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**Spark assisted chemical engraving in the light of electrochemistry
**

V. Fascio∗ , R. Wüthrich, H. Bleuler

Laboratoire de systèmes robotiques, EPFL, CH-1015 Lausanne, Switzerland Received 16 October 2003; received in revised form 21 December 2003; accepted 21 December 2003 Available online 5 June 2004

Abstract A novel technology for glass microstructuration called spark assisted chemical engraving (SACE) is presented. This technology is based on electrochemical discharge phenomena. Beyond a critical voltage, electrical discharges occur through the gas ﬁlm around the electrode and the glass machining is possible. The SACE process is similar to the electrode effects. SACE has been analysed using an electrochemical approach (U–I plots), the experimental results clarify the onset of the discharge activity. Additionally, two theoretical models of the SACE phenomenon were introduced. Firstly a model, based on percolation theory, is brieﬂy described and predicts the critical parameters (voltage and current). Secondly a method to estimate the spark’s characteristics (amplitude and duration) is presented and with the help of these data the machining depth was estimated by a numerical simulation. Finally, some glass microstructuring examples are presented to show the potential of this technology. © 2004 Elsevier Ltd. All rights reserved.

Keywords: Spark assisted chemical engraving (SACE); Electrode effects; Percolation theory; Glass microstructuration

1. Introduction Since a decade, “lab-on-chip” devices and other miniaturised systems have known a great increase in the ﬁeld of chemical analysis due to their economical interest. More recently the development of microreactors and micropumps, made of glass, have been achieved with the use of several materials processing techniques like HF etching [1], sandblasting or laser machining. These technologies have limitations such as cost and machining time. Thus all these new products need new structuring technologies. Among the existing technologies, electrochemical methods are emerging as cost-effective alternatives for the micro- and nanomachining of metallic parts. Indeed electrochemical machining (ECM) was developed in the late 50s and is now widely used in heavy industries such as aerospace for shaping operations [2]. For the micro and nanostructuring, the promising electrochemical micromachining (EMM) was recently introduced by Ertl and co-workers [3] and allows high aspect ratio structures machining with submicron resolution [4]. The drawback for an extensive use of glass in microdevices is its limited 3D structuring possibilities. In this paper,

∗

Corresponding author. Fax: +41-21-693-38-66. E-mail address: valia.fascio@a3.epﬂ.ch (V. Fascio).

we discuss an original machining technology based on electrochemical phenomena: spark assisted chemical engraving (SACE). SACE was presented for the ﬁrst time in 1968 by Kurafuji as electrical discharges [5] and allows glass machining. Few literature is currently available on SACE and several names are given to describe SACE such as electrochemical discharge machining [6], spark assisted etching [7] or electrochemical spark machining [8]. The main contributions to the SACE research come from Asia (India, Japan) and Switzerland [6–9]. SACE can be described as follows. The sample to be machined is dipped in an electrolyte, typically sodium hydroxide (Fig. 1). A constant DC voltage is applied between the machining-tool or tool-electrode (cathode) and the counter-electrode (anode). The counter electrode is a ﬂat plate with a much larger surface than the tool surface (about a factor 100). When the applied voltage is below a critical voltage of about 25 V, electrolysis occurs. Hydrogen gas bubbles are formed at the tool-electrode and oxygen bubbles at the counter electrode. As voltage is increased, current density rapidly increases too. The density and the mean radius of the bubbles increase and bubbles ﬁnally coalesce into a gas ﬁlm around the tool-electrode. Light emission is observed in the gas ﬁlm where electrical discharges occur between the tool and the surrounding electrolyte as can be

0013-4686/$ – see front matter © 2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.electacta.2003.12.062

. State of the art Several systematic studies have been carried out to highlight the basic principles of the SACE process and the machining mechanism itself. 2. It is generally admitted that the onset of the spark region is linked to the applied voltage. the main open question is the mechanism of the transition between the traditional electrolysis regime and the electrochemical discharge regime. where light emission can be observed and glass micromachining is possible. Fig. 1. tool geometry) on the critical voltage Ucrit and found that Ucrit is essentially independent of the tool diameter but depends on the electrolyte concentration. The ﬁrst one is a bubble production process. Machining is possible if the tool-electrode is in the near vicinity of the glass sample (typically closer than about 25 m [10]). SACE is characterized by a sudden breakdown of the electrolysis [9. (BC) the limiting current region. there seems to be not yet a generally admitted explanation. Basak and Ghosh [6] proposed a model where they deﬁned the critical conditions to build the gas as the moment where the gas bubbles (electrochemically formed) and vapour bubbles (formed by Joule Heating) reach Fig. The gas ﬁlm formation and the discharge activity can be seen. The process is quite complex and understanding of SACE is still far from complete. Thus. Basak and Ghosh [6] studied the inﬂuence of cell parameters (electrolyte properties. chemistry. Among the many different explanations proposed in literature. Just as with the electrode effects. in the literature.3998 V. aluminium production. seen on Fig. e. (CD) the instability region and (DE) the arc region. critical phenomena. 2. / Electrochimica Acta 49 (2004) 3997–4003 2. (AB) the ohmic region.12]. understanding of SACE is a multidisciplinary problem involving physics of micro discharges. The sudden electrical resistance increase at the electrodes is called electrode effects. ﬂuid dynamics. Typical current–voltage plot with photographs obtained around the tool electrode in 30% NaOH. local Joule heating [14] and change in wettability of the electrode [15] are some examples. whereas the second one is an electrical discharge phenomenon in gas. Five regions can be identiﬁed: (OA) the thermodynamic and overpotential region. The goal of this contribution is to give a state of the art on SACE and to show the increasing knowledge on SACE thanks to electrochemical methods. Experimental set-up for glass microstructuring.g. especially concerning the discharge activity. However. electrochemistry and material science. Hydrodynamic instabilities [13]. Fascio et al. The same behaviour is known since a long time in a more general context.

3. Beyond point C. the current reaches a limiting value and is almost constant. this is the limiting current region. Temperature ﬁxed at 25 ◦ C.5–2. Based on this. 3. 4. between 2 and 10 V. the current decreases quasi instantly down to point D. / Electrochimica Acta 49 (2004) 3997–4003 3999 a maximum coverage fraction on the tool-electrode. Normalized current–voltage characteristics for NaOH solution. free of electrodes geometry and concentration inﬂuence. 20 and 40% in wt. Fig. This is the instability region. they could express the critical voltage in function of a few empirical coefﬁcient and the critical resistance. As the voltage slightly increases from 0 to 2 V. the mean current is very small (in the mA range) and the instantaneous current is characterized by a succession of short pulses of few s duration. In this case. Fascio et al. Basak and Ghosh claimed that discharge activity is comparable to switch phenomena observed in capacitive circuits. Electrolyte concentration has been shown to have the most signiﬁcant inﬂuence on Ucrit (Fig. 2 shows a typical current–voltage plot. Systematic studies on the experimental U–I plots showed [11] that the apparent resistance Rcrit of the electrolyte at the critical point C (deﬁned by Ucrit − Ud = Rcrit Icrit ). Experiments have been carried out on the inﬂuence of electrolyte properties and temperature on Ucrit [6. Using a semi-empirical model and applying this condition. 10. However this model does not describe what is happening for the voltages smaller than the critical voltage and needs the critical resistance as input.11. is linked to the electrolyte inter-electrode resistance R0 by: Rcrit = αR0 with α about 2. As an important result. Both theoretical models can well describe the experimental results but do not take into account the inﬂuence of bubble formation at the tool-electrode surface on the onset of discharge activity. The end of the region is at point C characterized by a critical voltage Ucrit (typically 20–30 V) and a critical current Icrit (typically around 1A). This region is Fig. It is experimentally known and admitted that in SACE the spark region starts from 30 to 40 V. Results of four different concentrations are presented (5. the current increases linearly with the voltage in the so-called ohmic region (AB). 3). It can be detailed as follows. 4 shows the This could also be predicted theoretically using a percolation approach detailed elsewhere [17].16].6 (1) followed by the arc region (DE). most of the research work on SACE is empirical and a theoretical understanding of the process is still lacking. it was shown that all the current–voltage measurements can be summarized on a unique plot called the normalized curve. Fig. Experimental facts: electrochemical investigations The most successful technique employed to study SACE is current–voltage measurements [9].17]. Machining is only possible beyond Ucrit and a crucial point is to ﬁnd the relevant parameters inﬂuencing the onset of the discharge activity. no current is ﬂowing through the cell. it was shown that the current behaviour is strongly related to the bubbles evolution around the tool-electrode. In this phase. Concentration and temperature both strongly inﬂuence the conductivity of the solution. [9. By increasing the voltage. Evolution of the critical voltage Ucrit with the concentration of the sodium hydroxide solution. the ﬁrst region (OA) appears and is called the thermodynamic and overpotential region.V. ﬁve domains (or regions) have been described by Sillen [15] and identiﬁed by Fascio et al. The spark region has also to be explained.) . In a previous paper [9]. Fig. where light emission is observed and where glass micromachining is possible. Jain underlined the weakness of this model and developed a ﬁnite elements approach to model SACE (called electrochemical spark machining) deﬁned as a phenomenon occurring in arc discharge valves [8]. electrical breakdown in gases happens under the most favourable conditions at 280–300 V according to Paschen’s curve. Above point B. To summarize. they proposed an equivalent circuit [6]. By scanning the voltage from 0 to 40 V. As pointed out by Basak and Ghosh.

The two different sections of the d dependence reﬂect two different physical mechanisms. the current signal becomes a succession of pulses due to electrical discharges (amplitude up to 1A). 5). We propose two power laws followed by λd [17]. The probability of gas discharge λd is evaluated by ﬁtting the Fig. 4.1. With the help of percolation theory. Predicting the critical parameters The new approach is to consider the electrical discharge has a consequence of the transition from bubble layer to gas ﬁlm around the tool electrode. machining is tied to discharge activity. The pulses were counted over a duration of 40 ms and the experiment was repeated 500 times and frequency distribution evaluated. 5. Fascio et al. 6. In these preliminary experiments. Firstly between Ucrit and 1. Parameters A and B are respectively equal to 3 × 10−9 V−2 s−1 and 5. / Electrochimica Acta 49 (2004) 3997–4003 corresponding Poisson distribution. a theoretical model describing the transition where Ud is the decomposition voltage. it was possible to show that the discharge activity follows a Poisson process.2 Ucrit . λd follows a ﬁeld emission law: λd = AE2 exp −B E (4) (3) counts 40 30 20 10 0 0 5 10 15 20 25 30 N Fig. . Superposed is the ﬁtted Poisson distribution. The algorithm counts the number of current pulses N(t) during a ﬁxed time.4000 80 70 60 50 V. We propose the following interpretation.18]. Counts of current pulses obtained at 28 V with a cylindrical tool. λd decreases with the voltage according to: λd (U) − λd (U crit ) ∝ −(U − Ud )2 And beyond 1.4 × 106 V m−1 . In the arc region (DE). Counting during 40 ms and 500 times. The experiments showed that the distribution of N(t) follows a Poisson law (see Fig.2 Ucrit . critical conditions are predicted in function of electrode geometry and electrolyte properties. Probability of gas discharges λd in 30 % NaOH solution as a function of the applied voltage U. According to this interpretation. in both cases. The ﬁrst region corresponds to the growth of the gas ﬁlm combined with the ﬁrst discharges while in the second section the gas ﬁlm is fully established and arc discharge only accounts for the full current ﬂow. Theoretical investigations 4. By considering bubble evolution at the tool-electrode as a stochastic phenomenon. 6. it appears that two behaviours can be identiﬁed as shown on Fig. By counting experimentally the number of these pulses in a ﬁxed time interval. obtained plots normalised as follows: J= j U − Ud and U = crit j crit U − Ud (2) where E is the electrical ﬁeld at the electrode surface. The details on the calculations are given elsewhere [17. We can expect that these two behaviours result in two different kinds of machining.

The heat raises the temperature of the glass sample. Thermal modelling where ρ is the density. The peak distribution is shown for an applied voltage equals to 36 V. a new analysis of the current is carried out and the heat released Q is estimated as: Q = UIte (5) Amplitude Fig. duration and statistical distribution. current peaks characteristics are determined: their amplitude. Workpiece domain for the ﬁnite elements model (geometry and boundary conditions). In particular the ohmic and saturation region are explained as a consequence of bubble coalescence. the coalescence process could be described and the critical values (voltage. 8. current density and resistance) predicted quantitatively in function of the electrolyte properties and the tool-electrode geometry. / Electrochimica Acta 49 (2004) 3997–4003 Peak number 300 4001 250 200 150 100 50 0 0 2 4 6 [A] The difference with the previous models of Basak and Ghosh [21] and Jain [8] is the estimation of the spark’s characteristics (heat released Q and duration te ). A cubic part of the glass is considered as the domain for the analysis. 7. occurs [20].V. z.2. 4. Cp the speciﬁc heat and k the thermal conductivity. described as a high temperature etching. Fascio et al. These results might shed a new light on the electrode effects as well (see [19]). This temperature satisﬁes the 3D heat equation: ρCp ∂T − (k∇ 2 T) = 0 ∂t (6) to the arc region has been built. We suppose that the heat ﬂowing through the planes Si (1 ≤ i ≤ 4) can be neglected. The geometry and boundary conditions are described on Fig. A simple thermal model is proposed to predict the machining depth. The treatment is similar to Basak’s model. In this case.8]. Each current peak is supposed to correspond to an electrical discharge. 8. For each voltage. . −k ∂T Qe = ∂n te a 2 for 0 ≤ t ≤ te (8) On Ss /Se : ∂T = H(T − T∞ ) ∂n for 0 ≤ t ≤ te (9) Fig. It has been highlighted that a chemical effect. As shown on Fig. Se is the spark location (black square). y. Result of the stochastic analysis of the current. 7. Moreover the complete current–voltage characteristics could be estimated. the thermophysical properties of glass are considered. The following initial and boundary conditions are used: T(x. Representation of the discharge as a square source. These parameters are evaluated through a statistical analysis of the current. Using percolation theory. 0) = 298 ◦ K At the spark’s location Se : (7) It is generally admitted that the heat released by the electrical discharges contributes to the glass machining [6.

Applications to glass microstructuration To demonstrate the potential of SACE machining. The criterion to evaluate the machining depth can be described as follows: as the temperature in glass reaches the glass softening temperature TS (about 1193 ◦ K) and not the melting temperature.is entirely new and original. Conclusion SACE. It is based on electrochemical discharge phenomena. equivalent to laser machining) contributes Table 1 Evolution of the machining depth vs. we assume machining takes place. (10) The ﬁrst condition means that the surface Se receives the heat Q from a discharge during a time te . This paper wanted to focus on the newest and not yet published theoretical research on SACE process. the applied voltage Applied voltage U (V) 28 30 36 Machining depth numerical model (m) 34 ± 2 35 ± 3 35 ± 5 Machining depth experimental (m) <5 34 ± 3 37 ± 4 to the prospect that SACE technology could become one of the key technology for glass microstructuration in the future. chemical etching occurs and glass is “polished”. experimentally showed that NaOH and NaNO3 provide the high removal rate. Thus the machining depth corresponds to the thickness of the glass heated above TS . we assume that the heat generation is a random process and the thermal conductivity k is constant. Nevertheless in our knowledge the role played by the electrolyte is not well elucidated and the current theoretical predicts do not correlate the experimental results. (B) Channels for micro reactor application. This chemical contribution allows to obtain good surface quality. the second one the convection losses due to the surrounding electrolyte on the remaining domain Ss /Se . / Electrochimica Acta 49 (2004) 3997–4003 and on Si: ∂T =0 ∂n where n is the normal vector . the temperature distribution has to be studied in detail. Theoretical results for each voltage are compared to measurements and are generally in the same range (Table 1). [20]. Kurafuji et al. activity loss of coated anodes). Moreover. The difference could probably be explained because the different thermophysical parameters (ρ. SACE is not based on electrochemical reactions alone but on a combination of thermal and chemical effects. Contrary to other electrochemical techniques. (A) Pattern machined at 30 V. According to the reaction occurring in sodium hydroxide solution: 2NaOH + SiO2 → Na2 SiO3 + H2 O (11) Fig. Comparison between experimental and theoretical results. The approach -considering SACE as a stochastic process. This reaction strongly depends on temperature and the discharge phenomenon increases the etching rate.3. is introduced. Fascio et al. a new 3D microstructuring technique for glass. 9A and B. For the lower voltages (below 25 V).5 mm3 /s. This paper has shown that research on SACE has opened a new way of analyzing a range of important phenomena in electrochemistry (electrode effects. Cp and k) are supposed to be independent of the temperature. . 4. who conﬁrmed that alkaline electrolytes are the most suitable for machining.4002 V. some microstructures were realized in Pyrex glass and are shown on Fig. To complete these results. But the chemical etching combined with the high removal rate (0. It also led to a new understanding of the electrode effects. 9. This was also described by Yang et al. 5. the thermal model is not convincing. Examples of SACE applications.

S. Acta 42 (1997) 2695. France. References [1] P. Vogt. Kalpakjian. Lichtenberg. 179. 5 (2003) 203. 4th ed.M.H. Kock. Kirchner. 1975. Jain. Viquerat. 2003. V. A. Ghosh. E.H. De Rooij.L. Fascio. Electrochim. P. V. Ann. P. Switzerland. Int. Technol. Special Issue Electrochim. [6] I. Ghosh. Vogt. Suda. J. [15] C. Janson. [2] S. Basak.00) for its ﬁnancial support. Upper Saddle River. H. [20] C. Wüthrich. Chem. Hudson. Guilpin. Technol. Science 289 (2000) 98. Dissertation Thesis. H. G. Bleuler. Dissertation Thesis no. CIRP 16 (1968) 415. 71 (1997) 350. K.R. École Polytechnique Fédérale de Lausanne. [18] R. Fascio. P. [7] A. S. Manufacturing Engineering and Technology. submitted for publication. Mater. Electrochem. 2002. S.L. [13] C. Fascio. Phys.T. Verpoorte. [16] V. Fascio.V. Lett. Langen. Schuster. [19] R. Proc. The Netherlands. 2003. EPFL. Dixit.M. Anal. J. [21] I. [4] A. A. Fuqua. Electrochim. Electrochim. P. NJ. N. H. 29 (1999) 137.S. 2691. in: Proceedings of SPIE on Laser Applications in Microelectronics and Optoelectronic Manufacturing 4 (3618) (1999) 213. H. École Polytechnique Fédérale de Lausanne. J. [8] V. Yang. V. Pedeferri. Comninellis. Prentice Hall. [14] H. Helvajian. Fascio. 82 (2003) 3327. B. Mater. Mater.W. H. Appl. Electrochem. Acta 23 (1978) 87. 196 (2001) 149. Langen. Université de Paris VI.. Appl. Fresenius J. [3] R. G. Wüthrich. Mach. 2776. Schuster. J. Dissertation Thesis no. H. Proc. Schmid. Bleuler. 1983. Hansen. Ho. Mazza. [12] B. [10] H.W. 23–26 November 1999. R. 62 (1996) 46. M. Yan. TU Eindhoven.D. Tools Manufact. Basak. J. Commun. J. Wüthrich. W. Fascio et al.K. Pandey. Langen. / Electrochimica Acta 49 (2004) 3997–4003 4003 Acknowledgements The authors would like to thank the Swiss National Science Foundation (FNS 061533. R. EPFL. Key Eng. [9] V. Allongue. Switzerland. Kurafuji. . D. Ertl. C. [11] V. [17] R. in: Proceedings of the 1999 International Symposium on Micromechanics and Human Science. Dissertation Thesis. Daridon. Trimmer. 39 (1999) 165.W.M. Bleuler. 2001. Re. Acta 49 (2004) 1547. [5] H. Acta. Bleuler. 371 (2001) 261. H. H. Wüthrich. R. p.P Sillen. Wüthrich.

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