Cyclodextrin-based host-guest hierarchical fire retardants: Synthesis and novel strategy to endow polylactic acid fire retardancy and UV resistance.

ß-Cyclodextrin (ß-CD) with a cage-like supramolecular structure possesses the hydrophobic internal ring and external hydroxyl groups, which are beneficial for intramolecular interactions known as "host-guest" chemistry. This study presents a ß-CD-based three-functions-in-one and host-guest fire retardant (ßCD-MOF@Schiff base), which incorporates self-crosslinking Schiff base into its cavity and modification of its surface by metal-organic framework (MOF). With the presence of 5 wt% of ßCD-MOF@Schiff base, the LOI value of PLA composites increased to 29 % and showed 15 %, 17 % and 62 % reductions in peak heat release rate (pHRR), total heat release (THR), and the yield of hazard gas carbon monoxide, respectively. The mode action of FR on fire retardation of PLA showed that the FR promoted the char formation with higher thermal stability and graphitization, and modified the decomposition path of PLA. Additionally, the PLA composites exhibited enhanced UV resistance in the UVA and UVB areas with improved UV absorbance and the UPF values improving and doubling. This work develops a new approach to preparing biodegradable FR, which simultaneously endows fire safety and anti-UV properties for PLA.

Dual function of carboxymethyl cellulose scaffold: A one-stone-two-birds strategy to prepare double-layer hollow ZIF-67 derivates for flame retardant epoxy composites.

Aluminum hypophosphite (AHP) has been used as a flame retardant for a long time. Previous studies about AHP employed in flame retardant materials mostly focus on coating, modification, and complex system. It is valuable to explore simple experimental steps to prepare nano hybrids with AHP and metal-organic frameworks (MOFs). We found acidic substances could etch zeolitic imidazolate framework-67 (ZIF-67) to obtain MOF derivatives. Unfortunately, AHP and ZIF-67 could not directly form a hybrid. Therefore, carboxymethylcellulose (CMC) is introduced as a dual function layer (buffer and support). The CMC resists the complete conversion of ZIF-67 etched by phosphoric acid to amorphous cobalt phosphate hydrate (ACP). Meanwhile, CMC containing hydroxyl groups combines with AHP through electrostatic interaction and coordination bonds. A double-layer hollow MOF derivative is synthesized through this one-stone-two-birds strategy. Due to multiple flame retardant elements and unique nanostructure, this MOF derivative endows epoxy (EP) resin with excellent flame retardancy. With 2.0 wt% addition, the peak heat release rate (pHRR) and total heat release (THR) of EP/AHP/ACP@CMC are decreased by 47.8 and 21.0 %, respectively. This study proposes a novel scheme that converts AHP into MOF derivatives as high-performance FRs.

Synchronous modification of ZIF-67 with cyclomatrix polyphosphazene coating for efficient flame retardancy and mechanical reinforcement of epoxy resin.

Cyclomatrix polyphosphazenes have attracted widespread attention in the field of polymer flame retardancy. Nevertheless, the optimal manifestation of their distinctive structural attributes and flame-retardant properties necessitates a judicious selection of condensation monomers and synergistic templates during the fabrication of polyphosphazene flame retardants. In our previous studies, it was discovered that when ZIF-67 is functionalized with polyphosphazene, the by-product HCl from phosphazene polycondensation causes etching on ZIF-67. Based on this "synchronous etching" effect, a series of hybrid materials comprising cyclomatrix polyphosphazene and ZIF-67, denoted as ZIF-67@PDS (PDS, poly-(cyclotriphosphazene-co-4,4'-diaminodiphenyl sulfone)), ZIF-67@PBS (PBS, poly-(cyclotriphosphazene-co-Bisphenol A)), and ZIF-67@PZS (PZS, poly-(cyclotriphosphazene-co-4,4'-sulfonyldiphenol)), was synthesized utilizing DDS (4,4'-diaminodiphenyl sulfone), BPA (Bisphenol A), and BPS (4,4'-sulfonyldiphenol) monomers as precursors, respectively. Upon the incorporation of 2.0 wt.% of ZIF-67@PDS, ZIF-67@PBS, and ZIF-67@PZS, the flame retardant and mechanical characteristics of EP composites exhibited marked enhancement. The unique structural characteristics of hybrid and the synergistic effects of Co-P-N contribute to the improvement of comprehensive properties. Compared with pure EP, EP/ZIF-67@PZS has the best enhancement effect, and its pHRR, THR, and TSP decreased by 34.0%, 30.0%, and 40.5%, respectively. In terms of mechanical strength, ZIF-67@PZS also increases the flexural strength of EP by 37.42%. Relying on the "synchronous etching" effect, this study explores and verifies the effective combination of ZIF-67 and different types of polyphosphazenes, and obtains a series of ZIF-67-derived cyclomatrix polyphosphazene hybrids with different morphologies and properties in one step. It provides a new idea and strategy for the simultaneous modification of polyphosphazene materials and the preparation of multifunctional flame retardants in the future.

Structure of Metal-Organic Frameworks Eco-Modulated by Acid-Base Balance toward Biobased Flame Retardant in Polyurea Composites.

Biobased-functionalized metal-organic frameworks (Bio-FUN-MOFs) stand out from the crowd of candidates in the flame-retardant field due to their multipathway flame-retardant mechanisms and green synthesis processes. However, exploring and designing Bio-FUN-MOFs tend to counteract the problem of compromising the flame-retardant advantages of MOFs themselves, which inevitably results in a waste of resources. Herein, a strategy in which MOFs are ecologically regulated through acid-base balance is presented for controllable preparation of Bio-FUN-MOFs by two birds with one stone, i.e., higher flame-retardant element loading and retention of more MOF structures. Specifically, the buffer layer is created on the periphery of ZIF-67 by weak etching of biobased alkali arginine to resist the excessive etching of ZIF-67 by phytic acid when loading phosphorus source and to preserve the integrity of internal crystals as much as possible. As a proof of concept, ZIF-67 was almost completely etched out by phytic acid in the absence of arginine. The arginine and phytic acid-functionalized ZIF-67 with yolk@shell structure (ZIF@Arg-Co-PA) obtained by this strategy, as a biobased flame retardant, reduces fire hazards for polyurea composites. At only 5 wt % loading, ZIF@Arg-Co-PA imparted polyurea composites with a limiting oxygen index of 23.2%, and the peaks of heat release rate, total heat release, and total smoke production were reduced by 43.8, 32.3, and 34.3%, respectively, compared to neat polyurea. Additionally, the prepared polyurea composites have acceptable mechanical properties. This work will shed light on the advanced structural design of polymer composites with excellent fire safety, especially environmentally friendly and efficient biobased MOF flame retardants.

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.

Three-Dimensional Printing of Large Ceramic Products and Process Simulation.

Ceramic 3D printing is a promising technology that overcomes the limitations of traditional ceramic molding. It offers advantages such as refined models, reduced mold manufacturing costs, simplified processes, and automatic operation, which have attracted a growing number of researchers. However, current research tends to focus more on the molding process and print molding quality rather than exploring printing parameters in detail. In this study, we successfully prepared a large-size ceramic blank using screw extrusion stacking printing technology. Subsequent glazing and sintering processes were used to create complex ceramic handicrafts. Additionally, we used modeling and simulation technology to explore the fluid model printed by the printing nozzle at different flow rates. We adjusted two core parameters that affect the printing speed separately: three feed rates were set to be 0.001 m/s, 0.005 m/s, and 0.010 m/s, and three screw speeds were set to be 0.5 r/s, 1.5 r/s, and 2.5 r/s. Through a comparative analysis, we were able to simulate the printing exit speed, which ranged from 0.0751 m/s to 0.6828 m/s. It is evident that these two parameters have a significant impact on the printing exit speed. Our findings show that the extrusion velocity of clay is approximately 700 times faster than the inlet velocity at an inlet velocity of 0.001-0.010 m/s. Furthermore, the screw speed is influenced by the inlet velocity. Overall, our study sheds light on the importance of exploring printing parameters in ceramic 3D printing. By gaining a deeper understanding of the printing process, we can optimize printing parameters and further improve the quality of ceramic 3D printing.

Metal-organic framework-derived bird's nest-like capsules for phosphorous small molecules towards flame retardant polyurea composites.

The loading treatment of phosphorus flame retardants can mitigate their migration and plasticization effect. However, designing suitable carriers has remained a great challenge. Herein, two kinds of Co-based isomers, namely cobalt-cobalt layered double hydroxides (CoCo-LDH) and cobalt basic carbonate (CBC), were synthesized by employing ZIF-67 as a self-template, assemblied into two different nanostructures namely multi-yolk@shell CBC@CoCo-LDH (m-CBC@LDH) and solid CBC nanoparticles by facilely tuning the reaction time, which were employed as carriers, respectively. Subsequently, triphenyl phosphate (TPP)-loaded m-CBC@LDH (m-CBC-P@LDH) was prepared using TPP as the guest. The m-CBC@LDH with high specific surface area and hollow structure exhibited up to more than 30% of TPP loading. The peak of heat release rate and total heat release of polyurea composite blended with 5 wt% m-CBC-P@LDH reduced by 41.7% and 20.6% respectively, and the mechanical properties were less damaged. This work complements a feasible approach for preparation of metal-organic frameworks-derived flame retardant carriers.

Multielement Flame-Retardant System Constructed with Metal POSS-Organic Frameworks for Epoxy Resin.

The direct coordination between polyhedral oligomeric silsesquioxane (POSS) and Co forms an assembly of nanoparticles with low specific surface area and leads to a poor dispersion state in the epoxy resin matrix, resulting in unsatisfactory flame-retardant efficiency. Metal-organic frameworks (MOFs), for instance, ZIF-67, provide not only the cobalt element but also the porous framework that endows the nanocomposite of MOFs and POSS with high specific surface area and abundant Co sites in the silica skeleton. Herein, ZIF-67 is hybridized with octacarboxyl POSS, resulting in the removal of the alkaline ligand to form novel metal POSS-organic frameworks (MPOFs). The size differences for organic groups and silica nanocages of POSS vs. micropores of ZIF-67 gave rise to a reverse click reaction, reforming octavinyl POSS isolated on the outer surface of the Co complex, which could be further modified by a phosphorous flame retardant using an addition reaction. The obtained MPOFs-P with 2 wt % loading in epoxy resin could improve the limiting oxygen index value of the composites to 27.0% and pass the V-0 rating in the UL-94 test. Meanwhile, the peaks of the heat release rate and especially the total smoke production were reduced by 46.6 and 25.2%, respectively. The robust char layer reduces the emission of toxic gas CO by 39.8%. The above epoxy product with promising flame retardancy also improved mechanical properties, thanks to the filler with a unique nanostructure. The ingenious work offers enlightenment for the hybridization method of MOFs and POSS to fabricate a multielement flame-retardant system for epoxy resin with high efficacy.

Macro and micro thermal investigation of nanoarchitectonics-based coatings on cotton fabric using new quaternized starch.

Implementation of a new cationizing reagent and its incorporation onto the backbone of starch was performed successfully, confirmed from the remarkable micro- and macro anti-flammable properties. The morphologies and localized compositional analysis of the modified starch-based LBL coatings on the cotton surface were carried out using LV-SEM and EDX: highly uniform coating layers and uptake of solution species for intermediate implant reagent concentrations were confirmed. The subject samples were further analyzed through thermogravimetric analysis (TGA), microcombustion experiments (MCC), flame testing (VFT) and afterburn measurements. The peak range of the degradation was highly improved from the lower range to the higher range (329.92-394.48 °C), together with significant mass residue for TBAB-0.7-17.02%. Moreover, a significant decrease in the absolute heat loss (THR ∼ 30%), heat dissipation competence (HRC ∼ 27.86%), and peak heat output (PHRR ∼ 23%) was achieved for a TBAB loading of ∼0.7 g. The results were further confirmed from the increase in the limiting oxygen index (LOI) to a higher rate of ∼23.2, improved structural integrity and higher quality of char obtained in the VFT and after-burn analysis.

Precise Control of a Yolk-Double Shell Metal-Organic Framework-Based Nanostructure Provides Enhanced Fire Safety for Epoxy Nanocomposites.

Nanomaterials derived from metal-organic frameworks (MOFs) are highly promising as future flame retardants for polymeric materials. The precise control of the interface for polymer nanocomposites is taking scientific research by storm, whereas such investigations for MOF-based nanofillers are rare. Herein, a novel yolk-double shell nanostructure (ZIF-67@layered double hydroxides@polyphophazenes, ZIF@LDH@PZS) was subtly designed and introduced into epoxy resin (EP) as a flame retardant to fill the vacancy of yolk/shell construction in the field. Meanwhile, the interface of the polymer nanocomposites can be further accurately tailored by the outermost layer of the nanofillers from PZS to Ni(OH)2 (NH), by which hollow nanocages with treble shells (LDH@PZS@NH) were obtained. It is remarkably interesting that LDH@PZS@NH endows the EP with the lowest peak of heat release rate in the cone calorimeter test, but the total heat and smoke releases (THR and TSP) of the nanocomposites are even higher than those of the neat polymer. In contrast, EP blended with ZIF@LDH@PZS shows outstanding comprehensive performance: with 2 wt.%, the limiting oxygen index is increased to 29.5%, and the peak heat release rate is reduced by 26.0%. The impact and flexural strengths are slightly lowered, while the storage modulus is enhanced remarkably compared with that for neat EP. The flame retardant mechanism is systematically explored focusing on the interfacial interactions of different hybrids within the epoxy matrix, ushering in a new stage of study of nanostructural design-guided interface manipulation in MOF-based polymer nanocomposites.

Delamination and Engineered Interlayers of Ti3C2 MXenes using Phosphorous Vapor toward Flame-Retardant Epoxy Nanocomposites.

As recently created inorganic nanosheet materials, more and more light has been shed on MXenes, which have emerged as a hotspot of intensive investigations. The simple exfoliation method for MXenes attracts numerous studies to pay efforts on. Compared with the extensive research about ultrasonication and mechanical milling, gas-assisted exfoliation has never been carried out for MXenes. Meanwhile, MXene-based nanocomposites are always prepared after exfoliation step by step. In this work, a facile way to fabricate a few-layered Ti3C2 MXene delaminated using phosphorous vapor evolved from commercial red phosphorous (RP) is put forward. The vapor deposits on the surface of Ti3C2 and also partially intercalates into the interlayers to obtain a novel two-dimensional RP/Ti3C2 nanocomposite directly. The P element strongly connects with the substrate by a covalent bond that improves the safety problems for RP during storage and usage. Due to the versatile feature of MXenes, the nanocomposite has the potential to be applied in a variety of fields. Herein, it is employed as a flame retardant for epoxide resin and effectively reduces fire disaster. The one-step exfoliation plus nanocomposite fabrication provides a more feasible way for the practical application of MXenes.

LBL generated fire retardant nanocomposites on cotton fabric using cationized starch-clay-nanoparticles matrix.

In this work, starch-clay-TiO2-based nanocomposites were deposited on cotton fabric through layer-by-layer (LBL) process and their effect on the flame retardancy, inhibition of pyrolysis and combustion processes were discussed in details. Polyelectrolyte solutions/suspensions of cationized starch and VMT (vermiculite)/TiO2 nanoparticles were used to deposit these nanocomposites in the form of multi-layered coatings (5, 7, 10 and 15 bilayers). Uniform fabric coverage and presence of electrolytes was imaged by scanning electron microcopy (LV-SEM), attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) and EDX characterizations. The greatest pyrolysis reduction was found for the StVT-7 sample (7 bilayers); ~30% and 21%, based on microscale combustion calorimetry (MCC) and thermogravimetric analysis (TGA). When using MCC, the improved values of the PHRR ~ 193 W/g, THR ~ 10.7 kJ/g), HRC ~ 390 J/g∙K and LOI ~ 22.2% were found for the StVT-7 sample which was strongly supported by the UL-94 test.

Nickle nanocrystals decorated on graphitic nanotubes with broad channels for fire hazard reduction of epoxy resin.

Carbon nanotubes (CNTs) are a sort of carbon-based nanofillers blended into polymer nanocomposites to improve both of the flame retardancy and mechanical properties. However, the CNTs tend to entangle into bundles and the channels are too narrow to allow the entry of polymer chains, harmful to the dispersion and interaction within the polymer matrix. Therefore, by means of a facile pyrolysis method, boron and nitrogen co-doped larger-diameter graphitic nanotubes with decorated nickel nanocrystals (Ni/GNTs) were developed as flame retardant for epoxy resin (EP). The nanotubes are short but with large specific surface area. Compared to the commercial CNTs, the epoxy chain could infiltrate into the channels of Ni/GNTs which was approved by different techniques. The unique nanostructure endowed the product with strong interaction with the polymer matrix. The fire behaviors were examined by cone calorimeter tests, and the results showed that with the addition of 2 wt% Ni/GNTs, the peak of heat release rate and the total smoke production values of the nanocomposites were reduced by 43.5 % and 22.8 % compared with those of pure epoxy, respectively. Meanwhile, the flexural and tensile properties of EP/Ni/GNTs were also enhanced.

Facile synthesis of transition metal containing polyhedral oligomeric silsesquioxane complexes with mesoporous structures and their applications in reducing fire hazards, enhancing mechanical and dielectric properties of epoxy composites.

Transition metal (Co or Fe) containing polyhedral oligomeric silsesquioxane complexes (M@POSS-COOH) were prepared from octa carboxyl polyhedral oligomeric silsesquioxane (OC-POSS). The structures of OC-POSS and M@POSS-COOH were characterized by FT-IR, NMR, MALDI-TOF MS and XRD. Fe@POSS-COOH and Co@POSS-COOH possess mesoporous structures, whose Brunauer-Emmett-Teller surface areas (SBET) are 58.7 m2/g and 46.3 m2/g, respectively. The remaining carboxyl groups of M@POSS-COOH that can react with epoxy groups along with the mesoporous structure increase the network strength of the epoxy resin (EP), and play a significant role in improving the mechanical properties, dielectric properties and thermal properties of the composites. Furthermore, the elemental composition of transition metal and silicon oxygen in the M@POSS-COOH structures significantly increases the amount of char residues of EP composites during the combustion of the material through elements catalysis and surface enrichment, which significantly reduces the toxic smoke density and fire hazards of EP composites. The structural and elemental merits of M@POSS-COOH significantly improve the overall performance of epoxy resin and occupy broad application space.

Mitigation the release of toxic PH3 and the fire hazard of PA6/AHP composite by MOFs.

Aluminum hypophosphite (AHP) is a high-efficiency phosphorus-based flame retardant with high P content, which is widely used in Polyamide 6 (PA6). However, AHP releases phosphine gas (PH3) at high temperatures, which is highly toxic to human's health and environment. Metal-organic frameworks (MOFs) have porous structure exhibiting high performance in gas adsorption. Therefore, mesoporous iron (III) carboxylate [MIL-100 (Fe)] was synthesized in this work and employed to study the adsorption capacity of toxic PH3 in PA6/AHP composite during processing. AHP was combined with melamine cyanurate (MCA) and MIL-100 (Fe) followed by blending with PA6 to prepare PA6 composites (PA6/MA and PA6/MAF). PA6/MAF with the weight ratio of 5:5 performed well in inhibiting the release of PH3 during the processing of composite as well as the accelerated thermal experiment devised by our group. Besides, PA6/MAF (5:5) showed relatively low fire hazard reflected by the reduction of the peak of heat release rate of PA6 composite from 962 to 260 kW/m2 compared with that of pure PA6 in the cone calorimeter test, and MIL-100 (Fe) along with MCA also presented synergistic effect in suppressing the emission of carbon monoxide. The subtle selection of MOFs herein has the potential to be used as a promising synergist for hazardous gases released from polymer composites to improve the occupational and fire safety in the society.

Confined Dispersion of Zinc Hydroxystannate Nanoparticles into Layered Bimetallic Hydroxide Nanocapsules and Its Application in Flame-Retardant Epoxy Nanocomposites.

In many fields, nanoparticles are frequently dispersed onto kinds of nanocarriers integrated into hybrid nanocomposites to acquire advanced performance. However, the nanoparticles usually tend to agglomerate on the surface, according to traditional synthetic methods. Besides, the exposed state of loaded nanoparticles and the weak adhesion with the supporters make them fall off during practical application, leading to "second agglomeration" of the nanoparticles and attenuated synergistic effects. In this work, we engineered layered bimetallic (Ni-Co) hydroxides (NCHs) into enclosed nanocages derived from metal organic frameworks (MOFs). Zinc hydroxystannate (ZHS) nanoparticles were selected to be confined dispersed within the hollow cavity of the three-dimensional nanocages. ZHS nanoparticles were tightly immobilized, monodispersing to form a novel multiyolk@shell nanostructure with NCH nanocages. To prove the effectiveness of this structural design, the as-synthesized hybrids ZHS@NCH were introduced into the epoxy matrix to inquiry its performance. Compared to neat ZHS, neat NCH, and physical mixture of ZHS and NCH, ZHS@NCH conferred better flame retardancy, thermal stability, and mechanical properties upon the epoxy nanocomposites. With the adding amount of 6 wt % ZHS@NCH, the UL-94 rating of the nanocomposite was V-0, and the peak of heat release rate value was reduced by 69.1%, while the mechanical properties were slightly influenced. The ingenious synthetic strategy gives insights into uniform distribution of nanoparticles within nanocapsules and enlightens the facile fabrication of multiyolk@shell nanomaterials.

Renewable vanillin based flame retardant for poly(lactic acid): a way to enhance flame retardancy and toughness simultaneously.

In this study, a novel bio-based flame retardant material consisting of modified vanillin and poly(lactic acid) (PLA) was developed by incorporation of newly discovered additive, bis(5-formyl-2-methoxyphenyl) phenylphosphonate (VP), into the PLA matrix. The chemical structure of VP was confirmed by 1H-, 13C- and 31P NMR and FTIR. The flame retardancy, thermal behavior as well as the mechanical properties of PLA/VP composites were evaluated. With 5 wt% of VP, the LOI of PLA increased from 21.4 to 25.8 and passed the UL-94 V-0 classification. Additionally, the elongation at break was improved from 3% to 11% without sacrificing tensile strength. In an effort to understand the mechanisms, TGA-FTIR, TGA and SEM were performed. This paper suggests a new possibility to prepare polymeric composites with enhanced flame retardancy from sustainable resources.

Fabrication of low-fire-hazard flexible poly (vinyl chloride) via reutilization of heavy metal biosorbents.

As a naturally abundant biopolymer, chitosan is considered to be a suitable adsorbent for stannate (SnO32-) in tin plating wastewater. However, mass transfer of the adsorbent and its recycling remain challenging problems. Though flexible poly(vinyl chloride) (PVC) is highly flammable due to the addition of plasticizers, the traditional flame retardant, antimony trioxide (Sb2O3), is potentially harmful. In this study, chitosan was anchored onto the surface of PVC resin to adsorb SnO32- from wastewater. Thereafter, tin-doped chitosan-coated PVC resin was readily recycled and processed into a flexible PVC composite (modified fPVC). The limiting oxygen index value of the modified fPVC increased to 33.1%, and the peak heat release rate decreased to 161kW/m2. In addition to reducing fire hazards, this approach also decreased the content of harmful hydrogen chloride gas released during the combustion of modified fPVC. Meanwhile, the tensile properties of modified fPVC were enhanced compared with those of the Sb2O3-treated sample. These results indicated the synthesis of an eco-friendly Sb2O3-free flexible PVC composite that poses a low fire hazard.