A facile one‐step synthesis of flame‐retardant coatings on cotton fabric via ultrasound irradiation

This article reports a facile one‐step methodology to increase fire resistance properties of cotton fabric. The flame‐retardant coating for cotton fabric was synthesized with methyltriethoxysilane and organophosphates (M102B) through an ultrasound irradiation process. The coating structure and surface morphology of uncoated and coated fabrics were investigated by Fourier transform infrared spectroscopy and scanning electron microscope, respectively. The flame‐retardant properties, bending modulus, air permeability and thermal stability were studied by vertical burning test, cantilever method, air permeability test and thermogravimetric analysis (TGA). As a result, the cotton fabric coated with 29.2% (mass increased) of flame‐retardant coating was able to balance the flame retardant property and wearing comfort of the fabrics. The TGA results showed that the residue char of cotton was greatly enhanced after treatment with the coating, which has a high char forming effect on cellulose during testing. Furthermore, flame‐retardant property of coated fabrics did not change significantly after 10 washing cycles. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45114.     

Antibacterial,flame retardant,and physico‐chemical properties of cotton fabric graft copolymerized with a binary mixture of acrylonitrile and 4‐vinylpyridine

Modification of cotton fabric has been carried out through chemically induced graft copolymerization of binary mixture of acrylonitrile (AN) and 4‐vinyl pyridine (4‐VP) using ceric ammonium nitrate, (CAN) as initiator. Maximum percentage of grafting (151.28%) has been obtained at [4‐VP] = 0.376 mol L^?1 and [AN] = 1.221 mol L^?1, [CAN] = 0.0255 mol L^?1 and [HNO₃] = 0.9585 mol L^?1 in 25mL of water at 70°C in 180 min. Post quarternization and phosphorylation reactions of the grey and grafted cotton fabrics have been carried out to study their antibacterial and flame retardant properties respectively. The fabrics have been characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). The physico‐chemical properties such as wettability, moisture regain, crease recovery and tensile strength of the grey and grafted cotton fabric have also been evaluated. The modified fabric has been shown to exhibit excellent antibacterial and flame retarding properties with improved physico‐chemical properties except for the mechanical properties. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40415.     

GMA改性磷酸腺苷的制备及其对棉织物的阻燃整理

为了提高磷酸腺苷单体在棉织物上的接枝改性程度及其阻燃效果,采用甲基丙烯酸缩水甘油酯（GMA）对一磷酸腺苷（AMP）、二磷酸腺苷（ADP）、三磷酸腺苷（ATP）进行改性,制得三种带有不饱和双键的阻燃单体AMP-m-GMA、ADP-m-GMA、ATP-m-GMA;然后通过紫外光接枝法将三种阻燃单体分别接枝到棉织物上,制备光接枝AMP-m-GMA、ADP-m-GMA和ATP-m-GMA阻燃棉织物;对三种阻燃单体进行了结构表征和热稳定性分析,并探究了三种阻燃单体光接枝阻燃棉织物的热稳定性、阻燃性能、燃烧行为和残炭结构。结果表明,三种磷酸腺苷通过GMA环氧基开环引入不饱和双键,且具有良好的热稳定性。相比于原棉织物,三种阻燃棉织物的最大热降解速率分别降低了60.0%、52.0%、60.0%,极限氧指数由16.1%分别提升到25.4%、27.4%、26.4%,织物热释放速率分别下降了15.09%、60.47%、37.82%,说明三种磷酸腺苷阻燃单体均有助于棉织物形成致密炭层,阻止热量扩散,获得良好的阻燃效果。其中,光接枝ADP-m-GMA阻燃棉织物的增重率可达22.4%,燃烧后损毁长度由30 cm缩短至14.2 cm,表现出更优异的阻燃性能。     

Effect of chicken‐feather protein‐based flame retardant on flame retarding performance of cotton fabric

A new kind of eco‐friendly chicken‐feather protein‐based phosphorus–nitrogen‐containing flame retardant was synthesized successfully with chicken‐feather protein, melamine, sodium pyrophosphate, and glyoxal. And its structure was characterized by Fourier transform infrared spectroscopy, and the thermogravimetry of the agent was analyzed. Then the flame retarding performances of the chicken‐feather protein‐based flame retardant and in combination with the borax and boric acid in application to a woven cotton fabric were investigated by the vertical flammability test and limited oxygen index test. In addition, the surface morphologies of the treated and untreated fabrics were conducted by the scanning electron micrographs (SEM), and the thermogravimetric analyses of the treated and untreated cotton were explored, and the surface morphologies of char areas of the treated and untreated fabrics after burnt were tested by the SEM. The results showed that the flame retardancy of the cotton fabric treated by the chicken‐feather protein‐based flame retardant in combination with borax and boric acid was improved further, and the combination of the chicken‐feather protein‐based flame retardant and borax and boric acid could facilitate to form a homogenous and compact intumescing char layer, and the combination of them plays a good synergistic effect in the improvement of the flame retardancy of the treated cotton fabric. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40584.     

Modification of cellulosic fabrics to impart flame retardancy properties

Graft copolymerization of dimethylaminoethyl methacrylate (DMAEMA) onto cotton‐cellulose in the fabric form was carried out using a cellulose‐thiocarbonate‐ammonium persulphate redox initiation system. Effects of the concentration of the monomer, effect of liquor ratio, grafting time, and temperature were studied. The results point out the following important aspects of flame retardation of cellulose fabrics. (1) The graft polymerization of DMAEMA can improve the flame retardant properties of cellulose fabrics. (2) Tertiary amine grafted to cellulosic fabrics is suitable for nitrogen compounds that can effectively operate as synergists. The flame retardant properties of the poly‐DMAEMA‐ grafted‐phosphorylated cellulosic materials were found to be excellent even after 25 dry clean washings. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

A novel halogen‐free and formaldehyde‐free flame retardant for cotton fabrics

A novel halogen‐free and formaldehyde‐free flame retardant (FR), which contains phosphorus, nitrogen, and silicon, was synthesized for cotton fabrics considering the synergistic effect of phosphorus, nitrogen, and silicon. The structure of the new FR was characterized by Fourier‐trans‐form infrared spectroscopy, and the surface morphology of the treated fibre was observed using scanning electron microscope. The thermal property of the FR treated cotton fabric was studied through thermal gravimetric analysis. The TG results indicate that the FR can protect cotton fabric from fire to a certain degree. The vertical flammability test and limiting oxygen index results further indicate that the FR has excellent FR properties. Finally, the durability and other performance properties of the treated fabric were studied and the results show that the new materials can be used as a semi‐durable FR for cellulosic fibres. Copyright © 2011 John Wiley & Sons, Ltd.     

聚丙烯纤维阻燃剂应用研究进展

绍了聚丙烯(PP)阻燃剂的种类及其在PP纤维中的应用。PP阻燃剂有含磷、含卤、含硅、金属氢氧化物及其氧化物以及纳米复合材料;讨论了阻燃剂的性能和提高阻燃效果的方法;提出新型阻燃剂必将朝着无卤、消烟的复合型阻燃剂方向发展     

多层阻燃织物整体热防护性能初探

研究了消防服用多层阻燃织物复合系统的整体热防护性及外层织物的阻燃性。将阻燃织物国产间位芳纶、杜邦NomexⅢ和芳纶3A面料与国产间位芳纶毡和阻燃棉布组合,模拟构成消防服的多层织物结构,通过垂直燃烧实验测试分析了阻燃外层织物的阻燃性能,通过热辐射和热对流综合热防护性能(TPP)实验测试分析了多层复合织物的整体热防护性能。实验结果表明:整体热防护性能最好的是国产间位芳纶织物、面密度200 g/m2的芳纶毡和阻燃棉布的组合,但最适宜用于消防服的是NomexⅢ织物、面密度200 g/m2的芳纶毡和阻燃棉布。     

Flammability testing of pure and flame retardant-treated cotton fabrics

A Controlled-atomosphere cone calorimeter was used to investigate the burning of pure and flame retardant-treated cotton fabrics. The condensed-phase flame retardants used were Morguard (containing ammonium dihydrogen phosphate and diammonium hydrogen phoisphate) and Nochar (containing ammonium sulfate and a sodium salt). The fabrics were tested at 25 kW m^?2 incident heat flux in environments containing 15–30% oxygen. The flame retardants increased the time to ignition, residue yield, and CO and CO₂ yields. The flame retardants decreased the peak and average mass loss rates, the peak and average heat release rates, the effective heat of combustion at peak heat release rate, and the propensity to flashover. The effect of oxygen concentration on the burning of pure and flame retardant-treated cotton fabrics has also been investigated. The flame retardants had better performance when the treated fabrics burned in the lower oxyge concentrations. The result of this study indicate that the controlled-atmosphere cone calorimeter is a good tool for studying the effect of flame retardant and oxygen concentration on the burning of materials.     

Effect of condensed-phase and gas-phase flame retardants on the ignition behaviour of cotton fabric

The purpose of this study is to evaluate the effect of some well-known flame retardants on the ignition behaviour of cotton fabric. Two types of flame retardants acting in different phases (e.g. condensed phase and gas phase) were used. At low add-on of the retardant acting in the condensed phase the ignition behaviour of the cotton is different from that treated with retardant acting in the gas phase. The condensed-phase retardant caused cotton to burn more rapidly than untreated fabrics. This was attributed to the fact that small add-on of the retardant makes the fuel for the flame available at a lower temperature. However, in the presence of sufficient amounts of retardant, the decomposition of cellulose becomes more directed towards the dehydration mechanism and thus the concentration of the flammable gases is insufficient to reach the flammability limits required. When gas-phase flame retardants were used, a linear dependency of ignition time on the concentration of additive was found. This is explained in terms of the dilution effect of this retardant on the fuel produced from the decomposing fabric.     

Development of flame retardancy properties of new halogen‐free phosphorous doped SiO2 thin films on fabrics

In this study, flame retardancy properties of fabrics treated with phosphorous (P) doped and undoped SiO₂ thin films were developed by sol–gel technique. As to this aim, P‐doped and undoped SiO₂ film were coated on cotton fabric from the solutions prepared from P, Si‐based precursors, solvent, and chelating agent at low temperature in air using sol–gel technique. To determine solution characteristics, which affect thin film structure, turbidity, pH values, and rheological properties of the prepared solutions were measured using a turbidimeter, a pH meter, and a rheometer machines before coating process. The thermal, structural, and microstructural characterization of the coating were done using differential thermal analysis/thermograviometry, fourier transform infrared spectroscopy, X‐ray diffractometry, and scanning electron microscopy. In addition, tensile strength, wash fastness, flame retandancy, and lightness properties of the coated fabrics were determined. To compensate the slight loss of tensile strength of samples, which occurred at the treated fabrics with P‐doped Si‐based solutions, the cotton fabrics were coated with polyurethane films during second step. In conclusion, the flame retardant cotton fabric with durability of washing as halogen‐free without requiring after treatment with formaldehyde was fabricated using sol–gel processing for the first time. Moreover the cotton fabrics, which were treated with P‐doped Si‐based solutions and then coated with polyurethane at second step, still has got nonflammable property. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Effects of phosphorus-containing flame retardants on pyrolysis of cotton cellulose

Unmodified cotton and cottons finished with high levels of seven different phosphorus-containing flame retardants were pyrolyzed in a temperature-programmed solid probe of a mass spectrometer, and mass spectra were recorded continuously throughout the pyrolyses. The spectra at the maximum rates of volatiles evolution during the pyrolyses were analyzed to determine relative amounts of water, carbon monoxide, carbon dioxide, furfural, furyl hydroxymethyl ketone, hydroxymethylfurfural, levoglucosan, and 1,6-anhydro-β-glucofuranose. These volatile materials accounted for 64% to 90% of the total ionization in the spectra. The flame retardants increased the fractions of nonfuel volatiles (water and carbon dioxide) and decreased those of anhydroglucoses, but had less effect on the carbon monoxide and furan derivatives. The flame retardant fabrics differed greatly in the fractions of anhydroglucoses (from 1% to 23%) and water (from 19% to 57%) in their pyrolysis products. These results indicate that mechanisms of flame retardant action differ among phosphorus-containing finishes.     

Correlation between limiting oxygen index and phosphorus/nitrogen content of cotton fabrics treated with a hydroxy‐functional organophosphorus flame‐retarding agent and dimethyloldihydroxyethyleneurea

The combination of a hydroxyl‐functional organophosphorus flame‐retarding agent (FR) and dimethyloldihydroxyethyleneurea (DMDHEU) was used as a durable flame‐retardant finish system for cotton fabrics. DMDHEU functions as a binder between FR and cotton cellulose, thus making this flame‐retarding system durable to home laundering. DMDHEU also provides nitrogen to this system, therefore enhances its performance. Limiting oxygen index (LOI) is one of the most commonly used parameters to indicate the flammability of textiles and other polymeric materials. In this research, we investigated the correlation between LOI and phosphorus/nitrogen content on the cotton fabric treated with that durable flame‐retardant system. Phosphorus concentration on the fabric was analyzed by inductively coupled plasma atomic emission spectroscopy, whereas the nitrogen content was determined indirectly by measuring the carbonyl band intensity in the infrared spectra of the treated fabric. We developed a statistical model to predict LOI of the cotton fabric treated with FR and DMDHEU based on the phosphorus concentration and the intensity of carbonyl band of DMDHEU on cotton. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1885–1890, 2003     

Layer‐by‐layer assembly of halogen‐free polymeric materials on nylon/cotton blend for flame retardant applications

Thin films of environmentally safe, halogen free, anionic sodium phosphate and cationic polysiloxanes were deposited on a Nyco (1:1 nylon/cotton blend) fabric via layer‐by‐layer (LbL) assembly to reduce the inherent flammability of Nyco fabric. In the coating process, we used three different polysiloxane materials containing different amine groups including, 35–45% (trimethylammoniummethylphenythyl)‐methyl siloxane‐55‐65% dimethyl siloxane copolymer chloride salt (QMS‐435), aminoethylaminopropyl silsesquioxane‐methylsilsesquioxane copolymer oligomer (WSA‐7021) and aminopropyl silesquioxane oligomers (WSA‐991), as a positive polyelectrolyte. Thermo‐gravimetric analysis showed that coated fabric has char yield around 40% at 600 °C whereas control fabric was completely consumed. The vertical flame test (VFT) on the LbL‐coated Nyco fabric was passed with after flame time, 2 s, and the char length of 3.81 cm. Volatile and nontoxic degradation products of flame retardant‐coated fabric were analyzed by pyrolysis gas chromatography mass spectroscopy (Py‐GCMS). Surface morphology of coated fabrics and burned fabric residues were studied by scanning electron microscopy. Copyright © 2014 John Wiley & Sons, Ltd.     

新型含磷阻燃剂的制备及性能

以双三羟甲基丙烷为原料合成一种新型含磷阻燃剂,该阻燃剂分子量较大,具有稳定的环状结构,热稳定性高于常用阻燃剂,阻燃效果好。探讨了原料配比、反应温度、反应时间对产率的影响,考察了目标产物的热稳定性能及其对不同织物的阻燃效果,用傅里叶变换红外光谱仪表征了中间体及目标产物的结构。结果表明,当原料配比为1∶3时,磷化温度为50℃,磷化时间5h,胺化温度为75℃时,反应效果较好,收率可达90%以上。目标产物对于锦纶的阻燃效果比较明显,对涤纶、棉有一定的阻燃效果,对于混纺、腈纶阻燃效果不明显。     

PP电缆料无卤阻燃技术的研究与应用进展

综述了用于无卤阻燃聚内烯(PP)电缆料的主要阻燃体系的研究进展,介绍了金属氧化物水合物体系、磷-氮膨胀型阻燃体系、有机硅复合体系和纳米复合材料阻燃体系的开发应用情况。建议加强对无卤阻燃PP电缆料的研究,以开发出力学性能优异的无卤阻燃PP电缆料。     

Grafting multi-elements hybrid polymer brushes on graphene oxide for epoxy composite with excellent flame retardancy

In this paper, a silicon-oxygen coupling agent (MPS) with a double bond is hydrolyzed with graphene oxide (GO) to obtain MPS-GO. The polymerization of MPS-GO with the phosphorus-containing monomer (HEPO) is initiated with 2,2′-Azobis(2-methylpropionitrile) (AIBN) to obtain multi-elements hybrid polymer brushes grafting graphene oxide (HM-GO). As a flame retardant, different amounts of HM-GO are added to obtain EP composites. In this system, the properties of composite flame retardant obviously increase with the increasing of HM-GO. The limiting oxygen index (LOI) value of composites with 4 wt% addition of HM-GO is 31.0%, while the LOI value of EP-0 is only 23.9%. And the peak heat release rate (PHRR) value is reduced from 515.8 W g⁻¹ of pure epoxy resin to 376.9 W g⁻¹. In addition, with the increase of HM-GO addition, the T_g value, flexural strength and flexural modulus of EP composites are improved. Through calculation, it is proved that the rising of T_g was due to the increase of crosslink density of the system. The flame retardant performance and mechanical properties of the composite materials are steadily improved, indicating that such flame retardants are dispersed well in the epoxy resin. HM-GO is an efficient macromolecular modified graphene oxide halogen-free flame retardant, which can improve both flame retardant properties and mechanical properties.     

The effect of laundering variables on the flame retardancy of cotton fabrics

Some durable flame retardant finishes for cotton fabrics can become ineffective if improper laundering procedures are used. For example, one flame resistant fabric will lose a significant amount of its flame resistance after 5, 10 or 20 soap launderings (yet show no reduction in phosphorus content) while another fabric treated with a different formulation will remain flame resistant. Synthetic detergents, rather than soap chips, and soft water have been recommended for some tetrakis (hydroxymethyl) phosphorium chloride-based flame retardant fabrics to prevent a “lime soap” deposit which impairs performance. The effect of these laundering variables has been studied in relation to a variety of different types of durable flame resistant fabrics. One of eight papers to be published from the Symposium “Surface Active Agents in the Textile Industry,” presented at the AOCS Meeting, New Orleans, April 1970. So. Utiliz. Res. Dev. Div., ARS, USDA.     

Studying smoldering to flaming transition in polyurethane furniture subassemblies: Effects of fabrics,flame retardants,and material type

The transition from smoldering to flaming was studied on fabric, batting, and foam assemblies via an electric spot ignition source of similar intensity to a cigarette. The materials studied included four different fabrics (cotton, polyester, cotton/polyester blend, flame retardant cotton/polyester blend), two types of batting (cotton, polyester), and three types of polyurethane foam (nonflame retardant, flame retardant by FMVSS 302 testing, flame retardant by BS5852 testing). The results from testing found that materials highly prone to smoldering could propagate smoldering into foams and lead to ignition, whereas materials that tended to melt back from the ignition source did not. Flame retardant fabrics or foam can and do prevent the transition from smoldering to flaming provided sufficient levels of flame retardants are incorporated in the upholstery fabric or foam. The transition from smoldering to flaming of cotton fabric/nonflame retardant foam assembly was also studied using temperature measurements and evolved gas analysis. It was determined that the transition takes place when the oxygen consumption by accelerating smoldering front exceeds the oxygen supply. At this point, the solid fuel gasification becomes driven by thermal decomposition rather than by surface oxidation which leads to high enough concentrations of fuel for flaming combustion to occur.     

Post-polymerization functionalization to a novel phosphorus- and nitrogen-containing polyether coating for flame retardant treatment of PET fabric

Concerns about the rising trend of stringent fire safety regulations and demands for reduction in the fire hazard call for a careful evaluation of the environmental impact of flame retardant materials choices. With the worldwide bans and restrictions in the use of traditional halogen-based fire retardant systems, phosphorus/nitrogen synergistic flame retardants became evident. We report here a novel phosphorus- and nitrogen-containing polyether (PN-PEO) prepared by post-polymerization functionalization. The resultant polyethers (PN-PEO) were subsequently coated onto the surface of poly(ethylene terephthalate) (PET) fabrics by a simple solution-dipping method to exploit a highly efficient fire retardant. It was found that the loadings of 17.8% PN-PEO had a strong barrier effect in the char layer of the PN-POE-coated PET fabrics after exposed to the torch flame, and resulted in complete suppression of PET fabrics ignition on radiant heat exposure. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47299.