Application of instrumental neutron activation analysis in Czochralski silicon crystal growth

Contamination sources of trace elements introduced into silicon crystals grown by the Czochralski technique are investigated: the signale comparator method in neutron activation analysis is applied to the determination of impurities in a silica crucible polycrystalline silicon, grown crystals and residual melt. When particular care is taken to avoid contamination during crystal growth, it is possible to obtain high purity silicon crystals in which impurity contents are almost below the detection limits of the analytical method.     

Ultra-trace analysis of U,Th, Ca and selected heavy metals in high purity refractory metals with isotope dilution mass spectrometry

A method for the determination of trace impurities (U, Th, Ca, Fe, Cr, Ni, Cu, and Cd) in the refractory metals molybdenum and tungsten with isotope dilution mass Spectrometry (IDMS) has been developed. This method enables determinations of uranium and thorium down to the lowest pg/g level with high precision and accuracy. Selective chromatographic, extractive and electrolytic methods for the trace-matrix separation were combined with positive thermal ionization mass spectrometry. Different samples of high purity (4N) and of ultra high purity (UHP) materials for advanced technologies were analysed. The detection limits reached are (in ng/g): U 0.006, Th 0.008, Ca 10, Fe 19, Cr 0.5, Ni 0.6, Cu 2.7, and Cd 0.12. A comparison of results with other sensitive analytical methods (ICP-MS, GDMS, SIMS) makes obvious the urgent necessity of a reliable calibration method like IDMS because the analytical results obtained by the other methods often spread over a wide range.     

Semi-automated peak trapping recycle chromatography instrument for peak purity investigations

A peak trapping recycle chromatography system has been developed and optimized for peak purity assessment of active pharmaceutical ingredients analyzed by high performance liquid chromatography (HPLC). After being analyzed using a reversed phase analytical column, peaks of interest are trapped and are subsequently introduced to a recycle chromatography system. In addition to the increased effective length afforded the recycling system, the small selectivity difference between the analytical and recycling methods help separate potential impurities under the main peak. For more difficult to separate components, the increased efficiency of recycle chromatography provides the necessary resolution. Over 227,000 theoretical plates have been obtained in the recycle dimension for some compounds. The sensitivity of the system fell short of the target (0.1%), but it did show sensitivity (0.5%) comparable to other peak purity techniques commonly used in the pharmaceutical industry. The recovery and repeatability have also been shown to be adequate for peak purity assessment. The system has also been automated using a Visual Basic macro, simplifying the interface allowing it to be used as an open access instrument.     

Isotope dilution mass spectrometry of microelectronically relevant heavy metal traces in high-purity cobalt

Summary Because cobalt and its silicides are increasingly used in microelectronic devices, an isotope dilution mass spectrometric (IDMS) method has been developed for trace analysis of relevant heavy metals (U, Th, Fe, Zn, Tl, and Cd) in high-purity cobalt. The measurements of the isotope ratios were carried out with a small thermal ionization quadrupole mass spectrometer by producing positive thermal ions in a single- or double-filament ion source. For the trace/matrix separation and the isolation of the different heavy metals, anion-exchange chromatography and an extraction method for iron were applied. The detection limits obtained were (in ng/g): U=0.007, Th=0.017, Tl=0.06, Cd=1, Zn=8, and Fe=11, which demonstrates that the particularly critical radioactive impurities uranium and thorium could be analysed down to the low pg/g range. Three cobalt samples of different purity were analysed with concentrations ranging from about 0.1 ng/g for U and Th in an ultra high-purity material produced for microelectronic purposes, up to about 70 g/g for Cd in a cobalt sample with declared purity of 99.8%. Because IDMS usually results in accurate analytical results, it can be used in the future for calibration of other methods like glow discharge mass spectrometry, as could be shown by analysing one cobalt sample by both methods. IDMS can also be applied for the production of urgently needed certified standard reference materials in this important field of high technology.Presented at the ANAKON '93 conference     

A pre-concentration neutron activation analysis method for the determination of 232Th utilizing a dry-tube irradiation facility

A revized method for determining ²³²Th using a pre-concentration neutron activation analysis (PCNAA) procedure was developed to accommodate irradiation in a dry irradiation tube environment. ²³²Th extracted by ion-exchange from a sample was electrodeposited onto 5/8″ diameter vanadium planchets, which are arranged in a stack and irradiated in the dry tube central irradiation facility (CIF) of the reactor. The higher neutron fluence of this facility improved sensitivity by approximately 37%, however, the higher temperatures required modifications to the irradiation procedure. Because the heat in the CIF would melt the plastic spacers used in the original method, a tube of high-purity quartz was used to contain samples, and high purity quartz spacers were used to separate the vanadium planchets during the irradiation. Test irradiations have determined that no significant transfer occurred from the disks to the silica disks and no significant variation in the neutron flux was observed. Finally, a thin film barrier was tested for its ability to reduce recoil contamination from ²²⁹Th onto the detector during alpha spectroscopy. The film was shown to reduce contamination to levels indistinguishable from normal background.     

Are analytical standards and reagents really reliable?

Quality assurance is one of the major challenges in analytical chemistry, whatever the scope of application. The quality of analytical standards is very seldom questioned; however, sometimes odd results are obtained, and all the other potential sources of discrepancies are eliminated. So, we investigated the reliability of three analytical standards and reagents implemented for radiochemical and chemical characterizations of nuclear waste. In particular, this work examined the purity of a source of tritiated dodecane, the trueness of a certified concentration value and the purity for a diethylenetriaminepentaacetic acid (DTPA) reagent and the trueness of a certified concentration value for a multi-anion standard used in an interlaboratory comparison exercise. It was shown that the source of tritiated dodecane contains 60 % of tritiated impurities. The trueness of the DTPA concentration certified by the supplier was questioned due to the presence of impurities in the solution. It was proven that the long-term stability of the multi-anion standard was not guaranteed for nitrite. The results clearly demonstrated that, despite the certificates delivered by the suppliers, caution has to be taken toward the reliability of the analytical standards and reagents.     

High NIR-purity index single-walled carbon nanotubes for electrochemical sensing in microfluidic chips

Single-walled carbon nanotubes (SWCNTs) should constitute an important natural step towards the improvement of the analytical performance of microfluidic electrochemical sensing. SWCNTs inherently offer lower detection potentials, higher surfaces and better stability than the existing carbon electrodes. However, pristine SWCNTs contain some carbonaceous and metallic impurities that influence their electrochemical performance. Thus, an appropriate processing method is important for obtaining high purity SWCNTs for analytical applications. In this work, a set of 0.1 mg mL(-1) SWCNT dispersions with different degrees of purity and different dispersants (SDBS; pluronic F68 and DMF) was carefully characterized by near infrared (NIR) spectroscopy giving a Purity Index (NIR-PI) ranging from 0.039 to 0.310. The highest purity was obtained when air oxidized SWCNTs were dispersed in SDBS, followed by centrifugation. The SWCNT dispersions were utilized to modify microfluidic chip electrodes for the electrochemical sensing of dopamine and catechol. In comparison with non-SWCNT-based electrodes, the sample with the highest NIR-PI (0.310) exhibited the best analytical performance in terms of improved sensitivity (3-folds higher), very good signal-to-noise ratio, high resistance-to-fouling in terms of relative standard deviation (RSD 7%; n = 15), and enhanced resolution (2-folds higher). In addition, very well-defined concentration dependence was also obtained with excellent correlation coefficients (r ≥ 0.990). Likewise, a good analytical sensitivity, suitable detection limits (LODs) and a very good precision with independence of the concentration assayed (RSDs ≤ 5%) was achieved. These valuable features indicate the suitability of this material for quantitative analysis. NIR-PI and further TEM and XRD characterization demonstrated that the analytical response was driven and controlled by the high NIR-PI of the SWCNTs used. The significance of this work is the demonstration for the first time of the sensitivity-purity relationship in SWCNT microfluidic chips. A novel and valuable analytical tool for electrochemical sensing has been developed: SWCNTs with high purity and a rich surface chemistry with functional groups, both essential for analytical purposes. Also, this work helps to better understand the analytical potency of SWCNTs coupled to microfluidic chips and it opens new gates for using these unique dispersions in real-world applications.     

Precise non-destructive X-ray fluorescence method for uranium and thorium concentration measurements

A precise non-destructive radioisotope X-ray fluorescence method for uranium and thorium concentration measurements was developed. A beta-emitting⁹⁰Sr−⁹⁰Y source was used for excitation of characteristic X-ray lines. It is proved that the beta-excited X-ray fluorescence method (in spite of the significant bremsstrahlung intensity) has essential advantages for analysis of high concentrations of U and Th, characteristic for nuclear power cycle materials, because of the higher sensitivity of the method. (3% changes of the intensity per 1% change of the concentration.) Portable semiconductor or scintillation detectors and multichannel analysers are used for detection of analytical lines. The accuracy achieved by this method is 0.2–0.3% for 15 minutes measurement and 0.1 mCi activity of the source. This work was performed under contract with the International Atomic Energy Agency, Vienna.     

高效液相色谱-离子阱/飞行时间质谱鉴定违禁药品邻氯苯基环戊酮中杂质及其标准物质的制备

建立了高效液相色谱-离子阱/飞行时间质谱（HPLC-IT/TOF MS）分析违禁药品邻氯苯基环戊酮样品中杂质成分的方法。对邻氯苯基环戊酮标准品进行多级质谱分析,根据各碎片离子的精确质量数推测邻氯苯基环戊酮的裂解路径,并利用该方法检测出邻氯苯基环戊酮样品中的2种杂质成分：2-氯苯甲酸酸酐和1,2-二邻氯苯甲酰基环戊烯,推断出该违禁药品的合成方法,为追溯其来源提供了重要依据。同时建立了制备邻氯苯基环戊酮标准品的方法,制备高效液相色谱条件是流动相甲醇-水（85∶15,v/v）,流速8 mL/min,进样量1 mL。制备得到的邻氯苯基环戊酮标准物质纯度为99.53%。该方法简单、高效,可拓展应用于其他违禁药物标准物质的制备。     

Measurement of physical strength of pharmaceutical extruded pellets

This paper describes a novel and simple method for measuring the physical strength of pharmaceutical pellets prepared by extrusion granulation. Pharmaceutical powders composed of lactose, cornstarch, and microcrystalline cellulose were kneaded with purified water and dry binder (hydroxypropylcellulose), then extruded through a dome-type extrusion granulator. The physical strength of the dried extruded pellets was measured with a novel system: pellets and grinding alumina media were both fed into a ball mill pot and then "grinding degree" was measured as defined by the ground fine powder fraction after being rotated in the pot. The grinding conditions such as grinding time and number of alumina balls were optimized. The measured physical strength and pellet strength measured with a typical strength tester was compared. Quantitative relationships between the strength and the physical properties of the pellets such as friability and disintegration time were also investigated. It was found that the newly developed system could easily and accurately evaluate the physical strength of extruded pellets and could also predict the various physical properties.     

Analytical scheme for tracing sources of contamination during processing of Si3N4 in clean rooms

This work investigates the uptake of impurities during processing of Si₃N₄ and describes an analytical scheme for detecting sources of contamination. For this purpose a process as simple and short as possible was chosen, using commercial starting materials with a high standard of purity and reproducibility. The uptake of non-metallic and metallic contaminants was investigated by choosing elements which were specific for individual processing steps. This was difficult in the determination of metallic impurities in a powder consisting of Si₃N₄ with Y₂O₃/Al₂O₃ additives, because the powder mixture and the sources of contamination (milling balls, attritor disk, wall materials) were similar in composition and the available analytical methods were not precise enough to detect the small increase in concentration that occurred. Therefore pure Si₃N₄ powders were milled in order to get an indication of the kind and concentration of impurity introduced by the individual milling materials and steps. These elements can then be used as monitor elements to trace sources of contamination and to optimize processing parameters. Experience with the processing of Si₃N₄ with Y₂O₃/Al₂O₃ additives by cyclic milling, spray drying, burn-out and isopressing are reported. Contamination by carbon is unavoidable. Its concentration during the process is relatively high, as it is added in the form of processing aids (deflocculants, binders), but temporary, as it can be completely burned out. Oxygen is predominantly taken up during milling. Good deflocculation reduces the milling time and thus limits the uptake of oxygen. As a consequence of these findings the processing parameters could be optimized. Thus the uptake of metallic impurities, e.g. Fe could be limited to 10 g/g and the uptake of oxygen was found to be less than 0.2 wt%.     

Comparative study on Th(IV) sorption on alumina and silica from aqueous solutions

The effects of pH, ionic strength and concentration on the sorption of Th(IV) on alumina and silica were investigated and the sorption isotherms of Th(IV) on alumina and silica at different pH values were determined. It was found for both sorbents that the absorbability of silica is less than that of alumina. The relative sorption rate of silica is similar to that of alumina. The sorption edges are similar to each other, that the insensitivity of sorption to ionic strength is about the same. These similarities between the sorbents suggest that the speciation of Th(IV) in aqueous solutions plays a significant, but subtle role, in controlling the sorption process, because the charges of both sorbents are distinctly different. The mechanism of Th(IV) sorption on alumina is distinctly different from that of the sorptions of Cs⁺, Eu³⁺ and Yb³⁺ on alumina, and similar to that of the sorption of Co(II) on alumina.     

Purity assessment of crystalline zearalenone

Commercially available solid zearalenone (ZON) to be used as a certified liquid calibrant (BCR-699) in a project funded by the European Commission within the Standard Measurement and Testing program was characterized and its purity determined. The degree of purity of the ZON was examined by UV spectrophotometer, liquid chromatography (LC) with diode array and fluorescence detection, 1H and 13C-NMR spectrometry, LC-mass spectrometry (LC/MS/MS), ion chromatography (IC), and differential scanning calorimetry (DSC). The diagrams obtained from DSC analysis and the UV spectrum showed no detectable impurities. Likewise, no impurities were observed by LC analysis with both diode array and fluorescence detection. IC determination revealed negligible contamination of ZON with chloride of 0.020 +/- 0.005% and nitrate of 0.016 +/- 0.006%. Zearalanone (ZAN) was identified as one of 2 minor (0.2%) impurities by LC/MS/MS. The 1H-NMR measurements revealed an additional peak, which has not been previously reported in the literature. It could be identified as part of the ZON spectrum as the signal arising from the phenolic proton attached to C4'. The manufacturer states an additional contamination with 0.2% methylene chloride, which could be confirmed to an extent of 0.1% by 1H-NMR. Minor impurities, whose structures remain unknown, were discovered at 3.5 and < 1 ppm. Total percentage of impurities based on NMR measurement was estimated not to exceed 1%. A purity of 99.5% with a tolerance of +/- 0.5% was finally attributed to the ZON studied in this project.     

Influence of two grinding methods on the uncertainty of determinations of heavy metals in atomic absorption spectrometry/electrothermal atomisation of plant samples

 Chemical analyses of trace elements are affected by relatively high analytical errors due to the different steps of the laboratory procedures: samples grinding, mineralisation and instrumental measurements. In the present communication, the influence of the grinding phase on the global uncertainty of Pb, Cd, Ni and Cr determinations in plant samples by the classical method of atomic absorption spectrometry/electrothermal atomisation (AAS-ETA) after dry ashing is quantified. Two grinding machines, a planetary mill with balls and jars of agate versus a stainless steel grinder were compared by analysing leaf samples of cucumber, strawberry, kiwivines, apple trees and grapevines from agricultural experimental plots under controlled conditions. Variance components due to the difference between grinding methods and experimental plots were estimated. Further, the simultaneous effects of the grinding methods on all considered metals have been evaluated by analysis of variance. With the stainless steel grinder, on average, higher levels of the considered heavy metals were obtained (up to 67% of the mean values). On average, the increments were similar for metals contained in steel (Ni and Cr) and those not contained (Pb and Cd). The true causes of these differences need further investigation to determine whether the higher metal detection is due to possible contamination, to a different grinding quality or to other reasons. Finally, the grinding methods did not seem to affect the combined uncertainty of the analyses. Received: 3 November 1997 · Accepted: 29 November 1997     

Determination of alpha-emitting isotopes of uranium and thorium in vegetables and excreta

A radiochemical procedure for the determination of alpha-emitting isotopes of uranium and thorium in vegetables and excreta has been optimized, involving sample dissolution, separation by ionic exchange resin, electrodeposition and alpha-spectroscopy. Uranium and thorium isotopes were determined separately to prevent interference of ²²⁸Th from ²³²U tracer with ²²⁸Th from natural series of 232Th. This procedure was applied to faeces from people living in the Poços de Caldas plateau, a high natural radioactivity region of Brazil, and vegetables from the Laboratory of Environmental Monitoring (EML/DOE). Results show a chemical recovery of 80–95% for uranium and 46–72% for thorium.     

多面体低聚八硝基苯基硅倍半氧烷纯度分析

使用高效液相色谱-电喷雾四级杆飞行时间质谱(HPLC-ESI-Q-TOF MS)联用技术对八硝基苯基硅倍半氧烷(ONPS)纯度进行分析, 从而判定ONPS产物峰及杂质峰的位置, 根据ONPS峰和杂质峰的面积比计算ONPS的纯度. 通过改变HPLC的洗脱梯度和测试时间, 将ONPS产物中的杂质峰完全分开, 测得硝基苯基硅倍半氧烷(NPS)质量分数为97.55%, 其中ONPS的纯度约为92.42%, 产物中含有九硝基八苯基硅倍半氧烷(9-NPS)约5.13%, 其它杂质含量约为2.45%. 通过对ONPS高效液相色谱图峰形和同分异构体极性情况分析, 进一步证明ONPS分子中硝基取代发生于对位和间位. 使用超高效液相色谱(UPLC)对ONPS进行分析, 以更高的分离效率验证了HPLC的结果. 该方法可作为ONPS纯度的分析方法.     

2-乙基己基磷酸单(2-乙基己基)酯萃淋树脂分离-火花源质谱法测定高纯氧化镱中痕量稀土杂质

本文采用萃取色谱法以2-乙基已基膦酸单(2-乙基已基)酯(P_507)萃淋树脂为固定相,以HCI-NH_4CI体系为淋洗液,研究了99.999%~99.9999%的高纯Yb_2O_3中稀土杂质和Yb基体的分离条件,将杂质淋洗液富集于复合螯合剂-活性碳上,经灼烧灰化后制成样品电极,进行质谱测定.测定下限达 0.01~0.05 μg/g,可用于高纯 Yb_2O_3中杂质的测定.回收率在80%以上.     

Purity assessment of recombinant human granulocyte colony‐stimulating factor in finished drug product by capillary zone electrophoresis

Current methods for determination of impurities with different charge‐to‐volume ratio are limited especially in terms of sensitivity and precision. The main goal of this research was to establish a quantitative method for determination of impurities with charges differing from that of recombinant human granulocyte colony‐stimulating factor (rhG‐CSF, filgrastim) with superior precision and sensitivity compared to existing methods. A CZE method has been developed, optimized, and validated for a purity assessment of filgrastim in liquid pharmaceutical formulations. Optimal separation of filgrastim from the related impurities with different charges was achieved on a 50 μm id fused‐silica capillary of a total length of 80.5 cm. A BGE that contains 100 mM phosphoric acid adjusted to pH 7.0 with triethanolamine was used. The applied voltage was 20 kV while the temperature was maintained at 25°C. UV detection was set to 200 nm. Method was validated in terms of selectivity/specificity, linearity, precision, LOD, LOQ, stability, and robustness. Linearity was observed in the concentration range of 6–600 μg/mL and the LOQ was determined to be 0.3% relative to the concentration of filgrastim of 0.6 mg/mL. Other validation parameters were also found to be acceptable; thus the method was successfully applied for a quantitative purity assessment of filgrastim in a finished drug product.     

Study of radiation-induced polymerization of vinyl monomers adsorbed on inorganic substances. VIII. Polymerization of styrene and methyl methacrylate adsorbed on aerosil

Aerosil is silica having a purity which is very high compared with that of silica gel and having, unlike silica gel, no micropores. To investigate the effects of impurities and micropores on the radiation-induced polymerization of styrene and methyl methacrylate adsorbed on silica gel, the radiation-induced polymerization of styrene and methyl methacrylate adsorbed on Aerosil was carried out. The results of both the styrene–Aerosil 300 system and the methyl methacrylate–Aerosil 300 system were similar to those of the styrene–silica gel and methyl methacrylate–silica gel systems, respectively. This suggests that in the radiation-induced polymerization of both styrene–silica gel and methyl methacrylate–silica gel systems the impurity and the presence of micropores have almost no effects on the reaction mechanism. The effect of aluminum as an impurity was investigated on the styrene–Aerosil MOX 170 system. It was found that aluminum accelerated the cationic polymerization.     

Graphite furnace for alternative combination with d.c. arc or inductively coupled plasma. Introduction and analysis of solid samples

Summary A graphite furnace and d.c. arc combined source with the use of halogenating atmosphere in the furnace is described. The construction makes possible the introduction and analysis of both liquid and solid samples at minimum risk of contamination. Spectrographic detection resulted in background equivalent mass values below 10 ng for 22 from 36 elements applied in solution (Ar + CCl₄ atmosphere and NaCl matrix). The intensity-time profiles indicated high rates of distillation of the impurities (including B, Cr, Hf, Mo, Ti, V, W and Zr) from silicon carbide and silicon nitride samples in the first 40 s of heating under chlorination (CCl₄ vapour). Two versions of the exit part of the furnace are described for coupling to an ICP source; one of them has been used for the determination of titanium in alumina (spectrometric detection). Standardization with solution standards for solid sample analysis was unsuccessful. Based on the analytical curve obtained with variable amounts of solid standards (5–20 mg), a detection limit of 0.32 g/g Ti was found for 20 mg alumina.