Electrochimica Acta 48 (2003) 3063 /3070 www.elsevier.

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Interface behaviour in nickel composite coatings with nano-particles of oxidic ceramic

F. Erler a,*, C. Jakob a, H. Romanus a, L. Spiess a, B. Wielage b, T. Lampke b, S. Steinhauser b
a

Department of Electrochemistry and Metal Finishing, TU Ilmenau, PF 100 565, 98684 Ilmenau, Germany b Institute of Composite Materials, TU Chemnitz, 09107 Chemnitz, Germany Received 26 November 2002; received in revised form 14 April 2003; accepted 14 April 2003

Abstract Advances in micro-technology demand that new functional materials be developed so that the technical properties of microdevices can be improved at reasonable cost. The co-deposition of nanoscaled particles during an electroplating process has been shown to bring such an improvement. This work focuses on particles of oxidic ceramics, in this case those of Al2O3 and TiO2. The diameters of the primary particles ranges from 10 to 30 nm, electrodeposited by means of a conventional Watts nickel electrolyte. A series of nickel nano-ceramic composites were produced, with co-deposition of particles as a single primary particle in the nanometre range at one end of the scale and as agglomerates up to a size of a micrometer at the other. The influence of the presence of particles on crystallisation behaviour, residual stress and texture of the deposited nickel coatings was examined by X-ray diffraction (XRD). There is a report on the interfaces between the nickel grains and the oxidic ceramic particles, investigated using transmission electron microscopy (TEM). A decreasing corrosion stability indicates an attack along the interface nickel/particles. # 2003 Elsevier Ltd. All rights reserved.
Keywords: Nano-composite; Aluminium oxide; Titanium oxide; XRD; TEM

1. Introduction There is widespread use in engineering of electrodeposited nickel composite coatings which conventionally have particles of a diameter ranging between 1 and 100 mm. There is now a trend to using solid powder of primary particle diameter below 100 nm as the additional ingredient of the nickel composite [1 /3]. This kind of nano nickel composite coating may find application in micro-technology and in thin film coatings. The properties of the material can be improved by varying the type, size, amount and distribution of the incorporated particles. The optimum dispersion hardening effect in composite materials, calculated theoretically, appears when a ductile matrix contains 10 nm-

* Corresponding author. Tel.: '/49-3677-69-3110; fax: '/49-367769-3104. E-mail address: f.erler@web.de (F. Erler). 0013-4686/03/$ - see front matter # 2003 Elsevier Ltd. All rights reserved. doi:10.1016/S0013-4686(03)00380-3

particles spaced 100 nm apart [4]. In this case, there are only 0.86 vol% particles in the composite material, a low quantity of incorporated particles. The literature, indeed, predicts this low quantity, attributing it to physical and chemical effects between particle and growing surface [5]. The very high surface energy and agglomeration tendency of the nanoparticles in high conductive metal electrolytes will tend to impede uniform distribution of the particles [6]. Furthermore, the compression of the double layer by the high-conductivity electrolyte together with the low particle surface charge (three orders of magnitude less in comparison to nickel ions) will render any transport of particles by means of electrophoresis or their migration within the electrolyte highly unlikely [7]. Uniform co-deposition would then appear to be wellnigh impossible in microstructures with a high aspect ratio. The very presence of particles in the metal electrolyte will, furthermore, affect the metal deposition process itself.

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Nickel composite coatings containing an amount up to 2 vol% of nanoscaled oxidic ceramic particles have, notwithstanding, been subjected to examination by a number of methods, all focusing on the interface between the particle and the nickel matrix.

2. Experimental The behaviour of nanoscaled Aluminiumoxide C and Titaniumoxide P25 particles (manufacturer: Degussa-Huls AG) in aqueous electrolytes was studied first. A Malvern Zetasizer 3000HS was used to measure the average particle size and zeta potential. Some of the suspensions were subjected to mechanical agitation either by an ultrasonic sonotrode (UP200S , 24 kHz, maximum power 0/200 W) or a Miccra dispersing rod (up to 30 000 per min). The pH value was measured using a glass electrode single-rod measuring cell specially adapted to suspensions with nanoparticles. A Watts nickel electrolyte was used to deposit Ni/ Al2O3 and Ni/TiO2 nano-composite coatings onto flat stainless steel substrates under the following conditions: / Composition: 250 g/l NiSO4 /7H2O, 30 g/l NiCl2 / 6H2O, 30 g/l H3BO3. / Wetting agent: 0.3 g/l sodium dodecyl sulphate. / pH-value: 4.29/0.2. / Temperature: 559/2.0 8C / Current density: 0.5 /8.0 A/dm2. / Concentration of dispersed particles: 0.5 /50 g/l. / Anode: sulphur depolarised nickel, pretreated in HCl 1:1. The substrates were ground using SiC-paper down to a granulation of 1200, degreased, and treated in H2SO4 for 30 s prior to the deposition. The composite films were removed from the substrate for further examination. Micro-structured PMMA was also used as a substrate for similar deposition. A deposition cell was specially designed for use in all the electroplating processes (Fig. 1). It turned out to be difficult and time-consuming to determine particle incorporation rate and distribution with certainty. Optical microscopy and scanning electron microscopy (SEM), the methods usually applied for investigating transverse micro-sections of standard dispersion coatings fail to work efficiently for low primary particle size of the powder used. Transmission electron microscopy (TEM) will give information on the incorporation of the individual particles but elaborate sample preparation is necessary. In [6] a method of determining the incorporation rate of particles with photon correlation spectroscopy (PCS) in a speedy and easy manner is described. The direct dependence of the light scanning reflex quantity (mea-

Fig. 1. Lab facility for manufacturing nano-composite coatings: a gentle, vertical ow of electrolyte is achieved in the upper deposition cell.

sured in the sizer mode of the Zetasizer ) on the particle concentration assists in the determination of incorporation rate for dispersion coatings dissolved in a sulphuric acid/nitric acid mixture at about 40 8C, and this method was applied in the present work. To determine the residual stress of the first order in the composite during the electroplating process, in situ measurements of strip contraction [8,9] were carried out. X-ray diffraction (XRD, Siemens D5000 ) was used as the basis for analysing possible texture formation. Because nickel has low X-ray fluorescence, a molybdenum tube (wave length of Ka 0/0.7093 nm) was employed. The corrosion behaviour of the composite coatings was also examined by measuring mass loss during a salt spray test according to ASTM B117-73 and taking potentiodynamic measurements in substitute ocean water (ASTM D1141-98) using a Potentiostat/Galvanostat Model 273A (EG&G Princeton Applied Research, software: Model 352 Corrosion Analysis Software */ PARCALC). The measuring cell contained approximately 100 ml water, which was changed before each new measurement. A standard calomel electrode (SCE) was used as reference electrode and the counter electrode was platinum. The working electrode (i.e. the sample) had a surface area of 1 cm2 and was ground using SiC-paper till a granulation of 4000 was reached, then degreased and treated in HCl 1:1 for 30 s prior to the measurement cycle. After the sample was fitted, the set-up reached a steady state potential after approximately 15 min. Then a potential leap of (/250 mV was triggered, followed by an increase up to '/250 mV in steps of 0.25 mV per 1.5 s. The CV graphs measured were analysed by PARCALC applying Tafelplots.

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SEM, XL30ESEM/FEI , LaB6-cathode(30 keV), including energy dispersive X-ray analysis (EDX), was carried out on ground and polished cross sections of plated nickel foils and filled microstructures as another means of examining the incorporation behaviour of particles. Disks of the nickel foil, thinned by ion beams (PIPS 691 , 3 /5 keV, 3 rpm, upper/lower angle 0/4/28) were subjected to TEM(Tecnai S20, 200 keV, Gatan GIF 2000 energy filter), so that the interfaces between nickel grains and oxidic ceramic particles could be observed. Thinning of disks by electro-polishing (TwinJet Electropolisher, Fischione ) was not successful, despite the fact that different electrolytes and polishing conditions were applied. As an example, Fig. 2 shows a TEM image of a Ni/TiO2 coating. On electron energy loss spectroscopy (EELS) only TiO2-particles can be observed in the thinned area around the electro-polished hole. The nickel matrix is completely dissolved in the electron transparent field. Consequently, no comparison between the two different preparation methods could be made. A possible explanation is that recrystallisation or growth of nickel grains is induced by the energy input of ion beam bombardment.

for Al2O3 and 600 nm for TiO2. Experiments with a Miccra dispersing rod had only a very slight effect on agglomerate size, whereas treatment of the suspension with an ultrasonic sonotrode at low amplitudes (20%) broke the agglomerates down to a size of approximately 150 nm for Al2O3 and 300 nm for TiO2. At higher amplitudes of ultrasound (80%), a slightly increased agglomerate size was observed. New size measurements were carried out after the suspension had been left unattended for about a week, but no modification of average agglomerate size was observed. The summarised results for the behaviour of nanoscaled aluminium oxide and titanium oxide particles in relation to the concentration of nickel sulphate are shown in Fig. 3. Fig. 4 shows the dependence of the measured average agglomerate size, the zeta potential and the pH value on the concentration of nickel chloride. Even a low concentration of NiSO4 results in enhanced growth of agglomerates up to 4 mm for Al2O3 and 1.5 mm for TiO2. It also results in a strict reduction of zeta-potential from positive values down below zero. The pH value decreases from approximately 6.6 to 5.2 for Al2O3 and from 6 to 4.6 for TiO2-particles.

3. Results and discussion 3.1. Behaviour of nanoparticles in aqueous electrolytes Mechanical stirring was used for the mixing of particles in distilled water. The agglomerates formed reached an average diameter of approximately 250 nm

Fig. 2. TEM image of an electro-polished Ni/TiO2 nano-composite coating; TiO2-particles are clearly visible, no nickel is detected by EELS.

Fig. 3. Agglomeration behaviour of nanoscaled Al2O3 and TiO2 in aqueous electrolyte in relation to nickel sulphate concentration.

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Fig. 5. Particle content in nickel layers in relation to current density and particle content in electrolyte.

examinations that the relatively high particle content at 0.5 g/l Al2O3 and 50 g/l TiO2 (Fig. 5 4 A/dm2) is caused by such dense agglomerates. 3.3. Residual stress of the rst order and XRD examination of texture The results of in situ measurements of strip contraction are shown in Fig. 6. The residual stresses in nickel coatings deposited without particles show a minimum of approximately 120 N/mm2 at a current density of 4 A/ dm2. At lower and higher current densities the residual stress rises to a maximum of 170 N/mm2 at 0.5 A/dm2. The addition of 0.5 or 5 g/l of Al2O3-particles to the electrolyte has little influence on the residual stress in the deposited composite coatings, whereas 50 g/l particle content reduces the stress, to a minimum of approximately 40 N/mm2 at 1 A/dm2. On the other hand, an

Fig. 4. Agglomeration behaviour of nanoscaled Al2O3 and TiO2 in aqueous electrolyte in relation to nickel chloride concentration.

Concentrations of NiCl2 above 0.1 mol/l leads to less growth of Al2O3- and TiO2-agglomerates than with NiSO4. Likewise, the zeta-potential drops only slightly with increased concentration of NiCl2. With TiO2particles, the pH-value of the electrolyte is approximately constant with increasing content of NiCl2, whereas it decreases if Al2O3-particles are used. 3.2. Proportion of particles in composite coatings measured by PCS The proportion of incorporated particles in deposited nickel layers increases with increasing particle content of the electrolyte and decreasing deposition current density (see Fig. 5). The deviation between measurements under same conditions was found to be 10 /15%. Above and beyond this, the agglomerate size in the electrolyte prior to deposition has a marked influence on the incorporation rate and thus also any mechanical treatment (ultrasound, dispersing rod) and the hydrodynamic conditions in front of the cathode. All these factors have to be kept constant during plating experiments. Larger and denser agglomerates facilitate a higher incorporation rate. It can be deduced from SEM

Fig. 6. Residual stress of the rst order in nickel composite coatings in relation to current density and particle content in electrolyte.

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amount of only 0.5 g/l TiO2-particles in the electrolyte causes the stress to drop to 60 N/mm2 at 2 A/dm2. The reasons for this behaviour are assumed to be the particles influence on the crystallisation mechanism of nickel and the development of different types of texture. The grain size of nickel might be smaller with high Al2O3-particle content in the electrolyte, so that residual stress of the first order cannot accumulate as much as with larger grains. On the other hand, residual stress of a higher order may be caused by the presence of Al2O3particles. The XRD patterns of nickel nano-composite coatings indicate changes in texture of such coatings which are dependent on the plating current density and the particle content in electrolyte (Fig. 7, Table 1). This dependency of texture on super-saturation is described in [10,11], where the crystal orientation is predicted from calculations including two-dimensional nucleation. At a current density of 1 A/dm2 the main orientation of crystallites switches from (220) plane without particles to (200) plane with 50 g/l particle content in electrolyte (see Table 1), whereas at higher current densities the [200] orientation is preferred, independently of particle content during the plating process. During all experiments in the plating cell employed, the hydrodynamic conditions were constant, so that the development of different textures was reproducible.

The 328 h of testing applied indicate no noticeable loss in mass for nickel coatings deposited from a particle free electrolyte. On the other hand, an appreciable mass loss is observed at nickel coatings with incorporated nanoparticles. A higher corrosion rate is noted if Al2O3 particles were co-deposited, and the amount of corrosion varies intensely between different specimens produced under the same plating conditions. Likewise, potentiodynamic measurements of corrosion current density (Fig. 9) indicate an increased corrosion intensity if nanoparticles are codeposited in nickel layer. Due to the dependence of differences in corrosion current density on pre-treatment of samples, no information on the effect of the particle type is given. A possible explanation for the greater susceptibility to pitting corrosion might be an accelerated diffusion of chloride ions along the interface between the nickel and the incorporated particles.

3.5. SEM examinations*/incorporation behaviour of particles Investigations of cross sections of the nickel dispersion coatings produced were carried out using SEM and EDX in order to clarify the structural composition and particle distribution. The incorporation of both types of nanoparticles occurs in the form of clusters. The particles are not uniformly distributed. An interesting observation is an initial layer with no or very few particles of approximately 2 /3 mm occurring in each sample examined, whatever the particle type. A sample micrograph with verification by EDX is shown in Fig. 10. A possible theory to describe this effect may be as follows. At the initial stage, super-saturation of nickel adsorption atoms and three-dimensional nucleation can occur only on particle-free areas of the substrate. Therefore, a particle free layer has to be deposited by the growth of the first crystals. Now particles can stick to the rough nickel surface and will be overgrown. The proportion of incorporated particles increases to a stationary value. Another field of interest is the variation in the amount of particles incorporated in the depth of a microstructure. For example, an EDX-measurement series is mapped in Fig. 11. The sample was deposited at 2 A/ dm2 from an electrolyte containing 50 g/l TiO2 for 20 h. The structure was overgrown to provide a comparison between the incorporation rate inside and outside the structure. No clear dependency of incorporation rate on depth of structure was observed. Outside the structure, a slightly increased amount of particles was incorporated in the nickel coating. This might be due to the better hydrodynamic transport conditions for the particles (see chapter 1).

3.4. Corrosion behaviour */salt spray test and potentiodynamic measurements of corrosion current density The measurements of the corrosion behaviour of nickel nano-composite coatings demonstrate the basic necessity to take account of the environment during application of such coatings even as micro-structured components. The results of salt spray fog tests are combined in Fig. 8 for different samples.

Fig. 7. Examples of XRD patterns of nickel nano-composite coatings (Mo radiation, Zr lter was damaged).

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Table 1 Texture of nickel depending on plating current density and particle content in electrolyte: lattice planes parallel to the surface detected by XRD Current density Without particles 0.5 g/l particles in electrolyte Al2O3 1 A/dm 2 A/dm2 4 A/dm2
2

5.0 g/l particles in electrolyte Al2O3 (220), (200), (331) (200), (331) (200), (331) TiO2 (220) (200), (331) (200), (331)

50.0 g/l particles in electrolyte Al2O3 (200), (331) (200), (331) (200), (331) TiO2 (220) (200), (331) (200), (331)

TiO2 (220) (200), (331) (200), (331)

(220) (200), (331) (200), (331)

(220) (200), (331) (200), (331)

Fig. 8. Salt spray fog testing of 8 specimen according to ASTM B117(73) (similar to DIN 50 021-SS (1988); DIN ISO 7253 (1998)).

3.6. TEM investigations */particle /nickel interface To analyse the interface between grains and incorporated particles, ion beam thinned nickel disks were observed by TEM. In Fig. 12 an example of pointEDX and EDX-mapping (STEM) is shown, incorporated nanoscaled TiO2 particles are clearly detected.

Fig. 10. SEM and EDX examination of an initial layer without particles in a Ni/TiO2 nano composite coating.

In high resolution mode TEM (Fig. 13), the pore-free growth of nickel around the particles is visible. As the distribution of the diameters of the particles used is not uniform, there are larger particles within the composite coating. From TiO2-particles, twins sometimes develop, having possibly been induced by stress from lattice misfit between nickel and particle. Incoherent areas of nickel are observed all round the Al2O3-particle shown on the right-hand side of Fig. 13.

4. Conclusions The potential hardness of dispersion coatings has been mentioned by way of introduction and the difficulties met during co-deposition of nanoscaled oxidic ceramic particles in electroplated nickel coatings described. The agglomeration tendency of particles in aqueous electrolytes has also been carefully considered.

Fig. 9. Potentiodynamic measurements of corrosion current density in substitute ocean water (preparation and chemical composition: ASTM D1141(98)).

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Fig. 11. Proportion of incorporated TiO2 particles in the depth of a micro-structure with an aspect ratio of 5:1 measured by EDX.

Successful incorporation of particles up to 2 vol% has been established despite the problems. The influence of the particles on the crystallisation mechanism of nickel has been shown to produce to a change in residual

tensile stress in comparison with that of particle-free deposited coatings. A deterioration in corrosion resistance was observed by salt spray test and potentiodynamic measurements of

Fig. 12. STEM examinations, example for detection of incorporated nanoscaled TiO2-particles, point-EDX and EDX-mapping of an area of 200 nm)/200 nm.

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Fig. 13. HRTEM examinations of the interface between nickel grains and incorporated nanoparticles (2 A/dm2, each with 50 g/l particles in electrolyte).

corrosion current density if particles were co-deposited. This behaviour might be explained by an accelerated diffusion of chloride ions along the interface between nickel and the incorporated particles. A possible theory to describe an initial layer with very few particles found by SEM examinations has been given and particle incorporation in a deep microstructure is characterised. The paper ends with TEM observations of the interface between nickel grains and incorporated nanoparticles.

References
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Acknowledgements This work was nancially supported by the Deutsche Forschungsgemeinschaft (FRG, DFG) under contract no. JA 825/2-2 and STE 758/5-2 (2001 /2003). The authors are grateful to Isabel Diaz and team at the Instituto de Corrosio y Proteccion/PUCP in Lima/Peru n for the assistance during the corrosion measurements.