Ultrasonic-aided fabrication of gold nanofluids
© Chen and Wen; licensee Springer. 2011
Received: 23 November 2010
Accepted: 7 March 2011
Published: 7 March 2011
A novel ultrasonic-aided one-step method for the fabrication of gold nanofluids is proposed in this study. Both spherical- and plate-shaped gold nanoparticles (GNPs) in the size range of 10-300 nm are synthesized. Subsequent purification produces well-controlled nanofluids with known solid and liquid contents. The morphology and properties of the nanoparticle and nanofluids are characterized by transmission electron microscopy, scanning electron microscope, energy dispersive X-ray spectroscope, X-ray diffraction spectroscopy, and dynamic light scattering, as well as effective thermal conductivities. The ultrasonication technique is found to be a very powerful tool in engineering the size and shape of GNPs. Subsequent property measurement shows that both particle size and particle shape play significant roles in determining the effective thermal conductivity. A large increase in effective thermal conductivity can be achieved (approximately 65%) for gold nanofluids using plate-shaped particles under low particle concentrations (i.e.764 μM/L).
In recent years, there have been intensive efforts in the synthesis and application of nanomaterials in different fields, from energy to biomedicine sectors. Widespread interest has been generated in tailoring gold nanoparticles (GNP) for non-invasive medical applications, either as a heating or a targeting agent for detection, diagnosis, or treatment . GNPs are popularly chosen because of their unique physical and chemical properties, such as high conductivity (for both heat and electricity), easy functionalization and bio-compatibility, as well as prior clinical experience of gold-based pharmaceuticals. One example is in cancer therapy where functionalized GNPs are proposed as potential agents for non-invasive thermal treatment, and the feasibility has been proven in preliminary studies on non-targeted particles in vitro, and later in vivo[2, 3]. Almost all these applications involve delivering bio-modified nanoparticles to malignant cells and rapidly heating nanoparticles with an external source such as laser, ultrasound, or an electromagnetic wave to produce a therapeutic effect or to release drugs . The interaction of nanoparticles with the external source and subsequent heating effect are fundamental for the successful deployment of these novel techniques, where the thermophysical properties of nanoparticle suspensions play a key role.
The last decade witnessed a quick development of nanofluids field especially on its application in heat transfer field. While the original idea of nanofluids was to enhance the thermal conductivities of some typical heat transfer fluids including water, mineral oil, and ethylene glycol, the influence of nanoparticles has been found to be more profound than the mean thermal conductivity effect for application in different situations. This field has developed very rapidly in the past few years. However, a large number of controversies have been reported, ranging from basic properties such as thermal conductivity, viscosity, and single phase convection to boiling heat transfer . It has been suggested that current uncertainties on the content of nanofluids, including both solid and liquid phases, are one of the main reasons responsible for many of the observed controversies and inconsistencies [4, 5], highlighting the importance of nanoparticle synthesis and nanofluids formation.
Two methods are generally used for nanofluid formulation, namely, the top-down method through size reduction (the two-step method), and the bottom-up approach through simultaneous production and dispersion of nanoparticles (the one-step method) [5, 6]. For the two-step method, nanoparticles are either synthesized or purchased first in the form of dry powders, and the nanofluid formulation process involves properly separating the aggregated dried particles into individual particles and keeping them from re-agglomeration under suitable ionic or surfactant conditions. How well the final dispersion is achieved depends on (i) the degree of agglomeration of the dried nanoparticles (which depends on the nature of the manufacturing, handling and storage process), (ii) the shear forces applied in separating agglomerations (weakly bonded agglomerates could be broken to their primary sizes by high shearing, but strongly bonded ones are difficult to be separated), and (iii) the liquid environment (pH or ionic conditions to keep separated particles from re-aggregation). As a result of these complicated factors and a lack of detailed characterization of the content and morphology of the liquid and solid phases, it is very difficult to compare the result from one study with another even using same nanoparticles. The formulation of nanofluids by the bottom-up approach through physical or chemical reactions has been gaining increasing interests . Such a method has been practiced for a long time in the colloid industry, i.e., colloidal gold. A number of other nanofluids have also been formulated including copper and iron nanofluids through a modified physical vapor deposition method and a hydrothermal chemical reduction of salts [8, 9]. For nanofluids formulated through the one-step method, the stability of nanofluids can be improved through proper surface functionalization without involving mechanical facilities. This approach, however, suffers the problem of impurities, i.e., residual reactants are generally left in the nanofluids because of incomplete reaction or stabilization. It is difficult to elucidate the nanoparticle effect without eliminating this impurity effect.
Using gold nanofluids as an example, this study aims to engineer a number of nanofluids with different particle sizes and shapes (spherical and plate shaped) under controlled liquid conditions, and characterize their thermophysical properties accordingly. Gold nanoparticles can be generally synthesized by the citrate reduction (CR) method , the Brust-Schiffrin method , and the modified Brust-Schiffrin method that contains different sulfur-containing ligands. The size of GNPs can be tuned by controlling the ratio of thiol or other ligands to Au ions used in the synthesis. In the nanofluids community, GNPs have been investigated only by a few studies because of its high cost . To achieve better control of nanoparticle morphology, sonochemical technique, especially ultrasound will be used in this study for particle shape control. Such a technique is based on the acoustic cavitation: the rapid collapse of small gas bubbles in sonicated solutions promotes the reaction to be more homogeneous. A number of metallic-based spherical particles with narrow size distribution, such as Au, Ti, Pt, Pd, Fe, MnO2, and CdS, have been successfully produced ultrasonically [13–15]. The experiment of using sonication technique to improve the quality of other-shaped nanomaterials, however, is seldom reported, which will be another novel point of this study.
Gold nanofluids formulation
Four groups (Group A, B, C and D below) of gold nanomaterials, with particle size ranging from 10 to 300 nm in spherical and plate shapes, will be synthesized using different methods.
Gold nanofluids with spherical particles
CR method as the control group (Group A)
The modified CR method  was first used to produce spherical GNPs as the control group. In this method, 5.0 × 10-6 mol of HAuCl4 in 190 ml of DI water was heated until boiling. While the solution was kept heated and stirred by a magnetic blender, 10 ml of 0.5% sodium citrate was added. The solution was kept stirring for the next 30 min until the reaction was completed.
CR with ultrasonic irradiation method (Group B)
Same chemicals as the conventional CR were used in this method. 5.0 × 10-6 mol of HAuCl4 in 190 ml of DI water was heated until boiling. It was then subjected to heating, and stirred using a magnetic blender; 10 ml of 0.5% sodium citrate was added into the solution until its color changed to wine-red. To examine the influence of controlling factors, the solution with wine-red color was further divided into four groups at different temperature and ultrasonic or stirring time:
▪ The first solution was placed in the ultrasonic bath at 80°C for 30 min;
▪ The second solution was placed in the ultrasonic bath at 80°C for 45 min;
▪ The third solution was stirred and heated at 100°C by magnetic blender for 10 min and was then placed in the ultrasonic bath at 80°C for 20 min;
▪ The fourth solution was stirred and heated at 100°C by magnetic blender for 20 min and was then placed in the ultrasonic bath at 80°C for 10 min.
Gold nanofluids with plate-shaped particles
Synthesis of gold nanoplates through CR at room temperature (Group C)
Similar method as proposed by Huang et al.  was used for synthesizing gold nanoplates. Based on the CR method, 1.3 ml of 1% HAuCl4 was added to 100 ml of DI water at 25°C, and stirred by a magnetic blender for 1 min. 0.4 ml of sodium citrate (38.8 mmol/l) was then introduced in the HAuCl4 solution and stirred for the next 30 min.
The resultant solution was exposed under natural light in the laboratory for 16 h.
Synthesis of gold nanoplates through CR at room temperature with the aid of ultrasonication (Group D)
Based on CR method, 1.3 ml of 1% HAuCl4 was added to 100 ml of DI water at room temperature and was sonicated for 1 min. 0.4 ml of sodium citrate (38.8 mmol/l) was then added in the HAuCl4 solution. The resultant solution was divided into five groups, each treated further with ultrasonication times of 10, 20, 30, 45, and 60 min. Subsequently, these resultant solutions were exposed under natural light in the laboratory for another 16 h, which changed the solution color to cloudy blue.
The synthesized gold nanoproducts are separated by the centrifugation method, re-dispersed into DI water, and further purified through membrane filters for 4-6 days where some residual reactants and stabilizer are diffused away. The purified nanofluids are stored for further morphological and property characterization.
Gold nanofluids characterization
The primary size and shape of all gold nanomaterials are identified using a transmission electron microscopy (TEM) and a scanning electron microscope (SEM) equipped with an energy dispersive X-ray spectroscope (EDX). In this process, the TEM was performed using a Jeol JEM-2010 electron microscope at a bias voltage of 200 kV, and SEM image was taken at 10/20 kV accelerating voltage. The particle size distribution in liquid was identified by a dynamic light scattering (DLS) device (Malvern nanosizer). The crystal structure and elemental information were provided by X-ray diffraction spectroscopy. The size distribution of GNP in DI water was measured by a Zetasizer Nano-Z (Malvern Instruments Ltd, Worcestershire, UK) with a minimum of 15 runs being performed. Each result was the average of three consequent measurements. A KD2 Pro Thermal Properties Analyzer device was employed to measure the thermal properties of gold nanomaterial dispersions at different concentrations (1.1, 11.1, 33.3, 330, 764 μM/l). DI water as a control group was measured, and each sample was repeated at least three times.
Result and discussion
Characterization of nanofluids
Groups A and B: spherical particles and particle size control
Chemically, the size of GNPs can be controlled by the ratio of the reducing/stabilizing agents to the gold (III) derivatives. In this study, 15-nm GNPs were produced by adding 0.5% (wt%) of sodium citrate, which acted as a reducing agent at the beginning and a stabilizer subsequently. Larger GNPs can be engineered by using a reduced amount of sodium citrate. Stoichiometrically, 0.05% (wt%) of sodium citrate is required to reduce all the gold (III) derivatives in this sample. Incomplete reaction occurs if the sodium citrate concentration is smaller than 0.05% (wt%), and vice versa. For concentrations less than 0.5%, the amount of extra citrate ions will not be sufficient to stabilize all the GNPs, which would result in an aggregation phenomenon producing large nanoparticles. As a consequence, a general trend of GNP size reduction with the increase of sodium citrate is observed in the experiments, which is consistent with other studies. By properly controlling the ratio of sodium citrate to gold (III) derivatives, the GNP size can be engineered in the range of 10-150 nm.
Group C and D: gold nanoplates and size control
The effective particle size reduction by ultrasonic irradiation is because of the acoustic cavitation, which is affected by the growth and collapse of cavitation bubbles. The cavitation process introduces a disintegration of water or volatile precursors (RH) into hydrogen and hydroxyl because of the high temperature and strong pressure in collapsing cavities. Consequently the existence of an ultrasonic field enables the control of the rate of AuCl4- reduction in an aqueous solution. The sizes of formed GNPs or gold nanoplates can be controlled by parameters, such as the temperature of the solution, the intensity, direction, and duration of the ultrasound source. Prolonged directional irradiation would cause the development of either anisotropic or aggregated Au nanoparticles.
It has been demonstrated that the synthesis of anisotropic nanostructures in the liquid phase is commonly related to two features: (1) surfactant-based soft template approach that provokes the exclusive growth direction of the nanoparticles, and (2) the selective adsorption of small molecules or polymers on specific crystal planes that controls the growth rate along a specific direction . In the synthesis of gold nanoplates, ultrasonic irradiation is employed to replace magnetic blender as it can induce strong pressure in collapsing cavities locally and immediately in solution, promoting a quasi-balance growth of gold nanomaterials. The formation of gold nanoplates may be associated with the cavitation efficiency, i.e., the amount and division of bubbles, the size and lifetime of bubbles, the dynamics and shape of the collapsing bubble, as well as the resultant temperature and pressure within the cavitation bubbles. These factors would affect the final morphology of gold nanoplates, as also shown by Okitsu et al. .
Effective thermal conductivities of nanofluids
In contrast to the particle size effect, when we compare the results of the 250-nm gold plates with that of spherical particle nanofluids, a reverse trend is obtained. The thermal conductivities of nanofluids containing 250-nm gold nanoplate is always higher than that of 15-nm spherical particles. The particle at the concentration of 764 μM/L reaches approximately 1.0 and 0.8 W/mK, respectively, for 250-nm gold plates and 15-nm spherical particles. Such a result shows that apart from the particle size, particle shape also plays a significant role in determining the effective thermal conductivity. While the effect of shape is small at low particle concentrations, it signifies its influences as the concentration increases. Qualitatively, such a result is consistent with a few other studies. Analytically, the Hamilton-Crosser equation  predicts the effective thermal conductivity of a heterogeneous mixtures by incorporating a shape factor, i.e., the higher the shape factor, the higher the predicted thermal conductivity. Experimentally, for instance, Kim and Peterson  also showed that different morphologies of carbon nanotubes affected effective thermal conductivity significantly, and a 37% increase in multiwalled carbon nanotube dispersion could be predicted by the Hamilton-Crosser equation with a massive shape factor of 36. Recently, the International Nanofluid Properties Benchmark Exercise (INPBE) showed that the effective thermal conductivities of alumina nanorod nanofluids (80 nm in length and 10 nm in diameter) were 45% and 30% higher than that of 10-nm spherical alumina nanofluids at concentrations of 3% and 1% volume fraction of nanomaterials, respectively . A few other studies have also reached similar conclusion .
There is a long debate in the nanofluid community on the mechanisms of thermal conductivity of nanofluids. A number of theories have been proposed including the interfacial layering, Brownian motion, ballistic transport of energy carriers, the interfacial resistance, the structure effect, and particle aggregation and percolation effects . As reviewed recently, the Brownian motion and its associated micro-convection as well as the interfacial layer mechanism would not be responsible. The effect of particle morphology in the liquid, i.e., through aggregation or percolation, has been proposed by a number of researchers recently [27, 28]. Those studies emphasized that the enhancement of thermal conductivity was a function of nanoparticle aggregation and showed that there would exist an optimized aggregation structure to achieve the maximum thermal conductivity, which could be far beyond the prediction from homogeneous dispersions. A recent study reported a switchable thermal conductivity of ferrofluids through an external magnetic field by engineering particle morphology in the liquid . An extraordinary enhancement of thermal conductivity, approximately 300%, is observed when linear chain-like percolating structures are generated and uniformly dispersed in the base fluid, while negligible enhancement is obtained for the well-dispersed particles. Similarly, Horton et al.  showed a time-dependent thermal conductivity of nickel-coated carbon nanotubes with the application of an external magnetic field, which was related to the structuring, percolation, and agglomeration of carbon nanotubes influenced by the magnetic field. At its peak value, the thermal conductivity was found to be approximately 80% higher than that of water. The difference in the absolute values in the enhancement might be related to different contributions from microstructures and the interfacial resistance. A recent simulation showed that the radius of gyration and particle-fluid interfacial area are the two important parameters in characterizing microstructures . The increase in thermal conductivity due to the increase of the shape factor could be offset by a negative contribution of increased heat flow resistance at the solid-liquid interface . Although further study is still needed, these studies illustrate that the effective thermal conductivity of nanofluids could be adjusted by proper control of the external magnetic field to generate different nanoparticle-percolating structures. Properly engineered, such an approach could open a new window for engineering unique nanofluid properties for different applications. It appears reasonable to conclude that different shaped nanoplates, as shown in Figure 4, might be responsible for the large thermal conductivity increase, although this still requires further detailed examination.
Although loose percolation structures may exclude thermal conductivity as an inherent physical property as they can be destroyed under flow and heating conditions, these studies did show that the particle morphology in the liquid could significantly affect the effective thermal conductivity. The potential influence of particle structure on thermal conduction emphasizes that colloid chemistry will play a significant role in optimizing the thermal conductivity of nanofluids. For instance, through the current nanoplate approach, the morphology will not be destroyed under any shearing or heating conditions. However, further careful examinations are still required regarding to the influence of particle morphology structure on other effective properties, especially surface tension, wettability, viscosity, and specific heat . The gain from thermal conductivity could be offset by an increase in viscosity or interfacial resistance, and a decrease in specific heat. Other areas of future research should pay more attention to the linkage between the rheology and thermal properties, nanoparticle interactions and particle-fluid-surface interactions, which calls for interdisciplinary collaboration among nanomaterials, colloid science, and engineering researchers.
different nanofluids containing different sizes and shapes of GNP can be engineered by properly controlling the reaction process.
The ultrasonication is a very powerful tool in engineering particle size and shape. By applying ultrasonication, the spherical particle size can be controlled in the range of 10-20 nm, and the average size of gold nanoplate can be reduced from 300 to 50 nm, with more uniform and regular shapes.
Large increase in the effective thermal conductivity of nanofluid is found for gold nanofluids, especially under relatively higher particle concentrations, i.e., >33 μM/L.
The effective thermal conductivity of gold nanofluids is not only dependent on particle size, but also heavily influenced by particle shape, whereas further mechanistic understanding is required.
dynamic light scattering
energy dispersive X-ray spectroscope
International Nanofluid Properties Benchmark Exercise
plasmonic photothermal therapy
scanning electron microscope
surface plasmon resonance
transmission electron microscopy.
The authors would like to extend their thanks to EPSRC for their financial support under Grant No: EP/E065449/1, and Dr. Zofia Luklinska of Queen Mary University of London for helping in electron microscopic analysis of samples.
- Wen DS: Intracellular hyperthermia: nanobubbles and their biomedical application. Int J Hyperth 2009, 25(7):533–541. 10.3109/02656730903061617View Article
- Gannon CJ, Patra CP, Bhattacharya R, Mukherjee P, Curley SA: Intracellular gold nanoparticles enhance non-invasive radiofrequency thermal destruction of human gastrointestinal cancer cells. J Nanobiotechnol 2008, 6: 2. 10.1186/1477-3155-6-2View Article
- Cardinal J, Klune JR, Chory E, Jeyabalan G, Kanzius JS, Nalesnik M, Geller DA: Noninvasive radiofrequency ablation of cancer targeted by gold nanoparticles. Surgery 2008, 144: 125–32. 10.1016/j.surg.2008.03.036View Article
- Wen DS, Lin G, Vafaei S, Zhang K: Review of nanofluids for heat transfer applications. Particuology 2009, 7(2):141–150. 10.1016/j.partic.2009.01.007View Article
- Wen DS, Ding YL: Formulation of nanofluids for natural convective heat transfer applications. Int J Heat Fluid Flow 2005, 26: 855–864. 10.1016/j.ijheatfluidflow.2005.10.005View Article
- Wen DS, Ding Y, Williams R: Pool boiling heat transfer of aqueous based TiO2nanofluids. J Enhanced Heat Transfer 2006, 13: 231–244. 10.1615/JEnhHeatTransf.v13.i3.30View Article
- Zhang YX, Jiang W, Wang LQ: Microfluidic synthesis of copper nanofluids. Microfludics and Nanofluidics 2010, 9(4–5):727–735. 10.1007/s10404-010-0586-3View Article
- Eastman JA, Choi SUS, Li S, Yu W, Thompson LJ: Anomalously increased effective thermal conductivity of ethylene glycol-based nanofluids containing copper nanoparticles. Appl Phys Lett 2001, 78(6):718–720. 10.1063/1.1341218View Article
- Zhu HT, Lin YS, Yin YS: A novel one-step chemical method for preparation of copper nanofluids. J Colloid Interface Sci 2004, 277: 100–103. 10.1016/j.jcis.2004.04.026View Article
- Turkevich K, Stevenson PC, Hillier J: A study of the nucleation and growth processes in the synthesis of colloidal gold. Discuss Faraday Soc 1951, 11: 55–75. 10.1039/df9511100055View Article
- Brust M, Walker M, Bethell D, Schriffrin DJ, Whyman RJ: Synthesis of thiol-derivated gold nanoparticles in a 2-phase liquid-liquid system. J Chem Soc Chem Commun 1994, 801–802. 10.1039/c39940000801
- Tsai CY, Chien HT, Ding PP, Chan B, Luh TY, Chen PH: Effect of structural character of gold nanoparticles in nanofluid on heat pipe thermal performance. Mater Lett 2004, 58: 1461–1465. 10.1016/j.matlet.2003.10.009View Article
- Caruso RA, Ashokkumar M, Grieser F: Sonochemical formation of gold sols. Am Chem Soc 2002, 18: 7831–7836.
- Li C, Cai W, Li Y, Hu J, Liu P: Ultrasonically induced Au nanoprisms and their size manipulation based on aging. J Phys Chem B 2006, 110: 1546–1552. 10.1021/jp055522lView Article
- Radziuk D, Grigoriev D, Zhang W, Su D, Möhwald H, Shchukin D: Ultrasound-assisted fusion of performed gold nanoparticles. J Phys Chem C 2010, 114: 1835–1843. 10.1021/jp910374sView Article
- Frens G: Controlled nucleation for the regulation of the particle size in monodisperse gold Suspensions. Nat Phys Sci 1973, 241: 20–22.View Article
- Huang L, Guo ZR, Weng M, Gu N: Facile synthesis of gold nanoplates by Citrate Reduction of AuCl4¯ at room temperature. Chin Chem Lett 2006, 17(10):1405–1408.
- Orendoff CJ, Sau TK, Murphy CJ: Shape-dependent plasmon-resonant gold nanoparticles. Small 2006, 5: 636–639. 10.1002/smll.200500299View Article
- Pisswan D, Valenzuela SM, Cortie MB: Therapeutic possibilities of plasmonically heated gold nanoparticles. Trends Biotechnol 2006, 24: 62–67. 10.1016/j.tibtech.2005.12.004View Article
- Huang X, Jain PK, El-Sayed IH, EI-Sayed MA: Plasmonic photothermal therapy (PPTT) using gold nanoparticles. Lasers Med Sci 2008, 23: 217–228. 10.1007/s10103-007-0470-xView Article
- Okitsu K, Ashokkumar M, Grieser F: Sonochemical synthesis of gold nanoparticles: effects of ultrasound frequency. J Phys Chem B 2005, 109: 20673–20675. 10.1021/jp0549374View Article
- Paul G, Pal T, Manna I: Thermo-physical property measurement of nano-gold dispersed water based nanofluids prepared by chemical precipitation technique. J Colloid Interface Sci 2010, 349: 434–437. 10.1016/j.jcis.2010.05.086View Article
- Hamilton RL, Crosser OK: Thermal conductivity of heterogeneous two-component systems. Volume 1. I&EC Fundam; 1962:187–191.
- Kim BH, Peterson GP: Effect of morphology of carbon nanotubes on thermal conductivity enhancement of nanofluids. J Thermophys Heat Transf 2007, 21: 451–459. 10.2514/1.18341View Article
- Buongiorno J, Venerus D, et al.: A benchmark study on the thermal conductivity of nanofluids. J Appl Phys 2009, 106: 094312. 10.1063/1.3245330View Article
- Timofeeva EV, Routbort JL, Singh D: Particle shape effects on thermophysical properties of alumina nanofluids. J Appl Phys 2009, 106(014304):1–10.
- Evans W, Prasher R, Fish J, Meakin P, Phelan P, Keblinski P: Effect of aggregation and interfacial thermal resistance on thermal conductivity of nanocomposite and colloidal nanofluids. Int J Heat Mass Transf 2008, 51: 1431–1438. 10.1016/j.ijheatmasstransfer.2007.10.017View Article
- Eapen J, Li J, Yip S: Mechanism of thermal transport in dilute nanocolloids. Phys Rev Lett 2007, 98: 028302. 10.1103/PhysRevLett.98.028302View Article
- Philip J, Shima PD, Raj B: Evidence for enhanced thermal conduction through percolating structures in nanofluids. Nanotechnology 2008, 19: 305706. 10.1088/0957-4484/19/30/305706View Article
- Horton M, Hong HP, Li C, Shi B, Peterson GP, Jin SH: Magnetic alignment of Ni-coated single wall carbon nanotubes in heat transfer nanofluids. J Appl Phys 2010, 107(104320):1–4.
- Fan J, Wang LQ: Effective thermal conductivity of nanofluids: the effects of microstructures. J Phys D 2010, 43(16):165501. 10.1088/0022-3727/43/16/165501View Article
- Vafaei S, Wen DS: Formation of microscale bubble in a quiescence pool of gold nano-suspensions. Adv in Colloids Surface Science 2010, 159(1):72–93. 10.1016/j.cis.2010.05.005View Article
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