Abs. 670, 204th Meeting, 2003 The Electrochemical Society, Inc.

Adhesion of Titania Films on Alumina Kailash .C. Jain Delphi Research Labs, 51786 Shelby Parkway, Shelby Township MI 48315 Semiconducting oxides such as SnO2, WO3, ZnO, TiO2 are especially useful for sensing residuals of combustion components from automobile exhausts, diesel engines, and home heating systems due to their chemical and thermal stability. Lambda sensors using TiO2 are simpler in construction to zirconia sensors that require closed-tube technology. The rutile titania film is also the material of choice for photochemical hydrogen production from water [1]. The durability of such devices however relies upon the adhesive strength of the titania films to the substrates [2]. This paper focuses on assessing and improving the adhesive strength of titania films onto alumina substrates. Three types of Al2O3 substrates measuring 57x26x1mm were obtained by co-firing two pieces of green alumina tapes at 1500C with or without screenprinted Pt or Pt- TiO2 [2]. The Pt and Pt- TiO2 inks were prepared using Pt powder, an organic binder, a solvent, and TiO2 powder (grain size: 1-5m) 10-20 wt% such that the inks had a solid content of roughly 65% by weight. On these substrates, TiO2 islands were screen-printed using an oil slip made from a 2m grain size nominal TiO2 powder. Two pre-fired titania film thicknesses, H =15m and H =65m and two slip mediums were selected for screen printing. The printed test pattern consisted of seven blocks of titania islands on alumina, measuring L =14mm and W =5mm. These samples were dried at 150C, sintered for 1 hr in the 900C-1300C range. A Revetest Automatic Scratch Tester equipped with a Rockwell C diamond (conical angle: 120; hemispherical tip: 200m radius) was used for the scratch tests. Six to twelve separate parallel scratches were performed under linearly increasing load for each of the sintering temperatures. A loading rate of 100N/min and a table speed of 10mm/min were used. These parameters yielded a load-distance rate, dL/dx, of 10 N/mm as recommended in the literature [3]. The acoustic emission, tangential frictional force, and optical observations were used to determine the critical load shown in Figure 1. For the pull-tests tapered aluminum pins pre-coated with an epoxy were bonded to the film by curing the epoxy adhesive at 150C for one hour. The adhesive strength was calculated as the force required for pulling a pin from the specimen divided by the area of the 3.58mm diameter pin. Typically 5-10 pulls were made on each sample at a given sintering temperature. Adequate adhesion tests were obtained by incorporating two improvements to a Comten Industries pull-tester. First, a universal joint was designed and installed on the pull-test fixture that allowed the fixture to rotate in the x-y plane. Next, a redesign of the clamps using a concentric washer with the pull-stud in the test machine resulted in reproducible pull-strength values over the range of sintering temperature as shown in Figure 2. As shown in Figure 2 there is a large range in pull strength of 15-20m films obtained from either the aqueous or oil slip mediums. The SEM and optical microscopy of the fracture surfaces revealed that purely mechanical interlocks and a lack of oxide on the surface of platinum were most likely the cause of very low to practically no adhesion with the TiO2 film on the Al2O3 surface. Figure 3 shows the pull strength of 65m titania films over Pt/TiO2 coated substrate and compares with pull strengths over Pt/Al2O3 and Al2O3 substrates. As seen from the figure the 65m films over Pt/TiO2 have narrow distribution and an order of magnitude higher pull strength as compared to Pt/Al2O3 or Al2O3 substrates. The chemical-mechanical interlocks provided 65m titania films sintered at 1300C that were tightly bound and had pull strength of 25 MPa. Recent work on toughening composites [4] may be important in further optimizing the adhesive strength of TiO2 films. REFERENCES 1. R. Schaub et. al., Physical Review Letters, Vol. 87, No. 26, 2001. 2. R.G. Fournier, K.C. Jain, & C.A. Valdes, U.S. Patent # 5,776,601, 1998. 3. P.A. Steinmann, Y. Tardy, H.E. Hintermann, Thin Solid Films, 154, pp.333-349, (1987). 4. I.J. Merchant, H.W. Chandler, R.J. Henderson, T. Stebbings, & D.E. Macphee, Mat. Res. Soc. Symp. Proc. Vol. 702 (2002).
Normal Force, N @ sudden incr. In acoustic signal

30 25 20 15 10 5 0 850

15-90um aq. Slip 15um sq. oil slip 62 um sq. oil slip

1050

1250

Sintering Temperature, (o C)

Fig.1 Step increase in acoustic emission vs. sintering temperature. Thick films (62 m) require higher normal force and overlap of both of these bands with 15-90m films suggests that both slip mediums behave similarly.
20 Squeegee oil slip Aqueous slip 15-20 m films

Pull Strength, (MPa)

15 10 5

0 800

1200 1000 Sintering Te mpe rature, o C

1400

Fig.2 Pull strength of titania films vs. firing temperature.

30 TiO2 on Pt - TiO2 coated Al2 O3 TiO2 over Pt coated Al2 O3 20 TiO2 on Al2 O3

Pull Strength, (MPa)

10

0 1200

1250

1300

Temperature, o C

Fig.3. Pull strengths of TiO2 films on alumina surfaces with or without Pt or Pt- TiO2 coatings.