Study on the Formation Mechanism of Cutting Dead Metal Zone for Turning AISI4340 with Different Chamfering Tools.

Tools with chamfered edges are often used in high speed machining of hard materials because they provide compelling cutting toughness and reduced tool wear. Chamfered tools are also responsible for the dead metal zone (DMZ). Through numerical simulation of orthogonal cutting with AISI 4340 steel, this paper examines the mechanism of the DMZ, the cutting speed, the impacts of the chamfer angle, and the coefficient of friction on the generation of the DMZ. The analysis is based upon the Arbitrary Lagrangian-Eulerian (ALE) finite element method (FEM) for the continuous process of chip formation. The different chamfered angles, cutting speeds, and friction coefficient conditions are utilized in the simulation. The research demonstrates that a zone of trapped material called DMZ has been formed beneath the chamfer and serves as an effective cutting edge of the tool. Additionally, the dead metal zone DMZ becomes smaller while the cutting speed increases or the friction coefficient decreases. The machining forces rise with increasing chamfer angles, rise with increasing friction coefficients, and fall with increasing cutting speed in both the cutting and thrust directions. In this paper, the effect of different chamfering tools on AISI 4340 steel using carbide tools in the simulation environment is studied. It has certain reference significance for studying the formation mechanism of the dead zone of difficult-to-machine materials such as AISI4340 and improving the processing efficiency and workpiece surface quality.

Interactions of sulfuric acid with common atmospheric bases and organic acids: Thermodynamics and implications to new particle formation.

Interactions of the three common atmospheric bases, dimethylamine ((CH3)2NH), methylamine (CH3NH2), ammonia (NH3), all considered to be efficient stabilizers of binary clusters in the Earth's atmosphere, with H2SO4, the key atmospheric precursor, and 14 common atmospheric organic acids (COAs) (formic, acetic, oxalic, malonic, succinic, glutaric acid, adipic, benzoic, phenylacetic, pyruvic, maleic acid, malic, tartaric and pinonic acids) have been studied using the density functional theory (DFT) and composite high-accuracy G3MP2 method. The thermodynamic stability of mixed (COA)(H2SO4), (COA)(B1), (COA)(B2) and (COA)(B3) dimers and (COA)(H2SO4)(B1), (COA)(H2SO4)(B2) and (COA)(H2SO4)(B3) trimers, where B1, B2 and B3 refer to (CH3)2NH, CH3NH2 and NH3, respectively, have been investigated and their impacts on the thermodynamic stability of clusters containing H2SO4 have been studied. Our investigation shows that interactions of H2SO4 with COA, (CH3)2NH, CH3NH2 and NH3 lead to the formation of more stable mixed dimers and trimers than (H2SO4)2 and (H2SO4)2(base), respectively, and emphasize the importance of common organic species for early stages of atmospheric nucleation. We also show that although amines are generally confirmed to be more active than NH3 as stabilizers of binary clusters, in some cases mixed trimers containing NH3 are more stable thermodynamically than those containing CH3NH2. This study indicates an important role of COA, which coexist and interact with that H2SO4 and common atmospheric bases in the Earth atmosphere, in formation of stable pre-nucleation clusters and suggests that the impacts of COA on new particle formation (NPF) should be studied in further details.

Propionamide participating in H2SO4-based new particle formation: a theory study.

Propionamide (PA), an important pollutant emitted into the atmosphere from a variety of sources, is abundant in many areas worldwide, and could be involved in new particle formation (NPF). In this study, the enhancement of the H2SO4 (SA)-based NPF by PA was evaluated through investigating the formation mechanism of (PA) m (SA) n (m = 0-3 and n = 0-3) clusters using computational chemistry and kinetics modeling. Our study proved that the formation of all the PA-containing clusters is thermodynamically favorable. Furthermore, the [double bond, length as m-dash]O group in PA plays an important role in the clusters with more PA than SA, and the basicity of bases exerts a greater influence with an increasing amount of SA. We demonstrate that although the enhancing potential of PA is lower than that of the strongest enhancers of SA-based NPF such as methylamine (MA) and dimethylamine (DMA), PA can enhance the SA-based NPF at the parts per billion (ppb) level, which is typical for concentrations of C3-amides in, for example, urban Shanghai (China). The monomer evaporation is the dominant degradation pathway for the (PA) m (SA) n clusters, which differs from that of the SA-DMA system. The formation rate of PA-containing clusters is comparable to the rate coefficients for PA oxidation by hydroxyl (OH) radicals, indicating that participating in the SA-based NPF is a crucial sink for PA.

Towards understanding the role of amines in the SO2 hydration and the contribution of the hydrated product to new particle formation in the Earth's atmosphere.

By theoretical calculations, the gas-phase SO2 hydration reaction assisted by methylamine (MA) and dimethylamine (DMA) was investigated, and the potential contribution of the hydrated product to new particle formation (NPF) also was evaluated. The results show that the energy barrier for aliphatic amines (MA and DMA) assisted SO2 hydration reaction is lower than the corresponding that of water and ammonia assisted SO2 hydration. In these hydration reactions, nearly barrierless reaction (only a barrier of 0.1 kcal mol-1) can be found in the case of SO2 + 2H2O + DMA. These lead us to conclude that the SO2 hydration reaction assisted by MA and DMA is energetically facile. The temporal evolution for hydrated products (CH3NH3+-HSO3--H2O or (CH3)2NH2+-HSO3--H2O) in molecular dynamics simulations indicates that these complexes can self-aggregate into bigger clusters and can absorb water and amine molecules, which means that these hydrated products formed by the hydration reaction may serve as a condensation nucleus to initiate the NPF.

Characterization of dissolved organic nitrogen in wet deposition from Lake Erhai basin by using ultrahigh resolution FT-ICR mass spectrometry.

Dissolved Organic Nitrogen (DON) of wet deposition in Erhai basin (EWD) was characterized at the molecular level by using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS). The structure and composition of DON were investigated by the combined ESI FT-ICR MS, UV-Vis absorbance and fluorescence techniques. The FT-ICR MS measurements indicate that a large (∼790) number of organic species present in the wet deposition, in which DON account for 18.3%, with most of DON containing a single nitrogen atom. The typical relative molecular mass of the DON species was found to be in the range of 200-400 Da. Approximately 57.2% of DON species are highly unsaturated (DBE (Double Bond Equivalent) > 5) with the nitrogen- and sulfur-containing species, which are probably represented mainly by active nitrooxy organosulfates, accounting for âˆ¼ 19.3% of the total DON. The low average SUVA254 and A253/A203 values (0.02 and 0.06, respectively), indicates that the aromaticity of the EWD samples is particularly weak. The average values of E2/E3 and E4/E6 in the EWD samples were 6.84 and 1.84, respectively. This is a clear indication of the low degree of humification of EWD samples, in agreement with ESI FT-ICR MS measurements. Our study demonstrates that multiple experimental techniques combined with FT-ICR MS, UV-Vis absorbance and fluorescence can be efficiently used for in-depth studying the DON at the molecular level. Thus it allows us to achieve a deep and insightful understanding of the DON structure and composition.

Interaction between common organic acids and trace nucleation species in the Earth's atmosphere.

Atmospheric aerosols formed via nucleation in the Earth's atmosphere play an important role in the aerosol radiative forcing associated directly with global climate changes and public health. Although it is well-known that atmospheric aerosol particles contain organic species, the chemical nature of and physicochemical processes behind atmospheric nucleation involving organic species remain unclear. In the present work, the interaction of common organic acids with molecular weights of 122, 116, 134, 88, 136, and 150 (benzoic, maleic, malic, pyruvic, phenylacetic, and tartaric acids) with nucleation precursors and charged trace species has been investigated. We found a moderate strong effect of the organic species on the stability of neutral and charged ionic species. In most cases, the free energies of the mixed H(2)SO(4)-organic acid dimer formation are within 1-1.5 kcal mol(-1) of the (H(2)SO(4))(NH(3)) formation energy. The interaction of the organic acids with trace ionic species is quite strong, and the corresponding free energies far exceed those of the (H(3)O(+))(H(2)SO(4)) and (H(3)O(+))(H(2)SO(4))(2) formation. These considerations lead us to conclude that the aforementioned organic acids may possess a substantial capability of stabilizing both neutral and positively charged prenucleation clusters, and thus, they should be studied further with regard to their involvement in the gas-to-particle conversion in the Earth's atmosphere.

Anomalously strong effect of the ion sign on the thermochemistry of hydrogen bonded aqueous clusters of identical chemical composition.

The sign preference of hydrogen bonded aqueous ionic clusters X+/-(H(2)O)(i) (n =1-5, X = F; Cl; Br) has been investigated using the Density Functional Theory and ab initio MP2 method. The present study indicates the anomalously large difference in formation free energies between cations and anions of identical chemical composition. The effect of vibrational anharmonicity on stepwise Gibbs free energy changes has been investigated, and possible uncertainties associated with the harmonic treatment of vibrational spectra have been discussed.

Quantum-mechanical solution to fundamental problems of classical theory of water vapor nucleation.

The inconsistent temperature dependence of nucleation rates, disagreement of theoretical critical or onset supersaturations with experimental data, and insufficiently accurate predictions of nucleation rates are fundamental problems of the classical nucleation theory (CNT) of water vapors, which is a foundation of various multicomponent nucleation models widely used in the aerosol microphysics, physical chemistry, and chemical technology. In the present study, a correction to the CNT obtained from "first principles" has been derived and significant progress has been made in solving the fundamental problem of predicting nucleation rates of water vapors. The modified model with the quantum-mechanical correction incorporated is in very good agreement with experiments over the full range of temperatures (T=210-290K) , saturation ratios (S=2-100) , and nucleation rates (J= approximately 10{1}-10{17} cm-3).

Towards understanding the sign preference in binary atmospheric nucleation.

The role of the ion sign in the binary H2SO4-H2O nucleation remains unclear despite significant progress in both theory and instrumentation achieved within the last decade. In order to advance the understanding of ion nucleation phenomena, a quantum-chemical study of binary sulfuric acid-water ionic clusters nucleating in the atmosphere has been carried out. We found a profound sign effect caused by the pronounced difference in the structure and properties of clusters formed over core ions of different sign. The sign preference is found to be controlled by two somewhat competing factors: hydration and sulfuric acid attachment. While hydration of cations is clearly favorable, the affinity of sulfuric acid, which largely controls the nucleation intensity, to negative ions is much higher than that to positive ions. The presence of a very large difference in the affinity of sulfuric acid between positive and negative ions suggests that nucleation of negative ions is likely favorable.

Anomalously large difference in dipole moment of isomers with nearly identical thermodynamic stability.

Sulfuric acid is a primary atmospheric nucleation precursor, with the ability to form stable aqueous hydrogen-bonded clusters/complexes. The electrical dipole moment of such clusters/complexes is important for ion-induced nucleation, largely controlled by dipole-charge interaction of airborne ions with vapor monomers and pre-existing clusters. Although experiments typically trace a single lowest energy conformer at low temperatures, the present study shows that the immediate vicinity (<1 kcal mol (-1)) of the global minima may be populated with a number of isomers of nearly identical spectral characteristics and drastically different dipole moments. The difference in the dipole moment of mono-, di-, and trihydrates of the sulfuric acid exceeds 1.3-1.5 Debyes ( approximately 50-60%), 1.4-2.6 Debyes ( approximately 50-90%), and 3.8-4.2 Debyes ( approximately 370-550%), respectively. Being driven by the temperature dependence of the Boltzmann distribution, the difference between the Boltzmann-Gibbs average dipole moment and the dipole moment of the most stable isomer increases with the ambient temperature, leading to large variations in the dipole-ion interaction strength, which may have important implications for the ion-mediated production of ultrafine aerosol particles associated with various climatic and health impacts.

Effect of ammonia on the gas-phase hydration of the common atmospheric ion HSO(4)(-).

Hydration directly affects the mobility, thermodynamic properties, lifetime and nucleation rates of atmospheric ions. In the present study, the role of ammonia on the formation of hydrogen bonded complexes of the common atmospheric hydrogensulfate (HSO(4) (-)) ion with water has been investigated using the Density Functional Theory (DFT). Our findings rule out the stabilizing effect of ammonia on the formation of negatively charged cluster hydrates and show clearly that the conventional (classical) treatment of ionic clusters as presumably more stable compared to neutrals may not be applicable to pre-nucleation clusters. These considerations lead us to conclude that not only quantitative but also qualitative assessment of the relative thermodynamic stability of atmospheric clusters requires a quantum-chemical treatment.

Quantum nature of the sign preference in ion-induced nucleation.

Observed first in Wilson's pioneering experiments in the cloud chamber, the sign preference has remained a mystery for more than a century. We investigate the sign preference using a quantum approach and show that this puzzling phenomenon is essentially quantum in nature. It is shown that the effect of the chemical identity of the core ion is controlled by the electronic structure of the core ion through the influence on the intermolecular bonding energies during the initial steps of cluster formation. Our results demonstrate the superiority of the quantum approach and indicate fundamental problems of conventional ion-induced nucleation theories, in which the electronic structure of the core ion is either ignored or not treated rigorously.

Simple correction to the classical theory of homogeneous nucleation.

Formation of the new disperse phase via homogeneous nucleation plays a fundamental role wherever the first-order phase transitions occur. Inconsistent temperature dependence of the nucleation rates and poor agreement of theoretical critical supersaturations with experimental data for a number of substances are fundamental problems of the classical nucleation theory (CNT). Here we show that these problems can be solved with a simple empirical correction to CNT. Despite its simplicity, the corrected CNT (CCNT) accurately predicts temperature dependences and absolute values of the critical supersaturations for both organic and inorganic substances with widely varying properties at different ambient conditions and it works surprisingly well in a wide size range down to few molecules. The difference in predictions of CCNT and other versions of the classical nucleation theory commonly used in analyzing experimental data is discussed. It has been found that CCNT consistently gives better agreement with experimental data than other versions of classical nucleation theory.