EP1932953B1 - Procédé galvanique avec analyse du bain electrolytique par extraction en phase solide - Google Patents
Procédé galvanique avec analyse du bain electrolytique par extraction en phase solide Download PDFInfo
- Publication number
- EP1932953B1 EP1932953B1 EP06025569A EP06025569A EP1932953B1 EP 1932953 B1 EP1932953 B1 EP 1932953B1 EP 06025569 A EP06025569 A EP 06025569A EP 06025569 A EP06025569 A EP 06025569A EP 1932953 B1 EP1932953 B1 EP 1932953B1
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- European Patent Office
- Prior art keywords
- column
- components
- eluent
- sample
- carried out
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
- C25D21/14—Controlled addition of electrolyte components
Definitions
- the present invention relates to a method for the electrodeposition of a metal layer from an electrolyte bath, wherein the concentration of at least two components of the electrolyte bath is monitored by means of a column for solid-phase extraction.
- the galvanic deposition of metal layers from electrolyte baths is widely used industrially.
- the electrolyte bath in addition to a compound of the metal to be deposited or of the metals to be deposited, the electrolyte bath generally contains further components which are necessary for carrying out the deposition process and for improving the quality of the deposited metal layer.
- These substances are organic compounds. Examples of such components are grain refiners, wetting agents, brighteners, complexing agents, inhibitors. These components are generally more or less rapidly consumed, destroyed or removed from the bath by carry-out when performing the deposition process. The concentration of components therefore decreases more or less rapidly over time.
- the monitoring of the concentration of the component (s) of an electrolyte bath requires the determination of the concentration of the component (s) in the electrolyte bath at regular time intervals. So far, this is often done in such a way that the electrolyte bath individual samples are removed manually and these are optionally subjected to a sample enrichment and purification of a chemical and / or physical analysis. Here, the individual analysis steps of the separation of the additives, purification and concentration determination are carried out separately. In addition to the increased expenditure of time and the resulting additional costs, the result is available only considerably delayed for a valuation. The goal of ensuring increased process safety and enabling rapid intervention if concentrations or concentration ratios change or degradation products of the additives accumulate in the electrolyte is very limited, if any, achievable.
- Solid Phase Extraction is the most widely used method for sample enrichment and purification, ie, sample preparation method, for modern liquid chromatography. It is used in particular for the analysis of active pharmaceutical ingredients and in environmental technology Enrichment of the substances to be determined used in the water analysis.
- the components to be extracted are enriched on special adsorbents and then eluted with a solvent.
- a vacuum can be applied to the cartridges used.
- Solid phase extraction has the great advantage over liquid-liquid extraction (LLE) of being able to handle much lower volumes of solvent, resulting in higher analyte concentration in less time.
- the separation is more complete compared to the LLE because the choice of adsorbent and eluent allows for a wide range of polarity and optimal extraction of the desired components of the solution.
- the above-mentioned sample enrichment and purification is carried out as a separate step before the actual separation and determination of the substances of interest.
- This separation and determination is often performed by subsequent liquid chromatography (e.g., HPLC, UPLC), i.
- the sample preparation and the actual determination are carried out in several consecutive steps.
- the quasi-continuous monitoring of a plating process becomes viable when the process and / or bath conditions change faster than can be measured using traditional manual analysis and automation techniques. This is especially true for processes with a narrow concentration range, small bath volumes and high throughputs (high deposition rate, introduction and removal).
- the invention has for its object to provide a method for the electrodeposition of a metal layer of an electrolyte bath, wherein the concentration of at least two Components of the electrolyte bath can be monitored in a simple manner.
- the quasi-continuous monitoring of the concentration of at least two components should be possible.
- a method of electrodepositing a metal layer from an electrolyte bath wherein the concentrations of at least two components of the electrolyte bath are monitored by performing the following steps: (a) a sample is taken from the electrolyte bath; (b) the sample is fed to a solid phase extraction column containing a solid sorbent; (C) the column is subjected to a washing process with a first eluent, wherein the at least two components remain on the column and unwanted components are eluted from the column; (d) the at least two components are eluted from the column by means of a second eluent; (e) the concentrations of the at least two components in the eluate obtained in step (d) are determined without separating the components.
- the present invention provides for the first time a method for the automatic, quasi-continuous solid-phase extraction of the components to be determined (in particular organic additives) with subsequent direct concentration determination without the requirement of prior separation of the components.
- the direct determination of the concentration of the components can be carried out by means of photometry, in particular UV detection, or by means of electrochemical detection methods, in particular polarography, or else by refractometry.
- the present invention enables the analysis of the additives in particular of tin, tin / lead, zinc, copper, nickel electrolytes and of noble metal electrolytes, in particular palladium and gold electrolytes.
- FIG. 1 shows a schematic representation of the stages of the sample application, the washing and the elution of the column for solid phase extraction according to an embodiment of the inventive method.
- FIG. 2 shows a schematic representation of the stages of sample application, washing and elution of the column for solid phase extraction according to another embodiment of the method according to the invention.
- FIG. 3 shows a schematic representation of the stages of sample application, washing and elution of the column for solid phase extraction according to another embodiment of the method according to the invention.
- FIG. 4 shows a schematic representation of an analysis system for the method according to the invention with switching valves, wherein the sample or a washing solution in the forward direction are passed over the column for solid phase extraction and an optional collecting and mixing container is provided.
- FIG. 5 shows a schematic representation of an analysis system for the method according to the invention with switching valves, wherein the eluent is passed in the reverse direction over the column for solid phase extraction and an optional collecting and mixing container is provided.
- the invention provides a method of electrodepositing a metal layer from an electrolyte bath.
- the metal to be deposited is not particularly limited.
- the metal may be tin, tin / lead, zinc, copper, nickel, a noble metal such as palladium or gold, or a combination of these or other metals.
- the method according to the invention makes it possible to monitor the concentrations of at least two components of the electrolyte bath.
- the components are preferably organic components of the electrolyte bath.
- the components whose concentration can be monitored include, in particular, flavones, chalcones, maltols, naphthols and UV-active ionic and nonionic surfactants.
- a component whose concentration is monitored may also be a grain refiner.
- the grain refiner may in particular be morin, e.g. used in electrolyte baths for the deposition of tin layers.
- the component may further be a conventional additive used in electrolyte baths for deposition of tin layers.
- the concentration of at least two components of the electrolyte bath can be monitored.
- the stages of sampling, the solid phase extraction, the washing process and the elution for the component to be monitored are preferably carried out simultaneously or in parallel.
- the determination of the concentration of the components takes place without the components being separated from one another.
- the determination of the concentration of the individual components is not necessarily simultaneous, but usually one after the other.
- the determination of the concentration of the individual components can preferably take place in one measuring cycle.
- sample volumes can be used for each component to be monitored, depending on the concentration of the particular component and the sensitivity of the determination method used.
- the method according to the invention makes it possible to monitor components which differ greatly from one another with regard to their concentration in the electrolyte bath and / or their absorption coefficient ⁇ and which can therefore not be determined simultaneously using conventional methods.
- a sample is first taken from the electrolyte bath. This can be done in particular by sucking in a small partial volume of the electrolyte bath via a pump.
- the sample is then fed to a solid phase extraction column containing a solid sorbent.
- the sorbent is selected according to the solution character, polarity, hydrophilicity and lipophilicity of the substances to be separated.
- the macromolecular backbone of the sorbent is preferably a copolymer of divinylbenzene and N-vinylpyrrolidone or a crosslinked polystyrene (formed by copolymerization of styrene with divinylbenzene).
- the sorbent can also consist of silica (silica gel).
- the average pore diameter of the poly (divinylbenzene-co-N-vinylpyrrolidone) used, for example, as a sorbent is preferably about 82 , the specific surface is preferably about 831 m 2 / g, the pore volume is preferably about 1.4 cm 3 / g, the average particle diameter is preferably about 31.4 microns and the proportion of fines ( ⁇ 10 microns) is preferably about 0.1%.
- Poly (divinylbenzene-co-N-vinylpyrrolidones) having these properties are commercially available (eg from Waters Corporation).
- RP18 lipophilic character
- RP18 means "reversed phase” with 18 C atoms in the side chain. This term is used for a particular stationary phase of liquid chromatography. In the RP phases, the polarity ratios are reversed compared to the normal phases. Nonpolar side chains are attached to a silica backbone or to a polymer. In general, silica-based column materials having 8 to 18 carbon atoms can be used.
- the solid phase extraction leads to an accumulation of the components to be monitored.
- the column is then subjected to a wash with a first eluent, leaving the at least two components to be monitored on the column and eluting undesired components from the column.
- the first eluents which may be used are in particular: water, dilute acid, methanesulfonic acid, acetates, carbonates, bases, or mixtures thereof, a mixture of alcohol and sulfuric acid or a mixture of alcohol and water.
- the eluents are, depending on the solution character, the polarity, hydrophilicity and lipophilicity of the substances to be separated.
- the washing process also serves to wash out or filter out impurities and larger particles that can not pass through the column with the aqueous matrix. Otherwise, such particles would enter the measuring chamber in the subsequent elution step and adversely affect the measurement there.
- the at least two components to be monitored are then eluted from the column by means of a second eluent.
- a second eluent water, methanol, a mixture of water and methanol, alkanes, methyl chloride, alcohols, dimethyl sulfoxide, acetonitrile or mixtures thereof.
- the eluents are selected according to the solution character, the polarity, the hydrophilicity and lipophilicity of the substances to be separated.
- the first eluent and the second eluent may be supplied to the column in the same direction as the sample of the electrolyte bath first supplied (see FIG. 1 ). This direction is referred to here as "forward".
- first eluent and / or second eluent may be fed to the column in the opposite direction (see Figures 2 and 3 ). This direction is referred to here as "backwards”.
- the reversal of the Elutionsoplasty can be realized in a simple manner by means of switching valves, as shown in the FIGS. 4 and 5 is shown.
- the valve setting allows adjustment of the flow direction.
- This process variant is preferred.
- a collecting and mixing container be provided to dilute the eluate before measuring if its concentration is too high.
- the extended column passage is avoided in the case of maintaining the flow direction during the elution.
- the exit path of the components to be monitored or of the undesired components is thereby shortened and the analysis time is considerably reduced.
- the reproducibility of the values is significantly improved.
- the concentrations of the at least two components to be monitored are determined in the eluate obtained by elution with the second eluent. From the concentration in the eluate, the concentration of the component in the electrolytic bath can be calculated (based on the volume of the eluate and the volume of the initially charged sample).
- the concentration can be determined photometrically.
- the eluate obtained by the elution with the second eluent is supplied to a measuring cell, where UV light is preferably radiated in perpendicular to the direction of flow from an external source and detected in a photometer and recorded by means of a computer program.
- the at least two components do not have to be separated for this purpose. Rather, it is possible to determine the concentrations of different components separately by using light of different wavelengths without separation of the components.
- the determination of the concentrations of the individual components can be carried out in succession.
- the determination of the concentrations of the individual components can also be carried out in different devices and using different sample volumes.
- a physical measuring method is selected in which the physical parameters of the at least two components are different so that a determination can be made without separation of the components.
- concentration determination include electroanalytical methods such as coulometry and voltammetry.
- mass spectrometry is suitable for determining the concentration.
- the column is subjected to conditioning before the supply of the sample of the electrolyte bath.
- conditioning agents methanol or an acidic solution.
- acidic conditioning solutions is particularly advantageous in order to avoid the precipitation of poorly soluble substances and thus the clogging of the column.
- the concentration of at least two components of an electrolyte bath can be monitored quasi-continuously.
- quasi-continuous means that the determination of the concentrations in a relatively short time interval is repeated regularly.
- the time interval can be, for example, 10 hours, 5 hours, 2 hours, 1 hour, 30 minutes, 10 minutes, or 1 minute.
- the monitoring of the concentration of the at least two components of the electrolyte bath can advantageously be carried out automatically.
- automated means that all steps of the procedure are performed without manual intervention.
- the monitoring of the at least two components is combined with the control of a dosing system which supplies a fresh amount of the consumed or destroyed component to the electrolyte bath as needed to achieve a nearly constant concentration of the monitored components during operation of the deposition process.
- a steady state is achieved in which all components that deplete are supplemented by a suitable dosing system and the components that accumulate are removed by appropriate regeneration measures.
- the method according to the invention is easy to handle and offers a cost-effective alternative to manual sampling with subsequent sample enrichment and final concentration determination and to known methods with separation of the components to be monitored.
- the quality and the Proof of quality and troubleshooting in current production are demonstrably improved.
- the present invention makes it possible to monitor at least two components of electrolytic baths in electroplating technology in a highly efficient, cost-effective, easy-to-handle and highly reproducible manner.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Automation & Control Theory (AREA)
- Organic Chemistry (AREA)
- Sampling And Sample Adjustment (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Investigating And Analyzing Materials By Characteristic Methods (AREA)
Claims (18)
- Un procédé pour le dépôt électrolytique d'une couche métallique à partir d'un bain d'électrolyte, dans lequel les concentrations d'au moins deux composants du bain d'électrolyte sont surveillées en conduisant les étapes suivantes:(a) un échantillon est prélevé du bain d'électrolyte;(b) l'échantillon est amené à une colonne d'extraction en phase solide qui contient un sorbant solide;(c) le colonne est soumise à une opération de lavage avec un premier éluant, les au moins deux composants restant sur la colonne et des composants indésirables sont élués de la colonne;(d) les au moins deux composants sont élués de la colonne au moyen d'un deuxième éluant;(e) les concentrations des au moins deux composants dans l'éluat obtenu dans l'étape (d) sont déterminées sans que les composants soient séparés.
- Le procédé selon la revendication 1, dans lequel le métal est l'étain, le zinc, le cuivre, le nickel ou un métal noble.
- Le procédé selon la revendication 2, dans lequel le métal noble est le palladium ou l'or.
- Le procédé selon l'une quelconque des revendications précédentes, dans lequel le composant à surveiller est une flavone, une chalcone, le maltol, le naphthol ou un tensio-actif UV-actif ionique ou non-ionique.
- Le procédé selon l'une quelconque des revendications précédentes, dans lequel le composant à surveiller est un affineur de grain ou un additif.
- Le procédé selon la revendication 5, dans lequel l'affineur de grain structurel est la morine.
- Le procédé selon l'une quelconque des revendications précédentes, dans lequel le sorbant est un copolymère de divinylbenzène et de N-vinylpyrrolidone.
- Le procédé selon l'une quelconque des revendications précédentes, dans lequel le premier éluant est l'eau, un acide dilué, un mélange d'alcool et de l'acide sulfurique ou un mélange d'alcool et d'eau.
- Le procédé selon l'une quelconque des revendications précédentes, dans lequel le deuxième éluant est l'eau, le méthanol, un mélange d'eau et de méthanol ou l'acétonitrile.
- Le procédé selon l'une quelconque des revendications précédentes, dans lequel la fourniture du premier éluant à la colonne dans l'étape (c) a lieu dans le même sens que la fourniture de l'échantillon dans l'étape (b).
- Le procédé selon l'une quelconque des revendications 1 à 9, dans lequel la fourniture du premier éluant à la colonne dans l'étape (c) a lieu dans le sens opposé à la fourniture de l'échantillon dans l'étape (b).
- Le procédé selon l'une quelconque des revendications précédentes, dans lequel la fourniture du deuxième éluant à la colonne dans l'étape (d) a lieu dans le même sens que la fourniture de l'échantillon dans l'étape (b).
- Le procédé selon l'une quelconque des revendications 1 à 11, dans lequel la fourniture du deuxième éluant à la colonne dans l'étape (d) a lieu dans le sens opposé à la fourniture de l'échantillon dans l'étape (b).
- Le procédé selon l'une quelconque des revendications précédentes, dans lequel la détermination de concentration dans l'étape (e) est effectuée en utilisant la photométrie, la polarographie, la réfractométrie.
- Le procédé selon l'une quelconque des revendications précédentes, dans lequel la séquence des étapes (a) à (e) est répétée à intervalles de temps réguliers de 1 minute à 10 heures.
- Le procédé selon l'une quelconque des revendications précédentes, dans lequel la surveillance de la concentration des au moins deux composants est réalisée en combinaison avec un système de dosage qui fournit une quantité appropriée fraîche du composant (des composants) selon le résultat de la détermination de la concentration.
- Le procédé selon l'une quelconque des revendications précédentes, dans lequel avant l'étape (b) la colonne est conditionnée avec du méthanol ou une solution acide et ensuite la colonne est équilibrée avec d l'eau.
- Un utilisation de poly(divinylbenzène-co-N-vinylpyrrolidone) pour l'extraction en phase solide des composants d'un bain galvanique d'électrolyte.
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ES06025569T ES2394910T3 (es) | 2006-12-11 | 2006-12-11 | Procedimiento galvánico con análisis del baño electrolítico mediante una extracción en fase sólida |
EP06025569A EP1932953B1 (fr) | 2006-12-11 | 2006-12-11 | Procédé galvanique avec analyse du bain electrolytique par extraction en phase solide |
US12/312,940 US9057145B2 (en) | 2006-12-11 | 2007-12-10 | Electrodeposition method with analysis of the electrolytic bath by solid phase extraction |
JP2009539668A JP5279720B2 (ja) | 2006-12-11 | 2007-12-10 | 固相抽出による電解質浴の分析を伴う電気的析出方法 |
PCT/EP2007/010753 WO2008071371A2 (fr) | 2006-12-11 | 2007-12-10 | Procédé galvanique avec analyse du bain électrolytique par extraction en phase solide |
CN200780045675.6A CN101553603B (zh) | 2006-12-11 | 2007-12-10 | 通过固相萃取分析电解液的电沉积法 |
TW96147247A TW200839037A (en) | 2006-12-11 | 2007-12-11 | Electrodeposition method with analysis of the electrolytic bath by solid phase extraction |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP06025569A EP1932953B1 (fr) | 2006-12-11 | 2006-12-11 | Procédé galvanique avec analyse du bain electrolytique par extraction en phase solide |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1932953A1 EP1932953A1 (fr) | 2008-06-18 |
EP1932953B1 true EP1932953B1 (fr) | 2012-11-14 |
Family
ID=37989636
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP06025569A Not-in-force EP1932953B1 (fr) | 2006-12-11 | 2006-12-11 | Procédé galvanique avec analyse du bain electrolytique par extraction en phase solide |
Country Status (7)
Country | Link |
---|---|
US (1) | US9057145B2 (fr) |
EP (1) | EP1932953B1 (fr) |
JP (1) | JP5279720B2 (fr) |
CN (1) | CN101553603B (fr) |
ES (1) | ES2394910T3 (fr) |
TW (1) | TW200839037A (fr) |
WO (1) | WO2008071371A2 (fr) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102505072A (zh) * | 2011-10-13 | 2012-06-20 | 云南民族大学 | 一种硫代若丹宁类试剂及其在钯固相萃取中的应用 |
CN105457336B (zh) * | 2014-09-04 | 2017-05-17 | 中国科学院大连化学物理研究所 | 一种铜离子的固相萃取方法 |
CN109371436A (zh) * | 2018-12-30 | 2019-02-22 | 丰顺县达森科技有限公司 | 一种水溶性酸性镀锌光亮剂及其制备方法 |
CN111257470B (zh) * | 2020-03-03 | 2023-05-23 | 广州天赐高新材料股份有限公司 | 电解液有机溶剂检测的前处理方法及检测方法 |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
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ATE49613T1 (de) * | 1986-05-21 | 1990-02-15 | Siemens Ag | Verfahren zur polarographischen bestimmung von zusaetzen in galvanischen baedern. |
JPH0762667B2 (ja) * | 1987-12-11 | 1995-07-05 | 株式会社日立製作所 | 溶液定量分析装置、定量分析方法および原子炉の水質制御システム |
JPH01269052A (ja) * | 1988-04-20 | 1989-10-26 | Sumitomo Metal Ind Ltd | ポリオキシアルキレン化合物の分離方法 |
US5296128A (en) * | 1993-02-01 | 1994-03-22 | Technic Inc. | Gallic acid as a combination antioxidant, grain refiner, selective precipitant, and selective coordination ligand, in plating formulations |
US5882521A (en) * | 1996-04-18 | 1999-03-16 | Waters Investment Ltd. | Water-wettable chromatographic media for solid phase extraction |
US6605204B1 (en) * | 1999-10-14 | 2003-08-12 | Atofina Chemicals, Inc. | Electroplating of copper from alkanesulfonate electrolytes |
CA2290731A1 (fr) * | 1999-11-26 | 2001-05-26 | D. Jed Harrison | Appareil et methode de piegeage de reactifs en forme de perles, dans le cadre d'un systeme d'analyse de microfluides |
US6645364B2 (en) * | 2000-10-20 | 2003-11-11 | Shipley Company, L.L.C. | Electroplating bath control |
JP3821000B2 (ja) * | 2002-01-29 | 2006-09-13 | 住友電気工業株式会社 | 高濃度塩溶液中の有機成分分析方法 |
US20030217923A1 (en) * | 2002-05-24 | 2003-11-27 | Harrison D. Jed | Apparatus and method for trapping bead based reagents within microfluidic analysis systems |
FR2840406B1 (fr) * | 2002-06-03 | 2005-02-25 | Aventis Pharma Sa | Methode de determination de profils de concentration a partir de profils infrarouges et de donnees clhp |
US6808611B2 (en) * | 2002-06-27 | 2004-10-26 | Applied Materials, Inc. | Methods in electroanalytical techniques to analyze organic components in plating baths |
EP1540046A4 (fr) * | 2002-07-19 | 2007-04-04 | Technic | Procede et appareil de surveillance en temps reel d'electrolytes industriels |
US20050032231A1 (en) * | 2003-08-06 | 2005-02-10 | Paris Smaragdis | Identifying component groups with independent component analysis of chromatographicdata |
-
2006
- 2006-12-11 EP EP06025569A patent/EP1932953B1/fr not_active Not-in-force
- 2006-12-11 ES ES06025569T patent/ES2394910T3/es active Active
-
2007
- 2007-12-10 US US12/312,940 patent/US9057145B2/en not_active Expired - Fee Related
- 2007-12-10 WO PCT/EP2007/010753 patent/WO2008071371A2/fr active Application Filing
- 2007-12-10 CN CN200780045675.6A patent/CN101553603B/zh not_active Expired - Fee Related
- 2007-12-10 JP JP2009539668A patent/JP5279720B2/ja not_active Expired - Fee Related
- 2007-12-11 TW TW96147247A patent/TW200839037A/zh unknown
Non-Patent Citations (3)
Title |
---|
MUSTAFA TUZEN; MUSTAFA SOYLAK: "Chromium speciation in environmental samples by solid phase extraction on Chromosorb 108", JOURNAL OF HAZARDOUS MATERIALS, 2006, pages 266 - 273 * |
SITKI BAYTAK; A. REHBER TÜRKER: "Determination of lead and nickel in environmental samples by flame atomic absorption spectrometry after column solid-phase extraction on Ambersorb-572 with EDTA", JOURNAL OF HAZARDOUS MATERIALS, 2006, pages 130 - 136 * |
VALERIE CAMEL: "Solid phase extraction of trace elements", SPECTROCHIMICA ACTA PART B, 2003, pages 1177 - 1233 * |
Also Published As
Publication number | Publication date |
---|---|
JP2010512504A (ja) | 2010-04-22 |
CN101553603B (zh) | 2010-12-22 |
JP5279720B2 (ja) | 2013-09-04 |
US9057145B2 (en) | 2015-06-16 |
TW200839037A (en) | 2008-10-01 |
US20100059384A1 (en) | 2010-03-11 |
CN101553603A (zh) | 2009-10-07 |
WO2008071371A3 (fr) | 2009-02-26 |
ES2394910T3 (es) | 2013-02-06 |
EP1932953A1 (fr) | 2008-06-18 |
WO2008071371A2 (fr) | 2008-06-19 |
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