Maider Vidal

Image analysis for maintenance of coating quality in nickel electroplating baths--real time control.

The aim of this paper is to show how it is possible to extract analytical information from images acquired with a flatbed scanner and make use of this information for real time control of a nickel plating process. Digital images of plated steel sheets in a nickel bath are used to follow the process under degradation of specific additives. Dedicated software has been developed for making the obtained results accessible to process operators. This includes obtaining the RGB image, to select the red channel data exclusively, to calculate the histogram of the red channel data and to calculate the mean colour value (MCV) and the standard deviation of the red channel data. MCV is then used by the software to determine the concentration of the additives Supreme Plus Brightner (SPB) and SA-1 (for confidentiality reasons, the chemical contents cannot be further detailed) present in the bath (these two additives degrade and their concentration changes during the process). Finally, the software informs the operator when the bath is generating unsuitable quality plating and suggests the amount of SPB and SA-1 to be added in order to recover the original plating quality.

Flatbed scanners as a source of imaging. Brightness assessment and additives determination in a nickel electroplating bath

Desktop flatbed scanners are very well-known devices that can provide digitized information of flat surfaces. They are practically present in most laboratories as a part of the computer support. Several quality levels can be found in the market, but all of them can be considered as tools with a high performance and low cost. The present paper shows how the information obtained with a scanner, from a flat surface, can be used with fine results for exploratory and quantitative purposes through image analysis. It provides cheap analytical measurements for assessment of quality parameters of coated metallic surfaces and monitoring of electrochemical coating bath lives. The samples used were steel sheets nickel-plated in an electrodeposition bath. The quality of the final deposit depends on the bath conditions and, especially, on the concentration of the additives in the bath. Some additives become degraded with the bath life and so is the quality of the plate finish. Analysis of the scanner images can be used to follow the evolution of the metal deposit and the concentration of additives in the bath. Principal component analysis (PCA) is applied to find significant differences in the coating of sheets, to find directions of maximum variability and to identify odd samples. The results found are favorably compared with those obtained by means of specular reflectance (SR), which is here used as a reference technique. Also the concentration of additives SPB and SA-1 along a nickel bath life can be followed using image data handled with algorithms such as partial least squares (PLS) regression and support vector regression (SVR). The quantitative results obtained with these and other algorithms are compared. All this opens new qualitative and quantitative possibilities to flatbed scanners.

Quantitative determination of additives in a commercial electroplating nickel bath by spectrophotometry and multivariate analysis

An electroplating nickel bath is usually composed of a number of organic additives to improve the plating process as well as to preserve its durability. Supreme Plus Brightener (SPB) and A-5(2X), used in a commercial electroplating nickel bath show highly overlapped UV-Vis spectra. These two additives are the only ones that present absorbance in the UV-Vis wavelength range. Therefore, a mixture of them can be resolved using multivariate calibration methods of UV-Vis measurements. In this work, Partial Least Squares (PLS) regression and Classical Least Squares (CLS) have been used to quantify both additives during the whole duration of an electroplating nickel bath. It was found that PLS regression provided the best results. To avoid negative influence of baseline drifts, first derivative spectra were used. Between 0.14 and 1.40 mL of the commercial product SPB per L of nickel bath can be determined with mean errors of about 6%. Between 4 and 24 mL of the commercial product A-5(2X) per L of nickel bath can be determined with mean errors of about 8%. The limits of detection (LOD) found for SPB and A-5(2X) were 0.11 mL L−1 and 3 mL L−1 respectively. The calibration models proved to be valid for at least eight months, including a change of spectrophotometer. The SPB concentration decays along the bath life according to a first order rate law, but A-5(2X) remains unchanged. Independent brightness measurements showed that it was intimately related to the SPB concentration, in such a way that any of them can be deduced from the other one. This is of prime importance to keep the bath conditions under control.

Fluorescence of the Flavin group in choline oxidase. Insights and analytical applications for the determination of choline and betaine aldehyde

Choline oxidase (ChOx) is a flavoenzyme catalysing the oxidation of choline (Ch) to betaine aldehyde (BA) and glycine betaine (GB). In this paper a fundamental study of the intrinsic fluorescence properties of ChOx due to Flavin Adenine Dinucleotide (FAD) is presented and some analytical applications are studied in detail. Firstly, an unusual alteration in the excitation spectra, in comparison with the absorption spectra, has been observed as a function of the pH. This is ascribed to a change of polarity in the excited state. Secondly, the evolution of the fluorescence spectra during the reaction seems to indicate that the reaction takes place in two consecutive, but partially overlapped, steps and each of them follows a different mechanism. Thirdly, the chemical system can be used to determine the Ch concentration in the range from 5×10(-6)M to 5×10(-5)M (univariate and multivariate calibration) in the presence of BA as interference, and the joint Ch+BA concentration in the range 5×10(-6)-5×10(-4)M (multivariate calibration) with mean errors under 10%; a semiquantitative determination of the BA concentration can be deduced by difference. Finally, Ch has been successfully determined in an infant milk sample.

SIMULTANEOUS DETERMINATION OF COLOR ADDITIVES TARTRAZINE AND ALLURA RED IN FOOD PRODUCTS BY DIGITAL IMAGE ANALYSIS

A method based on digital image is described to quantify tartrazine (E102), yellow, and allura red (E129) colorants in food samples. HPLC is the habitual method of reference used for colorant separation and quantification, but it is expensive, time-consuming and it uses solvents, sometimes toxic. By a flatbed scanner, which can be found in most laboratories, images of mixtures of colorants can be taken in microtitration plates. Only 400 µL of sample are necessary and up to 92 samples can be measured together in the same image acquisition. A simple-to-obtain color fingerprint is obtained by converting the original RGB image into other color spaces and individual PLS models are built for each colorant. In this study, root mean square errors of 3.3 and 3.0 for tartrazine and 1.1 and 1.2 for allura red have been obtained for cross-validation and external validation respectively. Results for repeatability and reproducibility are under 12%. These results are slightly worse but comparable to the ones obtained by HPLC. The applicability of both methodologies to real food samples has proven to give the same result, even in the presence of a high concentration of an interfering species, provided that this interference is included in the image analysis calibration model. Considering the colorant content found in most samples this should not be a problem though and, in consequence, the method could be extended to different food products. Values of LODs of 1.8 mg L-1 and 0.6 mg L-1 for tartrazine and allura red have been obtained by image analysis.

Uncertainty in CCD detectors with and without cooling devices when used for molecular fluorescence measurements

The performance of CCD detectors for fluorescence measurements is evaluated through uncertainty studies, mainly as a function of both the signal intensity and the detector temperature. Two CCD detectors, one furnished with a cooling device and the other without a cooling device, were used, and the results were compared. The dependence of uncertainty on the instrumental signal was evaluated simultaneously for both detectors at temperatures ranging between −23 and 23 °C. The tested detectors required temperature increments between 30 and 50 °C to double dark noise (the random part of dark current). The detector temperature affects uncertainty, but this is basically related to dark noise in fluorescence measurements. The consequence of this is that the temperature does not significantly affect the signal-to-noise ratio (S/N); thus, the presence of a cooling device does not significantly improvement the performance, and the limit of detection (LOD) does not depend strongly on the detector temperature. The quality of the two-dimensional array does affect uncertainty, the value of S/N, and the LOD. A good CCD detector can perform at a level similar to a spectrofluorometer furnished with a photomultiplier tube. Laboratory data are given to show how the three components of uncertainty (dark noise, shot noise and flicker noise) behave at different signal intensities and temperatures. Dark noise is the most important factor, shot noise has relevance only at high signal values, and flicker noise is practically irrelevant. The classical model of the dependence of S/N on the fluorescence signal is applied, and the uncertainty constants that govern the performance of the apparatus used are given.

Determination of food colorants in a wide variety of food matrices by microemulsion electrokinetic capillary chromatography. Considerations on the found concentrations and regulated consumption limits

Color additives are used widely by the food industry to confer a desirable appearance. Some of the most used colorants (Tartrazine (E102), Sunset Yellow (E110), Red Allure (E129) and Blue Brilliant (E133)) were determined in this study using microemulsion electrokinetic capillary chromatography (MEEKC). Regression coefficients were greater than 0.9981; intra- and inter-day precisions, in terms of percentage RSD, were less than 7.01% and 8.55%, respectively; recoveries were between 90 and 100% in most cases. LODs and LOQs ranged from 0.24 to 1.21 mg L-1 and from 0.80 to 4.03 mg L-1, respectively. Moreover, MEEKC consumed less solvent than HPLC, making the analysis more environmentally friendly. The proposed method is suitable for the determination of colorants in a wide variety of foods. Results showed that consumers should be aware of colorants to avoid consumption exceeding recommended amounts.

Development and validation of a method for the determination of regulated fragrance allergens by High-Performance Liquid Chromatography and Parallel Factor Analysis 2

This work presents the development and validation of a multivariate method for quantitation of 6 potentially allergenic substances (PAS) related to fragrances by ultrasound-assisted emulsification microextraction coupled with HPLC-DAD and PARAFAC2 in the presence of other 18 PAS. The objective is the extension of a previously proposed univariate method to be able to determine the 24 PAS currently considered as allergens. The suitability of the multivariate approach for the qualitative and quantitative analysis of the analytes is discussed through datasets of increasing complexity, comprising the assessment and validation of the method performance. PARAFAC2 showed to adequately model the data facing up different instrumental and chemical issues, such as co-elution profiles, overlapping spectra, unknown interfering compounds, retention time shifts and baseline drifts. Satisfactory quality parameters of the model performance were obtained (R2≥0.94), as well as meaningful chromatographic and spectral profiles (r≥0.97). Moreover, low errors of prediction in external validation standards (below 15% in most cases) as well as acceptable quantification errors in real spiked samples (recoveries from 82 to 119%) confirmed the suitability of PARAFAC2 for resolution and quantification of the PAS. The combination of the previously proposed univariate approach, for the well-resolved peaks, with the developed multivariate method allows the determination of the 24 regulated PAS.

Process analytical chemistry in a nickel electroplating bath. Automated sequential injection for additive determination

Most of the useful parameters of a nickel electroplating bath can be monitored along the bath life. Process analytical chemistry (PAC) has been applied to follow parameters such as temperature, pH, chloride or nickel concentration. The monitoring of additives has special relevance because the final quality of finish depends on them. Two out of the four additives used in the commercial nickel bath used in this paper show UV absorption (A-5(2X) and SPB) and a sequential injection (SI) method has been developed to conduct and automatically dilute aliquots from the bath to a diode-array detector where UV spectra are acquired. Because the UV bands of the absorbing additives overlap, partial least squares (PLS) regression is used as a calibration method to resolve the mixture. A commercial software program has been used for the automated data acquisition. The program configuration and the SI manifold are given. The results obtained for additives are compared with those obtained from a manual method that is used as a reference. Mean random errors under 8% were always obtained. The limits of detection (LOD) found for A-5(2X) and SPB were 0.2 mL L−1 and 0.09 mL L−1 respectively. The SI methodology was applied with excellent results along a whole bath life and can be used to maintain the proper coating conditions.