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1.
At present, thermoplastic polyurethane (TPU) is widely used, but there are still many defects in fire safety, such as burning with heavy smoke and dripping. In this article, OS@MP was synthesized by modifying oyster shell (OS) powder with melamine polyphosphate (MP) and then served as fire‐safe agent for TPU. The fire performance of TPU composites were investigated using microscale combustion colorimeter (MCC), cone calorimeter test (CCT), smoke density test (SDT), and thermogravimetric analysis/Fourier transform infrared (TG‐FTIR) spectrum analysis. The MCC and CCT results revealed that OS@MP could reduce the fire hazards of TPU composites. The peak heat release rate (pHRR) of the sample with 10.0 wt% OS@MP decreased to 170.86 kW/m2 from 1772.37 kW/m2 for pure TPU. And, the SDT results showed that OS@MP could significantly reduce the smoke production of TPU composites. The TG‐FTIR also confirmed that the noncombustible gases (including CO2, ammonia, and water vapor) produced by OS@MP have played a reinforcing role in TPU composites as well as a char formed on the surface of composites, which could act as a barrier to prevent the heat and air, reinforce the fire safety of TPU.  相似文献   

2.
APP@ETA, as a new type of flame retardant, was prepared by chemically modifying ammonium polyphosphate (APP) with ethanolamine (ETA) and applied to thermoplastic polyurethane (TPU) in this study. Then, the smoke suppression properties and flame‐retardant effects of APP@ETA in TPU composites were evaluated using smoke density test, cone calorimeter test, etc. And, the thermal degradation properties of flame‐retardant TPU composites were investigated by thermogravimetric analysis/infrared spectrometry. The smoke density test results indicated that APP@ETA could obviously improve the luminous flux of TPU composites in the test with or without flame. The cone calorimeter test results showed that total smoke release, smoke production rate and smoke factor of the composites with APP@ETA were significantly decreased than those of the composites with APP. For example, when the loading of APP@ETA or APP was 12.5 wt%, the total smoke release of the sample with APP@ETA decreased to 3.5 m2/m2 from 6.0 m2/m2, which was much lower than that of the sample with APP, reduced by 41.7%. The thermogravimetric analysis results demonstrated that APP@ETA could decrease the initial decomposition temperature and improve the thermal stability at high temperature for TPU composites. Copyright © 2017 John Wiley & Sons, Ltd.  相似文献   

3.
It is mainly studied that the smoke-suppression properties and synergistic flame-retardant effect of hollow glass microsphere (HM) in flame retardant thermoplastic polyurethane (TPU) composites based on ammonium polyphosphate (APP) as a flame-retardant. Also, the smoke suppression properties and flame-retardant effect were investigated by smoke density test (SDT), cone calorimeter test (CCT), limiting oxygen index, and thermogravimetric analysis, separately. The char residues left after CCT were examined by scanning electron microscopy. The data of SDT shows that HM could effectively decrease smoke production of TPU composites. The results of CCT reveal that the system of APP/HM could reduce heat release rate, smoke production rate, and total smoke release. It is shown that APP/HM is a good system with smoke-suppression and synergistic flame-retardant properties in flame-retardant TPU composites.  相似文献   

4.
The application of chitosan (CS) in new materials is a hot research topic. In this paper, CS was used alone as flame retardant to prepare thermoplastic polyurethane elastomer (TPU) composites. Then, the flame retardancy and thermal decomposition behavior of TPU/CS composites were intensively investigated using cone calorimeter test (CCT), scanning electron microscope (SEM), microscale combustion colorimeter (MCC) test, thermogravimetric analysis/infrared spectrometry (TG‐IR), and gas chromatography‐mass spectrometry (GC‐MS). The results showed that CS can reduce the fire risk of TPU; 2.0‐wt% CS could make the peak value of heat release rate (pHRR) decreased to 457.2 kW/m2, reduced by 65.9% compared with TPU. And the peak value of smoke production rate (pSPR) and total smoke release (TSR) of the same sample was decreased by 79.4% and 54.2%, respectively. The TG‐IR and GC‐MS results confirmed that CS could promote TPU decomposition in advance, reacting with the decomposition products of TPU. Therefore, the production of combustible gas was reduced. The GC‐MS results showed that the production of isocyanates and ethers was reduced with the addition of CS. The digital photographs of SEM for the samples after CCT were shown that the char residue layer of the sample containing 2.0‐wt% CS was fibrous in shape. It could be speculated that the thermal decomposition products from TPU could react with CS at low temperature, which reduced the production of flammable gases. So CS had a good prospect in reducing the fire hazard for TPU.  相似文献   

5.
Three novel phosphorus‐containing Salen‐based derivatives (Salen‐DPCP‐M: M = Ni, Zn, and Mn), which include both phenyl phosphate structures (DPCP) and Salen‐metal complexes, were prepared for enhancing the fire safety of thermoplastic polyurethane (TPU). Thermogravimetric analysis (TGA) showed that Salen‐DPCP‐M altered the thermal degradation pathways of TPU probably due to the phosphorus‐containing structure of Salen‐DPCP‐M. The cone calorimeter test showed that the addition of 3 wt% of Salen‐DPCP‐Ni, Salen‐DPCP‐Zn, and Salen‐DPCP‐Mn lowered the peak of heat release rate (PHRR) from 1495 kW/m2 for neat TPU to 690, 875, and 813 kW/m2, respectively, for the TPU composites, which demonstrated that Salen‐DPCP‐M improved the fire safety of TPU. In addition, the release of toxic CO gas from the Salen‐DPCP‐Ni/TPU and Salen‐DPCP‐Zn/TPU composites was reduced by 78.2% and 80.0%, respectively. The results of TGA/infrared spectrometry (TG‐FTIR) showed that the incorporation of Salen‐DPCP‐Ni promoted the release CO2, while reducing the formation of harmful gases. Laser Raman spectroscopy (LRS) and scanning electron microscopy (SEM) showed that Salen‐DPCP‐Ni/TPU and Salen‐DPCP‐Zn/TPU composites formed a dense and stable char layer. Herein, the mechanism of these flame retardants containing novel phosphorus‐containing Salen‐metal complexes is also proposed.  相似文献   

6.
A comparison of melamine salt of pentaerythritol phosphate (MPP), and a synergistic agents, iron–graphene (IG) was performed in thermoplastic polyurethane (TPU) by masterbatch‐melt blending on thermal and flame retardant properties. The flame retardant properties of TPU composites were characterized by limiting oxygen index (LOI), UL 94 and cone calorimeter test (CCT). The CCT results revealed that IG can significantly enhance flame retardant properties of MPP in TPU. The peak heat release rate of neat TPU and flame retardant TPU/MPP composites decreased from 2192.6 and 226.7 to 187.2 kW/m2 compared with that of TPU containing 0.25 wt% IG. The thermal stability and thermal decomposition of TPU composites were characterized by thermogravimetric analysis (TGA) and thermogravimetric/Fourier infrared spectrum analysis (TG‐IR). The results indicated IG and MPP can improve the thermal stability of TPU. The formation of thermal conductive network by IG can promote the decomposition of MPP into nonflammable melt, which can play the role of heat barrier and restrict the diffusion of fuels into combustion zone and access of oxygen to the unburned fuels. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   

7.
In this paper, fumaric acid (FA) which was a new type of environmental and low‐cost flame retardant was applied for thermoplastic polyurethane elastomer (TPU). The flame‐retardant properties of TPU were tested using limiting oxygen index, cone calorimeter test, smoke density test, and thermogravimetric/Fourier transform infrared spectroscopy. It has been proved that FA could improve the difficulty of the ignition of the sample; the limiting oxygen index value of the sample (FA‐4) increased by 29.7% when 2.0 wt% FA was added to TPU. The cone calorimeter test showed that FA can greatly reduce heat release and smoke production during the combustion process of TPU composites. For example, compared with the pure TPU, the peak heat release rate and total smoke release of the sample (FA‐4) with 2.0 wt% FA were decreased by 50.8% and 51.5% respectively. The results of smoke density test showed that the luminous flux of the samples contained 0.5 wt% FA was increased by 79.2% compared with the pure TPU. The TG results revealed that the sample of FA‐4 had higher char residue content compared with the sample of TPU. The results of thermogravimetric/Fourier transform infrared spectroscopy proved that FA could decrease the initial decomposition temperature for TPU composites and increase the release of CO2 and H2O. All results of test illustrated that FA had good flame‐retardant effect on TPU.  相似文献   

8.
Phosphorus tailings and fly ash both are solid wastes and do harm to the environment. Here, they were added into thermoplastic polyurethane (TPU) matrices together with intumescent flame retardants (IFR), and the synergistic effects between IFR and phosphorus tailings or fly ash for improving the flame retardancy of TPU were investigated. The cone calorimeter test (CCT) results indicated that adding phosphorus tailings or fly ash substitute for part of IFR could obtain a better flame retardant effect. The peak heart release rate (PHRR) of TPU/25 wt% IFR composites exhibited a reduction of 77% than that of neat TPU, and the total smoke production presented a reduction of 16%. However, the PHRR value and total smoke production of the sample TPU/20 wt% IFR/5 wt% phosphorus tailings were reduced by 91% and 57%, respectively, compared to that of neat TPU. The dense char promoted by the presence of IFR and phosphorus tailings or fly ash delayed the diffusion of volatile pyrolysis products and transmission of heat and oxygen to the underlying material. Therefore, a certain amount of phosphorus tailings or fly ash can be used as synergistic agents with IFR to enhance the fire safety of TPU materials. From another aspect, it also provides a promising way for recycling use of phosphorus tailings and fly ash.  相似文献   

9.
In this paper, a new type of flame retardant (AF‐Fe) based on para‐aramid fiber (AF) which was modified with iron diethyl phosphinate was applied for thermoplastic polyurethane elastomer (TPU). The flame‐retardant properties of TPU were tested using cone calorimeter test, smoke density test, and thermogravimetric analysis/infrared spectrometry. The cone calorimeter test showed that AF‐Fe can greatly reduce the heat release rate, total heat release, smoke factor, and other parameters of TPU composites compared with the sample of TPU/AF. For example, the pHRR of the composite with 1.0 wt% AF‐Fe was reduced by 15.19% compared with the sample with the same content of pure AF. In addition, the smoke factor of TPU/AFFe3 was reduced by 50.52% and 15.63% compared with TPU0 and TPU/AF respectively. The results of smoke density test showed that the luminous flux of TPU/AFFe3 was increased by 79.26% compared with the sample of TPU/AF. The TG results revealed that the sample with TPU/AFFe3 had lower weight loss rate and higher char residue content at 700°C compared with the sample of TPU/AF.  相似文献   

10.
Molybdenum trioxide (MoO3) microrods, nanofibers, and nanoplates were synthesized via the hydrothermal method and high‐temperature calcination method, respectively. Then the MoO3 was added into polyurethane elastomer, respectively. The flame retardancy and smoke suppression of the composites added with different MoO3 were studied by thermal gravimetric analysis, cone calorimeter, and smoke density. The results show that the three kinds of MoO3 with different morphologies could promote the formation of char and possess flame retardancy and smoke suppression, and MoO3 nanofibers exhibit a higher degree of flame retardancy, and 1 wt% addition could make the peak heat release rate of polyurethane elastomer composites reduce from 881.6 kW m?2 for a pure sample to 343.4 kW m?2, a decrease by 61.0%. As for smoke suppression, MoO3 nanoplates possess the best smoke suppression; 5 wt% could decrease a pure sample's smoke density by 41.3% from 361 to 212. Moreover, the char residue of composites after combustion was analyzed by Raman spectra and X‐ray photoelectron spectroscopy, and the flame retardancy and smoke suppression mechanisms of MoO3 were discussed.  相似文献   

11.
Cellulose microcrystalline (CMC), a linear polysaccharide with glucosidic bond, was successfully extracted from bamboo powder and modified by 3‐aminopropyltriethoxy silane coupling agent (KH550) to prepare KH550‐CMC. The prepared KH550‐CMC, in association with ammonium polyphosphate (APP), was introduced into epoxy resin (EP) by casting process to obtain flame retardant composites. The fire performance evaluation indicated that the presence of 10‐phr APP and 5‐phr KH550‐CMC in EP achieved the maximal LOI value of 28.9%, passed the UL‐94 V‐0 rating, and significantly decreased the peak heat release rate from 1055 kW/m2 of neat EP to 286 kW/m2. The improved fire performance is due to the improvement of dispersity of CMC in EP matrix and formation of better char layer, thus protecting the matrix effectively. Moreover, the introduction of KH550‐CMC could also partly eliminate the negative influence of flame retardants on the mechanical properties of EP composites due to the strengthening effect of CMC and better interfacial compatibility after modification with KH550.  相似文献   

12.
The massive accumulation of phosphorus tailings (PT) not only occupies land resources and also causes great threat to ecological environment and human security. It is of great significance to explore the resource utilization of PT in some fields. Herein, aluminum hypophosphite (AHP) and PT are blended together to enhance the flame retardancy of thermoplastic polyurethane (TPU) composites, and the synergistic effects between AHP and PT are investigated systematically. Cone calorimeter test (CCT) results indicate that the peak heat release rate (PHRR) and total heat release (THR) of the samples containing 25 wt% AHP are decreased by 89% and 68%, respectively, and the total smoke release (TSR) show a reduction of 58.8%, in comparison with those of neat TPU. For the sample TPU/22.5AHP/2.5PT, the PHRR, THR, and TSR are decreased by 91.2%, 70%, and 63%, respectively. Scanning electron microscopy (SEM) analysis results demonstrate that the addition of PT can facilitate the generation of dense and compact char layers, preventing the release of heat and smoke effectively. All the abovementioned results indicate that the synergistic effects are existed between AHP and PT for enhancing the fire safety of TPU composites, which can provide a new way for the utilization of PT.  相似文献   

13.
Microencapsulated ammonium polyphosphate (MAPP) is prepared using hydroxyl silicone oil by in situ polymerization and characterized by XPS. Microencapsulation gives MAPP better water resistance and flame retardance compared with APP in thermoplastic polyurethane (TPU). Thermal stability and fire resistance behavior have been analyzed and compared. The LOI value of the TPU/MAPP composite is higher than that of the TPU/APP composite. The UL 94 rating of the TPU/MAPP composite is V-0 at the 20 wt% additive level, whereas TPU/APP gives V-2 rating at the same loading level. The water resistant properties of the TPU composites are studied. Results of the cone calorimeter and microscale combustion calorimeter experiment show that MAPP is an effective flame retardant in TPU compared with APP.  相似文献   

14.
The objective of the study was to investigate the effect of the organo‐modified nanosepiolite (ONSep) on improving the fire safety of polypropylene (PP). The composites based on PP, flame retardant master batch (MB‐FR, 25 wt% PP+50 wt% decabromodiphenyl ether (DBDPE)+25% antimony trioxide (ATO)) and ONSep were prepared via melt blending. The results of the limiting oxygen index (LOI) and vertical burning rating (UL‐94) test indicated that PP/40 wt% MB composites had no rating with seriously dripping phenomenon, while the LOI value was only 22.5. However, as 4 wt% ONSep was added in PP/40 wt% MB composites, the composites achieved UL94 V‐0 rating and the LOI value was 24.3. In comparison, PP/50 wt% MB composites could not reach the V‐0 rating either. The TGA results revealed that the addition of ONSep enhanced the thermal stability of the PP/MB‐FR composites. The cone calorimeter results indicated that the heat release rate, average mass loss rate, smoke production rate and smoke temperature of the PP/40 wt% MB‐FR/4 wt% ONSep composites decreased in comparison with those of PP/40 wt% MB‐FR composites. Simultaneously, the Young modulus and impact strength were also much better improved with the increase of ONSep loading. Therefore, the synergistic flame retardancy of ONSep in PP/MB‐FR matrix significantly containing a halogen based flame retardant (DBDPE) significantly improved the fire safety and mechanical properties of the composites, and allowed to decrease the total amount of brominated fire retardants.  相似文献   

15.
《先进技术聚合物》2018,29(1):69-83
Thermal stability and fire retardancy of poly(1,4‐butanediol succinate) (PBS) nanocomposites with sepiolite and 2 halloysites was investigated using thermogravimetric analysis. Despite detrimental influence on thermal stability, confirmed by the use of isoconversional methods, nanoclays improve PBS fire behavior, studied using pyrolysis combustion flow calorimetry and cone calorimeter. Combinations of nanoclays with ammonium polyphosphate (APP) and aluminum diethyl phosphinate at 20 wt% global loading were tested using cone calorimeter at 50 kW/m2. It was noticed that the formation of protective structures of metallic phosphates with APP improves fire performance. The influence of ternary compositions combining sepiolite, APP, and lignin on fire performance was investigated. The composition having equimassic loading of each component leads to strong reductions in peak of heat release rate and Maximum of Average Heat Release Evolved (MAHRE) through the formation of a cohesive protective residue, containing new types of metallic phosphates and reinforced by sepiolite particles. This composition also allows smoke release rate to be minimized.  相似文献   

16.
A crosslinked silicone‐containing macromolecular charring agent (CSi‐MCA) was synthesized via “one‐pot” process, and it was combined with ammonium polyphosphate (APP) to synergistically improve the flame retardancy of poly(l ‐lactic acid) (PLA). The chemical structure of synthesized CSi‐MCA was characterized by Fourier transform infrared spectroscopy and solid‐state 13C nuclear magnetic resonance. The thermal gravimetric analyzer indicated that the CSi‐MCA displayed good thermal stability and high residue via the catalytic crosslinking. Furthermore, the flame retardant effect of CSi‐MCA and APP as intumescent flame retardants in PLA system was investigated by limited oxygen index, UL94, and cone calorimeter test. When the content of CSi‐MCA was 5 wt% and APP was 10 wt% (CSi‐MCA/APP = 1/2), the limited oxygen index value of composites was 33.6 and UL94 classed a V‐0 rating. The peak heat release rate and total heat release of PLA composites containing both APP and CSi‐MCA decreased significantly in comparison with those with APP or CSi‐MCA alone. The flame retardancy mechanism was investigated via analyzing residual chars by scanning electron microscopy and X‐ray photoelectron spectroscopy as well as the possible chemical reaction between APP and CSi‐MCA by thermal gravimetric analyzer and Fourier transform infrared spectroscopy. The results showed that the enhanced flame retardancy was attributed mainly to synergistic effect of CSi‐MCA and APP, which could form a compact, continuous, and protective layer during combustion. Copyright © 2017 John Wiley & Sons, Ltd.  相似文献   

17.
A novel halogen‐free flame retardant (FR) consisting of brucite, aluminum phosphate (AlP), and silane coupling agent (B/AlP/A) was prepared via co‐precipitation assembly technique. The morphology, chemical compositions, size distribution, and thermal stability of B/AlP/A were investigated. When used in ethylene‐vinyl acetate (EVA) resin, the B/AlP/A could significantly enhance the flame retardant and smoke suppression performance of the EVA composites, which is mainly attributed to the AIP. With 50 wt% FR loading, the peak heat release rate (PHRR) of EVA‐B/AlP/A (299.2 kW · m?2) is much lower than that of EVA‐B/A (387.4 kW · m?2). Moreover, B/AlP/A shows an excellent smoke suppression performance. For example, the smoke production rate is 0.017 m2 · g?1 that has been decreased by 72.1%, compared with B/A. The improvement arises from the amorphous AlP layer on brucite, which helps to create a firm and porous protective char layers on the burning EVA composites. Meanwhile, better mechanical property could be simultaneously obtained with the large FR amount. The fluffy surface of B/AlP/A has good compatibility with EVA and tangle more polymer chains, enhancing the mechanical properties. In a word, this simple and convenient method could pave the way for developing a more efficient and cost‐effective brucite‐based FR.  相似文献   

18.
Polypropylene (PP)/sepiolite/zinc borate (BZn) composites were prepared by melt extrusion after pre‐modification of sepiolite with cetyltrimethylammonium bromide. The synergistic effects of organo‐sepiolite (OSEP) and BZn on the fire retardancy of PP were studied. X‐ray diffraction and transmission electron microscopy were used to characterize the morphology of the composite. Thermogravimetric analysis, cone calorimetric analysis, limiting oxygen index, and the UL‐94 protocol (Demaisheng technology Co. Ltd.,Shenzhen,China) were used to assess the thermal stability and fire retardancy of the composites. The fire retardancy of PP was greatly improved by introducing OSEP and BZn. The reduction in peak heat release rate for PP/BZn composites at 10% BZn loading is 62% compared with pristine PP, but increased to 78% for PP/10%BZn/10%OSEP composite. Other fire retardant parameters were also improved. The fire performance index of PP/10%BZn/10%OSEP composite was 0.045 sm2/kW compared with 0.014 sm2/kW of pristine PP. The average mass loss rate was 12.1 g/sec/m2 for the composite with both additives compared with 30.1 g/sec/m2 for pristine PP; the smoke production rate decreased by 37% from 0.117 m2/s of pristine PP to 0.074 m2/s of PP/OSEP/BZn. The char residue of composite increased from 0.6% in pristine PP to 12.19% in the composite. The limiting oxygen index increased from 17.1 in pristine PP to 20.8 in the composite: all the samples could obtain a UL‐94 horizontal burn rating. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   

19.
Thermoplastic polyurethane (TPU) elastomer has a widely application because of its perfect physical and chemical properties. However, it was limited by its low reliability in fire safety. In this paper, a new fire agent integrated with molecular sieve and tetrafluoroborate ionic liquid ([EOOEMIm][BF4]) was used to improve fire safety of TPU. The fire safety of TPU composites was investigated by cone calorimeter test, smoke density test, and thermogravimetric/infrared spectroscopy, respectively. The results showed that modified molecular sieve (MMS) can improve fire safety of TPU effectively. The luminous flux increased to 10.10%, total smoke release decreased by 58%, and heat release rate declined of 65% than pure TPU when the addition of MMS was 0.5 wt%. In addition, MMS can improve thermal stability of TPU even in nitrogen according to thermogravimetric/infrared spectroscopy test. These proved that MMS has a satisfactory application prospect in fire safe polymer materials.  相似文献   

20.
In order to explore the structure mode of intumescent flame retardants (IFRs) with higher efficiency, IFR particles with joint‐aggregation structure (@IFR) were obtained through the treatment of ammonium polyphosphate (APP) and a charring agent (PT‐Cluster) in their aqueous solution. Then, the joint‐aggregation IFR effect was researched using its application in polypropylene. In case of 20 wt% IFR loading, the limiting oxygen index (LOI) value of @IFR/PP was 1.1% higher than that of 15APP/5PT‐Cluster/PP mixture, and a 1.6 mm‐thick @IFR/PP composite passed the UL 94 V‐2 rating test, while 15APP/5PT‐Cluster/PP demonstrated no flame‐retardant rating in UL 94 vertical burning tests. In a cone calorimeter test, @IFR also had a better inhibition effect on heat release. The average heat release rate (av‐HRR) value during 0 to 120 seconds of @IFR/PP was only 41 kW m?2, which was 33.9% lower than that of the 15APP/5PT‐Cluster/PP. Furthermore, the peak heat release rate (pk‐HRR) of @IFR/PP was 20.5% lower than that of 15APP/5PT‐Cluster/PP, and the time to pk‐HRR of @IFR/PP was 710 seconds, while that of 15APP/5PT‐Cluster/PP was 580 seconds. The better inhibition effect on HRR and the delay of time to pk‐HRR were caused by the joint‐aggregated structure of @IFR, which can rapidly react to form stable and efficient char layers. This kind of join‐aggregation IFR effect has great significance in suppressing the spread of fire in reality. In addition, @IFR also increased the mechanical properties of PP composites slightly compared with the APP/PT‐Cluster mixture.  相似文献   

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