The structure-performance relationship of Cu/Al_(2)O_(3) catalysts in the hydrogenation of diethyl oxalate(DEO)for the synthesis of alcohol ether esters has been investigated by various characterization techniques inc...The structure-performance relationship of Cu/Al_(2)O_(3) catalysts in the hydrogenation of diethyl oxalate(DEO)for the synthesis of alcohol ether esters has been investigated by various characterization techniques including XRD,XPS,N2O titration,and 27Al MAS-NMR.The results showed that when the crystal configurations of Al_(2)O_(3) were the same,increasing the specific surface area could effectively refine the size of copper nanoparticles(Cu NPs),and ultimately improve the conversion of DEO.Meanwhile,the smaller size ofγ-Al_(2)O_(3)(HSAl and SBAl)loaded Cu NPs promotes the reaction towards the deep hydrogenation to produce ethanol(EtOH)and ethylene glycol(EG).Besides,the larger size of Cu NPs on the surface of amorphous Al_(2)O_(3)(HTAl and SolAl)resulted in a lower conversion rate,where ethyl glycolate(Egly)is the main product.Despite there are differences in Al^(3+)ionic coordination in Al_(2)O_(3) with different crystal structures,the experimental data showed that the differences in Al^(3+)ionic coordination did not significantly affect the catalytic performance in the hydrogenation reaction.The formation of alcohol-ether ester chemicals is critically dependent on the interactions between Cu sites and acidic sites.Among them,EG and EtOH were dehydrated to form 2-ethoxyethanol via the SN2 mechanism,while Egly and EtOH were reacted to form ethyl ethoxyacetate(EEA)via the SN2 mechanism.This study provides a theoretical basis for the optimization of the coal-based glycol processes to achieve a diversified product portfolio.展开更多
With the aim to effectively depolymerize polyethylene terephthalate(PET)under mild reaction conditions,PET methanolysis and dimethyl terephthalate(DMT)hydrolysis are integrated in a catalyst system.Firstly,methanolysi...With the aim to effectively depolymerize polyethylene terephthalate(PET)under mild reaction conditions,PET methanolysis and dimethyl terephthalate(DMT)hydrolysis are integrated in a catalyst system.Firstly,methanolysis of PET to DMT is achieved over Cu-Mg-Al oxide catalyst.Next,terephthalic acid(TPA)is prepared by DMT hydrolysis.It is found that hydrolysis of DMT to TPA can be promoted by introducing trace amount of water in this catalyst system.CuO-MgO-4.5Al_2O_(3)catalyst demonstrates the excellent catalytic performance for the depolymerization of PET with high conversion rate and TPA yield(100%and 99.5%,respectively)after reaction at 160℃for 6 h,which provides a new idea for the depolymerization of PET.展开更多
The effects of Yb/Zr micro-alloying on the microstructure,mechanical properties,and corrosion resistance of an Al-Zn-Mg-Cu alloy were systematically investigated.Upon the addition of Yb/Zr to the Al-Zn-Mg-Cu alloy,the...The effects of Yb/Zr micro-alloying on the microstructure,mechanical properties,and corrosion resistance of an Al-Zn-Mg-Cu alloy were systematically investigated.Upon the addition of Yb/Zr to the Al-Zn-Mg-Cu alloy,the grain boundaries were pinned by high-density nanosized Al_(3)(Yb,Zr)precipitates during extrusion deformation,consequently,the average grain size was significantly reduced from 232.7μm to 3.2μm.This grain refinement contributed substantially to the improvement in both strength and elongation.The ultimate tensile strength,yield strength,and elongation of the Yb/Zr modified alloy increased to 705.3 MPa,677.6 MPa,and 8.7%,respectively,representing enhancements of 16.2%,19.3%,and 112.2%compared to the unmodified alloy.Moreover,the distribution of MgZn_(2)phases along grain boundaries became more discontinuous in the Yb/Zr modified alloy,which effectively retarded the propagation of intergranular corrosion and improved the corrosion resistance.展开更多
Al-Mg-Mn-Sc-Zr alloys with excellent weldability have emerged as ideal candidates for aerospace applications.Currently,the investigations on the corrosion behavior of alloys under tungsten inert gas(TIG)welding condit...Al-Mg-Mn-Sc-Zr alloys with excellent weldability have emerged as ideal candidates for aerospace applications.Currently,the investigations on the corrosion behavior of alloys under tungsten inert gas(TIG)welding conditions are insufficient.Here,the stress corrosion cracking(SCC)behavior of base metal(BM)and weld zone(WZ)of TIG welded Al-Mg-Mn-Sc-Zr alloys was investigated by using pre-cracked compact tensile samples immersed in 3.5%NaCl solution.The direct current potential drop(DCPD)method was used to record the crack propagation.The microstructure and fracture morphology of different regions of TIG welded joints were studied by SEM,EBSD and TEM,and the SCC crack propagation mechanism of BM and WZ was analyzed.The results demonstrated that the critical stress intensity factor for stress corrosion cracking(K_(ⅠSCC))of BM and WZ was 7.05 MPa·m_(1/2) and 11.79 MPa·m_(1/2),respectively.Then,the crack propagation rate of BM was faster than that of WZ,and BM was more susceptible to SCC than WZ.Additionally,the fracture mode of the BM mainly exhibited transgranular fracture,while the fracture mode of the WZ mainly exhibited intergranular and transgranular mixed fracture.Moreover,SCC crack propagation was attributed to the combined effect of anodic dissolution and hydrogen embrittlement.This study will provide experimental and theoretical basis for the wide application of TIG welded Al-Mg-Mn-Sc-Zr alloys in aerospace.展开更多
文摘The structure-performance relationship of Cu/Al_(2)O_(3) catalysts in the hydrogenation of diethyl oxalate(DEO)for the synthesis of alcohol ether esters has been investigated by various characterization techniques including XRD,XPS,N2O titration,and 27Al MAS-NMR.The results showed that when the crystal configurations of Al_(2)O_(3) were the same,increasing the specific surface area could effectively refine the size of copper nanoparticles(Cu NPs),and ultimately improve the conversion of DEO.Meanwhile,the smaller size ofγ-Al_(2)O_(3)(HSAl and SBAl)loaded Cu NPs promotes the reaction towards the deep hydrogenation to produce ethanol(EtOH)and ethylene glycol(EG).Besides,the larger size of Cu NPs on the surface of amorphous Al_(2)O_(3)(HTAl and SolAl)resulted in a lower conversion rate,where ethyl glycolate(Egly)is the main product.Despite there are differences in Al^(3+)ionic coordination in Al_(2)O_(3) with different crystal structures,the experimental data showed that the differences in Al^(3+)ionic coordination did not significantly affect the catalytic performance in the hydrogenation reaction.The formation of alcohol-ether ester chemicals is critically dependent on the interactions between Cu sites and acidic sites.Among them,EG and EtOH were dehydrated to form 2-ethoxyethanol via the SN2 mechanism,while Egly and EtOH were reacted to form ethyl ethoxyacetate(EEA)via the SN2 mechanism.This study provides a theoretical basis for the optimization of the coal-based glycol processes to achieve a diversified product portfolio.
文摘With the aim to effectively depolymerize polyethylene terephthalate(PET)under mild reaction conditions,PET methanolysis and dimethyl terephthalate(DMT)hydrolysis are integrated in a catalyst system.Firstly,methanolysis of PET to DMT is achieved over Cu-Mg-Al oxide catalyst.Next,terephthalic acid(TPA)is prepared by DMT hydrolysis.It is found that hydrolysis of DMT to TPA can be promoted by introducing trace amount of water in this catalyst system.CuO-MgO-4.5Al_2O_(3)catalyst demonstrates the excellent catalytic performance for the depolymerization of PET with high conversion rate and TPA yield(100%and 99.5%,respectively)after reaction at 160℃for 6 h,which provides a new idea for the depolymerization of PET.
基金Project(51501228)supported by the National Natural Science Foundation of ChinaProject(202109)supported by the Open Sharing Fund for the Large-scale Instruments and Equipments of Central South University,China。
文摘The effects of Yb/Zr micro-alloying on the microstructure,mechanical properties,and corrosion resistance of an Al-Zn-Mg-Cu alloy were systematically investigated.Upon the addition of Yb/Zr to the Al-Zn-Mg-Cu alloy,the grain boundaries were pinned by high-density nanosized Al_(3)(Yb,Zr)precipitates during extrusion deformation,consequently,the average grain size was significantly reduced from 232.7μm to 3.2μm.This grain refinement contributed substantially to the improvement in both strength and elongation.The ultimate tensile strength,yield strength,and elongation of the Yb/Zr modified alloy increased to 705.3 MPa,677.6 MPa,and 8.7%,respectively,representing enhancements of 16.2%,19.3%,and 112.2%compared to the unmodified alloy.Moreover,the distribution of MgZn_(2)phases along grain boundaries became more discontinuous in the Yb/Zr modified alloy,which effectively retarded the propagation of intergranular corrosion and improved the corrosion resistance.
基金Project (2023GK1080) supported by the Major Special Projects of Hunan Province of China。
文摘Al-Mg-Mn-Sc-Zr alloys with excellent weldability have emerged as ideal candidates for aerospace applications.Currently,the investigations on the corrosion behavior of alloys under tungsten inert gas(TIG)welding conditions are insufficient.Here,the stress corrosion cracking(SCC)behavior of base metal(BM)and weld zone(WZ)of TIG welded Al-Mg-Mn-Sc-Zr alloys was investigated by using pre-cracked compact tensile samples immersed in 3.5%NaCl solution.The direct current potential drop(DCPD)method was used to record the crack propagation.The microstructure and fracture morphology of different regions of TIG welded joints were studied by SEM,EBSD and TEM,and the SCC crack propagation mechanism of BM and WZ was analyzed.The results demonstrated that the critical stress intensity factor for stress corrosion cracking(K_(ⅠSCC))of BM and WZ was 7.05 MPa·m_(1/2) and 11.79 MPa·m_(1/2),respectively.Then,the crack propagation rate of BM was faster than that of WZ,and BM was more susceptible to SCC than WZ.Additionally,the fracture mode of the BM mainly exhibited transgranular fracture,while the fracture mode of the WZ mainly exhibited intergranular and transgranular mixed fracture.Moreover,SCC crack propagation was attributed to the combined effect of anodic dissolution and hydrogen embrittlement.This study will provide experimental and theoretical basis for the wide application of TIG welded Al-Mg-Mn-Sc-Zr alloys in aerospace.
