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1.
利用9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)和马来酸酐(MA)对淀粉进行改性得到磷化淀粉(DOPOMASt),通过红外光谱(FTIR)、核磁共振谱(1H-NMR)和X射线光电子能谱(XPS)确定其结构.利用DOPOMASt作为碳源,与聚磷酸铵(APP)复配后通过熔融共混制备了阻燃聚乳酸(PLA)...  相似文献   

2.
The charring agent (CNCA‐DA) containing triazine and benzene rings was combined with ammonium polyphosphate (APP) to form intumescent flame retardant (IFR), and it was occupied to modify polylactide (PLA). The flame retardant properties and mechanism of flame retardant PLA composites were investigated by the limited oxygen index (LOI), vertical burning test (UL‐94), thermogravimetric analysis, microscale combustion calorimetry, scanning electron microscopy, laser Raman spectroscopy analysis and X‐ray photoelectron spectroscopy. The analysis from LOI and UL‐94 presented that the IFR was very effective in flame retardancy of PLA. When the weight ratio of APP to CNCA‐DA was 3:1, and the IFR loading was 30%, the IFR showed the best effect, and the LOI value reached 45.6%. It was found that when 20 wt% IFR was loaded, the flame retardancy of PLA/IFR still passed UL‐94 V‐0 rating, and its LOI value reached 32.8%. The microscale combustion calorimetry results showed that PLA/IFR had lower heat release rate, total heat release, and heat release capacity than other composites, and there was an obvious synergistic effect between APP and CNCA‐DA for PLA. IFR containing APP/CNCA‐DA had good thermal stability and char‐forming ability with the char residue 29.3% at 800°C under N2 atmosphere. Scanning electron microscopy observation further indicated that IFR could promote forming continuous and compact intumescent char layer. The laser Raman spectroscopy analysis and X‐ray photoelectron spectroscopy analysis results indicated that an appropriate graphitization degree of the residue char was formed, and more O and N were remained to form more cross‐linking structure. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   

3.
A series of FR-RPUF composites were prepared by a one-step water foaming process with ammonium polyphosphate (APP) and steel slag (SS) as flame retardants. Thermogravimetric analysis (TG), limiting oxygen index (LOI), UL-94 vertical combustion test, microscale combustion calorimetry (MCC), TG-Fourier transform infrared spectrometry (TG-FTIR), scanning electron microscopy (SEM), Raman spectra and FTIR were used to investigate the thermal stability, flame retardancy, combustion performance, gas phase products, and char residue morphology of FR-RPUF composites. TG test results showed that the initial decomposition temperature (T-5wt%) and char residue rate at 700°C of RPUF/APP/SS composites were significantly enhanced by the addition of APP and SS, and the thermal stability of the composites was improved. Flame retardant test results confirmed the significantly increased LOI values of RPUF/APP/SS composites with V-0 rating. TG-FTIR also confirmed the obviously decreased release of toxic gases and flammable gases in the combustion of RPUF/APP/SS composites. SEM and Raman spectra of char residues for the composites suggested that APP/SS system improved the compactness and graphitization degree of char layer for RPUF/APP/SS composite. The above researches provide a new strategy for the utilization of SS in fire safety engineering.  相似文献   

4.
In this study, some aspects concerning the thermal decomposition of starch/poly(vinyl alcohol) (PVA)/montmorillonite (MMT) nanocomposites with 2 wt% nanoclay, prepared by melt mixing method, were studied. For these loadings, the inorganic fillers are well dispersed through the PVA/starch matrix, i.e., the nanocomposites formed are mostly intercalated hybrids. The aim of this article is to establish the effect of the nanofiller nature on the thermal decomposition of the starch/PVA/MMT nanocomposites. The thermal behavior of the 50 wt% starch/50 wt% PVA blend and its nanocomposites with 2 wt% nanoclay has been investigated by thermogravimetric analysis coupled with Fourier transform-infrared spectroscopy and mass spectrometry (MS). The volatile compounds resulting during the thermal degradation were studied by in situ vapor phase FT-IR spectroscopy and MS technique under a controlled temperature/time program. Apart from the identification of the volatile compounds, some conclusions on the nanoclays effect on the degradation mechanism and formation of the volatile compounds in accordance with the previously developed general mechanisms for PVA and starch degradation have been formulated. The clay–PVA/starch nanocomposites show completely different degradation product distribution patterns, which may be attributed to the presence of the head-to-head structures and Si–O–C linkages formed between clay and blend components.  相似文献   

5.
Starting from gypsum, a by-product of lactic acid fabrication process, novel “green” composites have been produced by melt-blending polylactide (PLA) and this filler after a previous specific dehydration to obtain anhydrite II (AII). Such a material is potentially interesting in biodegradable/rigid packaging and in technical applications requiring rigidity, heat resistance and dimensional stability. In order to obtain PLA-AII composites characterized by specific end-use flame retardant properties, the addition of selected organo-modified layered silicates (OMLS) was considered. Co-addition of AII and OMLS leads to PLA (nano)composites characterized by good (nano)filler dispersion, thermal stability and adequate mechanical resistance. The flame retardant properties as shown by cone calorimetry showed significant increase in the ignition time compared to neat PLA and a substantial decrease, i.e., ca. 40%, of the maximum rate of heat release, whereas the UL94 HB test was successfully passed revealing non-dripping effect and extensive char formation. The study represents a new approach in formulating novel PLA grades with improved characteristic features.  相似文献   

6.
The thermal and flame performances of intumescent flame retarded polypropylene (PP/IFR) composites with organically modified clay or sodium dodecyl sulfonate intercalated layered double hydroxide (SDS-LDH) were studied. The organo-clay particles were partially exfoliated in the PP matrix, while intercalation and aggregation was obtained for SDS-LDH. Incorporation of SDS-LDH improved the thermal stability and flame retardancy of the intumescent flame retarded PP composite in the early stage of heating and combustion; while the effects of organo-clay came into play in the middle-later stage. Differences in degradation pathway of clay and LDH were responsible for the above phenomenon which bore important implication for the barrier mechanism. The introduction of organo-clay into PP/IFR not only increased the char residue, but also formed compact and folded morphology of char residue which provided more effective protect for underlying materials against heat and oxygen relative to LDH, thus improved the flame retardancy of intumescent flame retarded PP samples more efficiently.  相似文献   

7.
In this study, a hybrid nanopaper consisting of carbon nanofiber (CNF) and polyhedral oligomeric silsequioxane (POSS) or cloisite Na+ clay, has been fabricated through the papermaking process. The hybrid nanopaper was then coated on the surface of glass fiber (GF) reinforced polymer matrix composites through resin transfer molding (RTM) process. The morphologies of the hybrid nanopaper and resulting nanocomposites were characterized with scanning electron microscopy (SEM). It can be seen that the nanopaper had a porous structure with highly entangled carbon nanofibers and the polyester resin completely penetrated the nanopaper throughout the thickness. The thermal decomposition behavior of the hybrid nanopapers and nanocomposites was studied with the real‐time thermogravimetric analysis/ flourier transform infrared spectrometry (TGA/FTIR). The test results indicate that the addition of pristine nanoclay increased the thermal stability of the nanopaper, whereas the POSS particles decreased the thermal stability of the nanopaper. The fire retardant performance of composite laminates coated with the hybrid nanopaper was evaluated with cone calorimeter tests using a radiated heat flux of 50 kW/m2. The cone calorimeter test results indicate that the peak heat release rate (PHRR) decreased dramatically in composite laminates coated with the CNF‐clay nanopaper. However, the PHRRs of the CNF‐POSS nanopaper coated composite laminates increased. The formation of compact char materials was observed on the surface of the residues of the CNF‐clay nanopaper after cone calorimeter test. The flame retardant mechanisms of the hybrid nanopaper in the composite laminates are discussed. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

8.
《先进技术聚合物》2018,29(3):1068-1077
The effect of 1,3,5‐triglycidyl isocyanurate (TGIC) as a synergistic agent on the fire retardancy, thermal, and mechanical properties for polyamide 6/aluminium diethylphosphinate (PA6/AlPi) composites were investigated in detail by limiting oxygen index; vertical burning (UL‐94); cone calorimeter; thermal gravimetric analysis; rheological measurements; and the tests of tensile, flexural, and Izod impact strength. The morphologies and chemical compositions of the char residue were investigated by scanning electron microscopy, X‐ray photoelectron spectroscopy, and Fourier transform infrared spectra. The results demonstrated that AlPi and TGIC exerted an evident synergistic effect for flame retardant PA6 matrix, and the PA6/AlPi/TGIC composites with the thickness of 1.6 mm successfully passed UL‐94 V‐0 rating with the limiting oxygen index value of 30.8% when the total loading amount of AlPi/TGIC with the mass fraction of 97:3 was 11 wt%. However, the samples failed to pass the UL‐94 vertical burning tests when AlPi alone is used to flame retardant PA6 matrix with the same loading amount. The thermal gravimetric analysis data revealed that the introduction of TGIC promoted the char residue formation at high temperature. The rheological measurement demonstrated that the incorporation of TGIC improved the storage modulus, loss modulus, and complex viscosity of PA6/AlPi/TGIC composites comparing with that of neat PA6 and PA6/AlPi composites due to the coupling reaction between TGIC and the terminal groups of PA6 matrix. The morphological structures of char residues demonstrated that TGIC benefited to the formation of more homogenous and integrated char layer with no defects and holes on the surface comparing with that of PA6/AlPi composites during combustion. The higher melt viscosity of composites and the integrated and sealed char layer effectively inhibited the volatilization of flammable gas into the combustion zone and then led to the reduction of the heat release. The results of mechanical properties revealed that the incorporation of TGIC enhanced the mechanical properties for PA6/AlPi/TGIC composites comparing with that of PA6/AlPi composites with the same loading amount of flame retardant caused by the chain extension effect of TGIC. As a result, the flame retardancy and mechanical properties of PA6/AlPi composites simultaneously enhanced due to the introduction of TGIC.  相似文献   

9.
Novel intumescent flame-retardant poly(lactic acid) (PLA/IFR)/organo-modified α-zirconium phosphate(OZrP) nanocomposites were prepared via incorporation of charring agent (CA), ammonium polyphosphate (APP) and OZrP into PLA. OZrP was synthesized directly by a solvent thermal method. The morphological characterization of PLA/IFR/OZrP nanocomposites was conducted by wide angle X-ray diffraction (WXRD) and transmission electron microscopy (TEM). The effect of the OZrP on flame retardancy and the thermal stability of PLA/IFR composites were studied by thermogravimetric analysis (TGA), limiting oxygen index (LOI), vertical burning test (UL-94) and cone calorimeter test. The TGA data illustrated that the OZrP could increase the residue and significantly improve the flame retardancy of PLA/IFR/OZrP nanocomposites showing an excellent synergistic effect. The addition of OZrP to the flame-retardant PLA increases the LOI and enhances the UL-94 rating. Cone calorimeter tests gave clear evidence that the incorporation of OZrP into PLA/IFR composites resulted in the significant reduction of the heat release rate (HRR), low total heat release (THR) and high amount of char residues during combustion. The flame-retardant mechanism of PLA/IFR/OZrP nanocomposites may correspond to the intumescent flame-retardant mechanism and catalyzed carbonization mechanism caused by OZrP.  相似文献   

10.
A hybrid nanopaper consisting of carbon nanofibre (CNF) and/or clay, polyhedral oligomeric silsesquioxane (POSS), ammonium polyphosphate (APP), has been fabricated through the papermaking process. The as-prepared hybrid nanopaper was then incorporated onto the surface of glass fibre (GF) reinforced polymer matrix composites through injection moulding. The morphologies of hybrid nanopapers with and without the polymer resin were characterized with scanning electron microscopy (SEM). The polymer resin penetrated the entire nanopaper under a high-pressure compressed air system. The thermal decomposition behaviour of hybrid nanopapers infused with resin was studied with real-time thermogravimetric analysis/Fourier transform infrared spectrometry (TGA/FTIR). The test results indicate that the addition of clay in the hybrid paper increased the char residues of the nanocomposites. The fire retardant performance of composite laminates incorporating hybrid nanopaper was evaluated by cone calorimeter testing using a radiant heat flux of 50 kW/m2. The cone test results indicated that the peak heat release rate (PHRR) decreased dramatically in the case of laminate composites incorporating CNF/clay/APP hybrid paper. However, the extent of reduction of PHRR of the composite laminates incorporated with CNF/POSS/APP hybrid paper was lower. The formation of compact char materials was observed on the surface of the residues and analyzed by SEM and X-ray photoelectron spectroscopy (XPS). The flame retardant mechanisms of hybrid nanopapers in composite laminates are discussed.  相似文献   

11.
庞永艳 《高分子科学》2015,33(5):772-782
The mechanism of char formation effect of zinc acetylacetonate(Zn(acac)2) on acrylonitrile-butadiene-styrene copolymer(ABS) was studied. Thermal gravimetric analysis(TGA) was used to study the mass loss and char yield of ABS composites. In situ temperature-dependent Fourier transform infrared spectroscopy(FTIR) was used to characterize the chemical change during thermal decomposition. Roman spectroscopy and scanning electron microscopy(SEM) were applied to characterize the structure and morphology of the char after combustion. Results showed that the presence of Zn(acac)2 not only slowed down thermal decomposition of the ABS composites, but also increased the charred residue. A more compact and denser char layer with higher graphitization degree was formed for ABS composites with Zn(acac)2. To study the char formation mechanism of Zn(acac)2 on ABS, thermal decomposition was analyzed for the composites of Zn(acac)2 with PB, PS and SAN, respectively. Also, the chemical structure change was investigated for Zn(acac)2 during thermal decomposition. Based on these results, it was deduced that the increase of char yield of ABS composites was probably attributed to the interaction between the units of acrylonitrile in ABS and zinc acetate, produced during the thermal decomposition of Zn(acac)2. A proposed mechanism for crosslinking and the subsequent char formation was presented.  相似文献   

12.
Melamine salt of pentaerythritol phosphate kaolin (MPPK) was synthesized by the reaction of pentaerythritol phosphate with kaolin (K) and melamine. The structure of MPPK was confirmed by EDXS, 1H NMR, FTIR, and XRD. MPPK was blended with polypropylene (PP) at different loading levels. Thermogravimetric analysis (TGA) results showed that MPPK improved the thermal stability of PP at high temperatures in all PP composites. Vertical burning rate test manifested that PP composites can achieve V0 at 20% and 25% MPPK loading levels. Cone calorimeter data exhibited that addition of 25% MPPK to PP reduced peak of heat release rate (pHRR) and total heat release (THR) by 86% and 76% and increased the char residue after test to 67%. The results of PP/25% MPPK composite were compared with the data obtained from PP containing 25% K and 25% of traditional intumescent flame retardant composed of melamine phosphate (MP), pentaerythritol (PE), and K. The outcomes indicated that MPPK was more efficient in flame retardancy than the other systems. The digital photographs and SEM images for char residue demonstrated that MPPK succeeded in forming cellular and coherent char layer on the PP surface. The main advantage of adding 25% MPPK to PP was its ability to preserve nearly the inner half of the sample without burning after cone calorimeter test.  相似文献   

13.
A novel hyperbranched polyamine charring agent (HPCA), a derivative of triazines, was synthesized and well characterized by 1H NMR and FTIR. HPCA and ammonium polyphosphate (APP) were added into polylactide (PLA) resin as an intumescent flame retardant (IFR) system to impart flame retardancy and dripping resistance to PLA. The flammability and thermal stability of IFR-PLA composites were investigated by limiting oxygen index (LOI), UL-94 vertical burning, cone calorimetry and thermogravometric analysis (TGA) tests. The results showed that the IFR system had both excellent flame retardant and anti-dripping abilities for PLA. The TGA curves suggested that HPCA has good ability of char formation and when combined with APP, would induce synergistic effect which could be clearly observed. This effect greatly promoted the char formation of IFR-PLA composites, hence improved the flame retardant property. Additionally, the structure and morphology of char residues were studied by XPS, FTIR and SEM.  相似文献   

14.
Polyurethane/polyhedral oligomeric sisesquioxane (PU/POSS) nanocomposites were syn-thesized via polymerization utilizing the compatibility between POSS nanoparticles and 4,4'-diphenyl methylene diisocyanate. Scanning electron microscope images and Fouriertransform infrared spectra revealed that POSS nanoparticles were dispersed in PU matrix.Thermal gravimetric analysis was employed to investigate the thermal decomposition be-havior of PU/POSS nanocomposites at elevated temperatures. Then fire performance wasevaluated by limiting oxygen index, underwriters laboratories 94 testing and char residue morphology. These results showed that the addition of POSS promoted the formation of char residues which were covered on the surface of polymer composites, leading to the im-provement of thermal stability and flame retardancy.  相似文献   

15.
In this work, a flame-retardant polypropylene(PP)/ramie fiber(RF) composite was prepared. The ramie fibers were wrapped chemically by a phosphorus- and nitrogen-containing flame retardant(FR) produced via in situ condensation reaction so as to suppress their candlewick effect. Fourier transform infrared spectroscopy(FTIR), X-ray photoelectron spectroscopy(XPS) and scanning electron microscopy(SEM) demonstrated that the ramie fibers wrapped chemically by FR(FR-RF) were obtained successfully. Thermogravimatric test showed that the PP/FR-RF composite had more residue and better thermal stability at high temperatures than the PP/RF composite. Cone calorimeter(CC) results indicated that the peak of heat release rate(PHRR) and total heat release(THR) correspondingly decreased by 23.4% and 12.5% compared with the values of neat PP/RF. The PP/FR-RF composite created a continuous and compact char layer after the combustion. Combining FTIR analysis of char residue after CC test with heat conduction coefficient results, it could be concluded that the charring of FR on RF greatly weakened the candlewick effect of RF, and more char residue in the RF domain facilitated the formation of more continuous and compact char layer in the whole combustion zone, consequently protected PP composites during combustion, resulting in the better flame retardancy of PP/FR-RF composite than that of PP/RF composite.  相似文献   

16.
Thermal decomposition of pentaerythritol phosphate (PEPA) and its blend (PEPAMP) with melamine phosphate were studied by TG, DSC, TOF MS, and FTIR of volatile and solid decomposition products. Both PEPA and PEPAMP produce intumescent char on heating, however that of PEPAMP is less stable to thermo-oxidative decomposition. The main decomposition pathway of PEPA is liberation of phosphoric acid followed by formation of a foamed carbonized residue. In the mixture of PEPAMP, reaction between the components occurs, which strongly reduces the heat release peaks of PEPA. In addition, condensates of melamine and their products of hydrolysis are formed. The hydrolysis reaction causes a low-temperature decomposition of the melamine ring, which results in the formation of urea, carbon dioxide and ammonia. The thermal decomposition of PEPA and PEPAMP is discussed.  相似文献   

17.
The effect of hydrophilic fillers (starch and wood-flour) on the degradation and decomposition of poly(lactic acid) (PLA) based materials was investigated. Biodegradation was evaluated by composting under controlled conditions in accordance with AS ISO 14855. Thermal decomposition was studied by thermogravimetry (TGA). Morphological variations during biodegradation were investigated by SEM examination. It was found that biodegradation rates of PLA/starch blends and PLA/wood-flour composites were lower than that of pure cellulose but higher than that of pure PLA. The biodegradation rate was increased from about 60% to 80% when the starch content was increased from 10% to 40% after 80 days. Both starch and wood-flour accelerated thermal decomposition of PLA, and starch exhibited a relatively stronger affect then wood-flour. The decomposition temperature of PLA was decreased about 40 °C when the filler content was increased to 40%. Small polar molecules released during thermal decomposition of starch and wood-flour were attributed to the thermal decomposition behaviours of the PLA based blends and composites and their role is further discussed in this paper.  相似文献   

18.
伍聪  杨丹丹  吴刚  陈思翀 《高分子学报》2021,(2):176-185,I0004
通过将双端羟基的聚己内酯(PCL)、聚乳酸(PLA)预聚物以及苯基次磷酸离子盐扩链得到一种含苯基次磷酸盐的离子共聚物,将其与聚磷酸铵(APP)复合用于协同改性聚乳酸,离聚物中苯基次磷酸盐结构与APP具有优异的协同阻燃PLA的作用,同时该离聚物中PLA与苯基次磷酸盐结构有效提升了APP在PLA中的分散能力,最后该离聚物中PCL柔性链段有效改善了PLA的韧性,最终得到更高效阻燃性能且韧性也较好改善的PLA/PCLA-PIU/APP复合材料.一方面,离聚物中苯基次磷酸盐结构与APP协同有效促进了PLA的成炭,形成更连续致密的炭层从而阻隔可燃气体的释放,达到更好的阻燃效果.锥形量热、残炭的扫描电子显微镜(SEM)、能谱分析(EDS)、拉曼光谱等测试证实了这一结果,与纯PLA以及仅使用APP的PLA/APP相比,PLA/PCLA-PIU/APP的热释放速率与总热释放均降低,同时残炭的石墨化程度更高,形成了更为致密的炭层.另一方面,力学性能测试结果表明,离聚物中PCL柔性链段的存在使得与APP复合改性后的PLA的韧性相比纯PLA和PLA/APP有较大的提升;SEM测试表明,离聚物中PLA与苯基次磷酸盐结构起到增容作用,提升了APP在PLA中的分散性.  相似文献   

19.
Composites have been produced by melt-blending biodegradable polylactide (PLA) with commercially available expanded graphite (EG). Using different techniques of addition, the manifold effects of EG on PLA molecular, thermo-mechanical and fire-retardant properties were evaluated. The EG nanofiller provides PLA composites with competitive functional properties. They have a high rigidity, with Young's modulus and storage modulus increasing with EG content. They also have excellent thermal stability while preserving the glass transition and melting temperature of the original PLA matrix. Purification and pre-dispersion of EG nanofiller proved beneficial for preserving PLA molecular weights and led to improved mechanical performance. The presence of dispersed graphene nanolayers in PLA significantly accelerated the polyester crystallization process. The flame retardant properties also displayed improvements with a large decrease in the maximum rate of heat release as recorded by cone calorimetry, whereas the horizontal burning test (UL94 HB) was successfully passed revealing non-dripping and char formation.  相似文献   

20.
The effect of phosphorus content on thermal degradation and burning behavior of poly(acryloyloxyethyl diethyl phosphate) or PADEP-coated cotton was studied. The results showed that PADEP-coated cotton prepared by admicellar polymerization using hexadecyltrimethylammonium bromide (HTAB) as a surfactant has higher amounts of phosphorus than that prepared using dodecyltrimethylammonium bromide (DTAB). Higher phosphorus content led to lower decomposition temperatures and greater amounts of char formation after thermal degradation. The effectiveness of the amount of phosphorus on the burning behavior of the treated cotton was investigated by an ASTM flammabilty test. In the case of PADEP-coated cotton prepared with DTAB, the flame spread slowly and extinguished with char formation on the fabric. For untreated cotton however, the flame spread quickly and burned the fabric entirely without char formation. Cotton coated with PADEP using HTAB exhibited self-extinguishing behavior after removing the ignition source. Decrease in decomposition temperature, increase in char formation and the burning behavior of PADEP-coated cotton are all consistent with phosphorus content on the treated fabric.  相似文献   

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