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Preparation of high quality Al TEM specimens via a double-jet electropolishing technique

Necip nl
Istanbul Technical University, Faculty of Chemistry-Metallurgy, Materials Science and Metallurgical Engineering Department, 34469 Maslak, Istanbul, Turkey

AR TIC LE D ATA
Article history: Received 2 February 2007 Received in revised form 28 March 2007 Accepted 6 April 2007 Keywords: Electropolishing Aluminum TEM Specimen

ABSTR ACT
Obtaining clean, uniformly thin and high-quality TEM specimens entails a great deal of work that has a number of parameters that have to be considered carefully depending on specimen preparation technique(s). The parameters, such as voltage, current density, temperature, time, electrolyte, and electrolyte flow rate, have the most significant importance in a double-jet electropolishing technique. Useful hints to have the least failures in preparing TEM specimens and optimum values of the above parameters for pure Al are given and discussed. 2007 Elsevier Inc. All rights reserved.

1.

Introduction

To understand and correlate the nature of the microstructure of metals and their alloys directly with their physical, chemical and mechanical properties, TEM analysis has been a major tool. TEM analysis requires successfully prepared thin foils about a few hundred nanometers or less thick from bulk materials [1,2]; the success of the TEM analysis critically depends on the quality of the thin foils prepared. Various techniques, such as electropolishing using pointed cathodes [3], jet machining [46], low voltage electropolishing using a special cathode design [7], and jet electropolishing [4,810], have been developed and used for the thin foil preparation since 1949. Additionally, a number of experimental techniques and theoretical knowledge on the preparation of thin films have been summarized in specialized books, textbooks and papers [1116]. In 1966, Schoone and Fischione [10] designed a simple submerged double-jet technique [9] that enables the polishing of metal disks simultaneously from both sides and

automatically stops the polishing operation when perforation occurs. Basically, the preparation of the thin foils for TEM analysis is comprised of three steps, (i) obtaining a sample piece 12 mm thick, (ii) thinning the sample piece to about 0.2 mm, and (iii) electropolishing the sample to a thin foil which enables sufficient electron beam penetration [17]. Electropolishing (EP) is a well-known method in an electric potential passed through the chemical solution utilizing the specimen as the anode [18,19]. Although this description seems to be straightforward, to have reproducible optimum conditions, the EP parameters (i.e., voltage, current density, temperature, time, and flow rate) and characteristics of the TEM specimen (thickness, conductivity, and its nature as brittle or ductile) must be taken into consideration in the thin foil preparation due to the fact that electropolishing rates and ideal polishing conditions vary for most metals and alloys [11,2023]. This paper describes the effects of both EP parameters and the thickness of the TEM specimens with regard to preparation of thin foils for TEM analysis.

Tel.: +90 212 285 3382; fax: +90 212 285 2925. E-mail address: unlu@itu.edu.tr. 1044-5803/$ see front matter 2007 Elsevier Inc. All rights reserved. doi:10.1016/j.matchar.2007.04.003

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2.

Experimental Details

The size, shape, and micro- and macrostructure of the hole and time for hole formation were determined as a function of the specimen thickness, electropolishing voltage and the pump flow rate of the electropolisher. These characteristics served as guides to determine the optimum electropolishing conditions. Pure Al sheet with 99.99999% purity used in this study was obtained from Alfa Aesar, a Johnson Matthey Company. Square 1 1 cm samples were gently cut from the pure aluminum sheet by a precision diamond saw. Each sample was mechanically ground on SiC abrasive papers (80, 120, 300, 600, 1000, and 1200) to five different thicknesses, 70, 100, 150, 200, and 250 m. During each grinding step, the thickness was controlled using a Chicago Brand model digital micrometer. 15 samples were prepared for each different thickness. Then, 3-mm diameter disks were punched from the square foils by using a Gatan Disk punch. These samples were electropolished using a solution consisting of 25 vol.% HNO3 and 75% methanol at different voltages in the range of 660 V in a TenuPol-5 digitally controlled automatic electropolisher with program storage capabilities. This instrument was developed by Struers A/S [24] for twin-jet thinning samples for transmission electron microscopy (TEM). The pump flow rate of the electropolisher was adjusted as 15. The temperature of the electrolyte was held constantly at 20 2 C by using Lauda Proline RP 870 model cooling system. The polishing time was recorded from the digital screen of the TenuPol-5 for each TEM foil. After polishing, the foil in the holder was immediately rinsed three times in methanol. Then the holder was opened gently and the foil was removed with tweezers and rinsed in three small ethanol cups, gently

rinsing each sample 30 times in each cup. Each rinsing step was done slowly so as not to damage the thinned area around the hole. Some ethanol remaining on the tweezers with the TEM sample was removed by blotting with a filter paper, and the TEM sample was then put on another clean and dry filter paper for 1 or 2 min to make it fully dry. These samples were stored in labeled polyethylene vials to protect them from mechanical damage and contamination. Each TEM sample was investigated in detail under a Leica DM6000 M Model optical microscope and Leica EC3 Model stereomicroscope; images were recorded to describe the quality of the hole formation.

3.
3.1.

Results and Discussion

Affect of Electropolishing Voltage

A stereomicroscopic view of the pure Al specimens, 200 m thick and 3 mm in diameter, prepared using different electropolishing voltage values, i.e., 16, 30, 45 and 60 V with the constant pump flow rate of 15 (arbitrary units as indicated on the polishing unit), is presented in Fig. 1ad. Increasing the electropolishing voltage above 12 V resulted in specimens with smooth and clean surfaces, and holes were successfully obtained near to the center of the polished circle area. The peripheral alterations around the polished circle area due to the increase in voltage from 16 V through 60 V can be seen in Fig. 1ad. No hole formation occurred at the central areas of the specimens exposed to excessive voltages such as 45 and 60 V. Fig. 2 shows optical micrographs of the holes produced and the general effect of increasing the electropolishing voltage; again the failure to form a hole at 45 V is seen in

Fig. 1 Stereomicroscope views of high purity Al disks, 200 m thick and 3 mm diameter in size, after electropolishing at different voltages (a) 16 V, (b) 30 V, (c) 45 V, and (d) 60 V. The peripheral alterations around the polished circular areas are shown with arrows.

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Fig. 2 Optical micrographs showing the resulting holes after electropolishing at different voltages (a) 8 V, (b) 10 V, (c) 12 V, (d) 16 V, (e) 30 V, and (f) 45 V.

Fig. 2f. After electropolishing at different voltages, elliptical holes were observed, as seen from Fig. 2ae. It is also evident that the voltage above 12 V resulted in wider holes (Fig. 2de). The variation of the time for hole formation and the calculated hole area of the high purity Al disks as a function of the electropolishing voltage are shown in Fig. 3. As can be seen, it is clear that the time for hole formation decreases with increasing the applied electropolishing voltage. The time for hole formation of the specimens prepared at the voltage range from 8 to 12 V decreases sharply from 380 s to 106 s. This value decreased further to 15 and 12 s when the specimens were prepared at 45 and 60 V, respectively, although for the latter specimens the holes were not centrally located. Determination of the suitable and correct electropolishing parameters is not easy due to the fact that these parameters have a wide range that makes repeatability difficult. The voltage adjustment needs to be done properly to achieve the ideal electropolishing. During this process, the formation of an anodic viscous layer of electrolyte on the specimen surface is responsible for thinning. The ideal thinning will create a smooth surface and polished specimen by removing both the

macroscopic bumps and microscopic irregularities, respectively [12,15]. Although it is not resolvable in Fig. 3, the calculated hole area increases fourfold from 0.0035 mm2 at 8 V to

Fig. 3 The variation of the time for hole formation and the calculated hole area of the high purity Al disks as a function of electropolishing voltage.

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0.0141 mm2 at 16 V. Above 16 V, the hole area increases by nearly a factor of five to 0.0650 0.0186 mm2 at 30 V. Even though there is no circular or elliptical shaped hole to be studied for the specimens prepared at 45 and 60 V, the calculated hole areas are approximately 1.49 and 5.08 mm2, respectively. The excessive voltage results in electrolysis of the aqueous solution which creates bubbles on the specimen surface; consequently these bubbles mask the surface locally and cause pitting [25].

3.2.

Affect of the Pump Flow Rate

Figs. 4 and 5 show the optical micrographs of the holes of the pure Al specimens, prepared using five different pump flow settings, i.e., 5, 15, 25, 35, and 45, at a constant electropolishing voltage, 8 V. Smooth, clean and well-polished surfaces were observed on the specimens prepared in the range of pump flow rates from 5 to 35 (Figs. 4a, c, e, and 5a). The effect of the high flow rates, 35 and 45, on the specimen surface is obvious in Fig. 5b and Fig. 5d, respectively. In the range of the pump flow between 5 and 35, the locations of the holes were usually near to the central area of the TEM disks. The location of the

hole for the specimen prepared with a 45 pump flow rate was further removed from the central area (Fig. 5c and d); the higher pump flow rates caused torn elliptical shaped holes (Fig. 5b and d) and led to the surface distortion seen in Fig. 5c. Fig. 6 shows the variation of the time for hole formation and the calculated hole area of the high purity Al disks as a function of the pump flow setting. The values of the time for hole formation significantly decrease from approximately 610 s for a pump flow setting of 5 to approximately 240 s for a pump flow setting of 25. When the pump flow was increased through 45, the time for the hole formation slightly decreases to about 210 s. The calculated hole area was determined as 0.0086 mm2 on average for the pump flow range from 5 to 25. When the pump flow setting was increased from 25 to 45, the calculated hole area significantly increased from 0.0120 mm2 to 0.1763 mm2. Fig. 6 also clearly shows that increasing the pump flow rate from 5 to 25 resulted in a decrease in the time for hole formation whereas no significant difference in the values of the calculated hole areas was observed. An increasing in the time for hole formation with a decrease of pump flow rate from 25 to 5 indicates a delay in the polishing action because of the presence of gas bubbles formed by anodic

Fig. 4 Optical micrographs showing the holes after electropolishing at different pump settings: (a) and (b) 5, (c) and (d) 15, (e) and (f) 25.

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Fig. 5 Optical micrographs showing undesirable thin regions after electropolishing at different pump settings: (a) and (b) 35, (c) and (d) 45.

dissolution of the metal, which remain in the polishing area [26]. When the pump flow setting was increased from 25 to 45, there was no significant change in the values of the time for hole formation, but the values of the calculated hole areas increased.

3.3.

Affect of the Specimen Thickness

Fig. 7 shows optical micrographs of the holes produced in the high purity Al disks starting with specimens thinned to five different thicknesses, i.e., 70, 100, 150, 200 and 250 m, and prepared using a constant 8 V electropolishing voltage and a pump flow rate setting of 15. Elliptical-shaped holes were produced in each, irrespective of starting thickness (Fig. 7ae). In the present study, the thinnest specimen with a thickness

of 70 m (Fig. 7a) developed a larger hole and more etched surface than the thicker specimens (Fig. 7be). The variation of the time for hole formation and the calculated hole area of the high purity Al disks as a function of the specimen thickness are given in Fig. 8. The shortest time for hole formation, 84 s, was observed with the 70 m thick specimens. This time increased to about 130135 s, when the specimen thickness increased to 100 and 150 m, respectively, and increased further up to 440 s for specimen thicknesses from 150 m through 250 m. When the specimen thickness increased from 70 m to 100 m, the hole area decreased from approximately 0.009 mm2 to 0.003 mm2. However, for specimens thicknesses greater than 100 m no further changes were observed.

4.

Conclusion

The quality of the information from TEM analysis study is directly related to the quality of the thin foils being examined. Electropolishing is the most common and physically deformation-free specimen preparation technique available for examining electrically conductive materials. In the present study the twin-jet electropolishing parameters for producing highquality disks of high purity Al were studied with the purpose of both showing the effects of the polishing parameters, achieving well-prepared reproducible TEM disks and adding to the general knowledge basis for workers in this area of scientific research. On the basis of the results reported in the present investigations, the following conclusions can be drawn. Fig. 6 The variation of time for hole formation and the calculated hole area of the high purity Al disks as a function of the pump flow rate. 1. At a polishing voltage range between 8 and 12 V, specimens with smooth and clean surfaces and with holes near the center of the polished area were successfully produced.

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Fig. 7 Optical micrographs showing the holes in the high purity Al disks thinned to five different thicknesses and prepared using a constant 8 V electropolishing voltage and a pump setting of 15: (a) 70 m, (b) 100 m, (c) 150 m, (d) 200 m and (e) 250 m.

2. It was clearly demonstrated that increasing the applied electropolishing voltage resulted in decreasing the required time for the hole formation. However, at higher

voltages, such as 45 and 60 V, the holes were unnecessarily large and not centrally located in the disks. 3. Smooth, clean and well-polished surfaces were observed on specimens prepared using the range of pump flow settings from 5 to 35. Also, it was observed that the required time for hole formation decreases with an increase of the pump flow rate. 4. When the electropolishing voltage and the pump flow rate are maintained constant, there is a significant increase in the specimen thickness; the variation in the size of the hole area is negligible due to the endpoint detection sensitivity of the polishing unit. 5. An increase in the specimen thickness resulted in a significant increase in the required time for the hole formation.

Acknowledgements
Fig. 8 The variation of time for hole formation and the hole area of the high purity Al disks as a function of the sample thickness. The author would like to thank Prof. Hseyin imenolu from Istanbul Technical University for his help during the optical and stereomicroscope investigations of this study. The author

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is grateful to Bernard J. Kestel for his supports on providing the literature and sharing his own experience. In addition, Santhana Eswaramoorthy and Eric Lass from University of Virginia for their help on providing literature are gratefully acknowledged. The author also would like to thank Dr. Brian Gable for his helpful discussion.

[13]

[14]

[15]

REFERENCES
[1] Wilhelm FJ. The preparation of beryllium specimens for transmission electron microscopy by the knuth system of electropolishing. J Sci Instrum 1964;42:3434. [2] Riesz RP, Bjorling CG. Sample preparation for transmission electron microscopy of germanium. Rev Sci Instr 1961;32:88991. [3] Bollmann W. Interference effects in the electron microscopy of thin crystal foils. Phys Rev 1956;103:15889. [4] Kelley PM, Nutting J. Techniques for the direct examination of metals by transmission in the electron microscope. J Inst Met 195859;87:38591. [5] Stickler R, Engle RJ. Microjet method for preparation of wire samples for transmission electron microscopy. J Sci Instrum 1963;40:51820. [6] Thomas G. Transmission electron microscopy of metals. New York: John Wiley & Sons, Inc.; 1962. [7] Glen RC, Raley JC. Improved procedure for thinning metallic specimens for transmission microscopy. ASTM Spec Tech Publ 1962;339:60. [8] Heindenreich RD. Electron microscope and diffraction study of metal crystal textures by means of thin sections. J Appl Phys 1949;20:9931012. [9] Glenn RC, Schoone RD. Electropolishing unit for rapid thinning of metallic specimens for transmission electron microscopy. Rev Sci Instrum 1964;35:12234. [10] Schoone RD, Fischione EA. Automatic unit for thinning transmission electron microscopy specimens of metals. Rev Sci Instrum 1966;37:13513. [11] Goodhew PJ. Specimen preparation in materials science. Practical methods in electron microscopy. New York: North-Holland Publishing; 1973. [12] Kestel BJ. Improved methods and novel techniques for jet electropolishing o TEM foils. Proc. Mat. Res. Soc. Symp. on workshop on specimen preparation for transmission electron [16]

[17] [18]

[19]

[20]

[21]

[22] [23]

[24] [25]

[26]

microscopy of materials II. San Francisco, CA, April 1621; 1990. Madsen LD, Jacobsen SN. Material consideration for TEM sample preparation of thin films. Report no R-209, Linkping University, S-581 83 Linkping, Sweden; 1994. p. 4. Weaver L. Plan view TEM sample preparation for non-continuous and delaminating thin films. Microsc Res Tech 1977;36:3789. Kestel BJ. Polishing methods for metallic and ceramic transmission electron microscopy specimens. Report ANL-80-120, Argonne National Laboratory, Argonne, Illinois, USA; 1986. p. 165. Williams DB, Carter CB. Transmission electron microscopy, a textbook for materials science. New York: Plenum Publishing Corp; 1996. p. 15773. Van Zuilichem AG, Zeedijk HB. An electrolytic grinding machine. J Sci Instrum 1968;1:1023. Kirchheim R, Maier K, Tlg G. Diffusion and solid-film formation during electropolishing of metals. Kinet Anal 1981;128:102734. Mukhapadhyay SM. Sample preparation for microscopic and spectroscopic characterization of solid surfaces and films. In: Mitra S, editor. Sample preparation techniques in analytical chemistry. New Jersey: John Wiley & Sons, Inc; 2003. p. 377411. Lee PJ. Enhanced control of electropolishing for the preparation of thin foils for transmission electron microscopy: artificial and multiple phase micro-electropolishing. Proc. microscopy and microanalysis. Minneapolis, MN, August 1115; 1996. Lee PJ. A microchemical study of surface films on aluminum alloy foils for AEM. In: Williams DB, Joy DC, editors. Analytical electron microscopy. San Francisco: San Francisco Press Inc; 1984. p. 6972. Lee P.J. Multi-element microelectropolishing method. US Patent, 5354437, October 11; 1994. Madsen LD, Weaver L, Jacobsen SN. Influence of material properties on TEM specimen preparation of thin films. Microsc Res Tech 1997;36:35461. Struers A./S., Pederstrupvej 84, DK-2750 Ballerup, Denmark. Fischione PE. Materials specimen preparation for transmission electron microscopy. http://www.fischione. com/product_support/PDF/Matpreplo.pdf. Dewey MPA, Lewis TG. A holder for the rapid electrolytic preparation of thin metal foils for transmission electron microscopy. J Sci Instrum 1963;4:3856.