Flame retardancy of glass fiber reinforced high temperature polyamide by use of aluminum diethylphosphinate: thermal and thermo‐oxidative effects

Glass fiber reinforced polyamide (PA) 6 T/DT flame retarded with aluminum diethylphosphinate (AlPi) was tested to assess its flame retardant properties. Models for the decomposition of PA 6T/DT with and without AlPi are presented. Thermal decomposition was measured by performing TGA with Fourier transform infrared (FTIR) spectroscopy and FTIR spectroscopy in the condensed phase. Fire behavior was studied using a cone calorimeter and flammability was tested with UL 94 and the limiting oxygen index. AlPi works as an effective flame retardant for glass fiber reinforced PA 6T/DT materials, acting in the gas phase. Also observed was condensed‐phase action, which occurs especially under oxidative conditions before the samples ignite. © 2013 Society of Chemical Industry     

Investigation on effects of aluminum and magnesium hypophosphites on flame retardancy and thermal degradation of polyamide 6

Two hypophosphites, aluminum hypophosphite (AlHP) and magnesium hypophosphite (MgHP), were applied to obtain flame retardant polyamide 6 (FR-PA6) composites. UL-94 and limiting oxygen index results indicated that AlHP contributed both good flame retardance and antidripping ability for PA6, while MgHP did not. Based on thermogravimetric analysis (TGA), AlHP and MgHP presented the different thermal degradation behavior. That is, the quick decomposition of AlHP took place at lower temperature than that of MgHP. AlHP promoted the early thermal degradation of PA6 and formed more char residue. The thermal decomposition mechanisms of AlHP and MgHP in nitrogen or air were suggested. Scanning electron microscope and X-ray photoelectron spectroscopy indicated that in the existence of AlHP, the morphological structures of char residue were more homogenous, and compact, and more char residue was formed. These results well illustrated the difference of the flame retardancy between AlHP and MgHP. Mechanical properties of PA6/AlHP and PA6/MgHP were also obtained. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

次磷酸铝协效MCA阻燃三元乙丙橡胶的研究

以三聚氰胺氰尿酸盐（MCA）为阻燃剂、二乙基次膦酸铝（ADP）和次磷酸铝（PAH）为阻燃协效剂,制备了无卤阻燃三元乙丙橡胶（EPDM）材料,并研究了其阻燃性能和力学性能。结果表明,当阻燃剂MCA用量为76份、ADP用量为14份、PAH用量为10份时,EPDM垂直燃烧级别达到FV-0,氧指数为30%,拉伸强度为6.7 MPa,拉断伸长率为330%。     

木质素/LDPE-EVA共混材料的力学性能及热性能

以天然热塑材料木质素和LDPE-EVA为原料,研究了不同木质素以及增容剂含量对木质素/LDPE-EVA共混材料的力学及热性能影响。结果表明,20份木质素与LDPE-EVA共混效果较好,拉伸强度达到最大（25.88 MPa）,较LDPE-EVA聚合物提高了9%,且共混物在100 ℃附近的吸热峰出现一定左移（3.6 ℃）,降解性能增加;10份增容剂LDPE-g-MAH的加入使体系拉伸强度达到35.66 MPa,较未加增容剂时提高了26.6%,100℃附近的吸热峰进一步左移（2 ℃）,降解性能小幅降低,显著提高了共混物的相容性。     

The flame retardant effect of aluminum phosphinate in combination with zinc borate,borophosphate, and nanoclay in polyamide‐6

The effect of zinc borate (ZnB), borophosphate (BPO₄), and organoclay were studied to improve the flame retardancy of polyamide‐6 composites containing organic phosphinates. The flame retardancy of polyamide‐6 composites was investigated using limiting oxygen index (LOI), Underwriters Laboratories (UL‐94) standard, thermogravimetric analysis, Fourier transform infrared spectroscopy, and mass loss calorimeter. The addition of 15 wt% aluminum phosphinate (AlPi) increased the LOI value from 22.5 to 29.5, and V0 rating was obtained from UL‐94 test. The addition of organoclay, ZnB, and borophosphate does not change the predominant gas phase mechanism of AlPi during LOI and UL‐94 tests. The addition of organoclay increased the condensed phase mechanism of AlPi physically by the protective effect of layered silicate, whereas the addition of ZnB increased the condensed phase mechanism of AlPi chemically by the formation of boron aluminum phosphate species deducted from mass loss calorimeter studies. Copyright © 2012 John Wiley & Sons, Ltd.     

Grafting modification bamboo kraft lignin and its performance in rigid polyurethane foams

In order to improve the efficiency of intumescent flame retardant (IFR), bamboo kraft lignin (BKL) was chemically functionalized by grafting melamine (MEL) and diethyl phosphite (DEP) and used for rigid polyurethane (RPU) foam. The BKL, MEL, and DEP in IFR system were used as char forming agent, gas, and acid source, respectively. The FTIR and XPS results indicated that the nitrogen (N) and phosphorus (P) containing BKL was successfully synthesized. The limiting oxygen index (LOI) value of N-BKL and N/P-BKL RPU foams were higher than BKL RPU foam, suggesting that N-BKL and N/P-BKL improved flame retardancy of the foams. The total heat release (THR), heat release rate (HRR), effective heat of combustion (EHC), and fire growth rate (FIGRA) values of N-BKL and N/P-BKL RPU foams were much lower than that of BKL RPU foam. The flame retardancy index value of N/P-BKL RPU foams was higher comparing to N-BKL RPU foam. These results indicated that the synergistic interaction between N containing compound of MEL and P containing compound of DEP led to the improvement flame retardant properties. Comparing to BKL RPU foam, the N/P-BKL RPU foam increased 74°C of maximum weight loss temperature and decreased 18.1 wt% of mass loss, indicating enhanced thermal stability. The morphology of char after cone calorimeter testing showed the N/P-BKL RPU foam presented more continuous and compact char residues, which could reduce heat and mass transfer, protecting underlying materials from further combustion in a fire, thus resulting in good flame retardancy and thermal stability properties. This work suggests a promising route to enhancing the flame-retardant performance of RPU foam using nontoxic and more environmentally friendly grafted bamboo lignin.     

Influence of nano silica hybrid expandable graphite on flammability,thermal stability,and mechanical property of polypropylene/polyamide 6 blends

Silica (SiO₂) nanohybrid expandable graphite (nEG) particles fabricated through one-step method are used as an efficient flame retardant for polypropylene (PP)/polyamide 6 (PA6) blends. The effect of nEG on the flammability, thermal stability, crystallization behaviors, and mechanical properties of PP/PA6 composites is investigated by using limit oxygen index (LOI), UL-94 test, cone calorimeter test (CCT), thermogravimetric analysis, differential scanning calorimetry, Fourier transform infrared, scanning electron microscopy, and mechanical tests. Compared with pure expandable graphite (EG), nEG improves the flame retardancy of composites. The results of LOI show that LOI of PP/PA6/nEG10 and PP/PA6/nEG15 composites are 26.0% and 27.2%, respectively. But the LOI values of PP/PA6/EG10 and PP/PA6/EG15 composites are 25.7% and 26.9%, respectively. The UL-94 test results show that PP/PA6/nEG10 composites reach V-1 level when the nEG content is only 10%. However, the PP/PA6 composites with 10% EG does not pass the UL-94 test. In addition, PP/PA6 composites with 15% nEG can reach V-0 level. The CCT results further show that nEG has a higher flame-retardant efficiency than pure EG for PP/PA6 blends. The thermal stability of PP/PA6/nEG composites is better than that of PP/PA6/EG composites. The mechanical property tests indicate that nEG is more conducive to maintain the tensile and impact strengths of PP/PA6 blends than EG due to the enhanced compatibility and interfacial adhesion.     

Influence of fullerenes on the thermal and flame-retardant properties of polymeric materials

At present, the application of fullerene in polymer materials has become an attractive issue. Fullerene can enhance the thermal and flame-retardant properties of polymers due to its high capacity to trap free radicals. Fullerene also has good synergistic effect with inorganic metal flame retardant, intumescent flame retardant, brominated flame retardant (BFR), clay, carbon nanotubes, graphene oxide, and so on. In this review, the impact and mechanism of fullerene and its derivatives on the thermal and flame-retardant properties of polymeric materials are discussed. And the prospect of fullerene in flame-retardant polymer composites is also briefly introduced by analyzing the research progress in the recent years. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 47538.     

玻纤增强聚酰胺6/次磷酸钇复合材料的制备及其阻燃性能

以六水合氯化钇(YCl3?6H2O)和次磷酸钠(NaH2PO2)为原料,采用共沉淀法制备了一种新型稀土金属次磷酸盐-次磷酸钇(YHP),对其进行了表征;以YHP为阻燃剂,采用熔融共混法制备了系列玻纤增强聚酰胺6(GFPA)/次磷酸钇复合材料(GFPA/YHP),采用热重、极限氧指数(LOI)、UL-94垂直燃烧和微型量热测试研究了YHP添加量对复合材料热稳定性、阻燃性能及燃烧性能的影响. 结果表明,YHP已成功制备,其具有棒状结构,长度为20?100 ?m,宽度为5?20 ?m,热稳定性很高,降解温度T5%为410℃,最大热失重速率温度Tmax为412℃,750℃下热解的残炭率为90.8wt%. 加入YHP降低了GFPA/YHP复合材料的热分解温度,但提高了其成炭率和高温稳定性,YHP添加量为20wt%时,复合材料的热分解温度为373℃,最大热失重速率温度为414℃,700℃下热解的残炭率为50.42wt%;YHP可有效提高复合材料的阻燃性能,极限氧指数(LOI)达27.5vol%,垂直燃烧级别达UL-94 V-1级;YHP可有效降低复合材料燃烧过程的热释放速率峰值(PHRR)和总放热(THR)量,二者分别降至327 W/g和15.8 kJ/g,比GFPA分别下降了14.1%和25.4%,表明YHP有效降低了GFPA/YHP复合材料燃烧的火灾危险性.     

Synthesis of novel phosphorus-containing epoxy hardeners and thermal stability and flame-retardant properties of cured products

Two novel flame-retardant curing agents for epoxy resins, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO)-containing 4-[(phenylamino)methyl]phenol (P-Ph) and DOPO-containing Mannich-type bases (P-DDS-Ph), were synthesized by the condensation of 4-hydroxybenzaldehyde with 4-aminophenol and DDS, respectively, followed by the addition of DOPO to the resulting imine linkage. Chemical structures of these materials were characterized with FTIR, ¹H-NMR spectra, ³¹P-NMR spectra, and elemental analysis. The thermal properties and flame retardancy of o-cresol novolac epoxy resin (CNE) cured with different contents of the phosphorus-containing compounds were investigated by nonisothermal differential scanning calorimetry, thermogravimetric analysis, and limiting oxygen index (LOI). The obtained results showed that more char was formed while containing lower contents of the phosphorus-containing compounds in the P-Ph/CNE and P-DDS-Ph/CNE indicating their excellent flame retardancy. Moreover, the P-DDS-Ph/CNE exhibited higher T_g (224°C) and better thermal stability (T_10%, 330°C) than that of P-Ph/CNE. Therefore, the developed P-DDS-Ph/CNE may be potentially used as environmentally preferable products in electronic fields. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation,thermal properties and permeabilities of aluminum-coated fabrics destined for thermal radiation protective clothing

In this study, radiant reflective, flame retardant and water vapor permeable coatings were fabricated on aramid fabric (AF) for thermal radiation protective clothing by using a simple cost-effective coating method, which included an aluminum paste, APP-PER-MEL and a silk fibroin powder in the TPU solution system. The permeability, flame retardancy, thermal stability, radiative spectral reflectance, as well as RPP of these prepared fabrics were characterized and compared with the pure AF and aluminum-foiled AF (AF-AF). Results show that the newly developed aluminized AF had rather high permeability, and the permeable capability would be further enhanced with the additive of silk fibroin powder. The flame retardancy (FR) of the coated fabric sample was also achieved by introducing an intumescent FR system. In contrast to the pure AF, the aluminum-coated AF provided higher levels of radiation protection in RPP testing. This was further confirmed by the fact that aluminum-coated AF exhibited comparative high average reflectivities (more than 0.7) in the radiant spectral range of 1547 nm to 2500 nm. Thus, the aluminum-coated AF prepared by functional coating method exhibit great and competitive practicability in thermal protective clothing due to their excellent moisture comfort and radiant thermal protection.     

Enhanced mechanical and thermal properties of graphene nanoplatelets-reinforced polyamide11/poly(lactic acid) nanocomposites

The present paper aims to obtain a sustainable nanocomposite by using bio-based polyamide 11 and biodegradable poly (lactic acid) blend as matrix and graphene nanoplatelets (GNP) as nanofiller. GNP was incorporated in the PA11/PLA blend matrix in the ratio of 0.5-1-3-5-10 wt% through the twin-screw extruder. The crystallinity of PA11 in the blend, which was 12.9%, increased with the inclusion of GNP, and the highest crystallinity value was observed at 20% for the 1GNP sample. The crystallinity of PLA in the blend, which was 2.3%, increased to 4.6% with 5 wt% GNP addition. The inclusion of GNP to PA11/PLA improved the thermal degradation temperatures and increase the char residue. Also, increments were observed for storage modulus, loss modulus, and glass transition temperature of the matrix with the inclusion of GNP. The addition of GNP caused the tensile strength of the matrix to increase first and then decrease at higher amounts due to the agglomerations. 0.5–1 wt% GNP increased tensile strength by 10% and 5%, respectively. Increasing the amount of GNP to 10 wt% led to a sharp decrease in tensile strength by 24%. Overall, GNP is a suitable nanofiller to enhance the thermal and mechanical features of the PA11/PLA blend.     

Fiber formation and properties of polyester/lignin blends

Thermotropic liquid crystalline polyesters with varied chemical structure are synthesized by melt transesterification polycondensation. They are employed as matrix for blends with lignin materials to obtain melt-spinnable precursors for carbon fibers. The lignin samples are carefully purified by fractionation, enzymatic removal of reducing sugars, and subsequent modification of the terminal OH groups. Effective melt blending is achieved with liquid-crystalline aromatic–aliphatic polyesters having melting ranges that match the softening temperature of the lignin fractions, which is necessary to prevent thermal decomposition of the lignin. Polyester/lignin blends are partially compatibilized, phase-separated materials. The polyester/lignin materials are melt-spun successfully. The fiber properties depend on the lignin purification process. X-ray scattering reveals that orientation in lignin-containing fibers is maintained. First experiments show that the fibers can be converted successfully to carbon fibers by thermal annealing procedures. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48257.     

Adhesion at copper- polyamide 11- copper and aluminum-poly amide 11-aluminum laminate interfaces: influence of metal surface oxidation

Adhesion at copper-polyamide 11-copper and at aluminum-polyamide 11-aluminum laminate interfaces was studied. Metal-polymer-metal laminates were prepared by compression molding using processing conditions similar to the normal melt processing of polyamide 11. The results show that the time of contact at the molding temperature required to reach a constant level of adhesion is significant. Mild oxidation of the metal prior to molding improves the adhesion of polyamide 11 to aluminum; with copper, a monotonic slow decrease in adhesion with the oxidation time is observed. The presence of a metal surface affects the crystallization behavior of polyamide. With a cooling rate of 40-50°C/min, an approximately 15 μm transcrystalline polymer layer is formed with a degree of crystallinity that is almost 10% higher than the material away from the interface. The metal substrate surface oxidation prior to molding does not change the crystallinity profile of the polymer in the bulk. The polymer surface crystallinity is also a function of the time of contact with the metal substrate. The cooling rate and the metal substrate structure and its nucleating activity are responsible for the surface/bulk crystallinity ratio. Although the highly-crystalline polymer surface layer improves the adhesion to some extent, the formation of active species on the polymer surface which are able to react with the metal surface is mostly responsible for the increase of adhesion with time and its ultimate strength.     

碳纳米管改性方法对聚酰胺11性能影响研究

采用酸处理和聚乙烯亚胺(PEI)表面修饰两种方法对多壁碳纳米管(MWCNTs)进行改性,将改性碳纳米管与聚酰胺11(PA11)熔融共混,制备了聚酰胺11/酸刻蚀碳纳米管(PA11/a-MWCNTs)和聚酰胺11/聚乙烯亚胺接枝碳纳米管(PA11/PEI-MWCNTs)复合材料,并通过扫描电子显微镜(SEM)、热重分析仪...     

Enhancement of flame retardancy and mechanical properties of polyamide 6 by incorporating melamine cyanurate combined with attapulgite

In this study, the nanocomposites are prepared which used polyamide 6 (PA6) composite as matrix, melamine cyanurate (MCA) as fire retardant and attapulgite (AT) as synergistic agent. The mathematical model between MCA content, AT content, and limited oxygen index (LOI) is established by multiple linear regression fitting. The polymer materials are characterized using Fourier transform infrared spectroscopy, X-ray diffraction, Thermogravimetric Analysis, and scanning electron microscopy. Through response surface methodology, the important variables (polymerization time, the content of MCA, and the content of AT) affecting the mechanical strength of composites are modeled. Results demonstrate that when the t is 0.6 h, the AT content is 6.2%, and the MCA content is 11.5%, the mechanical properties of the PA6/MCA/AT composite are up to 44.81 MPa, and the sample passes the UL-94 V-0 flammability rating, and the LOI reaches 27.9%. Therefore, polymers with highly effective flame retardancy and optimal mechanical properties are prepared. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 47298.     

Efficient synthesis of phosphorus containing melamine salt for enhancing flame retardancy of poly(lactic acid)/polyamide 11 blends

A tetrakis (melamine)-1-hydroxyethylidene-1,1-diphosphonic acid salt (EA-MEL) was synthesized by a straightforward acid–base neutralization reaction between 1-hydroxyethylidene-1,1-diphosphonic acid (EA) and melamine (MEL). This compound, which contains phosphorus and nitrogen elements, exhibits a 40% carbon residue at a temperature of 800°C. When combined with diethyl aluminium hypophosphite (OP1230) as a flame-retardant composite in polylactic acid (PLA)/polyamide 11 blends through melt blending, a synergistic effect between the two flame retardants is observed. Consequently, the limiting oxygen index value significantly increases to 34.3, showcasing a remarkable 64.6% improvement. Additionally, the material achieves a V-0 rating according to UL-94 standards, and the peak heat release rate drops to 269 kW∙m⁻² with the addition of just 5 wt% EA–MEL. These results demonstrate that EA-MEL and OP1230 contribute to the generation of phosphoric acid derivatives and the formation of a crosslinked ( P N )_n or ( P O N )n network. This network enables the formation of a complete, compact, and expanded char residue, effectively isolating heat and oxygen.     

Flame retardancy and thermal stability of polyhedral oligomeric silsesquioxane nanocomposites

The flame retardancy and thermal stability of polyhedral oligomeric silsesquioxane (POSS) nanocomposites are reviewed. Results are summarized and compared on the basis of structure–property relationships. Because of the variability of groups attached on POSS, they exhibit different performance in polymer nanocomposites: metal‐containing POSS show good catalytic charring ability; vinyl‐containing and phenyl‐containing POSS promote the strength of char. Improvements in the cone calorimeter (such as reduced peak heat release rate) are advantages of POSS as preceramics for fire retardancy compared with traditional flame retardants, and it will pave the way to the design of inorganic–organic hybrid polymer nanocomposites with enhanced flame retardancy and thermal stability. Copyright © 2011 John Wiley & Sons, Ltd.     

Effect of talc on thermal stability and flame retardancy of polycarbonate/PSBPBP composite

A novel flame retardant poly(3-aminopropyl methylsiloxane bis(3-hydroxy phenyl spirocyclic pentaerythritol bisphosphate)) (PSBPBP) in combination with talc was blended into polycarbonate (PC) by melt compounding. The flame retardancy and thermal stability of PC/PSBPBP/talc composites were investigated by limiting oxygen index (LOI) test, UL-94 rating test, thermogravimetric analysis (TGA), Raman spectroscopy (RS), and scanning electron microscope (SEM). The mechanical properties were also measured in this work. Increasing talc content leads to observed improvement on flame retardancy of PC composites. LOI value of PC/PSBPBP/10 wt % talc system was 34, and this system passed V0 rating in the UL-94 test. The char yield at 700°C was 28.2% and the onset decomposition temperature shifted up to 540°C for PC/10% PSBPBP/10% talc system in TGA. In the Raman measure, the R value and G linewidth of PC/PSBPBP with 10 wt % talc composite increased to 1.41 and 65 cm⁻¹ from 1.12 and 43 cm⁻¹ of pure PC, respectively. The Raman results suggest that the char residue of PC/PSBPBP with talc composites was denser and had better barrier property, which is agreement with the SEM results. Besides, talc had no remarkable influence on the mechanical properties of PC/PSBPBP composites. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

The effect of different organic modified montmorillonites (OMMTs) on the thermal properties and flammability of PLA/MCAPP/lignin systems

The effect of different organic modified montmorillonites (DK1, DK2, and DK4) based on a novel intumescent flame retardant (IFR) poly(lactic acid) (PLA) system is reported. The IFR system was composed of microencapsulated ammonium polyphosphate and lignin. The morphological characterization of PLA/OMMT nanocomposites was conducted by X‐ray diffractometry and transmission electron microscopy. The flame retardant and thermal properties of the composites were evaluated by limiting oxygen index (LOI), vertical burning test (UL‐94), and cone calorimeter. From the results, it could be seen that the sample containing DK2 possessed the best flame retardance, such as lower peak heat release rate (pHRR) and higher LOI value. The thermal degradation and gas products of the samples were monitored by thermogravimetric analysis and thermogravimetric analysis infrared spectrometry. Scanning electron microscopy was used to explore the surface morphology of the char residues. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2013