Formaldehyde-free flame retardant finishing of silk using a hydroxyl-functional organophosphorus oligomer

Flame retardancy is a desirable property for silk textiles, and it becomes necessity when silk textiles are for interior decorative use in building with public access. However, the flame retardant finishing technology available for silk has significant limitations. In this research, we studied the use of the combination of a hydroxyl-functional organophosphorus oligomer (HFPO) and 1,2,3,4-butanetetracarboxylic acid (BTCA) as a formaldehyde-free flame retardant finishing system for silk. When BTCA is applied to silk, most of BTCA reacts with the hydroxyl group on silk by single ester linkage. In the presence of HFPO, BTCA is able to bond HFPO onto silk by either a BTCA “bridge” between silk and HFPO or a BTCA-HFPO-BTCA cross-linkage between two silk protein molecules. We evaluated the flammability and physical properties of the silk fabric treated with HFPO and BTCA. The treated silk fabric demonstrated a high level of flame retardancy with modest loss in fabric tensile strength. The treated silk passed the vertical flammability test after 15 hand wash (HW) cycles. Increasing the HFPO concentration from 20% to 30% does not show significant improvement in the flame retardant performance of the treated silk. The thermal analysis data demonstrated that HFPO reduces silk's initial thermal decomposition temperature and promotes char formation.     

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.     

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.     

Applications of micro-scale combustion calorimetry to the studies of cotton and nylon fabrics treated with organophosphorus flame retardants

Effective testing methods are critical for developing new flame retardant textiles by the industry. However, the current testing methods all have limitations. In this research, we applied micro-scale combustion calorimetry (MCC) for evaluating the flammability of the cotton woven fabric treated with a traditional reactive organophosphorus flame retardant in combination with a synergistic nitrogen-containing additive and the nylon-6,6 woven fabric treated with a hydroxyl-functional organophosphorus oligomer and crosslinkers. We found that MCC is capable of differentiating small differences among the treated fabric samples with similar flammability. MCC is able to make quantitative measurement of the peak heat release rate, the most important parameter related to fire hazard of materials, of textile whereas such analysis is more difficult using cone calorimetry due to textile fabrics’ low thickness. By using the thermal combustion parameters measured by MCC, we were able to calculate the limiting oxygen index (LOI) of various treated cotton fabric samples with near-perfect agreement between the experimentally measured and the predicted LOI values of treated cotton fabrics. We also compared the capability of MCC and differential scanning calorimetry for analyzing flame retardant cotton textiles.     

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.     

The use of indium(III) as a complexing counter-ion to enable the separation of chloride,bromide, and iodide using isotachophoresis

A new method has been devised to enable the determination of halide anions by isotachophoresis. This method uses an electrolyte system that employs indium(III) as a counter-ion to manipulate the effective mobilities of sample species by means of complexation reactions. This new procedure successfully enabled the simultaneous determination of the halide ions chloride, bromide, and iodide when a 12 mmol L^–1 nitrate-based leading electrolyte containing 3.5 mmol L^–1 indium(III) at pH 3.0 was used.