Nanostructural deactivating agents selective to caesium
The chemical reactivity of nanostructural clinoptilolite and γ-hematite which have highly selective for ¹³²Cs sorption from polyethylene surface and for liquid environments are studied. There are different components besides clinoptilolite and γ-hematite were chosen to examine as model of deactivati...
Gespeichert in:
| Veröffentlicht in: | Вопросы атомной науки и техники |
|---|---|
| Datum: | 2011 |
| Hauptverfasser: | , , , , , , , , |
| Format: | Artikel |
| Sprache: | Englisch |
| Veröffentlicht: |
Національний науковий центр «Харківський фізико-технічний інститут» НАН України
2011
|
| Schlagworte: | |
| Online Zugang: | https://nasplib.isofts.kiev.ua/handle/123456789/111132 |
| Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
| Назва журналу: | Digital Library of Periodicals of National Academy of Sciences of Ukraine |
| Zitieren: | Nanostructural deactivating agents selective to caesium / N.P. Dikiy1, A.N. Dovbnya, Yu.V. Lyashko, E.P. Medvedeva, D.V.Medvedev, V.L. Uvarov, I.D. Fedorets, N.P. Khlapova, D.S. Bakay // Вопросы атомной науки и техники. — 2011. — № 3. — С. 35-41. — Бібліогр.: 22 назв. — англ. |
Institution
Digital Library of Periodicals of National Academy of Sciences of Ukraine| _version_ | 1860109739994644480 |
|---|---|
| author | Dikiy, N.P. Dovbnya, A.N. Lyashko, Yu.V. Medvedeva, E.P. Medvedev, D.V. Uvarov, V.L. Fedorets, I.D. Khlapova, N.P. Bakay, D.S. |
| author_facet | Dikiy, N.P. Dovbnya, A.N. Lyashko, Yu.V. Medvedeva, E.P. Medvedev, D.V. Uvarov, V.L. Fedorets, I.D. Khlapova, N.P. Bakay, D.S. |
| citation_txt | Nanostructural deactivating agents selective to caesium / N.P. Dikiy1, A.N. Dovbnya, Yu.V. Lyashko, E.P. Medvedeva, D.V.Medvedev, V.L. Uvarov, I.D. Fedorets, N.P. Khlapova, D.S. Bakay // Вопросы атомной науки и техники. — 2011. — № 3. — С. 35-41. — Бібліогр.: 22 назв. — англ. |
| collection | DSpace DC |
| container_title | Вопросы атомной науки и техники |
| description | The chemical reactivity of nanostructural clinoptilolite and γ-hematite which have highly selective for ¹³²Cs sorption from polyethylene surface and for liquid environments are studied. There are different components besides clinoptilolite and γ-hematite were chosen to examine as model of deactivation agents for ¹³²Cs sorption. Photon activation analysis was used for study of element composition in samples of natural clinoptilolite and hematite. The chemiluminescence method was used for definition of chemical reactivity of iron-exchanged form of the clinoptilolite to produce hydroxyl radicals from H²O² (Fenton reaction). The formation of volatile compounds in process of ¹³²Cs sorption was detected . The deactivation agent on basic of thermomodified clinoptilolite with γ-hematite nanoparticles was shown the highly synergistic effect for ¹³²Cs sorption from polyethylene surface and for liquid system.
Досліджувалась хімічна реактивність природного кліноптилоліту та наночастинок γ-гематиту, які володіють високою здатністью до сорбції ¹³²Cs. У якості моделі дезактивуючого засобу для сорбції ¹³²Cs з поліетиленових поверхонь і водних розчинів, окрім клиноптилоліту та наночатинок γ-гематиту, були використані допоміжні стандартизовані речовини. Фотоактиваційний аналіз був використаний для вивчення домішкового складу зразків природного кліноптилоліту і активованого γ-гематиту. Квантометричний метод використовувався для визначення інтенсивності генерації вільнорадикальних продуктів при індукції пероксидом водню. Вимірювання за допомогою Ge(Li)-детектора залишкової активності ¹³²Cs в осадовій та рідкій фракціях дезактивуючих засобів виявило, що процес сорбції ¹³²Cs супроводжується утворенням летючих форм ¹³²Cs. Високий синергетичний ефект сорбції ¹³²Cs виявляється при умові, коли в складі дезактивуючого засобу присутні прирордний клиноптилоліт та наночастинки γ-гематиту.
Исследовалась химическая реактивность природного клиноптилолита и наночастиц γ-гематита, которые обладают высокой селективной сорбционной способностью в отношении ¹³²Cs. В качестве модели дезактивирующего средства для сорбции ¹³²Cs с полиэтиленовых поверхностей и водных растворов, помимо клиноптилолита и наночастиц γ-гематита, были использованы дополнительные (вспомогательные) компоненты. Фотоактивационный анализ был использован для изучения примесного состава образцов природного клиноптилолита и активированного γ-гематита. Квантометрический метод применялся для определения интенсивности генерации свободнорадикальных продуктов в присутствии перексида водорода (Fenton reaction). Измерение с помощью Ge(Li)-детектора остаточной активности ¹³²Cs в твердой и жидкой фракциях дезактивирующих средств показало, что процесс сорбции ¹³²Cs сопровождается образованием летучих форм ¹³²Cs. Высокий синергетический эффект сорбции ¹³²Cs показан с использованием дезактивирующего средства на основе наноструктурного термомодифицированного природного клиноптилолита и наночастиц γ-гематита.
|
| first_indexed | 2025-12-07T17:33:20Z |
| format | Article |
| fulltext |
NUCLEAR-PHYSICAL METHODS AND PROCESSING OF DATA
NANOSTRUCTURAL DEACTIVATING AGENTS
SELECTIVE TO CAESIUM
N.P. Dikiy1∗, A.N. Dovbnya1, Yu.V. Lyashko1, E.P. Medvedeva1,
D.V.Medvedev1,V.L.Uvarov1, I.D.Fedorets2, N.P.Khlapova2,D.S.Bakay2
1National Science Center ”Kharkov Institute of Physics and Technology”, 61108, Kharkov, Ukraine
2V.N. Karazin Kharkov National University, 61077, Kharkov, Ukraine
(Received April 7, 2011)
The chemical reactivity of nanostructural clinoptilolite and γ-hematite which have highly selective for 132Cs sorption
from polyethylene surface and for liquid environments are studied. There are different components besides clinop-
tilolite and γ-hematite were chosen to examine as model of deactivation agents for 132Cs sorption. Photon activation
analysis was used for study of element composition in samples of natural clinoptilolite and hematite. The chemilumi-
nescence method was used for definition of chemical reactivity of iron-exchanged form of the clinoptilolite to produce
hydroxyl radicals from H2O2 (Fenton reaction). The formation of volatile compounds in process of 132Cs sorption
was detected . The deactivation agent on basic of thermomodified clinoptilolite with γ-hematite nanoparticles was
shown the highly synergistic effect for 132Cs sorption from polyethylene surface and for liquid system.
PACS: 68.43.-h; 82.75.-z
1. INTRODUCTION
Accumulation and distribution of radioactive pollu-
tion in an environment demands production of ef-
fective sorption materials for radionuclide extraction.
The new sorbents should have high stability to leach-
ing and stability to long radiating influence. Vari-
ous sorption materials are already applied: natural
and synthetic sorbents, complex-formative, compos-
ite materials. Inorganic sorbents find the increas-
ing application for sorption of various kinds of pol-
lution. These sorbents have higher chemical and ra-
diation stability and show selectivity to the some ra-
dionuclides. For example, γ-Fe2O3 has high sorp-
tion ability in relation to uranium, plutonium, neptu-
nium, americium; phosphates Ca5(PO4)3(OH,F,Cl)
- to uranium, thorium, americium, etc. [1,2]. Be-
sides selectivity the sorption materials should provide
high speed of substance extraction. Kinetic charac-
teristics are determined by the nature and the form
sorption material (granulated, fine-dispersed, fibrous,
etc.) [3]. Such factors are necessary for taking into
account convenience and good value of used sorbents
for a choice of sorption material.
Zeolites are inorganic solids consisting of enclosed
regular cavities or channel of well-defined size and
shape, that are widely used in industry in separa-
tion processes, such as catalysts, and in nano-reactors
[4,5]. Clinoptilolite with ratio Si/Al> 4 is widely used
as natural sorbent [6]. Selectivity of ionic-exchange
properties of clinoptilolite is used for sorption of cae-
sium and strontium from radioactive waste on the
atomic power station, for removal from waste waters
NH4
+, and also for sorption from industrial emissions
of amines and heavy metals [7]. In many cases (in
medicine, atomic engineering, ecology and so forth)
clinoptilolite is suitable to application only in finely
divided condition, with the sizes of particles from sev-
eral units up to tens and hundreds of nanometer [8].
For example, new technology of membranous sorp-
tion for neutralization of liquid radioactive waste is
possible only with application crushed up to nanosize
of powder clinoptilolite.
Various applications of clinoptilolite are caused
by its structural features. Most remarkable of these
features is presence in its crystal skeleton of empti-
ness and the channels filled in natural clinoptilo-
lite by molecules of crystalline hydrate. The three-
dimensional crystal skeleton of clinoptilolite has legi-
ble sublayered structure and two-dimensional system
of channels with the aperture 0.3×0.76; 0.33×0.46
and 0.26×0.47 nm. Each atom of aluminium has one
outskeleton cation (Na+, K+, Ca2+, Mg2+, etc.) [9].
In many cases, activity outskeleton cations defines
possibility of practical use clinoptilolite (Fig.1). The
major factor of increase of cation activation is cor-
rect selection of conditions of preliminary processing
of a mineral before its application [10]. Interest about
nanoparticles is caused by a specific set of properties
which correspond to nanosize conditions. One of such
properties is multiple increase of surface to volume
[11]. Influence on cation activity of their size, charge,
density and distribution in porous structure, till now
remain not clear. The high efficiency of caesium sorp-
tion is detected in clinoptilolite after superficial
∗Corresponding author E-mail address: ndikiy@kipt.kharkov.ua
PROBLEMS OF ATOMIC SCIENCE AND TECHNOLOGY, 2011, N3.
Series: Nuclear Physics Investigations (55), p.35-41.
35
Fig.1. Distribution of cations in the clinoptilolite
channels
modification by nanoparticles of hematite [12,13].
In clinoptilolite there are 4 types of places of lo-
calization of the basic cations: M(1), M(2), M(3) and
M(4)[14-17]. The M(1) is in the channel A (Fig.1, a),
cation in this position is surrounded by two lattice
atoms of oxygen and five molecules of water. In places
of M(1) are located sodium and calcium cations, the
M(2) represents a place of cation localization in the
channel B with three lattice oxygen atoms and three
molecules of water. The cations of sodium and cal-
cium are located in this position, but population of
Na+ ions in M(1) is higher, than in M(2). M(3) -
places of localization in the channel C(b), located
along an axis a about the center of hexamerous rings.
These places basically are populated cations of potas-
sium and coordinated by six lattice atoms of oxygen
and three molecules of water. The position of M(3) is
located near to M(1). The M(4) places are located in
the channel A in the center of inversion. The ions of
magnesium are usually located in these places and are
connected with six molecules of water. Distribution
and coordination of potassium ions in clinoptilolite is
the factor determining thermal stability of zeolites of
heulandite group.
The purpose of the given work consisted of de-
velopment and approbation of deactivation agents on
a basis of thermomodified natural clinoptilolite and
nanohematite for caesium-132 sorption.
2. MATERIALS AND METHODS
Clinoptilolite (NaK)4Ca[Al6Si30O72]·24H2O of the
Sokirnitsky deposit (district ”Sargich”, Ukraine) and
nanohematite (Fe2O3) (Alta Aesar, Germany) have
been used. Optical properties and X-ray structural
analysis of the initial and irradiated samples were
investigated previously [18,19]. The size of clinop-
tilolite particle was of 110 nm, γ-hematite - 40 nm.
Preliminarily clinoptilolite has been reduced to frag-
ments in an agate mortar. For spherical particles of
clinoptilolite sedimentation speed V in a gravitational
field equals to:
V =
2g(ρ− ρo)r2
9η
,
where ρ, ρo - density of clinoptilolite particles and
water, accordingly, g-acceleration of free falling, r-
particle radius, η-dynamic viscosity of water.
Fig.2. Gamma spectrum clinoptilolite
The sedimentation in water (within 6 days) and
centrifugation at 1,2·104 turn/min. has been real-
ized for obtaining size 110 nm for clinoptilolite parti-
cles. The fraction of clinoptilolite nanoparticles has
equaled 110 nm.
High-temperature processing of clinoptilolite
nanopowder at 260oC has been executed. Pho-
ton activation analysis on the linear electron acce-
lerator (LAE) with E=22 MeV and I=500 µA has
been used for determination of impurity of sam-
36
ples. Spectra of γ-radiation have been detected by
means of Ge(Li)-detector, volume 50 cm3 with the
energy resolution 3.25 keV on line 60Co 1332 keV.
Ge(Li)-detector was equipped by three-layer (Pb-
Cu-Al) background protection. Fig.2 shows the
γ-spectrum of the irradiated sample of natural clinop-
tilolite (195 g). The intensity of γ-lines of the clinop-
tilolite radiation exceeds those of the background, as
well as those corresponding to 40K nuclide, and the
families of the 238U, 235U and 232Th. The content of
elements in the clinoptilolite was U - 2.75·10−6, Th -
1.06·10−5 and K - 2.49·10−2 g/g. These data are close
to the passport ones of the clinoptilolite from the
Sokirny deposit: Th - 1.2·10−5 and K - 2.45·10−2 g/g,
respectively. The capsulation of the clinoptilolite
samples allowed to prevent the leakage of radon. In
this case the constant intensity of γ-lines from the
228Ac and 40K radionuclides was observed. At the
same time the intensity of γ-lines from the 214Pb,
214Bi, 212Pb, 208Tl radionuclides increased and coin-
cided for the two latter radionuclides with the activity
of 228Ac. This result is accounted by the volatiliza-
tion from the open samples of 15...20% of the high
mobility radon. The content of Th and U in the
samples was approximately equal to the abundance
of these elements in the Earth crust (Th≈1.0·10−5
and U≈3.6·10−6 g/g) with their ratio (3.87) slightly
higher than the average one in the Earth crust (2.78).
The chemical compound and the trace element
content of clinoptilolite according to data of the
Sokirnitsky zeolitic factory of Ministry of Emer-
gency Situations of Ukraine are shown in Tabl.1.
Table.1 Chemical compound and the trace element
content of clinoptilolite
compound %,weight compound %,weight
SiO2 66.7 Na2O 2.06
Al2O3 12.3 MgO 1.07
Fe2O3 1.05 P2O5 0.04
FeO 0.78 K2O 2.96
TiO2 0.18 SO2 0.04
MnO 0.19 F 0.03
CaO 2.10 H2O 10.0
element µg/g element µg/g
Mn 242 Zn 45
Zr 235 Y 22
Ba 232 Nb 22
Rb 110 Ga 20
Ce 52 Th 12
After activation of clinoptilolite and γ-hematite
together with standards the element content in sam-
ples has been defined by analysis of γ-spectra (Fig.3).
Fig.3. Gamma spectrum hematite
High crystallinity level, lattice fluctuations char-
acter: Si-O-Al-links in tetrahedral positions of
clinoptilolite and Fe-O-links in cubic structure of
γ-hematite have been noted in all investigated sam-
ples - before and after γ-activation [9,18].
Chemical activity of nanostructure materials has
been investigated by means of registration of intensity
of Fenton-reactions on quantometer with PEM-140.
Research of kinetics of quantum processes in the pro-
tective materials which were used for radionuclide
sorption allows to study intermediate stages of chem-
ical reactions. These reactions stipulate formation
of excited particles. The method essence consists of
the following: thermostatically controlled chamber at
37oC for measurement takes places above photocath-
ode of photoelectronic multiplier with investigation
object.
The spontaneous luminescence of the sample is
37
measured, then by means of the special channel in
the cavity is added inductor. The typical kinetics
of luminescence is being detected. The luminescence
is detected in the form of the maximum intensity of
flash in imp./sec, intensity of final value of a lumines-
cence after 4 minutes of measurement and lightsum
reactions for 4 minutes of supervision.
Fig.4. Gamma spectrum solution CsNO3
CsNO3 salt has been preliminarily irradiated by
bremsstrahlung with maximum energy E=23 MeV
and I=700 µA (reaction 133Cs(γ,n)132Cs). Activity
of CsNO3 solution was equaled 6.5·106 Bk/l (Fig.4).
Influence of pH on sorption efficiency of caesium has
been checked by pH instrument-340.
3. RESULTS AND DISCUSSION
Deactivation is a process of removal of radionuclide
from a surface for the purpose of decrease of level of
radiating influence on the person. Following require-
ments have been considered at making of deactivating
agents: 1. pollution kind; 2. material of a processed
surface; 3. cost of spent works; 4. processing of waste;
5. not to render of destroying action and not to raise
sorption ability of a surface.
Such thermodynamic properties should be consid-
ered: 1. surface characteristic; 2. superficial tension;
3. waterproof interaction; 4. superficial energy; 5.
capillary pressure; 6. wettability and flowing; 7. dis-
persion; 8. selectivity of an ionic exchange; 9. con-
centration dependence of viscosity, etc.
Selection of auxiliary substances has been spent
taking into account the above-stated requirements:
1. neutral salts of organic acids; 2. alkaline salts of
weak acids; 3. solutions of organic acids of 0.3...0.4%;
4. surface-active substance 0.3%; 5. pyrophosphate
of sodium - Na4P2O710H2O; 6. salt of the higher
fat acids RCOONa; 7. primary aliphatic alcohol;
8. complexing substances: trilon, sulfonic acids,
hexmetaphosphate sodium.
Agents for deactivation of the polymeric surfaces
132Cs polluted, offered by us, included following com-
ponents:
1. Thermomodified clinoptilolite (technical con-
ditions 21, USSR 485-90).
2. Synthetic zeolite NaA (technical conditions-U-
320.00.15.8764-023-97).
3. Nanohematite (particles less than 40 nm),
(EEC No:215-168-2, LOT AIITO16 Alfa Aesor).
4. Superficially active substances (State Standard
237708-88).
5. Synthetic washing-up liquid (technical condi-
tions 2383-075-00204300-99).
6. Organic acid (party 20051012).
7. Distilled water.
The 132Cs solution has been put on plastic sur-
faces in amount of 5 ml and left before full drying.
Then various variants of deactivating agents have
been put on these surfaces.
1. Polyethylene surface with 5 ml of 132Cs +
surface-active substance.
2. Polyethylene surface with 5 ml of 132Cs + ther-
momodified clinoptilolite + synthetic zeolite NaA +
organic acid + surface-active substance.
3. Polyethylene surface with 5 ml of 132Cs
+ thermomodified clinoptilolite + nanoparticles of
γ-hematite + organic acid + surface-active sub-
stance.
4. Polyethylene surface with 5 ml of 132Cs + dis-
tilled water.
After drying during 20 hours the deactivating
agents have been washed off by the distilled water.
Residual 132Cs activity on a plastic surface and the
washed off solutions has been measured by Ge(Li)-
detector.
The received results have shown, that residual ac-
tivity 132Cs on a plastic surface after deactivation
equal 0.99±0.006%, 0.41±0.004%, 0,13±0.003% and
0.42±0.005%, accordingly.
Themomodified at 260oC clinoptilolite which is
enriched nanostructural γ-hematite are the most ef-
fective agents for deactivation of caesium-137. The
intracrystal space of themomodified clinoptilolite is
free from molecules of intraframe water. Therefore
ratio of active centers on a sorbent surface changes.
That is cause of improvement of their selectivity and
kinetic characteristics for sorption 137Cs. Also the
sorption capacity of deactivating agents increases ow-
ing to use nanoparticles.
Oxidative processes on a surface of the developed
sorbents strengthen as a result of use of such combi-
nation of components in deactivating agents and in
consequence of oxidant formation.
For determination chemical reactivity this model
system we focused on the ability of the iron-
exchanged forms of zeolites to produce hydroxyl radi-
cals from H2O2. Fenton‘s reagent generates powerful
oxidants called hydroxyl radicals (•OH) through the
reaction of ferrous iron and hydrogen peroxide [20]:
Fe2++H2O2 → Fe3+ + •OH + OH− .
It is one of the few methods available to genera-
tion these powerful oxidants without requiring light,
additional energy or sophisticated equipment.
The method of chemiluminescence was used for
determination intensity of the oxidative burst from
different system. Light emission of decontamination
38
agent with 132Cs was detected by photomultiplier-140
(range 350-750 nm).
Comparison of the levels of chemiluminescence of
isolation components which are part of deactivating
agents for 132Cs sorption are presented in Fig.5.
Fig.5. Intensity of the emission from solution
The highest chemiluminescence signal was regis-
tered in the system themomodified clinoptilolite with
nanohematite. Obviously nanohematite plays an im-
portant part in the radical production. Natural
clinoptilolite and artificial zeolite produce free rad-
icals too. Even CsNO3 solution generate hydroxyl
radicals as a result of initiated chemiluminescence.
The small amounts of hydroxyl radicals produced in
clinoptilolite + CsNO3, artificial zeolite + CsNO3
and CsNO3 show low activity of Fenton reaction.
Generation of singlet oxygen was observed by the
H2O2 - OCl− system [21,22].
The sodium hypochlorite (NaClO) has been re-
ceived by means of electrolysis of sodium chloride
(NaCl 0.9 %) before the beginning of experiment dur-
ing hour. The anode material was pyrolitic graphite,
and the cathode - spectroscopic pure graphite. Elec-
trolysis carried out (I = 15 A/cm2, U = 3.5 V) in
the quartz cell which was placed on magnetic mixer.
Electrolysis time was 60 minutes. Primary processes
on electrodes: on the anode 2Cl− → Cl2 + 2e; on the
cathode 2H2O + 2e → 2OH− + H2. Hypochlorite
and hypochlorous acid are formed at intermixing of
anode and cathodic products:
Cl2 + 2OH− = ClO− + Cl− + 2H2O;
Cl2 + OH− = HClO + Cl−.
pH of sodium hypochlorite (NaClO) was 8.2. For-
mation of singlet oxygen (1O2) was induced by reac-
tion:
H2O2 + OCl− = Cl− + H2O + 1O2.
Lifetime of singlet oxygen in a water phase is
rather insignificant. The singlet oxygen lets out light
quanta in visible and infra-red areas of a spectrum at
transition in triplet condition. The quantum exit in
a water phase is 10−10...10−12 (calculation data).
The interference filter (634 nm) for measurements
singlet oxygen was placed above photomultiplier.
That system was able register single oxygen in
different decontamination agents with 132Cs. It
was shown, the level of spontaneous chemilumi-
nescence in system nanoparticles γ-hematite and
thermomodified clinoptilolite was the most high
(I=11230±147 imp./sec).
The knowledge of the intensity of single oxygen
in similar system is essential for an understanding of
the mechanism of the oxidation process.
Sorption abilities of thermomodified clinoptilolite
(260oC) have been studied at temperature 20oC and
under the influence of VHF field with 10 % intensity
at 65oC. For this purpose the samples were placed
on incubation (24 hours) in alkaline solution NaOH
(pH=8) with addition of activated solution of nitrate
caesium. Centrifugation of solution has been realized
after incubation. Solutions of leachate were trans-
parent, did not contain suspensions and deposits,
pH≈8...8.5.
The sorption material deposits and leachate have
been analysed on Ge(Li)-detector. The indicators of
132Cs sorption efficiency counted according to values
of initial solution activity, leachate and deposits.
The comparative analysis of the investigated sam-
ples has shown, that at 20oC the rate of sorption
of 132Cs in a deposit (hematite + clinoptilolite) has
amount 60%, in a deposit (themomodified 260oC
clinoptilolite) - 81%, in a deposit (VHF themomodi-
fied clinoptilolite) - 79%. The rate of the contents
132Cs in supernatant fraction has amount 1.1, 7.8
and 5.0%, accordingly. Discrepancy of total values
(100%) of 132Cs contents in solutions and deposits,
in our opinion, can be explained by formation of
volatile forms of 132Cs. Besides it can be peroxide
compounds of caesium Cs2O2 and Cs2O3 which are
powerful oxidizers. The last vigorously incorporate
to water, forming hydroxides CsOH which, in turn,
cooperating with ozone and form volatile compounds.
The method of registration of high reactive prod-
ucts has been used as a express-estimation of ac-
tion of an irradiation and influence of additional sub-
stances on physic mechanical properties of developed
sorbents.
Features of induced by peroxide hydrogen of lu-
minescence of the 132Cs solution in different com-
binations of a solution of themomodified clinop-
tilolite without and with addition nanoparticles of
hematite have been investigated. The carried out
measurements have shown, that the maximal inten-
sity of flash of a luminescence of the 132Cs solu-
tion has made 1563±63 imp./s, intensity of final
value 250±24 imp./s, lightsum Σ=1066·102 imp.; for
a sample of themomodified clinoptilolite with addi-
tion of the 132Cs solution the maximal flash of a lumi-
nescence has made 2460±58 imp./s, intensity of final
value 324±28 imp./s, lightsum Σ=1800·102 imp.; for
a sample of themomodified clinoptilolite with addi-
tion nanohematite and 132Cs the maximal flash of a
luminescence has made 3210±103 imp./s, intensity of
final value 266±32 imp./s, lightsum Σ=2055·102 imp.
39
4. CONCLUSIONS
1. Deactivating agents which included of natural
clinoptilolite and nanoparticles γ-hematite is devel-
oped and approved.
2. Modified clinoptilolite is effective sorbent of
132Cs with plastic surfaces.
3. The created deactivating agents has the im-
proved selective and kinetic characteristics for sorp-
tion 132Cs out of the liquid medium.
4. High intensity of chemical Fenton reaction
for 132Cs sorption by nanostructure materials with
clinoptilolite + hematite was detected.
5. Formation of volatile compounds (Cs2O2 and
Cs2O3) in process of 132Cs sorption by nanostructure
materials (hematite + clinoptilolite) is revealed.
References
1. G. Lujaniene, S. Meleshevych, V. Kanibolotsryy,
et al. Synthesis and Characterization of Inorganic
Sorbents and Their Application to Sorption of
Radionuclides // Lithuanian Journal of Physics.
2008, v.48, N.1, p.107-114.
2. A. Jain, N. Rawat, S. Kumar, et al. Sorption of
Neptunium by Hematite Colloids // Radiochim-
ica Acta. 2007, N.95, p.501-506.
3. L. Sharygin, A. Muromskiy, M. Kalyagina. A
Granular Inorganic Cation-Exchanger Selective
to Cesium // J. of Nuclear Science and Tech-
nology. 2007, v.44, N.5, p.767-773.
4. N.F. Chelishchev, B.G. Berenshtejn,
V.F. Volodin. Zeolites - new type of min-
eral raw materials. M: ”Nedra”, 1987, 176 p, (in
Russian).
5. H.Van Bekkum, E.M. Flaningen, J.C. Jansen. In-
troduction to Zeolit Science and Practic. Amster-
dam: ”Elsevier”, 1991, 355 p.
6. P. Rajec, F. Macasek, P. Misaealides. Sorption
of heavy metals and radionuclides // Natural Mi-
croporous Material in Environmental Technology.
2007, v. 362, Ser.E: Applied Sciences, p.353-363.
7. A.M. Grancaric, A. Tarbuk, I. Kovacek.
Nanoparticles of activated natural zeolite on tex-
tiles for protection and therapy // Chemical In-
dustry & Chemical Quarterly. 2009, v. 15(4),
p.203-210.
8. N.K. Moroz, J.V. Seretkin, I.S. Afanasev,
V.V. Bakakin. Structure and diffusion mobility
extraskeleton subsystems in hydrated ammonium
forms of zeolites clinoptilolite and chabazite //
Jour. Struct. Chem. 2002, v. 43, p.642-648 (in
Russian).
9. N.P. Dikiy, E.P. Medvedeva, I.D. Fedorets,
N.P. Khlapova. Thermoupdating nanopowder
natural clinoptilolite // Vesnyk KNU Ser.:
Physics. Nuclears, Particles, Fields. 2009, N.880,
iss.4(44), p.84-90 (in Russian).
10. D.T. Breck. Zeolites molecular sieves: structure,
chemistry and use. New York: ”John Wiley &
Sons Inc.”, 1974, 663 p.
11. O.V. Salata. Application of nanoparticales in bi-
ology and medicine // Journ. Nanobiothechnol-
ogy. 2004, v. 2:3, p.1-6.
12. B. Dousova, T. Grygar, A. Martaus, et al. Sorp-
tion of AsV on aluminosilicates treated with FeII
nanoparticles // J. Colloid. & Inter. Sci. 2006,
v. 302, p.424-431.
13. I. Melian-Cabrera, F. Kapteijn, J.A. Moulijn.
Innovation in the synthesis of Fe-(exchanged)-
zeolites // Catal.Today. 2005, v. 110, p.225-263.
14. K. Kayama, Y. Takeushi, Clinoptilolite: The dis-
tribution of Potassium atoms and its role in ther-
mal stability // Z. Kristallogr. 1977, v.Bd.145,
p.216-239.
15. Th. Armbruster Dehydration mechanism of
clinoptilolite and heulandite: Single crystal X-ray
study of Na-poor, Ca-, K-, Mg-rich clinoptilolite
at 100 K // Americal Mineralogist. 1993, v. 78,
p.260-264.
16. M. Jhonson, D. O’Connor, P. Barnes, at al.
Cation exchange, Dehydration, and Calculation
in Clinoptilolite: in Situ X-ray Diffraction and
Computer Modeling // J. Phys. Chem. 2003, v.
B107, p.942-951.
17. A. Godelitsas, Th. Armbruster HEU-type zeo-
lites modified by transition elements and lead //
Micropor. Mesopor. Mater. 2003, v.61, p.3-24.
18. N.P. Dikiy, E.P. Medvedeva, I.D. Fedorets,
N.P. Khlapova. Structure and magnetic proper-
ties of gamma activated nanoparticles of mag-
netite // Vesnyk KNU Ser.: Physics. Nuclears,
Particles, Fields. 2009, N.859, iss.2(42), p.89-94
(in Russian).
19. N.P. Dikiy, A.N. Dovbnya, E.P. Medvedeva,
et al. Gamma activation and spectral analy-
sis of element composition, structure and sorp-
tion activity of radiation synthesized magnetite
and osmium nanoparticles // Vesnyk KNU Ser.:
Physics. Nuclears, Particles, Fields. 2008, N.823,
iss.3(39), p.78-84 (in Russian).
20. How Rusting Iron Can Clean up Toxic Spills //
Science. 2005, N.823, iss.3(39), p.19-21.
21. S. Jockusch, J. Sivaguru, N.J. Turro, V. Rama-
murthy. Direct measure of singlet oxygen lifetime
in zeolites by near-IR phosphorescence // Pho-
tochem. Photobiol. Sci. 2005, N.4, p.403-405.
22. R.L. Arudi, H.J. Bielski, A.O. Allen. Search for
singlet oxygen luminescence in the disproportion
of HO2/O2
−// Photochem and Photobiol. 1984,
v.139, N.5, p. 703-706.
40
СЕЛЕКТИВНЫЕ К ЦЕЗИЮ НАНОСТРУКТУРИРОВАННЫЕ
ДЕЗАКТИВИРУЮЩИЕ СРЕДСТВА
Н.П. Дикий, А.Н. Довбня, Ю.В. Ляшко, Е.П. Медведева, Д.В. Медведев, В.Л. Уваров,
И.Д. Федорец, Н.П. Хлапова, Д.С. Бакай
Исследовалась химическая реактивность природного клиноптилолита и наночастиц γ-гематита, кото-
рые обладают высокой селективной сорбционной способностью в отношении 132Cs. В качестве модели
дезактивирующего средства для сорбции 132Cs с полиэтиленовых поверхностей и водных растворов,
помимо клиноптилолита и наночастиц γ-гематита были использованы дополнительные (вспомогатель-
ные) компоненты. Фотоактивационный анализ был использован для изучения примесного состава об-
разцов природного клиноптилолита и активированного γ-гематита. Квантометрический метод при-
менялся для определения интенсивности генерации свободнорадикальных продуктов в присутствии
перексида водорода (Fenton reaction). Измерение с помощью Ge(Li)-детектора остаточной активности
132Cs в твердой и жидкой фракциях дезактивирующих средств показало, что процесс сорбции 132Cs
сопровождается образованием летучих форм 132Cs. Высокий синергетический эффект сорбции 132Cs
показан с использованием дезактивирующего средства на основе наноструктурного термомодифици-
рованного природного клиноптилолита и наночастиц γ-гематита.
СЕЛЕКТИВНI ДО ЦЕЗIЮ НАНОСТРУКТУРOВАНI ДЕЗАКТИВАЦIЙНI ЗАСОБИ
М.П. Дикий, А.М. Довбня, Ю.В. Ляшко, О.П. Медведєва, Д.В. Медведєв, В.Л. Уваров,
I.Д. Федорець, Н.П. Хлапова, Д.С. Бакай
Дослiджувалась хiмiчна реактивнiсть природного клiноптилолiту та наночастинок γ-гематиту, якi во-
лодiють високою здатнiстью до сорбцiї 132Cs. У якостi моделi дезактивуючого засобу для сорбцiї 132Cs
з полiетиленових поверхонь i водних розчинiв, окрiм клиноптилолiту та наночатинок γ-гематиту, були
використанi допомiжнi стандартизованi речовини. Фотоактивацiйний аналiз був використаний для вив-
чення домiшкового складу зразкiв природного клiноптилолiту i активованого γ-гематиту. Квантомет-
ричний метод використовувався для визначення iнтенсивностi генерацiї вiльнорадикальних продуктiв
при iндукцiї пероксидом водню. Вимiрювання за допомогою Ge(Li)-детектора залишкової активностi
132Cs в осадовiй та рiдкiй фракцiях дезактивуючих засобiв виявило, що процес сорбцiї 132Cs супро-
воджується утворенням летючих форм 132Cs. Високий синергетичний ефект сорбцiї 132Cs виявляється
при умовi, коли в складi дезактивуючого засобу присутнi прирордний клиноптилолiт та наночастинки
γ-гематиту.
41
|
| id | nasplib_isofts_kiev_ua-123456789-111132 |
| institution | Digital Library of Periodicals of National Academy of Sciences of Ukraine |
| issn | 1562-6016 |
| language | English |
| last_indexed | 2025-12-07T17:33:20Z |
| publishDate | 2011 |
| publisher | Національний науковий центр «Харківський фізико-технічний інститут» НАН України |
| record_format | dspace |
| spelling | Dikiy, N.P. Dovbnya, A.N. Lyashko, Yu.V. Medvedeva, E.P. Medvedev, D.V. Uvarov, V.L. Fedorets, I.D. Khlapova, N.P. Bakay, D.S. 2017-01-08T15:01:27Z 2017-01-08T15:01:27Z 2011 Nanostructural deactivating agents selective to caesium / N.P. Dikiy1, A.N. Dovbnya, Yu.V. Lyashko, E.P. Medvedeva, D.V.Medvedev, V.L. Uvarov, I.D. Fedorets, N.P. Khlapova, D.S. Bakay // Вопросы атомной науки и техники. — 2011. — № 3. — С. 35-41. — Бібліогр.: 22 назв. — англ. 1562-6016 PACS: 68.43.-h; 82.75.-z https://nasplib.isofts.kiev.ua/handle/123456789/111132 The chemical reactivity of nanostructural clinoptilolite and γ-hematite which have highly selective for ¹³²Cs sorption from polyethylene surface and for liquid environments are studied. There are different components besides clinoptilolite and γ-hematite were chosen to examine as model of deactivation agents for ¹³²Cs sorption. Photon activation analysis was used for study of element composition in samples of natural clinoptilolite and hematite. The chemiluminescence method was used for definition of chemical reactivity of iron-exchanged form of the clinoptilolite to produce hydroxyl radicals from H²O² (Fenton reaction). The formation of volatile compounds in process of ¹³²Cs sorption was detected . The deactivation agent on basic of thermomodified clinoptilolite with γ-hematite nanoparticles was shown the highly synergistic effect for ¹³²Cs sorption from polyethylene surface and for liquid system. Досліджувалась хімічна реактивність природного кліноптилоліту та наночастинок γ-гематиту, які володіють високою здатністью до сорбції ¹³²Cs. У якості моделі дезактивуючого засобу для сорбції ¹³²Cs з поліетиленових поверхонь і водних розчинів, окрім клиноптилоліту та наночатинок γ-гематиту, були використані допоміжні стандартизовані речовини. Фотоактиваційний аналіз був використаний для вивчення домішкового складу зразків природного кліноптилоліту і активованого γ-гематиту. Квантометричний метод використовувався для визначення інтенсивності генерації вільнорадикальних продуктів при індукції пероксидом водню. Вимірювання за допомогою Ge(Li)-детектора залишкової активності ¹³²Cs в осадовій та рідкій фракціях дезактивуючих засобів виявило, що процес сорбції ¹³²Cs супроводжується утворенням летючих форм ¹³²Cs. Високий синергетичний ефект сорбції ¹³²Cs виявляється при умові, коли в складі дезактивуючого засобу присутні прирордний клиноптилоліт та наночастинки γ-гематиту. Исследовалась химическая реактивность природного клиноптилолита и наночастиц γ-гематита, которые обладают высокой селективной сорбционной способностью в отношении ¹³²Cs. В качестве модели дезактивирующего средства для сорбции ¹³²Cs с полиэтиленовых поверхностей и водных растворов, помимо клиноптилолита и наночастиц γ-гематита, были использованы дополнительные (вспомогательные) компоненты. Фотоактивационный анализ был использован для изучения примесного состава образцов природного клиноптилолита и активированного γ-гематита. Квантометрический метод применялся для определения интенсивности генерации свободнорадикальных продуктов в присутствии перексида водорода (Fenton reaction). Измерение с помощью Ge(Li)-детектора остаточной активности ¹³²Cs в твердой и жидкой фракциях дезактивирующих средств показало, что процесс сорбции ¹³²Cs сопровождается образованием летучих форм ¹³²Cs. Высокий синергетический эффект сорбции ¹³²Cs показан с использованием дезактивирующего средства на основе наноструктурного термомодифицированного природного клиноптилолита и наночастиц γ-гематита. en Національний науковий центр «Харківський фізико-технічний інститут» НАН України Вопросы атомной науки и техники Ядернo-физические методы и обработка данных Nanostructural deactivating agents selective to caesium Селективнi до цезiю наноструктурoванi дезактивацiйнi засоби Селективные к цезию наноструктурированные дезактивирующие средства Article published earlier |
| spellingShingle | Nanostructural deactivating agents selective to caesium Dikiy, N.P. Dovbnya, A.N. Lyashko, Yu.V. Medvedeva, E.P. Medvedev, D.V. Uvarov, V.L. Fedorets, I.D. Khlapova, N.P. Bakay, D.S. Ядернo-физические методы и обработка данных |
| title | Nanostructural deactivating agents selective to caesium |
| title_alt | Селективнi до цезiю наноструктурoванi дезактивацiйнi засоби Селективные к цезию наноструктурированные дезактивирующие средства |
| title_full | Nanostructural deactivating agents selective to caesium |
| title_fullStr | Nanostructural deactivating agents selective to caesium |
| title_full_unstemmed | Nanostructural deactivating agents selective to caesium |
| title_short | Nanostructural deactivating agents selective to caesium |
| title_sort | nanostructural deactivating agents selective to caesium |
| topic | Ядернo-физические методы и обработка данных |
| topic_facet | Ядернo-физические методы и обработка данных |
| url | https://nasplib.isofts.kiev.ua/handle/123456789/111132 |
| work_keys_str_mv | AT dikiynp nanostructuraldeactivatingagentsselectivetocaesium AT dovbnyaan nanostructuraldeactivatingagentsselectivetocaesium AT lyashkoyuv nanostructuraldeactivatingagentsselectivetocaesium AT medvedevaep nanostructuraldeactivatingagentsselectivetocaesium AT medvedevdv nanostructuraldeactivatingagentsselectivetocaesium AT uvarovvl nanostructuraldeactivatingagentsselectivetocaesium AT fedoretsid nanostructuraldeactivatingagentsselectivetocaesium AT khlapovanp nanostructuraldeactivatingagentsselectivetocaesium AT bakayds nanostructuraldeactivatingagentsselectivetocaesium AT dikiynp selektivnidoceziûnanostrukturovanidezaktivaciinizasobi AT dovbnyaan selektivnidoceziûnanostrukturovanidezaktivaciinizasobi AT lyashkoyuv selektivnidoceziûnanostrukturovanidezaktivaciinizasobi AT medvedevaep selektivnidoceziûnanostrukturovanidezaktivaciinizasobi AT medvedevdv selektivnidoceziûnanostrukturovanidezaktivaciinizasobi AT uvarovvl selektivnidoceziûnanostrukturovanidezaktivaciinizasobi AT fedoretsid selektivnidoceziûnanostrukturovanidezaktivaciinizasobi AT khlapovanp selektivnidoceziûnanostrukturovanidezaktivaciinizasobi AT bakayds selektivnidoceziûnanostrukturovanidezaktivaciinizasobi AT dikiynp selektivnyekceziûnanostrukturirovannyedezaktiviruûŝiesredstva AT dovbnyaan selektivnyekceziûnanostrukturirovannyedezaktiviruûŝiesredstva AT lyashkoyuv selektivnyekceziûnanostrukturirovannyedezaktiviruûŝiesredstva AT medvedevaep selektivnyekceziûnanostrukturirovannyedezaktiviruûŝiesredstva AT medvedevdv selektivnyekceziûnanostrukturirovannyedezaktiviruûŝiesredstva AT uvarovvl selektivnyekceziûnanostrukturirovannyedezaktiviruûŝiesredstva AT fedoretsid selektivnyekceziûnanostrukturirovannyedezaktiviruûŝiesredstva AT khlapovanp selektivnyekceziûnanostrukturirovannyedezaktiviruûŝiesredstva AT bakayds selektivnyekceziûnanostrukturirovannyedezaktiviruûŝiesredstva |