A Thermogravimetric Study of Cotton Fabric Flame‐Retardancy by Means of Impregnation with Red Phosphorus

The effect of red phosphorus was found to be effective for flame‐retardancy of a pure cotton fabric. The laundered bone‐dried weighed samples were impregnated with red phosphorus at suitable concentrations. Vertical flame spread test was accomplished. The optimum add‐on value to impart flame‐retardancy onto cotton fabric was determined around 3.95 g of red phosphorus per 100 g of fabric. TG/DTG curves of treated samples showed a well‐timed weight loss occurred with regard to untreated specimens. This illustrates the sufficiency of impregnation and support its catalytic action on flame‐retardancy, which is compliance with data obtained via flammability test. The results are in favor of "Chemical Action Theory", "Gas Theory" and "Condensed Phase Retardation".     

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.     

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 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’.     

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.     

Thermogravimetry of deposited caustic soda used as a flame-retardant for cotton fabric

We have investigated the effect of caustic soda as a nondurable finish on the flammability of 100% cotton fabric (plain 180 g m^?2). On the contrary to the mercerization, during the impregnation process, no tension was applied. In order to attain the alkali cellulose onto the fabric, the subsequent neutralization was not followed. Each bunches of fabrics were dipped into individual aqueous solutions of sodium hydroxide, followed by means of squeeze rolls and drying at 110°C. After conditioning nightlong, by using our ‘vertical flame test’ the optimum add-on values to impart flame-retardancy into cotton fabric was determined as 1.3 g sodium hydroxide per 100 g fabric. Thermogravimetry and derivative thermogravimetry (TG/DTG) of pure cotton, treated cotton with sodium hydroxide at its optimum efficiency to impart flame-retardancy into the fabric was fulfilled and the obtained curves were compared and commented. The effectiveness of this hydroxide is attributed to the heat dissipation by the remaining material in the consumed ash. The results obtained are in favour of ‘dust or wall effect theory’ and also gas dilution theory.     

XRD characterization of the ashes from a burned cellulosic fabric impregnated with magnesium bromide hexahydrate as flame-retardant

The effect of magnesium bromide hexahydrate [MgBr₂·6H₂O] as a nondurable finish on the flammability of 100% cotton fabric, (woven construction, massing 150 g m⁻²) has been investigated. The laundered bone-dried, massed fabrics were impregnated with various concentrations of the aqueous above-mentioned salt solutions by means of squeeze rolls and drying in an oven at 110°C for 30 min. The specimens were then cooled in a desiccator, re-massed with an analytical balance and kept under standard conditions before the fulfillment of the vertical flame spread test. After several experiments the optimum add-on values to impart flame-retardancy expressed in g anhydrous magnesium bromide hexahydrate per 100 g fabric were determined to be about 5.6%. The ashes of the treated specimens were subjected to X-ray diffraction analysis (XRD), and the result was compared with data for pure MgO powder and/or MgBr₂ specimens. Consequently the existence of MgO was detected in the ashes.     

Synthesis and characterization of a novel phosphorus–nitrogen‐containing flame retardant and its application for textile

The economic and environmentally friendly flame‐retardant compound, tetramethyl (6‐chloro‐1,3,5‐triazine‐2,4‐diyl)bis(oxy)bis(methylene) diphosphonate ( CN‐1 ), was synthesized by a simple two‐step procedure from dimethyl phosphate, and its chemical structure was characterized by ¹H, ¹³C, and ³¹P nuclear magnetic resonance and gas chromatography mass spectroscopy. Using the traditional pad–dry–cure method, we obtained several different add‐ons (wt%) by treating cotton twill fabric with flame retardant ( CN‐1 ). Thermogravimetric analysis, in an air and nitrogen atmosphere, of the modified cotton showed that decomposition occurred ~230°C with 16% residue weight char yield at 600°C, indicating high thermal stability for all treated levels. Limiting oxygen index (LOI) and the vertical flammability test were employed to determine the effectiveness of the flame‐retardant treatments on the fabrics. LOI values increased from ~18 vol% oxygen in nitrogen for untreated fabric to maximum of 34 vol% for the highest treatment level. Fabrics with higher levels of flame retardant also easily passed the vertical flammability test. Furthermore, Fourier transform infrared and scanning electron microscopy were utilized to characterize the chemical structure as well as the surface morphology of the flame‐retardant treated twill fabrics, including char area and the edge between unburned fabric and char area. Copyright © 2011 John Wiley & Sons, Ltd.     

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.     

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.     

Thermogravimetric analysis of polyester/cotton blends treated with Thpc-urea-poly(vinyl bromide)

Polyester/cotton fabric swith blend ratios of 0/100, 11/89, 20/80, 30/70, 50/50, and 65/35 were investigated via thermogravimetric analysis in both nitrogen and air atmospheres. The samples were heated from ambient to 750°C at a heating rate of 5°C min^?1. The same fabrics were analyzed after treatment with tetrakis (hydroxymethyl) phosphonium chloride-urea-poly(vinyl bromide) (Thpc-urea-PVBr) flame retardant.Weight losses observed during pyrolysis were assigned to the cotton and polyester portions of the blends. Both cotton and polyester thermally decompose to yield gases and solid char byproducts. In nitrogen the 100% cotton fabric undergoes one major weight loss between 270 and 370°C, with the maximum rate of weight loss, 0.15 mg/min-mg occurring at 346°C. Thermal decomposition of the 100% polyester occurs over a range of 335–470°C, with the peak rate of weight loss, 0.11 mg/min-mg, measured at 416°C. In an air atmosphere, both volatile gases and solid char by- products of pyrolysis undergo combustion. The combustion reactions are associated with measured weight losses. The maximum rate of weight loss for the cotton portion increases to 0.25 mg/min-mg and occurs at 317°C. The maximum rate of polyester decomposition remains the same in both air and nitrogen, but the temperature decreases to 405°C.     

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.     

Cotton fabric modification for imparting high water and oil repellency using perfluoroalkyl phosphate acrylate via γ-ray-induced grafting

The perfluoroalkyl phosphate acrylates were grafted onto a cotton fabric via γ-ray irradiation to improve the hydrophobic and oleophobic properties. The change in chemical structure of grafted cotton fabric was detected by the Fourier transform infrared spectroscopy and the X-ray photoelectron spectroscopy. The contact angles for water and sunflower oil were determined to be over 150° and 140°, respectively, after irradiated with a dose range of 471–5664 Gy. The flame retardancy of the fabric with a grafting ratio of over 13.0 wt% was improved, reaching to 24 compared with 18 of which before grafted, according to the limiting oxygen index measurement. The microstructure of the fabric before and after grafted was observed by the scanning electron microscope.     

Detection of copper(II) sulfate’s uniformity and its thermal behavior in flammability of cotton fabric

Blue vitriol (copper(II) sulfate pentahydrate), CuSO₄·5H₂O has been chosen and investigated for its effectiveness as a flame-retardant, when impregnated into cotton fabric (cotton with a plain structure; woven 180 g m⁻², with 22 numbers of yarns per 10 mm). Using the vertical flame test, the extent of resistance to burning of the specimens has been determined. The impregnation was accomplished via dipping and stirring of bone-dried, weighed fabrics into the individual and suitable concentrations of the salt at room temperature. Afterwards the samples were squeeze rolled and dried horizontally at 110°C for 30 min in an oven and cooled in a desiccator and reweighed with an analytical precision. They were then kept under ordinary conditions overnight prior the fulfillment of the vertical flame test. The efficient quantities of the aforesaid salt expressed in g per 100 g dry fabric have been determined in an average figure of 12.75%. Estimation of uniformity in a selected sample was carried out via a spectrophotometer and results are in favor of the heterogeneous distribution of the salt in the fabric’s middle sectors. However initial and final parts of specimen showed to be rather uniformed. Thermogravimetric analysis of the pure cotton and the treated ones with insufficient and effective amounts of the salt were fulfilled and their thermograms were compared and commented. The results obtained for the effect of copper(II) sulfate comply with ‘The Dust or Wall Effect Theory’. This action is also assigned to the condensed phase retardation.     

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.     

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.     

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.     

Enhanced thermal properties and flame retardancy from a thermosetting blend of a phosphorus‐containing bismaleimide and epoxy resins

Epoxy resins modified by an organosoluble phosphorus‐containing bismaleimide (3,3′‐bis(maleimidophenyl) ­phenylphosphine oxide; BMPPPO) were prepared by simultaneously curing epoxy/diaminodiphenylmethane (DDM), and BMPPPO. The resulted epoxy resins were found to exhibit glass transition temperatures as high as 212 °C, thermal stability at temperatures over 350 °C, and excellent flame retardancy with Limited oxygen index (LOI) values around 40. Incorporation of BMPPPO into epoxy resins via the thermosetting blend was demonstrated to be an effective way to enhance the thermal properties and flame retardancy simultaneously. Copyright © 2003 John Wiley & Sons, Ltd.     

Microwave‐assisted synthesis of nanocomposites from polyimides chemically cross‐linked with functionalized carbon nanotubes for aerospace applications

Polymer‐carbon nanotube nanocomposites are extensively investigated for microelectronics and aerospace applications. In this study, novel polyimide/f‐MWCNT nanocomposites made from 2,4‐bis(4‐aminophenylamido)‐6‐chloroquinazoline, pyromellitic dianhydride and functionalized‐Multi Walled Carbon Nanotubes (f‐MWCNT) by an efficient microwave assisted method were investigated. The structure of the prepared diamine monomer was confirmed by FT‐IR, ¹H‐NMR, and ¹³C‐NMR spectral techniques. The prepared nanocomposites (T_g values from 338°C to 375°C) show improved thermal property as indicated by differential scanning calorimetry and thermogravimetric analysis. Polyimide/f‐MWCNT nanocomposites were found to have higher dielectric constant, and the limiting oxygen index values of prepared nanocomposites are in the range of 29.5 to 35.5, indicating a high flame retardancy. Additionally, the morphological studies were conducted by X‐ray diffraction and scanning electron microscopy. Overall, it is observed that chemically connected polyimide‐functionalized carbon nanotube nanocomposites could be used for aerospace and microelectronics applications that require high T_g, dielectric constant and high flame retardancy.     

Estimation of Flame Retardancy Effect by Thermal Analysis Using Kinetic Parameters Obtained under Non-Isothermal Conditions in Air

A series of compounds obtained from urea, phosphoric acid and inorganic salts of Zn, Ni and Ca, were tested in respect of their flame‐retardancy behavior. The estimation criteria were the kinetic parameters obtained in air, under non‐isothermal conditions, on a Perkin‐Elmer Diamond device, at heating rates of 5, 10, 12 and 15 deg·min^?1. The flame‐retardancy effect was assigned to the significant endothermic decomposition at relatively low temperature (150–200°C). The quantitative estimation of the thermal behavior was performed by comparison of the kinetic data obtained by Flyn‐Wall‐Ozawa, Friedman and NPK (Sempere‐Nomen) methods. The kinetic homogeneity and a very good quality of the model are arguments in favour of the NPK method. The Ni containing material exhibited the best flame‐retardancy behavior, i.e. higher activation energy and mass loss, respectively a single decomposition step with both physical and chemical processes. The results were validated by fire resistance tests.