The Zn and Fe modified /ZrO<sub>2</sub>-Al<sub>2</sub>O<sub>3</sub> catalyst (Zn-Fe-SZA) was prepared and mechanisms of deactivation and methods for regeneration of as-prepared cata...The Zn and Fe modified /ZrO<sub>2</sub>-Al<sub>2</sub>O<sub>3</sub> catalyst (Zn-Fe-SZA) was prepared and mechanisms of deactivation and methods for regeneration of as-prepared catalyst were explored with n-pentane isomerization as a probe reaction. The results indicated that the isopentane yield of the fresh Zn-Fe-SZA-F catalyst was about 57% at the beginning of the run, and declined gradually to 50% within 1500 min, then fell rapidly from 50% to 40% between 1500 and 2500 minutes. The deactivation of Zn-Fe-SZA catalyst may be caused by carbon formation on surface of the catalyst, sulfate group attenuation owing to reduction by hydrogen, removal of sulfur species and the loss of strong acid sites. It was found that the initial catalytic activity over Zn-Fe-SZA-T catalyst was 48%, which recovered by 84.3% as compared to that of fresh catalyst (57%). However, it showed a sharp decrease in isopentane yield from 48% to 29% within 1500 minutes, showing poor stability. This is associated to the loss of acidity caused by removal of sulfur species cannot be basically restored by thermal treatment. Resulfating the calcined catalyst could improve the acidity of catalyst significantly, especially strong acid sites, as compared with the calcined sample. The improved stability of the resulfated catalyst can be explained by: 1) eliminaton of carbon deposition to some extent by calcination process, 2) formation of improved acidic nature by re-sulfation, favoring isomerization on acidic sites, 3) restructuring of the acid and metal sites via the calcination-re-sulfation procedure.展开更多
Within the framework of the density functional theory and the pseudopotential method,the electronic structure calculations of the“metal-Si(100)”systems with Li,Be and Al as metal coverings of one to four monolayers(...Within the framework of the density functional theory and the pseudopotential method,the electronic structure calculations of the“metal-Si(100)”systems with Li,Be and Al as metal coverings of one to four monolayers(ML)thickness,were carried out.Calculations showed that band gaps of 1.02 eV,0.98 eV and 0.5 eV,respectively,appear in the densities of electronic states when the thickness of Li,Be and Al coverings is one ML.These gaps disappear with increasing thickness of the metal layers:first in the Li-Si system(for two ML),then in the Al-Si system(for three ML)and then in the Be-Si system(for four ML).This behavior of the band gap can be explained by the passivation of the substrate surface states and the peculiarities of the electronic structure of the adsorbed metals.In common the results can be interpreted as describing the possibility of the formation of a two-dimensional silicide with semiconducting properties in Li-Si(100),Be-Si(100)and Al-Si(100)systems.展开更多
Twenty kinds of adsorptions of HCN on the Fe（100）, Fe（111） and Fe（110） surfaces at the 1/4 monolayer coverage are found using the density functional theory. For Fe（100）, the adsorption energy of the most stabl...Twenty kinds of adsorptions of HCN on the Fe（100）, Fe（111） and Fe（110） surfaces at the 1/4 monolayer coverage are found using the density functional theory. For Fe（100）, the adsorption energy of the most stable configuration where the HCN locates at the fourfold site with the C-N bonded to four Fe atoms is 1.928 eV. The most favored adsorption structure for HCN on Fe（111） is f-η3（N）-h-η3（C）, in which the C-N bond is almost parallel to the surface, and the adsorption energy is 1.347 eV. On Fe（110）, the adsorption energy in the most stable configuration in which HCN locates at the two long-bridge sites is 1.777 eV. The adsorption energy of the parallel orientation for HCN is larger than that of the perpendicular configuration. The binding mechanism of HCN on the Fe（100）, Fe（111） and Fe（110） surfaces is also analyzed by Mulliken charge population and the density of states in HCN. The result indicates that the configurations in which the adsorbed HCN becomes the non-linear are beneficial to the formation of the addition reaction for hydrogen. The nature that the introduction of Fe into the catalyst could increase the catalytic activity of the bimetallic catalyst in the addition reaction of hydrogen for nitriles is revealed.展开更多
First-principles calculations based on density functional theory （DFT） and the generalized gradient approximation （GGA） have been used to study the adsorption of CO molecule on the perfect and defective FeS 2 （10...First-principles calculations based on density functional theory （DFT） and the generalized gradient approximation （GGA） have been used to study the adsorption of CO molecule on the perfect and defective FeS 2 （100） surfaces. The defective Fe 2 S（100） surfaces are caused by sulfur deficiencies. Slab geometry and periodic boundary conditions are employed with partial relaxations of atom positions in calculations. Two molecular orientations, Cand O-down, at various distinct sites have been considered. Total energy calculations indicated that no matter on perfect or deficient surfaces, the Fe position is relatively more favored than the S site with the predicted binding energies of 120.8 kJ/mol and 140.8 kJ/mol, respectively. Moreover, CO was found to be bound to Fe atom in vertical configuration. The analysis of density of states and vibrational frequencies before and after adsorption showed clear changes of the C–O bond.展开更多
Grinding operation is a finishing process often employed when high precision and narrow geometric tolerances are required.These requirements can be achieved only if cutting conditions are properly selected,especially ...Grinding operation is a finishing process often employed when high precision and narrow geometric tolerances are required.These requirements can be achieved only if cutting conditions are properly selected,especially the cooling-lubrication technique.In general,grinding is performed in presence of cutting fluid,however,due to the environmental impacts and costs of the conventional coolant delivery technique(flow rates from 4 L/min to 300 L/min),alternative cooling-lubrication techniques have been developed on restriction of the coolants use.Among the several techniques,MQL(minimum quantity of lubricant)technique has received special attention from machining users because of its advantages in terms of surface quality of workpiece and drastic reduction in use of coolant.In this context,this paper evaluated the performance of the MQL technique as compared to the flood coolant in peripheral surface grinding of AISI P100(VP100)steel with conventional aluminum oxide grinding wheel in relation to the surface roughness(Ra and Rz).Input parameters tested were equivalent chip thickness(0.09μm,0.18μm and 0.27μm)and flow rate of the cutting fluid(60 mL/h,150 mL/h and 240 mL/h)of the MQL system.Results showed that the grinding with MQL technique provided lower surface roughness values compared to conventional flood cooling,especially when machining under the intermediary cutting conditions.Also,with exception of heq of 0.09 m,the MQL technique resulted in lower values of Rz parameter as compared to the conventional coolant technique,regardless of the flow rate tested.展开更多
To reveal the relative contribution of the components, Fe, Mn oxides or organic materials（OMs） in the surficial sediments（SSs）, and the natural surface coating samples（NSCSs） to adsorbing atrazine（AT）, a selec...To reveal the relative contribution of the components, Fe, Mn oxides or organic materials（OMs） in the surficial sediments（SSs）, and the natural surface coating samples（NSCSs） to adsorbing atrazine（AT）, a selective chemical extraction technique was employed, to remove the different components, and the adsorption characteristics of AT on the SSs and the NSCSs were investigated. The observed adsorptions of AT on the original and extracted SSs and NSCSs were analyzed by nonlinear least squares fitting（NLSF） to estimate the relative contribution of the components. The results showed that the maximum adsorption of AT on the NSCSs was greater than that in the SSs, before and after extraction treatments, implying that the NSCSs were more dominant than the SSs for organic pollutant adsorption. It was also found that the Fe oxides, OMs, and residues in SSs（NSCSs） facilitated the adsorption of AT, but Mn oxides directly or indirectly restrained the interaction of AT with SSs（NSCSs） particles. The contribution of the Fe oxides to AT adsorption was more than that of OMs; the greatest contribution to AT adsorption on a molar basis was from the Fe oxides in the nonresidual fractions, indicating that the Fe oxides played an important role in controlling the environmental behavior of AT in an aquatic environment.展开更多
T shaped skin-stiffener joint are one of the most commonly used structures in aerospace components.It has been proven in various studies that these joints are susceptible to failure when loaded in pull out conditions ...T shaped skin-stiffener joint are one of the most commonly used structures in aerospace components.It has been proven in various studies that these joints are susceptible to failure when loaded in pull out conditions however,in specific applications these joints undergo pull loading.De-lamination/de-bond nucleation and its growth is one of the most common failure mechanisms in a fiber reinforced composite structure.Crack growth takes place due to the induced interlaminar normal and shear stresses between different structural constituents when a load is applied.In this study,Finite Element Analysis has been performed using cohesive contact interactions on a composite T-joint to simulate the pull out test conditions.A simplified shell based model coupled with CZM is proposed,which can evaluate the failure initiation and progression accurately with lesser computational efforts.The final failure occurred at a displacement of 4.71 mm at the computed failure load of 472.57 kgf for basic configuration.Computed Failure load for the padded configuration is 672.8 kgf and corresponding displacement is 4.6 mm.The results obtained by the proposed numerical model are validated by experimental results and it is observed that predicted failure displacements and failure load calculated were correlating reasonably well with the experiment.展开更多
The surface disproportionation reaction mechanism of aluminum subchloride on the aluminum （100） surfaces has been investigated by the plane-wave density functional theory （DFT）. Three kinds of possible reaction me...The surface disproportionation reaction mechanism of aluminum subchloride on the aluminum （100） surfaces has been investigated by the plane-wave density functional theory （DFT）. Three kinds of possible reaction mechanism of AlCl disproportionation reaction on the aluminum （100） surfaces have been taken into account. The structures of reactants and products have been optimized, transition states have been confirmed and activation energies have been calculated. The adsorption energy of reactants and desorption energy of products have been determined. All of these have been employed to confirm the reaction mechanism and the rate determining step ofAlCl disproportionation reaction on the aluminum （100） surfaces.展开更多
Pyrite （FeS2） bulk and （100） surface properties and the oxygen adsorption on the surface were studied by using density functional theory methods. The results show that in the formation of FeS2 （100） surface, the...Pyrite （FeS2） bulk and （100） surface properties and the oxygen adsorption on the surface were studied by using density functional theory methods. The results show that in the formation of FeS2 （100） surface, there exists a process of electron transfer from Fe dangling bond to S dangling bond. In this situation, surface Fe and S atoms have more ionic properties. Both Fe2+ and S2- have high electrochemistry reduction activity, which is the base for oxygen adsorption. From the viewpoint of adsorption energy, the parallel form oxygen adsorption is in preference. The result also shows that the state of oxygen absorbed on FeS2 surface acts as peroxides rather than O2.展开更多
文摘The Zn and Fe modified /ZrO<sub>2</sub>-Al<sub>2</sub>O<sub>3</sub> catalyst (Zn-Fe-SZA) was prepared and mechanisms of deactivation and methods for regeneration of as-prepared catalyst were explored with n-pentane isomerization as a probe reaction. The results indicated that the isopentane yield of the fresh Zn-Fe-SZA-F catalyst was about 57% at the beginning of the run, and declined gradually to 50% within 1500 min, then fell rapidly from 50% to 40% between 1500 and 2500 minutes. The deactivation of Zn-Fe-SZA catalyst may be caused by carbon formation on surface of the catalyst, sulfate group attenuation owing to reduction by hydrogen, removal of sulfur species and the loss of strong acid sites. It was found that the initial catalytic activity over Zn-Fe-SZA-T catalyst was 48%, which recovered by 84.3% as compared to that of fresh catalyst (57%). However, it showed a sharp decrease in isopentane yield from 48% to 29% within 1500 minutes, showing poor stability. This is associated to the loss of acidity caused by removal of sulfur species cannot be basically restored by thermal treatment. Resulfating the calcined catalyst could improve the acidity of catalyst significantly, especially strong acid sites, as compared with the calcined sample. The improved stability of the resulfated catalyst can be explained by: 1) eliminaton of carbon deposition to some extent by calcination process, 2) formation of improved acidic nature by re-sulfation, favoring isomerization on acidic sites, 3) restructuring of the acid and metal sites via the calcination-re-sulfation procedure.
文摘Within the framework of the density functional theory and the pseudopotential method,the electronic structure calculations of the“metal-Si(100)”systems with Li,Be and Al as metal coverings of one to four monolayers(ML)thickness,were carried out.Calculations showed that band gaps of 1.02 eV,0.98 eV and 0.5 eV,respectively,appear in the densities of electronic states when the thickness of Li,Be and Al coverings is one ML.These gaps disappear with increasing thickness of the metal layers:first in the Li-Si system(for two ML),then in the Al-Si system(for three ML)and then in the Be-Si system(for four ML).This behavior of the band gap can be explained by the passivation of the substrate surface states and the peculiarities of the electronic structure of the adsorbed metals.In common the results can be interpreted as describing the possibility of the formation of a two-dimensional silicide with semiconducting properties in Li-Si(100),Be-Si(100)and Al-Si(100)systems.
文摘Twenty kinds of adsorptions of HCN on the Fe（100）, Fe（111） and Fe（110） surfaces at the 1/4 monolayer coverage are found using the density functional theory. For Fe（100）, the adsorption energy of the most stable configuration where the HCN locates at the fourfold site with the C-N bonded to four Fe atoms is 1.928 eV. The most favored adsorption structure for HCN on Fe（111） is f-η3（N）-h-η3（C）, in which the C-N bond is almost parallel to the surface, and the adsorption energy is 1.347 eV. On Fe（110）, the adsorption energy in the most stable configuration in which HCN locates at the two long-bridge sites is 1.777 eV. The adsorption energy of the parallel orientation for HCN is larger than that of the perpendicular configuration. The binding mechanism of HCN on the Fe（100）, Fe（111） and Fe（110） surfaces is also analyzed by Mulliken charge population and the density of states in HCN. The result indicates that the configurations in which the adsorbed HCN becomes the non-linear are beneficial to the formation of the addition reaction for hydrogen. The nature that the introduction of Fe into the catalyst could increase the catalytic activity of the bimetallic catalyst in the addition reaction of hydrogen for nitriles is revealed.
基金supported by the National Natural Science Foundation of China (No 90922022)the NCETFJ Program (No. HX2006-103)+1 种基金the Science and Technology Foundation of Fujian Education Bureau (No. JA08019)the Foundation of State Key Laboratory of Coal Combustion (No. FSKLCC0814)
文摘First-principles calculations based on density functional theory （DFT） and the generalized gradient approximation （GGA） have been used to study the adsorption of CO molecule on the perfect and defective FeS 2 （100） surfaces. The defective Fe 2 S（100） surfaces are caused by sulfur deficiencies. Slab geometry and periodic boundary conditions are employed with partial relaxations of atom positions in calculations. Two molecular orientations, Cand O-down, at various distinct sites have been considered. Total energy calculations indicated that no matter on perfect or deficient surfaces, the Fe position is relatively more favored than the S site with the predicted binding energies of 120.8 kJ/mol and 140.8 kJ/mol, respectively. Moreover, CO was found to be bound to Fe atom in vertical configuration. The analysis of density of states and vibrational frequencies before and after adsorption showed clear changes of the C–O bond.
基金This study was financed in part by the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior—Brasil(CAPES)—Finance Code 001The authors are grateful too to the FAPEMIG and the Post Graduate Program of Mechanical Engineering of UFU for financial support.Authors are also grateful to Villares Metals(Brazil)+1 种基金Saint Gobain Abrasives for supporting this work with workpiece material and wheel.One of authors thanks CNPq(PQ 2013 Project No.308067/2013)for the research scholarship and FAPEMIG project process No.PPM-00265-13 for financial supportThe authors are also thankful to ABCM for transferring the copyright of the article.
文摘Grinding operation is a finishing process often employed when high precision and narrow geometric tolerances are required.These requirements can be achieved only if cutting conditions are properly selected,especially the cooling-lubrication technique.In general,grinding is performed in presence of cutting fluid,however,due to the environmental impacts and costs of the conventional coolant delivery technique(flow rates from 4 L/min to 300 L/min),alternative cooling-lubrication techniques have been developed on restriction of the coolants use.Among the several techniques,MQL(minimum quantity of lubricant)technique has received special attention from machining users because of its advantages in terms of surface quality of workpiece and drastic reduction in use of coolant.In this context,this paper evaluated the performance of the MQL technique as compared to the flood coolant in peripheral surface grinding of AISI P100(VP100)steel with conventional aluminum oxide grinding wheel in relation to the surface roughness(Ra and Rz).Input parameters tested were equivalent chip thickness(0.09μm,0.18μm and 0.27μm)and flow rate of the cutting fluid(60 mL/h,150 mL/h and 240 mL/h)of the MQL system.Results showed that the grinding with MQL technique provided lower surface roughness values compared to conventional flood cooling,especially when machining under the intermediary cutting conditions.Also,with exception of heq of 0.09 m,the MQL technique resulted in lower values of Rz parameter as compared to the conventional coolant technique,regardless of the flow rate tested.
基金Supported by the National Natural Science Foundation of China(No.50879025)the Scientific Start-up Fund from North China Electric Power University, China(No.X60218)the National Basic Research Program of China(No.2004CB3418501).
文摘To reveal the relative contribution of the components, Fe, Mn oxides or organic materials（OMs） in the surficial sediments（SSs）, and the natural surface coating samples（NSCSs） to adsorbing atrazine（AT）, a selective chemical extraction technique was employed, to remove the different components, and the adsorption characteristics of AT on the SSs and the NSCSs were investigated. The observed adsorptions of AT on the original and extracted SSs and NSCSs were analyzed by nonlinear least squares fitting（NLSF） to estimate the relative contribution of the components. The results showed that the maximum adsorption of AT on the NSCSs was greater than that in the SSs, before and after extraction treatments, implying that the NSCSs were more dominant than the SSs for organic pollutant adsorption. It was also found that the Fe oxides, OMs, and residues in SSs（NSCSs） facilitated the adsorption of AT, but Mn oxides directly or indirectly restrained the interaction of AT with SSs（NSCSs） particles. The contribution of the Fe oxides to AT adsorption was more than that of OMs; the greatest contribution to AT adsorption on a molar basis was from the Fe oxides in the nonresidual fractions, indicating that the Fe oxides played an important role in controlling the environmental behavior of AT in an aquatic environment.
文摘T shaped skin-stiffener joint are one of the most commonly used structures in aerospace components.It has been proven in various studies that these joints are susceptible to failure when loaded in pull out conditions however,in specific applications these joints undergo pull loading.De-lamination/de-bond nucleation and its growth is one of the most common failure mechanisms in a fiber reinforced composite structure.Crack growth takes place due to the induced interlaminar normal and shear stresses between different structural constituents when a load is applied.In this study,Finite Element Analysis has been performed using cohesive contact interactions on a composite T-joint to simulate the pull out test conditions.A simplified shell based model coupled with CZM is proposed,which can evaluate the failure initiation and progression accurately with lesser computational efforts.The final failure occurred at a displacement of 4.71 mm at the computed failure load of 472.57 kgf for basic configuration.Computed Failure load for the padded configuration is 672.8 kgf and corresponding displacement is 4.6 mm.The results obtained by the proposed numerical model are validated by experimental results and it is observed that predicted failure displacements and failure load calculated were correlating reasonably well with the experiment.
基金Supported by the Joint Funds of the National Natural Science Foundation of China(No.u0837604) the Funds for Applied Basic Researches of Yunnan Province(No.2010CD022)
文摘The surface disproportionation reaction mechanism of aluminum subchloride on the aluminum （100） surfaces has been investigated by the plane-wave density functional theory （DFT）. Three kinds of possible reaction mechanism of AlCl disproportionation reaction on the aluminum （100） surfaces have been taken into account. The structures of reactants and products have been optimized, transition states have been confirmed and activation energies have been calculated. The adsorption energy of reactants and desorption energy of products have been determined. All of these have been employed to confirm the reaction mechanism and the rate determining step ofAlCl disproportionation reaction on the aluminum （100） surfaces.
文摘Pyrite （FeS2） bulk and （100） surface properties and the oxygen adsorption on the surface were studied by using density functional theory methods. The results show that in the formation of FeS2 （100） surface, there exists a process of electron transfer from Fe dangling bond to S dangling bond. In this situation, surface Fe and S atoms have more ionic properties. Both Fe2+ and S2- have high electrochemistry reduction activity, which is the base for oxygen adsorption. From the viewpoint of adsorption energy, the parallel form oxygen adsorption is in preference. The result also shows that the state of oxygen absorbed on FeS2 surface acts as peroxides rather than O2.
