"One for two" strategy to construct an organic-inorganic polymer colloid for flame-retardant modification of flax fabric and rigid polyurethane foam.

Polymeric materials such as fabric and foam have high flammability which limits their application in the field of fire protection. To this end, an organic-inorganic polymer colloid constructed from carboxymethyl chitosan and ammonium polyphosphate was used to improve the flame retardancy of flax fabric (FF) and rigid polyurethane foam (RPUF) based on a "one for two" strategy. The modification processes of FF and RPUF relied on pad-dry-cure method and UV-curing technology, respectively, and the modified FF and RPUF were severally designated as CMC/APP-FF and RFR-RPUF. Flame retardancy studies showed that CMC/APP-FF and RFR-RPUF exhibited limiting oxygen index values as high as 39.4 % and 42.6 %, respectively, and both achieved self-extinguishing behavior when external ignition source was removed. Thermogravimetric analysis and cone calorimetry test confirmed that CMC/APP-FF and RFR-RPUF had good charring ability and demonstrated reduced peak heat release rate values of 90.1 % and 10.8 %, respectively, distinct from before they were modified. In addition, condensed phase analysis showed that after burning, CMC/APP-FF became an integration char structure, whereas RFR-RPUF turned into a sandwiched char structure. In summary, the "one for two" strategy reported in this work provides a new insight into the economical fabrication of flame-retardant polymeric materials.

Asymmetric ionic bond shielding encountering with carboxylate capturing metal ions for enhancing the flame retardant durability of regenerated cellulose fibers.

Enhancing the flame retardancy and durability of cellulose fibers, particularly environmentally friendly regenerated cellulose fibers types like Lyocell fibers, is essential for advancing their broader application. This study introduced a novel approach to address this challenge. Cationic-modified Lyocell fibers (Lyocell@CAT) were prepared by introducing quaternary ammonium structures into the molecular chain of Lyocell fibers. Simultaneously, a flame retardant, APA, containing -COO-NH4+ and -P=O(O-NH4+)2 groups was synthesized. APA was then covalently bonded to Lyocell@CAT to prepare Lyocell@CAT@APA. Even after undergoing 30 laundering cycles (LCs), Lyocell@CAT@APA maintained a LOI value of 37.2 %, exhibiting outstanding flame retardant durability. The quaternary ammonium structure within Lyocell@CAT@APA formed asymmetric ionic bonds with the phosphate and carboxylate groups in APA, effectively shielding the binding of Na+ ions with phosphate groups during laundering, thereby enhancing the durability. Additionally, the consumption of Na+ ions by carboxylate groups further prevented their binding to phosphate groups, which contributed to enhance the durability properties. Flame retardant mechanism analysis revealed that both gas and condensed phase synergistically endowed excellent flame retardancy to Lyocell fibers. Overall, this innovative strategy presented a promising prospect for developing bio-safe, durable, and flame retardant cellulose textiles.

Bioinspired phosphorus-free and halogen-free biomass coatings for durable flame retardant modification of regenerated cellulose fibers.

Inspired by mussel adhesion and intrinsic flame retardant alginate fibers, a biomass flame retardant (PPCA) containing adhesive catechol and sodium carboxylate structure (-COO-Na+) based on biomass amino acids and protocatechualdehyde was designed to prepare flame retardant Lyocell fibers (Lyocell@PPCA@Na). Furthermore, through the substitution and chelation of metal ions by PPCA in the cellulose molecular chain, flame retardant Lyocell fibers chelating copper and iron ions (Lyocell@PPCA@Cu, Lyocell@PPCA@Fe) were prepared. Compared with the original sample, the peak heat release rate (PHRR) and total heat release (THR) for modified Lyocell fibers were significantly reduced. In addition, the modified sample exhibited a certain flame retardant durability. TG-FTIR analysis showed that the release of flammable gaseous substances was inhibited. The introduction of Schiff bases and aromatic structures in PPCA, as well as the decomposition of carboxylic metal salts were beneficial for the formation of char residue containing metal carbonates and metal oxides to play the condensed phase flame retardant effect. This work develops a new idea for the preparation of eco-friendly flame retardant Lyocell fibers without the traditional flame retardant elements such as P, Cl, and Br.

One-pot strategy to simultaneously prepare dyed, flame retardant and UV-resistant silk fabric based on a safflower yellow derivative.

To give silk fabric multiple functions and improve its application range, a facile and eco-friendly one-pot technique was used to endow silk fabric with dyeing, flame retardant and ultraviolet (UV)-resistant performance based on a safflower yellow derivative. The structure, surface morphology, elemental composition, thermal properties and combustion behavior of the silk samples before and after modification were all characterized. In addition, the color depth and color fastness of the dyed silk (D-silk) and flame retardant silk (FR-silk) were evaluated and measured. The positive b* value in the CIELAB color space defined the yellow color of the dyed silk fabric. The char residue increased from 2.9 wt% of the original sample to 17.4 wt% of the FR-silk at 800 °C in air atmosphere. The limiting oxygen index (LOI) of FR-silk increased from 23.3% of the control sample to 32.8% with an increase of 40.7%. The peak of heat release rate (pHRR) and total heat release (THR) of FR-silk were much lower than that of the original sample. Furthermore, the UV protection factor (UPF) of FR-silk was 73.79, indicating excellent UV-resistance properties. The preparation process was green and environment-friendly, and the FR-silk had a good application prospect.

Comparison of Tensile Properties and Knot Security of Surgical Sutures: An In Vitro Mechanical Study.

PURPOSE: Studies on the mechanical properties and knot security of smaller sutures used in oral and maxillofacial surgery are limited. The objective of this study is to measure the tensile properties and knot security depending on the suture materials, knotting techniques, and number of throws using 5-0 sized sutures. METHODS: Seven 5-0 sized sutures were measured in both straight-pull and knot-pull according to the procedures outlined by the United States Pharmacopeia. Regarding knot security, there were 3 predictor variables: suture material, knot technique, and number of throws. Two surgical tying techniques were square knot and surgeon's knot and the number of throws were 3, 4, and 5. One-way analysis of variance was applied to test tensile properties (α = 0.05). The dichotomous outcome of knot security (stable or unstable) was analyzed using logistic regression analysis and odds ratios with Tukey-adjusted 95% confidence intervals. RESULTS: Ethicon polyglactin 910 was found to have the highest failure load (18.0 N) of straight, while silk sutures had the lowest of both straight and knotted. A higher elongation rate was found in the 2 monofilament suture materials polypropylene and polydioxanone. Knot security depended on the suture technique, material, and number of throws. Surgeon's knots were stronger than square knots. The number of throws required to achieve knot security depends on the specific combination. For polypropylene or Jinhuan silk with the surgeon's knot, 3 throws can probably achieve knot security. CONCLUSIONS: The new data presented in the study provided important information for guiding the selection of smaller suture materials for oral and maxillofacial surgery. A wider range of suture combinations should be tested, and more in vivo studies are needed to clarify the characteristics of sutures and knots.

Synthesis of Novel Arginine-Based Flame Retardant and Its Application in Lyocell Fabric.

Lyocell fabrics are widely applied in textiles, however, its high flammability increases the risk of fire. Therefore, to resolve the issue, a novel biomass-based flame retardant with phosphorus and nitrogen elements was designed and synthesized by the reaction of arginine with phosphoric acid and urea. It was then grafted onto the lyocell fabric by a dip-dry-cure technique to prepare durable flame-retardant lyocell fabric (FR-lyocell). X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared spectroscopy (FTIR) analysis demonstrated that the flame retardant was successfully introduced into the lyocell sample. Thermogravimetric (TG) and Raman analyses confirmed that the modified lyocell fabric featured excellent thermal stability and significantly increased char residue. Vertical combustion results indicated that FR-lyocell before and after washing formed a complete and dense char layer. Thermogravimetric Fourier-transform infrared (TG-FTIR) analysis suggested that incombustible substances (such as H2O and CO2) were produced and played a significant fire retarding role in the gas phase. The cone calorimeter test corroborated that the peak of heat release rate (PHRR) and total heat release (THR) declined by 89.4% and 56.4%, respectively. These results indicated that the flame retardancy of the lyocell fabric was observably ameliorated.

Enhancing the flame retardancy of lyocell fabric finished with an efficient, halogen-free flame retardant.

A novel flame retardant (PNPG) containing phosphorus and nitrogen was synthesized through the reaction of neopentyl glycol, phosphoric acid and urea, and was then used for preparation of flame retardant lyocell fabric through a dip-dry-cure finishing process. The structure of the PNPG was confirmed by proton nuclear magnetic resonance spectroscopy (1H-NMR) and Fourier transform infrared spectroscopy (FT-IR). The flame retardancy and thermal stability of the treated fabric were evaluated by a cone calorimetry test and thermogravimetric analysis (TG), which showed that the char residue of the treated fabric at 800 °C was as high as 39.7% under a nitrogen atmosphere. At the same time, the peak heat release rate (PHRR) and total heat release (THR) were significantly reduced by 92.9% and 81.2%, respectively. Obviously, the presence of flame retardant can effectively improve the thermal stability and flame retardancy of lyocell fabrics. In addition, thermogravimetric analysis combined with Fourier transform infrared spectroscopy (TG-IR), scanning electron microscopy (SEM), and Raman spectroscopy indicated that the flame retardant mechanism was consistent with the condensed phase and gas phase mechanism. The limiting oxygen index (LOI) of the treated samples could reach 39.3%, moreover, even after 20 laundering cycles (LCs), the LOI values of the samples finished at 28.3% with 120 g L-1 flame retardant remaining, which confirmed the durability and high flame retardancy of the treated samples. In addition, the mechanical properties, whiteness, rigidity and flexibility of the fabrics treated with PNPG were insignificantly reduced within a more acceptable range than the original samples. In summary, the flame retardant described herein has excellent flame retardant properties and char-forming ability, and it is suitable for the preparation of flame retardant lyocell fibers.

Fabrication of Chitosan-Based Intumescent Flame Retardant Coating for Improving Flame Retardancy of Polyacrylonitrile Fabric.

In order to improve the flame retardancy of polyacrylonitrile (PAN) fabrics, glycidyl methacrylate (GMA) was first grafted onto the surface of PAN fabric (PAN-g-GMA) by means of UV-induced photo grafting polymerization process. Then, PAN-g-GMA was chemically grafted with chitosan to obtain a bigrafted PAN fabric (PAN-g-GMA-g-CS). Finally, the flame-retardant PAN fabric (FR-PAN) was prepared by phosphorylation. The structure and elemental analysis of the samples were characterized by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The thermal degradation properties and combustion characteristics of the fabrics were accessed by thermogravimetric analysis (TG), differential scanning calorimetry (DSC), and cone calorimeter (CC). The results show that the onset thermal decomposition temperature of FR-PAN fabric is lower than that of the control sample due to the degradation of the grafting groups. The combustion test indicates that the FR-PAN fabric has an excellent flame-retardant property and the combustion rate is significantly reduced. In addition, the char residue of the burned FR-PAN fabric is over 97%, indicating excellent char-forming ability.

Polyvinyl Alcohol Reinforced Flame-Retardant Polyacrylonitrile Composite Fiber Prepared by Boric Acid Cross-Linking and Phosphorylation.

To improve the strength and maintain the inherent properties of flame-retardant polyacrylonitrile (FR-PAN) fiber, a commercialized hydrocarbon polymer, i.e., poly (vinyl alcohol) (PVA), used as an enhancement component, was blended with polyacrylonitrile (PAN) spinning dope to fabricate a PVA/PAN composite fiber through wet-spun technology. Then, cross-linked PVA/PAN composite fiber (C-PVA/PAN) was acquired via boric acid cross-linking. Finally, flame-retardant C-PVA/PAN fiber (FR-PVA/PAN) was prepared by phosphorylation. The structures of the samples were characterized by Fourier transform infrared analysis (FTIR) and X-ray photoelectron spectroscopy (XPS). The thermogravimetric analysis (TGA) results reveal that the thermal stability of the composite fiber is lower than that of the pristine PAN fiber. However, the char residue of the composite fiber is higher than that of the control sample, wherein, FR-PVA/PAN has the highest char residue of 62.5 wt% at 800 °C. The results regarding the combustion properties of FR-PVA/PAN show that the fire hazard of FR-PVA/PAN is restrained greatly, indicating excellent flame-retardant performance. The corresponding flame-retardant mechanism of FR-PAV/PAN is investigated by Pyrolysis gas chromatography and mass spectrometry (Py-GC/MS) and thermogravimetric analysis coupled with Fourier transform infrared analysis (TG-FTIR). The results indicate the gas-phase and condensed-phase flame-retardant mechanisms.

Preparation of Flame Retardant Polyacrylonitrile Fabric Based on Sol-Gel and Layer-by-Layer Assembly.

This paper aims to develop a novel method, i.e., sol-gel combined with layer-by-layer assembly technology, to impart flame retardancy on polyacrylonitrile (PAN) fabrics. Silica-sol was synthesized via the sol-gel process and acted as cationic solution, and phytic acid (PA) was used as the anionic medium. Flame-retardant-treated PAN fabric (FR-PAN) could achieve excellent flame retardancy with 10 bilayer (10BL) coating through layer-by-layer assembly. The structure of the fabrics was characterized by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). The thermal stability and flame retardancy were evaluated by thermogravimetric (TG) analysis, cone calorimetry (CC) and limiting oxygen index (LOI). The LOI value of the coated fabric was up to 33.2 vol % and the char residue at 800 °C also increased to 57 wt %. Cone calorimetry tests revealed that, compared to the control fabric, the peak of heat release rate (PHRR) and total heat release (THR) of FR-PAN decreased by 66% and 73%, respectively. These results indicated that sol-gel combined with layer-by-layer assembly technique could impart PAN fabric with satisfactory flame-retardant properties, showing an efficient flame retardant strategy for PAN fabric.

Durable flame retardant polyacrylonitrile fabric via UV-induced grafting polymerization and surface chemical modification.

To improve the flame retardancy of polyacrylonitrile (PAN) fabric, glycidyl methacrylate (GMA) was firstly grafted onto the surface of PAN fabric. Then, the GMA grafted PAN fabric (PAN-g-GMA) was chemically modified with hydrazine hydrate and phosphorus acid in sequence to obtain ammoniated PAN-g-GMA fabric (Am-PAN-g-GMA) and flame retardant PAN fabric (FR-PAN), respectively. The structures, thermal properties and combustion characteristics of the samples were researched in detail. The results indicate that the fire retardant PAN fabric has good char-forming ability. Cone calorimeter tests show that the total heat release (THR) of FR-PAN declines by 38.4%, while the peak heat release rate (PHRR) of FR-PAN decreases by 60.2%. Moreover, the total smoke production (TSP) and the peak smoke production rate (PSPR) of FR-PAN dropped from 1.5 m2 and 0.06 m2 s-1 for the control sample to 0.4 m2 and 0.01 m2 s-1, respectively, indicating excellent smoke repression performance. The LOI value of FR-PAN fabric was 29.3% after 30 washing cycles showing good washing resistance and excellent flame retardant durability.

4-Benzyl-4-ethyl-morpholin-1-ium hexa-fluoro-phosphate.

The asymmetric unit of the title compound, C(13)H(20)NO(+)·PF(6) (-), contains two cations, one complete anion and two half hexa-fluoro-phosphate anions having crystallographically imposed twofold rotation symmetry. In the cations, the morpholine rings are in a chair conformation. In the crystal, ions are linked by weak C-H⋯F hydrogen bonds into a three-dimensional network.

4-Benzyl-4-methyl-morpholinium hexa-fluoro-phosphate.

In the title compound, C(12)H(18)NO(+)·PF(6) (-), the asymmetric unit consists of two cation-anion pairs. The six F atoms of one anion are disordered over two sets of sites in a 0.592 (6):0.408 (6) ratio. The morpholinium rings adopt chair conformations.