the thermal decomposition were evaluated for the neat and mica incorporated epoxy nanocomposites epoxy with varying Mica and Mica-IM amounts in the system (0.5, 2.0 and 5.0 wt.%) and heating rates. The epoxy/Mica-IM at 2.0 wt.% of nanoparticle showed the highest thermal stability, featured by the maximum value of activation energy devoted to the assigned system. The kinetics of the network formation and network degradation were correlated to demonstrate how molecular-level transformations can be viewed semi-experimentally.

Polypropylene (PP) is a commodity plastic known for high rigidity and crystallinity, which is suitable for a wide range of applications. However, high flammability of PP has always been noticed by users as a constraint; therefore, a variety of additives has been examined to make PP flame-retardant. In this work, research papers on the flame retardancy of PP have been comprehensively reviewed, classified in terms of flame retardancy, and evaluated based on the universal dimensionless criterion of Flame Retardancy Index (FRI). The classification of additives of well-known families, i.e., phosphorus-based, nitrogen-based, mineral, carbon-based, bio-based, and hybrid flame retardants composed of two or more additives, was reflected in FRI mirror calculated from cone calorimetry data, whatever heat flux and sample thickness in a given series of samples. PP composites were categorized in terms of flame retardancy performance as Poor, Good, or Excellent cases. It also attempted to correlate other criteria like UL-94 and limiting oxygen index (LOI) with FRI values, giving a broad view of flame retardancy performance of PP composites. The collected data and the conclusions presented in this survey should help researchers working in the field to select the best additives among possibilities for making the PP sufficiently flame-retardant for advanced applications.

Crystallization kinetics of various blends of poly(lactic acid) (PLA)/polyolefin elastomer (POE) was studied through nonisothermal experimental investigations and theoretical approaches. The PLA/POE blends were prepared in a melt mixing process by using two types of POEs and compatibilizers. The rubber phases used were adopted on the basis of polyethylene (PE) and polypropylene (PP) type olefin elastomers. The effects of two kinds of compatibilizers containing ethylene vinyl acetate copolymer (EVA) and ethylene acrylic ester-glycidyl methacrylate terpolymer (EGMA) on the morphology and various parameters of crystallization of PLA were investigated using scanning electron microscopy (SEM) and differential scanning calorimeter (DSC) measurements, respectively. The morphology investigations on PLA blends containing PP based olefin elastomers showed that the introduction of EGMA compatibilizer into the matrix led to a more than 100% reduction in the size of the rubber droplets. The experimental measurements of crystallization behavior of various PLA/POE blends showed that the POEs and compatibilizers could cause a fall in the initial crystallization temperature more than 13 °C. The theoretical approaches used for studying the kinetics of crystallization of PLA in the presence of various POEs and compatibilizers indicated a decrease in the crystallinity of PLA and a 64% reduction in the activation energy compared to the neat PLA. The results suggest that the largest variation in the crystallization kinetic parameters of PLA was resulted from the PP based olefin elastomer and EGMA compatibilizer.

Epoxy coatings are developing fast in order to meet the requirements of advanced materials and systems. Progress in nanomaterial science and technology has opened a new era of engineering for tailoring the bulk and surface properties of organic coatings, e.g., adhesion to the substrate, anti-corrosion, mechanical, flame-retardant, and self-healing characteristics. Metal-organic frameworks (MOFs), a subclass of coordinative polymers with porous microstructures, have been widely synthesized in recent years and applied in gas and energy storage, separation, sensing, environmental science and technology, and medicine. Nevertheless, less attention has been paid to their performance in coatings. Well-known as micro- and nanoporous materials, with a tailorable structure consisting of metal ions and organic linkers, MOFs have a huge loading capacity, which is essential for the delivery of corrosion inhibitors. This review paper attempts to highlight the importance of epoxy/MOF composites for coating applications. A particular emphasis was explicitly placed on the anti-corrosion, flame-retardant, mechanical, and dielectric properties of epoxy/MOF coatings.

Sustainable polymers are emerging fast and have received much more attention in recent years compared to petro-sourced polymers. However, they inherently have low-quality properties, such as poor mechanical properties, and inadequate performance, such as high flammability. In general, two methods have been considered to tackle such drawbacks: (i) reinforcement of sustainable polymers with additives; and (ii) modification of chemical structure by architectural manipulation so as to modify polymers for advanced applications. Development and management of bio-based polyurethanes with flame-retardant properties have been at the core of attention in recent years. Bio-based polyurethanes are currently prepared from renewable, bio-based sources such as vegetable oils. They are used in a wide range of applications including coatings and foams. However, they are highly flammable, and their further development is dependent on their flame retardancy. The aim of the present review is to investigate recent advances in the development of flame-retardant bio-based polyurethanes. Chemical structures of bio-based flame-retardant polyurethanes have been studied and explained from the point of view of flame retardancy. Moreover, various strategies for improving the flame retardancy of bio-based polyurethanes as well as reactive and additive flame-retardant solutions are discussed.

The epoxy/clay nanocomposites have been extensively considered over years because of their low cost and excellent performance. Halloysite nanotubes (HNTs) are unique 1D natural nanofillers with a hollow tubular shape and high aspect ratio. To tackle poor dispersion of the pristine halloysite (P-HNT) in the epoxy matrix, alkali surface-treated HNT (A-HNT) and epoxy silane functionalized HNT (F-HNT) were developed and cured with epoxy resin. Nonisothermal differential scanning calorimetry (DSC) analyses were performed on epoxy nanocomposites containing 0.1 wt.% of P-HNT, A-HNT, and F-HNT. Quantitative analysis of the cure kinetics of epoxy/amine system made by isoconversional Kissinger–Akahira–Sunose (KAS) and Friedman methods made possible calculation of the activation energy (Eα) as a function of conversion (α). The activation energy gradually increased by increasing α due to the diffusion-control mechanism. However, the average value of Eα for nanocomposites was lower comparably, suggesting autocatalytic curing mechanism. Detailed assessment revealed that autocatalytic reaction degree, m increased at low heating rate from 0.107 for neat epoxy/amine system to 0.908 and 0.24 for epoxy/P-HNT and epoxy/A-HNT nanocomposites, respectively, whereas epoxy/F-HNT system had m value of 0.072 as a signature of dominance of non-catalytic reactions. At high heating rates, a similar behavior but not that significant was observed due to the accelerated gelation in the system. In fact, by the introduction of nanotubes the mobility of curing moieties decreased resulting in some deviation of experimental cure rate values from the predicted values obtained using KAS and Friedman methods.

For the first time, nano-scale aluminum hypophosphite (AlPO2) was simply obtained in a two-step milling process and applied in preparation of epoxy nanocomposites varying concentration (0.1, 0.3, and 0.5 wt.% based on resin weight). Studying the cure kinetics and thermal stability of these nanocomposites would pave the way toward the design of high-performance nanocomposites for special applications. Scanning electron microscopy (SEM) and transmittance electron microscopy (TEM) revealed AlPO2 particles having domains less than 60 nm with high potential for agglomeration. Excellent (at heating rate of 5 °C/min) and Good (at heating rates of 10, 15 and 20 °C/min) cure states were detected for nanocomposites under nonisothermal differential scanning calorimetry (DSC). While the dimensionless curing temperature interval (ΔT*) was almost equal for epoxy/AlPO2 nanocomposites, dimensionless heat release (ΔH*) changed by densification of polymeric network. Quantitative cure analysis based on isoconversional Friedman and Kissinger methods gave rise to the kinetic parameters such as activation energy and the order of reaction as well as frequency factor. Variation of glass transition temperature (Tg) was monitored to explain the molecular interaction in the system, where Tg increased from 73.2 °C for neat epoxy to just 79.5 °C for the system containing 0.1 wt.% AlPO2. Moreover, thermogravimetric analysis (TGA) showed that nanocomposites were thermally stable.

There have been several attempts to improve the cellular and molecular interactions at the tissue−implant interface. Here, the biocompatibility of titanium-based implants (e.g., Grade 2 Titanium alloy (Ti-40) and titanium−niobium alloy (Ti-Nb)) has been assessed using different cellular and molecular examinations. Cell culture experiments were performed on three substrates: Ti-40, Ti-Nb, and tissue culture polystyrene as control. Cells number and growth rate were assessed by cell counting in various days and cell morphology was monitored using microscopic observations. The evaluation of cells’ behavior on the surface of the implants paves the way for designing appropriate biomaterials for orthopedic and dental applications. It was observed that the cell growth rate on the control sample was relatively higher than that of the Ti-40 and Ti-Nb samples because of the coarse surface of the titanium-based materials. On the other hand, the final cell population was higher for titanium-based implants; this difference was attributed to the growth pattern, in which cells were not monolayered on the surface. Collagen I was not observed, while collagen III was secreted. Furthermore, interleukin (IL)-6 and vascular endothelial growth factor (VEGF) secretion were enhanced, and IL-8 secretion decreased. Moreover, various types of cells can be utilized with a series of substrates to unfold the cell behavior mechanism and cell−substrate interaction.

Nowadays, epoxy composites are elements of engineering materials and systems. Although they are known as versatile materials, epoxy resins suffer from high flammability. In this sense, flame retardancy analysis has been recognized as an undeniable requirement for developing future generations of epoxy-based systems. A considerable proportion of the literature on epoxy composites has been devoted to the use of phosphorus-based additives. Nevertheless, innovative flame retardants have coincidentally been under investigation to meet market requirements. This review paper attempts to give an overview of the research on flame retardant epoxy composites by classification of literature in terms of phosphorus (P), non-phosphorus (NP), and combinations of P/NP additives. A comprehensive set of data on cone calorimetry measurements applied on P-, NP-, and P/NP-incorporated epoxy systems was collected and treated. The performance of epoxy composites was qualitatively discussed as Poor, Good, and Excellent cases identified and distinguished by the use of the universal Flame Retardancy Index (FRI). Moreover, evaluations were rechecked by considering the UL-94 test data in four groups as V0, V1, V2, and nonrated (NR). The dimensionless FRI allowed for comparison between flame retardancy performances of epoxy composites. The results of this survey can pave the way for future innovations in developing flame-retardant additives for epoxy.

From a set of around 100 phosphorus-containing polymers tested in pyrolysis−combustion flow calorimetry, the contributions to flammability of two phosphorus-containing pendant groups (called 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and PO3) were calculated using an advanced method previously proposed and validated. The flammability properties include total heat release (THR) and heat release capacity (HRC) measured in standard conditions, i.e., anaerobic pyrolysis and complete combustion. The calculated contributions are in good agreement with the main modes of action of both phosphorus groups, i.e., flame inhibition for DOPO and char promotion for PO3. Moreover, the results provide first conclusions about the cooperative interaction between phosphorus and nitrogen, as well as the influence of the architecture of tested co-polymers.

A series of samples based on poly(3-hydroxybutyrate) (PHB) containing five different additives were prepared and their thermal stability and flammability were discussed. The samples first underwent flammability screening by using Pyrolysis Combustion Flow Calorimeter (PCFC) analyses. Then, four samples were selected for further investigations. PHB composites containing sepiolite (Sep.) inorganic nanofiller, and also organic ammonium polyphosphate (APP) were examined for flammability and thermal behavior using PCFC, thermogravimetric analysis (TGA), flame test, and Differential Scanning Calorimetry (DSC) analyses. Moreover, burning behavior of samples were captured on a digital camera to give a deeper sense of their flammability character for comparison. The results revealed a significant improvement of flammability and thermal stability of composites, particularly in the presence of sepiolite with respect to the value obtained for unfilled PHB. Regarding TGA results, the char residue yield was increased to ca. 20.0 wt.% in the presence of sepiolite, while 0.0 wt.% was observed for PHB. PCFC measurements uncovered higher performance of PHB-Sep. sample as signaled by 40% reduction in the peak of heat release rate with respect to PHB. According to observations, PHB-Sep. sample showed non-dripping behavior with high capacity of charring in the presence of Sep. in a vertical flame test.

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

Flame Retardancy Index, FRI, was defined as a simple yet universal dimensionless criterion born out of cone calorimetry data on thermoplastic composites and then put into practice for quantifying the flame retardancy performance of different polymer composites on a set of reliable data. Four types of thermoplastic composites filled with a wide variety of flame retardant additives were chosen for making comparative evaluations regardless of the type and loading level of the additive as well as the irradiance flux. The main features of cone calorimetry including peak of Heat Release Rate (pHRR), Total Heat Release (THR), and Time-To-Ignition (TTI) served to calculate a dimensionless measure that reflects an improvement in the flame retardancy of nominated thermoplastic composites with respect to the neat thermoplastic, quantitatively. A meaningful trend was observed among well-classified ranges of FRI quantities calculated for the studied dataset on thermoplastic composites by which “Poor”, “Good”, and “Excellent” flame retardancy performances were explicitly defined and exhibited on logarithmic scales of FRI axis. The proposed index remains adaptable to thermoplastic systems whatever the polymer or additive is.