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13Journal of Siberian Federal University. Engineering & Technologies 5 (2011 4) 465-473
yflK 533.528+621.74+539.2
Recycling Carbonaceous Materials by Cavitation Nanotechnology Techniques
Ludmila V. Kashkina, Vladimir A. Kulagin*, Olesya P. Stebeleva and Ludmila V. Kulagina
Siberian Federal University, 79 Svobodny, Krasnoyarsk, 660041 Russia 1
Received 4.10.2011, received in revised form 11.10.2011, accepted 18.10.2011
The purpose of this paper was the studying of hydrodynamic cavitation effect on physical properties of carbonaceous material - heat-treated cellulose. The heat-treated cellulose powders have been investigated by the method of X-ray phase analysis (XPA). Hence it was possible to obtain nanofluid -a water suspension with the features characteristic of weak water suspension offulleroids as a result of rather short cavitation processing of the weak water suspension of heat-treated cellulose, nanofluid is very perspective for industrial technologies.
Keywords: cavitation nanotechnology, activated carbonaceos materials, cement stone, micro constancy, nanostructures
Introduction
At present all over the world there is a rapid development of new ideas and experimental approaches to creating efficient technologies on the basis of nanomaterials.
It is considered that there should be no gap or "vacuous" link in the chain of knowledge about biosphere which conservation is the most important problem of ecology. In the new millennium in Russia this gap proved to be the problem of disposal of utilized polymer substances, among them packings, and also combustion products in the form of incineration ashes, carbon-blacks, and the like.
Solid domestic refuse (SDR) is a special danger for environment although industrial waste considerably contributes to pollution as well. Dumping-grounds are a terminal point of empty packaging where it is combined with other solid domestic refuse making up much more than 50 % of the total waste.
According to the "INECO" agency data by the end of 1990s in Russia there had been accumulated more than 55 million tonnes of waste products only at the registered urban dumping grounds. As this takes place, the bulk of SDR has amounted to 250-300 kg per person annually, and the total increase has reached 6 % a year.
The dumping grounds pollute free air, soils and ground waters with various compounds that are harmful and poisonous for humans and habitat: methane, sulfur dioxide, dioxin, high-density
* Corresponding author E-mail address: [email protected]
1 © Siberian Federal University. All rights reserved
metals salts, vapors of solvents, and other pollutants. They are followed by withdrawal of vast areas from advantageous use and result in arising a great amount of rodents and insects that are an epidemiological threat to the population. Within recent years the sanctioned dumping grounds have been removed further on and on to "green" and residential suburbs. At the same time there are cases of advantageous use of utilization products including waste products under their appropriate structural transformation, e.g. into nano-objects or near to them in size [1, 2]. The research people's heightened interest in nano-objects is caused by detecting their unusual physical and chemical properties.
A nano-object is a physical object greatly distinguished by properties from the corresponding massive substance and which has as a minimum one size in the nano-range (no more than 100 nanometers). The nanomaterials fall into compact substances and nanodispersions. The former are referred to as so-called "nanostructured" substances, i.e. isotropic substances by their composition, which repetitive structural elements are nano-objects contacting with each other.
Unlike nanostructured substances, nanodispersions consist of a homogeneous medium of dispersion (gas, fluid, or solid) and nanoinclusions distributed in this medium and isolated from each other.
Nanocluster carbon substances are the substances including or consisting of carbon particles of nanoscopic sizes (e.g. fullerenes, fullereniferous and diamond-bearing carbon-blacks).
As of now, research is done on expediency of the application of various superdispersed carbonaceous powders for solid additives to oil lubricants. The application of superdispersed materials for additives has been rather widely used for the past decade when there appeared technological opportunities for industrial-scale production of powders of various nature with particle sizes up to 100 A.
The addition of a small amount of carbon nanomaterials dramatically changes properties of any material-carrier. At present there are pursued investigations of efficiency of application of various superdispersed carbonaceous powders for solid additives to oil lubricants. At introducing the superdispersed powders of diamond-graphite into grease, the friction coefficient decreases by 14-40% and in particular cases up to 60% depending on a kind of base grease material [4].
In works [5, 6] there was explored an effect of small additives of C60 fullerene and fullerene carbon-black on tribological properties of fluid mineral oil. It was shown that cheaper fullerene carbonblack takes practically the same positive effect as pure fullerene does. The following conclusion was made: the role of fullerene is reduced to the triggering of processes of tribopolymerization of the organic components that are in mineral oils and the forming of a protective polymer film on a friction surface.
In Fig. 1 are presented two most typical dependences of frictional torque (M) on time. Curve 1 is characteristic for pure oil H-40A. The frictional torque increase resulting in a tear, begins at rather low loadings (300-600 N) whilst the friction assembly with a lubricant containing C60 (Curve 2), is capable to operate for a long time at loadings over the range of 800-1200 N. In this case the friction coefficient becomes stable on a very low level of 0.015-0.030 which is not attained with using pure oil and the same oil with other carbon additives [5].
There have been developed some methods of forming properties of high-quality concretes with the application of nanomaterials (carbon nanotubes and big multilayer polyhedral nanoparticles of fulleroid type - astralenes) [7].
t
10 20 30 40 t, mill
Fig. 1. Dependence of frictional torque (M) on time
a)
b)
a) ordinarystructureof thecementstoneshowingupas isotropicallylocatedflakes
b) fibrillar structure of the cement stone in the modified composition including conventional water slurry of ful-leroids
Fig. 2. A photomicrograph of the cement stone structure (magnification 5000x)
Electron shells of fulleroiwalare characterized by the presence of a great quantity of delocalized n-conjugate electrons. On the bounds the filling compound is the cement stone coming into being in which the fulleroids act the part of centers of oriented crystallization resulting, on the one hand, in emerging cement stone fibrillar structures, and on the other hand, in emerging strain-hardening permolecular structure of polymeric additives. Generating a filiform fibrillar microscopic structure results in strengthening physical and mechanical features of composite concretes. In this process the total number of fulleroids (nanotubes and astralenes in this case) per 1 t of the composition did not exceed 6.5 x 10-6. The application of modification of phase transitions in the composite materials will RrgOrd when erecting
jaeBilSJgfB|H^^^^^ructing in regions with higher seismic activity [8].
FgliaEAjRnOtOmij^ ncrete
com osition.
Research methodologies
The purpose of this paper was the studying of hydrodynamic cavitation effect on physical properties of carbonaceous material - heat-treated cellulose. The heat-treated cellulose powders have
- 467 -
Fig.3. The XPA spectrum ofheat-treatedcellulosepowder
hes-ra^diffractomitbi smartapex yu^m xpa ^spectrsm3sap^i^a y diffractometer smart
^o^^ioj^^^sa£line3amp>e3figS3 ]s characteristic of a polycrystalline sample (Fig. 3).
i||j|0nffifBnitia!30sdlis3sfflsiainid3ySslS-l33 SpletSm mitsodp method analysis on the
^bon&ue%sfsmp3ritiisQjssii9ai3g3sisu icu ^^^concie rasonss^ 60% of carbon, 40% of
MffllSsillgg! qfeinj^ ^^^fi^^^^^^^t^^^n^^^'^^^S^^^^j^f^n^^^i^^r^impuriiies are of only sub percent - size (for Cu, Ni - 0.07%, Fe - 0.4%).
^^pei28hingnili!itie&ss0S j|ai|^|au^bii^di|icuid^|^3iliicroscope of transmission ySSs§jSP-128H (magnification 400x) there have been detected a two-phase composition: jjislbbE5mpjiuieyb3?nibSi jujosii]^- ellulose).
¡irsi^ibsis^jsiesija^ai^ par ^csmpjiiijyEsseid Bu- d cellulose).
^^ ons of powders in distilled ¡isti[li^^l^|i|Hint formula:
C =—m--100 %,
m1 + m2
where m1 is the sample mass, m2 is the water mass. The powders were weighed by the KERN 770 GS/ GL balance to the nearest 10-4gram. The concentrations of the prepared water suspensions were up to 0.1%.
The water suspension was put into a supercavitation mixer with the cuneiform cavitator (the vertex angle at the wedge was 60 degrees) and rotated at room temperature with the rotor fixed velocities from 5000 up to 20000 rpm.
The equipment and experimental technique are described in [3]. With the rotation mode from 15000 go 20000 rpm and the rotation time of 1.5-2 minutes there was observed a water suspension temperature rise from room temperature up to 90 °C.
Interpretation and discussion of research results
The cavitation experiment having been performed, the water suspensions were settled during 48 hours in closed plastic cups until sediment. The sediment was poured out in Petri dishes and dried in the air at t = 25 °C (Fig. 4, 5).
In the performed experiments there was observed self-organization of heat-treated cellulose particles into fine tubes. The tubes were found during electron microscope studies of the samples on the scanning electron microscope Hitachi TM-100 9 (accelerating voltage is 15 kV) (Fig. 6) and on the transmission electron microscope JEOL JEM-2100 (accelerating voltage 200 kV), Fig. 7.
The observable tubes are similar in their shape with carbon nanotubes which have been obtained by various tec£QTeWithR!h£|Tgt orders of magnitude lo
It is knoMgflnmOKenRTQ^^nRlmgllm 500 m/s and
temperature in this local spot rises up to 103-104 K as a result of adiabatic compression.
At the cavity bubble collapse in the locinterpretati&ns9dd3cu3MiOQffiEMeieari
high pressure (up to 20
and mechanics1inimffln3u9RnR848|h0g
The pulsation gU^^Mffiffl^dflSRffinlindlffrn^ which there are
MgWan) rpU£rcifflHQ| mJJHH] Wghut^gCRne make it possible
time of the cavity during the collapse generates it into surrounding
effliHIn.
iffi|Im9en^№flOI9IK9H|iifflS|Q (atoms,
cavitation effect. The
vicinity around a cavitation bubble after the «collapse» can be considered as plasma. In this case the mechanism of particles self-organizing is probably similar to that of formation of tubular structures in dust plasma. There have been found tubes of the sizes that are typical for individual carbon multilayer tubes (from several nanometers up to twenty-thirty nanometers), tubular structures with a diameter of 50-100 nanometers which are built from smaller tubes. The tubular units are joined
Fig. 4. View of the cavitation sediment of heat-treated cellulose in the Petri dish
optical microscope of transmission type XSP-128H (magnification400x)
HM.lOOO.DlM 3004 »ÛÎ il.fts jCjm
Fig. 6. Photo taken on the electronEgaBBaha ui£a33k]yy|Jh!]
Fig. 7. Photos taken on the transmission electron micJugÎHffjlphOWSyakO
nw oejajiscjnerTsUiszjh
S j^^^^^jy^^jHT^^^RtUbuj^inj^^^^ in the formation of the
structureo^uneroids especially of rather large sizes (lughee fullerenes,tubulenes, multilayer nanotubes,
and intensive external
¡s^^^ii^^^TRf^siHiiize ^¡gCjSs^^ehSEigzcifei^ue^sss ¡aQZttSssn s^^s^^e^iEez^^s^
Eil
Fig. pUgm-glge) graph of astralene agglomeration phenomenononmultilayernanotubes[8]
Fig. 9. Agglomeration of heat-treated cellulose particles after the cavitation processing. Rotating 5000 rpm during 2 min. The electron microscope photo obtained on the JEOT JEM-2100 microscope
iJM
v-rr—
77K
1H J№ W
W № №
1ÏO
<w
.
«Û-I
Iff
«aJ w> 0-
rrr"
77K
buret tokos
Fig. 10. EPR spectra (black flakes)
The EPR spectra were taken on the initial samples of heat-treated cellulose. The EPR spectra were taken at temperatures of 300 K, 77 K on the Bruker EPR spectrometer E-500 (Figs. 10, 11).
At 293 K the EPR spectrum will comprise a wide band and a central narrow band. The wide band is caused by the presence of ferric oxide. The narrow band - by a free radical of carbon atom. After the cavitation processing, the shape of the EPR spectra changed and there was observed some broadening of the wide band of the spectrum at 77 K and its intensity decreasing. It may be connected with the presence of superparamagnetic particles in the sample. It is possible that large paramagnetic particles of iron toUajtse as a resglt of the cavtiatlon precersing, ih. in tlie cavitation
pSu^^^sp^r^^aEiiiiiiSoiSiiiiesiSyOii^^^a^^iiiy^ troEo&reoei ssacrssauig 53213 sEsssriSEK^ ms
crusBed but aleo amfuritiet incSudlng pnramagnelic imnuriairs. Tie procersgo es oeameSeculrr
lS«
Semmary anp Conelusiens
Hcmce it waa gee si^^e>as too entaig niusotlssig- a water.uegansionwith theOeatgaescharaateristic of \®aS as a result of rather short cavitation processing of the weak
watgaoeicts isnEfBrss 'tisa^^11^^ qcarbs^s^s^XiSsrai^ iSg^KsascaEr0 the
- 471 -
77K
* urn 31» iü «u vh ■■
Fig. 11. EPR spectra (grey part)
obtained nanofluid features in solving ecological problems to obtain constructional materials with new operational properties for industrial application.
The article is published with the support ofthe Program of Development ofthe Siberian Federal University. Electron-microscopic research has been carried out in the laboratory of electronic microscopy of the Collective Using Center of Siberian Federal University.
References
oeBingaand nSSmeffl ngnaSlheS 9№ 7llQI№flli.
2. Fullerenes: Synthesis and the theory of formation / G. N. Churilov, N. V. Bulina, A. S. Fedorov; ed. V. F. Shabanov. - Novosibirsk: Publishing House of the Siberian Branch of the Russian Academy
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219 p.
mmmmmEMmimmtmimimm friction surface in the presence of
[0dUCn]0M|/ /3. VERuKElEEB-eLpkyM.Bj?SB]n2R| V. A. Solovjev // The Journal of Engineering Physics. 1999. - V. 69. - Issue 11. - P. 113-116.
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6. Ginzburg, B. M. Effect of C60 fullerene carbon-blacks and other carbon materials on boundary friction of metals sliding / B. M. Ginzburg, O. F. Kireyenko, M. V. Baydakova, et al. // The Journal of Theoretical Physics. 2000. - V. 70.
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8. Ponomarev, A. N. High-quality concretes. The analysis of opportunities and practical use of nanotechnology methods / A. N. Ponomarev // The Construction-Engineering Journal. 2009. - № 6.
9. Kulagin, V. A. Nanotechnology cavitational effects in the heat-and-power engineering and other branches of production / V. A. Kulagin, L. V. Kulagina, Т. А. Kulagina // Journal of Siberian Federal University. Engineering & Technologies 1 (2008) 76 - 85.
10. Kukushkin, A. B. Simulation of magnetic aggregation of nanodust in electric discharges / A. B. Kukushkin, K. V. Tcherepanov // The Research Records of XXXIII International (Zvenigorod) Conference on plasma physics and carbon tube structures. - М., 2006.
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Утилизация углеродосодержащих материалов методами кавитационной нанотехнологии
Л. В. Кашкина, В. А. Кулагин, О. П. Стебелева, Л. В. Кулагина
Сибирский федеральный университет, Россия 660041, Красноярск, пр. Свободный, 79
Изучено влияние эффектов гидродинамической кавитации на физические свойства углеродосодержащего материала - термообработанной целлюлозы. Порошки термообработанной целлюлозы изучены методом рентгеновского фазового анализа (РФА). В результате достаточно короткого кавитационного воздействия на низкоконцентрированную водную суспензию термообработанной целлюлозы удалось получить наножидкость - водную взвесь с особенностями, присущими низкоконцентрированной водной суспензии фуллероидов, перспективной для использования в промышленных технологиях.
Ключевые слова: кавитационная нанотехнология, активированные углеродосодержащие материалы, цементный камень, микротвердость, наноструктуры.
