We have studied the effect of nanosecond laser pulses on the optical properties of onion-like (OLC) and multi-wall carbon nanotubes (MWNTs) suspensions in N,N-dimethylformamide (DMF). The results demonstrate that both suspensions irreversibly bleach under high-intensity laser radiation. The bleaching is accompanied by losing optical limiting (OL) in suspensions.
When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/3542

Bulatov, D.L.

Mikheev, K.G.

Shuvaeva, M.A.

SocioEconomic Challenges Journal (Sumy State University)

PROCEEDINGS OF THE INTERNATIONAL CONFERENCE  
NANOMATERIALS: APPLICATIONS AND PROPERTIES 
Vol. 2 No 3, 03NCNN22 (2pp) (2013) 
 
 
2304-1862/2013/2(3) 03NCNN22 (2) 03NCNN22-1  2013  
Laser-Induced Bleaching of Carbon Nanomaterials Suspensions 
 
D.L. Bulatov1,*, K.G. Mikheev1,†, M.A. Shuvaeva2,‡ 
 
1  Institute of Mechanics, Ural Branch of RAS, 34, T. Baramzina Str., 426067 Izhevsk, Russia 
2 Institute of Catalysis, Siberian Branch of RAS, 5, Ak. Lavrent’eva Ave., 630090 Novosibirsk, Russia 
 
(Received 30 May 2013; published online 1 September 2013) 
 
We have studied the effect of nanosecond laser pulses on the optical properties of onion-like (OLC) and 
multi-wall carbon nanotubes (MWNTs) suspensions in N,N-dimethylformamide (DMF). The results 
demonstrate that both suspensions irreversibly bleach under high-intensity laser radiation. The bleaching 
is accompanied by losing optical limiting (OL) in suspensions.  
 
Keywords: Onion-Like Carbon, Multi-Wall Carbon, Optical Limiting, Suspension, Bleaching. 
 
 PACS numbers: 78.67.Ch, 78.67.Bf, 85.60.Bt 
 
 
                                                          
* dlbulatov@udman.ru 
† k.g.mikheev@gmail.com 
‡
 mas@catalysis.ru 
1. INTRODUCTION 
 
The laser radiation interaction with suspensions of 
various carbon nanoparticles is of interest for the de-
velopment of optical limiters and passive laser switches 
intended to protect light sensors and human eyes from 
optical damage [1-4]. In contrast to fullerene solu-
tions [5], suspensions of OLC and MWNTs have a 
broad absorption band [6, 7]. At the same time our ex-
periments have shown the suspensions of OLC and 
MWNTs in DMF to be sufficiently stable in contrast to 
the similar aqueous suspensions [6]. This makes such 
suspensions potentially attractive for the development 
of broadband optical limiters. In this paper we summa-
rize the studies of laser radiation effect on optical prop-
erties of the suspensions of OLC and MWNTs in 
DMF [7, 8]. 
 
2. EXPERIMENTAL 
 
2.1 OLC suspension 
 
OLC samples were prepared by annealing detona-
tion nanodiamond particles in vacuum at 1800 K [9]. 
Annealing leads to nanodiamond graphitization and 
conversion to OLC. The OLC powders were dispersed 
in DMF by sonication. The suspension with an OLC 
concentration of 1 mg/ml was found to be stable. The 
average size of the OLC agglomerates was about 
170 nm as determined by photon correlation spectros-
copy (PSS Nicomp 380/ZLS instrument). The transmis-
sion electron microscopic (TEM) image of the OLC 
sample is shown in the Fig. 1a.  
The suspension was injected into an optical cuvette 
and affected by the laser pulses, with the duration of 
20 ns and the wavelength of 1064 nm.  
 
2.2 MWNTs suspension 
 
The MWNTs were produced by the CVD technology 
in the reaction of ethylene thermal decomposition on the 
Fe/Co catalysts. Its average diameter and length were 
7-9 nm and 10-20 µm, respectively. Synthesized 
MWNTs contained impurities of iron on account of the 
Fe/Co catalyst used, hereupon, the bundles of MWNTs 
possessed paramagnetic properties that revealed itself 
in their feature of attracting to one or the other 
constant magnet pole. The stable suspension of MWNTs 
in DMF was obtained using ultrasonic dispersion. The 
MWNTs concentration was 0.015 g/l. The TEM image of 
MWNTs is shown in Fig. 1b. 
 
 
 
Fig. 1 – TEM images of OLC sample (a) and MWNTs 
sample (b). The dark lines represent projections of graphene 
shells perpendicular to the image plane. 
 
The suspension was injected into an optical cuvette 
and affected by the laser pulses, with the duration of 
17 ns and the wavelength of 532 nm. 
 
3. RESULTS AND DUSCUSSION  
 
The transmittances of the cuvettes with studied 
suspensions τ = Eout/Ein 100  (where Eout, Ein are the 
energies of transmitted and incident pulse, 
respectively) are presented in Figure 2a,b. These 
curves illustrate that after a certain number of laser 
shots the irradiated zones of both suspensions become 
essentially transparent. At the same time the first la-
ser pulses experience optical limiting in both suspen-
sions, however, after the suspensions treatment by a 
large number of laser pulses the suspensions bleach 
and cease to absorb the incident radiation in the laser 
beam area. 
Though the suspensions lose optical limiting, with 
the small bleached part moving upward due to the 
 D.L. BULATOV, K.G. MIKHEEV, M.A. SHUVAEVA PROC. NAP 2, 03NCNN22 (2013) 
 
 
03NCNN22-2 
thermal convection, they can operate as the OL. 
Thereto it is necessary for the non-bleached portion of 
the suspension to get into the interaction area after 
each laser flash. It is evident that it can be realized by 
simple suspension mixing, but can also be put into 
effect by another way. It was mentioned above that 
MWNTs obtained possess paramagnetic properties, with 
the motion of the nanotubes particles bundles in the 
field of constant magnet being observed by an unaided 
eye in the non-dispersed suspension. It was also estab-
lished that bleached fraction of the OLC suspension 
possess pronounced diamagnetic properties (initial 
OLC suspension did not possess such properties) that 
reveals itself in the motion of the bleached fraction in 
the non-uniform magnet field as a diamagnetic parti-
cle. So it was possible to initiate the both suspensions 
motion by a field effect of a constant magnet situated 
near the cuvette in certain way.  
It is clear that the chaotic motion of the suspension 
elements can be initiated by other methods, such as a 
nonuniform heating of the cuvette with the suspension. 
However, the technique described allows the suspen-
sions to operate as optical limiters without contact with 
the heater elements. 
 
 
 
Fig. 2 – Transmittance τ of the OLC (a) and MWNTs (b) suspensions in DMF as a function of N at laser pulses energies of 0.5 mJ 
and 0.079 mJ, respectively.  
 
4. CONCLUSION 
 
The results presented demonstrate that high-power 
nanosecond laser pulses have a significant effect on 
optical properties of OLC and MWNTs suspensions in 
DMF. The optical limiters and passive laser switches 
based on the phenomenon of laser-induced bleaching in 
these suspensions can be designed.  
 
AKNOWLEDGEMENTS 
 
The work was supported by RFFR grant № 12-02-
31724 
 
 
REFERENCES 
 
1. L. Vivien, D. Riehl, P. Lancon, et al, Opt. Lett. 26, 223 
(2001). 
2. G.M. Mikheev, D.L. Bulatov, T.N. Mogileva, et al., Tech. 
Phys. Lett. 33, 41 (2007) 
3. H.B. Qin, Y.G. Wang, H.B. Zhang, et al., Laser Phys. 22, 
684-687 (2012). 
4. H. Iliev, I. Buchvarov, S. Y, Choi, et al., Appl. Phys. B: 
Lasers Opt. 106, 1 (2012). 
5. K. Dou, E.T. Knobbe, J. Nonlinear Opt. Phys. Mater. 9, 
269 (2000). 
6. E. Koudoumas, O. Kokkinaki, M. Konstantaki, et al., 
Chem. Phys. Lett. 357, 336 (2002). 
7. V.L. Kuznetsov, S.I. Moseenkov, K.V. Elumeeva, et al., 
Phys. Status Solidi B 248, 2572 (2011). 
8. G.M. Mikheev, V.L. Kuznetcov, D.L. Bulatov, et al., Quan-
tum Electron. 39, 342 (2009). 
9. G.M. Mikheev V.L. Kuznetcov, K.G. Mikheev, et al. Tech. 
Phys. Lett. 39, 337 (2013). 
 


Laser-Induced Bleaching of Carbon Nanomaterials Suspensions

Electronic Sumy State University Institutional Repository

PROCEEDINGS OF THE INTERNATIONAL CONFERENCE  NANOMATERIALS: APPLICATIONS AND PROPERTIES Vol. 2 No 3, 03NCNN22 (2pp) (2013)   2304-1862/2013/2(3) 03NCNN22 (2) 03NCNN22-1  2013  Laser-Induced Bleaching of Carbon Nanomaterials Suspensions  D.L. Bulatov1,*, K.G. Mikheev1,†, M.A. Shuvaeva2,‡  1  Institute of Mechanics, Ural Branch of RAS, 34, T. Baramzina Str., 426067 Izhevsk, Russia 2 Institute of Catalysis, Siberian Branch of RAS, 5, Ak. Lavrent’eva Ave., 630090 Novosibirsk, Russia  (Received 30 May 2013; published online 1 September 2013)  We have studied the effect of nanosecond laser pulses on the optical properties of onion-like (OLC) and multi-wall carbon nanotubes (MWNTs) suspensions in N,N-dimethylformamide (DMF). The results demonstrate that both suspensions irreversibly bleach under high-intensity laser radiation. The bleaching is accompanied by losing optical limiting (OL) in suspensions.   Keywords: Onion-Like Carbon, Multi-Wall Carbon, Optical Limiting, Suspension, Bleaching.   PACS numbers: 78.67.Ch, 78.67.Bf, 85.60.Bt                                                             * dlbulatov@udman.ru † k.g.mikheev@gmail.com ‡ mas@catalysis.ru 1. INTRODUCTION  The laser radiation interaction with suspensions of various carbon nanoparticles is of interest for the de-velopment of optical limiters and passive laser switches intended to protect light sensors and human eyes from optical damage [1-4]. In contrast to fullerene solu-tions [5], suspensions of OLC and MWNTs have a broad absorption band [6, 7]. At the same time our ex-periments have shown the suspensions of OLC and MWNTs in DMF to be sufficiently stable in contrast to the similar aqueous suspensions [6]. This makes such suspensions potentially attractive for the development of broadband optical limiters. In this paper we summa-rize the studies of laser radiation effect on optical prop-erties of the suspensions of OLC and MWNTs in DMF [7, 8].  2. EXPERIMENTAL  2.1 OLC suspension  OLC samples were prepared by annealing detona-tion nanodiamond particles in vacuum at 1800 K [9]. Annealing leads to nanodiamond graphitization and conversion to OLC. The OLC powders were dispersed in DMF by sonication. The suspension with an OLC concentration of 1 mg/ml was found to be stable. The average size of the OLC agglomerates was about 170 nm as determined by photon correlation spectros-copy (PSS Nicomp 380/ZLS instrument). The transmis-sion electron microscopic (TEM) image of the OLC sample is shown in the Fig. 1a.  The suspension was injected into an optical cuvette and affected by the laser pulses, with the duration of 20 ns and the wavelength of 1064 nm.   2.2 MWNTs suspension  The MWNTs were produced by the CVD technology in the reaction of ethylene thermal decomposition on the Fe/Co catalysts. Its average diameter and length were 7-9 nm and 10-20 µm, respectively. Synthesized MWNTs contained impurities of iron on account of the Fe/Co catalyst used, hereupon, the bundles of MWNTs possessed paramagnetic properties that revealed itself in their feature of attracting to one or the other constant magnet pole. The stable suspension of MWNTs in DMF was obtained using ultrasonic dispersion. The MWNTs concentration was 0.015 g/l. The TEM image of MWNTs is shown in Fig. 1b.    Fig. 1 – TEM images of OLC sample (a) and MWNTs sample (b). The dark lines represent projections of graphene shells perpendicular to the image plane.  The suspension was injected into an optical cuvette and affected by the laser pulses, with the duration of 17 ns and the wavelength of 532 nm.  3. RESULTS AND DUSCUSSION   The transmittances of the cuvettes with studied suspensions τ = Eout/Ein 100  (where Eout, Ein are the energies of transmitted and incident pulse, respectively) are presented in Figure 2a,b. These curves illustrate that after a certain number of laser shots the irradiated zones of both suspensions become essentially transparent. At the same time the first la-ser pulses experience optical limiting in both suspen-sions, however, after the suspensions treatment by a large number of laser pulses the suspensions bleach and cease to absorb the incident radiation in the laser beam area. Though the suspensions lose optical limiting, with the small bleached part moving upward due to the  D.L. BULATOV, K.G. MIKHEEV, M.A. SHUVAEVA PROC. NAP 2, 03NCNN22 (2013)   03NCNN22-2 thermal convection, they can operate as the OL. Thereto it is necessary for the non-bleached portion of the suspension to get into the interaction area after each laser flash. It is evident that it can be realized by simple suspension mixing, but can also be put into effect by another way. It was mentioned above that MWNTs obtained possess paramagnetic properties, with the motion of the nanotubes particles bundles in the field of constant magnet being observed by an unaided eye in the non-dispersed suspension. It was also estab-lished that bleached fraction of the OLC suspension possess pronounced diamagnetic properties (initial OLC suspension did not possess such properties) that reveals itself in the motion of the bleached fraction in the non-uniform magnet field as a diamagnetic parti-cle. So it was possible to initiate the both suspensions motion by a field effect of a constant magnet situated near the cuvette in certain way.  It is clear that the chaotic motion of the suspension elements can be initiated by other methods, such as a nonuniform heating of the cuvette with the suspension. However, the technique described allows the suspen-sions to operate as optical limiters without contact with the heater elements.    Fig. 2 – Transmittance τ of the OLC (a) and MWNTs (b) suspensions in DMF as a function of N at laser pulses energies of 0.5 mJ and 0.079 mJ, respectively.   4. CONCLUSION  The results presented demonstrate that high-power nanosecond laser pulses have a significant effect on optical properties of OLC and MWNTs suspensions in DMF. The optical limiters and passive laser switches based on the phenomenon of laser-induced bleaching in these suspensions can be designed.   AKNOWLEDGEMENTS  The work was supported by RFFR grant № 12-02-31724   REFERENCES  1. L. Vivien, D. Riehl, P. Lancon, et al, Opt. Lett. 26, 223 (2001). 2. G.M. Mikheev, D.L. Bulatov, T.N. Mogileva, et al., Tech. Phys. Lett. 33, 41 (2007) 3. H.B. Qin, Y.G. Wang, H.B. Zhang, et al., Laser Phys. 22, 684-687 (2012). 4. H. Iliev, I. Buchvarov, S. Y, Choi, et al., Appl. Phys. B: Lasers Opt. 106, 1 (2012). 5. K. Dou, E.T. Knobbe, J. Nonlinear Opt. Phys. Mater. 9, 269 (2000). 6. E. Koudoumas, O. Kokkinaki, M. Konstantaki, et al., Chem. Phys. Lett. 357, 336 (2002). 7. V.L. Kuznetsov, S.I. Moseenkov, K.V. Elumeeva, et al., Phys. Status Solidi B 248, 2572 (2011). 8. G.M. Mikheev, V.L. Kuznetcov, D.L. Bulatov, et al., Quan-tum Electron. 39, 342 (2009). 9. G.M. Mikheev V.L. Kuznetcov, K.G. Mikheev, et al. Tech. Phys. Lett. 39, 337 (2013).  

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