Flame retardant properties of plasma pre-treated/diamond-like carbon (DLC) coated cotton fabrics

Textiles with superior anti-flammability properties combined with minimal environmental impact are extremely necessary to reduce fire-related issues. In this regard, diamond-like carbon (DLC) coatings on cotton fabrics may represent promising candidates as potential flame-retardant (FR) materials. Herein, superhydrophobic and fire-resistant cotton fabrics were fabricated through a two-step plasma strategy by alternately exposing substrates to H₂ and O₂ plasma pre-treatments and subsequent DLC deposition. Fourier transform-infrared spectroscopy analysis has revealed that different plasma pre-treatments can impose surface modifications on the chemical structure of cotton, especially in carboxylic and hydroxyl groups, leading to a radical alteration of surface roughness and of the crystalline cellulosic external structure. These changes deeply influenced the growth of DLC thin films and the surface properties of cotton fabric because of the combination of a hierarchical structure and surface chemistry as verified using field emission gun-scanning electron microscopy and water contact angle measurements. The effects of both specific gases used in the pre-treatment step and duration of pre-treatment were analysed and compared using thermogravimetric analyses. The H₂-pre-treated DLC cottons exhibited good potential as an FR material, showing improved thermal stability in respect to untreated cotton, as evidenced by increased ignition times. Moreover, vertical burning tests have demonstrated that DLC-cotton systems exhibit enhanced flammability resistance.     

Comparison of different reactive organophosphorus flame retardant agents for cotton: Part I. The bonding of the flame retardant agents to cotton

N-Methylol dimethylphosphonopropionamide (MDPA), known as “Pyrovatex CP” and “Pyrovatex CP New” commercially, has been one of the most commonly used durable flame retardant agents for cotton for many years. In our previous research, we developed a flame retardant finishing system for cotton based on a hydroxy-functional organophosphorus oligomer (HFPO) in combination with a bonding agent such as trimethylolmelamine (TMM) and dimethyloldihydroxyethyleneurea (DMDHEU). In this research, we investigated the bonding of these two flame retardant finishing agents to cotton. We found that the majority of MDPA is bound to cotton by its N-methylol group and that the use of TMM as a co-reactant modestly increases the fixation of MDPA onto cotton. For HFPO, however, the use of a bonding agent is necessary to form a covalent linkage between HFPO and cotton. Both the fixation of HFPO on cotton and its laundering durability are influenced by the effectiveness and concentration of the bonding agent. The commercial product of HFPO contains approximately 33% more phosphorus than that of MDPA and the percent fixation of HFPO on cotton is also moderately higher than that of MDPA. The bonding between MDPA and cotton is significantly more resistant to hydrolysis during multiple launderings than that between HFPO and cotton. The selection of catalyst also plays a significant role in influencing the bonding of the flame retardant agents to cotton.     

Permanent flame retardant finishing of textile materials by a photochemical immobilization of vinyl phosphonic acid

A new photochemical method for a permanent flame retardant finishing of textiles made of cotton (CO), polyamide (PA) and polyester (PET) is described. Using a mercury vapour UV lamp vinyl phosphonic acid (VPA) can be fixed durable to different fabrics made of CO, PA and PET in the presence of a cross-linking agent and a photo-initiator. After a home laundering cycle up to 50 wt% of the reaction mixture is retained on the fabrics and the absolute phosphorus content was found to be more than 2.0% in all investigated cases. The photochemically modified textiles showed high levels of flame retardant performance and passed a vertical flammability test for protective clothing.     

A simple method for determining the total amount of physically and chemically bound water of different cements

A novel environmentally friendly flame-retardant compound, diethyl 3-(triethoxysilanepropyl) phosphoramidate (DTP) was synthesized via a simple one-step procedure with good yield and characterized by FT-IR and ¹H-NMR, ³¹P-NMR and ²⁹Si-NMR. The synthesized compound was coated onto cotton fabrics with different levels of add-ons (5–17 mass%) using the traditional pad-dry-cure method. SEM and XPS were conducted to characterize the surfaces of the coated cotton fabrics. The XPS results showed that DTP was attached to cotton through covalent bond. Cone calorimeter test showed that the cotton fabric treated with DTP became less flammable due to the lower HRR, THR and CO₂/CO ratio. The modified cotton fabrics exhibited efficient flame retardancy, which was evidenced by limiting oxygen index (LOI) and vertical flammability test. Cotton fabrics treated with DTP in 5–17 mass% add-ons had high LOI values of 23–32%. Thermogravimetric analysis results show that the usage of DTP promotes degradation of the cotton fabrics and catalyzes its char formation.     

Construction of crosslinking network structures by adding ZnO and ADR in intumescent flame retardant PLA composites

Different proportion of nano zinc oxide (nano ZnO) and chain extender (ADR) were combined with the intumescent flame retardant and then added into the PLA matrix. The thermal stability, flame retardant performance, and mechanical properties were studied. The gel content results showed that crosslinking structures were obtained after the addition of nano ZnO and ADR, which were generated by the catalytic chain scission effect of nano ZnO and chain extension effect of ADR. With addition of 1% nano ZnO and 1.6% ADR, the gel content of flame retardant PLA composite reached the highest value (14.2%). Meanwhile, the corresponding flame retardant PLA composite with 1% nano ZnO and 1.6% ADR, named FRPLA/ZnO/ADR-1, exhibited an overall improved properties including the flame retardant properties and mechanical performance, which passed the UL94 V-0 level with a limiting oxygen index value of 40.1%. Compared to FRPLA (flame retardant PLA without ZnO and ADR), the peak heat release rate and the total smoke production of FRPLA/ZnO/ADR-1were reduced by 60% and 67% respectively, and the final mass improved from 12% to 38%. In addition, the tensile strength and elongation at break of FRPLA/ZnO/ADR-1 increased by 25%, 14% compared with that of FRPLA. The impact strength was 15.1 kJ/m², which is similar to the pure PLA (15.6 kJ/m²). It indicated that the addition of nano ZnO and ADR could balance the flame retardant performance and the mechanical properties of the flame retardant PLA.     

Flame retardant property of nanopowder aerosols toward methane

The flame retardant property of aerosols formed from 18 different nanopowders has been studied. The diameter of nanocrystalline powders was determined by XRD and TEM. The concentration of combustible gas was determined by gas chromatography. It was found that ZrO₂ nanocrystalline powdered aerosol can effectively retard the burning of CH₄. The flame retardation caused by ZrO₂ toward the combustion reaction of methane is through an inhibitory mechanism, which was further confirmed by contrasting it with Halon extinguishing agent and flame retardant property of ZrO₂-aerosol toward CH₃CH₂CH₃ or CO. The type of nanopowder aerosols as anti-explosion and fireproof agents was researched preliminarily in theory, too. The current ZrO₂-aerosol study will find extensive applications in the field of fire-extinguishing and anti-explosion agents used in case of combustible gas.     

Investigation of the flammability of different textile fabrics using micro-scale combustion calorimetry

Evaluating and analyzing the performance of flame retardant (FR) textiles are a critical part of research and development of new FR textiles products by the industry. The testing methods currently used in the industry have significant limitations. Most analytical and testing techniques are not able to measure heat release rate (HRR), the single most important parameter in evaluating the fire hazard of materials. It is difficult to measure HRR of textile fabrics using cone calorimetry because textile fabrics are dimensionally thin samples. The recently developed micro-scale combustion calorimetry (MCC) is able to measure the following flammability parameters for textile using milligram sample sizes: heat release capacity, HRR, temperature at peak heat release rate (PHRR), total heat release and char yield. In this research, we applied MCC to evaluate the flammability of different textile fabrics including cotton, rayon, cellulose acetate, silk, nylon, polyester, polypropylene, acrylic fibers, Nomex and Kevlar. We also studied the cotton fabrics treated with different flame retardants. We found that MCC is able to differentiate small differences in flammability of textile materials treated with flame retardants. We were also be able to calculate the limiting oxygen index (LOI) using the thermal combustion properties of various textile samples measured by the MCC. The calculated LOI data have yielded good agreement with experimental LOI results. Thus, we conclude that MCC is an effective new analytical technique for measuring textile flammability and has great potentials in the research and development of new flame retardants for textiles.     

Physical and chemical analysis of plasma-treated cotton fabric subjected to wrinkle-resistant finishing

Cotton fabrics were treated with oxygen plasma gas and/or wrinkle-resistant finishing agent with polycarboxylic acid. The results of wicking rate, contact angle and wettability tests revealed that the atmospheric plasma treatment significantly improved hydrophilicity of cotton fiber. Such improvement greatly enhances the effectiveness of post-finishing processes. The study showed that chemical composition of cotton fabric surface changed after plasma and wrinkle-resistant treatment. Chemical composition of surface of treated cotton specimens was evaluated with different characterization methods, namely, FTIR-ATR and EDX. The experimental results are thoroughly discussed.     

Thermal properties of cotton fabric modified with poly (propylene imine) dendrimers

For the first time, thermal stability and flame retardant properties of cotton fabrics modified with poly (propylene imine) dendrimer (PPI-dendrimer) using cross linking agents have been reported. The PPI-dendrimers can be considered as novel nitrogen flame retardant agents, because they contain a large number of nitrogen-containing groups (amine end groups), which may release nitrogen gas or ammonia. In this paper, the effect of the PPI-dendrimers on thermal behavior of cotton fabric is investigated through thermogravimetric analysis, differential scanning calorimetry, flammability (in vertical configuration) and limiting oxygen index tests. Indeed, both thermal stability and flame retarancy of the modified fabrics have significantly enhanced. Furthermore, field emission scanning electron microscopy micrographs have been studied in order to evaluate morphology of the cotton samples. Crystallinity and physical properties including crease recovery angle, breaking strength, whiteness index and hygroscopicity of the samples have been also assessed.     

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.     

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.     

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.     

Binary mixtures of metal compounds as flame retardants for organic polymers

Studies have been made of the effect on the flammability of thermoplastic polymers of the partial or total replacement of one metal compound by another in the presence also of a suitable halogen compound; particular attention has been paid to systems where the primary flame retardant is antimony(III) oxide. With each binary metal compound system investigated, ten different compositions have been chosen so as to provide a symmetrical arrangement of points within a triangular design; resulting calculated values of the limiting oxygen index for each polymer-flame retardant system for a given polymer are shown as a graphical contour analysis. Comprehensive studies of several systems show that both iron(III) oxide and aluminium oxide monohydrate can significantly enhance the flame-retardant action of antimony(III) oxide but that several other metal compounds, although not as effective as Sb₂O₃, may nevertheless be used as adequate partial replacements for it. The Fe₂O₃-SnO₂-H₂O system can also act as an effective flame retardant under certain conditions. The SnOZnO system perhaps best illustrates the importance of the polymer substrate and of the total additive loading as factors controlling the flame-retardant effectiveness. For all the systems studied, however, ABS is a much better substrate than HDPE. The results of a reasonably detailed study of the flame retardance conferred by several different compositions of a binary metal compound mixture give a much more reliable indication of the effects on polymer flammability of the constituent metal compounds than are obtained simply by replacement of a given concentration of one compound by another.     

Effects of thermal-oxidative aging on the flammability and thermal-oxidative degradation kinetics of tris(tribromophenyl) cyanurate flame retardant PA6/LGF composites

The influence of thermal-oxidative aging on the flame retardancy of the flame retardant long-glass-fiber reinforced polyamide 6 composites (FR/PA6/LGF) with different thermal-oxidative exposure times at 160 °C were studied in this work. The flammability and flame-retardant properties of FR/PA6/LGF were investigated by means of the limiting oxygen index (LOI), vertical burning test (UL-94), cone calorimeter test (CONE), and scanning electronic microscopy (SEM), before and after thermal-oxidative aging. The thermal-oxidative stability and degradation kinetics of the unaged and aged composites were studied by thermogravimetric analysis (TGA) with the methods of Kissinger and Ozawa in dynamic measurements (10 °C/min–40 °C/min). The results indicated that the flammability properties mirrored the degradation behaviors of these FR/PA6/LGF composites whatever their forms (aged or not). The Ozawa method showed that the causes of the first peak in the heat release rate change by CONE measurement corresponded to the apparent activation energies of the first stage degradation of aged FR/PA6/LGF composites, and the same conclusion with respect to the other heat release rate peak. Moreover, this aging slightly enhanced the solid phase flame-retardant mechanism by a char-promotion function, but had no effect on the gaseous flame-retardant mechanism and the decrease of harmful gas release rates. The existence of a surface migration effect on the flame retardant would endow FR/PA6/LGF composites with better LOI values, a more protective char layer structure, and excellent UL-94 ratings.     

Preparation, properties and characterizations of halogen-free nitrogen-phosphorous flame-retarded glass fiber reinforced polyamide 6 composite

Halogen free nitrogen-phosphorous flame retardants (PMOP) were prepared through reaction of melamine and polyphosphoric acid in the presence of flame retardant modifier CM with silicotungistic acid as a catalyst in aqueous solution. FT-IR, XRD, DSC and TGA techniques were used to characterize the reaction product PMOP. The obtained flame retardants were then used to prepare flame retardant (FR) polyamide 6 (PA6) composite reinforced with glass fiber (GF) and the factors affecting the flame retardancy of the material were also investigated. The FR GF reinforced PA6 composite and the obtained charred layers were analyzed by utilizing TGA, SEM, FT-IR and XRD. The properties of the charred layer were connected with the flame retardancy of the corresponding material to reveal the flame retarding mechanism of FR GF reinforced PA6 composite. The experimental results show that PMOP flame retardant consists of melamine polyphosphate, melamine phosphate and possible melamine pyrophosphate. The presence of CM was found to improve the flame retardancy of FR GF reinforced PA6 composite. It was experimentally found that PMOP flame retardant, which is comparatively stable in the range of processing temperatures of PA6, is particularly suitable for flame retarding PA6 reinforced with GF. With increasing the flame retardant content, the flame retardancy of the FR reinforced material is not improved so obviously. However, the increase in the GF content greatly improves the flame retardancy of the composite, because GF greatly increases the char yield of material, decreases the maximal thermal decomposition rate, promotes the formation of charred layer with (PNO)_x structure and greatly increases the strength of the charred layer. The prepared FR GF reinforced PA6 composites have good comprehensive properties with flame retardancy 1.6 mm UL 94 V-0 level, tensile strength 76.8 MPa, Young's modulus 11.7 GPa, Izod notched impact strength 4.5 kJ/m², flexural strength 98.0 MPa and flexural modulus 7.2 GPa, showing a better application prospect.     

可膨胀石墨阻燃体系在聚丙烯中的作用

采用可膨胀石墨(EG)为主阻燃剂,包裹红磷(MRP)为阻燃协效剂制备阻燃聚丙烯(PP)。在mEG∶mMRP≥2时,阻燃效果最佳。阻燃剂(FR)含量达到30%后,阻燃效果大幅度提高,氧指数大于28。采用热失重和流变学方法分析了炭层质量,探讨了在mEG∶mMRP≥2时,阻燃效率最高的原因。相容剂马来酸酐接枝聚丙烯(PP-g-MAH)能够改善阻燃剂和聚丙烯之间的相容性,提高粘结力,改善炭层质量,提高材料的氧指数,PP-g-MAH用量为30%时,材料的氧指数达到31.4。     

Growth and fire resistance of colloidal silica-polyelectrolyte thin film assemblies

Thin films of colloidal silica were deposited on cotton fibers via layer-by-layer (LbL) assembly in an effort to reduce the flammability of cotton fabric. Negatively charged silica nanoparticles of two different sizes (8 and 27 nm) were paired with either positively charged silica (12 nm) or cationic polyethylenimine (PEI). PEI/silica films were thicker due to better (more uniform) deposition of silica particles that contributed to more than 90% of the film weight. Each coating was evaluated at 10 and 20 bilayers (BL). All coated fabrics retained their weave structure after being exposed to a vertical flame test, while uncoated cotton was completely destroyed. Micro combustion calorimetry confirmed that coated fabrics exhibited a reduced peak heat release rate, by as much as 20% relative to the uncoated control. The 10 BL PEI-8 nm silica recipe was the most effective because the coating is relatively thick and uniform relative to the other systems. Soaking cotton in basic water (pH 10) prior to deposition resulted in better assembly adhesion and flame-retardant behavior. These results demonstrate that LbL assembly is a useful technique for imparting flame retardant properties through conformal coating of complex substrates like cotton fabric.     

Functionalization of cotton fabrics with corona/air RF plasma and colloidal TiO2 nanoparticles

This study discusses the possibility of using a corona discharge at atmospheric pressure and air RF plasma at low pressure for the cotton fibre activation prior to deposition of colloidal TiO₂ nanoparticles in order to enhance antibacterial, UV protective and self-cleaning properties. X-ray photoelectron spectroscopy (XPS) analysis confirmed the presence of TiO₂ nanoparticles on the surface of cotton fibres. XPS elemental mapping indicated that TiO₂ nanoparticles were more evenly distributed across the surface of untreated and corona pre-treated cotton fabrics in comparison with RF plasma pre-treated fabric. Atomic absorption spectroscopy measurements revealed that the equivalent total content of TiO₂ in the cotton fabrics pre-treated by corona and RF plasma was 31% higher than in the fabric that did not undergo any treatment prior to loading of TiO₂ nanoparticles. In order to achieve maximum bacteria (Gram-negative bacteria Escherichia coli) reduction, untreated cotton fabric had to be loaded with colloidal TiO₂ nanoparticles twice, but only once following corona or RF plasma pre-treatment. Deposition of TiO₂ nanoparticles onto cotton fabrics provided maximum UV protective rating of 50+. Extraordinary photocatalytic activity of TiO₂ nanoparticles deposited onto cotton fabrics was proved by self-cleaning of blueberry juice stains and photodegradation of methylene blue in aqueous solution under UV illumination.     

Optimization of monoguanidine dihydrogen phosphate and amino propylethoxysilane based flame retardant formulations for cotton

Different formulations based on monoguanidine dihydrogen phosphate (MGHP) and 3-amino propylethoxysilane (APS) were evaluated as flame retardant in padding for cotton. The formulations can be classified into two groups. The first corresponds to the formulations of MGHP and APS, at pH 4 (obtained by the addition of phosphoric acid) and the second group to formulations at pH 9.5. Their thermal stability is then examined using thermal analysis. TG analysis reveals a significant difference in the thermal degradation of these two groups. While the degradation is initiated at lower temperatures for all padded fabrics compared to untreated cotton, the residual amounts of char are higher at 800 °C for formulations with phosphoric acid. Flame behaviour of the treated cotton fabrics was evaluated using the electrical burner test and was studied with cone calorimeter as fire model. The RHR peak was decreased very much for all the formulations, compared to the RHR peak of the virgin cotton. The highest decrease was achieved with the formulations at pH 4. The padded fabrics evolve smallest quantity of CO₂.     

Nanocarbon-Based Flame Retardant Polymer Nanocomposites

In recent years, nanocarbon materials have attracted the interest of researchers due to their excellent properties. Nanocarbon-based flame retardant polymer composites have enhanced thermal stability and mechanical properties compared with traditional flame retardant composites. In this article, the unique structural features of nanocarbon-based materials and their use in flame retardant polymeric materials are initially introduced. Afterwards, the flame retardant mechanism of nanocarbon materials is described. The main discussions include material components such as graphene, carbon nanotubes, fullerene (in preparing resins), elastomers, plastics, foams, fabrics, and film–matrix materials. Furthermore, the flame retardant properties of carbon nanomaterials and their modified products are summarized. Carbon nanomaterials not only play the role of a flame retardant in composites, but also play an important role in many aspects such as mechanical reinforcement. Finally, the opportunities and challenges for future development of carbon nanomaterials in flame-retardant polymeric materials are briefly discussed.