research article preparation of graphene oxide stabilized nickel nanoparticles...

Hindawi Publishing CorporationJournal of NanomaterialsVolume 2013 Article ID 986764 9 pageshttpdxdoiorg1011552013986764

Research ArticlePreparation of Graphene Oxide Stabilized Nickel Nanoparticleswith Thermal Effusivity Properties by Laser Ablation Method

Amir Reza Sadrolhosseini1 A S M Noor12 Kamyar Shameli3 Alireza Kharazmi4

N M Huang5 and M A Mahdi12

1 Wireless and Photonics Networks Research Center of Excellence (WiPNET) Faculty of Engineering University Putra Malaysia43400 Serdang Malaysia

2 Department of Computer and Communication Systems Engineering Faculty of Engineering University Putra Malaysia43400 Serdang Malaysia

3 Department of Chemistry Faculty of Science University Putra Malaysia 43400 Serdang Malaysia4Department of Physics Faculty of Science University Putra Malaysia 43400 Serdang Malaysia5 Low Dimensional Materials Research Centre Physics Department University of Malaya Malaysia

Correspondence should be addressed to A S M Noor ashuriupmedumy

Received 4 May 2013 Revised 20 August 2013 Accepted 28 August 2013

Academic Editor Tianxi Liu

Copyright copy 2013 Amir Reza Sadrolhosseini et al This is an open access article distributed under the Creative CommonsAttribution License which permits unrestricted use distribution and reproduction in any medium provided the original work isproperly cited

Nickel nanoparticles were dispersed uniformly in a graphene oxide solution using a laser ablation technique with different ablationtimes that ranged from 5 to 20 minutes The results indicate that the nickel nanoparticle sizes inside the graphene oxide decreasedand the volume fraction for the nickel nanoparticles in the graphene oxide increasedwith an increasing ablation time Further usingFourier Transform Infrared Spectroscopy the nickel nanoparticles in the graphene oxide demonstrate greater stability frompossibleagglomerationwhen the nanoparticlewas cappedwith oxygen from the carboxyl groupof the graphene oxideThe thermal effusivityof the graphene oxide and nickel nanoparticle graphene oxide composite was measured using a photoacoustic technique Theconcentration of graphene oxide shifted from 005mgL to 2mgL and the thermal effusivity increased from 0153Wsdots12sdotcmminus2sdotKminus1

to 0326Wsdots12sdotcmminus2sdotKminus1 In addition the thermal effusivity of the nickel nanoparticles graphene oxide composite increased withan increase in the volume fraction of nickel nanoparticles from 01612Wsdots12sdotcmminus2sdotKminus1 to 0228Wsdots12sdotcmminus2sdotKminus1

1 Introduction

Nickel nanoparticles (Ni-NPs) have many important appli-cations as catalysts conducting and magnetic materials [1]and an electrode layer in multilayer ceramic capacitors [2 3]and have both unique properties and potential applicationsin a variety of fields including electronics [4] magnetic [5]energy technology [6] and biomedicine [7] Ni-NPs canbe synthesized using many methods including photolyticreduction [8] radiolytic reduction [9] sonochemical [10]solvent extraction reduction [11] microemulsion technique[12] polyol method [13] and microwave irradiation [14]

Graphene Oxide (GO) is obtained from the oxidationof graphite crystals a single-atomic-layered material It can

dissolve and disperse in a variety of solutions including waterGO has more applications for use in composites materials[15] solar cells [16] medicine [17 18] antibacterial materials[19] and inorganic optoelectronic devices [20] The GOmolecular structure includes hydroxyl (OHndash) and epoxy(ndashCOOminus) groups at the basal plane Further it also containscarboxyl groups (ndashCOOminus) at the edge of the molecularstructure [21 22]

Metal nanoparticles can improve andmodify the physicalproperties of GO [20] as can be seen in [20] where the alter-ation of light scattering was achieved allowing an improvedabsorption of light in the solar cell Further Benayad etal improved the resistivity of GO by the use of metalnanoparticles [23]

2 Journal of Nanomaterials

NdYAG laser

Lens

Holder

Ni plate

Mechanical stirrer

Ni-NPs

Figure 1 Laser ablation setup for preparation of Ni-NPs in theGO solution The nickel plate is ablated by the tense pulsed laser atdifferent times of 5 10 15 and 20 minutes

A Ni-NPs-GO composite was used as a catalyst forfabrication of carbon nanotube [24] to determine the concen-tration of glucose in human blood [25] remove and detectaromatic compounds like benzene and toluene in environ-mental circumstances [26] and develop an electrochemicalelectrode for sensing carbohydrates [27]

The application of the laser ablation technique offers anovel unique tool for nanofabrication [28] When the laserablation is used to produce the metal nanoparticles in anaqueous solution the nanoparticles are released inside thesolution and nanofluid is formed [29 30] Metal nanoparti-cles preparations are relatively difficult to create because theyare easily oxidizedTheproperties of nanoparticles using laserablation are unique and they are not reproducible by anyother method [31 32] For example the fabrication of Ni-NPsin liquid does not require any chemical reduction agent [33]and dimension control is easier than with chemical methods

The thermal properties are significant to characterizethe nanofluid Thermal effusivity explains the aptness ofnanofluid to be able to exchange heat or thermal energywith the environment and measure the thermal impedanceof fluids The relationship between the thermal effusivity (120576)and the thermal conductivity (119896) is given as [34]

120576 = radic119896 120588 119888

119901 (1)

where 120588 and 119888119901are the density of the sample and specific

heat A photoacoustic (PA) application is used tomeasure thethermal properties of the nanomaterial for example thermaleffusivity

In this study Ni-NPs was synthesized in GO using laserablation The size shape distribution and concentration ofNi-NPs in GO were obtained through transmission elec-tron microscopy (TEM) and atomic absorption spectroscopy(AAS) and the binding ofNi-NPs toGOwas analyzed using aFourier Transform Infrared Spectroscopy (FT-IR) Moreover

He-Ne laser

Mirror Chopper

Microphone

Fluid CellAl foil

Preamplifier Lock in amplifier

Figure 2 Photoacoustic open cell setup contains a He-Ne laser achopper a mirror a microphone a preamplifier a lock-in amplifierand a fluid cell

the thermal effusivity of the GO and Ni-NPs-GO compositewas measured using an open cell photoacoustic technique

2 Materials and Methods

21 Sample Preparation The preparation of GO followed theprevious reports by Huang et al [35] A final concentration of2mgL GO in water was used for this study

Figure 1 shows the schematic diagram for the laser abla-tion setupThe nickel plate (9999 purity SigmaAldrich StLouis MO) was immersed in 30mL GO and ablated with apulsed Q-Switched NdYAG laser A pulse duration of 10 nsand 40Hz repetition rate at wavelength 532 nm with 1200mJpower was applied to prepare Ni-NPs in GO solution Duringthe ablation a stirrer was used to uniformly disperse the Ni-NPs in GO The laser beam was focused on the nickel targetusing a 300mm focal length lens The ablation was carriedout at room temperature with different duration times 5 1015 and 20 minutes The nickel nanofluids were characterizedusing an atomic absorption spectroscopy (AAS S series)a transmission electron microscopy (TEM Hitachi H-7100Hitachi Chula Vista CA) and a Fourier Transform InfraredSpectroscopy (FT-IR)

22 Photoacoustic Setup Figure 2 depicts the photoacousticsetup containing aHe-Ne laser (75mW 6328 nm) a choppera mirror a fluid cell a microphone a preamplifier and alock in amplifier The chopper frequency was controlled bya computer program that shifted from 21Hz to 236Hz

The bottom of the fluid cell was closed and shut using a0017mm thick aluminum sheet and the fluid cell was filledwith the nanofluid To measure thermal effusivity of the Ni-NPs-GO composite the photoacoustic signals were detectedusing an electret microphone connected to a preamplifierand lock-in amplifier The phase and amplitude of the signalswere registered as a function of a light beam modulationfrequency Measurements were carried out at room temper-ature for an empty fluid cell and a fluid cell with Ni-NPs-GO composite In order to obtain thermal effusivity theamplitude of the photoacoustic signal was analyzed using theRosencwaig-Gersho (RG) theory

Journal of Nanomaterials 3

(a) (b)

(c) (d)

Figure 3 TEM images for Ni-NPs distribution in the GO solution for different ablation times (a) 5min (b) 10min (c) 15min and (d) 20min

3 Results and Discussion

Figure 3 shows the TEM patterns achieved by using the sameaccelerating voltage of 120 kV and the patterns explain theshape particle size and distribution of Ni-NPs inside theGO As shown in Figures 3 and 4 the Ni-NPs which weredistributed evenly in the GO had a spherical shape and theparticle size decreased with an increase of the ablation timeThis results is illustrated in Figure 4 which shows that themean sizes of Ni-NPs in the GO decreased from 1553 nm to683 nm In addition Figure 4 shows the distribution of Ni-NPsrsquo increasing with a longer ablation time

The Ni-NPs concentrations were measured by AAS andthe concentrations increased with increases in the ablationtime Volume fractions (V) were calculated by the followingequation

119881 =

119881

119901

119881

119901+ 119881

119871

(2)

where 119881119871and 119881

119901are the volume of liquid and the volume of

the particles (119898120588 where 120588 and 119898 are the mass density ofthe nickel and the particles mass dispersed in the GO resp)Hence (3) was derived from a modification of (2) as follows

119881 =

119862Particle119862Particle + 120588

(3)

Table 1 Pertinent parameters ofNi nanoparticles in graphene oxide

Sample Size (nm) Concentration (ppm) Volume fraction5min 1553 09 0101 times 10

minus6

10min 1230 173 01942 times 10

minus6

15min 976 323 03626 times 10

minus6

20min 683 486 05456 times 10

minus6

where 119862Particle are the concentrations of the Ni-NPs-GOcomposite obtained from AAS resultThe pertinent parameters are displayed in Table 1

The FT-IR spectra were recorded to identify capping ofthe Ni-NPs in the GO Figure 5 shows the FT-IR spectrum ofthe GO where plot (a) did not contain any impurity and plot(b) showed the spectrum containingNi-NPs dispersed inGOBoth results exhibit the FT-IR spectra of the GO and the Ni-NPs-GO composite at a frequency range of 4000ndash300 cmminus1The spectrum in plot (a) shows transmission peaks at 32322829 1719 1611 1401 1155 1029 856 564 and 412 cmminus1Similarly transmission peaks for the Ni-NPs in the GO wereobtained at 3218 2914 1718 1595 1411 1037 792 736 665 615587 543 438 and 375 cmminus1 for plot (b) The FT-IR spectra ofthe GO and Ni-NPsGO hybrid showed the peak at 1719 1611and 1401 cmminus1 had shifted to 1718 1595 and 1411 cmminus1


6

5

4

3

2

1

0

Num

ber o

f par

ticle

5 10 15 20 25Particle diameter (nm)

Mean = 1553

(a)

5

4

3

2

1

0

Num

ber o

f par

ticle

0 5 10 15 20 25Particle diameter (nm)

Mean = 1230

(b)

10

8

6

4

2

0

Num

ber o

f par

ticle

5 10 15Particle diameter (nm)

Mean = 976

(c)

Num

ber o

f par

ticle

0

30

20

10


Mean = 683

(d)

Figure 4The distribution of size and the volume concentration of Ni-NPs inside the GO solution were (a) 5min (b) 10min (c) 15min and(d) 20min

In Figure 5 the broad peak at 1719 and 1611 cmminus1 cor-responding to ] (C=O) of ndashCOOH on the GO shifts to1718 and 1595 cmminus1 due to the formation of ndashCOOminus aftercoating with Ni-NPs The characteristic peak correspondingto the stretching vibration of Ni-O bond shifts to lower wavenumber that suggests that Ni-NPs are bound to the ndashCOOminuson the GO surface In plot 5(b) the broad peaks of 792 736665 615 587 543 438 and 375 cmminus1 are related to Van derWaals forces that are bonding with oxygen on the of GOsurface with surface charges of Ni-NPs [36] Consequentlythe Ni-NPs were located on the GO surface and between theGO sheets (see Figure 5(c))

In accordance with RG theory the amplitude of the pho-toacoustic signal is inversely proportional to the modulationfrequency [36] The amplitude of pressure fluctuations (120575119875)in the presence of Ni-NPsGO was calculated as

|120575119875| =

119875

1

119891

1198752(1 + 119875

3radic119891 + (119875

2

3)radic2119891)

12 (4)

where

119875

3=

2120576

119904

120576Al119897Al(

120572Al120587

)

12

(5)


OH

OH

OH

O

OO

O

OO

O

O

CO2H CO2H CO2H

CO2HCO2H CO2H

CO2H

CO2H

HO HO HO

OH

OH

OH

O

OO

O

OO

O

O

CO2H

CO2H

CO2H

CO2H

HO HO HOOOOOOOOOOOOOOOOOOOOOOOOO

OOOOOOOOOOOO

Laser ablation

Graphene oxide

(a)

(b)

(c) Ni-NPsGO composite

Tran

smitt

ance

(au

)

Wavelength (cmminus1)4000 3000 2000 1000 300

32182914

32322829

17181595 1411

17191611

14011155

1037

1029

736615

543

792665

587 375

438

412

564859

Figure 5 Plots (a) and (b) show the FT-IR results for pure GO and GO with Ni-NPs respectively Plot (c) graphene oxide sheet before andafter laser ablation shows the Ni-NPs located on the surface of the GO and between the GO sheets

005

004

003

002

001

0000 50 100 150 200 250

Frequency (Hz)

PA i

nten

sity

Water

Ethylene glycol

Experimental data for waterTheory

TheoryExperimental data for ethylene glycol

Figure 6 Photoacoustic signal to calibrate and test the setup The thermal effusivity of water and ethylene glycol are 01631 and00931Wsdots12sdotcmminus2sdotKminus1 respectively


(5) (6)

(4)

(2)(1)

(3)

0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

001

003

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y

Experimental dataTheory


Figure 7 Photoacoustic signals for measurement of thermal effusivity of the GO indicate the concentration (1) 005mgL (2) 01mgL (3)03mgL (4) 05mgL (5) 08mgL and (6) 2mgL

120572Al 120576Al and 119897Al are the thermal diffusivity thermal effusivityand thickness of the aluminium foil To measure the thermaleffusivity of the GO and Ni-NPsGO composite 119875

1and

119875

2have to obtain from the Al foil signal as a function of

modulation frequency Adjustable parameters (1198751and 119875

2)

must be calculated by fitting the former data to [34]

1003816

1003816

1003816

1003816

120575119875Al1003816

1003816

1003816

1003816

= 119875

1119891

1198752 (6)

The experiment was carried out with deionized (DI) waterand ethylene glycol to calibrate the setup (see Figure 6)

The measurement of thermal effusivity was done for theGO and Ni-NPsGO composite with different concentrationof GO and Ni-NPs respectively The photoacoustic signalsused for measuring of thermal effusivity are depicted inFigures 7 and 8 120576

119886 119897Al and 120572Al are 236 Wsdots12sdotcmminus2sdotKminus1

00017 cm and 099 cm2s respectively and the results arefurther sorted in Table 2

The concentration of the GO solution was shifted from01mgL to 2mgL and the thermal effusivity of the GOsolution increased when increasing the concentration of theGO from 0153Wsdots12sdotcmminus2sdotKminus1 to 0326Wsdots12sdotcmminus2sdotKminus1(Figure 9(a)) The variation in the thermal effusivityof the Ni-NPsGO composite is shown in Figure 9(b)enhanced by increasing the volume fraction of Ni-NPs from01612Wsdots12sdotcmminus2sdotKminus1 to 0228Wsdots12sdotcmminus2sdotKminus1 The ther-mal effusivity concept is an exchange of heatwith the environ-mentThe effective nanofluid surface expanded by increasingthe volume fraction and the ability of the nanofluid toexchange heat with the environment was enhanced whenthe volume fraction increased causing an increase in thethermal effusivity of the Ni-NPs-GO composite


0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

001

004

003

Frequency (Hz)

P A

int

ensit

y0 50 100 150 200 250

0

002

004

006

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y



5 min 10 min

15 min 20 min

Figure 8 Photoacoustic signals for Ni-NPs-GO composite with different ablation times are displayed

026

024

022

020

018

0160 05 1 15 2

Concentration (mgL)

Ther

mal

effus

ivity

(Wmiddots1

2middotcm

minus2middotK

minus1)

(a)

025

024

023

022

021

020

019

018

017

016

1 2 3 4 5 6

Ther

mal

effus

ivity

(Wmiddots1

2middotcm

minus2middotK

minus1)

Volume fraction times10minus7

(b)

Figure 9 Variation of thermal effusivity versus (a) concentration of GO and (b) volume fraction of Ni-NPs in graphene oxide

4 Conclusions

The Ni-NPs were synthesized in the GO using the laserablation method The binding between the carboxyl groups(ndashCOOminus) on the GO and Ni-NPs occurred and achieved viaFT-IR spectroscopyThe particle sizes of 1553 1230 976 and683 nm were obtained in 5 10 15 and 20 minutes ablationtimes respectively The GO controls the particle size and

shape and prevents agglomeration between the ablated Ni-NPsHence theNi-NPs stay completely stable for a long timeand with an increase in the ablation time the particle sizereduces and both absorption and volume fraction increase

Consequently laser ablation is an environmentallyfriendly simple and green method for preparation ofNi-NPs in the GO Moreover the photoacoustic signals canbe registered for a determination of thermal effusivity of


Table 2 Pertinent parameters of theGOandNi-NPsGO compositefor measuring thermal effusivity

Sample 119875

3120576

119904(Wsdots12sdotcmminus2sdotKminus1)

Water 45631 0163Ethylene glycol 26038 0093GO

005mgL 43064 015301mgL 46578 016603mgL 47457 016905mgL 48791 017408mgL 60731 02162mgL 91474 0326

Ni-NPs5min 45127 016110min 47125 016815min 54725 019520min 63792 0228

the Ni-NPsGO composite The results show that with anincreasing volume fraction of Ni nanofluid the thermaleffusivity does increase

Acknowledgments

The authors acknowledge Universiti Putra Malaysia for thefund from the Research University Grant Scheme (05-02-12-2015RU05-01-12-1626RU05-01-12-1627RU) and the post-doctoral fellowship under the Wireless and Photonics Net-work Research Centre (WiPNet)

References

[1] S H Wu and D H Chen ldquoSynthesis and characterization ofnickel nanoparticles by hydrazine reduction in ethylene glycolrdquoJournal of Colloid and Interface Science vol 259 no 2 pp 282ndash286 2003

[2] W Wang Y Itoh I Lenggoro and K Okuyama ldquoNickeland nickel oxide nanoparticles prepared from nickel nitratehexahydrate by a lowpressure spray pyrolysisrdquoMaterials Scienceand Engineering B vol 111 no 1 pp 69ndash76 2004

[3] R Eluri and B Paul ldquoMicrowave assisted greener synthesis ofnickel nanoparticles using sodium hypophosphiterdquo MaterialsLetters vol 76 pp 36ndash39 2012

[4] W Tseng and C Chen ldquoDispersion and rheology of nickelnanoparticle inksrdquo Journal of Materials Science vol 41 no 4pp 1213ndash1219 2006

[5] S P Gubin Y A Koksharov G B Khomutov and G YYurkov ldquoMagnetic nanoparticles preparation structure andpropertiesrdquo Russian Chemical Reviews vol 74 no 6 pp 489ndash520 2005

[6] R Karmhag T Tesfamichael E Wackelgard G Niklasson andM Nygren ldquoOxidation kinetics of nickel particles comparisonbetween free particles and particles in an oxide matrixrdquo SolarEnergy vol 68 no 4 pp 329ndash333 2000

[7] S R Llamazares J Mercha I Olmedo et al ldquoNiNi oxidesnanoparticles with potential biomedical applications obtainedby displacement of a nickel-organometallic complexrdquo Journal

of Nanoscience and Nanotechnology vol 8 no 8 pp 3820ndash38272008

[8] F Alonso P Riente J A Sirvent and M Yus ldquoNickel nanopar-ticles in hydrogen-transfer reductions characterisation andnature of the catalystrdquo Applied Catalysis A vol 378 no 1 pp42ndash51 2010

[9] S Remita M Mostafavi and M O Delcourt ldquoBimetallic AgndashPt and AundashPt aggregates synthesized by radiolysisrdquo RadiationPhysics and Chemistry vol 47 no 2 pp 275ndash279 1996

[10] Y Mizukoshi K Okitsu Y Maeda T A Yamamoto ROshima and Y Nagata ldquoSonochemical preparation of bimetal-lic nanoparticles of goldpalladium in aqueous solutionrdquo Jour-nal of Physical Chemistry B vol 101 no 36 pp 7033ndash7037 1997

[11] M BrustMWalker D Bethell D J Schiffrin and RWhymanldquoSynthesis of thiol-derivatised gold nanoparticles in a two-phase liquid-liquid systemrdquo Journal of the Chemical SocietyChemical Communications no 7 pp 801ndash802 1994

[12] K Osseo-Asare and F J Arriagada ldquoSynthesis of nanosizeparticles in reverse microemulsionsrdquoCeramic Transactions vol12 no 3 pp 3ndash16 1990

[13] L K Kurihara G M Chow and P E Schoen ldquoNanocrystallinemetallic powders and films produced by the polyol methodrdquoNanostructured Materials vol 5 no 6 pp 607ndash613 1995


[15] S Stankovich D A Dikin G H B Dommett et al ldquoGraphene-based composite materialsrdquo Nature vol 442 no 7100 pp 282ndash286 2006

[16] Y Zhu S Murali W Cai et al ldquoGraphene and graphene oxideSynthesis properties and applicationsrdquo Advanced Materialsvol 22 no 35 pp 3906ndash3924 2010

[17] Y Song K Qu C Zhao J Ren and X Qu ldquoGraphene oxideIntrinsic peroxidase catalytic activity and its application toglucose detectionrdquoAdvancedMaterials vol 22 no 19 pp 2206ndash2210 2010

[18] M Lv Y Zhang L Liang et al ldquoEffect of graphene oxide onundifferentiated and retinoic acid-differentiated SH-SY5Y cellslinerdquo Nanoscale vol 4 no 13 pp 3861ndash3866 2012

[19] W Hu C Peng W Luo et al ldquoGraphene-based antibacterialpaperrdquo ACS Nano vol 4 no 7 pp 4317ndash4323 2010

[20] M Choe C Y Cho J P Shim et al ldquoAu nanoparticle-decoratedgraphene electrodes for GaN-based optoelectronic devicesrdquoPhysics Letters vol 101 no 3 Article ID 031115 2012

[21] G Eda andMChhowalla ldquoChemically derived graphene oxidetowards large-area thin-film electronics and optoelectronicsrdquoAdvanced Materials vol 22 no 22 pp 2392ndash2415 2010

[22] D S Sutar G Singh and V D Botcha ldquoElectronic structureof graphene oxide and reduced graphene oxide monolayersrdquoApplied Physics Letters vol 101 Article ID 103103 2012

[23] A Benayad H-J Shin H K Park et al ldquoControlling workfunction of reduced graphite oxide with Au-ion concentrationrdquoChemical Physics Letters vol 475 no 1ndash3 pp 91ndash95 2009

[24] H Qing-Hua X-T Wang H Chen and Z-F Wang ldquoSynthesisofNigraphene sheets by an electrolessNi-platingmethodrdquoNewCarbon Materials vol 27 no 1 pp 35ndash41 2012

[25] Y Zhanga Y Wangb J Jia b and J Wanga ldquoNonenzymaticglucose sensor based on graphene oxide and electro spun NiONanofibersrdquo Sensors and Actuators B vol 171-172 pp 580ndash5872012


[26] S Li Z Niu X Zhong et al ldquoFabrication of magneticNi nanoparticles functionalized water-soluble graphene sheetsnanocomposites as sorbent for aromatic compounds removalrdquoJournal of Hazardous Materials vol 229-230 pp 42ndash47 2012

[27] W Qu L Zhang and G Chen ldquoMagnetic loading of graphene-nickel nanoparticle hybrid for Electrochemical sensing of car-bohydratesrdquo Biosensors and Bioelectronics vol 42 pp 430ndash4332013

[28] A V Kabashin and M Meunier Recent Advances in LaserProcessing Material Elsevier Amsterdam The Netherlands2006

[29] J P Sylvestre A V Kabashin E Sacher M Meunier and J HT Luong ldquoStabilization and size control of gold nanoparticlesduring laser ablation in aqueous cyclodextrinsrdquo Journal of theAmerican Chemical Society vol 126 no 23 pp 7176ndash7177 2004

[30] J P Sylvestre A V Kabashin E Sacher and M MeunierldquoFemtosecond laser ablation of gold in water influence of thelaser-produced plasma on the nanoparticle size distributionrdquoApplied Physics A vol 80 no 4 pp 753ndash758 2005

[31] F Mafune J Y Kohno Y Takeda T Kondow and H SawabeldquoStructure and stability of silver nanoparticles in aqueous solu-tion produced by laser ablationrdquo Journal of Physical ChemistryB vol 104 no 35 pp 8336ndash8833 2000

[32] S Besner A V Kabashin F M Winnik and M MeunierldquoUltrafast laser based ldquogreenrdquo synthesis of non-toxic nanopar-ticles in aqueous solutionsrdquo Applied Physics A vol 93 no 4 pp955ndash959 2008

[33] A V Kabashin and M Meunier ldquoSynthesis of colloidalnanoparticles during femtosecond laser ablation of gold inwaterrdquo Journal of Applied Physics vol 94 no 12 pp 7941ndash79432003

[34] J A Balderas-Lopez D Acosta-Avalos J J Alvarado et alldquoPhotoacoustic measurements of transparent liquid samplesthermal effusivityrdquoMeasurement Science and Technology vol 6no 8 pp 1163ndash1168 1995

[35] N M Huang H N Lim C H Chia M A Yarmo andM R Muhamad ldquoSimple room-temperature preparation ofhigh-yield large-area graphene oxiderdquo International Journal ofNanomedicine vol 6 pp 3443ndash3448 2011

[36] O Delgado-Vasallo and E Marin ldquoApplication of the photoa-coustic technique to the measurement of the thermal effusivityof liquidsrdquo Journal of Physics D vol 32 no 5 pp 593ndash597 1999

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Smart Materials Research



MetallurgyJournal of


BioMed Research International

MaterialsJournal of


Nano

materials


Journal ofNanomaterials


NdYAG laser

Lens

Holder

Ni plate

Mechanical stirrer

Ni-NPs

Figure 1 Laser ablation setup for preparation of Ni-NPs in theGO solution The nickel plate is ablated by the tense pulsed laser atdifferent times of 5 10 15 and 20 minutes

A Ni-NPs-GO composite was used as a catalyst forfabrication of carbon nanotube [24] to determine the concen-tration of glucose in human blood [25] remove and detectaromatic compounds like benzene and toluene in environ-mental circumstances [26] and develop an electrochemicalelectrode for sensing carbohydrates [27]

The application of the laser ablation technique offers anovel unique tool for nanofabrication [28] When the laserablation is used to produce the metal nanoparticles in anaqueous solution the nanoparticles are released inside thesolution and nanofluid is formed [29 30] Metal nanoparti-cles preparations are relatively difficult to create because theyare easily oxidizedTheproperties of nanoparticles using laserablation are unique and they are not reproducible by anyother method [31 32] For example the fabrication of Ni-NPsin liquid does not require any chemical reduction agent [33]and dimension control is easier than with chemical methods

The thermal properties are significant to characterizethe nanofluid Thermal effusivity explains the aptness ofnanofluid to be able to exchange heat or thermal energywith the environment and measure the thermal impedanceof fluids The relationship between the thermal effusivity (120576)and the thermal conductivity (119896) is given as [34]

120576 = radic119896 120588 119888

119901 (1)

where 120588 and 119888119901are the density of the sample and specific

heat A photoacoustic (PA) application is used tomeasure thethermal properties of the nanomaterial for example thermaleffusivity

In this study Ni-NPs was synthesized in GO using laserablation The size shape distribution and concentration ofNi-NPs in GO were obtained through transmission elec-tron microscopy (TEM) and atomic absorption spectroscopy(AAS) and the binding ofNi-NPs toGOwas analyzed using aFourier Transform Infrared Spectroscopy (FT-IR) Moreover

He-Ne laser

Mirror Chopper

Microphone

Fluid CellAl foil

Preamplifier Lock in amplifier

Figure 2 Photoacoustic open cell setup contains a He-Ne laser achopper a mirror a microphone a preamplifier a lock-in amplifierand a fluid cell

the thermal effusivity of the GO and Ni-NPs-GO compositewas measured using an open cell photoacoustic technique

2 Materials and Methods

21 Sample Preparation The preparation of GO followed theprevious reports by Huang et al [35] A final concentration of2mgL GO in water was used for this study

Figure 1 shows the schematic diagram for the laser abla-tion setupThe nickel plate (9999 purity SigmaAldrich StLouis MO) was immersed in 30mL GO and ablated with apulsed Q-Switched NdYAG laser A pulse duration of 10 nsand 40Hz repetition rate at wavelength 532 nm with 1200mJpower was applied to prepare Ni-NPs in GO solution Duringthe ablation a stirrer was used to uniformly disperse the Ni-NPs in GO The laser beam was focused on the nickel targetusing a 300mm focal length lens The ablation was carriedout at room temperature with different duration times 5 1015 and 20 minutes The nickel nanofluids were characterizedusing an atomic absorption spectroscopy (AAS S series)a transmission electron microscopy (TEM Hitachi H-7100Hitachi Chula Vista CA) and a Fourier Transform InfraredSpectroscopy (FT-IR)

22 Photoacoustic Setup Figure 2 depicts the photoacousticsetup containing aHe-Ne laser (75mW 6328 nm) a choppera mirror a fluid cell a microphone a preamplifier and alock in amplifier The chopper frequency was controlled bya computer program that shifted from 21Hz to 236Hz

The bottom of the fluid cell was closed and shut using a0017mm thick aluminum sheet and the fluid cell was filledwith the nanofluid To measure thermal effusivity of the Ni-NPs-GO composite the photoacoustic signals were detectedusing an electret microphone connected to a preamplifierand lock-in amplifier The phase and amplitude of the signalswere registered as a function of a light beam modulationfrequency Measurements were carried out at room temper-ature for an empty fluid cell and a fluid cell with Ni-NPs-GO composite In order to obtain thermal effusivity theamplitude of the photoacoustic signal was analyzed using theRosencwaig-Gersho (RG) theory


(a) (b)

(c) (d)





119881 =

119881

119901

119881

119901+ 119881

119871

(2)

where 119881119871and 119881



119881 =


(3)



minus6

10min 1230 173 01942 times 10

minus6

15min 976 323 03626 times 10

minus6

20min 683 486 05456 times 10

minus6




6

5

4

3

2

1

0

Num

ber o

f par

ticle


Mean = 1553

(a)

5

4

3

2

1

0

Num

ber o

f par

ticle


Mean = 1230

(b)

10

8

6

4

2

0

Num

ber o

f par

ticle


Mean = 976

(c)

Num

ber o

f par

ticle

0

30

20

10


Mean = 683

(d)




|120575119875| =

119875

1

119891

1198752(1 + 119875

3radic119891 + (119875

2

3)radic2119891)

12 (4)

where

119875

3=

2120576

119904

120576Al119897Al(

120572Al120587

)

12

(5)


OH

OH

OH

O

OO

O

OO

O

O

CO2H CO2H CO2H

CO2HCO2H CO2H

CO2H

CO2H

HO HO HO

OH

OH

OH

O

OO

O

OO

O

O

CO2H

CO2H

CO2H

CO2H


OOOOOOOOOOOO

Laser ablation

Graphene oxide

(a)

(b)


Tran

smitt

ance

(au

)


32182914

32322829

17181595 1411

17191611

14011155

1037

1029

736615

543

792665

587 375

438

412

564859


005

004

003

002

001

0000 50 100 150 200 250

Frequency (Hz)

PA i

nten

sity

Water

Ethylene glycol





(5) (6)

(4)

(2)(1)

(3)

0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

001

003

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y





1and

119875



2)


1003816

1003816

1003816

1003816

120575119875Al1003816

1003816

1003816

1003816

= 119875

1119891

1198752 (6)







0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

001

004

003

Frequency (Hz)

P A

int

ensit

y0 50 100 150 200 250

0

002

004

006

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y



5 min 10 min

15 min 20 min


026

024

022

020

018

0160 05 1 15 2

Concentration (mgL)

Ther

mal

effus

ivity

(Wmiddots1

2middotcm

minus2middotK

minus1)

(a)

025

024

023

022

021

020

019

018

017

016

1 2 3 4 5 6

Ther

mal

effus

ivity

(Wmiddots1

2middotcm

minus2middotK

minus1)


(b)


4 Conclusions






Sample 119875

3120576






Acknowledgments


References














































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




(a) (b)

(c) (d)





119881 =

119881

119901

119881

119901+ 119881

119871

(2)

where 119881119871and 119881



119881 =


(3)



minus6

10min 1230 173 01942 times 10

minus6

15min 976 323 03626 times 10

minus6

20min 683 486 05456 times 10

minus6




6

5

4

3

2

1

0

Num

ber o

f par

ticle


Mean = 1553

(a)

5

4

3

2

1

0

Num

ber o

f par

ticle


Mean = 1230

(b)

10

8

6

4

2

0

Num

ber o

f par

ticle


Mean = 976

(c)

Num

ber o

f par

ticle

0

30

20

10


Mean = 683

(d)




|120575119875| =

119875

1

119891

1198752(1 + 119875

3radic119891 + (119875

2

3)radic2119891)

12 (4)

where

119875

3=

2120576

119904

120576Al119897Al(

120572Al120587

)

12

(5)


OH

OH

OH

O

OO

O

OO

O

O

CO2H CO2H CO2H

CO2HCO2H CO2H

CO2H

CO2H

HO HO HO

OH

OH

OH

O

OO

O

OO

O

O

CO2H

CO2H

CO2H

CO2H


OOOOOOOOOOOO

Laser ablation

Graphene oxide

(a)

(b)


Tran

smitt

ance

(au

)


32182914

32322829

17181595 1411

17191611

14011155

1037

1029

736615

543

792665

587 375

438

412

564859


005

004

003

002

001

0000 50 100 150 200 250

Frequency (Hz)

PA i

nten

sity

Water

Ethylene glycol





(5) (6)

(4)

(2)(1)

(3)

0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

001

003

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y





1and

119875



2)


1003816

1003816

1003816

1003816

120575119875Al1003816

1003816

1003816

1003816

= 119875

1119891

1198752 (6)







0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

001

004

003

Frequency (Hz)

P A

int

ensit

y0 50 100 150 200 250

0

002

004

006

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y



5 min 10 min

15 min 20 min


026

024

022

020

018

0160 05 1 15 2

Concentration (mgL)

Ther

mal

effus

ivity

(Wmiddots1

2middotcm

minus2middotK

minus1)

(a)

025

024

023

022

021

020

019

018

017

016

1 2 3 4 5 6

Ther

mal

effus

ivity

(Wmiddots1

2middotcm

minus2middotK

minus1)


(b)


4 Conclusions






Sample 119875

3120576






Acknowledgments


References














































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




6

5

4

3

2

1

0

Num

ber o

f par

ticle


Mean = 1553

(a)

5

4

3

2

1

0

Num

ber o

f par

ticle


Mean = 1230

(b)

10

8

6

4

2

0

Num

ber o

f par

ticle


Mean = 976

(c)

Num

ber o

f par

ticle

0

30

20

10


Mean = 683

(d)




|120575119875| =

119875

1

119891

1198752(1 + 119875

3radic119891 + (119875

2

3)radic2119891)

12 (4)

where

119875

3=

2120576

119904

120576Al119897Al(

120572Al120587

)

12

(5)


OH

OH

OH

O

OO

O

OO

O

O

CO2H CO2H CO2H

CO2HCO2H CO2H

CO2H

CO2H

HO HO HO

OH

OH

OH

O

OO

O

OO

O

O

CO2H

CO2H

CO2H

CO2H


OOOOOOOOOOOO

Laser ablation

Graphene oxide

(a)

(b)


Tran

smitt

ance

(au

)


32182914

32322829

17181595 1411

17191611

14011155

1037

1029

736615

543

792665

587 375

438

412

564859


005

004

003

002

001

0000 50 100 150 200 250

Frequency (Hz)

PA i

nten

sity

Water

Ethylene glycol





(5) (6)

(4)

(2)(1)

(3)

0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

001

003

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y





1and

119875



2)


1003816

1003816

1003816

1003816

120575119875Al1003816

1003816

1003816

1003816

= 119875

1119891

1198752 (6)







0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

001

004

003

Frequency (Hz)

P A

int

ensit

y0 50 100 150 200 250

0

002

004

006

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y



5 min 10 min

15 min 20 min


026

024

022

020

018

0160 05 1 15 2

Concentration (mgL)

Ther

mal

effus

ivity

(Wmiddots1

2middotcm

minus2middotK

minus1)

(a)

025

024

023

022

021

020

019

018

017

016

1 2 3 4 5 6

Ther

mal

effus

ivity

(Wmiddots1

2middotcm

minus2middotK

minus1)


(b)


4 Conclusions






Sample 119875

3120576






Acknowledgments


References














































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




OH

OH

OH

O

OO

O

OO

O

O

CO2H CO2H CO2H

CO2HCO2H CO2H

CO2H

CO2H

HO HO HO

OH

OH

OH

O

OO

O

OO

O

O

CO2H

CO2H

CO2H

CO2H


OOOOOOOOOOOO

Laser ablation

Graphene oxide

(a)

(b)


Tran

smitt

ance

(au

)


32182914

32322829

17181595 1411

17191611

14011155

1037

1029

736615

543

792665

587 375

438

412

564859


005

004

003

002

001

0000 50 100 150 200 250

Frequency (Hz)

PA i

nten

sity

Water

Ethylene glycol





(5) (6)

(4)

(2)(1)

(3)

0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

001

003

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y





1and

119875



2)


1003816

1003816

1003816

1003816

120575119875Al1003816

1003816

1003816

1003816

= 119875

1119891

1198752 (6)







0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

001

004

003

Frequency (Hz)

P A

int

ensit

y0 50 100 150 200 250

0

002

004

006

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y



5 min 10 min

15 min 20 min


026

024

022

020

018

0160 05 1 15 2

Concentration (mgL)

Ther

mal

effus

ivity

(Wmiddots1

2middotcm

minus2middotK

minus1)

(a)

025

024

023

022

021

020

019

018

017

016

1 2 3 4 5 6

Ther

mal

effus

ivity

(Wmiddots1

2middotcm

minus2middotK

minus1)


(b)


4 Conclusions






Sample 119875

3120576






Acknowledgments


References














































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




(5) (6)

(4)

(2)(1)

(3)

0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

001

003

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y





1and

119875



2)


1003816

1003816

1003816

1003816

120575119875Al1003816

1003816

1003816

1003816

= 119875

1119891

1198752 (6)







0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

001

004

003

Frequency (Hz)

P A

int

ensit

y0 50 100 150 200 250

0

002

004

006

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y



5 min 10 min

15 min 20 min


026

024

022

020

018

0160 05 1 15 2

Concentration (mgL)

Ther

mal

effus

ivity

(Wmiddots1

2middotcm

minus2middotK

minus1)

(a)

025

024

023

022

021

020

019

018

017

016

1 2 3 4 5 6

Ther

mal

effus

ivity

(Wmiddots1

2middotcm

minus2middotK

minus1)


(b)


4 Conclusions






Sample 119875

3120576






Acknowledgments


References














































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

001

004

003

Frequency (Hz)

P A

int

ensit

y0 50 100 150 200 250

0

002

004

006

Frequency (Hz)

P A

int

ensit

y

0 50 100 150 200 2500

002

004

006

Frequency (Hz)

P A

int

ensit

y



5 min 10 min

15 min 20 min


026

024

022

020

018

0160 05 1 15 2

Concentration (mgL)

Ther

mal

effus

ivity

(Wmiddots1

2middotcm

minus2middotK

minus1)

(a)

025

024

023

022

021

020

019

018

017

016

1 2 3 4 5 6

Ther

mal

effus

ivity

(Wmiddots1

2middotcm

minus2middotK

minus1)


(b)


4 Conclusions






Sample 119875

3120576






Acknowledgments


References














































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials





Sample 119875

3120576






Acknowledgments


References














































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials






















CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials



research article preparation of graphene oxide stabilized nickel nanoparticles...

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