Extension of the Coherent Gradient Sensor (CGS) to the Combined Measurement of In-Plane and Out-of-Plane Displacement Field Gradients

The Coherent Gradient Sensor (CGS) is extended to the optical differentiation of specular, diffracted wave fronts leading to the combined measurement of in- and out-of-plane displacement field gradients. A derivation of the underlying optical interference principles is presented along with an analysis of the effective instrument sensitivity. In order to demonstrate the capabilities of the technique, experimental measurements of crack-tip deformation fields were conducted under various loading conditions corresponding to mode-I, mode-II, and mixed mode near-tip crack fields. The experimental procedures and results of these tests are presented as validation of the technique.     

Optimization of a high-performance liquid chromatography method for the analysis of complex polyphenol mixtures and application for sainfoin extracts (Onobrychis viciifolia)

A pentafluorophenylpropyl (PFP) stationary phase was tested for the simultaneous determination of several classes of phenolic compounds. The chromatographic results were compared with those obtained by using a bifunctional phase constituted of octadecyl and phenylpropyl bonded silica and three conventional C18 columns. The elution gradient was optimized with 5% formic acid and sodium acetate in combination with acetic acid as additives and methanol as solvents. For these evaluations, a complex phenolic extract of Onobrychis viciifolia (sainfoin) and test mixtures containing 54 standard substances including 2 simple phenolic compounds, 1 amino acid, 4 hydroxybenzoic acids (HBA), 6 hydroxycinnamic acids (HCA), 3 flavan-3-ols, 9 anthocyanins, 2 dihydroflavonols, 1 chalcone, 4 flavones, 1 isoflavone and 21 flavonols have been assayed. The perfluorinated column showed good resolution for the studied phenolic compounds which have the following elution order: HBA, HCA, flavan-3-ols, anthocyanins, dihydroflavonols, flavones, flavonols and isoflavones. Compared with other columns, it provides longer elution ranges for HBA, HCA and flavan-3-ols and increased retention times for all compound classes except anthocyanins which were similarly retained on a C18 column. Its selectivity is different from C18 and bifunctional phases. A high-performance liquid chromatography (HPLC) method with diode array detection (DAD) and post-column derivatization with p-dimethyl-aminocinnamic aldehyde (DMACA) has been validated for the analysis of individual phenolic compounds from a sainfoin plant extract (O. viciifolia).     

Selection of suitable operating conditions to minimize the gradient equilibration time in the separation of drugs by Ultra-High-Pressure Liquid Chromatography with volatile (mass spectrometry-compatible) buffers

Reversed phase gradient elution is the method of choice for pharmaceuticals analysis since it allows reducing the analysis time while improving both the quality of the separation and the detection limits. The current trends are towards faster separations which can be achieved thanks to equipments withstanding ultra-high pressures and/or high temperatures. Under such conditions, gradient separations can be carried out within a few minutes or even a few tens of seconds. A long equilibration time in addition to the gradient time can be therefore very detrimental. In this work, we investigated the extent to which the gradient equilibration time can be reduced and which parameters mainly affect the retention variability of ionizable compounds when using volatile buffers. We first found out an excellent repeatability between run-to-run experiments whatever the equilibration time and the operating conditions. We then pointed out the key operating parameters which allow achieving reproducible runs when varying the equilibration time between runs. With a view of reducing the equilibration time, the effects of various conditions were examined. The latter include the type of additive for mobile phase pH adjustment, the initial eluent composition, the type of stationary phase, the temperature and the flow-rate. Although much remains to be understood about the equilibration process, our study allows making progress in the knowledge of this phenomenon. Based on the present results, a beneficial effect of both temperature and flow-rate was highlighted and operating conditions leading to faster column equilibration are suggested.     

Evaluation of 1.0 mm i.d. column performances on ultra high pressure liquid chromatography instrumentation

The present study focuses on the evaluation of 1.0 mm i.d. (internal diameter) columns on a commercial Ultra-High Pressure system. These systems have been developed specifically to operate columns with small volumes, typically 2.1 mm i.d., by reducing extra-column volume dispersion. The use of columns with smaller i.d. results in a reduced solvent consumption and required sample volume. The evaluation of the columns was carried out with samples containing neutral and pharmaceutical compounds. In isocratic mode, the extra-column volume produced additional band broadening leading to poor performances compared to equivalent 2.1 mm i.d. columns. By increasing the length of the column, the influence of the extra-column bandspreading could be reduced and 75,000 plates were obtained when four columns were coupled. In gradient mode, the effect of the extra-column contribution on efficiency was limited and about 80% of the performance of the 2.1 mm i.d. columns was obtained. Optimum conditions in gradient mode were further investigated by changing flow rate, gradient time and column length. A different approach of the calculation of peak capacity was also considered for the comparison of the influence of these different parameters.     

Arsenic speciation by gradient anion exchange narrow bore ion chromatography and high resolution inductively coupled plasma mass spectrometry detection

Based on gradient anion exchange chromatography (AEC), a new strategy in As-speciation was evaluated. A narrow bore chromatographic system with lower flow rates (≤300 μL) well suitable for the low flow requirements of higher efficiency nebulizers was splitless coupled to a high resolution sector field ICP MS. The AEC system takes full advantage of the detector sensitivity allowing more diluted samples (50–100 times) to be injected, delivering substantially less sample matrix to the column and a lower eluent load to the plasma. The unique plasma compatibility of the NH₄NO₃-eluent salt used in this study enabled high linear salt ramps in gradient applications, highly reproducible retention times (±1%) and detection limits in the low ng/L range. The separation conditions were applied on two different polymeric anion-exchangers: a low capacity, weakly hydrophobic material (AS11, Dionex) and a more frequently used higher capacity, higher hydrophobic material (AS7, Dionex). On both columns, As-species (As(III/V), MMA, DMA, AsB) and Cl⁻ were separated in less than nine minutes and co-elution was circumvented by adapting the separation pH to the optimal column selectivity. The key-advantage of the NH₄NO₃-eluent is that it can adopt any separation pH without compromising the eluent strength which is not possible with all other eluents used so far. The influences of chloride and methanol were investigated and found not to affect the chromatographic performance. Column deposits caused strong reversible As(v) adsorption which reduced As(v) to As(III). A corresponding phosphate excess in the injected sample eliminated the adsorption and prevented artefacts in As(v)/As(III) ratios. The method applied to ground water samples provided robust separations and is compatible with any sample preservation procedure.     

Preparation of a novel Ni/Co-based alloy gradient coating on surface of the crystallizer copper alloy by laser

A high wear-resistant gradient coating made of Ni/Co-based alloys on the surface of a Cu alloy substrate was synthesized using a YAG laser induced in situ reaction method. The coating consists of three layers: the first is a Ni-based alloy layer, the second and third are Co-based alloy layers. The microhardness increases gradually from 98 HV in the Cu alloy substrate to the highest level of 876 HV in the third layer. The main phase of the Co-based alloy layer is CoCr₂(Ni,O)₄, coexisting with the Fe₁₃Mo₂B₅, Cr(Co(Mo, and FeCr_0.29Ni_0.16C_0.06 phases. Wear tests indicate that the gradient coating has good bond strength and wear properties with a wear coefficient of 0.31 (0.50 for the Cu alloy substrate). Also, the wear loss of the coating is only 0.01 g after it has been abraded for 60 min, which is only one fifth of that of the Cu alloy of the crystallizer. Wear tests of the gradient coating reveal good adhesive friction and wear properties when sliding against steel under dry conditions. This novel technique may have good application to make an advanced coating on the surface of the Cu alloy crystallizer in a continuous casting process.     

On Liouville type theorems for fully nonlinear elliptic equations with gradient term

In this paper, we prove a Hadamard property and Liouville type theorems for viscosity solutions of fully nonlinear elliptic partial differential equations with a gradient term, both in the whole space and in an exterior domain.     

高分子梯度溶液吸声机理的研究

制备了高分子均匀溶液和梯度溶液,并在声管中测试其声衰减性能.实验结果表明,高分子梯度溶液的声衰减效果明显优于(即大于)相应的均匀溶液的声衰减.根据连续分层介质中声波传播理论建立了计算高分子梯度溶液声衰减的数学模型.计算结果与实验结果一致.由实验和理论分析结果得出了高分子梯度溶液的梯度吸声机理,即多次反射、多次吸收,最终将声能转化为热能.     

Gradient methods for multiple state optimal design problems

We optimise a distribution of two isotropic materials α I and β I (α < β) occupying the given body in R ^d . The optimality is described by an integral functional (cost) depending on temperatures u ₁, . . . , u _m of the body obtained for different source terms f ₁, . . . ,f _m with homogeneous Dirichlet boundary conditions. The relaxation of this optimal design problem with multiple state equations is needed, introducing the notion of composite materials as fine mixtures of different phases, mathematically described by the homogenisation theory. The necessary conditions of optimality are derived via the Gateaux derivative of the cost functional. Unfortunately, there could exist points in which necessary conditions of optimality do not give any information on the optimal design. In the case m < d we show that there exists an optimal design which is a rank-m sequential laminate with matrix material α I almost everywhere on Ω. Contrary to the optimality criteria method, which is commonly used for the numerical solution of optimal design problems (although it does not rely on a firm theory of convergence), this result enables us to effectively use classical gradient methods for minimising the cost functional.      

Convexity estimates for nonlinear elliptic equations and application to free boundary problems

We prove the convexity of the set which is delimited by the free boundary corresponding to a quasi-linear elliptic equation in a 2-dimensional convex domain. The method relies on the study of the curvature of the level lines at the points which realize the maximum of the normal derivative at a given level, for analytic solutions of fully nonlinear elliptic equations. The method also provides an estimate of the gradient in terms of the minimum of the (signed) curvature of the boundary of the domain, which is not necessarily assumed to be convex.