Matrix effects in flow injection-inductively coupled plasma mass spectrometry

Matrix effects in now injection (FI) inductively coupled plasma mass spectrometry has been studied,and the results have been compared with those of continuous nebulization. The matrix element As and nu with higher ionization potential ( > 9eV) have enhancement effect on the analyte signal,and the heavier the analyte mass, the smaller the enhancement effects by Fl. The matrix elements Cu, In, Li, Na and Pb with lower ionization potential have suppression effect on the analyte signal. The heavier the matrix element mass, the more severe the suppression effects. The heavier the analyte mass, the smaller the suppression effects. The higher ionization potential of analyte, the more severe the suppression effects. Compared with continuous nebulization, the degree of suppression effect is smaller and the degree of the enhancement effect is larger by Fl.

关中盆地东部浅层地下水水化学与CFC年龄研究

Hydrochemistry, isotope and CFCs were used to determine groundwater transport in the eastern part of the Guanzhong Basin. In this paper, we systematically collected water samples and measured major ions, 2H-18O and CFCs in surface water and shallow groundwater. Groundwater in this region can be divided into three categories based on total dissolved solids (TDS): fresh water with TDS < 1g/L, brackish water with TDS between 1～3g/L, and saline water with TDS > 3g/L. Saline water is mainly located in the north of the Wei River, and saline groundwater is not in the south. Tributaries in the south of the Wei River and underlain groundwater had similar 2H-18O values, indicating a close hydraulic connection between them. Tributaries in the north of the Wei River characterized certain extent of evaporation, and 2H-18O values deviated to a differing extent between surface water and groundwater, indicating that surface water in the north bank of the Wei River has little hydraulic connection with underlain groundwater. The CFCs age of groundwater from the piedmont recharge area was young, and became older toward the Wei River valley. Vertically, the CFCs age of groundwater increased with well depth. The shallow groundwater is mainly composed of young water with ages < 60 years and old water with ages > 60 years. Young water is in a larger proportion. The NO3-N concentration positively correlates with the CFC-12 concentration in the groundwater, which indicates that young water is subjected to be contaminated. Keyword: Guanzhong Basin , shallow groundwater, isotope, CFC

流体地球化学：成因、流动和流体-岩石相互作用及塔里木盆地实例研究

Geofluid in sedimentary basins is related to petroleum generation, migration, accumulation and preservation, and is a topic of geological frontier. By integrating the multi-discipline methods of petroleum geochemistry, sedimentology, hydrogeology, petroleum geology and experimental geochemistry, the thesis has carried out experiments of microcline dissolution in solutions with organic acids, crude oil, brines with high total dissolved solids (TDS), and has dealt with Al distribution between the crude oil and the brines after the experiments. Cases for study includes Central Tarim, Hetianhe Gas Field and Kucha forland basin with data containing fluid chemistry and isotopic compositions, thin sections of sandstones and carbonates, homogenization temperatures and salinities of fluid inclusions, isotopic compositions of bulk rock and autigenic minerals. The aims are to elucidate fluid origin and flow in the three areas, effect of hydrocarbon emplacement on diagenesis, and to show occurrence of microbe-mediated, and thermochemical sulfate reduction in the Tarim Basin. Microcline dissolution experiments show that after 100 hour, part of the dissolved Al distributes in the crude oil, and the Al concentrations in the crude oil rise when organic acids are added. The result can be used to explain that most oilfield waters in the Tarim Basin are characterized by less than 3mg/L Al. Crude oil added to the solutions can enhance microcline dissolution, which is also observed in the case - Silurian sandstones with early crude oil emplacement in the Central Tarim. Al and Si have higher concentrations in the experiments of oxalic acid than of acetic acid under the same pH conditions, suggesting that there exist Al-oxalate and Si-oxalate complexes. Presence of acetate can enhance the activity of Ca and Al, but Al concentrations have not been increased significantly due to formation of small Al-acetate complex during the experiments. Relationships between δD and δ~(18)O in conjunction with chemistry of oilfield waters show that the waters are evaporated connate waters, which subsequently mixed with meteoric water, and were influenced by water-rock interactions such as salt dissolution, dolomitization of calcite, albitization of feldspar. In the Hetianhe Gas Field where salt dissolution took place, δD and δ~(18)O values can be used to trace nicely meteoric water recharge area and flow direction, but TDS can not. Part of the waters have high TDS but very light δD and δ~(18)O. When combined with paleo-topography, or fluid potentials, meteoric water is suggested to flow eastward in the Hetianhe Gas Field, which is the same with the Central Tarim. Whist in the Kuche forland basin, meteoric water may have permeated Cambrian-Ordovician strata. Relationship between ~(87)Sr/~(86)Sr and 1/Sr can be used to indicate migration and mixing of brines from carbonate strata (low ~(87)Sr/~(86)Sr ratio but high Sr content), clastic strata (high ~(87)Sr/~(86)Sr ratio but low Sr content) and crystalline basement (high ~(87)Sr/~(86)Sr ratio and heavy δ~(18)O value). Using this approach, it can be found that ~(87)Sr-depleted brine from Ordovician carbonates have migrated up to and mixed with ~(87)Sr-enriched waters from Silurian and Carboniferous sandstones, and that Silurian brines have mixed with meteoric water. In the Kuche forland basin, brines from the Cambrian and Ordovician carbonates have higher ~(87)Sr/~(86)Sr ratios than those from the overlying sandstones, when combined with chemistry, δ~(15)N and ~3He/~4He ratios of the coexisting natural gases, suggesting that the brines were derived from the basement. There exists some debate on the effect of hydrocarbon emplacement on mineral diagenesis. Case-study from Silurian sandstones in the Central Tarim show that quartz has kept overgrowing secondarily when oil saturation was decreased by meteoric water flushing subsequently to hydrocarbon emplacement. Silicon precipitates on the water-wet quartz surface, leading to decreased Si concentration close to the surface. A Si grads can result in Si diffusion, which supplies Si for quartz overgrowth. Hydrocarbon oxidation-sulfate reduction is an important type of organic-inorganic interaction. Not only can it make secondary alteration of hydrocarbons, but generate H_2S and CO_2 gases which can improve reservoir property. Thermochemical sulfate reduction took place at the temperatures more than 125 ℃ to 140 ℃ in the Cambrian-Ordovician carbonates, the products - H_2S and CO_2 gases migrated up to the Silurian, and precipitated as pyrite and calcite, respectively. The pyrite has an average δ~(34)S value close to those of Ordovician seawater and anhydrite, and calcite has δ~(13)C value as low as -21.5‰. In the Hetianhe Gas Field, sulfate reduction bacteria carried by meteoric water flowing eastward may have preferentially depleted ~(12)C of light hydrocarbon gases, and results in heavier δ~(13)C values of the residual hydrocarbon gases and higher molar CO_2 in the natural gases in the west than in the east. Coexisting pyrite has δ~(34)S values as low as -24.9‰.

Dislocation theory of the fracture criterion for anisotropic solids

A dislocation theory of fracture criterion for the mixed dislocation emission and cleavage process in an anisotropic solid is developed in this paper. The complicated cases involving mixed-mode loading are considered here. The explicit formula for dislocations interaction with a semi-infinite crack is obtained. The governing equation for the critical condition of crack cleavage in an anisotropic solid after a number dislocation emissions is established. The effects of elastic anisotropy, crack geometry and load phase angle on the critical energy release rate and the total number of the emitted dislocations at the onset of cleavage are analysed in detail. The analyses revealed that the critical energy release rates can increase to one or two magnitudes larger than the surface energy because of the dislocation emission. It is also found elastic anisotropy and crystal orientation have significant effects on the critical energy release rates. The anisotropic values can be several times the isotropic value in one crack orientation. The values may be as much as 40% less than the isotropic value in another crack orientation and another anisotropy parameter. Then the theory is applied to a fee single crystal. An edge dislocation can emit from the crack tip along the most highly shear stressed slip plane. Crack cleavage can occur along the most highly stressed slip plane after a number of dislocation emissions. Calculation is carried out step by step. Each step we should judge by which slip system is the most highly shear stressed slip system and which slip system has the largest energy release rate. The calculation clearly shows that the crack orientation and the load phase angle have significant effects on the crystal brittle-ductile behaviours.

General Relationship Between Contact Stiffness, Contact Depth, and Mechanical Properties for Indentation in Linear Viscoelastic Solids Using Axisymmetric Indenters of Arbitrary Profiles

We derive a relationship between the initial unloading slope, contact depth, and the instantaneous relaxation modulus for indentation in linear viscoelastic solids by a rigid indenter with an arbitrary axisymmetric smooth profile. Although the same expression is well known for indentation in elastic and in elastic-plastic solids, we show that it is also true for indentation in linear viscoelastic solids, provided that the unloading rate is sufficiently fast. Furthermore, the same expression holds true for both fast loading and unloading. These results should provide a sound basis for using the relationship for determining properties of viscoelastic solids using indentation techniques.

Scaling relationships in conical indentation of elastic perfectly plastic solids

Using dimensional analysis and finite element calculations we derive several scaling relationships for conical indentation into elastic-perfectly plastic solids. These scaling relationships provide new insights into the shape of indentation curves and form the basis for understanding indentation measurements, including nano- and micro-indentation techniques. They are also helpful as a guide to numerical and finite element calculations of conical indentation problems. Finally, the scaling relationships are used to reveal the general relationships between hardness, contact area, initial unloading slope, and mechanical properties of solids.

Strain gradient theory with couple stress for crystalline solids

A new phenomenological strain gradient theory for crystalline solid is proposed. It fits within the framework of general couple stress theory and involves a single material length scale Ics. In the present theory three rotational degrees of freedom omega (i) are introduced, which denote part of the material angular displacement theta (i) and are induced accompanying the plastic deformation. omega (i) has no direct dependence upon u(i) while theta = (1 /2) curl u. The strain energy density omega is assumed to consist of two parts: one is a function of the strain tensor epsilon (ij) and the curvature tensor chi (ij), where chi (ij) = omega (i,j); the other is a function of the relative rotation tensor alpha (ij). alpha (ij) = e(ijk) (omega (k) - theta (k)) plays the role of elastic rotation reason The anti-symmetric part of Cauchy stress tau (ij) is only the function of alpha (ij) and alpha (ij) has no effect on the symmetric part of Cauchy stress sigma (ij) and the couple stress m(ij). A minimum potential principle is developed for the strain gradient deformation theory. In the limit of vanishing l(cs), it reduces to the conventional counterparts: J(2) deformation theory. Equilibrium equations, constitutive relations and boundary conditions are given in detail. For simplicity, the elastic relation between the anti-symmetric part of Cauchy stress tau (ij), and alpha (ij) is established and only one elastic constant exists between the two tensors. Combining the same hardening law as that used in previously by other groups, the present theory is used to investigate two typical examples, i.e., thin metallic wire torsion and ultra-thin metallic beam bend, the analytical results agree well with the experiment results. While considering the, stretching gradient, a new hardening law is presented and used to analyze the two typical problems. The flow theory version of the present theory is also given.

Damage evolution, localization and failure of solids subjected to impact loading

In order to reveal the underlying mesoscopic mechanism governing the experimentally observed failure in solids subjected to impact loading, this paper presents a model of statistical microdamage evolution to macroscopic failure, in particular to spallation. Based on statistical microdamage mechanics and experimental measurement of nucleation and growth of microcracks in an Al alloy subjected to plate impact loading, the evolution law of damage and the dynamical function of damage are obtained. Then, a lower bound to damage localization can be derived. It is found that the damage evolution beyond the threshold of damage localization is extremely fast. So, damage localization can serve as a precursor to failure. This is supported by experimental observations. On the other hand, the prediction of failure becomes more accurate, when the dynamic function of damage is fitted with longer experimental observations. We also looked at the failure in creep with the same idea. Still, damage localization is a nice precursor to failure in creep rupture.

Relationship Between Contact Stiffness, Contact Depth, and Mechanical Properties for Indentation in Linear Viscoelastic Solids Using Axisymmetric Indenters

We derive a relationship between the initial unloading slope, contact depth, and the instantaneous relaxation modulus for indentation in linear viscoelastic solids by a rigid indenter with an arbitrary axisymmetric smooth profile. Although the same expres

Scaling approach to conical indentation in elastic-plastic solids with work hardening

We derive, using dimensional analysis and finite element calculations, several scaling relationships for conical indentation in elastic-plastic solids with work hardening. Using these scaling relationships, we examine the relationships between hardness, contact area, initial unloading slope, and mechanical properties of solids. The scaling relationships also provide new insights into the shape of indentation curves and form the basis for understanding indentation measurements, including nano- and micro-indentation techniques. They may also be helpful as a guide to numerical and finite element calculations of indentation problems.

Anisotropic thermopiezoelectric solids with an elliptic inclusion or a hole under uniform heat flow

The two-dimensional problem of a thermopiezoelectric material containing an elliptic inclusion or a hole subjected to a remote uniform heat flow is studied. Based on the extended Lekhnitskii formulation for thermopiezoelectricity, conformal mapping and Laurent series expansion, the explicit and closed-form solutions are obtained both inside and outside the inclusion (or hole). For a hole problem, the exact electric boundary conditions on the hole surface are used. The results show that the electroelastic fields inside the inclusion or the electric field inside the hole are linear functions of the coordinates. When the elliptic hole degenerates into a slit crack, the electroelastic fields and the intensity factors are obtained. The effect of the heat how direction and the dielectric constant of air inside the crack on the thermal electroelastic fields are discussed. Comparison is made with two special cases of which the closed solutions exist and it is shown that our results are valid.

Scaling relationships in indentation of power-law creep solids using self-similar indenters

We use dimensional analysis to derive scaling relationships for self-similar indenters indenting solids that exhibit power-law creep. We identify the parameter that represents the indentation strain rate. The scaling relationships are applied to several types of indentation creep experiment with constant displacement rate, constant loading rate or constant ratio of loading rate over load. The predictions compare favourably with experimental observations reported in the literature. Finally, a connection is found between creep and 'indentation-size effect' (i.e. changing hardness with indentation depth or load).

Effective elastic moduli of two-dimensional solids with multiple cracks

An accurate method which directly accounts for the interactions between different microcracks is used for analyzing the elastic problem of multiple cracks solids. The effective elastic moduli for randomly oriented cracks and parallel cracks are evaluated for the representative volume element (RVE) with microcracks in infinite media. The numerical results are compared with those from various micromechanics models and experimental data. These results show that the present method is simple and provides a direct and efficient approach to dealing with elastic solids containing multiple cracks.

Nonlinear Analysis of Oscillatory Indentation in Elastic and Viscoelastic Solids

Determining the mechanical properties at micro- and nanometer length scales using nanoindentation or atomic force microscopy is important to many areas of science and engineering. Here we establish equations for obtaining storage and loss modulus from oscillatory indentations by performing a nonlinear analysis of conical and spherical indentation in elastic and viscoelastic solids. We show that, when the conical indenter is driven by a sinusoidal force, the square of displacement is a sinusoidal function of time, not the displacement itself, which is commonly assumed. Similar conclusions hold for spherical indentations. Well-known difficulties associated with measuring contact area and correcting thermal drift may be circumvented using the newly derived equations. These results may help improve methods of using oscillatory indentation for determining elastic and viscoelastic properties of solids.

Interactions of Penny-Shaped Cracks in Three-Dimensional Solids

The interaction of arbitrarily distributed penny-shaped cracks in three-dimensional solids is analyzed in this paper. Using oblate spheroidal coordinates and displacement functions, an analytic method is developed in which the opening and the sliding displacements on each crack surface are taken as the basic unknown functions. The basic unknown functions can be expanded in series of Legendre polynomials with unknown coefficients. Based on superposition technique, a set of governing equations for the unknown coefficients are formulated from the traction free conditions on each crack surface. The boundary collocation procedure and the average method for crack-surface tractions are used for solving the governing equations. The solution can be obtained for quite closely located cracks. Numerical examples are given for several crack problems. By comparing the present results with other existing results, one can conclude that the present method provides a direct and efficient approach to deal with three-dimensional solids containing multiple cracks.