UNIVERSITI TEKNOLOGI MARA TERENGGANU

CHE 335 BASIC INSTRUMENTATION AND ANALYSIS

The reaction o !ater !ith a"ra#e# a$%&in%& '%r ace' a' 't%#ie# "( )o%rier tran' or& in rare# '*ectro'co*( +)TIR,

MUSTA-IM BIN .AKARIA /0012/5534 EHD1CA

Abstract Studies of silane adsorption onto aluminum surfaces cleaned using wet chemistry techniques indicate that adsorption is very rapid, on the order of tens of seconds. In contrast, an empirical study of the performance of adhesive joints as a function of silane deposition conditions on gritblasted aluminum surfaces, showed that the silane-containing solution needed to be left in contact with the surface for 10 to 0 min to obtain optimum performance. !his time lag is believed to result from the time required to hydroly"e #l$% bonds on the surface. !his hydrolysis process is shown to be much faster as the p& of the solution becomes more basic or acidic. #t p& ' or p& (, the hydrolysis is complete in less than 1 min.

1. Introduction In order to create a reliable adhesive joint, aluminum surfaces are commonly grit-blasted using fine alumina particles as the first step in a bonded repair. It has been found empirically in a study of adhesive bonding that when the coupling agent, )-glycido*ypropyltrimetho*y silane, is deposited from an aqueous solution, there is a degradation in the environmental durability of the bond as measured by the wedge test +#S!, -)./ 0 if the solution is not left on the aluminum surface for 10 to 0 min. !his result conflicts with the results obtained for silane deposited on 1orest 2roducts 3aboratory +1230-etched aluminum surfaces which indicate that the adsorbed silane reaches equilibrium with the depositing solution very quic4ly, certainly within min. Sabata and van %oij have indicated that the optimum deposition time for silanes on al4ali-etched surfaces is on the order of 1' s. %ne possible e*planation for this is that the grit blast surface is created under very dry conditions while the other two techniques mentioned involve wet chemistry. #n e*tremely dry air source, typically bottled air or nitrogen, is used to drive the grit in order to ma4e sure that oil is not deposited on the new surface. It is believed that the silane attaches to the aluminum surface through a condensation reaction with surface hydro*yl groups, just as it does on silica surfaces. !hese hydro*yl groups might be significantly depleted on the grit-blasted surface. !his letter reports the results of an e*perimental study to identify the basis for the increased time required to produce the optimum silane films on grit-blasted aluminum surfaces by investigating aluminum surfaces produced under dry conditions using gra"ing angle 1ourier transform infrared spectroscopy +1!I50 .

2. Materials and methods 6nfortunately, grit-blasted surfaces are too rough to be e*amined using 1!I5. Instead, fresh surfaces were prepared by abrading clean, dry .0.' aluminum slides using Scotch-7rite pads until a smooth shiny surface had been obtained. !he ambient humidity in the lab during this process was typically )08 5.&. %nce the slides had been abraded, they were used to obtain a bac4ground spectrum using a gra"ing angle reflection apparatus, which was based on a 9icolet '102 spectrometer. !he average reflection angle was :'; from the sample normal. !he slides were then immersed in deioni"ed water for a series of 1-min intervals. #fter each e*posure, the slide was quic4ly blown dry using dry, bottled nitrogen. !he surface was then e*amined in the 1!I5. !he results are shown in 1ig. 1 for the spectral region from .00 cm <1 to 1.00 cm<1. !his region contains the fingerprint bands for all the %& bend modes associated with the various hydro*ide forms of aluminum and also the %& bend for water. !he spectrum above 1.00 cm <1 shows no changes over the same time period and so has not been shown. !his latter region includes the %& stretch region from )000 cm<1 to ).00 cm<1. !he spectra in 1ig. 1 show the growth of two negative bands in the absorbance spectrum, a sharp one at ::1 cm <1 and a broad one centred on 1=:. cm<1. 7ecause these are negative bands, they indicate the loss of a chemical species that was present on the original abraded surface. It can also be seen that the intensity of these bands ceases to grow significantly after about = min. #fter 1= min of submersion, wea4 positive bands can be seen at 10:' cm <1 and (/0 cm<1. !hese can be associated with the 7oehmite or pseudo-7oehmite structure. #t much longer time intervals, on the order of many hours, a wea4 broad band can be seen at about )'00 cm <1, which can be associated with %& stretching. !he pea4s at 10:' and (/0 cm <1 also continue to grow. >hen the reaction is repeated using water with a p& of (.0 or '.0, the same result is obtained, but on a much faster time scale. In both of these cases, the negative going absorbance pea4s had ceased their rapid growth after no more than 1 min of e*posure to water. >hen p& ..0 water is used, the growth is much slower. #fter days of immersion, the pea4 at 1=:. cm <1 was still only two-thirds of the intensity achieved at p& '.0 in 1 min.

1igure 1. #bsorbance spectra obtained from an abraded aluminum surface e*posed to deioni"ed water. ?umulative e*posure times are given on the right-hand side. Spectra have been shifted vertically for clarity. >hile the p& of the solution plays a significant role in these changes, it was determined that the ionic strength of the solution did not. !he growth of the pea4s was monitored in both ultra-pure water +resistance greater than 1 ,@Acm 0 and in a 0.' , 9a?l aqueous solution. 9o difference was observed in the pea4 growth rates between the solutions.

3. Results and discussion 1ig. shows the absorbance spectrum obtained when the abraded surface is first heated to 100;?

for 1 h. !his treatment should desorb any bound water. It can be seen that there is a slight positive pea4 at 1=/ cm<1 and ('1 cm<1. !here is no loss of intensity in the %& stretch region above )000 cm<1. # negative pea4 would be e*pected to arise if there were any hydro*yls or water adsorbed to the original surface. !his confirms the suggestion that the dry Scotch-7rited surface contains very few %& groups. >hen this surface is e*posed to water for 10 min, a spectrum similar to that at the end of 1ig. 1 is obtained.

1igure . #bsorbance spectra obtained from an abraded surface following different treatments. !he surface was first heated then immersed in water. Spectra have been arbitrarily offset for clarity. !he bands at 1=/ and 1=:. cm<1 cannot be attributed to water adsorbed into or onto the aluminum surface since these are 4nown to absorb about 1/00 to 1/)0 cm<1. !hey are also higher in frequency than any of the 4nown %& bands associated with the various hydro*ides of alumina. ,iljevic et al. and -orsey have ascribed lines in the region from 1)=' to 1/(/ cm <1 to #l$% bonds. !his would certainly be consistent with the observation that the pea4 at 1=/ cm <1 grows slightly upon heating, since heating might be e*pected to increase the o*idation state of any #l atoms on the surface, possibly by the elimination of #lB%B%B#l bridge bonds. #lso, #l$% moieties might be e*pected to be subject to hydration to form two #lB%& bonds with the

adsorption of a water molecule. 1urthermore, the hydration reaction would be e*pected to be both acid- and base-cataly"ed as is observed e*perimentally. !he observation that no %& stretch or bend bands are observed to grow during this suggested hydration reaction could be e*plained if the resulting %& groups lay in the plane of the surface. 5eflection adsorption spectroscopy is only sensitive to dipoles lying normal to the surface and hence if they lay parallel to the surface they would be invisible to this form of spectroscopy. It is not clear what mode the sharp band at ::1 cm <1 can be ascribed to. 3ines in this region are usually ascribed to #l)C ions in tetrahedrally coordinated sites. &owever, this line appears to be anomalously sharp compared to the other substrate lines. Since its intensity is proportional to that of the 1=:. cm<1 band, it must arise from the destruction of the same centre. !he e*perimental evidence presented here strongly suggests that the =-min delay required to achieve optimum results in applying the silane D2S from a distilled water solution is due to the need to hydrate #l$% groups on the surface of the prepared aluminum. !his process can be greatly accelerated by using acidic or basic solutions, with p&s as close to neutral as ' and (.

4. Conclusion 1!I5 analysis of the time lag is to result from the time required to hydroly"e #l$% bonds on the surface. !his hydrolysis process is shown to be much faster as the p& of the solution becomes more basic or acidic. #t p& ' or p& (, the hydrolysis is complete in less than 1 min.