Preparation and smoke suppression mechanism of flame-retardant PBS composites with BNNS@DOPA

Currently, the flame-retardant modification of polybutylene succinate (PBS) is mainly focused on improving flame-retardant efficiency, ignoring the negative impact of the smoke produced by combustion on the human respiratory tract. To address this problem, PBS composites were prepared by melt blending method in this study. The effect of boron nitride-grafted DOPO flame retardant (BNNS@DOPA) on flame retardancy and smoke suppression of PBS composites was investigated. Incorporating 3% BNNS@DOPA into PBS composites results in a 90% improvement in thermal conductivity. This resulted in a reduction of the peak heat release rate, total heat release rate, and actual smoke rate to 453.7 kW m⁻², 86.3 MJ m⁻², and 1035.9 m², respectively, compared with pure PBS. The latter indicated a decrease of 34.0%, 37.6%, and 51.2%, respectively. Furthermore, the ignition time was extended by 45 s and the limiting oxygen index value increased by 12.5%. This functionalization approach presents a new way to study PBS flame retardancy improvement, consequently boosting its application in fire safety for polymer materials.     

典型添加型磷酸酯/可膨胀石墨阻燃聚氨酯泡沫行为研究

对比了3种典型的添加型磷酸酯,亚磷酸二甲酯（DP）、甲基膦酸(5乙基2甲基2氧代1,3,2二氧磷杂环己5基)甲基甲基酯（EMD）和甲基膦酸二甲酯（DMMP）分别与可膨胀石墨（EG）复合阻燃硬质聚氨酯泡沫（RPUF）,研究了3种不同结构的磷酸酯对材料阻燃性能的影响。结果表明,在3种磷酸酯添加相同质量的情况下,添加DMMP和DP样品的极限氧指数明显高于添加EMD的,且添加DMMP样品的热释放速率峰值和热释放总量最低,在3种磷酸酯中具有最好的阻燃行为表现;DP由于在燃烧过程中发生氧化反应而加剧了体系放热从而降低了阻燃效果;EMD通过分解首先释放DMMP,但由于其磷含量偏低,因此阻燃效率低于DMMP;DMMP由于具有磷含量高、气相和凝聚相阻燃效率高等优点与EG配合产生了最佳的阻燃效果。     

Lightweight,Elastomeric, and Flame‐Retardant Foams from Expanded Chlorinated Polymers

Intrinsically flame‐retardant polymers based on lightweight and elastomeric microcellular foams are successfully prepared from flexible chlorinated polyethylene (CPE)/chlorinated polyvinylchloride (CPVC) compounds through compression molding foaming technology. The incorporation of CPVC to CPE at once improves the foam characteristics, and enhances the mechanical and fire performances. Due to the plausible intermolecular and intramolecular crosslinking among the polymer chains, the dense network structure of CPE/CPVC with enhanced strength results in increased cell size, reduced cell density, and improved dimensional stability of CPE/CPVC foams (CCFs). These improvements are noticed to be enhanced with increasing CPVC content in the CCF. Also, the flame‐retardant properties of the foams (i.e., limiting oxygen index and cone calorimeter combustion) are found to be increased with the increase of CPVC content. For instance, a highly flame‐retardant CCF at CPE/CPVC ratio of 60/40 shows a shorter combustion period, as derived from the respective heat release rate vs time curve. Corresponding peaks of heat release rate, total heat release rate, peak of mass loss rate, total smoke release, and char residue are recorded to be 8.4%, 5.8%, 3.0%, 6.6%, and 1000.1% of those recorded for the pristine CPE foam.     

Simple and feasible strategy to fabricate microcellular poly(butylene succinate) foams by chain extension and isothermal crystallization induction

In this article, a facile and efficient isothermal crystallization induction method was proposed to fabricate microcellular poly(butylene succinate) (PBS) foams with supercritical CO₂. The good regularity of PE chain segments and high reactive epoxy groups in ethylene-glycidyl methacrylate copolymer (PE-g-GMA) serving as a chain extender were employed to improve the crystallization behaviors, viscoelasticity, and foaming behaviors of PBS through chain extension reaction. The effect of PE-g-GMA content on the thermal properties, rheological performances, and cellular morphology of various PBS samples was investigated systematically. When the PE-g-GMA content switched from 7.5 to 10 wt %, an interesting transition from fine cells to microcells was observed in PBS/PE-g-GMA foams. Microcellular PBS foam modified by 10 wt % PE-g-GMA was successfully prepared at the foaming temperature of 87 °C and the induction time of 7 min, in which its cell size and cell density could reach 6.63 ± 1.93 μm and 3.75 × 10⁹ cells cm⁻³, respectively. The formation of abundant but tiny spherocrystals in chain extended PBS samples made a considerable contribution for preparing microcellular PBS foams. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48850.     

Combustion behaviour of polyurethane flexible foams under Cone Calorimetry test conditions

The first part of this study focuses on the effect of cone calorimeter test variables on polyurethane flexible foam properties such as ignitability, heat release rate, effective heat of combustion and mass loss. Three of the main commercial foam types were used, i.e. conventional slabstock foams, high-resilience slabstock foams and all-MDI (methylene diphenyldiisocyanate) moulded foams. A decrease in heat flux (down to 40%) with increasing distance from the conical heater was measured. As a consequence, results were found to depend to a large extent on the thickness and the melting behaviour of the foam samples. To achieve a sufficiently constant and uniform heat flux exposure, sample thickness had to be limited to 25 mm. In addition, repeatability was found to be good under various conditions, with percentage standard deviations for effective heat of combustion, peak rate of heat release and mass loss below 10%. Levels of radiant flux above 25 kW m^?2 were found to be very severe to test flexible polyurethane foams. Under such conditions, foams that show large differences in combustion performance in small-scale flammability tests performed almost identically in the cone calorimeter. In the second part of this study the effects of foam variables, such as foam type, density and melamine content, are defined. These effects were clearly pronounced at radiant flux levels of 15–25 kWm^?2. Density was found to be the key variable in controlling ignition resistance. In addition, high-resilience slabstock foams and all-MDI moulded foams performed better than conventional slabstock foams of the same density. Melamine addition resulted in a delay of ignition for all three foam types and an incomplete combustion, decreased heat release and effective heat of combustion in HR-slabstock and all MDI moulded foams. However, melamine is not effective as a heat sink in conventional slabstock foams. The different performance of the foam types under study can be explained by a different melting behaviour.     

Vermiculite Filler Modified with Casein,Chitosan, and Potato Protein as a Flame Retardant for Polyurethane Foams

In this study, polyurethane (PU) composite foams were modified with 2 wt.% of vermiculite fillers, which were themselves modified with casein, chitosan, and potato protein. The impact of the fillers on selected properties of the obtained composites, including their rheological (foaming behavior, dynamic viscosity), thermal (temperature of thermal decomposition stages), flame-retardant (e.g., limiting oxygen index, ignition time, heat peak release), and mechanical properties (toughness, compressive strength (parallel and perpendicular), flexural strength) were investigated. Among all the modified polyurethane composites, the greatest improvement was noticed in the PU foams filled with vermiculite modified with casein and chitosan. For example, after the addition of modified vermiculite fillers, the foams’ compressive strength was enhanced by ~6–18%, their flexural strength by ~2–10%, and their toughness by ~1–5%. Most importantly, the polyurethane composites filled with vermiculite filler and modified vermiculite fillers exhibited improved flame resistance characteristics (the value of total smoke release was reduced by ~34%, the value of peak heat release was reduced by ~25%).     

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.     

Rheological properties and foam preparation of biodegradable poly(butylene succinate)

To produce biodegradable poly(butylene succinate) (PBS) foam by compression molding, high viscosity PBS was prepared with dicumyl peroxide (DCP) as a crosslinking agent and trimethylolpropane trimethacrylate (TMPTMA) as a curing coagent by crosslink method. The influences of various factors on the foaming process and the properties of PBS foams were investigated. The results show that the use of DCP and TMPTMA simultaneously can effectively increase the melt viscosity of PBS. Zinc oxide/zinc stearate was used to reduce the thermal decomposition temperature of the blowing agent azodicarbonamide, which can balance well the vulcanization of PBS and the decomposition of blowing agent. Finally, closed‐cell PBS foams with degradable property have been successfully prepared by a traditional chemical compression molding foaming way. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

淀粉改性PBS的燃烧性能研究

在35 kW/m2热辐射功率下,研究了淀粉含量对聚丁二酸丁二醇酯(PBS)燃烧性能的影响。结果表明:PBS/淀粉的总热释放量(THR)、热释放速率(HRR)和有效燃烧热(EHC)随着淀粉含量的增加先降低再升高。当PBS与淀粉的质量比为10:2时,PBS/淀粉的燃烧性能最好。比较了PBS、PBS/淀粉和PBS/木粉在同样条件下的燃烧情况,其HRR的大小为:PBS/木粉>PBS>PBS/淀粉,而生烟速率SPR的顺序为:PBS>PBS/木粉>PBS/淀粉。     

Influence of modified fiber–MHSH hybrids on fire hazards,combustion dynamics,and mechanical properties of flame-retarded poly(butylene succinate) composites

Environmental problems caused by polymers and polymers have historically dominated both academic and industrial attention. Sustainable biodegradable wood-plastic composites (WPCs) as an optimum can solve the environmentally critical problems caused by petroleum-based polymers. However, they are flammable, prone to fire accidents, and often have a contradiction between mechanical performance and flame-retardant properties, which limits their range of applications. Here, we reported a flame-retarded poly(butylene succinate) (PBS) WPC prepared with modified natural fiber-magnesium hydroxide sulfate whisker (MHSH) hybrids and intumescent flame retardant s (IFRs). The mechanical performance, flame-retardant properties , thermal stability, and actual fire simulation parameters of composites were investigated. Owing to the unique composition characteristics of modified cassava dregs-MHSH hybrids, the mechanical properties (70P/23I/5C/2M, flexural strength was 39.2 ± 1.960/MPa, impact strength was 7.95 ± 0.3975/ [KJ/m²]), flame retardant properties (70P/23I/5C/2M, the limiting oxygen index value was 39.6%, UL-94 was V0) and thermal stability of WPC have been improved. Thereby, the balance between mechanical performance and flame retardant properties of biocomposites has been achieved in the practical engineering requirements. Furthermore, cone calorimeter data indicated that modified cassava dregs–MHSH hybrids played a role in improving the fire safety of composites. The total heat release, total smoke produce, toxic gas release, and total oxygen consumed of 70P/23I/5C/2M were lowered compared with those of 70P/25I/5C. Dynamics analysis indicated that the addition of modified cassava dregs–MHSH hybrids increased the activation energy of composites. Based on the experimental and analyses data, especially the morphological characterization of char residue analysis, it illustrated that modified cassava dregs–MHSH hybrids have a reinforcement and flame-retardant effect. The combusted residue of the incorporated modified cassava dregs–MHSH hybrids could support the three-dimensional charred layer formed by the combustion products of the IFR and the PBS. Thus, the more stable three-dimensional charred layer could not only effectively reduce thermal conductivity of composites but also hinder the propagation of heat into the interior substrate, thereby improving the flame-retardant properties of the WPC. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48490.     

Fire performance and mechanical properties of phenolic foams modified by phosphorus-containing polyethers

Two kinds of novel phosphorus-containing polyether toughening agents were synthesized and characterized by ¹H nuclear magnetic resonance (¹H NMR) and Fourier transform infrared spectra (FTIR). Afterwards, a series of phenolic foams with different loadings of phosphorus-containing toughening agents were prepared. The apparent density and scanning electron microscopy (SEM) results showed that the addition of 5 wt% toughening agents increased the expansion ratio and promoted the formation of uniform cells. The limiting oxygen index (LOI) values of modified phenolic foams decreased with the increase of modifier content, but it still remained at 40% even if the amount of modifier loadings was 10 wt%. UL-94 results showed all samples can pass V0 rating, indicating the modified foams still have great flame retardance. Microscale combustion calorimetry (MCC) results indicated that the peak heat release rate (PHRR) and total heat release (THR) of the modified foams were reduced by 42% and 35%, respectively, compared to the pure phenolic foams. Moreover, the thermal stability of samples was investigated by thermogravimetric analysis (TGA). The mechanical properties were evaluated and correlated with composition and structural features.     

Flame resistance and foaming properties of NBR compounds with halogen‐free flame retardants

Acrylonitrile butadiene rubber (NBR) foams compounded with various halogen‐free flame retardants were prepared. The influence of nonhalogen flame retardants on the flame resistance and foaming properties of the NBR compounds were investigated. The foaming properties (expandability 980%–1050%, closed‐cell structure) of NBR compounds with expandable graphite (EG) and ammonium polyphosphate (APP) flame retardants were similar to the NBR base compounds which contained primarily aluminum hydroxide (ATH). The heat release capacity (HRC) ranged from 10 to 74 J/g‐K, the average heat release rate (A‐HRR) ranged from 8 to 60 kW/m², and the total heat release (THR) ranged from 2.6 to 7.3 MJ/m² for the nonhalogenated NBR foams with closed‐cell structure and were significantly decreased upon increasing the amounts of flame retardants. This reduction is attributed to the hard char formation and production of water from the interaction with ATH. The limiting oxygen index (LOI) and time to ignition (TTI) show opposite results. The smoke density (0.050–0.037) of the NBR foams with EG flame retardant was decreased when compared to the NBR foam (0.107). The EG flame retardant was more effective than the phosphorus/nitrogen flame retardants in reducing the HRR and smoke density. The use of both ATH and EG is very effective in improving flame resistance. POLYM. COMPOS., 2009. © 2009 Society of Plastics Engineers     

The preparation and properties of polystyrene/functionalized graphene nanocomposite foams using supercritical carbon dioxide

In this work, polystyrene (PS)/functionalized graphene nanocomposite foams were prepared using supercritical carbon dioxide. Thermally reduced graphene oxide (TRG) and graphene oxide (GO) were incorporated into the PS. Subsequently, the nanocomposites were foamed with supercritical CO₂. The morphology and properties of the nanocomposites and the nucleation efficiency of functionalized graphene in foaming PS are discussed. Compared with GO, TRG exhibited a higher nucleation efficiency and more effective cell expansion inhibition thanks to its larger surface area and better exfoliated structure. It is suggested that the factors that have a significant influence on the nucleation efficiency of TRG and GO originate from the differences in surface properties and chemical structure. Furthermore, PS/TRG nanocomposites and their nanocomposite foams also possess good electrical properties which enable them to be used as lightweight functional materials.© 2012 Society of Chemical Industry     

Preparation and characterization of the halogen-free,smoke suppression,organic–inorganic hybrid flame-retardant expandable polystyrene materials

Expandable polystyrene (EPS) is a plastic widely used in the field of construction, but it is flammable. This work provided a novel strategy for flame-retardant modification of EPS. A kind of polyester polyol (JZP) with the high content of phosphorus and nitrogen was synthesized. Then, intrinsic flame-retardant polyurethane (PFWPU) with the high content of phosphorus and nitrogen was synthesized by JZP acted as soft segment chain extender. Finally, a high-efficiency flame-retardant expandable polystyrene thermal insulation material (AF-EPS) was prepared by the organic–inorganic hybrid flame-retardant synergistic action of PFWPU and ammonium polyphosphate. The effects of different contents of inorganic flame retardants on flame retardancy of materials were studied by limiting oxygen index (LOI), cone calorimetry, thermogravimetric analysis/infrared spectrometry , scanning electron microscopy, and so on. The test results showed that the carbon residue rate of the modified material increased from 0 to 28.5%, the LOI increased from 17 to 35.8%, and the vertical combustion test reached the highest grade V-0. In addition, the total smoke production of AF-EPS samples decreased from 2.33 m² to 0.57 m², the time to ignition was increased to 41 s, and the peak heat release rate and the total heat release were decreased by 90.2 and 62.7%, respectively.     

EG和DBDPE/Sb_2O_3协同阻燃ABS的阻燃性能及机理研究

将可膨胀石墨(EG)与十溴二苯乙烷/三氧化二锑(DBDPE/Sb2O3)复配制备ABS阻燃复合材料,通过锥形量热仪和热重分析等方法研究了EG和DBDPE/Sb2O3协同阻燃ABS的燃烧性能,探讨了二者的协同阻燃机理。结果表明:与纯ABS相比,EG与DBDPE/Sb2O3共用使ABS阻燃复合材料的峰值和平均热释放速率分别下降了73.5%和63.8%,峰值质量损失速率降低52.04%,平均有效燃烧热降低19.96%,成炭量增加;EG阻燃ABS为典型的凝聚相阻燃机理,DBDPE/Sb2O3阻燃ABS为气相阻燃机理,二者并用时可以同时发挥凝聚相阻燃和气相阻燃作用,但以凝聚相阻燃机理为主;热重分析表明EG与DBDPE/Sb2O3具有协同作用,ABS分解峰的峰值热失重速率下降25.2%,二者可以互相促进ABS成炭,EG可以保护ABS成炭产物,提高实际成炭量。     

Effect of processing conditions on poly(butylene succinate) foam materials

Polymeric foams have many advantages such as light weight, high specific strength, strong energy absorption, as well as good sound and thermal insulation. Unfortunately, most polymeric foams such as polyvinyl chloride foams do not undergo natural degradation and thus giving rise to white pollution to the environment. Here, we report the preparation and properties of poly (butylene succinate) (PBS) foam which is a biodegradable plastic. Ammonium bicarbonate is used as the foaming agent during the formation of the PBS foam by the molding method, and under the optimal conditions of 5 wt % ammonium bicarbonate, 10 MPa pressure, and 5 min pressing time, the pristine PBS foam with the smallest bulk density can be obtained, whereas under the conditions of 5 wt % ammonium bicarbonate, 7.5 MPa pressure, and 7 min pressing time, the toughening PBS foam has the smallest bulk density. Adding talc as a nucleating agent can reduce the bulk density of the foam and in this case, an NH₄HCO₃ content of 3 wt % yields the best result. Moreover, addition of plasticizers can effectively improve the mechanical properties of the products. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

阻燃聚丁二酸丁二醇酯复合材料的制备及其阻燃性能研究

采用熔融共混技术,将次磷酸铝(AHP)和三聚氰胺氰尿酸盐(MC)引入聚丁二酸丁二醇酯(PBS),制备了一系列阻燃PBS复合材料,并采用极限氧指数、垂直燃烧、微型量热测试以及热失重分析研究了复合材料的阻燃性能以及热稳定性。结果表明,AHP可以有效提高PBS复合材料的阻燃性能;AHP与MC复配可以进一步提高复合材料的阻燃性能,两者质量比为2∶1,添加量为20 %（质量分数,下同）即可使复合材料达到UL 94 V 0级别,极限氧指数达到29 %;AHP以及复合阻燃体系可以有效提高复合材料初始分解温度及其高温稳定性。     

Broad-band electrical conductivity of carbon nanofibre-reinforced polypropylene foams

The influence of foaming a semi-crystalline polymer reinforced with different concentrations of carbon nanofibres (0–20 wt.%) on the formation of an electrically conductive network was studied at room temperature using an impedance analyzer over a wide interval of frequencies (from 10⁻² to 10⁶ Hz). Composites were prepared by melt-compounding using a twin-screw extruder, and later chemically foamed. Although composite materials displayed lower conductivities than expected, assuming a percolative behavior, foaming promoted a tunnel-like conduction at lower CNF concentrations than in the solids. At higher CNF concentrations, no great improvements were achieved as tunneling conduction decreased with increasing local crystallinity. Foams showed electrical conduction characteristics typical of a conductive random-distributed fibre-like system, while the behavior of the solids was closer to a system of spherical particles, related to CNF aggregation. The anisotropic cellular structure of the 20 wt.% CNF composite foamed by a physical foaming process disrupted the preferential in-plane CNF orientation attained during solid preparation, with these foams showing higher through-plane conductivity and more isotropic electrical properties than the chemically-foamed ones. It has been demonstrated that foaming PP–CNF composites resulted in the formation of a conductive network at lower CNF concentrations than in the solids, with foams showing the potential for use in conductive high-performance lightweight composite systems.     

Bi-phase flame-retardant effect of hexa-phenoxy-cyclotriphosphazene on rigid polyurethane foams containing expandable graphite

The flame-retardant rigid polyurethane (PU) foams with hexa-phenoxy-cyclotriphosphazene/expandable graphite (HPCP/EG) were prepared through box-foaming in our laboratory. The flame retardancy of PU foams was characterized using the limiting oxygen index and cone calorimeter. The results show that the incorporation of HPCP into the PU foams containing EG enhanced flame retardancy. The main degradation process of HPCP in PU foams was investigated by pyrolysis gas chromatography/mass spectroscopy. HPCP during combustion generated phenoxyl and PO₂ free radicals, which could quench the flammable free radicals produced by the matrix and hamper the free radical chain reaction of combustion. This observation shows that HPCP produced a gas-phase flame-retardant effect in this specimen. Additionally, micro-morphology, elemental composition and content of residual char of the flame-retardant PU foams after the cone calorimeter test were also characterized using scanning electron microscope and energy dispersive X-ray microanalyser. The results exhibit that the partial phosphorus from HPCP remained in the residual char, and HPCP significantly enhanced the strength and compatibility of the char layer formed by the PU foams containing EG. These results indicate the important function of HPCP in condensed phase. Thus, HPCP exhibited gas-phase and condensed-phase flame-retardant effects on the PU/EG foams.