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Int J Mater Form (2008) Suppl 1:463 466 DOI 10.

1007/s12289-008-0095-z # Springer/ESAFORM 2008

Formation and Defining the Different Aluminium Oxide Microstructures in Alkaline Solutions
S. Mahovic Poljacek, T. Cigula, M. Gojo
University of Zagreb Faculty of Graphic Arts Getaldiceva 2, P.O. BOX 225 10000 Zagreb, Croatia URL: www.grf.hr

e-mail: smahovic@grf.hr; tomislav.cigula@grf.hr; mgojo@grf.hr

ABSTRACT: The formation of different aluminium oxide microstructures on the offset printing plate during the plate making process influences the plates ability to adsorb and repel fluids. Adsorbing and repelling of the fountain solution and ink during the offset printing process have major influence on the plates stability and print quality. The aim of this research was to define the micro structural changes in the aluminium oxide layer during the plate making process, their influence on the surface free energy of the oxide, as well as contact angles of the adsorbed fluids. Key words: Microstructure, Aluminium oxide, SEM analysis, Surface free energy, Contact angle. plates is a thin and an extremely porous and that the standardized plate making process requires immersing of the plate in the alkaline solution, significant changes in the structure occurred during the immersion. These changes are the consequence of the amorphous properties of aluminium oxide that is soluble in different alkaline solutions. 1.2 Printing plate making process In the first stage, the printing plate surface has to be exposed to certain radiation which causes physical and chemical changes in the photosensitive coating. The result of this process is that exposed areas become soluble in alkaline solutions. In the next stage, the exposed parts of coating have to be removed from aluminium oxide by immersing the printing plate in alkaline solution. This process should not significantly affect the roughness of the substrate because it is essential for its function. Nevertheless, recent studies [5-6] have been confirmed that the chemical processing can also affect the micro-structural roughness inducing changes that impair the quality of printing plate. It has been detected that the extent of these undesired effects depends the working age of the processing solution.

1 INTRODUCTION Aluminium surface suitable for use as an offset printing plate consists of two different areas: inkreceptive image areas which carry a photosensitive coating and fountain solution-retaining non-image areas. In order to improve the fountain solution adhesion on the aluminium oxide film and to enhance the adhesion of the photosensitive coating during the printing process [1-2] the foil needs to be roughened by electrochemical graining and anodic oxidation [4]. 1.1 Production of the offset printing plates Roughening of the aluminium surface and forming the thin aluminium oxide film are necessary for a number of reasons. The most important one is that they enlarge the functional properties of the surface what causes better fountain solution adsorption and better ink adhesion. After the electrochemical graining process the rough aluminium surface has to be covered with a thin (less than 2 m) photosensitive coating, which will be receptive for printing ink in the printing process and present the image areas on the printing plate surface. Due to the fact that aluminium oxide layer on the printing

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2 MATERIALS AND METHODS 2.1 Preparation of samples In this study the surface properties of the aluminium oxide areas of the two different printing plates (commercial grade 0.3 mm tick AA1050 aluminium foils) was investigated. After the exposition the photosensitive coating was removed from exposed (non-image) areas of the plate. The removal is achieved by chemical processing in alkaline solution (pH 13) according to the standardized processing procedure: at the temperature of the processing solution 22 3C, processing speed in the range of 0.9-1.3 m/min and the processing time of 22 4 s. The reference samples (hereafter designated A0 and B0) was roughened and anodized by electrochemical processes without application of photosensitive coating and was not immersed into the processing alkaline solution. The other, initially identically prepared samples were after application of photosensitive coating and exposure processed in alkaline solutions of different age: from freshly prepared (samples designated A1, B1) up to 84husage-old solution (samples designated A8, B8). pH value of the processing solution was controlled at 12 h intervals of solutions usage accordingly to the periods of samples selection. pH value of the solutions was measured by pH meter pH 330/SET, WTW GmbH with the standard electrode. Before the measuring the calibration of device was made accordingly to the standard procedure. Results of the pH values are shown in figure 1.
13.15 13.10 13.05

shown that ageing causes certain changes of the solution properties. These observations were important in further research because changing of the pH value could cause different interaction between the solution and printing plates surface in different stages of processing and, accordingly could influence on the quality of processed printing plate. Because of that the quality control of all printing plate samples was conducted after the processing of each sample and results were compliant to the graphic technology standards [7-8]. The process of selecting and controling the plates was terminated after the selected printing plate did not comply any more with the requests of the applied standards. 2.2 Structural characterisation The optical micrographs used in this study were made by JEOL JMS T300 scanning electron microscope. To assure the uniform electrical properties and to avoid the charging/discharging of aluminium oxide surfaces the aluminium plate samples 5 mm x 5 mm were gold coated (>30nm thick) by magnetron sputter SC7620 Quorum Technologies, Polaron. SEM micrographs of reference (untreated) aluminium foil (A0, B0) at magnifications 3500x are presented in figure 2.

Processing solution A Processing solution B

pH value

Fig. 2. SEM micrographs of reference (untreated) aluminium foil (A0, B0) at magnifications 3500x

13.00 12.95 12.90 12.85 12.80 0 12 24 36 48 60 72 84

Time (h)

Fig. 1. pH values of the processing solutions

One can see that freshly prepared processing solutions have the highest pH value. During the processing time (i.e. solution ageing) the pH value of both solutions has been decreased, but still remaining in the alkaline area. These results have

One can see that the aluminium oxide surfaces of untreated samples A0 and B0 consist of completely different micro-structures. These kinds of surface structures are the consequence of different electrochemical conditions during the roughening process. Characteristic structures of the surfaces were the main reason why those two samples were selected for this paper, considering the fact that both of them can be used in the same reproduction process. Sample A0 consists of micro-structures, irregular in their size and shape. The peaks are sharp and connected while the pits are of different depths and sizes. The size of the pits is different, from 1 m to

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approximately 7 m. On the other hand, sample B0 consists of fine microstructures, irregular in their size and shape. One can see that the surface is dotted with fine peaks and pits of different sizes. Pits are relatively rounded and their size changes along with the changes of their depth. The size of the fine pits is less than 1 m and the size of the larger pits is approximately 3 m. 2.3 Contact angle measurement Videobased, optical contact angle measurement was performed by DataPhysics OCA30 device. It ensures the static and the dynamic characterization of liquid/solid interfaces by contact angle measurement procedure, the requirement for the calculation of surface free energy. By determination of contact angle between the defined liquid and certain surface it is possible to get the wetting properties of the solid surface [9], information about the homogeneity of the surface, roughness characteristics of the surface and an information about the interaction between the liquid and the solid. In this paper surface free energy of the aluminium oxide surfaces was calculated by measuring the contact angle of three liquids of known surface tension [10]. Surface tensions of the liquids are presented in table 1.
Table1. Surface tension ( polar ( plv) components Liquid lv Diiodomethane 50.8 Formamide 59.0 Water 72.8
lv)

3 RESULTS AND DISCUSSION 3.1 SEM analysis Figure 3. shows a series of SEM micrographs illustrating the surface topographical changes of the selected plate samples (A and B) during the plate making procedure. The samples are initially identically prepared (exposure process) and processed in alkaline solutions of different age: from freshly prepared (samples designated A1, B1) up to 84h-usage-old solution (samples designated A8, B8). The influence of solution age on topographical changes was checked on samples selected at 12 h intervals of solutions usage.

and their dispersive (


d lv

lv)

and

Surface tension (mJm-2)


p lv

48.5 39.4 21.8

2.3 19.6 51.0

Fig. 3. SEM micrographs of plate samples selected at intervals of 12 h from processing solution usage (magnification 3500x)

Contact angles of these liquids were calculated from average values of five liquid drops placed on different areas of the same printing plate sample. Results are presented in table 2. Surface free energies of the aluminium oxide printing plate samples were calculated by using harmonic mean equation [11].
Table2. Results of the contact angle measurement ( /) Sample Water Form Dim Sample Water Form A0 61.2 72.2 85.5 B0 32.9 20.3 A1 16.3 13.1 25.2 B1 30.2 18.3 A2 18.6 18 28.6 B2 12.7 9.4 A3 13.7 11.5 44.9 B3 7.4 8.2 A4 14.2 12.7 15.8 B4 9.2 10 A5 16.2 12.8 19 B5 7.9 13.6 A6 8.7 11.3 22.6 B6 8.9 11.7 A7 7.4 14 19.6 B7 8.4 10.1 A8 27.4 13 35.6 B8 12.8 12.3 Dim 58 39.5 28.3 19.3 21.5 37.8 22.9 25.4 26.2

One can see in the figure 3. that first stage of processing (in freshly prepared solution, samples A1 and B1) causes structural changes of the surfaces on both types of samples. The size of pits and peaks has been decreased, but they still remained isolated and unconnected. Microstructure of this samples are more homogeneous than the reference one (A0, B0) and are characterised by smaller pits and peaks. Decrease in roughness involving diminishing of pits and formation of plateaus is more pronounced in the early stages of solution aging. These changes can clearly be seen at samples A2-A4. In the later stage of solution aging (samples A5-A8 and B5-B8), the processing results in a smother structure of the printing plate surface, mainly due to shallower pits. The plateau areas are still present although not so prominent due to the decreased height differences between peaks and pits. One can see that the

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topographical changes are visually not as prominent as in the earlier stages. Plateaus areas and the presence of deeper furrows containing smaller pits are visible. 3.2 Surface characterisation The measurement results of the contact angle and surface free energy are presented in figure 4. Results of the contact angles have been obtained by application of fountain solution frequently used in graphic reproduction process. The correlation between these results has been made in order to define changes in physical and chemical properties of the printing plate surfaces caused by chemical processing.
A samples
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These kinds of surface transformations, formation of different porous structures of the aluminium oxide and their influence on the fountain solution adsorption have not yet been sufficiently explored in graphic technology and this paper is the first part of our enhanced research project.
ACKNOWLEDGEMENTS This work was supported by Croatian Ministry of Science, Education and Sports grants No. 128-1201785-2228 Development of methods for printing plates' surface measurements. REFERENCES 1. Th. Dimogerontakis, S. Van Gils, H. Ottevaere, H. Thienpont and H. Terryn, Quantitative topography characterisation of surfaces with asymetric roughness induced by AC-graining on aluminium, Surf. Coat. Technol. 201 (2006) 918-926. P.K.F. Limbach, M.P. Amor and J. Ball, U.S. Patent No. 6,524,768 B1 (25 Feb. 2003). C.S. Lin, C.C. Chang and H.M. Fu, AC electrograining of aluminum plate in hydrochloric acid, Materials Chemistry and Physics 68 (2001) 217-224. S. Mahovic Poljacek, D. Risovic, K. Furic and M.Gojo, Comparison of Fractal and Profilometric Methods for Surface Topography Characterization, App. Surf. Sci. (in press). S. Mahovic Poljacek, M. Gojo, P. Raos P. and A. Stoic, Different Approach to the Aluminium Oxide Topography Characterisation, 10th ESAFORM Conference on Material Forming, In: AIP Conference Proceedings Vol. 907, Zaragoza (2007) 64-69. ISO 12218:1997. Graphic technology - Process control Offset platemaking. ISO 12647-2:2004. Graphic technology - Process control for the production of half-tone colour separations, proof and production prints - Part 2: Offset lithographic processes. H. Al-Turaif and D.W. Bousfield, The influence of substrate absorbency on coating surface energy, Progress in Organic Coatings 49 (2004) 6268. S. Wu, Polar and Nonpolar Interactions in Adhesion, J. Adhesion 5 (1973) 3955. C. J. van Oss, R. F. Giese, Z. Li, K. Murphy, J. Norris, M. K. Chaudhury and R. J. Good, In: K. L. Mittal (Ed.): Contact Angle, Wettability and Adhesion, VSP, Utrecht, The Netherlands, 1993, 269284. R. Lizarbe, J.A. Gonzalez, W. Lopez and E. Otero, Autosealing of Aluminium Oxide Films, Aluminum 68 (1992), 140-144. J.A. Gonzalez, V. Lopez, A. Bautista, E. Otero and X.R. Nvoa, Characterization of Porous Aluminum Oxide Films from A.C. Impedance Measurements, Journal of applied Electrochemistry 29 (1999), 229-238. Xu-hui Zhao, Yu Zuo, Jing-mao Zhao, Jin-ping Xiong, Yu-ming Tang, A study on the self-sealing process of anodic films on aluminium by EIS, Surface&Coating Technology 200 (2006) 6864-6853.

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Fig. 4. Correlations between the results of contact angle ( /) and surface free energy ( /mJm-2)

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4 CONCLUSIONS
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The results have shown that by immersing of the aluminium plate, porous structure of the oxide has been significantly changed. Consequently, the surface free energy of the oxide, as well as contact angles of adsorbed liquids has been different. Those results are in correlation with other investigations of the aluminium porous structure where the sealing process and transformations of aluminium oxide have been observed by impedance spectroscopy [11-13].

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