Journal of the Australian Ceramic Society Volume 49[1], 2013, 62 69

62

Effects of surface treatments on adhesion of silver film on glass substrate fabricated by electroless plating
N. Chitvoranund1,2, S. Jiemsirilers1,2, and D.P. Kashima 1,2*
1) Research Unit of Advanced Ceramics, Department of Materials Science, Faculty of Science, Chulalongkorn University, Bangkok, Thailand 2) Center for Petroleum, Petrochemicals and Advanced Materials, Chulalongkorn University, Bangkok, Thailand Email: dujreutai@gmail.com Available Online at: www.austceram.com/ACS-Journal

Abstract Silver film was fabricated on a glass substrate by electroless plating technique. Plating solution, which also known as Tollens reagent, consisted of three main solutions: silver nitrate solution as a silver source, ammonia and sodium hydroxide as pH controllers and D-glucose as a reducing agent. Glass surface was treated by three different methods: HF acid etching, SnCl2 activation and silicon carbide paper grinding. After that, a glass slide was immersed in plating solution for 90 minutes at room temperature. The purpose of this work was to study the effects of different surface treatments on adhesion between substrate and film. X-ray diffraction (XRD) pattern confirmed that the obtained film was a silver phase. Surface morphology of glass slides, both before and after plating, was investigated by scanning electron microscope (SEM). Moreover, the adhesion of silver film to glass substrate was performed by crosscut test. Keywords: Surface treatments, Adhesion, Electroless plating, Silver film

INTRODUCTION Electroless plating is a simple coating process that a reaction spontaneously reacts without using external current [1]. This method has been widely studied because it can coat on a substrate both conductive and nonconductive materials, such as glass and plastic. Not only planar substrates, but also complex shapes can be coated on both sides at once [2]. Furthermore, using ultrasonic vibration during electroless plating increases agglomeration of particles and improves packing density [3]. Ultrasonic technique also plays an important role in fast deposition of particles on the substrate [4]. Furthermore, adhesion is one of the most important factor of film processing. To improve adhesion between the two phases, a glass substrate and film, a glass surface has to be treated prior to a coating process. There are many surface treatments applied on glass such as hydrofluoric acid (HF) etching, sensitizing with SnCl2, organic appling, sand blasting and sand paper grinding. The three surface treatments were chosen in this work. First, the etching technique using HF, a normal reagent which is widely used for glass, causes surface roughness by physical treatment

and promotes more silanol group (SiOH) formation producing the hexafluorosilicic acid (H2SiF6) [5]. Another method is a traditional surface sensitizing of glass with SnCl2 which is a special treatment by a chemical conditioning process. This process is frequently used for changing glass chemical nature [6, 7]. It is significant for film adhesion occurring before silver deposition process and to activate glass surface. The sensitizing solution contains tin ions which will be absorbed on a glass surface and acts as nucleation sites for silver particles. Besides the chemical treatment, there is a simple physical treatment that has been widely used. Silicon carbide (SiC) paper grinding is a method that increases surface roughness which continuously increases surface area. Subsequently, this will increase the area of Van der Waals force which is an effective area. Ultimately, these steps will enhance the adhesion [6, 8]. Silver coating, known as silver mirror, is the oldest wet film deposition process. The reaction contains the two main solutions that are a solution of a silver salt and a reducing compound [6]. Silver ions are reduced to be fine-grain metallic silver film then precipitates on a substrate surface. Since silver or silver ions have strongly bacterial inhibition property,

Chitvoranund et al.

63

there are many researches studying about this property in the last few decades [9, 10]. In this study, adhesion and morphology of silver film prepared by electroless plating was reported. The effect of surface treatments on adhesion was determined by crosscut test. Morphology of film surface was investigated by scanning electron microscope (SEM). X-ray diffractometer was used to confirm silver phase. Preparatory results from this research lead to a development of simple coating method for preparation of silver film coated on glass surface which is promising to use as antibacterial glass containers and glass windows.

processes in this experiment were divided into two types: with and without ultrasonic vibration. Characterization Phase analyses were carried out by XRD (Bruker AXS diffractometer, D8 Advance) using a CuK radiation (=0.154 nm). XRD patterns confirmed the phase of the obtained film. Surface morphology and thickness were performed by SEM (JSM-6480LV, JEOL, Japan) operating at 15 kV. Adhesion between a glass substrate and silver film was performed by crosscut test (ASTM D3359-B-02).

METHODS AND PROCEDURES Glass slide Preparation A glass slide of size 11 inch was immersed in reverse osmosis (RO) water, vibrated in ultrasonic bath (Transonic 310, Elma) with a constant frequency of 35Hz for 5 min. Then, a glass slide was immersed in ethanol 95% for 5 min with ultrasonic vibration repeatedly. Surface Treatments Glass slide was treated by one of the three different methods as follows; 1. HF etching: a glass slide was immersed in 1 M HF (Merck) solution for 60, 90 and 120 seconds. 2. SnCl2 sensitizing: a glass slide was immersed in concentration of 0.05, 0.1 and 0.5M SnCl2 acidic solution for 5 minutes. The solution was prepared by dissolving the exact amount of SnCl2 (Ajax Finechem) in RO water, then adjusting pH of acidic region by 1M HCl (Merck). 3. Silicon carbide paper grinding: a glass slide was grinded with different number of grinding paper (No.240, 320 and 600) for 5 minutes with 150 rpm. Plating Solution Preparation Plating solution was based on Tollens reagent [11], which consisted of three main precursors: AgNO3 (PROLABO) as a silver source, NH4OH (Merck), NaOH (Ajax Finechem) as pH controllers and Dglucose (Ajax Finechem) as a reducing agent. A 10 ml of 5% silver ammonia solution was mixed with a 5 ml of 10% NaOH solution. Next, 10 ml of 5% Dglucose was added into the mixing solution in order to reduce Ag+ to Ag0. Electroless Plating As-prepared glass slide was immersed for different times (60, 90 and 120 min) in the fresh plating solution by hanging in the solution in order to let the reaction occurred freely on both surfaces. The

RESULTS AND DISCUSSION The Tollens reaction started at room temperature after a few minutes of mixing the three precursors. The color of solution gradually changed from yellow to dark brown and then grey. Inside a beaker finally turned into silver mirror because silver ion was reduced to fine silver particles. Silver particles deposited on a glass substrate to be silver film. Silver film was formed very easily because wetting-contact angle between two phases (substrate and solution) was greater than zero and reduces the energy needed. From this reason, the Tollens reaction occurred as a heterogeneous nucleation. The particles not only deposited on a glass substrate, but also precipitated at the bottom of a beaker. This study focused on 4 different surface treatments that were untreated surface, HF treatment, SnCl2 sensitizing and SiC paper grinding. Also, effect of ultrasonic process on adhesion was observed. All 48 conditions were shown in Fig. 1. Effect of Surface Treatments on Adhesion Adhesion between silver film and a substrate was tested by crosscut test (test method B). The test method B is suitable for use in laboratory. A grid pattern of 55 mm was made on the film. A 2.5 inch tape (Transparent tape 600, 3M Scotch-tape) is applied over the grid and then removed as quickly as possible. Adhesion is evaluated in semiquantitative by comparison and description in the same set. The codes in this table shows percent of area removed from a substrate (ASTM3359-B-02). Adhesion scales range from 5 to 0. 5B the edges of the cuts are completely smooth; non of the squares of the grid is detached. 0% 4B small flakes of the coating are detached at intersection; less than 5% 3B small flakes of the coating are detached along edges and at intersections of cuts. The area affected is 5-15% of the grid 2B the coating has flaked along the edges and on parts of the squares. The area affected is 15-35% of the grid. 1B the coating has flakes along the edges of cuts in large ribbons and whole squares have

Journal of the Australian Ceramic Society Volume 49[1], 2013, 62 69

64

Glass slides Untreated surface HF etching (HF) 60s 90s 120s Surface treatment SnCl2 sensitizing (Sn) 0.05M 0.1M 0.5M SiC paper grinding (SP) 240 320 600

Plating for 60, 90 and 120 min With ultrasonic Without ultrasonic

Fig.1 Flow chart of silver film preparation in all conditions detached. The area affected is 35-65% of the grid. 0B Flaking and detachment worse than grade1. Different surface treatments showed different types of interfacial layer which exhibited the various type of adhesion of film to substrate. For HF etching, this case mixed between mechanical interfacial layer and monolayer on monolayer type; it created roughness and had no diffusion or chemical reaction. SnCl2 sensitizing is chemical-bonding interfacial layer because the interfacial layer was formed by the chemical reaction of film atoms with substrate atoms. The last treatment, SiC paper grinding, is mechanical interfacial layer type forming on rough or porous substrates [6]. According to the preliminary adhesion result, HF etching showed only a good condition of plating for 60 minutes, however the film could not stand for little scrapes. Moreover, sensitized surface with SnCl2 was easily torn off in every sample. Some of them appeared that there were two layers on the surface; the first layer which was very thin still a bit remained after pull the tape out. From all conditions in table 2, the best surface treatment was using SiC paper grinding No.320 and plating for 90 minutes. Although this condition showed good adhesion, the film was still a bit removed at grid lines. Therefore, the idea of combining two different surface treatments together was created in order to improve the adhesion. The first combination treatment was using SiC paper No.320 grinding before immersing in HF for 90 seconds (SP320-HF90/90). Grinding with SiC paper No.320 then immersed in SnCl2 for 5 minutes (SP320-Sn0.05/90) was the other way. A crosscut test result of combined treatment was presented in Table 3. As a result of combination treatment, SP320-HF90 presented an excellent adhesion; no flakes were exfoliated from the substrate. However, SP320-Sn0.05 exhibited only a fair adherence. When comparing of the adhesion test between a single treatment to a combined treatment, it was clear that combined treatment with two-step method could improve the adhesion of silver film to glass substrate. Using of HF was more beneficial than SnCl2 because HF simultaneously produced both of more roughness and more silanol group on glass substrate. On the contrary, SnCl2 acted as an accelerator and nucleation sites for silver mirror reaction. After a glass slide was covered with SnCl2, it was immersed in plating solution then shiny silver flakes suddenly occurred on the top of plating bath and small dark brown particles deposited on a glass substrate. From the crosscut test result, roughness played more important role in improving adhesion than chemical treatment which could enhance the adhesion of silver film to a substrate. Also, the appropriate film thickness to roughness would exhibit a good adhesion property. Phase Analysis Diffraction patterns confirmed that the obtained films in all conditions corresponded to silver phase which showed the highest peak at 38.2. As shown in this figure, there were not any characteristic peaks of AgO or any other phases. Fig 2 showed XRD patterns of the film prepared at different surface treatments, then plating for 90 minutes. There are 6 conditions: untreated surface, immersing in HF for 90 seconds (HF90), immersing 0.05M SnCl2 for 5 minutes (Sn), grinding with silicon carbide paper No. 320 (SP320), grinding with SiC paper No. 320 then immersed in HF for 90 seconds (SP320-HF90) and grinding with iC paper No. 320 then immersed in 0.05M SnCl2 for 5 minutes (SP320-Sn0.05).

Chitvoranund et al.

65

Table 1: Adhesion test result of 60 conditions plating for 60, 90 and 120 minutes; with and without ultrasonic vibration. sample treatment condition plating time without ultrasonic (min) 60 0B 3B 4B 3B 0B 0B 0B 1B 2B 1B 90 0B 0B 0B 1B 0B 0B 0B 2B 4B 1B 120 0B 0B 0B 1B 0B 0B 0B 1B 1B 0B plating time with ultrasonic (min) U60 0B 0B 0B 0B 0B 0B 0B 0B 0B 0B U90 0B 0B 0B 0B 0B 0B 0B 0B 0B 1B U120 0B 0B 0B 0B 0B 0B 0B 0B 0B 0B

untreated surface 60s HF 90s 120s 0.05M Sn 0.1M 0.5M No.240 SP No.320 No.600

Table 2: Adhesion test result of combined surface treatments in 2 conditions plating of silver film for 90 minutes Combined treatment SP320-HF90 SP320-Sn0.05 Plating for 90 min 5B 2B

Effect of different etching time in HF of 60, 90 and 120 seconds (3b, 3c and 3d) was obviously seen. HF etching created holes on the surface. The size of holes was increased with increasing of immersion time. On the other hand, the surface of coating SnCl2 on glass surface for sensitization (3f) looked similar to the untreated sample (3a) which was very smooth surface. SiC paper grinding made the surface to gain more roughness in a pattern of scratching.

Phase Analysis Diffraction patterns confirmed that the obtained films in all conditions corresponded to silver phase which showed the highest peak at 38.2. As shown in this figure, there were not any characteristic peaks of AgO or any other phases. Fig 2 showed XRD patterns of the film prepared at different surface treatments, then plating for 90 minutes. There are 6 conditions: untreated surface, immersing in HF for 90 seconds (HF90), immersing 0.05M SnCl2 for 5 minutes (Sn), grinding with silicon carbide paper No. 320 (SP320), grinding with SiC paper No. 320 then immersed in HF for 90 seconds (SP320-HF90) and grinding with SiC paper No. 320 then immersed in 0.05M SnCl2 for 5 minutes (SP320-Sn0.05). Effect of surface treatment on morphology Various surfaces before silver plating were investigated by SEM as shown in Fig 3. The morphology of a substrate surface was significant because it affected to physical and chemical behavior of materials [6]. Fig.2 XRD patterns of silver film prepared from different surface treatments with plating time for 90 minutes; untreated, HF90, Sn0.05, SP320, SP320-HF and SP320-Sn0.05.

Journal of the Australian Ceramic Society Volume 49[1], 2013, 62 69

66

Fig 3: Surface morphology of glass substrate before plating silver film in all conditions; (a) untreated surface (b) HF60 (c) HF90 (d) HF120 (e) SP320HF90 (f) Sn0.05 (g) SP240 (h) SP320 (i) SP600 (j) SP320Sn0.05 The more the lower number was used, the more roughness was observed (3g, 3h and 3i). Two step surface treatment by SiC paper grinding then immersed in HF produced very rough surface, no scratches could be seen, while the surface of grinding before SnCl2 immersion was quite similarly to a surface of single step grinding method. Nevertheless, the surface of SP320Sn0.05 was smoother than the one with treated only SP320. Besides, surfaces and cross-sectional images of after plating were shown in Fig. 4 and Fig. 5 respectively. Considering surfaces images, full packing of silver film could be observed in every condition, but they had different particle shapes. Particle size of untreated-surface sample (4a) was less than 1 micron while particles of treated-surface sample (4b-4f) were packing together which was bigger than 1 micron. The film surface of HF etching (4b) was similar to untreated-surface sample. It was packed in form of round shape. Using SnCl2 for surface activation (4c) was different from the others because it could be obviously seen particle packing on the top of silver film in large scale. Stannous () ions might effect on reducing process of initial reaction. Consequently, Dglucose was taken place from Sn2+ to be a reducing agent. Hence, silver film in the first layer was bound with Sn2+ and then other silver particles reduced by Dglucose were deposited on that layer [7]. Silver particles on the first layer were small and fully packing as shown in Fig 4c. After the first layer of silver film was formed, some particles that produced nearly the end of the reaction had no more space to deposit on a substrate. So, they most likely agglomerated and formed silver clusters [12]. From Fig. 4d, silver particles deposited on ground substrate were irregular shape filling in the surface gap. These grains were connected to each other and a continuous film was formed. Similarly, the film morphology of SP320HF90, Fig. 4e, was irregular shape but particles agglomerated creating bigger particle size. The final condition was SP320Sn0.05 (4f) which was dense film. It still had particle agglomeration dispersing on the top of the film surface, similar to the case of treated surface with pure SnCl2. Moreover, the agglomerate particle size of SP320Sn0.05 increased and less contacted in each other when compared to Sn.

Fig 4: Surface morphology of silver film plating for 90 minutes in different surface treatments; (a) untreated surface (b) HF90 (c) Sn0.05 (d) SP320 (e) SP320HF90 (f) SP320Sn0.05

Chitvoranund et al.

67

Fig 5: Cross-sectional morphology of silver film plating for 90 minutes in different surface treatments; (a) untreated surface, 90 (b) HF90 (c) Sn0.05 (d) SP320 (e) SP320HF90 (f) SP320Sn0.05. In addition, cross-sectional images (Fig. 5) of the samples could be implied about film thickness and preliminary information of adhesion between film and a substrate. From untreated surface (5a), there was a small gap between the obtained film and a substrate, thus it could be concluded that the adhesion between two phases was low. It could be clearly observed that there was a gap between silver film to glass substrate for untreated surface condition. On the other hand it was hardly seen the gap in treated surface samples. In Fig. 5b and 5d exhibited the wave of silver film at the edge of cutting area. This indicated that the obtained film was tough. Silver film coated on sample of SP320HF90 (5e) was rough following to the substrate surface. Roughness increased surface area; hence the area of Van der Waals force, an effective area, was increased. In other words, it was implied that roughness of the surface adhered these silver grains together via Van der Waals. Fig.5f (with magnification of 1000) exhibited the two phases of SP320Sn0.05 corresponding to Fig 4f. It could be seen that there were a lot of clusters deposited above the dense film. However, the film formed on a single step surface treatment of glass substrate had the same characteristic and performed a good toughness as shown in Fig.6. Particles were more strongly adhered to each other than to a substrate, thus silver film could detach from a substrate as a sheet form.

Fig. 6: SEM micrograph of cross-section sample (HF90) showing toughness of the obtained film on glass substrate. The primary study of antibacterial activity was performed by using spread-plate method comparing with and without silver film of the best surface treatment condition (SP320HF90), as shown in Table 3. It was clear that silver film could inhibit bacteria in 100% reduction of Escherichia coli that corresponded to Fig. 7. Obviously, there was no colony of E.coli appeared in the plate of silver film. Feng et al investigated the inhibition mechanism of silver ions on E.coli. They found that DNA replication ability was affected by silver ions and then bacterial protein becomes inactivated [13].

Journal of the Australian Ceramic Society Volume 49[1], 2013, 62 69

68

Table 3: % reduction of E. coli in different samples; pure(reference), blank ( a simple glass slide), SP320HF90(without silver film) and SP320HF9090(with silver film) The number of bacteria Sample %Reduction CFU/ml (6 h.) Pure Blank SP320HF90 SP320HF90-90 4.5 x 106 4.8 x 106 5.3 x 106 0 0 0 100

sample without the vibration. In addition, different surface treatments led to different film surface morphology. SEM micrographs gave preliminary information about toughness of the obtained film. Also, silver film could inhibit E.coli in 100% of reduction which was confirmed by spread-plate method.

ACKNOWLEDGEMENTS The authors would like to express our gratitude to Center for Petroleum, Petrochemicals and Advanced Materials, Chulalongkorn University , Research Unit of Advance Ceramics, Department of Materials Science, Faculty of Science, Chulalongkorn University, and Unit cell for research and development of herbs and natural products for dental application for their financial supports.

REFERENCES
1. R.E. Kirk and D.F. Othmer, Kirk Othmer Encyclopedia of Chemical Technology, Volume. 8, Wiley, New York (1979), 738-739. C.B. Carter and M.G. Norton, Ceramic Materials Science and Engineering, Springer, New York (2007), 484. M. Pattabi, J. Uchil and K.M. Rao, The effect of substrate vibration on mobility coalescence in silver island films, Thin solid films, 305 (1997), 196-200. Y. Lu, Improvement of copper plating adhesion on silane modified PET film by ultrasonicassisted electroless deposition Appl. Surf. Sci., 256 (2010), 3554-3558. M. Kolli, M. Hamidouche, N. Bouaouadja and G. Fantozzi, HF etching effect on sandblasted soda-lime glass properties, J. Eur. Ceram. Soc. 29 (2009), 2697-2704. H.K. Pulker, Coatings on Glass, Volume 6, Elsevier, New York (1984), 74, 94-95. L.R. Pederson, Comparison of stannous and stannic chloride as sensitizing agents in the electroless deposition of silver on glass using Xray photoelectron spectroscopy, Sol. Energy Mater. Vol. 6 (1982), 221-232. R-D Sun, D. A Tryk, K. Hashimoto and A. Fujishima, Adhesion of Electroless deposited Cu on ZnO-coated glass substrates: the effect of the ZnO surface morphology, J. Electrochem. Soc. 146 (1999), 2117-2122.

2.

3.

4. c d

Fig. 7: Inhibition tests of sample on Escherichia coli ATCC 25922 for 24 h., incubated at 37oC: (a) Pure (b) Blank (c) SP320HF90 [without silver film] (d) SP320HF90-90 [with silver film]

5.

CONCLUSIONS Silver film on glass substrate was fabricated by electroless plating in Tollens reagent. Effect of surface treatments on adhesion of silver film and a glass substrate were investigated by crosscut test. Roughness which was a physical treatment was an important factor for good adhesion, while chemical treatments had minor effect on adhesion. The sample treated surface with two-step of silicon carbide paper grinding and hydrofluoric acid etching (SP320HF90) was the best condition because adhesion between the two phases was excellent reported in 5B. However, Ultrasonic operation did not help adherence between silver film and glass surface. It only enhanced deposition rate, thus the film was thicker than the

6. 7.

8.

Chitvoranund et al.

69

9. G.J. Chi, S.W. Yao, J. Fan, W.G. Zhang and H.Z. Wang, Antibacterial activity of anodized aluminum with deposited silver Surf Coat. Technol. 157 (2002), 162-165. 10. S.M. Lee, B.S. Lee, T.G. Byun and K.C. Song, Preparation and antibacterial activity of silverdoped organic-inorganic hybrid coatings on glass substrates, Colloids Surf., A 355 (2010), 167171. 11. C.J. Lee, S.Y. Lee, M.R. Karim and M.S. Lee, Comparison of the adsorption orientation for 2mercaptobenzothiazole and 2mercaptobenzoxazole by SERS spectroscopy, Spectrochim. Acta, Part A 68 (2007), 1313-1319.

12. F. Mei and D. Shi,Electroless plating of thin silver films on porous Al2O3 substrate and the study of deposition kinetics, Tsinghua Sci. Technol. 10 (2005), 680-689. 13. Q.L. Feng, J. Wu, G.Q. Chen, F.Z. Cui, T.N. Kim and J.O. Kim, A mechanistic study of the antibacterial effect of silver ions on Escherichia coli and Staphylococcus aureus Biomed. Mater. Res. 52 (2000), 662-668.