Effect of zinc oxide on flame retardant finishing of plasma pre-treated cotton fabric

An organic phosphorus compound (flame retardant agent, FR) in combination with a melamine resin (crosslinking agent, CL), phosphoric acid (catalyst, PA) and zinc oxide (co-catalyst, ZnO/nano-ZnO) imparted effective and durable flame retardant properties. Also, atmospheric pressure plasma jet was applied as pre-treatment to improve post-finishing (flame retardant finishing) on cotton fabrics. In the present paper, surface morphology, chemical structure analysis, combustibility and mechanical properties of plasma pre-treated cotton fabrics subjected to flame-retardant treatment were investigated. Surface morphology of treated cotton specimens showed roughened and wrinkled fabric surface with high deposition of the flame retardant finishing agent, which was caused by the plasma etching effect and attack of acidic FR. The FTIR-ATR spectra for the treated cotton specimens showed some new characteristic peaks in chemical structure, interpreted as carbonyl bands, OH stretching vibration, COO⁻ stretching vibration, CH₂ rocking band and CH₃ asymmetric and CH₂ symmetric stretching. Moreover, FR-CL-PA-treated specimens showed remarkable flame-retardant property, which was further improved by the plasma pre-treatment and ZnO/nano-ZnO co-catalyst. However, flame-retardant-treated cotton specimens had poor mechanical strength when compared with control sample, resulting from side effects of the crosslinking agent used, while plasma pre-treatment and ZnO/nano-ZnO co-catalyst may compensate for the reduction in tensile and tearing strength caused by flame-retardant agents.     

Thermal degradation mechanism of flame retarded epoxy resins with a DOPO-substitued organophosphorus oligomer by TG-FTIR and DP-MS

A novel phosphorus-containing oligomeric flame retardant, poly(DOPO substituted hydroxyphenyl methanol pentaerythritol diphosphonate) (PDPDP) was synthesized and applied to flame retarded epoxy resins. The thermal degradation behaviors of flame retarded epoxy composites with PDPDP were investigated by thermogravimetric analysis (TGA), thermogravimetric analysis/infrared spectrometry (TG-FTIR) and direct pyrolysis-mass spectrometry (DP-MS) techniques. The identification of pyrolysis fragment ions provided insight into the flame retardant mechanism. The results showed that the mass loss rate of the EP/PDPDP composites was clearly lower than pure EP when the temperature was higher than 300 °C in air or nitrogen atmosphere. The results also suggested that the main decomposition fragment ions of the EP/PDPDP composite were H₂O, CO₂, CO, benzene, and phenol. The incorporation of PDPDP can reduce the release of combustible gas and induce the formation of char layer, hence the fire potential hazard was reduced.     

The study of mechanical behavior and flame retardancy of castor oil phosphate-based rigid polyurethane foam composites containing expanded graphite and triethyl phosphate

The goal of this work was the synthesis of novel flame-retarded polyurethane rigid foam with a high percentage of castor oil phosphate flame-retarded polyol (COFPL) derived from renewable castor oil. Rigid flame-retarded polyurethane foams (PUFs) filled with expandable graphite (EG) and diethyl phosphate (TEP) were fabricated by cast molding. Castor oil phosphate flame-retarded polyol was derived by glycerolysis castor oil (GCO), H₂O₂, diethyl phosphate and catalyst via a three-step synthesis. Mechanical property, morphological characterization, limiting oxygen index (LOI) and thermostability analysis of PUFs were assessed by universal tester, scanning electron microscopy (SEM), oxygen index testing apparatus, cone calorimeter and thermogravimetric analysis (TGA). It has been shown that although the content of P element is only about 3%, the fire retardant incorporated in the castor oil molecule chain increased thermal stability and LOI value of polyurethane foam can reach to 24.3% without any other flame retardant. An increase in flame retardant was accompanied by an increase in EG, TEP and the cooperation of the two. Polyurethane foams synthesized from castor oil phosphate flame-retarded polyol showed higher flame retardancy than that synthesized from GCO. The EG, in addition to the castor oil phosphate, provided excellent flame retardancy. This castor oil phosphate flame-retarded polyol with diethyl phosphate as plasticizer avoided foam destroy by EG, thus improving the mechanical properties. The flame retardancy determined with two different flame-retarded systems COFPL/EG and EG/COFPL/TEP flame-retarded systems revealed increased flame retardancy in polyurethane foams, indicating EG/COFPL or EG/COFPL/TEP systems have a synergistic effect as a common flame retardant in castor oil-based PUFs. This EG/COFPL PUF exhibited a large reduction of peak of heat release rate (PHRR) compared to EG/GCO PUF. The SEM results showed that the incorporation of COFPL and EG allowed the formation of a cohesive and dense char layer, which inhibited the transfer of heat and combustible gas and thus increased the thermal stability of PUF. The enhancement in flame retardancy will expand the application range of COFPL-based polyurethane foam materials.     

Synthesis and Characterization of Al(OH)<Subscript>3</Subscript>, Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Nanoparticles and Polymeric Nanocomposites

Applying of the most toxic halogenated and aromatic flame retardants is limited with respect to the environmental requirements. Nontoxic Al(OH)₃ nanoparticles were synthesized via a simple surfactant-free precipitation reaction at room temperature. The effect of various precipitation-agents on the morphology of the products was investigated. Al(OH)₃ nanoparticles were added to the polysulfone and poly styrene (PS) matrices. Electron microscope images show excellent dispersion of aluminium hydroxide in PS matrix. Nanoparticles appropriately enhanced both thermal stability and flame retardant property of the polymeric matrices. The enhancement of flame retardancy is due to endothermic decomposition of Al(OH)₃ that absorbs heat and simultaneously releases of water (makes combustible gases diluted and cold). Dispersed nanoparticles play the role of a barrier layer against flame, oxygen and polymer volatilization. Al(OH)₃ was converted to Al₂O₃ and its photo-catalyst property in degradation three different organic dyes as pollutants was investigated.     

Bi‐phase flame‐retardant effect of dimethyl methylphosphonate and modified ammonium polyphosphate on rigid polyurethane foam

The flame‐retardant rigid polyurethane foams (RPUFs) with dimethyl methylphosphonate (DMMP) and modified ammonium polyphosphate (MAPP) were prepared. The results showed that the limiting oxygen index (LOI) value was improved by adding DMMP into RPUF/MAPP composite; 10 wt% of DMMP addition can increase the LOI value from 24.3% to 26.0%, where the commercial application standard of RPUF is achieved. Further benefits of using DMMP/MAPP system included restraining of total heat and smoke release, improvement of thermal stability, and char yield of RPUF. The thermogravimetric analysis (TGA)‐gas chromatography‐mass spectrometer (GC‐MS) results indicated that DMMP/MAPP could continuously release PO₂ and PO·free radicals in the gas phase. In addition, DMMP/MAPP exhibited the charring effect and barrier effect in the condensed phase, such bi‐flame retardant effect exerted by DMMP/MAPP resulted in the enhanced flame retardant property of RPUF.     

Study on combustion property and synergistic effect of intumescent flame retardant styrene butadiene rubber with metallic oxides

Effect of metallic oxides on flame retardancy and the thermal stability of styrene butadiene rubber (SBR) composites based on ammonium polyphosphate (APP) and pentaerythritol (PER) was studied by the limiting oxygen index (LOI), UL 94, the cone calorimeter tests, and thermogravimetry analysis (TGA), respectively. Scanning electron microscopy (SEM) and wide‐angle X‐ray diffraction (WAXD) were used to analyze the morphological structure and the component of the residue chars formed from the SBR composites accordingly. The addition of zirconium dioxide (ZrO₂) at a loading of 3.4 phr could improve the UL 94 test rating of the composite to V‐0. The TGA data illustrated that the metallic oxides could enhance the thermal stability of the SBR/Intumescent flame retardant additives (IFRs) composites at high temperature and increase the residue. Cone calorimeter test gave much clear evidence that the incorporation of ZrO₂ into SBR/IFRs composites resulted in the significant deduction of the heat release rate (HRR) values, and the SEM images showed that the char layers of the composites containing the metallic oxides became more compact. From the WAXD pattern, zirconium phosphate (ZrP₂O₇) may be formed by the reaction between ZrO₂ and APP. Due to the addition of ZrO₂ and the formation of ZrP₂O₇, the flame retardancy of the composite was improved. Copyright © 2009 John Wiley & Sons, Ltd.     

Preparation of nanocrystalline Na2ZrO3 for high-temperature CO2 acceptors: chemistry and mechanism

Nanocrystalline Na₂ZrO₃ was demonstrated as a promising acceptor for CO₂ capture at elevated temperatures. The mechanism of nanocrystalline Na₂ZrO₃ formation from the soft-chemistry route is elucidated by varying precursors, preparation methods, and calciantion temperatures, combining detailed characterizations by X-ray diffraction (XRD) and scanning electron microscope (SEM) at different steps in the process. The results revealed that the drying method such as spraying drying and simple evaporation-drying did not influence the final product properties. However both Na and Zr precursors had remarkable influences on the Na₂ZrO₃ formation. The solid reaction of Na intermediate and nanocrystalline ZrO₂ in the calcination was identified as the key step for the Na₂ZrO₃ formation, where the formation of molten phase Na intermediate was found to be crucial to facilitate the solid reaction. We provided principles for rational design of the chemistry for the Na₂ZrO₃ formation where the formation of Na intermediate with low melting points is essential. Pure nanocrystalline Na₂ZrO₃ can be synthesized from a mixture containing sodium nitrate and zirconoxy citrate via the formation of NaNO₃ with low melting point. However, it is not possible to form pure nanocrystalline Na₂ZrO₃ at relatively low temperatures from the mixtures of NaAc/ZrO(NO₃)₂ or NaCA/ZrOCl₂ due to the formation of Na₂CO₃ and NaCl with high melting points.     

Effect of ethyl‐bridged diphenylphosphine oxide on flame retardancy and thermal properties of epoxy resin

Three commercialized flame retardants, 1,2‐bis(diphenylphosphinoyl)ethane (EDPO), 6,6‐(1,2‐phenethyl)bis‐6H‐dibenz[c,e][1,2]oxaphosphorin‐6,6‐dioxide (HTP‐6123), and hexa‐phenoxy‐cyclotriphosphazene (HPCTP), were used to prepare the flame retardant diglycidyl ether of bisphenol A (DGEBA) epoxy resin (EP) under the same experimental conditions. The effects of T_g, thermal stability, and water absorption properties of EP caused by the three flame retardants were investigated and compared, together with their flame retardant efficiency. Results showed that the introduction of the three flame retardants improved the flame retardant performance of EP but led to decreases in T_g and decomposition temperature. EDPO showed higher flame retardant efficiency than the other two flame retardants. EP/EDPO showed higher thermal stability, better flame retardant performance, higher T_g value, and lower water absorption than EP/HTP‐6123 and EP/HPCTP. The study discovered that EDPO and HTP‐6123 primarily act through the gas phase flame retardant mechanism, while HPCTP is primarily driven by the condensed phase mechanism.     

Kinetic studies of the decomposition of flame retardant containing high-impact polystyrene

The thermal decomposition of flame retardant free high-impact polystyrene (HIPS) and four HIPS samples containing brominated flame retardants has been studied using TGA at different heating rates between 2.5 and 10 K min⁻¹. Decabromodiphenyl ether (DPE) and decabromodibenzyl (DDB) were used as flame retardants, and two of the samples contained antimony trioxide (Sb₂O₃) synergist besides the brominated additives. The activation energies (E_A) and frequency factors (k₀) were calculated by the methods of Kissinger and Ozawa. A compensation effect was observed and used for the identification of changes in the degradation kinetics. In a third step, the kinetic model of the reaction was determined. Both Kissinger and Ozawa showed that the HIPS degraded with an E_A of 200 kJ mol⁻¹. The choice of the flame retardant had, however, little impact on the TGA plot. The addition of a flame retardant as well as the addition of Sb₂O₃ reduced the E_A. Fire retardant free HIPS degraded mainly by power-law kinetics, while the addition of a flame retardant caused the mechanism to change to a phase-boundary controlled mechanism after a weight loss of 80 wt%.     

Roles of organic intercalation agent with flame retardant groups in montmorillonite (MMT) in properties of polypropylene composites

Three kinds of organic intercalation agent containing flame retardant groups, melamine (MA), triphenylphonium (TPP) chloride, and tetradecyl trihexyl phosphonium (TTP) bromide were intercalated into montmorillonite (MMT) via cation exchange reactions. These modified MMTs are combined with intumescent systems and compounded with PP. The flame retardant and thermal properties of the PP composites are studied. The organic intercalation agents in the layers of MMT play important roles in the char formation and flame retardant properties of PP composites. MA shows a better performance in limiting oxygen index (LOI) value and TPP helps to increase UL‐94 properties, whereas TTP maintains or deteriorates the flame retardancy of polypropylene/intumescent flame retardant (IFR) composites. The LOI and UL‐94 properties increase firstly and then decrease as the content of MMT increases. The MA acts as a blowing agent and emits an inert gas to provide migration impetus, which results in a better intumescent structured and stronger char to endure heat erosion. Although TPP and TTP emit combustible gas that burn, especially for TTP as it has a more flammable aliphatic chain. The synergistic effect between MA‐MMT and IFR is better than that for TPP‐MMT and TTP‐MMT. Copyright © 2014 John Wiley & Sons, Ltd.     

Effects of phosphorus-containing thermotropic liquid crystal copolyester on pyrolysis of PET and its flame retardant mechanism

In order to compare their inherent flame retardancy and thermal stability, two phosphorus-containing thermotropic liquid crystalline copolyesters (P-TLCP) were synthesized by melting transesterification. Additionally based on the facts that the P-TLCP can work as a functional additive to enhance the flame retardancy and mechanical property of PET, we further studied the flame retardant mechanism. Scanning Electronic Microscope (SEM) observations show that the char from PET/P-TLCP is more compact, therefore more efficiently resists fire and heat attack than pure PET. Moreover, Fourier Transform Infrared Spectroscopy (FTIR) measurements of evolved gas, indicate that P-TLCP decomposes to produce phosphorus-containing small molecular compounds during the pyrolysis process, such that P-TLCP could play a flame retardant role in vapour phase. Furthermore, P-TLCP strongly inhibits the generation of combustible compounds in the pyrolysis of PET, which also helps to resist fire propagation.     

Regularities of formation of nanocrystalline particles in titanium subgroup dioxides

Trends in formation and evolution of nanocrystalline phases in TiO₂, ZrO₂, and HfO₂ powders were studied. The stability of metastable phases increases in the order of HfO₂ > ZrO₂ > TiO₂, and the probability of formation of thermodynamically stable phases increases in the order of TiO₂ > ZrO₂ > HfO₂. The enthalpies of formation were determined for TiO₂, ZrO₂, and HfO₂ nanocrystallites, as well as the activation energies of their subsequent growth. For TiO₂ and ZrO₂, a phenomenological model was advanced to describe nanocrystallite formation and subsequent polymorphic transformations.     

Preparation of 2CaO·3B2O3·H2O nanomaterials and evaluation of their flame retardant properties by a thermal analysis method

Different morphologies of calcium borate 2CaO·3B₂O₃·H₂O, nanoribbon, bundle-like nanostructure and fan-shaped non-nanostructure, have been prepared under hydrothermal conditions, which were characterized by XRD, FT-IR, TGA and SEM. Their flame retardant properties to the polypropylene were investigated by thermal analysis method (including TG, DSC and non-isothermal decomposition kinetics) and oxygen index method. With the decrease in TG mass loss, the increase in heat absorption for DSC in N₂ atmosphere, the increase in LOI values, and the increase in apparent activation energy E_a, the flame retardant properties of prepared 2CaO·3B₂O₃·H₂O samples increased gradually from non-nanostructure to bundle-like nanostructure and then to nanoribbon. This trend may be ascribed to their sizes being decreased accordingly. The flame retarding mechanism has been proposed. The mechanical property of polypropylene/2CaO·3B₂O₃·H₂O composite material has also been evaluated. It can be predicted that 2CaO·3B₂O₃·H₂O nanoribbon could serve as an excellent flame retardant.

     

Combined effect of transition metal phosphide (MxPy,M = Ni,Co, and Cu) and intumescent flame retardant system on polypropylene

In this paper, three typical transition metal phosphide nanocrystallines (M_xP_y, M = Ni, Co, and Cu) were synthesized by a novel hydrothermal method, and their structures were characterized by X‐ray diffraction and transmission electron microscopy. Then they were used as synergistic agents with intumescent flame retardant (IFR) to improve the fire safety of polypropylene (PP). Thermogravimetry analysis (TGA) results indicated that the introduction of these synergists could improve the thermal stability and char yields of the PP/IFR system. The addition of 2 wt.% Ni₁₂P₅ and Co₂P increased the limiting oxygen index values of the PP/IFR system significantly from 28% to 36% and 34%, respectively, and the system could reach V‐0 rating. The cone calorimeter test results revealed that the combination of transition metal phosphide nanocrystallines and IFR system could result in excellent flame retardancy. The incorporation of these synergists into IFR led to a remarkable influence on charring of PP composites as revealed by TGA and cone data. The morphological structure of char residue proved that the addition of transition metal phosphide nanocrystallines was capable of forming a compact and homogeneous char on the surface, which turned out to be of most importance for the flame retardancy. Thermogravimetric analysis/infrared spectrometry results indicated that the flame retardant mechanism of PP/IFR/M_xP_y (M = Ni, Co, and Cu) system was in the condensed phase rather than in the gas phase. Copyright © 2014 John Wiley & Sons, Ltd.     

Carbon Dioxide Destruction with Methane Reforming by a Novel Plasma-Catalytic Converter

A novel plasma-catalyst converter (NPCC) was engineered in applying the carbon capture utilization technology for the destruction of carbon dioxide (CO₂), which is a cause of global warming and is generated from the combustion of fossil fuels. The NPCC has an orifice-type baffle to improve an amount of gas feed with the higher CO₂ destruction for a stationary point sources application . To examine its ability for the CO₂ destruction, the performance analysis was conducted on the effects of methane additive, nozzle injection velocity, total gas feed, and catalyst type. The product gas from the NPCC was combustible components like CO, H₂, CH₄, THCs. The CO₂ destruction and the CH₄ conversion at a 1.29 CH₄/CO₂ ratio were 37 and 47 %, respectively, and the energy decomposition efficiency was 0.0036 L/min W. The nickel oxide catalyst among other catalysts showed the most effectiveness for the CO₂ destruction and CH₄ conversion at a lower temperature. The carbon-black produced without the catalytic bed has carbon nanoparticles with diverse shapes, such as spherical carbon particles and carbon nanotubes; and its high conductivity and specific surface area were suitable for special electronic materials, fuel cells, and nanocomponents.     

Preparation,Characterization, and Catalytic Behavior of Nanostructured Mesoporous CuO/ZrO2 Catalysts for Low-Temperature CO Oxidation

High-surface area mesoporous 20 mol% CuO/ZrO₂ catalyst was prepared by a surfactant-assisted method of nanocrystalline particle assembly, and characterized by x-ray powder diffraction (XRD), N₂ adsorption, transmission electron microscopy (TEM), H₂-TPR, TG-DTA, and x-ray photoelectron spectra (XPS) techniques. The catalytic properties of the CuO/ZrO₂ nanocatalysts calcined at different temperature were evaluated by low-temperature carbon monoxide oxidation using a CATLAB system. The results showed that these mesoporous nanostructured CuO/ZrO₂ catalysts were very active for low-temperature CO oxidation and the CuO/ZrO₂ catalyst calcined at 400°C exhibited the highest catalytic activity.     

Electrochemical behavior of nanocrystalline diamond thin films grown in electrical arc plasma

Nitrogenated nanocrystalline diamond films with controlled electrical conductivity are grown in electrical arc plasma in CH₄/H₂/Ar/N₂ gas mixtures and characterized by scanning electron microscopy and spectroscopic measurements. Their electrochemical properties are studied by electrochemical impedance spectroscopy. Transfer coefficients of reactions in the [Fe(CN)₆]^3−/4− redox system are determined. The electrochemical behavior of the material is controlled by its nitrogenation (3–20% N₂ in the reaction gas mixture). The nitrogenated nanocrystalline diamond has higher differential capacitance in indifferent electrolyte (1 M KCl) solution than not nitrogenated one; the nitrogenation also increases the reversibility of reactions in the [Fe(CN)₆]^3−/4− redox system. By and large, with nitrogenation of diamond, its electrochemical behavior changes from the one characteristic of a “poor conductor” to that characteristic of metallike conductor. In this respect the nanocrystalline diamond electrodes grown in the electrical arc plasma are similar to those grown in microwave plasma.     

Elucidating the Thermal Decomposition of Dimethyl Methylphosphonate by Vacuum Ultraviolet (VUV) Photoionization: Pathways to the PO Radical,a Key Species in Flame‐Retardant Mechanisms

The production of phosphoryl species (PO, PO₂, HOPO) is believed to be of great importance for efficient flame‐retardant action in the gas phase. We present a detailed investigation of the thermal decomposition of dimethyl methylphosphonate (DMMP) probed by vacuum ultraviolet (VUV) synchrotron radiation and imaging photoelectron photoion coincidence (iPEPICO) spectroscopy. This technique provides a snapshot of the thermolysis process and direct evidence of how the reactive phosphoryl species are generated during heat exposure. One of the key findings of this work is that only PO is formed in high concentration upon DMMP decomposition, whereas PO₂ is absent. It can be concluded that the formation of PO₂ needs an oxidative environment, which is typically the case in a real flame. Based on the identification of products such as methanol, formaldehyde, and PO, as well as the intermediates O?P?CH₃, H₂C?P?OH, and H₂C?P(?O)H, supported by quantum chemical calculations, we were able to describe the predominant pathways that lead to active phosphoryl species during the thermal decomposition of DMMP.     

Flame retardation of glass-fibre-reinforced polyamide 6 by a novel metal salt of alkylphosphinic acid

Aluminum salts of phosphinic acid mixture of diisobutylphosphinic acid and monoisobutylphosphinic acid (HPA-2TBA-Al) and glass fibres were compounded with polyamide 6 to prepare a series of flame retardant GF/PA6 composites via melt blending. The flame retardance and burning behaviors of the composites were investigated by limiting oxygen index (LOI), vertical burning test (UL-94), and Cone calorimeter test. The thermal properties and decomposition kinetics were investigated by thermogravimetric analysis (TGA) under N₂ atmosphere. Addition of HPA-2TBA-Al results in an increased LOI value, a UL-94 V-0 rating together with a decrease in both the values of PHRR and THR in Cone calorimetric analysis. Visual observations and scanning electronic microscopy (SEM) after flame retardant tests confirmed the char-formation which acts as a fire barrier in condense phase. Analysis of cone calorimeter data indicates that gas phase flame retardant mechanism exists in the GFPA6/HPA-2TBA-Al system.     

Relationship between structures of phosphorus compounds and flame retardancies of the mixtures with acrylonitrile–butadiene–styrene and ethylene–vinyl acetate copolymer

Various analogos of phosphonic acid, phosphinic acid, and CH₃? P(O) group containing organo‐phosphorus compounds were synthesized as model compounds to investigate the effects of P content and the structure of flame retardant (FR) on their fire retarding performances of acrylonitrile–butadiene–styrene (ABS) and ethylene–vinyl acetate (EVA) copolymer. The success of synthesis was confirmed by ¹H‐ and ³¹P‐NMR. The flame retarding efficiencies were evaluated by a UL‐94 vertical test method. Thermogravimetric analysis results reveal that all the mixtures of FRs with ABS or EVA exhibit no or very little charred residues at 600°C under inert atmosphere condition, indicating that all FRs work in the gas phase rather than in the condensed phase for both ABS and EVA. The fire retarding efficiency of FR depends not only on the P content in FR but also on the nature of its structure. UL‐94 results show that P FRs with ? CH₃ group attached to the P atom exhibits the best fire retarding performance on both ABS and EVA. It was found that at least 4 wt% P in the formulation is required to show self‐extinguishing ability for both ABS and EVA when P FRs having ? CH₃ group are employed. The fire retarding efficiency of P FRs with different attached group is in order of: ? CH₃ > ? C₆H₅ > ? OH > ? H. Copyright © 2009 John Wiley & Sons, Ltd.