Thermogravimetric Studies of Deposited Potash Impregnated for Flame-Retardancy into a Cotton Fabric

The effect of potash as a nondurable finish on the flammability of 100% cotton fabric （plain 180 g/m^2） was investigated. The bone-drled weighed fabrics were dipped into suitable concentrations of potash, with a volume of 100 mL at 20-2℃. The impregnation was followed by means of squeeze rolls and drying at 110 ℃. The samples were then reweighed with analytical precision. After conditioning overnight by using our ＂vertical flame tester＂ the optimum add-on values to impart flame-retardancy to cotton fabric was determined and expressed by 0.80 g of potash per 100 g fabric to be an efficient addition. Thermogravimetric analysis of pure cotton, treated cotton with potash at its optimum efficiency for donation of flame-retardancy into cotton fabric was fulfilled and the thermograms were compared and commented. The effectiveness of this hydroxide was attributed to the heat dissipation by the remaining consumed material during the combustion. The results obtained are in favor of ＂Dust or Wall Effect Theory＂.     

Flame‐retardancy of a Cellulosic Fabric by the Application of Synergistic Effect between Ammonium Bromide and Antimony(III) Oxide

The synergistic effect between ammonium bromide and antimony(III) oxide as a nondurable finish on the flammability of 100% woven plain cotton fabric (with a density of 144 g/m2, the number of yarns 21 per 10 mm), has been investigated in this study. The laundered totally-dried, weighed specimens were impregnated with suitable concentration individual aqueous ammonium bromide and/or antimony(III) oxide suspension solutions and some sets were impregnated with appropriate admixed solutions of the both chemicals. A vertical flame spread test was then carried-out to characterize the flammability of the samples. An acceptable synergistic effect was then experienced by using an admixed bath containing 0.1 molar ammonium bromide and 0.05 unit formal antimony trioxide solutions for impartation of flame-retardancy to a cotton fabric. The optimum mass of the mixture required to impart flame-retardancy was about 3.64 g of anhydrous additives per 100 g of fabric. The results obtained are in favor of Wall Effect Theory. Moreover synergistic effect indicating dehydration of the treated substrate by using this combination via thermogravimetry could be deduced.     

TG studies of synergism between red phosphorus (RP)–calcium chloride used in flame-retardancy for a cotton fabric favorable to green chemistry

The combined effect between calcium chloride and red phosphorus (RP) on the flame-retardancy of a cotton fabric (woven construction massing 152 g/m²) has been studied in this work. The laundered bone-dried massed samples were impregnated with suitable concentrations of individual aqueous red phosphorus suspensions and/or calcium chloride solutions and some bunches were impregnated with appropriate admixed solutions of the both chemicals. An acceptable synergistic effect was then experienced by using an admixed bath containing 0.20 F red phosphorus and 0.20 M calcium chloride for impartation of flame-retardancy to a cotton fabric. By using a vertical flame spread test the optimum mass of the mixture needed to donate flame-retardancy was obtained to be about 5.88 g anhydrous additives per 100 g dry fabric. Thermogravimetry (TG/DTG) results concerning untreated and treated cotton fabrics at the optimum addition were obtained and their curves were compared and commented, fortifying the flame spread tests outcomes. It can be deduced that the applied treatment functioned as a catalyst at the combustion’s temperature of the polymeric substrate and, thermosensibilized the combustion process. This synergism is in favor of green chemistry as well as the economical and industrial view points.     

表面化学接枝改性阻燃棉织物的制备与性能

采用高碘酸钠对棉织物表面进行选择性氧化生成醛基,选取乙二胺与醛基反应,通过膦氢化加成反应将阻燃剂亚磷酸二甲酯接枝到棉织物表面,最后通过三羟甲基三聚氰胺对棉织物表面进行接枝改性,制备了含三羟甲基三聚氰胺/乙二胺/亚磷酸二甲酯阻燃棉织物.通过傅里叶红外光谱（FTIR）对改性后棉织物的结构进行了表征,通过极限氧指数（LOI）测试研究了其阻燃性能,通过锥形量热测试研究了其燃烧行为,通过在40℃皂水中洗涤10次考察了其耐水性能,通过扫描电子显微镜测试了其表面及燃烧后炭层的形貌.研究结果表明,经表面改性后,棉织物的LOI值由（19.5±1.0）%提高到了（43.1±1.0）%,经耐水洗测试后,LOI值仅下降至（42.6±1.0）%,保持了非常好的阻燃性能,表明通过表面接枝方法制备的三羟甲基三聚氰胺/乙二胺/亚磷酸二甲酯阻燃棉织物具有非常好的耐水洗性能.表面阻燃改性提高了棉织物在燃烧过程中的成炭性能,形成的连续膨胀的炭层较好地保护了内部织物,抑制了织物的降解和燃烧,从而提高了棉织物的阻燃性能.     

Synthesis and Characterization of Nano‐sized Zinc Oxide Coating on Cellulosic Fibers: Photoactivity and Flame‐retardancy Study

We have investigated the effect of zinc oxide as a photocatalyst and durable flame‐retardant on cellulosic fibers. Zinc oxide nanocrystals were successfully synthesized and deposited onto cellulosic fibers using sol‐gel process at low temperature. The samples were characterized by means of several techniques such as scanning electron microscopy, transmission electron microscopy, diffuse reflectance spectroscopy, X‐ray diffraction and thermogravimetric analysis. The photocatalytic activity was tested by measuring the photodegradation of methylene blue under UV‐Vis illumination. Moreover, flame‐retardancy was tested by vertical flame spread test. The optimum add‐on value for donating flame‐retardancy onto cellulosic fabric was obtained to be in the range of 15.24 to 23.20 g of the ZnO per 100 g of fabric. Thermogravimetric analysis of pure and flame‐retarded samples were accomplished and discussed. The results obtained are in agreement with Wall effect theory and Coating theory. The originality of this work on introducing photoactive flame‐retarded fibers is highly valuable for industrial implementation.     

An amino trimethylene phosphonic acid-based chelated boric acid complex that works as a synergistic flame retardant for enhancing the flame retardancy of cotton fabrics

The chelating ligands of boric acid and amino trimethyl phosphonate prepared a novel flame retardant (BAP) for the cotton fabric. A stable chemical and coordination bond was formed on the surface of the cotton fibers by a simple three-curing finishing process to make the fabric exhibits excellent durable flame retardancy. Cotton fabrics' tensile strength and whiteness got substantially retained after BAP treatment. 90 g/L BAP-treated samples (3 curing times, 50 laundry cycles) showed good flame retardancy and durability, holding the largest limit oxygen index, 29.7%, and the shortest damage length, 61 mm. A condensed phase and gas phase synergistic flame retardant mechanism was concluded by thermogravimetric, cone calorimeter tests, and thermogravimetric infrared analysis.     

The effect of phosphorus content on the thermal and the burning properties of cotton fabric coated with an ultrathin film of a phosphorus-containing polymer

The effect of phosphorus content on thermal degradation and burning behavior of poly(acryloyloxyethyl diethyl phosphate) or PADEP-coated cotton was studied. The results showed that PADEP-coated cotton prepared by admicellar polymerization using hexadecyltrimethylammonium bromide (HTAB) as a surfactant has higher amounts of phosphorus than that prepared using dodecyltrimethylammonium bromide (DTAB). Higher phosphorus content led to lower decomposition temperatures and greater amounts of char formation after thermal degradation. The effectiveness of the amount of phosphorus on the burning behavior of the treated cotton was investigated by an ASTM flammabilty test. In the case of PADEP-coated cotton prepared with DTAB, the flame spread slowly and extinguished with char formation on the fabric. For untreated cotton however, the flame spread quickly and burned the fabric entirely without char formation. Cotton coated with PADEP using HTAB exhibited self-extinguishing behavior after removing the ignition source. Decrease in decomposition temperature, increase in char formation and the burning behavior of PADEP-coated cotton are all consistent with phosphorus content on the treated fabric.     

Effect of hybrid phosphorus-doped silica thin films produced by sol-gel method on the thermal behavior of cotton fabrics

The aim of this work was to prepare hybrid organic-inorganic silica thin films to provide cotton fabrics with flame retardant properties and to investigate the films’ influence on the thermal and burning behavior of the treated samples. The fabrics were modified with three different sols in order to study the effect of pure silica sol-gel precursor, γ-aminopropyltriethoxysilane (APTES), and that of the hybrid sols consisting of the APTES and the phosphorus compound diethylphosphite. Furthermore, in order to improve the cross-linking degree and the phosphorus-nitrogen synergistic effect on flame retardancy of the P-doped silica thin film the melamine-based resin was added in the third sol. To evaluate the chemical structure of the coating material, pure xerogels of the treatment solutions were applied to glass slides and tested by ATR FT-IR spectroscopy. The cotton fabrics were impregnated with the sols by a padding-squeezing process and then dried. Thermal behavior of the treated cotton samples was investigated by thermogravimetric/differential scanning calorimetry analysis (TGA-DTG/DSC) and compared to the untreated one. The flame retardancy was tested according to the ASTM D 1230 standard method. The results showed a substantial enhancement of char-forming properties and flame retardancy for the fabrics modified with the thin films.     

TG comparison between the efficiency of deposited ammonium bromide and ammonium chloride on the flame-retardancy imparted to cotton fabric

This study investigates the effect of ammonium bromide and/or ammonium chloride as nondurable finishes on the flammability of 100% cotton fabric, (woven construction, weighing 144 g m⁻²). The laundered bone-dried, weighed fabrics were impregnated with suitable concentrations of aqueous ammonium bromide and/or ammonium chloride solutions by means of squeeze rolls and dried at 110°C for 30 min. Afterwards they were cooled in a desiccator, re-weighed with an analytical precision and kept under ordinary conditions before the fulfillment of the vertical flame test. The optimum add-on values to impart flame retardancy expressed in g anhydrous ammonium bromide and ammonium chloride per 100 g fabrics were individually obtained to be about 3.5–3.89 and 17.31–17.99%, respectively. Thermogravimetric analysis (TG/DTG) of pure cotton and the salts treated fabrics were fulfilled and their curves were compared and commented. The results obtained comply with free radical theory, and also proved the superiority of ammonium bromide for the impartation of flame-retardancy in regard to ammonium chloride.     

The comparison of differences in flammability and thermal degradation between cotton fabrics treated with phosphoramidate derivatives

The effectiveness of a phosphoramidate tetraethyl piperazine‐1,4‐diyldiphosphoramidate (TEPP) as a flame retardant on cotton twill fabrics was compared with that of a previously studied diethyl 4‐methylpiperazin‐1‐ylphosphoramidate (DEPP). TEPP was formed in a reaction between two phosphonates and a piperazine then cotton twill fabrics were treated with TEPP at different levels of add‐on (2–19 wt%) and characterized using vertical flammability, limiting oxygen index, microscale combustion calorimetry, and thermogravimetric analysis methods. The results showed better flame retardancy and thermal behavior for TEPP fabrics when compared with DEPP fabrics. When the morphological structure of the formed char from the burned areas was examined by scanning electron microscopy, the results revealed a fairly insignificant difference in the mode of action between the two types of fabric. Copyright © 2014 John Wiley & Sons, Ltd.     

Thermal behavior and fire performance of nylon-6,6 fabric modified with acrylamide by photografting

Our previous study shows that surface photografting modification with maleic anhydride followed by reacting with triethanolamine can improve the flame retardancy of nylon-6,6 fabric. In this study, acrylamide was used as a grafting monomer to improve the flame retardancy of nylon-6,6 fabric. The effects of monomer concentration and irradiation time on photografting were investigated. The surface structure of the sample was analyzed by attenuated total reflection infrared spectroscopy (ATR-FTIR). Flame retardancy was characterized by limiting oxygen index test (LOI), the vertical burning test and cone calorimeter. The grafted sample has a higher LOI value than the untreated sample, and has no melting drip during the vertical burning test. The improvement of the flame retardancy and char formation of the nylon-6,6 fabric have also been verified by the thermogravimetric analysis (TGA) and scanning electron microscopy (SEM) analysis.     

Red phosphorus acts as second acid source to form a novel intumescent-contractive flame-retardant system on ABS

A novel halogen-free flame retardant prepared by poly(p-ethylene terephthalamide) and ammonium polyphosphate (APP) on acrylonitrile–butadiene–styrene (ABS) resin has a good flame retardancy when loading is 30 %; but, once the mass fraction is <30 %, the system does not maintain outstanding flame retardancy. To improve the efficiency of this kind of flame retardant and LOI values, higher thermal stability acid source-red phosphorus is introduced. It is found that a little quantity of red phosphorus will improve the flame retardancy of ABS remarkably and will change the process of charring; when the mass fractions of APP, PPTA, and red phosphorus are only 15, 5, and 2 %, respectively, though the LOI of flame-retardant ABS is 27, UL-94 vertical burning test still reach V-0. Thermogravimetric analysis data show that red phosphorus changes the thermal degradation behavior of IFR-ABS system, shrink digital photo display system, and yield more stable residue at higher temperature; Fourier transform infrared results and scanning electron microscopic micrographs show that red phosphorus can catalyze the charring and form much denser char to improve the flame-retardant performance of the materials.     

Layer-by-layer assembled thin films based on fully biobased polysaccharides: chitosan and phosphorylated cellulose for flame-retardant cotton fabric

Polyelectrolytes multilayer (PEM) films based on fully biobased polysaccharides, chitosan and phosphorylated cellulose (PCL) were deposited on the surface of cotton fabric by the layer-by-layer assembly method. Altering the concentration of PCL could modify the final loading on the surface of cotton fabrics. A higher PCL concentration (2 wt%) could result in more loading. Attenuated total reflection Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and energy-dispersive X-ray analysis directly showed that chitosan and PCL were successfully deposited onto the surface of cotton fabric. In the vertical flame test, the cotton fabric with 20 bilayers at the higher PCL concentration (2 wt%) could extinguish the flame. Microcombustion calorimetry results showed that all coated cotton fabrics reduced the peak heat release rate (HRR) and total heat release (THR) relative to the pure one, especially for (CH0.5/PCL2)₂₀, which showed the greatest reduction in peak HRR and THR. Thermogravimetric analysis results showed that the char residue at temperatures ranging from 400 to 700 °C was enhanced compared to that in the pure cotton fabric, especially in the case of higher PCL concentration (2 wt%). The work first provided a PEM film based on fully biobased polysaccharide, chitosan and PCL on cotton fabric to enhance its flame retardancy and thermal stability via the layer-by-layer assembly method.     

Development of an environmentally friendly halogen‐free phosphorus–nitrogen bond flame retardant for cotton fabrics

A novel flame retardant diethyl 4‐methylpiperazin‐1‐ylphosphoramidate (CN‐3) containing phosphorous and nitrogen was prepared. Its chemical structure was confirmed by nuclear magnetic resonance (¹H‐, ¹³C‐, and ³¹P‐NMR), Fourier transform infrared spectroscopy, and elemental analysis. Print cloth and twill fabrics were treated with CN‐3 to achieve different levels of add‐on (7–22 wt% add‐ons for print cloth and 3–18 wt% add‐ons for twill). Thermogravimetric analysis, vertical flame test, and limiting oxygen index (LOI) were performed on the treated cotton fabrics and showed promising results. When the treated print cloth and twill fabric samples were tested using the vertical flame test (ASTM D6413‐08), we observed that the ignited fabrics self‐extinguished and left behind a streak of char. Treated higher add‐ons fabrics were neither consumed by flame nor produced glowing ambers upon self‐extinguishing. LOI (ASTM 2863–09) was used to determine the effectiveness of the flame retardant on the treated fabrics. LOI values increased from 18 vol% oxygen in nitrogen for untreated print cloth and twill fabrics to maximum of 28 and 31 wt% for the highest add‐ons of print cloth and twill, respectively. The results from cotton fabrics treated with CN‐3 demonstrated a higher LOI value as well as a higher char yield because of the effectiveness of phosphorus and nitrogen as a flame retardant for cotton fabrics. Furthermore, FT‐IR and SEM were used to characterize the chemical structure on the treated fabrics as well as the surface morphology of char areas of treated and untreated fabrics. Published 2012. This article is a US Government work and is in the public domain in the USA.     

Flame‐retardant performance and mechanism of epoxy thermosets modified with a novel reactive flame retardant containing phosphorus,nitrogen, and sulfur

A novel phosphorus‐containing, nitrogen‐containing, and sulfur‐containing reactive flame retardant (BPD) was successfully synthesized by 1‐pot reaction. The intrinsic flame‐retardant epoxy resins were prepared by blending different content of BPD with diglycidyl ether of bisphenol‐A (DGEBA). Thermal stability, flame‐retardant properties, and combustion behaviors of EP/BPD thermosets were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), limited oxygen index (LOI) measurement, UL94 vertical burning test, and cone calorimeter test. The flame‐retardant mechanism of BPD was studied by TGA/infrared spectrometry (TGA‐FTIR), pyrolysis‐gas chromatography/mass spectrometry (Py‐GC/MS), morphology, and chemical component analysis of the char residues. The results demonstrated that EP/BPD thermosets not only exhibited outstanding flame retardancy but also kept high glass transition temperature. EP/BPD‐1.0 thermoset achieved LOI value of 39.1% and UL94 V‐0 rating. In comparison to pure epoxy thermoset, the average of heat release rate (av‐HRR), total heat release (THR), and total smoke release (TSR) of EP/BPD‐1.0 thermoset were decreased by 35.8%, 36.5% and 16.5%, respectively. Although the phosphorus content of EP/BPD‐0.75 thermoset was lower than that of EP/DOPO thermoset, EP/BPD‐0.75 thermoset exhibited better flame retardancy than EP/DOPO thermoset. The significant improvement of flame retardancy of EP/BPD thermosets was ascribed to the blocking effect of phosphorus‐rich intumescent char in condensed phase, and the quenching and diluting effects of abundant phosphorus‐containing free radicals and nitrogen/sulfur‐containing inert gases in gaseous phase. There was flame‐retardant synergism between phosphorus, nitrogen, and sulfur of BPD.     

Self-extinguishing cotton fabric with minimal phosphorus deposition

The phosphorus-containing acrylate monomer, 2-acryloyloxyethyl diethyl phosphate (ADEP), was synthesized and applied to cotton fabric by using the admicellar polymerization technique. A cationic surfactant (cetylpyridinium chloride, CPC) was used as the surfactant for admicellar polymerization. Results from FTIR-ATR and SEM showed that PADEP polymer film was successfully formed on the cotton fabric surface. TGA and DTG analyses showed that the phosphorus-containing PADEP lowered the decomposition temperature of the treated fabric resulting in a higher char yield than in the case of untreated cotton. The flammability tests showed that PADEP-coated cotton with the phosphorus content 4.18 mg/g cotton was self-extinguishing, with the flame extinguishing right after the removal of the ignition source leaving a small area of char formation.     

Dynamic and controlled rate thermal analysis of attapulgite

We have investigated the effect of magnesium chloride hexahydrate [MgCl₂·H₂O] as a nondurable finish on the flammability of 100% woven cotton fabric, (plain construction, with a density of 144 g m⁻², the number of yarns 21/10 mm). The laundered bone-dried, massed fabrics were impregnated with suitable concentrations of aqueous solution of the above-mentioned salt, by means of squeeze rolls. They were then dried horizontally in an oven at 110°C for 30 min. The optimum add-on value after the fulfillment of vertical flame spread test to donate flame-retardancy onto cotton fabric was obtained to be in the range of 6.73–8.30 g of the salt per 100 g fabric. Thermogravimetry (TG) of pure cotton, treated cotton and the salt was accomplished, and their TG curves were compared and commented. The results obtained are in favor of the ‘gas dilution theory’, chemical action theory and also in compliance with the ‘free radical theory’. The formation of sal ammoniac was proven by sprinkling concentrated ammonia upon the inflamed treated specimen.     

TG of a cotton fabric impregnated by sodium borate decahydrate (Na2B4O7·10H2O) as a flame-retardant

The effect of sodium borate decahydrate as a nondurable treatment on the flammability of 100% cotton fabric (woven plain 150 g m⁻²) has been investigated in this paper. The laundered bone-dried massed samples were impregnated with suitable concentrations of sodium borate decahydrate. Each bunches of fabrics were dipped into individual aqueous solutions of the salt, followed by means of squeeze rolls and drying at 110°C. By using a ‘vertical flame spread test’ the optimum add-on values to impart flame-retardancy onto cotton fabric was determined to be as 4.24 g salt per 100 g fabric. The objective of this study is thermogravimetry (TG) investigation of pure cotton, treated one with the salt at its optimum efficiency. So that outcomes could be compared and commented, finally the results obtained are in favor of ‘Chemical action theory’, ‘Condensed phase retardation’, ‘Dust or wall effect theory’ and also ‘Gas dilution theory’.     

Tailoring of multifunctional cellulose fibres with “lotus effect” and flame retardant properties

This research aimed to create multifunctional cellulose fibres with water- and oil-repellent, self-cleaning, and flame retardant properties. A sol mixture of fluoroalkyl-functional siloxane, organophosphonate and methylol melamine resin was applied to cotton fabric by the pad-dry-cure method. Successful coating was verified by atomic force microscopy and Fourier transform infrared spectroscopy. The functional properties of the coated fibres were investigated using the static contact angles of water and n-hexadecane, the water sliding angles, the vertical test of flammability, the limiting oxygen index, and simultaneous thermal analysis. The results reveal that a homogeneous composite inorganic–organic polymer film formed on the cotton fabric surface exhibited the following properties: static contact angle of water of 150° and of n-hexadecane of 128°, water sliding angle of 10°, limiting oxygen index of 34 %, and high thermal stability. These results demonstrate the synergistic activity of the compounds in the coating, which resulted in the creation of a “lotus effect” on the fabric surface as well as excellent flame retardancy and thermal stability.     

Comparison of different reactive organophosphorus flame retardant agents for cotton. Part II: Fabric flame resistant performance and physical properties

N-Methylol dimethylphosphonopropionamide (MDPA) is one of the most commonly used durable flame retardant agents for cotton. In our previous research, we developed a new flame retardant finishing system based on a hydroxy-functional organophosphorus oligomer (HFPO) and bonding agents, such as dimethyloldihydroxyethyleneurea (DMDHEU) and trimethylolmelamine (TMM). In this research, we compared the flame resistant performance as well as physical properties of the cotton fabric treated with these two flame retardant finishing systems. The cotton fabric treated with MDPA/TMM has a higher initial limiting oxygen index (LOI) than that of the fabric treated with HFPO/TMM due to higher nitrogen content in the system. The LOI of the cotton fabric treated with the HFPO and MDPA systems becomes identical when the treated fabric contains equal amount of phosphorus and nitrogen. The MDPA/TMM shows higher laundering durability on cotton than HFPO/TMM system. The fabric treated with HFPO/TMM and MDPA/TMM has low wrinkle resistance and low strength loss whereas the fabric stiffness significantly increases when the TMM concentration is increased.