Flame-retardant mechanism of magnesium oxychloride （M OC） in EP was in-vestigated by limiting oxygen index （LOI）, XRD, SEM, TG-DTG and DSC. The results show that MOC performed well as an inorganic flame-retardant ...Flame-retardant mechanism of magnesium oxychloride （M OC） in EP was in-vestigated by limiting oxygen index （LOI）, XRD, SEM, TG-DTG and DSC. The results show that MOC performed well as an inorganic flame-retardant in EP. When the content of MOC is 50%, the LOI of EP reaches 29.6% and mass of residual char reaches 9.6%. The flame retarde mechanism of MOC is due to the synergies of diluting, cooling, catalyzing char forming and obstructing effects.展开更多
Although epoxy resin has been widely used in various fields,it still suffers from some problems including brittleness and flammability.In this study,a new phosphonic acid,N,N-bis(phosphomethyl)glycine(GDMP),was prepar...Although epoxy resin has been widely used in various fields,it still suffers from some problems including brittleness and flammability.In this study,a new phosphonic acid,N,N-bis(phosphomethyl)glycine(GDMP),was prepared by Mannich reaction with bio-based glycine and then a novel layered zirconium phosphonate(ZrGDMP)was synthesized using GDMP and zirconyl chloride hydrate as reactants.The chemical structure of ZrGDMP was well characterized by 1 H and 31P NMR,SEM,XRD and XPS.The effect of ZrGDMP on the flame retardancy,smoke suppression,strengthening and toughening performances of the epoxy matrix was investigated and evaluated.TGA results indicated that compared with pure EP,ZrGDMP-EP composites showed higher char yield due to the catalytic charring effect of ZrGDMP.The pure EP exhibited high flammability,while ZrGDMP-EP composites possessed excellent thermal stability and remarkable fire resistance.The PHRR,THR,and TSP values of 3wt%ZrGDMP-EP were obviously declined by 39.6%,40.2%,and 24.9%compared to these of pure EP.Moreover,the tensile and impact tests implied that the addition of ZrGDMP can significantly reinforce the toughness as well as the strength of EP in terms of higher impact strength(24.8 kJ/m^(2))and tensile strength(57.7 MPa),which was mainly contributed to the uniform dispersion of ZrGDMP within the EP matrix.展开更多
Quest for bio-based halogen-free green flame retardant has attracted many concerns in recent years.Herein a reactive functional flame retardant containing phosphorus VDP is synthesized from vanillin,9,10-dihydro-9-oxa...Quest for bio-based halogen-free green flame retardant has attracted many concerns in recent years.Herein a reactive functional flame retardant containing phosphorus VDP is synthesized from vanillin,9,10-dihydro-9-oxa-10-phosphophene-10-oxide(DOPO)and phenol via a facile way.VDP is characterized with^(1)H NMR,^(31)P NMR,FTIR and Time of Flight Mass Spectrometry,and used as a new reactive flame retardant for bisphenol epoxy thermosets.Thermogravimetry analysis shows that when the VDP loading is only 0.5P%(based on phosphorus content),the residue increases from 14.2%to 21.1%at 750℃ in N_(2)compare with neat DGEBA.Correspondingly,the limit oxygen index increased to 29.6%,and flame retardancy reaches UL-94 V0 grade.Micro combustion calorimetry(MCC)and cone calorimetry analyses demonstrate that VDP can significantly lower flammability of the epoxy thermoset.With only 0.5P%of VDP,the heat release rate,total heat release rate and smoke production are reduced markedly.At the same time,the mechanical properties of the modified epoxy thermosets are also improved.The impact strength increases by 34%and the flexural strength increased by 23%,with 1.5P%of VDP.In short,VDP not only improves the flame retardancy,but also improves the mechanical properties of the epoxy thermosets.展开更多
To enhance the fire safety and wear resistance of epoxy,phosphorus-containing nickel phyllosilicate whiskers(FP-NiPS)were synthesized using a facile hydrothermal technology,with 9,10-dihydro-9-oxa-10-phosphaphenanthre...To enhance the fire safety and wear resistance of epoxy,phosphorus-containing nickel phyllosilicate whiskers(FP-NiPS)were synthesized using a facile hydrothermal technology,with 9,10-dihydro-9-oxa-10-phosphaphenanthrene as the organic modifier.The impacts of FP-NiPS on the thermal stability,flame retardancy,and mechanical and tribological properties of EP composites were explored.The findings demonstrated that 5 wt%FP-NiPS elevated the limiting oxygen index of the EP composite from 23.8%to 28.4%,achieving a V-0 rating during vertical burning tests.FP-NiPS could enhance the thermal stability of epoxy resin(EP)and facilitate the development of a dense and continuous carbon layer,thereby significantly improving the fire safety of the EP composites.The FP-NiPS led to an 8.2%increase in the tensile strength and a 38.8%increase in the elastic modulus of the EP composite,showing outstanding mechanical properties.Furthermore,FP-NiPS showed remarkable potential in enhancing the wear resistance of EP.The wear rate of 1 wt%FP-NiPS is 2.34×10^(−5) mm^(3)·N^(−1)·m^(−1),a decrease of 66.7%compared to EP.This work provides a novel promising modification method to enhance the fire safety,mechanical and wear resistance properties of EP.展开更多
In recent years,research has focused heavily on the investigation of functionalized ammonium polyphosphate(APP)flame retardants to improve the fire safety of epoxy resins(EP).The reason for this is the dual nature of ...In recent years,research has focused heavily on the investigation of functionalized ammonium polyphosphate(APP)flame retardants to improve the fire safety of epoxy resins(EP).The reason for this is the dual nature of APP's performance in fire protection of EP.This article provides a comprehensive overview of the advances in the use of functionalized APP flame retardants to improve the fire resistance of EP materials.It then presents the improvement of the modification of the functionalized APP flame retardants in terms of the hydrophobicity,compatibility and catalytic ability of the flame retardants,as well as the effects on the fire resistance,heat resistance,smoke reduction and mechanical properties of the EP composites.After the summary and comparison of the relevant studies,it is clear that the functionalized APP flame retardants can effectively improve the fire safety of EP composites and offset the adverse effects of APP in EP flame retardant applications.In addition,APP flame retardants can obtain various excellent functions through the use of materials with different properties,and the interaction between APP and materials can also lead to more efficient fire protection.However,the current problem is to find ways to streamline the process and minimise the costs associated with functionalized APP flame retardants,as well as to use them effectively in industrial production.We hope that this review can provide valuable hints and insights for the practical application of functionalized APP in EP and perspectives for future research.展开更多
To improve the dispersion of carbon nanotubes （CNTs） and flame retardancy of layered double hydroxide （LDH） in epoxy resin （EP）, organic nickel-iron layered double hydroxide （ONiFe-LDH-CNTs） hybrids were assem...To improve the dispersion of carbon nanotubes （CNTs） and flame retardancy of layered double hydroxide （LDH） in epoxy resin （EP）, organic nickel-iron layered double hydroxide （ONiFe-LDH-CNTs） hybrids were assembled through co-precipitation. These hybrids were further used as reinforcing filler in EP. EP/ONiFe-LDH-CNTs nano- composites containing 4 wt% of ONiFe-LDH-CNTs with different ratios of ONiFe-LDH and CNTs were prepared by ultrasonic dispersion and program temperature curing. The structure and morphology of the obtained hybrids were characterized by different techniques. The dispersion of nanofillers in the EP matrix was observed by transmission electron microscopy （TEM）. The results revealed a coexistence of exfoliated and intercalated ONiFe-LDH- CNTs in polymer matrix. Strong combination of the above nanofillers with the EP matrix provided an efficient thermal and flame retardant improvement for the nanocomposites. It showed that EP/ONiFe-LDH-CNTs nanocomposites exhibited superior flame retardant and thermal properties compared with EP. Such improved thermal properties could be attributed to the better homogeneous dispersion, stronger interfacial interaction, excellent charring performance of ONiFe-LDH and synergistic effect between ONiFe-LDH and CNTs.展开更多
Recent advances in epoxy resins have been forward to achieving high mechanical performance,thermal stability,and flame retardancy.However,seeking sustainable bio-based epoxy precursors and avoiding introduction of add...Recent advances in epoxy resins have been forward to achieving high mechanical performance,thermal stability,and flame retardancy.However,seeking sustainable bio-based epoxy precursors and avoiding introduction of additional flame-retardant agents are still of increasing demand.Here we report the synthesis of p-hydroxycinnamic acid-derived epoxy monomer(HCA-EP)via a simple one-step reaction,and the HCA-EP can be cured with 4,4′-diaminodiphenylmethane(DDM)to prepare epoxy resins.Compared with the typical petroleum-based epoxy resin,bisphenol A epoxy resin,the HCA-EP-DDM shows a relatively high glass transition temperature(192.9℃)and impressive mechanical properties(tensile strength of 98.3 MPa and flexural strength of 158.9 MPa).Furthermore,the HCA-EP-DDM passes the V-1 flammability rating in UL-94 test and presents the limiting oxygen index of 32.6%.Notably,its char yield is as high as 31.6%under N_(2),and the peak heat rate release is 60%lower than that of bisphenol A epoxy resin.Such findings provide a simple way of using p-hydroxycinnamic acid instead of bisphenol A to construct high-performance bio-based thermosets.展开更多
Fabricating a high-performing thermoset using bio-based flame retardant is critical for the sustain-able development of engineering materials with superior fire safety and robust mechanical properties.Herein,the epoxy...Fabricating a high-performing thermoset using bio-based flame retardant is critical for the sustain-able development of engineering materials with superior fire safety and robust mechanical properties.Herein,the epoxy(EP)composites with the industrial requirements are manufactured with a novel high-efficient,lignin-based flame retardant named DAL-x,which is fabricated by grafting 9,10-dihydro-9-oxa-10-phosphaze-10-oxide(DOPO)onto lignin.The resulting DAL-x/EP composite exhibits excellent flame retardancy with a desirable UL-94 V-0 rating and a satisfactory limiting oxygen index(LOI)of 29.8%due to the appropriate phosphorus content of DAL-x with adjustable molecular chain structure.More-over,the DAL-x/EP composite shows an unexpected improvement in the elastic modulus(∼36%)and well-preserved strength and ductility compared with those of pure EP.This work offers a feasible strat-egy for creating efficient bio-based flame retardants utilizing industrial waste lignin and preparing high-performance EP composites that meet the demanding requirement of fire retardancy in industries,con-tributing to the circular economy and sustainability.展开更多
基金Funded by the Defense Preresearch Project of the Eleventh-Five-Year-Plan of China (No. 51312040404)
文摘Flame-retardant mechanism of magnesium oxychloride （M OC） in EP was in-vestigated by limiting oxygen index （LOI）, XRD, SEM, TG-DTG and DSC. The results show that MOC performed well as an inorganic flame-retardant in EP. When the content of MOC is 50%, the LOI of EP reaches 29.6% and mass of residual char reaches 9.6%. The flame retarde mechanism of MOC is due to the synergies of diluting, cooling, catalyzing char forming and obstructing effects.
基金the National Natural Science Foundation of China(Grant Nos.22075265,51991352)the Youth Innovation Promotion Association of the Chinese Academy of Sciences(Grant Nos.2021459).
文摘Although epoxy resin has been widely used in various fields,it still suffers from some problems including brittleness and flammability.In this study,a new phosphonic acid,N,N-bis(phosphomethyl)glycine(GDMP),was prepared by Mannich reaction with bio-based glycine and then a novel layered zirconium phosphonate(ZrGDMP)was synthesized using GDMP and zirconyl chloride hydrate as reactants.The chemical structure of ZrGDMP was well characterized by 1 H and 31P NMR,SEM,XRD and XPS.The effect of ZrGDMP on the flame retardancy,smoke suppression,strengthening and toughening performances of the epoxy matrix was investigated and evaluated.TGA results indicated that compared with pure EP,ZrGDMP-EP composites showed higher char yield due to the catalytic charring effect of ZrGDMP.The pure EP exhibited high flammability,while ZrGDMP-EP composites possessed excellent thermal stability and remarkable fire resistance.The PHRR,THR,and TSP values of 3wt%ZrGDMP-EP were obviously declined by 39.6%,40.2%,and 24.9%compared to these of pure EP.Moreover,the tensile and impact tests implied that the addition of ZrGDMP can significantly reinforce the toughness as well as the strength of EP in terms of higher impact strength(24.8 kJ/m^(2))and tensile strength(57.7 MPa),which was mainly contributed to the uniform dispersion of ZrGDMP within the EP matrix.
基金This work is supported by the National Natural Science Foundation of China(NSFC)under the agreements of 21875131 and 21773150The Natural Science Basic Research Plan in Shaanxi Province of China(2020JM-283)the Fundamental Research Funds for the Central Universities(GK202003044 and GK201902014)are also acknowledged for partial support。
文摘Quest for bio-based halogen-free green flame retardant has attracted many concerns in recent years.Herein a reactive functional flame retardant containing phosphorus VDP is synthesized from vanillin,9,10-dihydro-9-oxa-10-phosphophene-10-oxide(DOPO)and phenol via a facile way.VDP is characterized with^(1)H NMR,^(31)P NMR,FTIR and Time of Flight Mass Spectrometry,and used as a new reactive flame retardant for bisphenol epoxy thermosets.Thermogravimetry analysis shows that when the VDP loading is only 0.5P%(based on phosphorus content),the residue increases from 14.2%to 21.1%at 750℃ in N_(2)compare with neat DGEBA.Correspondingly,the limit oxygen index increased to 29.6%,and flame retardancy reaches UL-94 V0 grade.Micro combustion calorimetry(MCC)and cone calorimetry analyses demonstrate that VDP can significantly lower flammability of the epoxy thermoset.With only 0.5P%of VDP,the heat release rate,total heat release rate and smoke production are reduced markedly.At the same time,the mechanical properties of the modified epoxy thermosets are also improved.The impact strength increases by 34%and the flexural strength increased by 23%,with 1.5P%of VDP.In short,VDP not only improves the flame retardancy,but also improves the mechanical properties of the epoxy thermosets.
基金Youth Scientific Research Project in Anhui Province(Grant No.2022AH020055)the Key Research and Development Projects in Anhui Province(Grant Nos.2022i01020016,2023g07020001)+1 种基金the National Natural Science Foundation of China(Grant No.52074011)the University Synergy innovation Program of Anhui Province(Grant No.GXXT-2022-018).
文摘To enhance the fire safety and wear resistance of epoxy,phosphorus-containing nickel phyllosilicate whiskers(FP-NiPS)were synthesized using a facile hydrothermal technology,with 9,10-dihydro-9-oxa-10-phosphaphenanthrene as the organic modifier.The impacts of FP-NiPS on the thermal stability,flame retardancy,and mechanical and tribological properties of EP composites were explored.The findings demonstrated that 5 wt%FP-NiPS elevated the limiting oxygen index of the EP composite from 23.8%to 28.4%,achieving a V-0 rating during vertical burning tests.FP-NiPS could enhance the thermal stability of epoxy resin(EP)and facilitate the development of a dense and continuous carbon layer,thereby significantly improving the fire safety of the EP composites.The FP-NiPS led to an 8.2%increase in the tensile strength and a 38.8%increase in the elastic modulus of the EP composite,showing outstanding mechanical properties.Furthermore,FP-NiPS showed remarkable potential in enhancing the wear resistance of EP.The wear rate of 1 wt%FP-NiPS is 2.34×10^(−5) mm^(3)·N^(−1)·m^(−1),a decrease of 66.7%compared to EP.This work provides a novel promising modification method to enhance the fire safety,mechanical and wear resistance properties of EP.
基金This work was financially supported by the General Program of Civil Aviation Flight University of China(Grant No.J2021-110)National Natural Science Foundation of China(NO:U2033206)+1 种基金The funding of Civil Aircraft Fire Science and Safety Engineering Key Laboratory of Sichuan Province(NO:MZ2022JB01)the project of Key Laboratory of Civil Aviation Emergency Science&Technology,CAAC(Grant No.NJ2022022,Grant No.NJ2023025).
文摘In recent years,research has focused heavily on the investigation of functionalized ammonium polyphosphate(APP)flame retardants to improve the fire safety of epoxy resins(EP).The reason for this is the dual nature of APP's performance in fire protection of EP.This article provides a comprehensive overview of the advances in the use of functionalized APP flame retardants to improve the fire resistance of EP materials.It then presents the improvement of the modification of the functionalized APP flame retardants in terms of the hydrophobicity,compatibility and catalytic ability of the flame retardants,as well as the effects on the fire resistance,heat resistance,smoke reduction and mechanical properties of the EP composites.After the summary and comparison of the relevant studies,it is clear that the functionalized APP flame retardants can effectively improve the fire safety of EP composites and offset the adverse effects of APP in EP flame retardant applications.In addition,APP flame retardants can obtain various excellent functions through the use of materials with different properties,and the interaction between APP and materials can also lead to more efficient fire protection.However,the current problem is to find ways to streamline the process and minimise the costs associated with functionalized APP flame retardants,as well as to use them effectively in industrial production.We hope that this review can provide valuable hints and insights for the practical application of functionalized APP in EP and perspectives for future research.
基金Acknowledgement This research is partly funded by the National Natural Science Foundation of China （No. 51603091）, the Natural Science Foundation of Jiangsu Province （Nos. BK20150505, BK20141262）, the Jiangsu Province College Students＇ Innovative Projects （No. 201510299006Z）, the China Postdoctoral Science Foundation （No. 2015M581744） and the Qing Lan Project of Jiangsu.
文摘To improve the dispersion of carbon nanotubes （CNTs） and flame retardancy of layered double hydroxide （LDH） in epoxy resin （EP）, organic nickel-iron layered double hydroxide （ONiFe-LDH-CNTs） hybrids were assembled through co-precipitation. These hybrids were further used as reinforcing filler in EP. EP/ONiFe-LDH-CNTs nano- composites containing 4 wt% of ONiFe-LDH-CNTs with different ratios of ONiFe-LDH and CNTs were prepared by ultrasonic dispersion and program temperature curing. The structure and morphology of the obtained hybrids were characterized by different techniques. The dispersion of nanofillers in the EP matrix was observed by transmission electron microscopy （TEM）. The results revealed a coexistence of exfoliated and intercalated ONiFe-LDH- CNTs in polymer matrix. Strong combination of the above nanofillers with the EP matrix provided an efficient thermal and flame retardant improvement for the nanocomposites. It showed that EP/ONiFe-LDH-CNTs nanocomposites exhibited superior flame retardant and thermal properties compared with EP. Such improved thermal properties could be attributed to the better homogeneous dispersion, stronger interfacial interaction, excellent charring performance of ONiFe-LDH and synergistic effect between ONiFe-LDH and CNTs.
基金supported by National Natural Science Foundation of China(Nos.52073189 and 51822304)Science and Technology Fund for Distinguish Young Scholars of Sichuan Province(No.2019JDJQ0025)+1 种基金State Key Laboratory of Polymer Materials Engineering(No.sklpme2020-3-09)the Fundamental Research Funds for the Central Universities。
文摘Recent advances in epoxy resins have been forward to achieving high mechanical performance,thermal stability,and flame retardancy.However,seeking sustainable bio-based epoxy precursors and avoiding introduction of additional flame-retardant agents are still of increasing demand.Here we report the synthesis of p-hydroxycinnamic acid-derived epoxy monomer(HCA-EP)via a simple one-step reaction,and the HCA-EP can be cured with 4,4′-diaminodiphenylmethane(DDM)to prepare epoxy resins.Compared with the typical petroleum-based epoxy resin,bisphenol A epoxy resin,the HCA-EP-DDM shows a relatively high glass transition temperature(192.9℃)and impressive mechanical properties(tensile strength of 98.3 MPa and flexural strength of 158.9 MPa).Furthermore,the HCA-EP-DDM passes the V-1 flammability rating in UL-94 test and presents the limiting oxygen index of 32.6%.Notably,its char yield is as high as 31.6%under N_(2),and the peak heat rate release is 60%lower than that of bisphenol A epoxy resin.Such findings provide a simple way of using p-hydroxycinnamic acid instead of bisphenol A to construct high-performance bio-based thermosets.
基金financially supported by the National Natural Science Foundation of China(Nos.51873196 and 51903222)the Australian Research Council(Nos.LP220100278,DP190102992 and FT190100188)+1 种基金the Natural Science Foundation of Zhejiang Province(No.LY21E030001)the“Pioneer”and“Leading Goose”R&D Program of Zhejiang(No.2022C03128).
文摘Fabricating a high-performing thermoset using bio-based flame retardant is critical for the sustain-able development of engineering materials with superior fire safety and robust mechanical properties.Herein,the epoxy(EP)composites with the industrial requirements are manufactured with a novel high-efficient,lignin-based flame retardant named DAL-x,which is fabricated by grafting 9,10-dihydro-9-oxa-10-phosphaze-10-oxide(DOPO)onto lignin.The resulting DAL-x/EP composite exhibits excellent flame retardancy with a desirable UL-94 V-0 rating and a satisfactory limiting oxygen index(LOI)of 29.8%due to the appropriate phosphorus content of DAL-x with adjustable molecular chain structure.More-over,the DAL-x/EP composite shows an unexpected improvement in the elastic modulus(∼36%)and well-preserved strength and ductility compared with those of pure EP.This work offers a feasible strat-egy for creating efficient bio-based flame retardants utilizing industrial waste lignin and preparing high-performance EP composites that meet the demanding requirement of fire retardancy in industries,con-tributing to the circular economy and sustainability.
