Journal of Colloid and Interface Science 238, 136146 (2001) doi:10.1006/jcis.2001.7506, available online at http://www.idealibrary.

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Aqueous Amino Silane Modication of E-glass Surfaces

Hazel Watson,1 Anne Norstr om, A sa Torrkulla, and Jarl Rosenholm
Department of Physical Chemistry, Abo Akademi University, Porthansgatan 3-5, Abo 20500, Finland Received September 22, 2000; accepted February 27, 2001
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The majority of work available in the literature examines the effect of epoxy silane, -aminopropyltrimethoxy silane, and methacrylate silane on E-glass surfaces. As alternatives to the most commonly used silanes, we investigated two novel silanes: -ureidopropyltriethoxy silane and N (aminoethyl) aminotrimethoxy silane and additionally an amino-functional polysiloxane. The ureido silane-treated E-glass bers demonstrated a zeta potential similar to that of the untreated E-glass bers, which was independent of deposition solution pH over the pH range investigated. A moderately hydrophobic E-glass surface, which was silane concentration dependent, was noted as being due to condensed SiOSi bonds at the surface. The diamino silane demonstrated an extremely basic surface at the higher silane concentrations investigated. These outer surface layers were modied by changing the pH and the concentration of the deposition solution. The polysiloxane produced an increase in the hydrophobicity of the E-glass ber, especially when deposited from extremely basic solutions. At the higher solution concentrations investigated, the silanes and the siloxane was initially deposited in patches and an outer surface or skin was formed over these patches, giving the appearance of fully coated bers. C 2001 Academic Press Key Words: silane; siloxane; zeta potential; contact angle; DRIFT; E-glass.

INTRODUCTION

It has long been known that treating the surface of a silica ller (colloidal, particulate, or brous) with a coupling agent improves the physical and chemical properties of a polymer matrix lled with such materials (14). The match between polymer matrix and silane organofunctional group type and length has a bearing on the mechanical properties of the product (5). Park and Subramanian suggested that if the silane was highly crosslinked, interpenetration of the silane/siloxane would be limited, leading to reduced interfacial properties of a polymer/ber matrix (6). Acid concentration (i.e., pH of the treatment solution) and the curing conditions used, can affect the molecular weight of the deposited silane oligomers and the amount of silane deposited onto the surface (79). The rate of hydrolysis of aminopropyltri-

ethoxy silane (APTES) was at a minimum at pH 7, while the rate of condensation was at a minimum at pH 4 (10). Premachandra et al. demonstrated a similar pH dependency for the hydrolysis of -ureidopropyltrimethoxy silane. They went on to note, however, that condensation of this silane was at a maximum between pH 9 and pH 10 (11). Leyden and Atwater showed how the organic functional group affected both the condensation and the hydrolysis reactions (12). Drying the E-glass bers accelerated the condensation of the surface silanols with the silane silanols, enhancing the chemisorption. Washing the E-glass bers stabilized the siloxane layer, thus improving the hydrolysis resistance and the hydrophobicity of the surface (13, 14). Research showed that ureido silanes were bonded to the surface by only a few SiOSi linkages (15). The remainder of the silane was present as a highly crosslinked mass attached to these few surface bonded silanes, resulting in rmly attached patches of a 3D polysiloxane network. Silane manufacturers recommend silanes for use with different surfaces on the basis that the organo-functional group can be expected to react with proposed matrix polymers (16, 17). Early results indicated that the ureido silane produced entirely unexpected results, with a condensed SiOSi surface as opposed to a ureido surface. Thus investigation of whether a ureido surface is achievable from this silane warrants further investigation. In order to ensure that the siloxane surface was not produced by our deposition method, a silane with primary and secondary amino functions (diamino silane) and a polysiloxane were investigated alongside the ureido silane. The aim of this work was to investigate the nature of the E-glass ber surface with different silane-based treatments, using a range of concentrations and pHs.
EXPERIMENTAL

We investigated the effect of treatment solution pH and concentration on two cationic silanes and a polysiloxane. The range chosen for investigation was pH 4 to pH 7, and additionally the polysiloxane molecule was investigated at pH 10.5. Materials

1 To whom correspondence should be addressed. Fax: +358 2 215 4706. E-mail: hazel.watson@abo..

Chopped industrial grade E-glass bers and an emulsion, siloxane AR433, were kindly supplied by Ahlstr om Glassbre
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0021-9797/01 $35.00
Copyright C 2001 by Academic Press All rights of reproduction in any form reserved.

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TABLE 1 Composition of E-glass Fibers Used

E-Glass, oxide constituents SiO2 Al2 O3 + Fe2 O3 CaO MgO Na2 O + K2 O B2 O3 wt% 55 14.5 21.5 0.5 <1.0 7.5 Elements as determined by XPS O1s C1s Si2p Ca2p B1s Al2p % 52.5 21 17.4 3.4 0.4 5.6

TABLE 2 pH and p K a Values of Aqueous Solutions of Silanes A1160 and A1126 and Siloxane AR433
A 1160 pH of a 0.15% solution pKa 8.6 8.6 A1126 10.1 9.4 AR433 9.4 9.0

Oy, Karhula, Finland. The E-glass bers were of diameter 11.0 106 m and length between 0.8 103 and 1.0 103 m (Table 1). The E-glass ber samples were water cooled, immediately after the E-glass bers were drawn from the spinning bush. The cationic aminosilanes used were, -ureidopropyltriethoxy silane (A1160) and N -(aminoethyl) -aminopropyltrimethoxy silane (A1126) (Fig. 1). The manufacturers did not reveal the chemical structure of siloxane Flexichem AR433 (Fig. 1), which was a milky emulsion with a siloxane content of approximately 37%, and an undisclosed amount of ethanol and methanol. Aspokem Oy (Finland) kindly donated the Witco silanes. All the silane products were used without further treatment.

Distilled water was passed thorough a Millipore Milli Q academic 10 deioniser to produce deionized water of 18.2 M cm at 25 C (pH 5.8). Glacial acetic acid (99100% Baker Analysed ACS reagent) and ammonium hydroxide (Baker Analysed [AR] 25% NH4 OH) were obtained from J. T. Baker. Methods Before treatment, the E-glass bers were sonicated in deionized water for 10 min and then vacuum dried at 50 C and 200 Torr for 24 h. The silanes were added to water, and the pH and p K a values were determined in aqueous solutions, the solutions were used immediately after pH adjustment (Table 2). Aqueous solutions (400 ml) of each silane were made at pH 4, pH 5, pH 6, and pH 7 using acetic acid to adjust the pH and additionally AR433 solutions were altered to pH 10.5 with 1 M ammonium hydroxide. Concentrations of 0.005, 0.01, 0.10, and 0.15 wt% were used for each material. Silanes A1160 and A1126 were supplied as 50 and 40% solutions in methanol, respectively, while the siloxane AR433 had a solids content of 37%. The amount of silane in each of the solutions was actually much lower than the concentrations noted above. To enable a reasonable comparison to be made among the three materials they will be referred to as 0.005, 0.01, 0.10, and 0.15 wt% of silane solutions (Table 3). E-glass bers (30 g) were added to each solution and stirred for 20 min. The solution was decanted and the E-glass bers oven dried at 120 C for 10 min, to condense the silane with the glass surface. The E-glass bers were then washed and sonicated in
TABLE 3 Actual Weight Percentages of Silanes A1160 and A1126 and Siloxane AR433 Used
Weight as supplied (wt%) A 1160 0.005 0.01 0.1 0.15 0.005 0.01 0.1 0.15 0.005 0.01 0.1 0.15 Actual silane content (wt%) 0.0025 0.005 0.05 0.075 0.0019 0.0037 0.037 0.055 0.002 0.004 0.04 0.059 Molar silane content 9.64 105 1.89 104 1.89 103 2.84 103 8.9 105 1.78 104 1.78 103 2.67 103 Proprietary formulae

A 1126

AR 433 FIG. 1. Schematic structures for (a) silane A1160, (b) silane A1126, and (c) siloxane AR 433.

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deionized water for 3 min to remove loosely bound silane (18). After careful ltration the E-glass bers were dried at 60 C for 24 h in a vacuum oven at 200 Torr. Premachamdra et al. demonstrated that hydrolysis of ureidopropyltrimethoxy silane in a water/methanol medium was extremely rapid at pH 4.87 and pH 9.83. Between these extremes a minimum rate of hydrolysis occurred at pH 7.44. They went on to qualitatively demonstrate that condensation was at a maximum between pH 8.97 and pH 9.87 (11). At lower pHs a preponderance of silanol groups existed which condensed at a much lower rate. Thus over the pH range examined it is reasonable to suggest that during the 20-min period, for which the silanes were allowed to hydrolyze, little or no condensation occurred, prior to deposition onto the E-glass bers. Streaming Potential (Zeta Potential ) Streaming potential was expedited using an Anton Parr Electrokinetic Analyser (EKA), with an automated pH titration apparatus, which has been described elsewhere (19, 20). The electrolyte solution used was 1.0 E + 03 M KCl, at a conductivity of 2.7 E + 01 mS/m at 23 2 C. Starting with the original solution the pH of the electrolyte solution was adjusted. Higher pH values were obtained by the addition of 0.25 M KOH and lower pH values by the addition of 0.25 M HCl. One step conformed to 0.5 of a pH unit. Two grams of carefully packed E-glass ber sample was used for each measurement. Similar packing density and overall consistency were required for every test; any differences could result in poor reproducibility. The equipment was carefully washed with KCl between each test. Mathematical treatment of the data used the FairbrotherMastin approximation (19, 20). A minimum of three measurements were carried out, to ensure reproducibility. Contact Angle A KSV Instruments Sigma 70 Wilhelmy balance was used to measure the advancing and receding contact angles. A single ber was attached, vertically, to a wire hook, using double-sided adhesive tape. The hook was suspended from an electrobalance, which had a range of 0.25 mN and a resolution of 0.05 N. The wetting liquid used was deionized water (pH 5.8). The beaker was moved in the vertical direction by a DC motor; the balance being automatically zeroed before each measurement. By raising and lowering the beaker at a known rate, receding and advancing contact angles were measured (21, 22). X-Ray Photoelectron Spectroscopy (XPS) XPS was carried out on a Perkin Elmer PHI 5400 apparatus, using an Mg K source. A 1-mm-diameter molybdenum mask was used to maintain the orientation and position of the E-glass bers and thus prevent shadowing. All the silanes were examined at pH 4 and pH 7 and at concentrations 0.005 and 0.15%. Siloxane AR433 solutions were also investigated at pH 10.5.

RESULTS

Titration of the silanes against HNO3 produced stoichiometric balance points, which were assigned to the functional groups on the silanes and the siloxane (Table 4). Silane A1160 The stoichiometric balance point was assigned as the terminal ureido group (Table 4). Measured IEPs (isoelectric point) did not match the stoichiometric balance point measured by titration, indicating that there were no ureidic functional groups at the surface (Table 5 and Fig. 2). The two lowest concentrations of the ureido silane (A1160) reduced the contact angle to below that of the untreated E-glass bers; i.e., the surface became more hydrophilic due to silane silanols at the surface. At higher deposition solution concentrations, the contact angle increased as a condensed SiOSi surface formed. Contact angle was also independent of deposition solution pH (Table 6). At the base plateau (pH 9.7 of the zeta potential curves) a correlation with contact angle was noted, which indicated that while hydrophobicity was augmented the surface charge remained relatively constant as pH rose (Fig. 3a). As deposition solution pH increased from 4 to 6, the zeta potential, at electrolyte pH 5.8, correlated with contact angle gave similar results. The pH 7 deposition solution demonstrated that an increase in zeta potential and contact angle occurred as the silane solution became more concentrated (Fig. 3b). This was due to enhanced condensation of SiO at pH 7. At high silane concentrations, there was sufcient nitrogen to be able to resolve the ESCA spectra into the peaks due to the different nitrogen binding energies (Table 7). At pH 4 and pH 7 free nitrogen accounted for less than 10% of the total nitrogen, the free nitrogen being assigned as the secondary amine. At pH 7 the ratio of hydrogen bonded to protonated nitrogen was almost 11:1. At pH 4 the ratio of hydrogen bonded to protonated nitrogen had decreased to 1:1. DRIFT versus iep and contact angle results conrmed that increased deposition solution concentration produced increased deposition without appreciably changing the surface charge of the treated bers (Figs. 4a and 4b). The contact angle, however, increased markedly. Minor changes in surface charge were noted at deposition solution pH 4 and low concentration, the point at

TABLE 4 Stoichiometric Balance Points of Silanes A1160 and A1126 and Siloxane AR433, Titrated against Nitric Acid
Stoichiometric balance point 1 Silane A1160 Silane A1126 AR433 6.2 (ureido group) 8.1 (diamine group) 8.0 (amine group) Stoichiometric balance point 2

4.9 (silane triols) 6.2 (benzene ring)

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TABLE 5 IEP Values for Silanes A1160 and A1126 and Siloxane AR433
pH 4 IEP A1160 A1126 AR433 0.005 4.7 5.2 5.4 0.01 4.4 5.0 5.2 0.1 4.6 7.8 5.9 0.15 4.5 8.9 5.7 0.005 4.7 5.9 5.5 pH 5 0.01 5.0 6.3 6.0 0.1 4.6 7.2 6.5 0.15 5 8.8 6.3 0.005 4.4 6.3 5.4 pH 6 0.01 4.1 6.8 6.0 0.1 4.4 8.9 6.9 0.15 4.4 8.8 6.6 0.005 4.4 6 5.6 pH 7 0.01 4.2 6.8 6.0 0.1 4.4 8.8 7.3 0.15 4.7 9.2 7.0 0.005 pH 10 0.01 0.1 0.15

4.5

4.5

8.3

9.3

TABLE 6 Advancing Contact Angles for Silanes A1160 and A1126 and Siloxane AR433
Silane A1160 pH 4 5 6 7 10.5 0.005 35 37 43 38 0.01 40 42 47 41 0.1 46 61 57 54 0.15 52 61 57 53 0.0025 58 50 59 41 Silane A1126 0.01 62 54 58 47 0.1 63 59 64 64 0.15 63 60 65 63 0.005 78 78 79 78 49 Polysiloxane AR433 0.01 78 90 85 84 60 0.1 88 94 93 94 104 0.15 94 97 101 101 107

FIG. 2. Zeta potential traces for silane A1160-treated E-glass bers at four concentrations: 0.005, 0.01, 0.1 and 0.15 wt%; (a) deposition pH 4; (b) deposition pH 5; (c) deposition pH 6, and (d) deposition pH 7.

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FIG. 3. (a) Advancing contact angle ( ) versus zeta potential at the electrolyte base plateau (electrolyte pH 9.7) for silane A1160. (b) Advancing contact angle ( ) versus zeta potential at electrolyte pH 5.8. The solid line indicates increasing contact angle and constant zeta potential with increasing concentration between deposition solution pH 4 and pH 6. The dotted line indicates the increase in both zeta potential and contact angle at deposition pH 7. For silane A1160.

FIG. 4. (a) Correlation of IEP and quantity of silane A1160 deposited as measured by DRIFT. (b) Correlation of contact angle ( ) and quantity of silane A1160 deposited as measured by DRIFT.

which condensation would be expected to be at a minimum (10, 11). Silane A1126 Zeta Potential results indicated that as the silane concentration was increased, the outer layer consisted mainly of amino functionality from the deposited silane. The amino functionality adsorbed H+ from the solution, producing NH+ 3 . The surface
TABLE 7 Ratios of Hydrogen-Bonded, Protonated, and Free Nitrogen for Silane A1160 (Measured by XPS)
A1160 0.15% 0.15% pH 4 7 Free N% 6.4 9.2 Hydrogenbonded N% 47.2 83.2 Protonated N% 46.2 7.6

was basic, with highly negative zeta potentials and IEPs between 8 and 9 (Figs. 5a5d). Titration of silane A1126 gave two balance points, the basic amine at pH 8.1 and a second, more acidic, point, possibly that of the silanol triols, at pH 4.9. At low silane concentrations metal oxides inherent to glass (SiO , Al2 O 3 , CaO ) were present in large concentrations. Dissociation of the metal oxides, produced an acidic surface and hence a negative zeta potential, with an IEP of between 5 and 6 (Figs. 5a5d). The IEP moved toward more basic values as the surface concentration of amino groups increased. As a surface modier A1126 was more efcient than A1160. The maximum changes in contact angle were achieved with the two lowest concentration solutions, both producing a hydrophobic surface, due to the amino groups being located on the outer surface. Increase in contact angle was linear between pH 4 and pH 6. Low silane concentration at deposition solution pH 7 did not increase the hydrophobic nature of the surface. This may have been due to a mixed amino, silanol, and silicate surface and the deposition of oligomers (Table 6). At electrolyte pH 9.7

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FIG. 5. Zeta potential traces for silane A1126-treated E-glass bers at four concentrations: 0.005, 0.01, 0.1, and 0.15wt%; (a) deposition pH 4; (b) deposition pH 5; (c) deposition pH 6; and (d) deposition pH 7.

the zeta potential results demonstrated only slight increases with increasing contact angle. The IEP was dependent upon both the deposition solution concentration and the pH. Sufcient silane A1126 was deposited on the surface to allow the nitrogen peaks at high and low concentration to be resolved (ESCA). Two peaks were detected, hydrogen bonded, and protonated nitrogen at 399.8 and 401.7 eV, respectively; no free nitrogen was detected. Four times the amount of protonated nitrogen was present in the low concentration samples, independent of pH. At high concentration the ratio of protonated nitrogen to hydrogen bonded nitrogen was 2:1 (Table 8). Silane A1126 appeared to show a negative correlation, between DRIFT and contact angle. An increased contact anTABLE 8 Ratios of Hydrogen-Bonded and Protonated Nitrogen for Silane A1126 (Measured by XPS)
A1126 % 0.005 0.005 0.15 0.15 pH 4 7 4 7 Hydrogen-bonded N% 16.7 16.9 30.4 33.3 Protonated N% 83.3 83.1 696 66.7

gle with a decreased intensity of the normalized CH2 peak at 2925 cm1 , was noted (Fig. 6). At rst these appeared to be contradictory, if one also includes the zeta potential versus contact angle results the implication is that as deposition solution

FIG. 6. Correlation between contact angle and quantity of silane A1126 deposited as measured by DRIFT.

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concentration increased the surface became more basic. Thus as the surface packing density increased so the CH2 was shielded by the amine, resulting in a reduced CH2 signal. Siloxane AR433 At 0.005% silane concentration the zeta potential and iep remained constant as pH was increased, up to and including pH 10.5 (Figs. 7a7e). At all pHs the IEP, of the 0.005% and the 0.01% surface treated E-glass bers, was at an electrolyte pH of between 4 and 6, indicating that the dominant surface was

ionizable metal oxides, with a few sparsely deposited siloxane patches (Figs. 7a and 7b). At concentrations of 0.1 and 0.15%, the IEP became more basic, rising from an electrolyte pH of 7 to an electrolyte pH of 8.5, caused by removal of acid sites by adsorption onto silanols and by the basic nature of the functional groups of the siloxane. Titration of the siloxane gave two poorly dened stoichiometric points at pH 8.0 and pH 6.2. The basic stoichiometric point was assigned to the amino function and the mildly acidic one to the aromatic functional groups.

FIG. 7. Zeta potential traces for siloxane AR 433-treated E-glass bers at four concentrations: 0.005, 0.01, 0.1, and 0.15 wt%; (a) deposition pH 4; (b) deposition pH 5; (c) deposition pH 6; and (d) deposition pH 7; (e) deposition pH 10.5.

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Low concentrations of this material had the greatest effect, increasing the contact angle some 30 more than did the two silane monomers. As a consequence the contact angle was almost twice that of the untreated E-glass bers. The increase in contact angle was linear with solution concentration between pH 4 and pH 7, but independent of pH. The surface was very hydrophobic, or conversely, oleophilic. TGA analysis of bers treated with a 0.15% deposition solution at pH 4 and at pH 10.5, indicated that at pH 10.5, 10 times more silane was deposited than at pH 4 (results not shown). Between deposition solution pH 4 and pH 7, again different surfaces were demonstrated, which were in the main due to concentration effects. A more negative zeta potential and increased contact angle were the result of larger amounts of silane being deposited from the higher concentration solutions, while pH had a minimal effect (Figs. 8a and 8b).

FIG. 9. (a) Correlation of contact angle ( ) with quantity of siloxane AR 433 deposited, as measured by DRIFT. (b) Correlation of IEP with quantity of siloxane AR 433 deposited, as measured by DRIFT.

The plot of the normalized CH2 peak at 2925 cm1 versus IEP indicated a gradual rise in IEP with surface coverage as monitored by CH2 intensity. A large jump between the 0.01 and 0.1% silane solution treated bers at pH 10.5, further demonstrating the large quantities deposited at this pH from the more concentrated deposition solutions (Fig. 9). Aluminum and calcium were not detected in the 0.15% siloxane AR433 sample, which was deposited from a solution at pH 10.5.
DISCUSSION

Silane A1160 By nature A1160 was a cationic silane; however, it appeared to behave as a nonionic silane. The results noted were consistent with a SiOSi surface. Even at pH 67 (the natural pH of the silane), where one would expect to see deposition of silanol monomers and hence a silanol or ureido surface, there was little difference in the zeta potentials. This implied that, at all deposition pHs the ureido silane deposited onto E-glass ber as

FIG. 8. Effect of increasing deposition solution pH and concentration on the relationship between contact angle ( ) and zeta potential at the base plateau pH 10.1 (a) and at the acid plateau pH 3.5 (b) for siloxane AR433.

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aggregates with a SiOSi outer shell. The results presented by Premachandra et al. indicated that condensates were unlikely to have formed at pH 4 in a ureido silane deposition solution and thus any condensation must have occurred with and at the E-glass surface. ESCA results indicated that as deposition solution pH was reduced to pH 4, the hydrogen bonds could not be maintained (Table 8). Decreasing the deposition pH below pH 4 may interfere with any hydrogen-bonded structure formed; allowing the silane to deposit with the ureido function outermost. The amount of protonated nitrogen could be expected to increase further in this scenario. Under these conditions the opportunity for formation of a ureido surface would be maximized. At lower pH the micelle like structures may be destroyed allowing the formation of a ureido surface. It should also be noted, however, that extremely low pH solutions have a deleterious effect on the physical nature of E-glass bers (18, 23). The zeta potentials of the silane A1160-treated E-glass bers, were independent of treatment solution pH and concentration (Fig. 2). Although silane A1160 is a cationic silane, on E-glass bers it behaved as a nonionic silane (zeta potential). When deposited onto metal surfaces from aqueous solutions, the ureido silane had the ability to behave as a cationic silane as demonstrated by van Ooij and by Puomi (24, 25). The conclusion was that the combination of E-glass ber and this silane induces the outer layers to deposit upside down, with a highly crosslinked SiOSi outer surface. Aluminium from the E-glass ber surface was detected (XPS) in the upper layers of this silane deposited from more concentrated organic solutions. We propose that the aluminum induced the formation of very stable hydrogen bonded micelle-like complexes with the ureido silane, which did not break down over the pH range of the deposition solutions, leading to a bilayer structure, with a siloxane outer surface and the aluminum condensed into the siloxane network (26, 27). Silane A1126 The surface basicity increased with deposition solution concentration and with pH, this was conrmed by DRIFT (Fig. 6), the amount of protonated nitrogen (ESCA, Table 8) and contact angle results (Fig. 3b and Table 5). The increase in basicity suggested that, at lower deposition pHs, some silane may have deposited with the silanols outermost. Additionally neutral (pH 7) deposition conditions were more favorable for this basic silane; at neutral deposition pHs the conditions were favourable for silane condensation (10) At neutral deposition pH the surface basicity approached the stoichiometric balance point of the amine, indicating a totally amine surface. This was conrmed by a plot of the contact angle versus zeta potential at pH 5.8, indicating that the surface charge was entirely due to the diamino functionality (Fig. 10a). Above 0.1% solution concentration and pH 6, the surface did not become any more basic with enhanced deposition (Fig. 10b). This may have been a result of increased condensation in solution, of the more concentrated systems as the pH increased to 7, as

indicated by Osterholtz and Pohl (10). Enhanced basicity was produced by a higher density of amino groups, as the deposition solution concentration and pH increased a more hydrophobic surface was produced. At the acid plateau (zeta potential) the effect of the acidic surface silanols and aluminum from the silicate could be seen at the lower deposition concentrations (0.005 and 0.01%) (Fig. 10c). At higher deposition solution concentrations the surface was due to NH+ 3 , resulting in a much higher zeta potential (Fig. 10c). Condensation of the silanols in solution at pH 7 formed oligomers, which then deposited right way up, resulting in an amino surface. The zeta potential and DRIFT effects can be explained using a combination of Ishidas and our own results. Ishida indicated that as silane concentration and hence packing of the silane patches increased, the deposited silane molecules were forced to change from the prone position to an upright position. The reduction in the intensity of the CH2 peak can be explained by increased shielding of the hydrocarbon chains by the amine functionality as the packing density increased. Siloxane AR433 The amino functionality resulted in an enhanced negative charge at high electrolyte solution pHs, especially when deposited from highly basic solutions (Fig. 7e). At low concentrations and pH 10.5 the contact angle was reduced almost to that of untreated E-glass bers. Surface silanol groups, which were produced by hydrolysis of the (SiO)mCH3 and (SiO)nCH3 groups, may have caused this effect. At high concentrations the contact angle was higher than all the other surface treatments, possibly because of complete coverage of the silane patches on the E-glass surface by the siloxane polymer, resulting in an extremely hydrophobic surface. We propose that the siloxane initially deposited in patches, which grew vertically, and that when large amounts of silane was deposited the upper layers of these patches were joined. Resulting in E-glass bers with an outer skin of siloxane, below which was an open porous structure. Siloxane AR433 was already hydrolyzed and condensed thus deposition pH had no effect upon the state of hydrolysis and condensation of the deposited material, but was able to affect the dynamic SiOSi 2SiOH. Different surfaces were implicit in the plots of zeta potential versus contact angle, at both the acid and the base plateau (Fig. 8a). The surfaces appeared to be dependent upon both deposition solution concentration and pH. At low deposition solution concentration, 0.005 and 0.01%, and pH 10.5 very small amounts of the siloxane were deposited, as demonstrated by a low contact angle and zeta potential close to that of untreated bers. Here the surface was due to SiOSi from the E-glass and from the polysiloxane (Fig. 8b). At electrolyte pH 3.5 a pH-dependant correlation between increasing zeta potential and contact angle was observed. For the deposition solution at pH 10.5 as the concentration was increased, very large amounts of silane were deposited, demonstrated by high contact angle and zeta potential (Figs. 8a and 8b).

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FIG. 10. (a) Effect of increasing deposition solution pH and concentration on the relationship between contact angle ( ) and zeta potential at the IEP for silane A1126. The area between the lines represents deposition of monomer and the hatched area deposition of oligomers. (b) Effect of increasing deposition solution pH and concentration on the relationship between contact angle ( ) and zeta potential at electrolyte pH 5.8 for silane A1126. The solid line represents deposition of monomer and the dotted line deposition of oligomers. (c) Effect of increasing deposition solution pH and concentration on the relationship between contact angle ( ) and zeta potential at the acid plateau (pH 3.5). The solid line representing a surface of silicate and mixed orientation deposition and the hatched area an amino surface consisting of oligomers and polymer for silane A1126.

We have seen little evidence in previous work of our own, or of others, which conrms complete surface coverage. We propose; therefore that the silane was chemisorbed in a patchy fashion as is generally accepted. Aluminum and calcium have been detected in the upper layers of all the condensed silanes, irrespective of the amount of silane deposited, which has been interpreted as evidence of their inclusion in the siloxane network. Aluminum was not detected in the upper layers of the sample of 0.15% AR433 deposited at pH 10.5%; being previously condensed it would be unlikely to have aluminum and calcium in the upper layers. The relationship between the deposition solution concentration and pH was clearer at pH 10.5, where an increase in the degree of hydrophobicity and amount deposited could be seen. At acid and neutral deposition solution pHs a gradual pHindependent increase with concentration was noted (Figs. 9a and 9b).

CONCLUSIONS

The zeta potential of A1160 was independent of pH over the range measured. This was as a result of the highly crosslinked SiOSi outer layer, at higher concentrations resulting in a hydrophobic surface. At low concentrations hydrophilic silanols were dominant. Unlike nonionic and cationic silane-treated Eglass bers there was little or no surface dissociation. The increase in hydrophobicity was solely due to increased coverage of the E-glass surface and not to solution pH, unlike the results presented by Nishyama et al. (79). According to Park and Subramanian a highly crosslinked silane layer would result in a reduction of the physical properties of a composite, due to reduced interpenetration of the siloxane and the matrix polymer, ensuing in a weak interphase (6). Correlation of the zeta potential, contact angle, and DRIFT results for concentrated solutions of silane A1126 (0.1 and 0.15%),

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WATSON ET AL. 3. Pluedemann, E., Silane Coupling Agents, 2nd ed. chap. 4. Plenum Press, New York, 1991. 4. Daniels, M. W., and Francis, L. F., J. Colloid Int. Sci. 205, 191 (1998). 5. Tesoro, G., and Wu, Y., J. Adhes. Sci. Technol. 5(10), 791 (1991). 6. Park, J. M., and Subramanian, R. V., J. Adhes. Sci. Technol. 5(6), 459 (1991). 7. Nishiyama, N., Asakura, T., and Horie, K., J. Colloid Int. Sci. 124(1), 14(1988). 8. Nishyama, N., Schick, R., and Ishida, H., J. Colloid Int. Sci. 143, 146 (1991). 9. Nishyama, N., Horrie, K., and Asakura, T., J. Colloid Int. Sci. 129, 113 (1989). 10. Osterholz, F. D., and Pohl, E. R., J. Adhesion Sci. Technol. 6, 127 (1992). 11. Premachandra, J. K., van Ooij, W. J., and Mark, J. E., J. Adhesion Sci. Technol. 12(12), 1361 (1998). 12. Leyden, D. E., and Atwater, J. B., J. Adhesion Sci. Technol. 5(10), 815 (1991). 13. Plueddemann, E. P., J. Paint Technol. 40, 1 (1986). 14. Pape, P. J., and Plueddemann, E. P., J. Adhesion Sci. Technol. 10, 5 (1991). 15. Watson, H., Norstr om, A., Root, A., Matisons, J., and Rosenholm, J., J. Adh. Sci. Technol., in press. 16. Arkles, B., Silanes, Silicones and Metal Organics. Gelest 2000 product information. 17. Silquest Silanes, Products and Applications Witco (1997). 18. Watson, H., Norstr om, A., Engstr om, B., and Rosenholm, J., Colloids and Surfaces A, in press. 19. Jacobasch, H. J., Baub ock, G., and Shurtz, J., Colloid Polym. Sci. 263, 3 (1985). 20. EKS 100. Control and evaluation software for EKA Instruction Handbook, Software version 4.25 Document A481B05-A Anton Paar GmbH Graz, Austria, 1997. 21. Sauer, B. B., and Carney, T. E., Langmuir 6, 1002 (1990). 22. Bascom, W. D., in Modern Approaches to Wettability: Theory and Applications (Schrader, M. E., and Loeb, G. I., eds.), P. 329. Plenum Press, New York, 1992. 23. Elmer, T. H., J. Am. Ceram. Soc. 67, 778 (1984). 24. Yuan, W. E., and van Ooij, W. J., J. Colloid Interface Sci. 185, 197 (1997). 25. Puomi, P., and Fagerholm, H., J. Adhes. Sci. Technol., in press. 26. Watson, H., Kaunisto, M., Gustafsson, J., and Paivarinta, J., J. Colloid Interface Sci., in press. 27. Wang, D., and Jones, F. R., Surf. Interface Anal. 20, 457 (1993).

indicated that the diamino silane was deposited right way up and moreover that the outer surface or skin of the samples was dependant upon both deposition solution pH and concentration. At low concentrations (0.005 and 0.01%), isolated patches of silane increased the hydrophobicity of the surface. A negative correlation between surface coverage, as measured by the intensity of the CH2 peak (DRIFT), was noted. The correlation was thought to be due to shielding of the terminal amino groups, giving the appearance of reduced deposition. Silane AR433 likewise demonstrated three concentrationdependant surfaces, one due mainly to silanols from the E-glass, with a low concentration of deposited siloxane. A second surface indicated a surface consisting of siloxane functional groups on the polymer. The third surface was apparent only at very high deposition pH (10.5), which was due to an outer skin of siloxane. We propose that at a deposition solution concentration of 0.15% and pH 10.5 the siloxane initially deposited in patches and that further siloxane deposition was as an overlay which joined the patches, giving the appearance of fully coated E-glass bers. The structure below the outer surface or skin was open and porous.
ACKNOWLEDGMENTS
The authors thank TEKES and the Graduate School of Materials Rea search (GSMR) for nancial support for J. Rosenholm, A . Torkulla, and H. Watson and Raisio Chemicals Ltd for A. Norstr om. Additionally we thank Dr. H. M. Fagerholm for XPS measurements and useful discussions.

REFERENCES
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