Influence of alkaline metal ions on flame retardancy and thermal degradation of cellulose fibers

Cellulose-Na and cellulose-K fibers are obtained by alkalization and etherification of viscose fiber. Flame retardancy and thermal degradation of cellulose-Na and cellulose-K fibers are investigated using limiting oxygen index (LOI), cone calorimetry (CONE), thermal gravimetry (TG), and differential TG (DTG). The LOI values of cellulose-Na and cellulose-K fibers are 33 and 30, compared with about 20 for viscose fiber. In CONE studies, cellulose-Na and cellulose-K fibers show much lower heat release rates, total heat release and effective heats of combustion than viscose fiber does. In addition, TG and DTG studies reveal that the second initial degradation temperature, the temperature of maximum degradation rate and the maximum degradation rate for cellulose-Na and cellulose-K fibers are much lower than those of viscose fiber. Cellulose-Na and cellulose-K fibers generate much more residue or carbonaceous char than viscose fiber does. Scanning electron microscopy studies of combustion residues after LOI testing indicate that cellulose-Na and cellulose-K fibers produce massive, thick residue crusts.     

磷-氮-硼复合阻燃橡胶木的燃烧性能研究

采用磷酸二氢铵（DAP）和硼砂（SB）复配制备磷-氮-硼（P-N-B）复合阻燃剂,对橡胶木进行真空加压浸渍处理。通过极限氧指数（LOI）和锥形量热仪（CONE）测试不同配方阻燃剂处理橡胶木的燃烧性能。结果表明：P-N-B复合阻燃剂对橡胶木表现出较好的阻燃抑烟效果。载药率为10.67 wt%时,阻燃橡胶木的LOI值为52.3%,达到难燃或不燃材料标准;阻燃橡胶木的热释放速率降低约60%,热释放总量降低约50%,有效燃烧热明显降低,质量损失速率降低,总发烟量最高减少约97%,CO和CO₂生成总量降低95%以上。氮磷硼协效阻燃橡胶木达到建筑材料阻燃B1级,3种元素协同抑烟效果显著。     

Effect of boron phosphate on the mechanical, thermal and fire retardant properties of polypropylene and polyamide-6 fibers

The effect of boron phosphate (BPO₄) nanoparticles on the mechanical, thermal, and flame retardant properties of polypropylene (PP) and polyamide 6 (PA-6) fibers are investigated by tensile testing, thermogravimetric analysis (TGA), differential scanning calorimeter (DSC), and micro combustion calorimeter (MCC). The addition of BPO₄ reduces the mechanical properties of the both PP and PA-6 fibers. According to the TGA results, the addition of BPO₄ does not change the thermal behavior of PP fiber and slightly reduces the thermal stability of PA-6 fiber by about 30 °C. According to MCC results, the addition of BPO₄ does not change the effective total heat evolution and heat release rate (HRR) peak for PP fibers. Although the inclusion of BPO₄ does not change the total heat evolution of PA-6 fiber, it reduces the HRR peaks due to increase in barrier effect of char.     

Preparation and characterization of intumescent flame retardant biodegradable poly(lactic acid) nanocomposites based on sulfamic acid intercalated layered double hydroxides

A novel sulfamic acid intercalated MgAl-LDH (SA-LDH) was prepared by intercalating NH₃SO₃^? into MgAl-layered double hydroxides (LDH), and it was then introduced into poly(lactic acid) (PLA) resin in association with intumescent flame retardant (IFR) by melt blending to prepare a flame-retardant biodegradable PLA composite. The effects of SA-LDH on the flame retardancy of PLA composites were characterized by limiting oxygen index (LOI), vertical burning test (UL-94) and cone calorimeter test (CONE). The results showed that the composite sample containing 19.0 wt% IFR and 1.0 wt% SA-LDH achieved the maximal LOI value of 48.7 %, passed the UL-94 V-0 rating, and significantly decreased the peak heat release rate from 306.3 kW/m² of neat PLA to 58.1 kW/m². Thermogravimetric analysis showed that both the thermal stability and the char formation were enhanced. The char morphology observation revealed that SA-LDH was beneficial to form dense and compact char layers. It was demonstrated that there existed a synergistic effect between IFR and SA-LDH in promoting the char formation and enhancing the fire resistance. The mechanical and crystallization properties were also tested and discussed.     

Synthesis and Structure Properties of Flame Retardant and Cationic Dyeable Polyamide 6 Modified with 5-sulfoisophthalic Acid Sodium and Melamine Cyanurate

Unmodified polyamide 6 commonly dyed with acid dyes, and has no flame-retarded properties. So they are flammable and can be easily stained by foods or drinks that contain acid dyes. However, the acid groups react with amino groups that existed at the end of PA6 chain while using cationic dyes. Thus, the acid dyes can be washed immediately. In this study, the flame retardant and cationic dyeable polyamide 6 (FRCD-PA6) modified with 5-sulfoisophthalic acid sodium (5-SSIPA) and melamine cyanurate (MCA) was successfully prepared by the two-step-melt polymerization method. Firstly, cationic dyeable polyamide 6 (CD-PA6) was prepared with sodium salt from 5-sulfoisphthalic acid. Secondly, melamine cyanurate, as an efficient flame retardant, was blended into the reaction. The chemical and crystalline structures of FRCDPA6 were characterized by the Fourier transform infrared spectroscopy (FT-IR) and wide angle X-ray diffraction (XRD). Their thermal properties were tested by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), and morphology was analyzed by SEM, respectively. It had been measured to prove the dispersion of 5-SSIPA and MCA on polyamide 6 matrix. Incorporating with 5-SSIPA created more amorphous regions and rose up the dyeing rate easily, with a highest dyeing rate for about 96.79 %. The effect of varying MCA content on the composites showed more flame retardant and made better heat-resistance. Moreover, with the appropriate addition of MCA content, the limit oxygen index (LOI) reached up to 27, less smoking, no more black smoke, droplet phenomenon was slightly, and flame resistance had greatly improved. Because of the good synergy between 5-SSIPA and MCA, a kind of novel modified polyamide 6 which own both cationic dyeable and efficient flame retardant properties was born.     

Synthesis and Application of Phosphorus-containing Flame Retardant Plasticizer for Polyvinyl Chloride

A novel phosphorus-containing flame retardant plasticizer (PFRP) derived from castor oil acid methyl ester (COME) was synthesized to substitute dioctyl phthalate (DOP) for plasticizing polyvinyl chloride (PVC) products. The chemical structures of PFRP were confirmed by fourier transform infrared spectroscopy (FTIR) and ¹H nuclear magnetic resonance (¹H NMR). Meanwhile, the plasticizing effect, flammability and thermal stability of plasticized PVC films were investigated by dynamic mechanical analyzer (DMA), limiting oxygen index (LOI) test, scanning electron microscope (SEM) and thermogravimetric analysis (TGA). As the PFRP content increasing from 0 wt% to 50 wt% amount of plasticizers, the plasticizing efficiency and the mechanical properties showed a slightly decreasing tendency compared with that of DOP, while the LOI value of plasticized PVC increased remarkably from 21.5 % to 25.2 %, showing a combined plasticizing efficiency and flame retardancy. SEM and TGA analysis indicated that PFRP had little effect on thermal stability but was effective to promote the formation of compact carbon residue.     

A novel DDPSi-FR flame retardant treatment and its effects on the properties of wool fabrics

A novel flame retardant monomer DDPSi-FR containing organophosphorus and silicon was prepared using 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 4-hydroxybenzaldehyde (HBA), and 3-glycidoxypropyltrimethoxysilane (GPTMS). The chemical structure of DDPSi-FR was characterized by Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). Subsequently, after treating the wool fabrics, the effects of the monomer on the flame retardancy, thermal stability, and mechanical properties were studied. The flame retardant and thermal properties were evaluated by conducting vertical flame tests, limiting oxygen index (LOI) determination, and thermogravimetric analysis (TGA). The results showed that improved flame retardancy and thermal stability were achieved. Notably, the flame retardancy was retained even after 15 washing cycles. The mechanical properties were evaluated using the bursting strength, and the results indicated that DDPSi-FR treatment improved the breaking strength.     

Encapsulation of phase change materials by complex coacervation to improve thermal performances and flame retardant properties of the cotton fabrics

This paper reports a study on the thermal stability and flame-retardant properties of microencapsulated phase change materials (PCMs) with clay nano-particles (Clay-NPs) doped gelatin/sodium alginate shell. The novel microcapsules were fabricated by the technique of complex coacervation using gelatin and sodium alginate as the shell and PCM n-eicosane as the core. Their flame retardant property as well as their practicable thermal performances when incorporated into woven cotton fabrics by pad-dry-cure were investigated. Thermal storage/release properties of the prepared microcapsules were analyzed using DSC instrument. Thermal gravimetry (TG) analysis was performed to measure the thermal stability and surface morphology of the microcapsules was observed by means of optical microscopy and SEM. The DSC results indicated that the latent heat storage capacity of prepared microcapsules changed in range of 97-114 J/g. The microcapsules had spherical shape with particle sizes between 1.37 μm and 1.6 μm. The PCM microcapsules (PCMMs) and nano-composite PCM microcapsules (NCPCMMs) with clay-NPs doped gelatin/sodium alginate shell were found to have good potential for developing thermal comfort in textiles. Comparing with conventional PCMMs, NCPCMMs have significantly better thermal stability. Nano-composite structure of the NCPCMMs, in which clay-NPs doped in the polymeric shell structure, attributed to increase the shell thermal stability. Improved flame retardant properties of the cotton fabrics treated with NCPCMs were declared as a result of flame retardant tests. Thermo-regulating properties of the fabrics were proved by thermal history (THistory) measurement results from releasing heat from microcapsules.     

Properties of flame-retardant cellulose fibers with ionic liquid

Flame-retardant cellulose fibers were prepared by dissolving cellulose in tetrabutylammonium acetate and dimethyl sulfoxide, and blending with amino silicone oil (ASO). The ASO was used as a novel fabric softener and flame retardant for cellulose fibers. Fourier-transform infrared spectroscopy showed that blending with ASO did not adversely affect the cellulose fibers. The flame retardancy of the cellulose fibers blended with ASO was determined based on the limiting oxygen index (LOI). Cellulose fibers blended with 8 wt% (add-on) ASO gave the best flame retardancy, with an LOI of 28, which was higher than that of the virgin fibers. The thermal properties of the flame-retardant cellulose fibers were investigated using differential scanning calorimetry and thermogravimetric analysis. The results showed that ASO prevented degradation of the cellulose fibers, hindered the formation of volatile species, and favored char formation. The mechanical properties of the flame-retardant cellulose fibers were better than those of virgin cellulose fibers.     

Inherently Flame Retardant Nylon 6 Nanocomposite Fibers

In this study, inherently flame retardant nanocomposite nylon 6 fibers infused with nanoclay and intumescent additives were compounded and melt-spun. Two approaches were adopted to mitigate the loss of mechanical properties typically observed nanocomposite fiber systems: (a) additive particle size reduction; and (b) elastomer toughening of the nanocomposite system. As a result, the ductility of the FR nanocomposite formulations was improved significantly. Structural and morphological characterization of the melt-spun fibers using TEM and XRD demonstrated good dispersion of the additives and exfoliation of the nanoclay platelets. Microscale Combustion Calorimetry analysis demonstrated effective reduction of heat release capacity and thus significant enhancement of flame retardant performance of the compounded fibers.     

Effects of carbon nanotubes on morphological structure, thermal and flammability properties of electrospun composite fibers consisting of lauric acid and polyamide 6 as thermal energy storage materials

The ultrafine composite fibers consisting of lauric acid (LA) and polyamide 6 (PA6) as form-stable phase change materials (PCMs), were prepared successfully by electrospinning. The effect of carbon nanotubes (CNTs) on the structural morphology, phase change behaviors, thermal stability, flammability and thermal conductivity properties of electrospun LA/PA6 composite fibers was investigated by field-emission scanning electron microscopy (FE-SEM), differential scanning calorimetry (DSC), thermogravimetric analyses (TGA), microscale combustion calorimeter (MCC) and melting/freezing times measurements, respectively. SEM observations indicated that the LA/PA6 and LA/PA6/CNTs composite fibers possessed flat and ribbon-shaped morphologies, but the neat PA6 fibers had cylindrical shape with smooth surface; and the average fiber diameters for LA/PA6 composite fibers decreased generally with the addition of CNTs. DSC measurements indicated that the heat enthalpies of the composite fibers were lower that that of neat LA powders, while the amounts of CNTs had no appreciable effect on the phase change temperatures and heat enthalpies of the composite fibers. TGA results showed that the addition of CNTs increased the onset thermal degradation temperature, maximum weight loss temperature and charred residue at 700 °C of the composite fibers, attributed to the improved thermal stability properties. It could be found from MCC tests that there were two-step combustion processes for composite fibers, and corresponded respectively to combustion of LA and polymer chains (PA6) in composite fibers. The addition of CNTs reduced the peak of heat release rate (PHRR) of electrospun composite fibers, contributing to the decreased flammability properties. The improved thermal conductivity performances of LA/PA6/CNTs composite fibers was also confirmed by comparing the melting/freezing times of LA/PA6 composite fibers with that of neat LA powders. The results from the SEM observation showed that the composite fibers had no appreciable variations in shape and diameter after heating/cooling processes.     

Thermal degradation behaviors and fire retardant properties of poly(1,3,4-oxadiazole)s (POD) and poly(m-phenylene isophthalamide) (PMIA) fibers

Thermal degradation behaviors and fire retardant properties of poly(1,3,4-oxadiazole)s (POD) and poly(m-phenylene isophthalamide) (PMIA) fibers were investigated. The thermal gravimetric analysis (TGA) demonstrated that POD exhibited higher onset thermal degradation temperature (T_onset) than PMIA, exceeding nearly 80 °C. The thermal degradation kinetics, evaluated by the modified Coats-Redfern method, displayed that the apparent activation energy (E_a) of POD and PMIA fibers was similar when the conversion rate (α) ranges from 0.2 to 0.5, while with the α from 0.6 to 0.8, the E_a of POD was significantly lower than that of PMIA. The fire retardant performance of POD and PMIA fibers were evaluated by cone calorimeter under heat fluxes of 35, 50 and 75 kW/m², during which the temperature of the fibers were monitored by a thermocouple. Surprisingly, POD fibers showed inferior fire retardant performance in comparison with PMIA, with lower time to ignition (TTI) and higher peak heat release rate (PHRR). The origin of the different fire retardant properties of both fibers was revealed by analyzing the residual chars and gaseous products during thermal pyrolysis. The morphology confirmed that stable and compact chars can be formed in PMIA. In addition, the Fourier Transform Infrared Spectroscopy (FTIR) characterization of the residual char revealed that POD can form carbonaceous chars at the heat flux of 50 kW/m², while the heat flux of PMIA was 75 kW/m². The pyrolysis products characterized by pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) indicated that POD can be pyrolyzed completely at 600 °C, while the temperature of PMIA was 700 °C.     

Flame retardancy,Thermal and mechanical properties of Kenaf fiber reinforced Unsaturated polyester/Phenolic composite

Unsaturated polyester (UP) resin has been blended with phenolic resin (PF) resole type at various ratios to obtain a homogeneous blend with improved flame resistance compared to its parent polymers. The polymer blend was reinforced with 20 wt% kenaf using hand lay out technique. Fourier transform infrared spectroscopy (FT-IR) was used to characterize changes in the chemical structure of the synthesized composites. The thermal properties of the composites were investigated using thermogravimetric analysis (TGA). The thermal stability of UP/PF kenaf composites co-varies with the PF content, as shown by the degradation temperature at 50 % weight loss. The char yield of the composites increases linearly with PF content as shown by the TGA results. The flammability properties of the composites were determined using the limiting oxygen index (LOI) and UL-94 fire tests. The LOI increased with the PF content while the composites exhibit improved flame retardancy as demonstrated by UL-94 test. The mechanical and morphological properties of the composites were determined by tensile test and scanning electron microscopy (SEM), respectively. The tensile strength and the Young’s modulus of the blend/composites slightly decreased with increasing PF content albeit higher than PF/kenaf fiber composites.     

Syntheses of flame-retardant cellulose esters and their fibers

3-(Hydroxyphenylphosphinyl)-propanoic acid (3-HPP) esters of cellulose (HPP-Cellulose) were synthesized homogeneously in ionic liquid 1-butyl-3-methylimidazoliumchloride by in situ activation. The chemical structure of the cellulose esters is characterized by FTIR and NMR. The degree of substitution was easily controlled within 0.38-1.51 by varying the molar ratio of 3-HPP/anhydroglucose unit, reaction time, and temperature. All the products showed excellent solubility in common organic solvents. The results of TGA, DTG, LOI, and cone calorimeter test show that 3-HPP has a positive influence on the thermal properties and flame retardance of cellulose. Based on the volatilized products analysis by TGA-IR, the presence of 3-HPP reduces the intensity of volatilized product and accelerates the dehydration action. Moreover, the addition of cellulose (3 wt%) is beneficial to prepare HPP-Cellulose fibers using a dry-wet spinning technique, and the blended fibers possess good mechanical properties as well as flame resistance.     

Flame retardant properties of triazine phosphonates derivative with cotton fabric

The flame retardant behavior of cotton fabric treated with phosphorus-nitrogen containing triazine compound was evaluated. It was found that cyanuric chloride (2,4,6-trichloro-1,3,5-triazine) is an excellent starting material for the preparation of phosphonate flame retardants that interact well with cotton to improve flame resistance (FR) performance. Tetraethyl 6-chloro-1,3,5-triazine-2,4-diyldiphosphonate (TECTDP) has been prepared by a simple one-step reaction in high yield (98.0 %). Cotton fabrics treated with TECTDP result in covalent bond formation between TECTDP and hydroxyl groups in cotton fabrics. This FR system provides an efficient flame retardant for cotton textiles at low cost to meet government mandates. In this study, the FR material was synthesized and characterized by ¹H and ¹³C nuclear magnetic resonance (NMR), and LC-MS spectroscopy. The chemical structure of cotton twill fabric treated with TECTDP by pad-dry-cure method was analyzed by FT-MIR and SEM. Furthermore, the thermal and flammability properties were evaluated by thermogravimetric analysis (TGA), limiting oxygen index (LOI, ASTM D-2863-09), and a vertical flame test (ASTM D-6413-08).     

Multifunctional,Hydrophobic and Flame-retarded Cotton Fabrics Modified with Liner Piperzine/Phosphorous/Polysiloxane Copolymer

α,ω-di[(4-butoxy-piperazin-1-yl)-phosphinic acid methyl ether]-terminated linear polysiloxane (PNPDMS) was synthesized and utilized as the flame retardant and hydrophobing agent. The flame retardance and thermal decomposition behaviors of cotton fabrics were systematically estimated by limiting oxygen index (LOI), thermogravimetric analysis and vertical burning test, respectively. It was found that the LOI of cotton fabric treated with PNPDMS enhanced to 29.82 % compared with cotton fabric without treatment, whose LOI was only 18.00 %. The treated cotton fabric showed a shorter char length, a shorter After-flame time, and no After-glow time as revealed in vertical burning test. The mechanical property in treated cotton fabric was slightly decrease. Furthermore, the grade of water repellency of treated cotton fabric reached to 90 and water contact angle (WCA) increased to 141.90° compared with cotton fabric without treatment whose WCA was 62.80°. The result showed that the cotton fabric treated with PNPDMS exhibited excellent flame retardance and hydrophobic properties.     

Preparation and characterization of fire resistant PLA fibers with phosphorus flame retardant

The fire resistant poly(lactic acid) fibers with polysulfonyldiphenylene phenyl phosphonate flame retardant were prepared by melt spinning. The rheology property and spinnability of samples were measured by a capillary rheometer and recording the number of fiber breakage during a 30-min melt spinning. The thermal stability and combustion behaviors of fibers were investigated by Thermogravimetric Analysis, Limiting Oxygen Index and Vertical Burning tests, respectively. It was found that the flame retardation and anti-dripping performance of PLA were distinctly improved by OP. The pyrolysis behavior of fibers was tested by a Pyrolysis-Gas Chromatography-Mass Spectrometry, the structure and degree of graphitization of char residue were analyzed by Scanning Electronic Microscopy and Raman Spectroscopy. The results suggested that OP can promote the forming of char layer on the surface of PLA matrix during burning. The miscibility and spinnability of PLA was negatively affected by OP and the breaking strength of FR-PLA fibers dropped from 3.30 to 2.30 cN/dtex at the presence of 10 wt. % OP.     

Investigation of the effect of cupric chloride on thermal stabilization of polyamide 6 as carbon fiber precursor

An investigation on the role of cupric (Cu²⁺) ion incorporation during the thermal stabilization of polyamide 6 fibers was carried out using a combination of differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and X-ray diffraction (XRD) measurements. Cupric chloride pretreated and thermally stabilized polyamide 6 (PA6) fibers was characterized by a reduction in fiber diameter and linear density values together with color changes from light brown to black with increasing stabilization time. PA6 fibers were properly stabilized after 8 h of stabilization time prior to carbonization. The results obtained from DSC and TGA measurements indicated that there was an improvement in the thermal stability when cupric (Cu²⁺) ions were incorporated into the polymer structure. TGA thermograms showed the relative improvement in thermal stability as indicated by increasing char yield with progressing time. Char yield reached a maximum value of 33.6 % at 1000 °C for the cupric chloride pretreated PA6 fibers stabilized for 12 h at 180 °C. Experimental results obtained from DSC and X-ray diffraction methods suggested the loss of crystallinity as a result of perturbation of hydrogen bonds with progressing time. The formation of cupric ion-amide coordination bonds improved the thermal stabilization by encouraging the development of ladder-like structures. The investigation resulted in a new method of evaluation of X-ray stabilization index specifically intended for the thermally stabilized PA6 fiber.     

Effects of the reaction degree of melamine-formaldehyde resin on the structures and properties of melamine-formaldehyde/polyvinyl alcohol composite fiber

Composite fibers made of polyvinyl alcohol (PVA) and melamine-formaldehyde (MF) resins with different reaction degrees were prepared by wet spinning. The phase structures of MF/PVA spinning dopes and composite fibers were observed by using optical microscope (OM) and scanning electron microscope with energy-dispersive X-ray spetroscopy (SEM-EDS). Crystal structures of composite fibers were studied by X-ray diffraction (XRD) and differential scanning calorimetry (DSC). The loss of MF resins in the spinning process was calculated by using Kjeldahl. The mechanical properties, the flame retardant property, the water resistant property, and the thermal stability of composite fibers were also tested. Results show that with an increase in the reaction degree of MF resin, the phase separation degrees of spinning dopes and composite fibers rise up, the size of MF microphase grows larger, and the loss of MF resin diminishes; consequently, the hot water resistance and the flame retardancy of the fiber ameliorate while the tensile strength and the thermal stability perform a tendency of dropping after rising.     

Dimensional,physical and thermal comfort properties of plain knitted fabrics made from modal viscose yarns having microfibers and conventional fibers

The dimensional, some physical and thermal comfort properties of the plain knitted fabrics having modal viscose microfibers in three different stitch lengths are investigated in comparison with the similar fabrics having conventional modal viscose fibers. The fabrics made from microfibers and conventional fibers exhibit different dimensional properties. The stitch density results and the dimensional constants calculated at the fully relaxed state reveal that the fabrics with microfibers tend to have lower shrinkage tendency than those with conventional fibers. The statistical results show that the fiber type (or fiber fineness) and the stitch length affect the some physical properties and all of the thermal comfort properties of the fabrics significantly. The bursting strength values of the fabrics with microfibers are observed to be slightly higher than those of the fabrics with conventional fibers. However, the difference between the bursting strength values of these fabrics is found to be statistically unimportant. The fabrics with microfibers reveal lower thickness and air permeability and, higher pilling tendency than those with conventional fibers. It is also observed from the thermal comfort results that the fabrics made from microfibers have higher thermal conductivity, thermal absorptivity and maximum heat flux values and, lower thermal resistance and thermal diffusivity values. Because of the higher thermal absorptivity and maximum heat flux values, the fabrics from microfibers provide cooler feeling when compared with those from conventional fibers.