红外吸收光谱法测定钒铝合金中的碳和硫

通过工作曲线法、增量法、回收率实验、重复性实验等研究,验证了红外吸收光谱法测定钒铝合金中碳、硫结果的准确度,从而确立了无标准样品情况下测定钒铝合金中碳、硫的红外吸收光谱分析方法。通过测定标准样品并与实际值对照得知方法准确度高,误差小,实用性强。     

脉冲加热-红外吸收光谱法测定钒铝合金中氢

对脉冲加热-红外吸收法测定钒铝合金中氢的分析方法进行了研究。通过实验对分析功率、称样量和校正标样等测试条件进行了讨论。实验表明钒铝合金中的氢易释放,对于AlV85样品中氢,热提取法和熔融法测定结果一致;但AlV50样品中氢,热提取法的结果略高于熔融法,故实验中选用热提取法测定钒铝合金中氢量。热提取法用0.75g金属锡作助熔剂,于4.0kW分析功率条件下测定钛标准样品中氢来确定氢工作曲线的校正系数,在1.5kW分析功率下测定钒铝合金中氢,测定结果与高频感应-热导法(用5g钢标准样品对氢的测定进行校正)结果吻合。对3个钒铝合金中氢量进行了测定,结果的相对标准偏差为2.2%～6.5%(n=8)。     

Simultaneous spectrophotometric determination of iron and vanadium by H-point standard addition method and partial least squares regression in micellar medium

Simultaneous determination of total iron and vanadium by H-point standard addition method (HPSAM) and partial least squares (PLS) is described. Gallic acid (GA) in a cationic micellar solution of CTAB was used for determination of iron and vanadium in different oxidation states at pH 5. The presence of a micellar system enables total iron and vanadium to be determined with improved sensitivities. The total relative standard error for applying the PLS method to 15 synthetic samples in the ranges 0.20–15.00 μg ml⁻¹ iron and 0.20–8.00 μg ml⁻¹ vanadium was 2.2%. The results of applying the H-point standard addition method showed that iron and vanadium can be determined simultaneously with the concentration ratios of iron to vanadium from 10:1 to 1:20 in the mixed sample. Both HPSAM and PLS methods showed suitable abilities to resolve accurately overlapped absorption spectra of the compounds. Both proposed methods were successfully applied to the determination of Fe and V in several synthetic alloy solutions.     

Rapid determination of indium,nickel and copper in NBS standard reference material by substoichiometric radioactivation analysis

A method of rapid determination for indium, nickel and copper in Spinach (NBS; SRM-1570) by substoichiometric radioactivation analysis is described. The method is based on the principle that an equal amount of non-irradiated test sample is added to the irradiated standard sample and subsequent substoichiometric extraction for the irradiated test and standard samples is carried out. Indium is extracted as diethyldithiocarbamate into carbon tetrachloride, nickel as dimethylglyoximate into chloroform and copper as dithizonate into carbon tetrachloride. The radioactivities of these extracts are measured by NaI(Tl) or Ge(Li) detector coupled with pulse-height analyser. The analytical results obtained by the method were in good agreement with our published values and certified values by NBS.     

The determination by radioactivation of the oxygen content of powdered metals with particular reference to beryllium

A radioactivation method for the determination of oxygen in beryllium metal powder is described. The sample, mixed with, lithium fluoride, is irradiated in the Harwell Pile, fluorine-18 chemically separated and its activity compared with that from standards similarly treated.The method has given reproducible results in reasonable agreement with those obtained by several other methods which were being investigated simultaneously.     

石墨炉原子吸收法测定钢铁及合金中微量钒

探讨了石墨炉子吸收法测定钢铁及合金中微量钒的各种实验条件及影响因素。实验表明，采用热解涂层管与光控升温相结合并在温度稳定的情况下原子化，可改善信号峰形，提高灵敏度，消除记忆效应。方法用于钢铁及合金中钒的分析，结果令人满意。     

An atomic absorption method for continuous analytical monitoring of metal and alloy refining processes

Atomic absorption spectrometry is discussed as a method of measurement for the investigation and continuous analytical monitoring of metal and alloy refining processes by electron beam melting. The theoretical dependence of the absorbance on the density of the atom flow of the component under investigation emanating from the melt surface is derived. In addition, the paper describes the use of this method for the continuous determination of the iron content in a vanadium melt and measurements of the evaporation rate of iron and its thermodynamic activity in the vanadium melt at high temperature.     

Quantitative LIBS analysis of vanadium in samples of hexagonal mesoporous silica catalysts

The method for the analysis of vanadium in hexagonal mesoporous silica (V-HMS) catalysts using Laser Induced Breakdown Spectrometry (LIBS) was suggested. Commercially available LIBS spectrometer was calibrated with the aid of authentic V-HMS samples previously analyzed by ICP OES after microwave digestion. Deposition of the sample on the surface of adhesive tape was adopted as a sample preparation method. Strong matrix effect connected with the catalyst preparation technique (1st vanadium added in the process of HMS synthesis, 2nd already synthesised silica matrix was impregnated by vanadium) was observed. The concentration range of V in the set of nine calibration standards was 1.3-4.5% (w/w). Limit of detection was 0.13% (w/w) and it was calculated as a triple standard deviation from five replicated determinations of vanadium in the real sample with a very low vanadium concentration. Comparable results of LIBS and ED XRF were obtained if the same set of standards was used for calibration of both methods and vanadium was measured in the same type of real samples. LIBS calibration constructed using V-HMS-impregnated samples failed for measuring of V-HMS-synthesized samples. LIBS measurements seem to be strongly influenced with different chemical forms of vanadium in impregnated and synthesised samples. The combination of LIBS and ED XRF is able to provide new information about measured samples (in our case for example about procedure of catalyst preparation).     

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.     

Application of HPLC to measure vanadium in environmental,biological and clinical matrices

Vanadate and vanadium compounds exist in many environmental, biological and clinical matrices, and despite the need only limited progress has been made on the analysis of vanadium compounds. The vanadium coordination chemistry of different oxidation states is known, and the result of the characterization and speciation analysis depends on the subsequent chemistry and the methods of analysis. Many studies have used a range of methods for the characterization and determination of metal ions in a variety of materials. One successful technique is high performance liquid chromatography (HPLC) that has been used mainly for measuring total vanadium level and metal speciation. Some cases have been reported where complexes of different oxidation states of vanadium have been separated by HPLC. Specifically reversed phase (RP) HPLC has frequently been used for the measurement of vanadium. Other HPLC methods such as normal phase, anion-exchange, cation-exchange, size exclusion and other RP-HPLC modes such as, ion-pair and micellar have been used to separate selected vanadium compounds. We will present a review that summarizes and critically analyzes the reported methods for analysis of vanadium salts and vanadium compounds in different sample matrices. We will compare various HPLC methods and modes including sample preparation, chelating reagents, mobile phase and detection methods. The comparison will allow us to identify the best analytical HPLC method and mode for measuring vanadium levels and what information such methods provide with regard to speciation and quantitation of the vanadium compounds.     

Trends in speciation analysis of vanadium in environmental samples and biological fluids--a review

A comprehensive review is presented addressing recent trends in the speciation and determination of vanadium in environmental and biological sample matrices, including important analytical aspects such as sample clean up, pre-concentration and method development. Methodology based on both separation and spectroscopic techniques for the determination of vanadium speciation is discussed. A brief outline of analytical principles, together with an overview of the recent developments and applications of vanadium speciation determination is included. The newer methods for detecting metal ions including hyphenated spectroscopic techniques and sample preparation schemes are also discussed.     

Simultaneous determination of trace uranium and vanadium in biological samples by radiochemical neutron activation analysis

Summary A radiochemical neutron activation analysis (RNAA) for simultaneous determination of uranium and vanadium in a single sample at trace levels is described. The method is based on post-irradiation wet-ashing and solvent extraction of vanadium with N-benzoyl-N-phenyl-hydroxylamine reagent. From the remaining aqueous phase, uranium is extracted into a toluene solution of tri-n-butyl phosphate. The chemical yields are determined spectrophotometrically for vanadium and by gamma-counting of the added natural uranium carrier for uranium. The method was evaluated by the analysis of reference materials and the results showed a good agreement with the certified values. The method was applied to the determination of vanadium and uranium in five military total diet samples in Slovenia.     

Determination of elements in lithium potassium niobate and lithium niobate containing vanadium by ICP-AES

The elements in lithium potassium niobate and lithium niobate containing vanadium (such as aluminum, lithium, niobium, potassium and vanadium) were determined by inductively coupled plasma atomic emission spectrometry after fusion of the sample with ammonium hydrogensulfate. The samples were completely decomposed and high precision results were obtained for the metallic elements. Oxygen has been determined by a helium carrier fusion thermal conductivity method using both a nickel capsule and tin as a melting flux in a graphite crucible.     

A rapid and selective method for direct gravimetric determination of vanadium(V) and its application to alloy steel and some rocks

N-o-Iodobenzoyl-o-tolyhydroxylamine has been synthesized and used as gravimetric reagent for direct determination of vanadium(V). The complex dried at 105-120 degrees has the definite composition VO(C(14)H(11)O(2)NI)(2)Cl. The method is simple, rapid, sensitive and selective and gives results reproducible within 0.1%. Precipitation is quantitative at room temperature over a wide range of acidity. The method is satisfactory for alloy steels and some rocks. The very low conversion factor (0.0632) is favourable for determining very small amounts of vanadium.     

电感耦合等离子体原子发射光谱（ICP-AES）法测定铁矿石中钒

建立了电感耦合等离子体原子发射光谱(ICP-AES)法测定铁矿石中钒含量的分析方法。采用盐酸、硝酸、氢氟酸、高氯酸分解试样,不溶物残渣碱熔融回收,稀盐酸溶解盐类的方式对样品进行分解。对仪器的主要工作参数和分析谱线进行了选择,讨论了基体和共存元素的干扰,以及溶解酸和熔剂等条件实验,确立了最佳分析条件。按实验方法对铁矿石标准样品和试样中钒量进行测定,测定值与标准值或其它方法的认定值基本一致,相对标准偏差RSD<6.5%。     

Effect of burn-up on the radioactivation behavior of cladding hull materials studied using the ORIGEN-S code

The effect of fuel burn-up on the radioactivation behavior of cladding hull materials was investigated using the ORIGEN-S code for various materials of Zircaloy-4, Zirlo, HANA-4, and HANA-6 and for various fuel burn-ups of 30, 45, 60, and 75 GWD/MTU. The Zircaloy-4 material is the only one that does not contain Nb as an alloy constituent, and it was revealed that ¹²⁵Sb, ^125mTe, and ⁵⁵Fe are the major sources of radioactivity. On the other hand, ^93mNb was identified as the most radioactive nuclide for the other materials although minor radioactive nuclides varied owing to their different initial constituents. The radioactivity of ⁹⁴Nb was of particular focus owing to its acceptance limit against a Korean intermediate-/low-level waste repository. The radioactivation calculation results revealed that only Zircaloy-4 is acceptable for the Korean repository, while the other materials required at least 4,900 of Nb decontamination factor owing to the high radioactivity of ⁹⁴Nb regardless of the fuel burn-up. A discussion was also made on the feasibility of Zr recovery methods (chlorination and electrorefining) for selective recovery of Zr so that it can be disposed of in the Korean repository.     

A modified catalytic-photometric method for the determination of vanadium in chloride rich hydro-geochemical samples

The vanadium content in chloride rich hydrogeochemical samples has been determined through a modification in the existing standard gallic acid oxidation method which has severe interference problem from halides. The modification incorporates a preliminary fume-drying of the sample aliquot with a mixture of perchloric and sulphuric acids. This ensures total removal of halides and hence their interference. The estimation is completed as per the standard method after taking the sample in 10 ml of 1% nitric acid. Also mercuric nitrate addition which forms a part of the standard procedure to prevent halide interference, is also dispensed with keeping in view the toxic nature of mercury. The method has been tried on a number of samples having varying chloride content. The results obtained compare well with the standard PAR method. The method can be used to determine vanadium down to 1 ppb. The relative standard deviation obtained for vanadium contents in the range 400–10 ppb is in the range 4–8.2%.     

Determination of vanadium in water by atomic absorption spectrometry with electrothermal atomization and using hot injection and preconcentration on the graphite tube

A sensitive method for the determination of vanadium in water by atomic absorption spectrometry with electrothermal atomization and using hot injection and preconcentration on the graphite tube is described. The water sample (200 μl) is added to the heated graphite tube in four portions over 200 s. Magnesium nitrate is used as matrix modifier. The precision, accuracy and interferences of the method were investigated. The method allows vanadium down to 0.27 μg l^?1 to be detected.     

Speciation analysis of plants in the determination of V(V) by ETAAS

Vanadium(IV) and vanadium(V) were easily separated from each other in the same plant sample and be determined independently by ETAAS (electrothermal atomic absorption spectrometry). This was achieved by treating the sample with 1 M (NH₄)₂HPO₄ which transfer only insoluble V(V) species into solution leaving V(IV) species in the solid part of the sample solution. V(IV) was then transferred into solution by ashing the precipitates and dissolving them in dilute acid. Statistical evaluations indicate that the sum of the concentrations of V(IV) and V(V) species is the same as the total concentration of vanadium determined by an independent method from the same plant sample at 95% level of confidence.

The maximum concentrations for V(V) and total vanadium in plants around the vanadium mine were found to be 24.3 and 350 μg g⁻¹, respectively.     

Pre-concentration and separation of vanadium on Amberlite IRA-904 resin functionalized with porphyrin ligands

Among several methods, enrichment techniques based on sorption onto chelating resins seem convenient, rapid and capable to achieve a high concentration factor. Amberlite IRA-904 resin modified with tetrakis (p-carboxyphenyl) porphyrin (TCPP) was used to pre-concentrate vanadium species. Several parameters, such as sorption capacity of the chelating resin, pH for retention of V(IV) and V(V), volume of sample and eluent, were evaluated. Both vanadium species sorbed on TCPP-modified resin were eluted by use of 2 M nitric acid and determined by atomic absorption spectrometry. The recovery values were >94% and pre-concentration factor of 110 was obtained. For speciation studies, CDTA was added to the sample for complexing vanadium(IV), which was not retained on the microcolumn. The proposed method was examined for reference standard material (TM-25.2) and river water sample.