The study of the mechanical property and damage state of coal materials under compression is a fundamental area of research in underground mining engineering.Drawing upon the compaction effect and linear energy dissip...The study of the mechanical property and damage state of coal materials under compression is a fundamental area of research in underground mining engineering.Drawing upon the compaction effect and linear energy dissipation(LED)law,a novel compressive damage constitutive model for brittle coal is proposed.Utilizing the energy-defined damage method for mate-rials,the LED law is innovatively introduced to accurately characterize the energy dissipation during the loading process,and a novel formula for characterizing the damage variable of brittle coal is proposed.On this basis,considering that the constitutive model based on the hypothesis of strain equivalence is incapable of accurately describing the compaction effect exhibited by coal material during the compression process,a correction coefficient is proposed and apply it in the novel damage constitutive model.The established conventional monotone loading and single-cyclic loading-unloading uniaxial compression damage constitutive models have been validated using experimental data from cylindrical and cuboid coal specimens.In addition,compared with the constitutive model obtained via the traditional energy calculation method based on the hypothesis that the unloading curve is a straight line,the constitutive model employing LED law can describe the stress-strain state of brittle coal more precisely.This approach introduces a new perspective and enhances the convenience for constructing the constitutive model based on energy theory.展开更多
Rocks will suffer different degree of damage under freeze-thaw(FT)cycles,which seriously threatens the long-term stability of rock engineering in cold regions.In order to study the mechanism of rock FT damage,energy c...Rocks will suffer different degree of damage under freeze-thaw(FT)cycles,which seriously threatens the long-term stability of rock engineering in cold regions.In order to study the mechanism of rock FT damage,energy calculation method and energy self-inhibition model are introduced to explore their energy characteristics in this paper.The applicability of the energy self-inhibition model was verified by combining the data of FT cycles and uniaxial compression tests of intact and pre-cracked sandstone samples,as well as published reference data.In addition,the energy evolution characteristics of FT damaged rocks were discussed accordingly.The results indicate that the energy self-inhibition model perfectly characterizes the energy accumulation characteristics of FT damaged rocks under uniaxial compression before the peak strength and the energy dissipation characteristics before microcrack unstable growth stage.Taking the FT damaged cyan sandstone sample as an example,it has gone through two stages dominated by energy dissipation mechanism and energy accumulation mechanism,and the energy rate curve of the pre-cracked sample shows a fall-rise phenomenon when approaching failure.Based on the published reference data,it was found that the peak total input energy and energy storage limit conform to an exponential FT decay model,with corresponding decay constants ranging from 0.0021 to 0.1370 and 0.0018 to 0.1945,respectively.Finally,a linear energy storage equation for FT damaged rocks was proposed,and its high reliability and applicability were verified by combining published reference data,the energy storage coefficient of different types of rocks ranged from 0.823 to 0.992,showing a negative exponential relationship with the initial UCS(uniaxial compressive strength).In summary,the mechanism by which FT weakens the mechanical properties of rocks has been revealed from an energy perspective in this paper,which can provide reference for related issues in cold regions.展开更多
To evaluate the coal burst proneness more precisely,a new energy criterion namely the residual elastic energy index was proposed.This study begins by performing the single-cyclic loading-unloading uniaxial compression...To evaluate the coal burst proneness more precisely,a new energy criterion namely the residual elastic energy index was proposed.This study begins by performing the single-cyclic loading-unloading uniaxial compression tests with five pre-peak unloading stress levels to explore the energy storage characteristics of coal.Five types of coals from different mines were tested,and the instantaneous destruction process of the coal specimens under compression loading was recorded using a high speed camera.The results showed a linear relationship between the elastic strain energy density and input energy density,which confirms the linear energy storage law of coal.Based on this linear energy storage law,the peak elastic strain energy density of each coal specimen was obtained precisely.Subsequently,a new energy criterion of coal burst proneness was established,which was called the residual elastic energy index(defined as the difference between the peak elastic strain energy density and post peak failure energy density).Considering the destruction process and actual failure characteristics of coal specimens,the accuracy of evaluating coal burst proneness based on the residual elastic energy index was examined.The results indicated that the residual elastic energy index enables reliable and precise evaluations of the coal burst proneness.展开更多
To study the energy storage and dissipation characteristics of deep rock under two-dimensional compression with constant confining pressure,the single cyclic loading-unloading two-dimensional compression tests were pe...To study the energy storage and dissipation characteristics of deep rock under two-dimensional compression with constant confining pressure,the single cyclic loading-unloading two-dimensional compression tests were performed on granite specimens with two height-to-width(H/W)ratios under five confining pressures.Three energy density parameters(input energy density,elastic energy density and dissipated energy density)in the axial and lateral directions of granite specimens under different confining pressures were calculated using the area integral method.The experimental results show that,for the specimens with a specific H/W ratio,these three energy density parameters in the axial and lateral directions increase nonlinearly with the confining pressure as quadratic polynomial functions.Under constant confining pressure compression,the linear energy storage law of granite specimens in the axial and lateral directions was founded.Using the linear energy storage law in different directions,the elastic energy density in various directions(axial elastic energy density,lateral elastic energy density and total elastic energy density)of granite under any specific confining pressures can be calculated.When the H/W ratio varies from 1:1 to 2:1,the lateral compression energy storage coefficient increases and the corresponding axial compression energy storage coefficient decreases,while the total compression energy storage coefficient is almost independent of the H/W ratio.展开更多
Many underground engineering projects show that rockburst can occur in rocks at great depth and high temperature, and temperature is a critical factor affecting the intensity of rockburst. In general, temperature can ...Many underground engineering projects show that rockburst can occur in rocks at great depth and high temperature, and temperature is a critical factor affecting the intensity of rockburst. In general, temperature can affect the energy storage, dissipation, and surplus in rock. To explore the influence of temperature on the energy storage and dissipation characteristics and rockburst proneness, the present study has carried out a range of the uniaxial compression(UC) and single-cyclic loading-unloading uniaxial compression(SCLUC) tests on pre-heated granite specimens at 20℃-700℃. The results demonstrate that the rockburst proneness of pre-heated granite initially increases and subsequently decreases with the increase of temperature. The temperature of 300℃ has been found to be the threshold for rockburst proneness. Meanwhile, it is found that the elastic strain energy density increases linearly with the total input strain energy density for the pre-heated granites, confirming that the linear energy property of granite has not been altered by temperature. According to this inherent property, the peak elastic strain energy of pre-heated granites can be calculated accurately. On this basis, utilising the residual elastic energy index, the rockburst proneness of pre-heated granite can be determined quantitatively. The obtained results from high to low are: 317.9 k J/m^(3)(300℃), 264.1 k J/m^(3)(100℃), 260.6 k J/m^(3)(20℃), 235.5 k J/m^(3)(500℃), 158.9 k J/m^(3)(700℃), which are consistent with the intensity of actual rockburst for specimens. In addition, the relationship between temperature and energy storage capacity(ESC) of granite was discussed, revealing that high temperature impairs ESC of rocks, which is essential for reducing the rockburst proneness. This study provides some new insights into the rockburst proneness evaluation in high-temperature rock engineering.展开更多
The rationality of using strain energy storage index(Wet)for evaluating rockburst proneness was theoretically verified based on linear energy storage(LES)law in this study.The LES law is defined as the linear relation...The rationality of using strain energy storage index(Wet)for evaluating rockburst proneness was theoretically verified based on linear energy storage(LES)law in this study.The LES law is defined as the linear relationship between the elastic strain energy stored inside the solid material and the input strain energy during loading.It is used to determine the elastic strain energy and dissipated strain energy of rock specimens at various loading/unloading stress levels.The results showed that the Wetvalue obtained from experiments was close to the corresponding theoretical one from the LES law.Furthermore,with an increase in the loading/unloading stress level,the ratio of elastic strain energy to dissipated strain energy converged to the peak-strength strain energy storage index(Wp et).This index is stable and can better reflect the relative magnitudes of the stored energy and the dissipated energy of rocks at the whole pre-peak stage than the strain energy storage index.The peak-strength strain energy storage index can replace the conventional strain energy storage index as a new index for evaluating rockburst proneness.展开更多
A heavy-ion irradiation experiment is studied in digital storage cells with different design approaches in 130？nm CMOS bulk Si and silicon-on-insulator （SOI） technologies. The effectiveness of linear energy transf...A heavy-ion irradiation experiment is studied in digital storage cells with different design approaches in 130？nm CMOS bulk Si and silicon-on-insulator （SOI） technologies. The effectiveness of linear energy transfer （LET） with a tilted ion beam at the 130？nm technology node is obtained. Tests of tilted angles θ=0 ° , 30 ° and 60 ° with respect to the normal direction are performed under heavy-ion Kr with certain power whose LET is about 40？MeVcm 2 /mg at normal incidence. Error numbers in D flip-flop chains are used to determine their upset sensitivity at different incidence angles. It is indicated that the effective LETs for SOI and bulk Si are not exactly in inverse proportion to cosθ , furthermore the effective LET for SOI is more closely in inverse proportion to cosθ compared to bulk Si, which are also the well known behavior. It is interesting that, if we design the sample in the dual interlocked storage cell approach, the effective LET in bulk Si will look like inversely proportional to cosθ very well, which is also specifically explained.展开更多
Several chromatography systems with ionic liquids and a mixture of water with the modifier as mobile phase were characterized via the linear solvation energy relationships（LSER） model. The effects of the ionic liqui...Several chromatography systems with ionic liquids and a mixture of water with the modifier as mobile phase were characterized via the linear solvation energy relationships（LSER） model. The effects of the ionic liquids and modifier（methanol） concentrations on the retention of 10 solutes（caffeine, pyridine, aniline, phenol, methylparaben, acetopenone, m-cresol, p-cresol, o-cresol, and benzene） were discussed. The LSER model demonstrated high potential to predict retention factors with high squared correlation coefficients（r^2〉 0.97）. A comparison of predictable and experimental retention factors revealed that LSER can adequately reproduce the experimental retention factors of the solutes under different investigated experimental conditions. This model is a helpful tool to evaluate the retention characteristics of ionic liquid systems and to understand the interactions of solutes and ionic liquids.展开更多
The correlation relationships of apparent extraction equilibrium constant (1gK(ex)) with the electronic effect parameter( Sigma sigma(Phi)) and the steric effect parameter ( Sigma upsilon ) of the substituents in extr...The correlation relationships of apparent extraction equilibrium constant (1gK(ex)) with the electronic effect parameter( Sigma sigma(Phi)) and the steric effect parameter ( Sigma upsilon ) of the substituents in extractant molecules are investigated by linear regression analysis in the extraction of rare earths by various classes and structures of monoacidic organophosphorus extractants. The results indicate that in Linear free energy relationship formula 1gK(ex) = rho Sigma sigma(Phi) + psi Sigma upsilon + h generally follows for this kind of extraction systems. Accordingly, the quantitative structure-behaviour relationships of extractants are discussed. These relationships can be preliminarily applied to predict the 1gK(ex) values of rare earth extraction with definite structures of this class of extractants, and thus can provide some directions for the design of new RE extractants.展开更多
The properties of absorption spectra are presented and the linear correlations of Hammett constants with the 0-0 transition energy(E_(o,o))of S_←S_o, and the ratios of oscillator strength(f/f)are used to probe the in...The properties of absorption spectra are presented and the linear correlations of Hammett constants with the 0-0 transition energy(E_(o,o))of S_←S_o, and the ratios of oscillator strength(f/f)are used to probe the interactions betwee π-electron of aromatic maerocycles or metal ion of complexes with the sub- stituents on β-position of benzene ring for porphyrin-like maerocyclic compounds.展开更多
To examine the effect of bedding angle upon burst proneness in terms of energy,phyllites with seven various bedding angles are selected for conventional uniaxial compression and single-cyclic loading eunloading uniaxi...To examine the effect of bedding angle upon burst proneness in terms of energy,phyllites with seven various bedding angles are selected for conventional uniaxial compression and single-cyclic loading eunloading uniaxial compression tests.The ejection and failure during compression process of phyllites are monitored in real-time by high-speed camera system.The results demonstrate that the phyllites with different bedding angles all consistently follow the linear energy storage and dissipation(LESD)law during compression.The ultimate energy storage of phyllites with varying bedding angles can be calculated precisely via using the LESD law.Based on this,four kinds of energy-based rockburst indices are applied to quantitatively assess the burst proneness for phyllites.Combined with the recorded images of high-speed camera system,ejection distance,and mass of rock fragments and powder,the burst proneness for phyllites with various bedding angles is qualitatively evaluated adopting the far-field ejection mass ratio.Next,burst proneness of anisotropic phyllites is assessed quantitatively and qualitatively.It is found that phyllites with bedding angles of 0°,15°,and 90°have a high burst proneness,and that with bedding angle of 30°has a medium burst proneness,whereas the ones with bedding angles of 45°,60°,and 75°have a low burst proneness.Finally,the published experimental data of shale and sandstone specimens with different bedding angles are extracted,and it is preliminarily verified that the bedding angle does not change the LESD law of rocks.展开更多
20 Quantum chemical parameters of chlorophenol compounds were fully optimized by using B3LYP method on both 6-31G^＊ and 6-311G^＊ basis sets. These structural parameters are taken as theoretical descriptors, and the ...20 Quantum chemical parameters of chlorophenol compounds were fully optimized by using B3LYP method on both 6-31G^＊ and 6-311G^＊ basis sets. These structural parameters are taken as theoretical descriptors, and the experimental data of 20 compounds＇ aquatic photogen toxicity（-lgEC50） are used to perform stepwise regression in order to obtain two predicted -lgEC50 correlation models whose correlation coefficients R^2 are respectively 0.9186 and 0.9567. In addition, parameters of chlorine atom＇s substitutive positions and their correlations （NPCs） are taken as descriptors to obtain another predicted -lgEC50 model with the correlation coefficient R2 of 0.9444. Correlation degree of each independent variable in the three models is verified by using variance inflation factors （VIF） and t value. In the cross-validation method, cross-validation coefficients q^2 of 3 models are respectively 0.8748, 0.9119 and 0.8993, which indicates that the relativity and prediction ability of this model are superior to those of the model obtained by topological and BLYP methods.展开更多
The theoretical linear solvation energy relationship(TLSER) approach was adopted to predict the aqueous solubility and n -octanol/water partition coefficient of three groups of environmentally important chemicals-poly...The theoretical linear solvation energy relationship(TLSER) approach was adopted to predict the aqueous solubility and n -octanol/water partition coefficient of three groups of environmentally important chemicals-polychlorinated biphenyls(PCBs), polychlorinated dibenzodioxins and dibenzofurans(PCDDs and PCDFs). For each compound, five quantum parameters were calculated using AM1 semiempirical molecular orbital methods and used as structure descriptors: average molecular polarizability(α), energy of the lowest unoccupied molecular orbit( E _ LUMO ), energy of the highest occupied molecular orbit( E _ HOMO ), the most positive charge on a hydrogen atom( q _+), and the most negative atomic partial charge( q _-) in the solute molecule. Then standard independent variables in TLSER equation was extracted and two series of quantitative equations between these quantum parameters and aqueous solubility and n -octanol/water partition coefficient were obtained by stepwise multiple linear regression(MLR) method. The developed equations have both quite high accuracy and explicit meanings. And the cross-validation test illustrated the good predictive power and stability of the established models. The results showed that TLSER could be used as a promising approach in the estimation of partition and solubility properties of macromolecular chemicals, such as persistent organic pollutants.展开更多
Twenty eight alkyl(1-phenylsulfonyl) cycloalkane carboxylates were computed at the B3LYP/6-31G* level. Based on linear solvation energy theory, two quantitative correlation equations of the molecular structures of alk...Twenty eight alkyl(1-phenylsulfonyl) cycloalkane carboxylates were computed at the B3LYP/6-31G* level. Based on linear solvation energy theory, two quantitative correlation equations of the molecular structures of alkyl(1-phenylsulfonyl) cycloalkane carboxylate com- pounds to their chromatographic retention (capacity factor lgKW) and the toxicity for photo- bacterium phosphoreum (–lgEC50) were developed by using the molecular structural parameters as theoretical descriptors (r2 = 0.9501, 0.9488). The two quantitative correlation equations were consequently cross validated by leave-one-out (LOO) validation method with q2 of 0.9113 and 0.9281, respectively. The result showed that the two equations achieved in this work by B3LYP/6-31G* are both more advantageous than those from AM1, and can be used to predict the lgKW and –lgEC50 of congeneric organics.展开更多
Quantum chemistry parameters of 22 fluorobenzenes were computed at six levels using Hartree-Fock and DFT methods. Based on the experimental data of n-octanol/water partition coefficient （lgKow）, a three-parameter （...Quantum chemistry parameters of 22 fluorobenzenes were computed at six levels using Hartree-Fock and DFT methods. Based on the experimental data of n-octanol/water partition coefficient （lgKow）, a three-parameter （dipole moments （μ）, zero point energy （ZPE） and free energy （G°）） quantitative correlation equation that can predict IgKow was developed using structural and thermodynamic parameters as theoretical descriptors. Similarly, based on experimental data of soil organic carbon sorption coefficient （lgKoc）, the other three-parameter （the most negative atomic net charge of molecule （q^-）, dipole moments （μ） and molecular volume （Vi）） quantitative correlation equation that can predict lgKoc was given. Quantitative correlation equations based on B3LYP/6- 311 G^＊＊ calculation were validated by VIF （variance inflation factors） and t-test and used to predict IgKow and lgKoc of a series of compounds. The result showed that the correlation and prediction ability of lgKoc equations based on three levels of HF/STO-3G, B3LYP/6-31 G^＊ and B3LYP/6- 311G^＊＊ are all more advantageous than those based on AMI.展开更多
In this work,the microstructural evolution,micro-crack formation,and mechanical anisotropy of the selective laser melted(SLM)carbon-free Mar-M509 Co-based superalloy were systematically studied under different linear ...In this work,the microstructural evolution,micro-crack formation,and mechanical anisotropy of the selective laser melted(SLM)carbon-free Mar-M509 Co-based superalloy were systematically studied under different linear energy densities(LED).Observation shows that the SLM Mar-M509 superalloy possesses a fully dense structure,whereas some microcracks exist along the building direction.The electron backscatter diffraction results reveal that dominant columnar grains tend to elongate along the building direction parallel to the XZ plane.Meanwhile,both a<001>near fiber texture and a{100}<001>near sheet texture are observed in different specimens.For the specimen with fiber texture,a high misorientation angle exists among different columnar grains,which aggravated the generation of micro-cracks under thermal stress.Higher LED results in higher micro-crack density in the SLM specimen due to higher thermal stress.Mar-M509 specimen fabricated under lower LED exhibits higher tensile strength due to more significant grain refinement.More prominent anisotropy of tensile performance was found in the high LED specimen,which can be attributed to the higher density of micro-cracks and crystallographic texture.Furthermore,the SLM Mar-M509 superalloy exhibits better mechanical properties than the traditional cast technique.In summary,this work can contribute to the development and the future application of SLM-fabricated Co-based superalloy.展开更多
Phenylthio-carboxylates were computed at the B3LYP/6-31G* level with DFT method. Based on linear solvation energy theory, the structural parameters were firstly taken as theoretical descriptors, and the correspondin...Phenylthio-carboxylates were computed at the B3LYP/6-31G* level with DFT method. Based on linear solvation energy theory, the structural parameters were firstly taken as theoretical descriptors, and the corresponding linear solvation energy relationship (LSER) equation (r = 0.8989) to the toxicity of photobacterium phosphoreum (–lgEC50) was thus obtained. Then the structural and thermodynamic parameters were taken as theoretical descriptors, and as a result the other corresponding correlation equation (r = 0.9274) relating to –lgEC50 was provided. The two equations achieved in this work by B3LYP/6-31G* are both more advantageous than that from AM1.展开更多
The ethylene aromatization is critical for the methanol to aromatics and light alkane dehydroaromatization process.The single-event microkinetic(SEMK)model combining the linear free energy theory and solid acid distri...The ethylene aromatization is critical for the methanol to aromatics and light alkane dehydroaromatization process.The single-event microkinetic(SEMK)model combining the linear free energy theory and solid acid distribution concept were established and extend for the ethylene aromatization process,which can reduce the kinetic parameters and simplify the reaction network by comparison with the SEMK model including subtype elementary steps based on the type of carbenium ions.Further introducing deactivation parametersφinto the model and applying the linear free energy model to the deactivation experimental data,the obtained deactivation parametersφindicate that the carbon deposition precursors have the greatest impact on reducing the reaction rate of single-molecular reactions and the smallest impact on the hydrogen transfer reaction.Meanwhile,according to the change of reaction enthalpy,effect of carbenium ion structure on methylation,ethylation,cyclization and endo-βscission was investigated by introducing linear free energy concept into the SEMK model.The effect of different acid strengths on elementary steps was investigated based on the acid strength distribution model,it was found that the methylation and oligomerization reactions,the ali-βscission reaction,endo-βscission reaction and the cyclization reaction were more sensitive to strong acidity sites.The physisorption and chemisorption heat are separated from the protonation heat in the linear free energy kinetic model and the acid strength distribution kinetic model,and the absolute values of the obtained physisorption and chemisorption heat increase with the carbon number of carbenium ions.Furthermore,the parameters of the acid strength distribution kinetic model were applied to propane dehydroaromatization on H-ZSM-5 and the ethane dehydroaromatization on Zn/ZSM-5 to confirm the independence of parameters in the SEMK model with the similar reaction network.展开更多
Molecular property parameters of 16 2-formamido-phenylacryiates were calculated with Hartree-Fock and DFT methods at six different levels. Using the molecular property parameters and dissolvability as theoretical desc...Molecular property parameters of 16 2-formamido-phenylacryiates were calculated with Hartree-Fock and DFT methods at six different levels. Using the molecular property parameters and dissolvability as theoretical descriptors, two quantitative correlation equations that could be used to predict lgKow were developed based on experimental lgKow data of 11 2-formamido-phenylacrylates. A three-parameter correlation equation posing the ability of predicting -lgSw value was computed at B3LYP/6-311G＊＊ level. The -lgSw values of five compounds that we have pre-designed were anticipated with the above equation, upon which lgKow were further calculated. The relativity （r^2≥0.94, q^2〉0.91, SD≤0.083） and prediction ability of obtained correlation equations in this work are more advantageous than those based on solvatochromism parameters.展开更多
Quantum chemistry parameters of 20 substituted phenols were computed at the 6- 31G＊ level using DFT method. Based on theoretical linear solvation energy theory, the correlation equation that can predict the retention...Quantum chemistry parameters of 20 substituted phenols were computed at the 6- 31G＊ level using DFT method. Based on theoretical linear solvation energy theory, the correlation equation that can predict the retention index （Ri） was developed using structural parameters of 15 substituted phenols with experimental data as theoretical descriptors, and the conventional correlation coefficient （R^2） is 0.9885. The correlation degree of each independent variable in the model was validated by variance inflation factors （VIF） and t-test. Cross-validation indicates that the model possesses high predicting ability. The correlation and predicting ability of the Ri equation are both more advantageous than those based on orientating group index, connectivity index, and topological index method. In addition, RI values of 5 compounds without experimental data were predicted with the model.展开更多
基金supported by the National Science Fund for Distinguished Young Scholars(52225403)the National Natural Science Foundation of China(42077244).
文摘The study of the mechanical property and damage state of coal materials under compression is a fundamental area of research in underground mining engineering.Drawing upon the compaction effect and linear energy dissipation(LED)law,a novel compressive damage constitutive model for brittle coal is proposed.Utilizing the energy-defined damage method for mate-rials,the LED law is innovatively introduced to accurately characterize the energy dissipation during the loading process,and a novel formula for characterizing the damage variable of brittle coal is proposed.On this basis,considering that the constitutive model based on the hypothesis of strain equivalence is incapable of accurately describing the compaction effect exhibited by coal material during the compression process,a correction coefficient is proposed and apply it in the novel damage constitutive model.The established conventional monotone loading and single-cyclic loading-unloading uniaxial compression damage constitutive models have been validated using experimental data from cylindrical and cuboid coal specimens.In addition,compared with the constitutive model obtained via the traditional energy calculation method based on the hypothesis that the unloading curve is a straight line,the constitutive model employing LED law can describe the stress-strain state of brittle coal more precisely.This approach introduces a new perspective and enhances the convenience for constructing the constitutive model based on energy theory.
基金Project(52174088)supported by the National Natural Science Foundation of ChinaProject(104972024JYS0007)supported by the Independent Innovation Research Fund Graduate Free Exploration,Wuhan University of Technology,China。
文摘Rocks will suffer different degree of damage under freeze-thaw(FT)cycles,which seriously threatens the long-term stability of rock engineering in cold regions.In order to study the mechanism of rock FT damage,energy calculation method and energy self-inhibition model are introduced to explore their energy characteristics in this paper.The applicability of the energy self-inhibition model was verified by combining the data of FT cycles and uniaxial compression tests of intact and pre-cracked sandstone samples,as well as published reference data.In addition,the energy evolution characteristics of FT damaged rocks were discussed accordingly.The results indicate that the energy self-inhibition model perfectly characterizes the energy accumulation characteristics of FT damaged rocks under uniaxial compression before the peak strength and the energy dissipation characteristics before microcrack unstable growth stage.Taking the FT damaged cyan sandstone sample as an example,it has gone through two stages dominated by energy dissipation mechanism and energy accumulation mechanism,and the energy rate curve of the pre-cracked sample shows a fall-rise phenomenon when approaching failure.Based on the published reference data,it was found that the peak total input energy and energy storage limit conform to an exponential FT decay model,with corresponding decay constants ranging from 0.0021 to 0.1370 and 0.0018 to 0.1945,respectively.Finally,a linear energy storage equation for FT damaged rocks was proposed,and its high reliability and applicability were verified by combining published reference data,the energy storage coefficient of different types of rocks ranged from 0.823 to 0.992,showing a negative exponential relationship with the initial UCS(uniaxial compressive strength).In summary,the mechanism by which FT weakens the mechanical properties of rocks has been revealed from an energy perspective in this paper,which can provide reference for related issues in cold regions.
基金This work was supported by the National Natural Science Foundation of China(No.41877272)the Fundamental Research Funds for the Central Universities of Southeast University(No.2242021R10080).
文摘To evaluate the coal burst proneness more precisely,a new energy criterion namely the residual elastic energy index was proposed.This study begins by performing the single-cyclic loading-unloading uniaxial compression tests with five pre-peak unloading stress levels to explore the energy storage characteristics of coal.Five types of coals from different mines were tested,and the instantaneous destruction process of the coal specimens under compression loading was recorded using a high speed camera.The results showed a linear relationship between the elastic strain energy density and input energy density,which confirms the linear energy storage law of coal.Based on this linear energy storage law,the peak elastic strain energy density of each coal specimen was obtained precisely.Subsequently,a new energy criterion of coal burst proneness was established,which was called the residual elastic energy index(defined as the difference between the peak elastic strain energy density and post peak failure energy density).Considering the destruction process and actual failure characteristics of coal specimens,the accuracy of evaluating coal burst proneness based on the residual elastic energy index was examined.The results indicated that the residual elastic energy index enables reliable and precise evaluations of the coal burst proneness.
基金Projects(41877272,51974359)supported by the National Natural Science Foundation of China。
文摘To study the energy storage and dissipation characteristics of deep rock under two-dimensional compression with constant confining pressure,the single cyclic loading-unloading two-dimensional compression tests were performed on granite specimens with two height-to-width(H/W)ratios under five confining pressures.Three energy density parameters(input energy density,elastic energy density and dissipated energy density)in the axial and lateral directions of granite specimens under different confining pressures were calculated using the area integral method.The experimental results show that,for the specimens with a specific H/W ratio,these three energy density parameters in the axial and lateral directions increase nonlinearly with the confining pressure as quadratic polynomial functions.Under constant confining pressure compression,the linear energy storage law of granite specimens in the axial and lateral directions was founded.Using the linear energy storage law in different directions,the elastic energy density in various directions(axial elastic energy density,lateral elastic energy density and total elastic energy density)of granite under any specific confining pressures can be calculated.When the H/W ratio varies from 1:1 to 2:1,the lateral compression energy storage coefficient increases and the corresponding axial compression energy storage coefficient decreases,while the total compression energy storage coefficient is almost independent of the H/W ratio.
基金supported by the National Natural Science Foundation of China (Grant No. 41877272)the Fundamental Research Funds for the Central Universities (Grant No.2242022k30054)the Fundamental Research Funds for the Central Universities of Central South University (Grant No.2021zzts0861)。
文摘Many underground engineering projects show that rockburst can occur in rocks at great depth and high temperature, and temperature is a critical factor affecting the intensity of rockburst. In general, temperature can affect the energy storage, dissipation, and surplus in rock. To explore the influence of temperature on the energy storage and dissipation characteristics and rockburst proneness, the present study has carried out a range of the uniaxial compression(UC) and single-cyclic loading-unloading uniaxial compression(SCLUC) tests on pre-heated granite specimens at 20℃-700℃. The results demonstrate that the rockburst proneness of pre-heated granite initially increases and subsequently decreases with the increase of temperature. The temperature of 300℃ has been found to be the threshold for rockburst proneness. Meanwhile, it is found that the elastic strain energy density increases linearly with the total input strain energy density for the pre-heated granites, confirming that the linear energy property of granite has not been altered by temperature. According to this inherent property, the peak elastic strain energy of pre-heated granites can be calculated accurately. On this basis, utilising the residual elastic energy index, the rockburst proneness of pre-heated granite can be determined quantitatively. The obtained results from high to low are: 317.9 k J/m^(3)(300℃), 264.1 k J/m^(3)(100℃), 260.6 k J/m^(3)(20℃), 235.5 k J/m^(3)(500℃), 158.9 k J/m^(3)(700℃), which are consistent with the intensity of actual rockburst for specimens. In addition, the relationship between temperature and energy storage capacity(ESC) of granite was discussed, revealing that high temperature impairs ESC of rocks, which is essential for reducing the rockburst proneness. This study provides some new insights into the rockburst proneness evaluation in high-temperature rock engineering.
基金supported by the National Natural Science Foundation of China(Grant Nos.42077244 and 41877272)the Fundamental Research Funds for the Central Universities(Grant No.2242022k30054)。
文摘The rationality of using strain energy storage index(Wet)for evaluating rockburst proneness was theoretically verified based on linear energy storage(LES)law in this study.The LES law is defined as the linear relationship between the elastic strain energy stored inside the solid material and the input strain energy during loading.It is used to determine the elastic strain energy and dissipated strain energy of rock specimens at various loading/unloading stress levels.The results showed that the Wetvalue obtained from experiments was close to the corresponding theoretical one from the LES law.Furthermore,with an increase in the loading/unloading stress level,the ratio of elastic strain energy to dissipated strain energy converged to the peak-strength strain energy storage index(Wp et).This index is stable and can better reflect the relative magnitudes of the stored energy and the dissipated energy of rocks at the whole pre-peak stage than the strain energy storage index.The peak-strength strain energy storage index can replace the conventional strain energy storage index as a new index for evaluating rockburst proneness.
基金Supported by the Key Laboratory of Microsatellites,Chinese Academy of Sciences
文摘A heavy-ion irradiation experiment is studied in digital storage cells with different design approaches in 130？nm CMOS bulk Si and silicon-on-insulator （SOI） technologies. The effectiveness of linear energy transfer （LET） with a tilted ion beam at the 130？nm technology node is obtained. Tests of tilted angles θ=0 ° , 30 ° and 60 ° with respect to the normal direction are performed under heavy-ion Kr with certain power whose LET is about 40？MeVcm 2 /mg at normal incidence. Error numbers in D flip-flop chains are used to determine their upset sensitivity at different incidence angles. It is indicated that the effective LETs for SOI and bulk Si are not exactly in inverse proportion to cosθ , furthermore the effective LET for SOI is more closely in inverse proportion to cosθ compared to bulk Si, which are also the well known behavior. It is interesting that, if we design the sample in the dual interlocked storage cell approach, the effective LET in bulk Si will look like inversely proportional to cosθ very well, which is also specifically explained.
基金Supported by the Center for Advanced Bioseparation Technology, Inha University, Korea
文摘Several chromatography systems with ionic liquids and a mixture of water with the modifier as mobile phase were characterized via the linear solvation energy relationships（LSER） model. The effects of the ionic liquids and modifier（methanol） concentrations on the retention of 10 solutes（caffeine, pyridine, aniline, phenol, methylparaben, acetopenone, m-cresol, p-cresol, o-cresol, and benzene） were discussed. The LSER model demonstrated high potential to predict retention factors with high squared correlation coefficients（r^2〉 0.97）. A comparison of predictable and experimental retention factors revealed that LSER can adequately reproduce the experimental retention factors of the solutes under different investigated experimental conditions. This model is a helpful tool to evaluate the retention characteristics of ionic liquid systems and to understand the interactions of solutes and ionic liquids.
文摘The correlation relationships of apparent extraction equilibrium constant (1gK(ex)) with the electronic effect parameter( Sigma sigma(Phi)) and the steric effect parameter ( Sigma upsilon ) of the substituents in extractant molecules are investigated by linear regression analysis in the extraction of rare earths by various classes and structures of monoacidic organophosphorus extractants. The results indicate that in Linear free energy relationship formula 1gK(ex) = rho Sigma sigma(Phi) + psi Sigma upsilon + h generally follows for this kind of extraction systems. Accordingly, the quantitative structure-behaviour relationships of extractants are discussed. These relationships can be preliminarily applied to predict the 1gK(ex) values of rare earth extraction with definite structures of this class of extractants, and thus can provide some directions for the design of new RE extractants.
文摘The properties of absorption spectra are presented and the linear correlations of Hammett constants with the 0-0 transition energy(E_(o,o))of S_←S_o, and the ratios of oscillator strength(f/f)are used to probe the interactions betwee π-electron of aromatic maerocycles or metal ion of complexes with the sub- stituents on β-position of benzene ring for porphyrin-like maerocyclic compounds.
基金supported by the National Natural Science Foundation of China(Grant No.42077244).
文摘To examine the effect of bedding angle upon burst proneness in terms of energy,phyllites with seven various bedding angles are selected for conventional uniaxial compression and single-cyclic loading eunloading uniaxial compression tests.The ejection and failure during compression process of phyllites are monitored in real-time by high-speed camera system.The results demonstrate that the phyllites with different bedding angles all consistently follow the linear energy storage and dissipation(LESD)law during compression.The ultimate energy storage of phyllites with varying bedding angles can be calculated precisely via using the LESD law.Based on this,four kinds of energy-based rockburst indices are applied to quantitatively assess the burst proneness for phyllites.Combined with the recorded images of high-speed camera system,ejection distance,and mass of rock fragments and powder,the burst proneness for phyllites with various bedding angles is qualitatively evaluated adopting the far-field ejection mass ratio.Next,burst proneness of anisotropic phyllites is assessed quantitatively and qualitatively.It is found that phyllites with bedding angles of 0°,15°,and 90°have a high burst proneness,and that with bedding angle of 30°has a medium burst proneness,whereas the ones with bedding angles of 45°,60°,and 75°have a low burst proneness.Finally,the published experimental data of shale and sandstone specimens with different bedding angles are extracted,and it is preliminarily verified that the bedding angle does not change the LESD law of rocks.
基金973 National Basic Research Program of China (2003CB415002)
文摘20 Quantum chemical parameters of chlorophenol compounds were fully optimized by using B3LYP method on both 6-31G^＊ and 6-311G^＊ basis sets. These structural parameters are taken as theoretical descriptors, and the experimental data of 20 compounds＇ aquatic photogen toxicity（-lgEC50） are used to perform stepwise regression in order to obtain two predicted -lgEC50 correlation models whose correlation coefficients R^2 are respectively 0.9186 and 0.9567. In addition, parameters of chlorine atom＇s substitutive positions and their correlations （NPCs） are taken as descriptors to obtain another predicted -lgEC50 model with the correlation coefficient R2 of 0.9444. Correlation degree of each independent variable in the three models is verified by using variance inflation factors （VIF） and t value. In the cross-validation method, cross-validation coefficients q^2 of 3 models are respectively 0.8748, 0.9119 and 0.8993, which indicates that the relativity and prediction ability of this model are superior to those of the model obtained by topological and BLYP methods.
基金TheNationalKeyBasicResearchFoundationofChina (No .G1 9990 4 571 1 )
文摘The theoretical linear solvation energy relationship(TLSER) approach was adopted to predict the aqueous solubility and n -octanol/water partition coefficient of three groups of environmentally important chemicals-polychlorinated biphenyls(PCBs), polychlorinated dibenzodioxins and dibenzofurans(PCDDs and PCDFs). For each compound, five quantum parameters were calculated using AM1 semiempirical molecular orbital methods and used as structure descriptors: average molecular polarizability(α), energy of the lowest unoccupied molecular orbit( E _ LUMO ), energy of the highest occupied molecular orbit( E _ HOMO ), the most positive charge on a hydrogen atom( q _+), and the most negative atomic partial charge( q _-) in the solute molecule. Then standard independent variables in TLSER equation was extracted and two series of quantitative equations between these quantum parameters and aqueous solubility and n -octanol/water partition coefficient were obtained by stepwise multiple linear regression(MLR) method. The developed equations have both quite high accuracy and explicit meanings. And the cross-validation test illustrated the good predictive power and stability of the established models. The results showed that TLSER could be used as a promising approach in the estimation of partition and solubility properties of macromolecular chemicals, such as persistent organic pollutants.
基金This work was financially supported by the National Basic Research Program of China (2003CB415002), the China Postdoctoral Science Foundation (No. 2003033486) and the Natural Science Research Fund of University in Jiangsu (04KJB150149)
文摘Twenty eight alkyl(1-phenylsulfonyl) cycloalkane carboxylates were computed at the B3LYP/6-31G* level. Based on linear solvation energy theory, two quantitative correlation equations of the molecular structures of alkyl(1-phenylsulfonyl) cycloalkane carboxylate com- pounds to their chromatographic retention (capacity factor lgKW) and the toxicity for photo- bacterium phosphoreum (–lgEC50) were developed by using the molecular structural parameters as theoretical descriptors (r2 = 0.9501, 0.9488). The two quantitative correlation equations were consequently cross validated by leave-one-out (LOO) validation method with q2 of 0.9113 and 0.9281, respectively. The result showed that the two equations achieved in this work by B3LYP/6-31G* are both more advantageous than those from AM1, and can be used to predict the lgKW and –lgEC50 of congeneric organics.
基金Project supported by the Chinese Postdoctoral Science Foundation (No. 2003033486) and the National Natural Science Foundation of China (20477018)
文摘Quantum chemistry parameters of 22 fluorobenzenes were computed at six levels using Hartree-Fock and DFT methods. Based on the experimental data of n-octanol/water partition coefficient （lgKow）, a three-parameter （dipole moments （μ）, zero point energy （ZPE） and free energy （G°）） quantitative correlation equation that can predict IgKow was developed using structural and thermodynamic parameters as theoretical descriptors. Similarly, based on experimental data of soil organic carbon sorption coefficient （lgKoc）, the other three-parameter （the most negative atomic net charge of molecule （q^-）, dipole moments （μ） and molecular volume （Vi）） quantitative correlation equation that can predict lgKoc was given. Quantitative correlation equations based on B3LYP/6- 311 G^＊＊ calculation were validated by VIF （variance inflation factors） and t-test and used to predict IgKow and lgKoc of a series of compounds. The result showed that the correlation and prediction ability of lgKoc equations based on three levels of HF/STO-3G, B3LYP/6-31 G^＊ and B3LYP/6- 311G^＊＊ are all more advantageous than those based on AMI.
基金financially supported by the National Key Research and Development Program of China(No.2019YFA0705300)the Chinese National Science and Technology Major Project“Aeroengine and Gas Turbine”(No.2017-VII0008-0102)+4 种基金the Shanghai Science and Technology Committee(No.19DZ1100704)Shanghai Shuguang Program(No.20SG42)Shanghai Sailing Program(No.19YF1415900)the National Natural Science Foundation of China(No.52001191)the Shanghai Rising-Star Program(No.20QA1403800)。
文摘In this work,the microstructural evolution,micro-crack formation,and mechanical anisotropy of the selective laser melted(SLM)carbon-free Mar-M509 Co-based superalloy were systematically studied under different linear energy densities(LED).Observation shows that the SLM Mar-M509 superalloy possesses a fully dense structure,whereas some microcracks exist along the building direction.The electron backscatter diffraction results reveal that dominant columnar grains tend to elongate along the building direction parallel to the XZ plane.Meanwhile,both a<001>near fiber texture and a{100}<001>near sheet texture are observed in different specimens.For the specimen with fiber texture,a high misorientation angle exists among different columnar grains,which aggravated the generation of micro-cracks under thermal stress.Higher LED results in higher micro-crack density in the SLM specimen due to higher thermal stress.Mar-M509 specimen fabricated under lower LED exhibits higher tensile strength due to more significant grain refinement.More prominent anisotropy of tensile performance was found in the high LED specimen,which can be attributed to the higher density of micro-cracks and crystallographic texture.Furthermore,the SLM Mar-M509 superalloy exhibits better mechanical properties than the traditional cast technique.In summary,this work can contribute to the development and the future application of SLM-fabricated Co-based superalloy.
基金This work was supported by the China Postdoctoral Science Foundation (No. 2003033486) National Natural Science Foundation of China (No. 20177008)
文摘Phenylthio-carboxylates were computed at the B3LYP/6-31G* level with DFT method. Based on linear solvation energy theory, the structural parameters were firstly taken as theoretical descriptors, and the corresponding linear solvation energy relationship (LSER) equation (r = 0.8989) to the toxicity of photobacterium phosphoreum (–lgEC50) was thus obtained. Then the structural and thermodynamic parameters were taken as theoretical descriptors, and as a result the other corresponding correlation equation (r = 0.9274) relating to –lgEC50 was provided. The two equations achieved in this work by B3LYP/6-31G* are both more advantageous than that from AM1.
基金supported by the Open Project of Key Laboratory of Green Chemical Engineering Process of Ministry of Education[grant number GCP20190204]Hubei Key Laboratory of Novel Reactor and Green Chemistry Technology(Wuhan Institute of Technology)[grant number 40201005]+1 种基金Engineering Research Center of Phosphorus Resources Development and Utilization of Ministry of Education[grant number LKF201908]Graduate Innovative Fund of Wuhan Institute of Technology[grant number CX2021028].
文摘The ethylene aromatization is critical for the methanol to aromatics and light alkane dehydroaromatization process.The single-event microkinetic(SEMK)model combining the linear free energy theory and solid acid distribution concept were established and extend for the ethylene aromatization process,which can reduce the kinetic parameters and simplify the reaction network by comparison with the SEMK model including subtype elementary steps based on the type of carbenium ions.Further introducing deactivation parametersφinto the model and applying the linear free energy model to the deactivation experimental data,the obtained deactivation parametersφindicate that the carbon deposition precursors have the greatest impact on reducing the reaction rate of single-molecular reactions and the smallest impact on the hydrogen transfer reaction.Meanwhile,according to the change of reaction enthalpy,effect of carbenium ion structure on methylation,ethylation,cyclization and endo-βscission was investigated by introducing linear free energy concept into the SEMK model.The effect of different acid strengths on elementary steps was investigated based on the acid strength distribution model,it was found that the methylation and oligomerization reactions,the ali-βscission reaction,endo-βscission reaction and the cyclization reaction were more sensitive to strong acidity sites.The physisorption and chemisorption heat are separated from the protonation heat in the linear free energy kinetic model and the acid strength distribution kinetic model,and the absolute values of the obtained physisorption and chemisorption heat increase with the carbon number of carbenium ions.Furthermore,the parameters of the acid strength distribution kinetic model were applied to propane dehydroaromatization on H-ZSM-5 and the ethane dehydroaromatization on Zn/ZSM-5 to confirm the independence of parameters in the SEMK model with the similar reaction network.
基金This work was supported by the Postdoctoral Science Foundation of China (No. 2003033486) and National Science Foundation of China (No. 20177008)
文摘Molecular property parameters of 16 2-formamido-phenylacryiates were calculated with Hartree-Fock and DFT methods at six different levels. Using the molecular property parameters and dissolvability as theoretical descriptors, two quantitative correlation equations that could be used to predict lgKow were developed based on experimental lgKow data of 11 2-formamido-phenylacrylates. A three-parameter correlation equation posing the ability of predicting -lgSw value was computed at B3LYP/6-311G＊＊ level. The -lgSw values of five compounds that we have pre-designed were anticipated with the above equation, upon which lgKow were further calculated. The relativity （r^2≥0.94, q^2〉0.91, SD≤0.083） and prediction ability of obtained correlation equations in this work are more advantageous than those based on solvatochromism parameters.
文摘Quantum chemistry parameters of 20 substituted phenols were computed at the 6- 31G＊ level using DFT method. Based on theoretical linear solvation energy theory, the correlation equation that can predict the retention index （Ri） was developed using structural parameters of 15 substituted phenols with experimental data as theoretical descriptors, and the conventional correlation coefficient （R^2） is 0.9885. The correlation degree of each independent variable in the model was validated by variance inflation factors （VIF） and t-test. Cross-validation indicates that the model possesses high predicting ability. The correlation and predicting ability of the Ri equation are both more advantageous than those based on orientating group index, connectivity index, and topological index method. In addition, RI values of 5 compounds without experimental data were predicted with the model.
