Validation requirements for chemical methods in quantitative analysis – horses for courses?

 Although the validation process necessary to ensure that an analytical method is fit for purpose is universal, the emphasis placed on different aspects of that process will vary according to the end use for which the analytical procedure is designed. It therefore becomes difficult to produce a standard method validation protocol which will be totally applicable to all analytical methods. It is probable that far more than 30% of the methods in routine laboratory use have not been validated to an appropriate level to suit the problem at hand. This situation needs to change and a practical assessment of the degree to which a method requires to be validated is the first step to a reliable and cost effective analytical industry. Received: 22 September 1997 · Accepted: 28 November 1997     

Analysis of meeting protocols by formalisation, simulation, and verification

Organizations depend on regular meetings to carry out their everyday tasks. When carried out successfully, meetings offer a common medium for participants to exchange ideas and make decisions. However, many meetings suffer from unfocused discussions or irrelevant dialogues. To study meetings in detail, we first formalize general properties of meetings and a generic meeting protocol to specify how roles in a meeting should interact to realize these properties. This generic protocol is used as a starting point to study real-life meetings. Next, an example meeting is simulated using the generic meeting protocol. The general properties are formally verified in the simulation trace. Next, these properties are also verified formally against empirical data of a real meeting in the same context. A comparison of the two traces reveals that a real meeting is more robust since when exceptions happen and the rules of the protocol are violated, these exceptions are handled effectively. Given this observation, a more refined protocol is specified that includes exception-handling strategies. Based on this refined protocol a meeting is simulated that closely resembles the real meeting. This protocol is then validated against another set of data from another real meeting. By iteratively adding exception handling rules, the protocol is enhanced to handle a variety of situations successfully.     

Verification of uncertainty budgets

The quality of analytical results is expressed by their uncertainty, as it is estimated on the basis of an uncertainty budget; little effort is, however, often spent on ascertaining the quality of the uncertainty budget. The uncertainty budget is based on circumstantial or historical data, and therefore it is essential that the applicability of the overall uncertainty budget to actual measurement results be verified on the basis of current experimental data. This should be carried out by replicate analysis of samples taken in accordance with the definition of the measurand, but representing the full range of matrices and concentrations for which the budget is assumed to be valid. In this way the assumptions made in the uncertainty budget can be experimentally verified, both as regards sources of variability that are assumed negligible, and dominant uncertainty components. Agreement between observed and expected variability is tested by means of the T-test, which follows a chi-square distribution with a number of degrees of freedom determined by the number of replicates. Significant deviations between predicted and observed variability may be caused by a variety of effects, and examples will be presented; both underestimation and overestimation may occur, each leading to correcting the influence of uncertainty components according to their influence on the variability of experimental results. Some uncertainty components can be verified only with a very small number of degrees of freedom, because their influence requires samples taken at long intervals, e.g., the acquisition of a new calibrant. It is therefore recommended to include verification of the uncertainty budget in the continuous QA/QC monitoring; this will eventually lead to a test also for such rarely occurring effects.     

A Sums-of-Squares extension of policy iterations

In order to address the imprecision often introduced by widening operators in static analysis, policy iteration based on min-computations amounts to considering the characterization of reachable value set of a program as an iterative computation of policies, starting from a post-fixpoint. Computing each policy and the associated invariant relies on a sequence of numerical optimizations. While the early research efforts relied on linear programming (LP) to address linear properties of linear programs, the current state of the art is still limited to the analysis of linear programs with at most quadratic invariants, relying on semidefinite programming (SDP) solvers to compute policies, and LP solvers to refine invariants.We propose here to extend the class of programs considered through the use of Sums-of-Squares (SOS) based optimization. Our approach enables the precise analysis of switched systems with polynomial updates and guards. The analysis presented has been implemented in Matlab and applied on existing programs coming from the system control literature, improving both the range of analyzable systems and the precision of previously handled ones.     

Upper error bounds on calculated outputs of interest for linear and nonlinear structural problems

This Note introduces new strict upper error bounds on outputs of interest for linear as well as time-dependent nonlinear structural problems calculated by the finite element method. Small-displacement problems without softening, such as (visco)plasticity problems, are included through the standard thermodynamics framework involving internal state variables. To cite this article: P. Ladevèze, C. R. Mecanique 334 (2006).     

基于数据挖掘对商业氧还原电催化剂Pt/C测试的综合分析

近几十年来,聚合物电解质膜燃料电池(PEMFC)因其在零排放汽车、固定式和便携式发电设备中的应用而得到迅速发展.燃料电池的阴极氧还原反应(ORR)和阳极氢氧化反应(HOR)常用的催化剂为Pt基催化剂,因此整个燃料电池系统的成本高昂.而ORR的反应速率比HOR慢得多,阴极上的Pt消耗量远高于阳极上.为了降低燃料电池Pt的...     

Change-of-bases abstractions for non-linear hybrid systems

We present abstraction techniques that transform a given non-linear dynamical system into a linear system, or more generally, an algebraic system described by polynomials of bounded degree, so that invariant properties of the resulting abstraction can be used to infer invariants for the original system. The abstraction techniques rely on a change-of-bases transformation that associates each state variable of the abstract system with a function involving the state variables of the original system. We present conditions under which a given change-of-bases transformation for a non-linear system can define an abstraction. Furthermore, the techniques developed here apply to continuous systems defined by Ordinary Differential Equations (ODEs), discrete systems defined by transition systems and hybrid systems that combine continuous as well as discrete subsystems.The techniques presented here allow us to discover, given a non-linear system, if a change-of-bases transformation involving degree-bounded polynomials yielding an algebraic abstraction exists. If so, our technique yields the resulting abstract system, as well. Our techniques enable the use of analysis techniques for linear systems to infer invariants for non-linear systems. We present preliminary evidence of the practical feasibility of our ideas using a prototype implementation.     

Study on verification device of screen spatial location parameters of sky screen target

For the original verification method of screen spatial location parameters of sky screen target is complex and low efficiency, the new verification device without disassembly the sky screen target is designed in this paper. The stroboscopic light sources including the LED, collimating lens, frosted glass and small aperture are designed, and the datum plane is precisely established. By setting the threshold method of oscilloscope, the translation stage moving distance relative to the datum plane are recorded, when the amplitude of the output signal of the sky screen target just reaches the preset threshold value. According to the formula, the screen spatial location parameters of sky screen target are achieved. Experimental results show that the calibration accuracy of screen surface space position parameters is better than ±1′, which is consistent with the theoretical error analysis. This verification device makes up for original verification deficiencies of disassembly sky screen target, saves test time, increases the verification efficiency of sky screen target, and has a broad range market demand.     

Repeated Richardson extrapolation applied to the two-dimensional Laplace equation using triangular and square grids

The focus of this work is to verify the efficiency of the Repeated Richardson Extrapolation (RRE) to reduce the discretization error in a triangular grid and to compare the result to the one obtained for a square grid for the two-dimensional Laplace equation. Two different geometries were employed: the first one, a unitary square domain, was discretized into a square or triangular grid; and the second, a half square triangle, was discretized into a triangular grid. The methodology employed used the following conditions: the finite volume method, uniform grids, second-order accurate approximations, several variables of interest, Dirichlet boundary conditions, grids with up to 16,777,216 nodes for the square domain and up to 2097,152 nodes for the half square triangle domain, multigrid method, double precision, up to eleven Richardson extrapolations for the first domain and up to ten Richardson extrapolations for the second domain. It was verified that (1) RRE is efficient in reducing the discretization error in a triangular grid, achieving an effective order of approximately 11 for all the variables of interest for the first geometry; (2) for the same number of nodes and with or without RRE, the discretization error is smaller in a square grid than in a triangular grid; and (3) the magnitude of the numerical error reduction depends on, among other factors, the variable of interest and the domain geometry.     

Computer Theorem Proving in Mathematics

We give an overview of issues surrounding computer-verified theorem proving in the standard pure-mathematical context. This includes the basic reasons why it should be interesting to pure mathematicians, some history, natural desiderata for a useful system, viewpoints on what kind of logic to use, a short explanation of how things work, an overview of different options for encoding sets, and perspectives on future developments.