scholarly journals Mass spectrometric investigation and electrode properties of the chalcogenide films MnCl2-GeS2-Ga2S3 and MnS-GeS2-Ga2S3, obtained by chemical deposition

2020 ◽  
Author(s):  
Д.Л. Байдаков ◽  
Е.В. Колужникова ◽  
Н.В. Михайлова
Keyword(s):  
Mass Spectrum ◽  
Detection Limit ◽  
Chalcogenide Glasses ◽  
Mass Spectra ◽  
Manganese Content ◽  
Mass Spectrometric ◽  
Exchange Reactions ◽  
Chloride System ◽  
Helium Atmosphere ◽  
Chalcogenide Films

Методом химического нанесения из растворов халькогенидных стекол в н-бутиламине получены пленки MnCl2GeS2Ga2S3 и MnSGeS2Ga2S3, исследованы масс-спектрометрические характеристики и изучены электродные свойства пленок. Нанесение халькогенидных пленок осуществляли согласно методике, подробно описанной в Байдаков, Виграненко, 2019. Магнитную восприимчивость в области температур 90293 К исследовали на установке, подробно описанной в Тверьянович, 1978. Измерения проводили в гелиевой атмосфере в режиме дискретного нагревания с термостабилизацией каждой ступени в течение 20 мин Байдакова, 1989. Для регистрации масс-спектров использовали времяпролетный масс-спектрометр типа масс-рефлектрон с разрешающей способностью на половине высоты пика в области массового числа 500 а.е.м., равной 5000. Описание прибора и условия эксперимента приведены в работе Каратаев, Любин, 1988. Ионизацию паров изучаемых образцов осуществляли в источнике ионов с электронным ударом. Обзорные масс-спектры наблюдали в диапазоне энергий 750 эВ. Остаточное давление в камере анализатора составляло 2,7.105 Па. Изготовление электродов на основе мембран халькогенидных пленок и методика электродных измерений подробно описаны в работе Baidakov, Shkolnikov, 2019. Для пленок MnSGeS2Ga2S3 наблюдается значительный рост с увеличением содержания марганца. В сульфидной системе величина 150 К (х 0,25), что свидетельствует о формировании фазы, обогащенной марганцем. Для пленок MnCl2-GeS2-Ga2S3 значение 30 К (х 0,20). С увеличением содержания марганца в хлоридной системе наблюдается рост абсолютной величины константы Вейсса. Из результатов магнитостатического исследования сделано предположение о наличии реакций обмена в пленках MnCl2GeS2Ga2S3. Масс-спектр пленок MnSGeS2Ga2S3 обусловлен диссоциацией трехкомпонентных марганецсодержащих структурных единиц, которым соответствуют соединения состава Mn2GeS4, MnGa2S4, Mn2Ga2S5, Mn3Ga2S6. Наличие спектра пара пленок MnCl2GeS2Ga2S3 только при температурах, превышающих 180 С, существенно отличающегося по составу от исходных пленок, указывает на то, что исходный спектр хлоридной системы обусловлен диссоциацией сульфида германия. Присутствие в масс-спектре фрагментов хлорида германия при 250 С указывает на его наличие в исходных пленках. Это, по-видимому, связано с обменными реакциями в системе MnCl2GeS2Ga2S3. Электроды с пленочными мембранами MnCl2GeS2Ga2S3 показали высокую чувствительность и низкий предел обнаружения катионов Mn2. Нернстовская область электродного отклика лежит в пределах 101106 моль/л нитрата марганца, предел обнаружения достигает 107 моль/л. Электродные свойства халькогенидных стекол и пленок аналогичного состава практически не отличаются. Chalcogenide films MnCl2GeS2Ga2S3 and MnSGeS2Ga2S3 were synthesized from the solutions of chalcogenide glasses in n-butylamine. The mass spectrometric characteristics and electrode properties of films were studied. The application of chalcogenide films was carried out according to the procedure described in detail in Baidakov, Vigranenko, 2019. The magnetic susceptibility in the temperature range 90293 K was studied using a setup described in detail in Tveryanovich, 1978. The measurements were carried out in a helium atmosphere in the mode of discrete heating with thermal stabilization of each stage for 20 min Baidakova, 1989. To record the mass spectra, we used a time-of-flight mass spectrometer of the mass-reflectron type with a resolution at half the peak height in the region of the mass number of 500 amu equal to 5000. A description of the device and experimental conditions are given in Karataev, Lyubin, 1988. Ionization of the vapors of the samples under study was carried out in a source of ions with electron impact. Survey mass spectra were observed in the energy range of 750 eV. The residual pressure in the analyzer chamber was 2,7-105 Pa. The manufacture of electrodes based on chalcogenide film membranes and the method of electrode measurements are described in detail in Baidakov, Shkolnikov, 2019. For MnS-GeS2-Ga2S3 films, a significant increase in with increasing manganese content. In the sulfide system, the quantity 150 K (x 0.25), which indicates the formation of a phase enriched in manganese. For MnCl2GeS2Ga2S3 films, the value 30 K (x 0.20). With an increase in the manganese content in the chloride system, an increase in the absolute value of the Weiss constant is observed. From the results of the magnetostatic study, an assumption was made about the presence of exchange reactions in MnCl2GeS2Ga2S3 films. The mass spectrum of MnSGeS2Ga2S3 films is due to the dissociation of three-component manganese-containing structural units, which correspond to compounds of the composition Mn2GeS4, MnGa2S4, Mn2Ga2S5, Mn3Ga2S6. The presence of the vapor spectrum of MnCl2GeS2Ga2S3 films only at temperatures exceeding 180 C and significantly differing in composition from the starting films indicates that the initial spectrum of the chloride system is due to the dissociation of germanium sulfide. The presence of germanium chloride fragments in the mass spectrum at 250 C indicates its presence in the starting films. This, apparently, is associated with exchange reactions in the MnCl2GeS2Ga2S3 system. MnCl2GeS2Ga2S3 film membrane electrodes showed high sensitivity and low detection limit of Mn2 cations. The Nernst region of the electrode response lies within 101106 mol/l of manganese nitrate, the detection limit reaches 107 mol/l. The electrode properties of chalcogenide glasses and films of a similar composition practically do not differ.

A device for controlling the energy of ionizing electrons in the low-energy range designed to form a complete mass spectrum of negative ions using a quadrupole mass spectrometer

2020 ◽  
Vol 86 (4) ◽  
pp. 12-20
Author(s):  
A. G. Terentyev ◽  
R. V. Khatymov ◽  
A. V. Maltsev
Keyword(s):  
Mass Spectrum ◽  
Energy Range ◽  
Electron Energy ◽  
Mass Spectrometer ◽  
Mass Spectra ◽  
Negative Ions ◽  
Mass Spectrometric ◽  
Low Energy ◽  
Quadrupole Mass ◽  
Positive Ions

Operation with positive ions formed from the impact of high energy electrons (usually 70 eV, which exceeds the ionization energy of the molecules) is a standard mode for mass spectrometric detectors of most gas chromatography-mass spectrometric complexes (GC/MS) in the basic configuration. At the same time, we have shown that the option of setting the energy of ionizing electrons (maintained in the design of some serial devices) within the pre-ionization region also allows one to obtain mass spectra of negative ions (NI) which, in turn, significantly expands the analytical potential of standard equipment. The formation of NI occurs in the low-energy range of 0 – 15 eV due to resonant capture of electrons by molecules (REC). In contrast to positive ions, the intensity of NI formation sharply (resonantly) depends on the electron energy and this dependence is characteristic of each chemical compound. Both the relative intensity of the mass-peaks and, in general, the ionic composition of the formed mass spectrum of NI significantly depend on the electron energy. The problem of choosing the optimal energy of ionizing electrons providing the same efficiency of mass-spectrometric determination of all components of complex mixtures of dissimilar compounds is also associated with the features of negative ion formation during chromatography-mass spectrometric analysis. To address the problem, we propose a technique providing generation of complete (in NI composition and intensities) mass spectra of NI through repeated variation of the energy of ionizing electrons in a given range of 0 – 10 eV. Technical implementation of the technique [1] was carried out at the Design Bureau «Chromatec «(Yoshkar Ola, Russia) in the form of a special electronic device, which was tested in pilot operation as part of the gas chromatograph complex with a quadrupole mass spectrometer «Chromatec». We describe the principle of operation of the device and present the results of tests.

scholarly journals Electrical conductivity and electrode properties of the chalcogenide films PbS-AgI-As2S3, PbS-Ag2S-As2S3 and PbI2-Ag2S-As2S3 obtained by chemical deposition

2019 ◽  
Author(s):  
Д.Л. Байдаков ◽  
Ю.Т. Виграненко
Keyword(s):  
Electrical Conductivity ◽  
Detection Limit ◽  
Chalcogenide Glasses ◽  
Lead Nitrate ◽  
Chemical Deposition ◽  
High Sensitivity ◽  
Nitrogen Atmosphere ◽  
Similar Composition ◽  
Chalcogenide Films ◽  
Electrode Response

Методом химического нанесения из растворов халькогенидных стекол в н-бутиламине получены халькогенидные пленки PbS-AgI-As2S3, PbS-Ag2S-As2S3 и PbI2-Ag2S-As2S3, изучена электропроводность и электродные свойства стекол и пленок аналогичного состава. Синтез стекол проводили согласно методике, описанной в [Легин, 1985]. Пленки наносили по следующей методике. Навеску стекла помещали в кипящий н-бутиламин, затем перемешивали в течение 3–4 ч до полного растворения стекла в амине. Для предотвращения окисления кислородом воздуха пленки наносили в закрытом боксе в атмосфере азота. Подложку помещали на устройство для вращения, наносили на нее раствор, а затем вращали подложку со скоростью 3000–4000 об/мин в течение 1 мин. Отжиг пленок проводили в боксе при температуре 90–100 С в течение 30–60 мин. Исследована электропроводность халькогенидных пленок PbS-AgI-As2S3, PbS-Ag2S-As2S3 и PbI2-Ag2S-As2S3. Величина электропроводности составляет 10–14–10–4 Ом.см–1. Установлено, что значения электропроводности стекол и пленок аналогичного состава практически не отличаются. Электроды с пленочными мембранами PbS- Ag2S-As2S3 и PbI2-Ag2S-As2S3 показали высокую чувствительность к катионам Pb2+. Нернстовская область электродного отклика лежит в пределах 10–2–10–6 моль/л нитрата свинца, предел обнаружения достигает 10–7 моль/л. Тонкопленочные электроды с мембранами PbS-AgI-As2S3 продемонстрировали достаточно высокую чувствительность к катионам Ag+. Нернстовская область электродного отклика составляет 10–1–10–6 моль/л AgNO3, предел обнаружения катионов серебра достигает 10–7 моль/л. Электродные свойства халькогенидных стекол и пленок аналогичного состава практически не отличаются. Chalcogenide films PbS-AgI-As2S3, PbS-Ag2S-As2S3 and PbI2-Ag2S-As2S3, were synthesized from the solutions of chalcogenide glasses in n-butylamine. The electrical conductivity and electrode properties of glasses and films of the same compositions were studied. The synthesis of glasses was carried out according to the procedure described in [Legin, 1985]. The films were prepared as follows. The sample of the glass was placed in boiling n-butylamine, then stirred for 3–4 hours until the glass was completely dissolved in the amine. To prevent oxidation by air oxygen, the films were applied in a closed box under a nitrogen atmosphere. The substrate was placed on a rotating device, a solution was applied thereto, and then the substrate was rotated at a speed of 3000–4000 rpm for 1 minute. Annealing of the films was carried out in the box at a temperature of 90–100 C for 30–60 min. Electrodes with membranes PbS-Ag2S-As2S3 and PbI2-Ag2S-As2S3 showed high sensitivity to cations Pb2+. The Nernst region of the electrode response lies in the range 10–2–10–6 mol/l lead nitrate, and the detection limit reaches 10–7 mol/l. Thin film electrodes with PbS-AgI-As2S3 membranes showed a fairly high sensitivity to the Ag+ cations. The Nernst region of the electrode response is 10–1–10–6 mol/l silver nitrate, the detection limit of Ag+ cations reaches 10–7 mol/l. It has been established that the electrode properties of chalcogenide glasses and films of similar composition are practically the same.

The diffusion coefficients 110mAg isotope in copper-contained chalcogenide films obtained by chemical deposition

2016 ◽  
Author(s):  
Д.Л. Байдаков
Keyword(s):  
Diffusion Coefficients ◽  
Chalcogenide Glasses ◽  
Film Formation ◽  
Polymer Network ◽  
Chemical Deposition ◽  
Film Deposition ◽  
Constant Current ◽  
Residual Pressure ◽  
Quartz Ampoule ◽  
Chalcogenide Films

Методом химического нанесения из растворов халькогенидных стекол в н-бутиламине получены многокомпонентные халькогенидные пленки CuI-As2Se3, CuI-PbI2-As2Se3, CuI-SbI3-As2Se3, CuI-SbI3-PbI2-As2Se3. Синтез многокомпонентных медьсодержащих халькогенидных стекол, использовавшихся для нанесения пленок, проводили методом вакуумной плавки в кварцевых ампулах при температуре 400…950 °С и остаточном давлении не более 0,13 Па. Закалку стекол производили от 600 °С в воду со льдом с разливом расплава в ампуле. Навеску стекла размельчали в порошок и кипятили в н-бутиламине до полного растворения. Для предотвращения процессов окисления, нанесение и отжиг пленок проводили в атмосфере химически инертного азота. Подложку помещали на устройство для вращения, наносили на нее раствор и вращали подложку со скоростью несколько тысяч оборотов в минуту. Отжиг пленок проводили при температуре 100 °С в течение 1 ч. Измерение электропроводности полученных пленок проводили на постоянном и переменном токе в зависимости от значений электропроводности в температурном интервале 20…100 °С. Измерение коэффициентов диффузии проводили абсорбционным методом. Из диффузионных экспериментов определены значения коэффициентов диффузии катионов изотопа 110mAg в медьсодержащих халькогенидных пленках. Установлено, что значения коэффициентов диффузии ионов Ag+ в химически нанесенных пленках и исходных стеклах практически не различаются. Аналогию значений коэффициентов диффузии изотопа 110mAg в халькогенидных стеклах и пленках на их основе можно объяснить сохранением полимерной сетки связей халькогенидных стекол при их растворении в органических основаниях (аминах). В процессе нанесения и формирования пленок полимерная (макромолекулярная) структура раствора халькогенидных стекол сохраняется. The method of chemical deposition from solutions of chalcogenide glasses in n-butyl amine obtained multicomponent chalcogenide films CuI-As2Se3, CuI-PbI2-As2Se3, CuI-SbI3-As2Se3, CuI-SbI3-PbI2-As2Se3. Synthesis of copper multicomponent chalcogenide glasses, used for film deposition was carried out by vacuum melting in quartz ampoule at a temperature of 400…950 °C and a residual pressure of not more than 0.13 Pa. The temperature of glass produced from the 600 °C to the ice water spill of the melt in the ampoule. Weigh glass comminuted to a powder and heated in n-butylamine until complete dissolution. To prevent oxidation, deposition and annealing of the films was carried out in an atmosphere of nitrogen chemically inert. The substrate is placed on a device for rotating, it was applied to the solution and the substrate was rotated at a speed of several thousand revolutions per minute. Annealing of the films was carried out at 100 °C for 1 hour. Measurement of the electrical conductivity of the obtained films was conducted at a constant current and variable depending on the conductivity values ​​in the temperature range from 20 to 100 °C. Measurement of diffusion coefficients was performed according to the absorption method. From diffusion experiments, the values ​​of the diffusion coefficients 110mAg isotope cations in copper chalcogenide films. It was found that the values ​​of the diffusion coefficients of the ions Ag+ in a chemically deposited films and the original glasses are indistinguishable. The analogy of the diffusion coefficient values ​​110mAg isotope in chalcogenide glasses and films based on them can be attributed to the preservation of the polymer network connections chalcogenide glasses when dissolved in organic bases (amines). During application and film formation the polymer (macromolecular) structure of chalcogenide glasses of the solution is maintained.

scholarly journals Mass Spectrometric Studies on Organic Selenium-Oxygen Compounds. 2. Mass Spectra of Diphenyl Selenoxide and 4,4'-Dimethyl-diphenyl Selenoxide.

1970 ◽  
Vol 24 ◽  
pp. 717-719 ◽  
Author(s):  
Erik Rebane ◽  
Kjell-Ivar Dahlqvist ◽  
Sture Forsén ◽  
Ulf Ragnarsson ◽  
S. E. Rasmussen ◽  
...  
Keyword(s):  
Mass Spectra ◽  
Mass Spectrometric ◽  
Organic Selenium

scholarly journals Mass Spectrometric Studies on Organic Selenium-Oxygen Compounds. 1. Mass Spectra of Methyl p-Chlorobenzene Selenonate and Methyl p-Bromobenzene Selenonate.

1969 ◽  
Vol 23 ◽  
pp. 1817-1819 ◽  
Author(s):  
Erik Rebane ◽  
P. Jakobsen ◽  
Ch. Larsen ◽  
P. H. Nielsen ◽  
Per-Erik Werner ◽  
...  
Keyword(s):  
Mass Spectra ◽  
Mass Spectrometric ◽  
Organic Selenium

scholarly journals On Mass Spectra of Primordial Black Holes

2021 ◽  
Vol 8 ◽  
Author(s):  
Alexander A. Kirillov ◽  
Sergey G. Rubin
Keyword(s):  
Black Holes ◽  
Mass Spectrum ◽  
Mass Spectra ◽  
Scalar Fields ◽  
Small Mass ◽  
Primordial Black Holes ◽  
Classical Motion ◽  
Multiple Production ◽  
Analytical Formulas ◽  
Intrinsic Feature

Evidence for the primordial black holes (PBH) presence in the early Universe renews permanently. New limits on their mass spectrum challenge existing models of PBH formation. One of the known models is based on the closed walls collapse after the inflationary epoch. Its intrinsic feature is the multiple production of small mass PBH which might contradict observations in the nearest future. We show that the mechanism of walls collapse can be applied to produce substantially different PBH mass spectra if one takes into account the classical motion of scalar fields together with their quantum fluctuations at the inflationary stage. Analytical formulas have been developed that contain both quantum and classical contributions.

Mass-spectrometric studies. I. Benzo[b]thiophen, some alkyl and aryl derivatives, and the 1,1-dioxide and 2,3-dihydro-1,1-dioxide

1967 ◽  
Vol 20 (1) ◽  
pp. 103 ◽  
Author(s):  
QN Porter
Keyword(s):  
High Resolution ◽  
Mass Spectra ◽  
Mass Spectrometric ◽  
High Resolution Mass ◽  
Resolution Mass

The high-resolution mass spectra of benzo[b]thiophen, some alkyl and aryl derivatives, and the sulphone and 2,3-dihydrosulphone have been obtained; compositions of all significant ions in the spectra have been determined. Fragmentations of the unoxidized compounds are dominated by losses of C2H2 and CS units, while the sulphones undergo initial isomerization to cyclic sulphinates followed by expulsion of SO and fragments containing a C-O bond. Structures have been suggested for most of the ions observed.

scholarly journals Spectrometric Study of the Nitrile-Ketenimine Tautomerism

2009 ◽  
Vol 2009 ◽  
pp. 1-18 ◽  
Author(s):  
Hebe Saraví Cisneros ◽  
Sergio Laurella ◽  
Danila L. Ruiz ◽  
Agustín Ponzinibbio ◽  
Patricia E. Allegretti ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Nuclear Magnetic Resonance ◽  
Mass Spectrum ◽  
Magnetic Resonance ◽  
Mass Spectra ◽  
Spectrometric Study ◽  
Mass Spectral ◽  
Ion Fragmentation ◽  
Nuclear Magnetic Resonance Spectra ◽  
Amination Product

Mass spectrometry is used to evaluate the occurrence of the nitrile-ketenimine tautomerism. Mass spectra of two differently substituted nitriles, ethyl-4,4-dicyano-3-methyl-3-butenoate and diethyl-2-cyano-3-methyl-2-pentenodiate are examined looking for common mass spectral behaviors. Ion fragmentation assignments for specific tautomers allow to predict the presence of the corresponding structures. Additionally, the mass spectrum and nuclear magnetic resonance spectra of ethyl-4,4-dicyano-2,2-diethyl-3-methyl-3-butenoate and that of the corresponding amination product support the occurrence of the ketenimine tautomer in the equilibrium.

Gas-Liquid Chromatographic-Mass Spectrometric Confirmation of Endosulfan and Endosulfan Sulfate in Apples and Carrots

1981 ◽  
Vol 64 (5) ◽  
pp. 1208-1210
Author(s):  
Perry S Wilkes
Keyword(s):  
Mass Spectra ◽  
Chemical Ionization ◽  
Mass Range ◽  
Mass Spectrometric ◽  
Chromatographic Retention ◽  
Gas Liquid Chromatography ◽  
Endosulfan Sulfate ◽  
Gasliquid Chromatography ◽  
Liquid Chromatographic ◽  
Chromatographic Mass

Abstract A gas-liquid chromatography-mass spectrometric (GLC-MS) procedure is described for the confirmation of endosulfan I, endosulfan II, and endosulfan sulfate in apples and carrots. After extraction, cleanup, and determination by electron capture gasliquid chromatography using current AOAC methodology, residues are confirmed by GLC-MS. The chemical ionization (CI) mode is used with methane as a reagent gas. Each residue is confirmed by a scan of only 4 regions of its mass spectrum rather than the full mass range. The 4 mass regions for the 2 endosulfan isomers are 274-280, 340-346, 368-374, and 404-412 atomic mass units (amu). For endosulfan sulfate, the mass regions are 286-294, 322-330, 384-392, and 420-428 amu. Four ions and their chlorine isotopic distributions are detected for each compound by this scanning technique. This method was developed by using carrots and apples to which had been added 0.1 ppm (50% of the current legal tolerance on carrots) of each of the 3 pesticides. The gas chromatographic retention times and the mass spectra of the 4 mass regions specified for the 3 pesticides were compared to those of reference standards injected under identical GLC-MS conditions and were used as the basis for confirming identity of the 3 compounds.

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