Indirect flame-photometric determination of silicon

An indirect flame-photometric method for the determination of silicon in terms of the potassium in precipitated K(2)SiF(6) has been developed. Optimum conditions have been found for the precipitation and the washing of the precipitate with aqueous ethanol. Satisfactory results have been obtained for silicon contents > 1 % in ores and alloys.     

Determination of calcium, magnesium and strontium in soils by flow injection flame atomic absorption spectrometry

Several procedures for the determination of Ca, Mg and Sr in soils have been compared on the basis of the accuracy of analysis of two NIST reference materials (Montana Soils SRM 2710 and SRM 2711). Samples were dissolved in a mixture of hydrofluoric and nitric acids in sealed vessels in a microwave oven and in teflon beakers on a hot plate. The digests obtained from both dissolution methods were evaporated to dryness in an attempt to remove silicon. Boric acid was added to prevent the precipitation of the lanthanum releasing agent (as lanthanum fluoride) and potassium was added as an ionization buffer. Determinations were made by flame atomic absorption spectrometry with both the nitrous oxide-acetylene flame and the air-acetylene flame, with calibration either by standard additions or against external standards matrix matched with respect to nitric acid, boric acid, lanthanum and potassium. The silicon remaining in the solution was also determined by external calibration. A single-line flow injection manifold was used to overcome any problems due to the presence of high dissolved solids. A volume of 300 mul was injected into a water carrier stream flowing at 8 ml min(-1). To determine Ca in the air-acetylene flame, it was necessary to remove silicon. Magnesium was determined in either flame without complete removal of the silicon, however, for the determination of Sr, it was necessary to remove the silicon and use the nitrous oxide-acetylene flame. The indicative value for Sr in SRM 2710 was too low: the value determined was 360+/-30 mug g(-1).     

示差光度法快速测定样品中高含量硅

根据硅钼蓝光度法原理,对高含量硅的测定条件进行了试验,采用示差光度法、反酸化处理、分段比色、标样紧密内插法等措施,试验出了能适用于各种系列样品中常量硅含量的快速测定方法。该方法准确、简便、快速、易掌握。     

Spectrophotometric determination of traces of boron in silicon by means of solvent extraction

A spectrophotometric method for the determination of boron in silicon based on the extraction of the methylene blue-fluoroborate complex has been improved. Some important points, such as the dissolution of silicon with hydrofluoric acid and hydrogen peroxide, the effect of various anions on the blank absorbance and the best working conditions for forming and extracting the complex, have been studied. The method is applied to the determination of boron in silicon containing at least 1 p.p.m. of boron, with a relative standard deviation of ±5%.     

Substoichiometric precipitation of fluoride with lanthanum

The substoichiometric precipitation of fluoride with lanthanum was studied by using¹⁸F and¹⁴⁰La tracers and it was found that fluoride could be precipitated substoichiometrically with lanthanum and the reaction ratio between fluoride and lanthanum was 3∶1. The pH range at which fluoride can be separated substoichiometrically with lanthanum is between 2 and 8. Barium and indium interfere in the precipitation of fluoride, sodium, copper and manganese, however, not. Fluorosilicate can also be precipitated substoichiometrically by using lanthanum as a precipitant and the reaction ratio between fluorosilicate and lanthanum was 1∶2. This separation was applied for the determination of oxygen in silicon crystals. The concentration of oxygen measured in some silicon crystals was between 5 and 27 ppm and in good agreement with those by non-destructive method and infrared spectrophotometry.     

Spectrophotometric determination of trace and ultratrace levels of boron in silicon and chlorosilane samples

Summary Spectrophotometric methods for the determination of boron in the low g/g and ng/g range in high-purity silicon and dichloro- and trichlorosilanes were investigated in detail. The procedures established involve dissolution of silicon samples and the hydrolyzed products of chlorosilane samples in hydrofluoric acid-containing reagents followed by evaporation of the silicon matrix as H₂SiF₆. The boron retained in the treated sample solution was then determined by a spectrophotometric method using carminic acid as a chromatic reagent. Special effort has been paid to the control of the analytical blank and reproducible determination of boron. The results indicate that addition of mannitol and proper control of the evaporation process are effective in preventing volatilization of boron during the evaporation of silicon matrix and can thus attain high recovery of boron and reproducible analysis. Through meticulous control of the analytical blank and experimental conditions, the limit of detection for boron determination with the established method can be as low as ng/g levels. Application of the methods to the determination of boron in various stages of purification of silicon and trichlorosilane as well as in borophosphosilicate film was conducted.     

Mikrobestimmung von freiem Silicium in Siliciumcarbid

Zusammenfassung Der teilweise sehr niedrige Gehalt an freiem Silicium in den Siliciumcarbid-Hüllschichten beschichteter Kernbrennstoffteilchen für einen Hochtemperatur-Reaktor sowie die geringe Probenmenge machte eine Modifizierung des BestimmungsVerfahrens nach DIN 51075 erforderlich.Die Apparatur wurde stark verkleinert. Die Bestimmung des Wasserstoffs, der bei der Umsetzung des freien Siliciums mit Natronlauge entsteht, wurde von der volumetrischen Methode auf die sehr viel empfindlichere Messung mit der Wärmeleitfähigkeitszelle umgestellt. Aufgrund der Eichmessungen mit Eichhähnen sowie Blindwertmessungen wurde eine Nachweisgrenze von 100 ppm für die Probeneinwaage von 100 mg erreicht. Diese Bestimmungsmethode ist bei entsprechend niedrigen Probeneinwaagen auch für die Bestimmung sehr hoher Gehalte von freiem Silicium geeignet.

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Micro determination of free silicon in silicon carbide

Summary The in part very low content of free silicon in the silicon carbide claddings of nuclear fuel particles for a high-temperature reactor, as well as the small sample quantity, made it necessary to modify the method of determination according to DIN 51075.The apparatus has been considerably scaled down. The determination of hydrogen arising during the conversion of free silicon with caustic soda lye has been changed from the volumetric method to much more sensitive measurements with a thermal conductivity cell. By means of calibration measurements with calibration volumes, and also blank value measurements, a detection limit of 100 ppm was achieved for the weighed sample quantity of 100 mg. With correspondingly low weighed sample quantities, this determination method is also suitable for determining very high contents of free silicon.

     

Destructive and non-destructive methods for the determination of micro-trace amounts of antimony in high purity silicon by neutron activation analysis

Destructive and non-destructive methods have been used for the determination of microtraces of antimony in high-purity silicon powder. The destructive method was based on substoichiometric radioactivation analysis with solvent extraction using BPHA and cupferron as organic reagents. The antimony contents in high-purity silicon can be determined by the proposed method.     

重量法-电感耦合等离子体原子发射光谱法联用测定无取向硅钢磷酸盐体系环保涂层液中二氧化硅含量

二氧化硅是无取向硅钢环保涂层液的核心成分,其含量直接影响硅钢涂层的固化工艺及涂层产品的磁性能。因此为保证涂覆过程的顺利进行,对涂层液中二氧化硅含量的检测是十分必要的。本方法采用样品中分别加入硝酸、双氧水及高氯酸,置于电热板上进行消解处理,处理后的样品经酸溶、过滤步骤,以重量法计算沉淀中二氧化硅的含量,采用电感耦合等离子体原子发射光谱（ICP-AES）仪测定滤液中可溶性硅含量,则样品中二氧化硅含量为重量法和电感耦合等离子体原子发射光谱法测定结果的合量。从而建立了重量法-电感耦合等离子体原子发射光谱法联用测定无取向硅钢磷酸盐体系环保涂层液中二氧化硅含量的方法。讨论了样品前处理用消解酸及消解温度、滤液中可溶性硅及含量、ICP-AES仪器检测时的元素干扰。结果表明：按照本实验方法测定无取向硅钢磷酸盐体系环保涂层液中二氧化硅含量,检测结果的相对标准偏差（RSD,n=12）在0.76%~1.08%之间,加标回收率在97.00%~104.0%之间。该方法可广泛应用于各检测部门对无取向硅钢磷酸盐体系环保涂层液中二氧化硅含量的监控。     

Dosage du silicium par précipitation du complexe silicomolybdique jaune par la quinoléine

The authors have studied the conditions of precipitation of complex silicomolybdic yellow by quinoline from the point of view of the determination of silicon.Under the conditions that produce complete development of the complex, the precipitation is itself quantitative in the presence of an excess of quinoline, the role of which is to make the precipitate insoluble in its formation surroundings. The precipitation of free molybdate is prevented by adding the quantity of acid necessary for complexing it.The precipitate thus obtained filters without difficulty, and only needs to be dried for 1 hour at 150° in order to attain constant weight. It corresponds then exactly to the formula: SiO₂.12MoO₃.4(C₉H₇N).2H₂O.     

Determination of nickel and copper by precipitation from homogeneous solution as their salicylaldimine complexes

A method has been developed for the gravimetric determination of copper and nickel as their salicylaldimine complexes, by precipitation from homogeneous solution. The complexes are crystalline precipitates which are very easy to filter off and wash. The accuracy of the determinations is higher than that of the conventional precipitation method.     

Improved Surface Enhanced Raman Scattering for Nanostructured Silver on Porous Silicon for Ultrasensitive Determination of 2,4,6-Trinitrotoluene

Label-free and low-cost surface-enhanced Raman scattering-active substrates of silver nanostructures on porous silicon have been synthesized. The morphology and spectroscopic properties were investigated as a function of concentration and immersion time. The enhancement factor of optimized silver-porous silicon substrate was estimated to be 2.18 × 10⁸ by the use of p-thiocresol as a Raman probe. The optimized substrate was used to determine 50 pg of 2,4,6-trinitrotoluene. These results demonstrate that the prepared silver-porous silicon substrates are promising for the ultra-sensitive determination of organic molecules.     

Possibilities of low-level determination of silicon in biological materials by activation analysis

The capabilities of neutron and photon activation analysis (NAA and PAA, respectively) for low-level determination of silicon in biological materials have been examined. Sensitivities of a variety of modes of NAA and PAA with radiochemical separation have been evaluated. Results are presented for silicon in reference materials CSRM 12-2-03 Lucerne, Bowen's Kale, NIST SRM-1571 Orchard Leaves, and NIST SRM-1515 Apple Leaves. The results were obtained by employing the 29Si(n,p)29Al reaction with fast reactor neutrons and the radiochemical procedure developed for aluminium separation. Possibilities of further improvement of the silicon determination limit down to the microg g(-1) level by employing NAA and PAA with radiochemical separation are outlined.     

Metal and metalloid indicator electrodes for the non-aqueous potentiometric titration of weak acids: comparative evaluation of group III, IV and V main-group elements

Indicator electrodes constructed from aluminium, gallium, indium, thallium, carbon, silicon, germanium, tin, lead, arsenic, antimony and bismuth have been evaluated for the potentiometric titration of solutions of benzoic acid in dimethylformamide and 4-methyl-2-pentanone. The aluminium, gallium, silicon and arsenic electrodes have also been evaluated for the determination of 3,5-xylenol in the same two solvents. Aluminium, gallium, indium, silicon, germanium, antimony and bismuth electrodes are superior to, or compare favourably with, a glass electrode for the determination of benzoic acid, when the criterion of efficiency is the sharpness of the end-point inflexion. In non-aqueous titrations of 3,5-xylenol, aluminium and gallium electrodes are similar in efficiency to the glass electrode for determinations in dimethylformamide solution, while the gallium electrode is superior to the glass electrode when 4-methyl-2-pentanone is the solvent. Possible relationships between the properties of the electrode element and the end-point sharpness when it is used as an indicator electrode are briefly considered.     

Separation et dosage de traces de bore dans le silicium : Nouvelle méthode de séparation et de dosage de traces de bore. application au dosage du bore dans le silicium

A new method is described for the separation and determination of traces of boron by extraction of methylene blue fluoroborate by dichlorethane The method has been applied to the determination of traces of boron in silicon and silica     

Simultaneous determination of silicon and aluminium in ferrosilicon by instrumental neutron activation analysis with the aid of an Ac-Be isotopic neutron source

A method has been developed for the accurate determination of silicon and aluminium by instrumental neutron activation analysis with the aid of an²²⁷Ac-Be isotopic neutron source. The samples are pellets made of 4.6 g of ferrosilicon and 0.9 g of a pelletizing agent. Each pellet is irradiated twice at two different fast-to-thermal neutron flux ratios. Each irradiation is followed by two integral mode countings. This allows correction for manganese activities and calculation of the fraction of the aluminium activity induced in silicon and aluminium. The method has been tested with laboratory-prepared synthetic samples as well as commercially certified ferrosilicon. For ferrosilicon containing 75% Si, a relative precision of 0.7% for the results of the silicon concentration has been obtained. For aluminium the relative precision varied from 2 to 7% for concentrations of 3.5 to 1.5%.     

Die F?llung der Dodekamolybdatokiesels?ure mit organischen Basen

Zusammenfassung Das FÄllungsverhalten von DodekamolybdatokieselsÄure gegenüber organischen Ammoniumionen wird qualitativ und quantitativ untersucht und eine Reihe geeigneter NiederschlÄge bezüglich Löslichkeit, Zusammensetzung und thermoanalytischen Verhaltens charakterisiert. Zwischen diesen Eigenschaften und der Konstitution des FÄllungsmittels besteht ein deutlicher Zusammenhang. Das günstigste analytische Verhalten zeigt das Pyridiniumsalz der DodekamolybdatokieselsÄure. Auf dieser Basis wurde ein Verfahren zur KieselsÄurebestimmung ausgearbeitet mit besonderer Rücksicht auf solche FÄlle, bei denen Abscheidemethoden Schwierigkeiten bereiten, so Siliciumbestimmungen in Fluorprodukten und Organosiliciumverbindungen. Arbeitsvorschriften sind angegeben für Flu\sÄure, Aluminiumfluorid, Flu\spat und für Peroxidaufschlüsse organischen Materials. Noch 0,1 mg SiO₂ in 400 ml Probelösung sind genau zu bestimmen.

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Summary The precipitation behaviour of 12-molybdato-silicic acid towards organic ammonium ions is examined both qualitatively and quantitatively and a number of suitable precipitates are characterized with regard to solubility, composition and thermoanalytical behaviour. A clear relationship exists between these properties and the constitution of the precipitating agent. The pyridinium salt of 12-molybdatosilicic acid gives the optimum behaviour in analysis. Using this finding as a basis, determination methods have been developed which, in particular, cover those cases where the conventional method presents difficulties, e.g. silicon determinations in fluorine containing products and organic silicon compounds. Instructions are given for the determination of silicon in hydrofluoric acid, cryolite, aluminium fluoride, fluorspar and organic materials. Accurate determination is possible even of quantities as small as 0.1 mg of SiO₂ in 400 ml of sample solution.

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Herrn Dr. G. Hentze, Ingenieurabteilung der Farbenfabriken Bayer, sei für die Ausführung der thermoanalytischen Messungen und für wertvolle Diskussionen herzlich gedankt.     

Quantitative Determination of Silicon in Organosilicon Compounds Using Low-Temperature RF-Discharge Oxygen Plasma

Abstract

The paper describes a technique for quantitative determination of silicon in organic monomer and polymer materials based on low-temperature decomposition of samples in rf-discharge oxygen plasmas. The final step of analysis involves gravimetric determination of silicon in the form of silicon dioxide. The presence of fluorine (up to 50%) does not interfere with the determination of silicon.     

水中微量硅的硅钼蓝光度法测定——还原剂的研究

研究和配制了一种甲醛合次硫酸氢钠和亚硫酸钠的混合液作为水中微量硅（硅钼蓝）光度法测定的还原剂，其还原能能力、稳定性、准确度均较好，适用于多种水源中微量硅的测定。     

Possibilities of low-level determination of silicon in biological materials by activation analysis

The capabilities of neutron and photon activation analysis (NAA and PAA, respectively) for low-level determination of silicon in biological materials have been examined. Sensitivities of a variety of modes of NAA and PAA with radiochemical separation have been evaluated. Results are presented for silicon in reference materials CSRM 12–2-03 Lucerne, Bowen’s Kale, NIST SRM-1571 Orchard Leaves, and NIST SRM-1515 Apple Leaves. The results were obtained by employing the ²⁹Si(n,p)²⁹Al reaction with fast reactor neutrons and the radiochemical procedure developed for aluminium separation. Possibilities of further improvement of the silicon determination limit down to the μg g^–1 level by employing NAA and PAA with radiochemical separation are outlined.