Enhancing char formation of flame retardant epoxy composites: Onigiri-like ZIF-67 modification with carboxymethyl ß-cyclodextrin crosslinking.

To enhance char formation of flame retardant epoxy (EP) composites, carboxymethyl ß-cyclodextrin (CM-ß-CD) is employed as an etchant for or ZIF-67 derivatives. In the early stage, etching plays a dominant role. The mismatch in size between CM-ß-CD opening and ZIF-67 pore leads to the stacking of carboxyl cobalt complexes on the shell. When the reaction time is prolonged, crosslinking occurs between carboxyl and hydroxyl groups. Crosslinked CM-ß-CD weakens and eventually stops the etching process. Triethyl phosphate (TEP), an additive to improve flame retardancy, is also absorbed on the shell in this one-pot synthesis. Herin, the synthesis of metal-organic framework (MOF) derivatives can impart multiple functions to MOF. This novel nanohybrid significantly improved flame retardancy of EP composites with only 2.0 wt% loading. The peak heat release rate (pHRR) and total smoke production (TSP) were reduced by 54.8 and 46.9%, respectively. The integrated multi-element system resulted in an expanded and reinforced char layer. This study proposes a simple and precise method for controlling the structure of MOF-carbohydrate hybrids through competition between chemical reactions.

A Gas-Steamed Route to Mesoporous Open Metal-Organic Framework Cages Enhancing Flame Retardancy and Smoke Suppression of Polyurea.

Up to now, metal-organic frameworks (MOFs) with open nanostructures have shown outstanding capabilities in trapping smoke particles compared to the original MOFs. However, only a few MOF-based strategies have been reported to synthesize hierarchical porous cages thus far, which are mainly restricted to environmentally unfriendly wet-chemical liquid methods. Herein, as a proof-of-concept, a gas-steamed metal-organic framework approach was designed to fabricate a series of cheeselike open cages with hierarchical porosity. Briefly, zeolitic imidazolate framework-67 (ZIF-67) and phytic acid were employed as precursor and etchant, respectively. Abandoning the conventional wet-chemical method, the coordination bond of ZIF-67 was cleaved by acidic steam, forming an open framework with a high specific surface area and a hierarchical porous structure. The universality of this method was also confirmed by the selection of different etchants. Impressively, they also show outstanding fume-toxic adsorption capability and labyrinth effects based on abundant and complex porous channels. At only 5 wt % loading, Co3O4@open ZIF-67 cage-2 (Co3O4@OZC-2) imparted polyurea (PUA) composites with a 21.2% limiting oxygen index, and the peak of heat release rate, total heat release, and total smoke production were reduced by around 37.5, 25.5, and 40.4%, respectively, compared to neat PUA. This work will shed light on the advanced structural design of polymer composites with high fire safety, especially smoke suppression performance, so as to obtain more feasible applications.

Hollow Superstructure In Situ Assembled by Single-Layer Janus Nanospheres toward Electromagnetic Shielding Flame-Retardant Polyurea Composites.

A dodecahedral superstructure consisting of a single layer of Janus spheres containing ZIF-67 nanodots is prepared by in situ polymerization, with ZIF-67 and bio-based phytic acid (PA) as templates and dopants. It is used to improve the flame retardant, electromagnetic (EMI) shielding, and thermal conductivity properties of polyurea (PUA). By adding 5 wt% polyaniline@cobalt phytate-2.0 (PANI@Co-PA-2.0), the peak of heat release rate and the peak of smoke production rate are reduced by 54.9 and 59.9%, respectively. The peak of CO and CO2 production also decreased by 46.2 and 53.1%, respectively. A decrease in the absorption intensity of aliphatic and aromatic volatiles is also observed. The fire safety of PUA is greatly improved. In addition, PUA/PANI@Co-PA-2.0 exhibits an EMI shielding capability of 22.4 dB with the help of reduced graphene oxide, which confirms the possibility of PUA material application in the field of electromagnetic shielding. The 5 wt% filler increases the tensile strength of the PUA matrix to 6.3 MPa, and the composite material obtains good thermal conductivity. This work provides a viable method for the preparation of a flame-retardant, conductive, and electromagnetic refractory PUA substrate.

Antimicrobial and Biodegradable 3D Printed Scaffolds for Orthopedic Infections.

In bone tissue engineering, the performance of scaffolds underpins the success of the healing of bone. Microbial infection is the most challenging issue for orthopedists. The application of scaffolds for healing bone defects is prone to microbial infection. To address this challenge, scaffolds with a desirable shape and significant mechanical, physical, and biological characteristics are crucial. 3D printing of antibacterial scaffolds with suitable mechanical strength and excellent biocompatibility is an appealing strategy to surmount issues of microbial infection. The spectacular progress in developing antimicrobial scaffolds, along with beneficial mechanical and biological properties, has sparked further research for possible clinical applications. Herein, the significance of antibacterial scaffolds designed by 3D, 4D, and 5D printing technologies for bone tissue engineering is critically investigated. Materials such as antibiotics, polymers, peptides, graphene, metals/ceramics/glass, and antibacterial coatings are used to impart the antimicrobial features for the 3D scaffolds. Polymeric or metallic biodegradable and antibacterial 3D-printed scaffolds in orthopedics disclose exceptional mechanical and degradation behavior, biocompatibility, osteogenesis, and long-term antibacterial efficiency. The commercialization aspect of antibacterial 3D-printed scaffolds and technical challenges are also discussed briefly. Finally, the discussion on the unmet demands and prevailing challenges for ideal scaffold materials for fighting against bone infections is included along with a highlight of emerging strategies in this field.

Flame Retardancy Index (FRI) for Polymer Materials Ranking.

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.

Sustainable Flame-Retardant Additives for Polymers: Future Perspectives.

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 [...].

Improved Processability and Antioxidant Behavior of Poly(3-hydroxybutyrate) in Presence of Ferulic Acid-Based Additives.

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.

GTR/Thermoplastics Blends: How Do Interfacial Interactions Govern Processing and Physico-Mechanical Properties?

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.

A recent advancement on preparation, characterization and application of nanolignin.

Each year, 50 to 70 million tonnes of lignin are produced worldwide as by-products from pulp industries and biorefineries through numerous processes. Nevertheless, about 98% of lignin is directly burnt to produce steam to generate energy for the pulp mills and only a handful of isolated lignin is used as a raw material for the chemical conversion and for the preparation of various substances as well as modification of lignin into nanomaterials. Thus, thanks to its complex structure, the conversion of lignin to nanolignin, attracting growing attention and generating considerable interest in the scientific community. The objective of this review is to provide a complete understanding and knowledge of the synthesis methods and functionalization of various lignin nanoparticles (LNP). The characterization of LNP such as structural, thermal, molecular weight properties together with macromolecule and quantification assessments are also reviewed. In particular, emerging applications in different areas such as UV barriers, antimicrobials, drug administration, agriculture, anticorrosives, the environment, wood protection, enzymatic immobilization and others were highlighted. In addition, future perspectives and challenges related to the development of LNP are discussed.

Crystalline polysaccharides: A review.

The biodegradability and mechanical properties of polysaccharides are dependent on their architecture (linear or branched) as well as their crystallinity (size of crystals and crystallinity percent). The amount of crystalline zones in the polysaccharide significantly governs their ultimate properties and applications (from packaging to biomedicine). Although synthesis, characterization, and properties of polysaccharides have been the subject of several review papers, the effects of crystallization kinetics and crystalline domains on the properties and application have not been comprehensively addressed. This review places focus on different aspects of crystallization of polysaccharides as well as applications of crystalline polysaccharides. Crystallization of cellulose, chitin, chitosan, and starch, as the main members of this family, were discussed. Then, application of the aforementioned crystalline polysaccharides and nano-polysaccharides as well as their physical and chemical interactions were overviewed. This review attempts to provide a complete picture of crystallization-property relationship in polysaccharides.

Epoxy/Ionic Liquid-Modified Mica Nanocomposites: Network Formation-Network Degradation Correlation.

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.

Additive manufacturing of polyhydroxyalkanoates (PHAs) biopolymers: Materials, printing techniques, and applications.

Additive manufacturing (AM) is recently imposing as a fast, reliable, and highly flexible solution to process various materials, that range from metals to polymers, to achieve a broad variety of customized end-goods without involving the injection molding process. The employment of biomaterials is of utmost relevance as the environmental footprint of the process and, consequently, of the end-goods is significantly decreased. Additive manufacturing can provide, in particular, an all-in-one platform to fabricate complex-shaped biobased items such as bone implants or biomedical devices, that would be, otherwise, extremely troublesome and costly to achieve. Polyhydroxyalkanoates (PHAs) is an emerging class of biobased and biodegradable polymeric materials achievable by fermentation from bacteria. There are some promising scientific and technical reports on the manufacturing of several commodities in PHAs by additive manufacturing. However, many challenges must still be faced in order to expand further the use of PHAs. In this framework, the present work reviews and classifies the relevant papers focused on the design and development of PHAs for different 3D printing techniques and overviews the most recent applications of this approach.

Flame Retardant Polypropylenes: A Review.

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.

Metal-Organic Framework (MOF)/Epoxy Coatings: A Review.

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.

Flame Retardancy of Bio-Based Polyurethanes: Opportunities and Challenges.

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.

Copper-enriched diamond-like carbon coatings promote regeneration at the bone-implant interface.

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.

Effect of Surface Treatment of Halloysite Nanotubes (HNTs) on the Kinetics of Epoxy Resin Cure with Amines.

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.

Curing Kinetics and Thermal Stability of Epoxy Composites Containing Newly Obtained Nano-Scale Aluminum Hypophosphite (AlPO2).

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.

Electroactive poly (p-phenylene sulfide)/r-graphene oxide/chitosan as a novel potential candidate for tissue engineering.

Designing novel biomaterials for tissue engineering purpose is an obvious necessary considering ever increasing need for appropriate biocompatibility and properties to achieve the maximum regeneration. In this research, a new type of biomaterial based on poly (phenylene sulfide) (PPS) and reduced graphene oxide (rGO) was synthesized and applied within chitosan based hydrogel to evaluate its performance as a wound dressing potentially. Fourier transform infrared spectroscopy (FTIR), X-ray diffraction spectrometry (XRD), scanning electron microscopy (SEM) and compression tests were performed to assess suitability of composite biomaterial. Thermal behavior of the PPS/rGO composite was evaluated by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). The PPS/rGO composition of 90: 10 (w/w) was selected because of having the highest biocompatibility and utilized in chitosan hydrogel. Chitosan hydrogel swelling ratio was declined from 800 to 200% by PPS/rGO addition; likewise, water vapor transition rate (WVTR) was dropped. A proper biocompatibility and cell attachment was confirmed, where porosity of ca. 80% appeared promising for tissue engineering uses. Overall, the result confirmed the appropriateness of PPS/rGO for tissue engineering uses.