Journal of Colloid and Interface Science 238, 136–146 (2001) doi:10.1006/jcis.2001.

7506, available online at http://www.idealibrary.com on

Aqueous Amino Silane Modification 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, γ -aminopropyltrimethoxy silane, and methacrylate silane on E-glass surfaces. As alternatives to the most commonly used silanes, we investigated two novel silanes: γ -ureidopropyltriethoxy silane and Nβ (aminoethyl) γ aminotrimethoxy silane and additionally an amino-functional polysiloxane. The ureido silane-treated E-glass fibers demonstrated a zeta potential similar to that of the untreated E-glass fibers, 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 Si–O–Si bonds at the surface. The diamino silane demonstrated an extremely basic surface at the higher silane concentrations investigated. These outer surface layers were modified by changing the pH and the concentration of the deposition solution. The polysiloxane produced an increase in the hydrophobicity of the E-glass fiber, 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 fibers. 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 filler (colloidal, particulate, or fibrous) with a coupling agent improves the physical and chemical properties of a polymer matrix filled with such materials (1–4). 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/fiber 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 (7–9). 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 γ -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 fibers accelerated the condensation of the surface silanols with the silane silanols, enhancing the chemisorption. Washing the E-glass fibers 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 Si–O–Si linkages (15). The remainder of the silane was present as a highly crosslinked mass attached to these few surface bonded silanes, resulting in firmly 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 Si–O–Si 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 fiber 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.fi.

Chopped industrial grade E-glass fibers and an emulsion, siloxane AR433, were kindly supplied by Ahlstr¨ om Glassfibre
136

0021-9797/01 $35.00
Copyright C 2001 by Academic Press All rights of reproduction in any form reserved.

and 0.15 0.5 with 1 M ammonium hydroxide. and the pH and p K a values were determined in aqueous solutions.0019 0. (b) silane A1126.1 9.2 M · cm at 25◦ C (pH 5. The E-glass fiber samples were water cooled.0025 0. Aqueous solutions (400 ml) of each silane were made at pH 4. Glacial acetic acid (99–100% “Baker Analysed” ACS reagent) and ammonium hydroxide (“Baker Analysed” [AR] 25% NH4 OH) were obtained from J.01 0.4 0. Finland. Karhula.0 × 10−6 m and length between 0. The amount of silane in each of the solutions was actually much lower than the concentrations noted above.4 5. 1.037 0.005 0. Distilled water was passed thorough a Millipore Milli Q academic 10 deioniser to produce deionized water of 18. .005 0.0 × 10−3 m (Table 1). Concentrations of 0.002 0.1 0. 0.005 0. 1).89 × 10−4 1. pH 5. immediately after the E-glass fibers were drawn from the spinning bush.1 0.01 0.075 0. The E-glass fibers were of diameter 11.10.9 × 10−5 1.4 9.15% solution pKa 8.055 0.6 A1126 10. and an undisclosed amount of ethanol and methanol.005. respectively. E-glass fibers (30 g) were added to each solution and stirred for 20 min.78 × 10−4 1.01.5 <1.005.5 0. and 0. 1).64 × 10−5 1.8).15 Actual silane content (wt%) 0.01 0. and (c) siloxane AR 433. to condense the silane with the glass surface. 0. T. 0.004 0. The E-glass fibers 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. Schematic structures for (a) silane A1160. pH 6. All the silane products were used without further treatment.01.84 × 10−3 8.8 × 10−3 and 1.5 21. Baker. while the siloxane AR433 had a solids content of 37%. The cationic aminosilanes used were. To enable a reasonable comparison to be made among the three materials they will be referred to as 0.89 × 10−3 2. γ -ureidopropyltriethoxy silane (A1160) and Nβ -(aminoethyl)γ -aminopropyltrimethoxy silane (A1126) (Fig.0037 0.5 Elements as determined by XPS O1s C1s Si2p Ca2p B1s Al2p % 52. and pH 7 using acetic acid to adjust the pH and additionally AR433 solutions were altered to pH 10.15 wt% of silane solutions (Table 3).04 0.1 0. The silanes were added to water.059 Molar silane content 9.4 3.15 0.6 8.78 × 10−3 2. The solution was decanted and the E-glass fibers oven dried at 120◦ C for 10 min.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. the E-glass fibers were sonicated in deionized water for 10 min and then vacuum dried at 50◦ C and 200 Torr for 24 h.15 wt% were used for each material.0 7.005 0.AQUEOUS AMINO SILANE MODIFICATION OF E-GLASS SURFACES 137 TABLE 1 Composition of E-glass Fibers Used E-Glass. The manufacturers did not reveal the chemical structure of siloxane Flexichem AR433 (Fig. which was a milky emulsion with a siloxane content of approximately 37%. the solutions were used immediately after pH adjustment (Table 2).0 Oy.4 AR433 9. oxide constituents SiO2 Al2 O3 + Fe2 O3 CaO MgO Na2 O + K2 O B2 O3 wt% 55 14. 0.10.5 21 17. Aspokem Oy (Finland) kindly donated the Witco silanes.05 0. Silanes A1160 and A1126 were supplied as 50 and 40% solutions in methanol. Methods Before treatment.67 × 10−3 Proprietary formulae A 1126 AR 433 FIG.

i. At pH 4 and pH 7 free nitrogen accounted for less than 10% of the total nitrogen.15%.005 and 0. The two lowest concentrations of the ureido silane (A1160) reduced the contact angle to below that of the untreated E-glass fibers.25 M KOH and lower pH values by the addition of 0. By raising and lowering the beaker at a known rate. The beaker was moved in the vertical direction by a DC motor. vertically.5 of a pH unit.97 and pH 9. with an automated pH titration apparatus. Contact angle was also independent of deposition solution pH (Table 6). any differences could result in poor reproducibility.. A 1-mm-diameter molybdenum mask was used to maintain the orientation and position of the E-glass fibers and thus prevent shadowing. Thus over the pH range examined it is reasonable to suggest that during the 20-min period. the zeta potential. indicating that there were no ureidic functional groups at the surface (Table 5 and Fig. which has been described elsewhere (19.0 E + 03 M KCl. 4a and 4b). which indicated that while hydrophobicity was augmented the surface charge remained relatively constant as pH rose (Fig. A single fiber was attached. DRIFT versus iep and contact angle results confirmed that increased deposition solution concentration produced increased deposition without appreciably changing the surface charge of the treated fibers (Figs. to ensure reproducibility. 22). at a conductivity of 2. The pH 7 deposition solution demonstrated that an increase in zeta potential and contact angle occurred as the silane solution became more concentrated (Fig. the contact angle increased as a condensed Si–O–Si surface formed.25 M HCl. 20). 3a).87 (11). Two grams of carefully packed E-glass fiber sample was used for each measurement. Starting with the original solution the pH of the electrolyte solution was adjusted. Streaming Potential (Zeta Potential ζ ) Streaming potential was expedited using an Anton Parr Electrokinetic Analyser (EKA). to a wire hook. RESULTS Titration of the silanes against HNO3 produced stoichiometric balance points. deionized water for 3 min to remove loosely bound silane (18).9 (silane triols) 6. 3b).25 mN and a resolution of 0. After careful filtration the E-glass fibers were dried at 60◦ C for 24 h in a vacuum oven at 200 Torr. The wetting liquid used was deionized water (pH 5. Contact Angle A KSV Instruments Sigma 70 Wilhelmy balance was used to measure the advancing and receding contact angles. prior to deposition onto the E-glass fibers.2 (benzene ring) . At lower pHs a preponderance of silanol groups existed which condensed at a much lower rate.8). The electrolyte solution used was 1. At pH 4 the ratio of hydrogen bonded to protonated nitrogen had decreased to 1:1.1 (diamine group) 8.0 (amine group) Stoichiometric balance point 2 4. the point at TABLE 4 Stoichiometric Balance Points of Silanes A1160 and A1126 and Siloxane AR433. Minor changes in surface charge were noted at deposition solution pH 4 and low concentration. 20).2 (ureido group) 8. Between these extremes a minimum rate of hydrolysis occurred at pH 7. Mathematical treatment of the data used the FairbrotherMastin approximation (19. the balance being automatically zeroed before each measurement. The contact angle. which were assigned to the functional groups on the silanes and the siloxane (Table 4). A minimum of three measurements were carried out. All the silanes were examined at pH 4 and pH 7 and at concentrations 0. using an Mg K α source. correlated with contact angle gave similar results. Similar packing density and overall consistency were required for every test.5. The hook was suspended from an electrobalance. increased markedly. Silane A1160 The stoichiometric balance point was assigned as the terminal ureido group (Table 4).138 WATSON ET AL. the surface became more hydrophilic due to silane silanols at the surface. As deposition solution pH increased from 4 to 6. Measured IEPs (isoelectric point) did not match the stoichiometric balance point measured by titration. at electrolyte pH 5.44.05 µN. which had a range of 0. At high silane concentrations. for which the silanes were allowed to hydrolyze. At the base plateau (pH 9.7 E + 01 mS/m at 23 ± 2◦ C. little or no condensation occurred. Siloxane AR433 solutions were also investigated at pH 10. the free nitrogen being assigned as the secondary amine. This was due to enhanced condensation of SiO at pH 7.7 of the zeta potential curves) a correlation with contact angle was noted.87 and pH 9.8. Higher pH values were obtained by the addition of 0.e. They went on to qualitatively demonstrate that condensation was at a maximum between pH 8. At higher deposition solution concentrations. receding and advancing contact angles were measured (21. demonstrated that hydrolysis of γ ureidopropyltrimethoxy silane in a water/methanol medium was extremely rapid at pH 4. One step conformed to 0. The equipment was carefully washed with KCl between each test. 2). Titrated against Nitric Acid Stoichiometric balance point 1 Silane A1160 Silane A1126 AR433 6. Premachamdra et al. there was sufficient nitrogen to be able to resolve the ESCA spectra into the peaks due to the different nitrogen binding energies (Table 7). using double-sided adhesive tape. X-Ray Photoelectron Spectroscopy (XPS) XPS was carried out on a Perkin Elmer PHI 5400 apparatus. At pH 7 the ratio of hydrogen bonded to protonated nitrogen was almost 11:1.83. however.

8 7.0 6.3 TABLE 6 Advancing Contact Angles for Silanes A1160 and A1126 and Siloxane AR433 Silane A1160 pH 4 5 6 7 10.01 0.01 5.9 5.9 6. (c) deposition pH 6.2 6.0 0.01 78 90 85 84 60 0. 2.1 4.6 0.005.7 0.005 pH 10 0.1 63 59 64 64 0.15 4.15 4.9 5.3 6.4 6 5. 0.0 0.15 4.005 4.005 78 78 79 78 49 Polysiloxane AR433 0.5 4.15 63 60 65 63 0. and (d) deposition pH 7.4 6.4 pH 6 0.01 4.01 62 54 58 47 0.8 6.1 46 61 57 54 0.1 4. 0.4 5.2 5.7 9.1 88 94 93 94 104 0.005 4.01 4.6 7.01 40 42 47 41 0.0 0.005 4.4 8.4 8.0 0.1 0.0 5.1 4. (b) deposition pH 5.5 0.7 5.3 5.15 52 61 57 53 0.6 pH 7 0.AQUEOUS AMINO SILANE MODIFICATION OF E-GLASS SURFACES 139 TABLE 5 IEP Values for Silanes A1160 and A1126 and Siloxane AR433 pH 4 IEP A1160 A1126 AR433 0. (a) deposition pH 4.8 5.5 0.15 wt%. .1 and 0.01 4.7 5.8 6.5 8.4 8.3 9.5 pH 5 0.01.4 0.2 7. Zeta potential traces for silane A1160-treated E-glass fibers at four concentrations: 0.8 6.1 4.2 0.9 0.15 5 8.0025 58 50 59 41 Silane A1126 0.5 8.6 7.1 6.15 4.2 6.005 4.3 0.8 6.9 0.15 94 97 101 101 107 FIG.005 35 37 43 38 0.3 0.

2 83. with an IEP of between 5 and 6 (Figs.2 7.7 .1 and a second. The surface TABLE 7 Ratios of Hydrogen-Bonded.2 Protonated N% 46. The IEP moved toward more basic values as the surface concentration of amino groups increased. the outer layer consisted mainly of amino functionality from the deposited silane. Titration of silane A1126 gave two balance points. point. 5a–5d).15% 0.8. The solid line indicates increasing contact angle and constant zeta potential with increasing concentration between deposition solution pH 4 and pH 6. the basic amine at pH 8. at pH 4.7) for silane A1160. At electrolyte pH 9. FIG. which condensation would be expected to be at a minimum (10.6 was basic. 4.15% pH 4 7 Free N% 6. At low silane concentrations metal oxides inherent to glass − (SiO− . Al2 O− 3 . Silane A1126 Zeta Potential results indicated that as the silane concentration was increased. Dissociation of the metal oxides. 5a–5d). The amino functionality adsorbed H+ from the solution.140 WATSON ET AL. and silicate surface and the deposition of oligomers (Table 6). Protonated.2 Hydrogenbonded N% 47. produced an acidic surface and hence a negative zeta potential. FIG. The maximum changes in contact angle were achieved with the two lowest concentration solutions. more acidic. Low silane concentration at deposition solution pH 7 did not increase the hydrophobic nature of the surface.9. (b) Correlation of contact angle (◦ ) and quantity of silane A1160 deposited as measured by DRIFT.4 9. possibly that of the silanol triols. (a) Correlation of IEP and quantity of silane A1160 deposited as measured by DRIFT. For silane A1160. producing NH+ 3 . and Free Nitrogen for Silane A1160 (Measured by XPS) A1160 0. The dotted line indicates the increase in both zeta potential and contact angle at deposition pH 7. 3. with highly negative zeta potentials and IEPs between 8 and 9 (Figs. (a) Advancing contact angle (◦ ) versus zeta potential at the electrolyte base plateau (electrolyte pH 9. silanol. (b) Advancing contact angle (◦ ) versus zeta potential at electrolyte pH 5. CaO ) were present in large concentrations. 11). This may have been due to a mixed amino. As a surface modifier A1126 was more efficient than A1160. Increase in contact angle was linear between pH 4 and pH 6. both producing a hydrophobic surface. due to the amino groups being located on the outer surface.

005 0.15 0.9 30.15 pH 4 7 4 7 Hydrogen-bonded N% 16. between DRIFT and contact angle.8 and 401. Silane A1126 appeared to show a negative correlation.3 83.4 33. and protonated nitrogen at 399.7 eV. hydrogen bonded.15wt%. Zeta potential traces for silane A1126-treated E-glass fibers at four concentrations: 0. independent of pH. respectively. and 0. if one also includes the zeta potential versus contact angle results the implication is that as deposition solution FIG.7 gle with a decreased intensity of the normalized CH2 peak at 2925 cm−1 . (b) deposition pH 5.3 Protonated N% 83. Four times the amount of protonated nitrogen was present in the low concentration samples. was noted (Fig. no free nitrogen was detected. At high concentration the ratio of protonated nitrogen to hydrogen bonded nitrogen was 2:1 (Table 8).1. An increased contact anTABLE 8 Ratios of Hydrogen-Bonded and Protonated Nitrogen for Silane A1126 (Measured by XPS) A1126 % 0. Two peaks were detected. . 0. At first these appeared to be contradictory.1 696 66.005. Correlation between contact angle and quantity of silane A1126 deposited as measured by DRIFT.005 0. 6). the zeta potential results demonstrated only slight increases with increasing contact angle. (a) deposition pH 4.01. 0.AQUEOUS AMINO SILANE MODIFICATION OF E-GLASS SURFACES 141 FIG. and (d) deposition pH 7. The IEP was dependent upon both the deposition solution concentration and the pH. Sufficient silane A1126 was deposited on the surface to allow the nitrogen peaks at high and low concentration to be resolved (ESCA).7 16. (c) deposition pH 6. 6. 5.

the IEP became more basic. (e) deposition pH 10.5. 7a and 7b).5.005% and the 0. was at an electrolyte pH of between 4 and 6.5 (Figs.01. (c) deposition pH 6.005. of the 0. The basic stoichiometric point was assigned to the amino function and the mildly acidic one to the aromatic functional groups. indicating that the dominant surface was ionizable metal oxides. At concentrations of 0.1.01% surface treated E-glass fibers.005% silane concentration the zeta potential and iep remained constant as pH was increased. . 7a–7e). caused by removal of acid sites by adsorption onto silanols and by the basic nature of the functional groups of the siloxane. 7.15 wt%. and (d) deposition pH 7. resulting in a reduced CH2 signal. Titration of the siloxane gave two poorly defined stoichiometric points at pH 8.0 and pH 6. Zeta potential traces for siloxane AR 433-treated E-glass fibers at four concentrations: 0. rising from an electrolyte pH of 7 to an electrolyte pH of 8. 0. and 0.15%. with a few sparsely deposited siloxane patches (Figs. FIG. (b) deposition pH 5.1 and 0. Siloxane AR433 At 0. At all pHs the IEP. (a) deposition pH 4. up to and including pH 10.142 WATSON ET AL. concentration increased the surface became more basic. Thus as the surface packing density increased so the CH2 was shielded by the amine.2. 0.

Between deposition solution pH 4 and pH 7. or conversely. oleophilic.5. The surface was very hydrophobic. TGA analysis of fibers treated with a 0. further demonstrating the large quantities deposited at this pH from the more concentrated deposition solutions (Fig. (b) Correlation of IEP with quantity of siloxane AR 433 deposited.15% deposition solution at pH 4 and at pH 10.5. it appeared to behave as a nonionic silane.AQUEOUS AMINO SILANE MODIFICATION OF E-GLASS SURFACES 143 Low concentrations of this material had the greatest effect. indicated that at pH 10.5. This implied that. DISCUSSION Silane A1160 By nature A1160 was a cationic silane. while pH had a minimal effect (Figs. at all deposition pHs the ureido silane deposited onto E-glass fiber as FIG. 8a and 8b). The increase in contact angle was linear with solution concentration between pH 4 and pH 7. again different surfaces were demonstrated. A large jump between the 0. 8.15% siloxane AR433 sample. Even at pH 6–7 (the natural pH of the silane). there was little difference in the zeta potentials.5 (b) for siloxane AR433. A more negative zeta potential and increased contact angle were the result of larger amounts of silane being deposited from the higher concentration solutions. Aluminum and calcium were not detected in the 0. where one would expect to see deposition of silanol monomers and hence a silanol or ureido surface.5. but independent of pH. 9).01 and 0. Effect of increasing deposition solution pH and concentration on the relationship between contact angle (◦ ) and zeta potential at the base plateau pH 10. The results noted were consistent with a Si–O–Si surface. however. FIG. . The plot of the normalized CH2 peak at 2925 cm−1 versus IEP indicated a gradual rise in IEP with surface coverage as monitored by CH2 intensity.1 (a) and at the acid plateau pH 3.1% silane solution treated fibers at pH 10. as measured by DRIFT. As a consequence the contact angle was almost twice that of the untreated E-glass fibers. increasing the contact angle some 30◦ more than did the two silane monomers. which was deposited from a solution at pH 10. 9. (a) Correlation of contact angle (◦ ) with quantity of siloxane AR 433 deposited. which were in the main due to concentration effects. as measured by DRIFT. 10 times more silane was deposited than at pH 4 (results not shown).

as indicated by Osterholtz and Pohl (10). ESCA results indicated that as deposition solution pH was reduced to pH 4. At electrolyte pH 3. as the deposition solution concentration and pH increased a more hydrophobic surface was produced. the surface did not become any more basic with enhanced deposition (Fig. Different surfaces were implicit in the plots of zeta potential versus contact angle. possibly because of complete coverage of the silane patches on the E-glass surface by the siloxane polymer. 23). 0. Enhanced basicity was produced by a higher density of amino groups. that extremely low pH solutions have a deleterious effect on the physical nature of E-glass fibers (18. indicating that the surface charge was entirely due to the diamino functionality (Fig. some silane may have deposited with the silanols outermost. 8a and 8b). At low concentrations and pH 10. especially when deposited from highly basic solutions (Fig. however. Here the surface was due to Si–O–Si from the E-glass and from the polysiloxane (Fig. We propose that the siloxane initially deposited in patches. At higher deposition solution concentrations the surface was due to NH+ 3 .005 and 0.5 a pH-dependant correlation between increasing zeta potential and contact angle was observed. For the deposition solution at pH 10. Silane A1126 The surface basicity increased with deposition solution concentration and with pH.8.5 as the concentration was increased. Siloxane AR433 The amino functionality resulted in an enhanced negative charge at high electrolyte solution pHs.005 and 0. the deposited silane molecules were forced to change from the prone position to an upright position. at lower deposition pHs. Above 0. 6). Additionally neutral (pH 7) deposition conditions were more favorable for this basic silane. Under these conditions the opportunity for formation of a ureido surface would be maximized. Ishida indicated that as silane concentration and hence packing of the silane patches increased. The results presented by Premachandra et al. Siloxane AR433 was already hydrolyzed and condensed thus deposition pH had no effect upon the state of hydrolysis and condensation of the deposited material.01%) (Fig. The zeta potentials of the silane A1160-treated E-glass fibers. . leading to a bilayer structure. were independent of treatment solution pH and concentration (Fig. and pH 10. below which was an open porous structure.1% solution concentration and pH 6. Aluminium from the E-glass fiber surface was detected (XPS) in the upper layers of this silane deposited from more concentrated organic solutions. 10c).5 very small amounts of the siloxane were deposited. 8b). 3b and Table 5).144 WATSON ET AL. indicating a totally amine surface. This was confirmed by a plot of the contact angle versus zeta potential at pH 5. 7e). 27). At lower pH the “micelle like” structures may be destroyed allowing the formation of a ureido surface. the ureido silane had the ability to behave as a cationic silane as demonstrated by van Ooij and by Puomi (24. The surfaces appeared to be dependent upon both deposition solution concentration and pH. the hydrogen bonds could not be maintained (Table 8). 25). 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. this was confirmed by DRIFT (Fig. Table 8) and contact angle results (Fig. which grew vertically. which did not break down over the pH range of the deposition solutions. which were produced by hydrolysis of the (SiO)m–CH3 and (SiO)n–CH3 groups. Resulting in E-glass fibers with an outer “skin” of siloxane. We propose that the aluminum induced the formation of very stable hydrogen bonded “micelle-like” complexes with the ureido silane. but was able to affect the dynamic Si–O–Si ↔ 2Si–OH. demonstrated by high contact angle and zeta potential (Figs. 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. Condensation of the silanols in solution at pH 7 formed oligomers. aggregates with a Si–O–Si outer shell. Although silane A1160 is a cationic silane.” with a highly crosslinked Si–O–Si outer surface. at both the acid and the base plateau (Fig. which then deposited “right way up. of the more concentrated systems as the pH increased to 7. 10a). 8a). the amount of protonated nitrogen (ESCA. as demonstrated by a low contact angle and zeta potential close to that of untreated fibers. When deposited onto metal surfaces from aqueous solutions. At high concentrations the contact angle was higher than all the other surface treatments. This may have been a result of increased condensation in solution. 2).5 the contact angle was reduced almost to that of untreated E-glass fibers. Decreasing the deposition pH below pH 4 may interfere with any hydrogen-bonded structure formed. 10c). and that when large amounts of silane was deposited the upper layers of these patches were joined. 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. The increase in basicity suggested that. 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. At low deposition solution concentration. with a siloxane outer surface and the aluminum condensed into the siloxane network (26.01%. Surface silanol groups. The conclusion was that the combination of E-glass fiber and this silane induces the outer layers to deposit “upside down. may have caused this effect.” resulting in an amino surface. allowing the silane to deposit with the ureido function outermost. resulting in a much higher zeta potential (Fig. It should also be noted. on E-glass fibers it behaved as a nonionic silane (zeta potential). resulting in an extremely hydrophobic surface. 10b). very large amounts of silane were deposited. The amount of protonated nitrogen could be expected to increase further in this scenario. The zeta potential and DRIFT effects can be explained using a combination of Ishida’s and our own results.

contact angle. therefore that the silane was chemisorbed in a patchy fashion as is generally accepted. (c) Effect of increasing deposition solution pH and concentration on the relationship between contact angle (◦ ) and zeta potential at the acid plateau (pH 3. CONCLUSIONS The zeta potential of A1160 was independent of pH over the range measured. unlike the results presented by Nishyama et al.1 and 0. (7–9).15%). where an increase in the degree of hydrophobicity and amount deposited could be seen. being previously condensed it would be unlikely to have aluminum and calcium in the upper layers. . or of others. Unlike nonionic and cationic silane-treated Eglass fibers there was little or no surface dissociation.8 for silane A1126. which confirms complete surface coverage. We propose.15% AR433 deposited at pH 10.5%. ensuing in a weak interphase (6). at higher concentrations resulting in a hydrophobic surface.5. Aluminum was not detected in the upper layers of the sample of 0. This was as a result of the highly crosslinked Si–O–Si outer layer. 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. (a) Effect of increasing deposition solution pH and concentration on the relationship between contact angle (◦ ) and zeta potential at the IEP for silane A1126. 9a and 9b).5). We have seen little evidence in previous work of our own. The solid line represents deposition of monomer and the dotted line deposition of oligomers. At acid and neutral deposition solution pHs a gradual pHindependent increase with concentration was noted (Figs. The relationship between the deposition solution concentration and pH was clearer at pH 10. Aluminum and calcium have been detected in the upper layers of all the condensed silanes. 10. Correlation of the zeta potential. 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. and DRIFT results for concentrated solutions of silane A1126 (0. due to reduced interpenetration of the siloxane and the matrix polymer. The increase in hydrophobicity was solely due to increased coverage of the E-glass surface and not to solution pH. At low concentrations hydrophilic silanols were dominant. irrespective of the amount of silane deposited.AQUEOUS AMINO SILANE MODIFICATION OF E-GLASS SURFACES 145 FIG. which has been interpreted as evidence of their inclusion in the siloxane network. According to Park and Subramanian a highly crosslinked silane layer would result in a reduction of the physical properties of a composite.

J. W. 459 (1991). 9. Technol. Colloid Polym. D. H. E. Technol. Technol. W. Norstr¨ om.. E. in press. 205.146 WATSON ET AL. Dwight. M. J. D.. Kaunisto.. Park. Nishiyama. and Plueddemann.. in press. R. Sci. Rosenholm. Technol.. C. Plenum Press. REFERENCES 1. Technol. 14(1988). 113 (1989). G.. Technol.. K. R. 457 (1993)... 23. 11. J. Adhesion Sci. W. 19.. J. . V. E. Elmer. 143.. Technol. B. J. and Pohl. 197 (1997). 20. Colloids and Surfaces A.. J.. D. J. 124(1). eds. H. and Rosenholm. J. H. I. Sci..25 Document A481B05-A Anton Paar GmbH Graz.01%). 27. N. Horrie. and Ishida. 4. J. Silicones and Metal Organics”. Watson. E. F. R. with a low concentration of deposited siloxane. in press. A. J. R. Premachandra. 15. H.. A. A negative correlation between surface coverage. Sci.. Fagerholm for XPS measurements and useful discussions. Langmuir 6.. 16. Technol. The structure below the outer surface or “skin” was open and porous. 13. 815 (1991). 191 (1998). Products and Applications Witco (1997). Colloid Interface Sci.. and Francis. P. J. and Mark. F. J. Colloid Int.. Norstr¨ om.. E. 14.. M. isolated patches of silane increased the hydrophobicity of the surface. one due mainly to silanols from the E-glass. and Jones. J. H. Adhesion Sci. D. T. P.. 17. Puomi. 8.. Adh. Adhes. 4. M.. J. Gustafsson. and Subramanian.. T. Pape. Colloid Interface Sci... M. J. F. 2. Y.. J. B. G. A . J. J. E.. 5(10).005 and 0. Asakura. C. 22. and van Ooij. Osterholz. which was due to an outer “skin” of siloxane. and Brackman. J. Sci.. 20. Yuan. Adhesion Sci. Interface Anal. J. J. Kulp. F. A second surface indicated a surface consisting of siloxane functional groups on the polymer. J. Nishyama.. Austria.).. W. and Shurtz. 263. M. H. Gelest 2000 product information. and H. B. W. Daniels. Silquest Silanes. 115 (1995). Jr. Additionally we thank Dr. J. 5 (1991).. ACKNOWLEDGMENTS The authors thank TEKES and the Graduate School of Materials Rea search (GSMR) for financial support for J. M.. B.. 619 (1990). E. At low concentrations (0. 129.... 18. 146 (1991). Matisons. and Asakura. Jacobasch.. Sci. 4. Sci. and Loeb. Salvati. Soc. as measured by the intensity of the CH2 peak (DRIFT).5 the siloxane initially deposited in patches and that further siloxane deposition was as an overlay which joined the patches. E. 7.5). Sci. “Silanes.. Baub¨ ock. K. Paint Technol.. van Ooij. P. Schottens. 329. in press. Sauer. J.. giving the appearance of fully coated E-glass fibers. A. in “Modern Approaches to Wettability: Theory and Applications” (Schrader. Root. R. and Fagerholm. 5. B. Software version 4. 10.. 5(10)... J. J. 25. Ceram.... L. G. D. P. T. 2nd ed. T.. was noted. and Rosenholm.15% and pH 10. Adhesion Sci. Sabat. Tesoro.. Surf. J. 778 (1984).. 1992. J. 67. J. Adhesion Sci. Boudewijn. Schick. 21. L. J. J. giving the appearance of reduced deposition. 791 (1991). 3. 1997.. H. 1 (1986). Am. W. “Silane Coupling Agents”. Watson. D. N. R. 10. J. Colloid Int. 12(12). and Wu. 1991. 5(6). New York. Fowkes.. Plenum Press. Adhes. Cole. 1361 (1998). Adhesion Sci. J. A. and Atwater. Sci... 1002 (1990). K. chap. J. Adhes... Watson and Raisio Chemicals Ltd for A. New York.. P. Watson. Wang. 127 (1992). Nishyama.. E. and Paivarinta. Arkles.. and Horie.. J. Engstr¨ om. The third surface was apparent only at very high deposition pH (10. Pluedemann. 3 (1985). and Huang. Colloid Int. T. Technol. 6. Leyden. N. 12. Plueddemann. and Carney. J.. We propose that at a deposition solution concentration of 0. Colloid Int. M. 24. Technol. 52. Bascom. Torkulla. 6. 40. H... Silane AR433 likewise demonstrated three concentrationdependant surfaces.. Sci. P.. 185. Control and evaluation software for EKA Instruction Handbook. J. 26.. 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. EKS 100... Norstr¨ om. The correlation was thought to be due to shielding of the terminal amino groups.