International Journal of Adhesion & Adhesives 31 (2011) 97103

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International Journal of Adhesion & Adhesives

journal homepage: www.elsevier.com/locate/ijadhadh

Characterization of polyurethane adhesives containing nanosilicas of different particle size

a-Pacios b, Mohammed A. Bahattab a,n, Jessica Donate-Robles b, Vanesa Garc b Miguel Mart n-Mart nez Jose
a b

Petrochemical Research Institute, King Abdulaziz City for Science and Technology, 11442 Riyadh, Saudi Arabia Adhesion & Adhesives Laboratory, University of Alicante, 03080 Alicante, Spain

a r t i c l e in f o
Article history: Accepted 17 October 2010 Available online 4 November 2010 Keywords: Polyurethane Stainless steel Lap shear

abstract
Three nanosilicas with different particle sizes were added to a polyurethane adhesive (PU). The lled adhesives were characterized by thermal gravimetric analysis (TGA), dynamic mechanical analysis (DMA), transmission electron microscopy (TEM), differential scanning calorimetry (DSC) and contact angle measurements. Adhesive strength was evaluated from single lap shear test of solvent wiped stainless steel/polyurethane adhesive joints. Addition of nanosilica ller altered the degree of phase separation between the hard and soft segments in the polyurethane, in different extent depending on the nanosilica particle size. Furthermore, upon curing higher degree of crosslinking was obtained in the nanosilica lled polyurethane. The nanosilicas agglomerated into the polyurethane matrix. On the other hand, the addition of nanosilica increased the surface energy of the polyurethane to a greater extent by increasing the nanosilica particle size and moderate increase in the single lap shear strength of stainless steel/polyurethane adhesive joints was obtained. & 2010 Elsevier Ltd. All rights reserved.

1. Introduction Adhesive formulation properties contain several components such as tackiers [1], adhesion promoters [2] and llers [3] among other additives to produce an adequate performance in different applications. Thermoplastic polyurethanes are commonly used as adhesives and they may contain llers to impart viscosity, improve mechanical properties and modify the rheological and surface properties [4]. Thermoplastic polyurethanes are segmented polymers that exhibit a two-phase microstructure, which arises from the incompatibility between the soft and hard segments. The hard rigid segment segregates into a glassy or semi-crystalline matrices, and the polyol soft segments form amorphous or rubbery matrices in which the hard segments are dispersed [5]. Fillers are usually added to polyurethane adhesives to impart improved mechanical, thermal and adhesion properties. Polyurethanes can be tailored to meet the highly diversied demand of modern technologies such as coatings, adhesives, bers, foams and thermoplastic elastomers. Several kinds of silicas have been added to improve different properties of polyurethanes. It has been shown [6] that the density and mechanical properties of rigid

Corresponding author. Tel.: + 966 14813634; fax: + 966 14813670. E-mail address: Bahattab@kacst.edu.sa (M.A. Bahattab).

polyurethane foams lled with precipitated silica were decreased with increased ller loading due to cell damage. On the other hand, the thermal conductivity of the silica lled polyurethane foam increased with ller loading. TiO2SiO2 nanoparticles of about 70 nm prepared by solgel process were incorporated as building blocks into polyurethane matrix [7]. The polyurethane/TiO2SiO2 hybrid showed higher thermal stability as compared with that of the unlled PU due to interactions between the polymer chains and the inorganic particles. On the other hand, polyurethane urea/silica-sol-modied nano-calcium carbonate hybrids exhibited excellent thermal stability, freezing resistance and mechanical stability [8]. Furthermore, the tensile strength and hardness increased with increase in the ller content. On the other hand, Tan et al. [9] prepared nanosilica particles by hydrolysis of tetraethoxyorthosilicate in the presence of methacryloxypropyltrimethoxy silane. The nanosilicas were dispersed evenly in PU matrix and imparted improved UVvis transmittance. It has been shown [10] that the incorporation of nanosilica particles to conductive polyurethane/polyaniline material increased its thermal stability, Tg and extensibility due to a higher degree of phase separation. Also, antimicrobial properties can be imparted to polyurethane by adding silica gel particles with amine covalently bonded moieties [11]. Furthermore, Vuillequez et al. [12] prepared by UV-light and thermal cure an interpenetrating

0143-7496/$ - see front matter & 2010 Elsevier Ltd. All rights reserved. doi:10.1016/j.ijadhadh.2010.11.001

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polymer network composed of polyurethane methacrylate and silica. The Tg decreased as the silica concentration increased, which was in accordance with the trend in surface hardness. Jang et al. [13] prepared shape-memory polyurethane-silica nanocomposites using fumed silica and hydrolyzed 3-aminopropyltriethoxysilane. Although aggregation of fumed silica particles in the polyurethane matrix was found, the modulus and tensile strength increased. On the other hand, a relatively narrow glass transition region and a large difference between the modulus at the glassy and rubbery plateau regions were obtained. In a different study, fumed silica (812 nm) was added to polyurethane in the presence of 3-amino-propyltriethoxysilane coupling agent [14]. A high connectivity between fumed silica and polyurethane was found and improved thermal, mechanical and dynamic mechanical properties were obtained. Finally, in a different study, nanosilicas of different particle size (150200 nm) modied by a cyclic carbonate functional organoalkoxysilane were used to prepare polyurethane-silica nanocomposite [15]. Addition of the nanosilicas increased the thermal decomposition as well as the abrasion resistance of the polyurethane. To our knowledge no papers dealing with precipitated nanosilica lled polyurethane adhesives have been published and also a complete study considering the structureproperties relationship has not been performed. Therefore, in this study, three nanosilicas of different particle sizes (20, 50 and 100 nm) were added to polyurethane adhesive formulations and the inuence of the nanosilica particle size on the structureproperties relationship of the lled polyurethane adhesives was studied.

2.2. Experimental techniques Particle size distribution: The particle size distribution of the nanosilicas was obtained in a nanoparticle size analyzer Nano-ZS (Malvern Instruments Ltd., Malvern, U.K.). The nanosilica was dispersed in ethylene glycol and the measurement was obtained at room temperature. A square glass round bottom cell was used for measurement. Transmission electron microscopy (TEM): The topography and particle size of the nanosilicas after ethylene glycol evaporation and the degree of dispersion of the nanosilicas in the polyurethane matrix were monitored by transmission electron microscopy (JEOL JEM-2010, Tokyo, Japan); an acceleration voltage of 100 kV was used. The lled polyurethane lms composites were cryogenically microtomed and placed on a copper grid for analysis. Thermal gravimetric analysis (TGA): TGA studies were carried out in a TA TGA Q500 instrument (TA Instruments, Newcastle, DE, USA), under nitrogen at a ow rate of 100 ml/min. Samples (1015 mg) were heated from 25 1C up to 600 1C using a heating rate of 101 C/min. Differential scanning calorimetry (DSC): DSC experiments were carried out in a TA DSC Q100 V6.2 instrument (TA Instruments, Newcastle, DE, USA). Aluminium pans containing 1015 mg sample were heated from 70 1C to 300400 1C under nitrogen atmosphere (gas ow: 50 ml/min). The heating rate was 5 1C/min. The rst heating run was carried out to remove the thermal history of the samples. From the second heating run the glass transition temperature (Tg), the crystallization temperature (Tc), and the melting temperature (Tm) of the polyurethanes were obtained.

2. Experimental 2.1. Polyurethane adhesive formulations Three commercial precipitated nanosilicas (20, 50 and 100 nm, manufactured by Nyacol, Ashland, USA) were incorporated in the polyurethane adhesive formulations. 160 g of hydroxyl polyacrylate polyol (Desmophen A-365, Bayer, Leverkusen, Germany) was stirred for 5 min at 3000 rpm. 2 g of dispersing agent BYK110 (BYK additives & instruments, Wesel, Germany) was added to the polyol and stirred for 5 min, followed by adding 10 g of leveling agent (EGAethylene glycol acetate) under stirring for 5 min more. Then 10 g of colloidal nanosilica solution (prepared by mixing each nanosilica with ethylene glycol) was added to the previous mixture and stirred for 15 min, followed by adding 5 g methyl ethyl ketone and 5 g xylene (Aldrich, Milwaukee, WI, USA) and additional stirring for 5 min more. 55 g of the hardener (N75, Bayer, Leverkusen, Germany) was added to the polyurethane solution by stirring for 5 min. Table 1 shows the PU formulations in wt% and Table 2 shows the nomenclature of the adhesives used in this study. The solid lled polyurethanes lms of about 1.5 mm thick were prepared by placing about 50 cm3 solutions in a glass mould (10 10 cm2) allowing curing and a slow evaporation of the remaining trapped solvent.
Table 1 Polyurethane adhesive formulations (in wt%). PU nomenclature Unlled 20 nm 50 nm 100 nm
a b c

Table 2 Nomenclature of the polyurethane adhesives. Filled polyurethane Nanosilica in the polyurethane None DP 5820 DP 5480 DP 5840

Unlled 20 nm 50 nm 100 nm

Table 3 Some characteristics of the nanosilicas. Property Nominal average primary particle size (nm) Actual particle size in ethylene glycol solution (nm) pH Medium Viscosity at 25 % C (mPa s) SiO2 content (wt%)
o

20 nm 20 8.1 3.0 Ethylene glycol 60 30

50 nm 50 10.1 3.0 Ethylene glycol 60 30

100 nm 100 25, 120 3.0 Ethylene glycol 85 30

Polyol 66.1 64.8 64.8 64.8

Disperser 1a

Disperser 2b 0.8

EGAc 4.1 4.1 4.1 4.1

Silica 20 nm

Silica 50 nm

Silica 100 nm

MEK 4.1 2.0 2.0 2.0

Xylene 2.1 2.0 2.0 2.0

Hardener 22.7 22.3 22.3 22.3

0.8 0.8 0.8

4.1 4.1 4.1

Disperser 1: BYK 110 (BYK additives & instruments, Wesel, Germany). Disperser 2: BYK 331 (BYK additives & instruments, Wesel, Germany). EGA: Ethylene glycol acetate.

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Dynamic mechanical analysis (DMA): The viscoelastic properties of the polyurethanes were measured in a TA DMA Q800 instrument (TA Instruments, Newcastle, DE, USA), using the shear sandwich mode. The experiments were carried out by heating the sample from 100 to 200 1C, using a heating rate of 51 C/min at a frequency of 1 Hz and a strain of 0.5%. Contact angle measurements: The wettability and the surface energy of the polyurethane lms surfaces were evaluated by -Hart 100 goniometer contact angle measurements using a Rame -Hart Instrument Co., Mountain Lakes, NJ, USA). The poly(Rame urethane lms were placed into the hermetic and isothermal (25 1C) chamber of the goniometer previously saturated with standard liquid. Two different standard liquids were used, bidistilled and deionized water and di-iodomethane. Drops (4 ml) of bidistilled and deionized water or di-iodomethane were placed on the polyurethane lm surface using a microsyringe provided with a at end needle, and static contact angle values were measured. The contact angle values were measured 5 min after drop deposition. Five drops placed on different places on the polyurethane lm surface were measured and averaged. The experimental error was 7 21. Adhesive joints formation: Adhesion was tested from single lap shear tests of stainless steel/lled polyurethane adhesive/stainless steel joints. Stainless steel test pieces were wiped with isopropanol. 0.20.3 g adhesive solution containing 22.7 (unlled polyurethane) or 22.3 (lled polyurethane) wt% hardener were mixed by hand for 5 min and spread evenly on 3 3 cm2 area on one of the stainless steel test pieces. The other test sample was placed on the area to be bonded and a pressure of 0.8 MPa was applied for 10 s to achieve a suitable joint. Adhesive joints were left to cure for 72 h before testing in an Instron 4505 universal testing machine (Instron Ltd., Norwood, USA) at a pulling rate of 100 mm/min. Four replicates were carried out and the results were averaged.

3. Results and discussion 3.1. Characterization of the nanosilicas Table 3 shows some properties of the nanosilicas used in this study. All nanosilicas have similar acidic nature. 30 wt% nanosilicas were dispersed in ethylene glycol to facilitate the addition into the polyurethane adhesive solutions. The actual particle size distribution of the nanosilicas in the ethylene glycol solution was measured (Fig. 1) and the values are given in Table 3. The actual particle size of the nanosilica dispersions is smaller than that in the nanosilica. All nanosilicas show monomodal particle size distribution always in the nanometer range, except nanosilica 100 nm in which a bimodal distribution of particles appears. The morphology and particle size of nanosilica agglomerates may change once the solvent (ethylene glycol) is removed. This issue is of great importance to understand the distribution of the

Fig. 2. TEM micrographs of the nanosilicas (after ethylene glycol removal).

Fig. 1. Particle size distribution of the nanosilicas in ethylene glycol solution.

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nanosilicas in the polyurethane matrix once the ller is added to the adhesive formulation. Thus, TEM was also used to determine the morphology and degree of agglomeration of the nanosilicas once the ethylene glycol is removed. Fig. 2 shows the TEM

micrographs of the nanosilicas. All nanosilica particles are spherical and very regular in size, the distribution of particles is wider in the 100 nm nanosilica. The evaporation of the solvent does not produce particle agglomeration.

Fig. 3. Derivative TGA thermograms of unlled and 20 nm nanosilica lled polyurethane.

Fig. 4. (a) TEM micrographs at low magnication of the nanosilica lled polyurethanes. (b) TEM micrographs at medium magnication of the nanosilica lled polyurethanes. (c) TEM micrographs at high magnication of the nanosilica lled polyurethanes.

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3.2. Characterization of the polyurethane-nanosilica mixtures Thermal gravimetric analysis is a useful technique to analyze the structure of the polyurethanes [16]. The TGA thermogram of the unlled polyurethane shows several decompositions (Fig. 3). Between 300 and 400 1C, the hard segments in the polyurethane decompose, giving two separate decompositions due to urethane (at lower temperature) and urea (at higher temperature). At 430 1C, the decomposition of the polyol (soft segments) is found, and about 500 1C the decomposition of the polymer is produced. Addition of nanosilica ller does not produce new thermal decompositions but the different decomposition steps are produced at different temperature and/or weight loss. The polyurethane lled with 20 nm nanosilica shows the decomposition of the hard segment at lower temperature and with higher weight loss than in the unlled polyurethane, indicating that nanosilica disrupts the interactions between the polymer chains affecting the extent of phase separation. The dispersion a degree of aggregation of the nanosilicas in the lled polyurethanes was analyzed by TEM. Addition of nanosilica changes the topography of the polyurethane matrix (Fig. 4a) creating bubbles and nanocracks on the surface. The higher the nanosilica particle size, the lower the bubble size and the higher the number of cracks. The bubbles can be created by segregation of the nanosilica and the cracks can be ascribed to stress concentrations in the vicinity of the nanosilica agglomerates. Fig. 4(b) shows that all nanosilicas tend to agglomeration the polyurethane matrix and the number of isolated nanosilica particles is quite reduced. The size of the nanosilica agglomerates is in the microns range (except in the 20 nm nanosilica lled polyurethane), the polydispersity of the agglomerates is more marked by increase in the nanosilica particle size. Fig. 4(c) shows the degree of agglomeration of the nanosilicas in more detail. The nanosilica particles do not interact

but they are compacted maintaining the individual entity of the particles. This is likely ascribed to the absence of adequate surface polarity and the lack of afnity of the inorganic particles and the organic polyurethane matrix. In summary, the polyurethane with 20 nm nanosilica shows the lowest degree of agglomeration. DSC is a sensitive technique to analyze the thermal stability and the structure of polyurethanes. The rst DSC heating run (not shown) of the unlled polyurethane shows a glass transition at 46 1C due to the soft segments (Table 4); the addition of nanosilica decreases the value of the glass transition to 49 or 57 1C due to higher degree of phase separation in the polyurethane induced by the nanosilica; the higher the nanosilica particle size, the lower the value of the glass transition temperature. On the other hand, the rst DSC heating runs of the polyurethanes show several exothermal peaks at about 40, 80 and 120 1C which may correspond to the complete curing of the polyurethane (Table 4), i.e. the starting samples were not fully cured. The enthalpy of curing of the polyurethane decreases upon addition of nanosilica indicating the positive effect of the ller on the kinetics of cure of the polymer. Furthermore, a melting process is always found at about 250 1C, due to the collapse of the polymeric chains (Table 4). The second DSC heating runs of the lled polyurethanes (Fig. 5) do not show any exothermal process indicating the full cure of the polyurethanes. As a consequence of the cure, two glass transition temperatures appear, one located at around 10 1C due to the soft segments and other at 65 1C likely due to the hard segments in the polyurethane. In general, the nanosilica particle size does not greatly inuence the values of the glass transition temperature. On the other hand, the melting of the fully cured polyurethanes is produced at 300350 1C, a melting temperature higher than in the incompletely cured lled polyurethanes (Table 4).

Table 4 Some parameters obtained from the DSC curves of nanosilica lled polyurethanes. First DSC heating run. PU Tg (1C) Curing process I T (1C) Unlled 20 nm 50 nm 100 nm 46 49 49 57 47 44 39 37 Curing process II T (1C) 80 75 81 Curing process III T (1C) 118 137 Tm (1C)

DHm (J/g)

DH (J/g)
17.7 1.3 3.5 5.8

DH (J/g)
2.6 5.3 4.9

DH (J/g)
1.2 0.2 257 245 246 4.8 0.4 1.1

100 20nm 50 nm

Fig. 5. DSC thermograms of the lled polyurethanes. Second heating run.

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DMA experiment was used to determine the viscoelastic properties of the lled polyurethanes. Fig. 6(a) shows the variation of the storage modulus (G0 ) as a function of the temperature. All polyurethanes exhibit the glassy region, the glass transition (noticed by a sudden decrease in storage modulus) and the rubbery plateau. In the glassy region the storage modulus does not vary with increase in temperature, because of the lack of movement of the polymer chains below the glass transition, and the addition of nanosilica decreases the storage modulus due to the lack of miscibility between the nanosilica particles and the polymer matrix. After glass transition is reached, the storage modulus in the rubbery plateau decreases in a greater extent in the lled polyurethanes. The values of the glass transition temperature and degree of crosslinking in the lled polyurethanes can be better analyzed from the curves of tan delta vs temperature (Fig. 6b). The unlled polyurethane shows two glass transition temperature values at 15 1C (due to the soft segments) and 67 1C (the main glass

transition likely due to the hard segments). The addition of the nanosilica ller removes the glass transition at lower temperature due to their inuence on the degree of phase separation between soft and hard segments in the polyurethane matrix. Furthermore, only the addition of 20 nm nanosilica decreases the glass transition temperature of the polyurethane, whereas the addition of the other nanosilicas does not signicantly change the glass transition temperature value of the polyurethane. On the other hand, the addition of nanosilica decreases the degree of crosslinking of the polyurethane, in a greater extent by adding 20 and 100 nm nanosilicas, because of an increase in the maximum value of the tan delta curve is noticed (Fig. 6b). This is in agreement with the lack of miscibility of the nanosilica particles in the polyurethane matrix. However, it should be considered that, according to the DSC experiments the starting samples were not fully cured (exothermic cure between 40 and 120 1CTable 4), hence additional cure may also take place during the DMA experiments.

7.5

log G'-Pa

6.5 unfilled 100 nm 6 20 nm 50 nm

5.5

5 -100

-50

50 Temperature (C)

100

150

200

0.9 0.8 0.7 0.6 Tan Delta 0.5 0.4 0.3 0.2 0.1 0 -100 -50 0 50 Temperature (C)

20 nm 100 nm

50 nm unfilled

100

150

200

Fig. 6. Variation of (a) the storage modulus and (b) tan delta as a function of temperature of unlled and nanosilica lled polyurethanes.

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Table 5 Contact angle values (25 1C) on the nanosilica lled polyurethane surfaces. PU Unlled 20 nm 50 nm 100 nm H2O (deg.) 75 67 53 57 CH2I2 (deg.) 42 36 39 40 Surface energy (mJ/m2) 40.21 44.87 50.63 48.22

4. Conclusions The nanosilicas aggregated into the polyurethane matrix due to lack of compatibility with the polyurethane matrix and the degree of agglomeration increased with particle size. Furthermore, the addition of nanosilica created bubbles and cracks on the lled polyurethanes likely due to stress concentration between the nanosilica agglomerates and the polyurethane matrix. As a consequence, the viscoelastic properties of the lled polyurethanes were inferior to that of the unlled polyurethane. However, the surface properties and adhesive strength of the stainless steel/ polyurethane adhesive joints increased by adding nanosilicas in a greater extent by increasing the nanosilica particle size. The increase in shear strength in stainless steel/polyurethane adhesive joints was small likely due to the lack of miscibility of the inorganic ller into the organic polymer matrix, and the lack of dispersion into separate particles.

Table 6 Single shear adhesion strength values of stainless steel/nanosilica lled polyurethane joints. 72 h after joint formation. PU Unlled 20 nm 50 nm 100 nm Shear strength (MPa) 14.2 7 0.1 14.4 7 0.2 14.7 7 0.1 15.3 7 0.3

Contact angle measurements were carried out on the surface of the lled polyurethanes to estimate the inuence of adding nanosilica on their wettability and surface energy. The contact angle values were measured using a polar (H2O) and a nonpolar (CH2I2) liquid, and the values obtained are given in Table 5. Addition of nanosilica ller decreases the water contact angle values in a greater extent by increasing the nanosilica particle size; therefore, the addition of the ller increases the wettability of the polyurethane. On the other hand, the di-iodomethane contact angle values practically do not change by adding nanosilica likely due to the polar nature of the nanosilica. The surface energy of the lled polyurethanes was calculated from the water and di-iodomethane contact angle values on the polyurethane lms using the Owens and Wendt equation.

Acknowledgments M.A. Bahattab thanks King Abdulaziz City for Science and Technology (Saudi Arabia) and University of Alicante (Spain) for nancial support, and the assistance in some experiments of Mr. Mohammad Asif Alam.

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mez TP, Ferna ndez-Garc a JC, Orgile s-Barcelo AC, Mart n-Marti[1] Ferrandiz-Go nez. JM. J Adhes Sci Technol 1996;10:83345. ndez-Garc a JC, Orgile s-Barcelo AC, Torregrosa-Mac a [2] Pastor-Sempere N, Ferna n-Mart nez. JM. J Adhes 1995;50:2542. R, Mart ndez-Garc a JC, Orgile s-Barcelo AC, Mart n-Martinez. JM. [3] Torro-Palau AM, Ferna Int J Adhes Adhes 2001;21:19. -Agullo TG, Ferna ndez-Garc a JC, Pastor-Sempere N, Orgile s-Barcelo AC, [4] Macia n-Mart nez. JM. J Adhes 1983;38:3153. Mart [5] Oertel G. Polyurethane handbook. 2nd ed.. New York: Hanser; 1993. p.7 [Chapter 7]. [6] Thirumal M, Khastgir D, Singha NK-, Manjunath BS, Naik YP. Cell Polym 2007;26(4):24559. [7] Chen L, Shen H, Lu Z, Feng C, Chen S, Wang. Y. Colloid Polym Sci 2007;285: 151520. [8] Dongya Y, Fengxian. Q. Polym Polym Compos 2008;16(6):395400. [9] Tan H, Yang D, Xiao M, Han J, Nie. J. J Appl Polym Sci 2009;111:193641. [10] Wang T, Yang Ch-H, Shieh Y-T, Yeh A-Ch. Eur Polym J 2009;45:38797. [11] Barnes K, Liang J, Worley SD, Lee J, Broughton RM, Huang. TS. J Appl Polym Sci 2007;105:230613. [12] Vuillequez A, Moreau J, Garda MR, Youssef B, Saiter. JM. J Polym Res 2008;15: 8996. [13] Jang MK, Hartwig A, Kim. BK. J Mater Chem 2009;19:116672. [14] Jeon HT, Jang MK, Kim BK, Kim. KH. Colloids Surf A: Physicochem Eng Aspects 2007;302:55966. [15] Turuc O, Kayaman N, Pohan A, Kahraman MV, Celoglu YM, Gungor. A. J SolGel Technol 2008;47:2909. n V, Va zquez P, Mart n-Mart nez. JM. Int J Adhes o [16] Vega-Baudrit J, Navarro-Ban Adhes 2006;26(5):37887.

gL 1 cos Y 2gsd gld 1=2 2gsp glp 1=2

in which gL is the surface tension of the liquid probe, Y the contact angle value, gsd the dispersive component of the surface energy of the solid, gld the dispersive component of the surface tension of the liquid, gsp the polar component of the surface energy of the solid, and glp the polar component of the surface tension of the liquid. The addition of ller increases the surface energy of the polyurethane (Table 5) this tends to increase with increase in the nanosilica particle size. Finally, the adhesion properties of the lled polyurethanes were obtained from single lap shear tests of stainless steel/polyurethane adhesive joints (72 h after joint formation). The shear strength slightly increases in the joints produced with the lled polyurethanes in a greater extent by increasing the nanosilica particle size (Table 6). The locus of failure in all joints was cohesive in the adhesive.