Tribology Letters, Vol. 24, No. 2, November 2006 ( 2006) DOI: 10.

1007/s11249-006-9043-6

119

Friction properties of triazine-containing hybrid composites

M. Mizerskia,b, I. Piwonskia, G. Celichowskia and S. Plazaa,*
a

Department of Chemical Technology and Environmental Protection, University of Lodz, Pomorska 163, 90-236 Lodz, Poland b Pharmaceutical and Clinical Research Center BIOFANA, Kutno, Poland

Received 20 September 2005; accepted 22 November 2005; published online 2 November 2006

This paper presents micro and nanofriction studies on thin silica/aminosilica-triazine hybrid composite coatings on silicon substrate. The silica/aminosilica coatings were made on silicon using the dip-coating method and then modied by alkoxy- and aryloxy-triazine derivatives. Formation of hybrid coatings permits a greater exibility of their resulting properties. Microfriction tests were carried out with a sliding ceramic ball (load range of 1080 mN) on the composite at surface, using a tribometer ball-onsample system. Sliding speed was 25 mm/min at room temperature. Nanofriction was measured using the Friction Force Microscopy. It is shown that surface modication of silica/aminosilica layers by triazine derivatives, to form inorganicorganic hybrid coatings, improves friction properties. All tested triazine derivatives, particularly long alkoxy- substituted s-triazines, cause a decrease in the friction coecients in microfriction tests, in comparison to a non-modied silica/aminosilica thin lm. The same eect was also observed for some tested triazine derivatives at nanofriction measurements. KEY WORDS: friction-reducing, coatings, ceramic composite, surface modication, AFM, nanotribology

1. Introduction Sol-gel processing is a method whereby small molecules can be converted into polymeric or ceramic materials. Typically, one starts with molecules of the M(OR)4 form, where R is an organic radical, such as CH3CH2, or a halogen. The sol-gel method oers several advantages. For example, the nanocomposite so obtained is very pure. The process occurs at a relatively low temperature that will not destroy the polymeric structure [1]. The hybrid coatings (thin lms and composites) can be formed in multiple steps, such as formation of a thin lm of SiO2, followed by formation of one containing an aminosilane, in order to put amino groups on top of the fully formed SiO2 thin lm. Holmes-Farley and Yanyo [2] observed that such bi-layer coatings gave better strength and corrosion protection, in comparison to one-layer coatings. Additionally, aminosilane-only coatings (thin lms) neither provide inhibition on their own, nor do they increase protection when applied on top of a silica-only coating. Their experiments also demonstrate that the structure of these types of coatings signicantly inuenced the adhesion characteristics of the surface involved. Cyanuric chloride and its derivatives have been widely studied in literature [3,4]. Such triazine derivatives are also useful as lubricating oil additives [5,6]. Our recent studies [7,8] conrmed that triazine derivatives
*To whom correspondence should be addressed. E-mail: splaza@uni.lodz.pl

are good friction modiers. Such coatings (also known as functionally gradient coatings) [2] permit the properties of dierent regions of a coating to be independently optimized for dierent properties. They might include elastic modulus, adhesion promotion, index of refraction, friction coecient, to name just a few. The key to the formation of triazine-containing hybrid composites is controlling the reactivity of various triazine components in the modication reaction (less or more reactivity, steric and electronic reasons). Also the choice of the organic group inuences frictional properties of the resulting composite material. The multiple procedures of the formation of multilayer coatings would be signicantly less desirable than one in which the layer is formed in a single step, like in the case of SiO2. The connection of inorganic silica with organic parts (aminosilica) improves the surface adhesion. Unfortunately, the porosity of the surface increases as well [2]. However, the amine group reacts easily with lots of chemicals (easy to substitute), the reaction with environmental vapor and carbon dioxide is the undesirable eect. In most cases, the surface modication allows resolving all of these problems. In this paper, the bi-layer composite materials, called hybrid composites, are presented. The reinforcement of silica/aminosilica bi-layer material by triazines should be better than the one in which one-layer aminosilica coating is modied. The methods of preparation and characterization of such composites form the second part of this paper.
1023-8883/06/1100-0119/0 2006 Springer Science+ Business Media, Inc.

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M. Mizerski et al./Friction properties of triazine composites

2. Experimental 2.1. Materials Commercial 3-aminopropyltriethoxysilane (APTS) and tetraethoxysilane (TEOS) were purchased from Fluka, and were used without further distillation. Tetrahydrofurane (THF) was purchased from P.O.Ch. Gliwice, Poland, and was dried by the distillation in the presence of Na/benzophenone and used directly after distillation. Toluene was also purchased from P.O.Ch. Gliwice, Poland, and azeotropically distillated before modication. Triazine modiers are shown in table 1. They were prepared and tested by use of common techniques [7,8].

The AFM/LFM topography of sample surfaces and nanofriction measurements were performed with a NT-MDT Solver system, using the Si/SiO2 tips.

2.3. Preparation of silica/aminosilica thin lms (TA) In the rst step, a thin lm of silica on silicon was prepared as follows: 2.07 g (0.1151 mol) water with hydrochloric acid (0.1 M HCl solution as catalyst) was added to 6 g (0.0288 mol) TEOS. After the hydrolysis of TEOS and the condensation processes, a clear silica precondensate was obtained, that was next diluted with ethanol (99.8% pure alcohol) in the ratios of 1:1 (w/w). Then, the solution of precondensate was ltered and deposited on a silicon wafer using the dip-coater at the sliding velocity of 25 mm/min, and next, the layer was dried and heated (100 C, 2 h). In the next step, the aminosilica precondensate was prepared as follows: 1.46 g (0.0813 mol) water with hydrochloric acid (0.1 M HCl solution as catalyst) was mixed with 6 g (0.0271 mol) of 3-APTS. After 24 h, with the clear precondensate, the procedure was repeated like in the silica thin lm method. The product, called TA (silica/ aminosilica), was preheated before further modication (80 C, 2 h), to decompose hydrocarbonate ammonium, which is formed in reaction of amine groups with CO2 in the presence of the ambient humidity [9]. The thickness of the active aminosilica layer in TA materials had been determined before, by combining SEM and FT-IR measurements [8]. The thickness of prepared aminosilica was $600 nm. The scheme of the process of preparation of the TA bi-layer coating is shown in gure 1.

2.2. Equipment A Dip-Coating machine from NIMA Technologies was used to deposit the silica and aminosilica pre-condensates onto the silicon surface, to obtain thin lms of bi-layer silica/aminosilica materials. FT-IR Spectra were recorded with a BIORAD FTS175C System at 4 cm)1 resolution, using Harrick Refractor Reactor reectance accessory with a MCT Detector, at room temperature. All spectra were obtained in the 4000650 cm)1 range, using Refractor Reactor accessory with MCT detector. Pure silicon wafer was used as a background sample. The samples were frictionally tested on the reciprocating ball-on-at machine, constructed in the Department of Chemical Technology and Environmental Protection, University of Lodz, Poland. The device consists of the control and the testing blocks. The control block is a computer-based unit, with four channels of data acquisition (total sampling rate up to 100 kHz) and computerized motor controllers for motion in the x and y-directions, and a system of normal load application. The Microtribometer can provide linear motion with a speed ranging from 2 to 2000 lm/s. Normal load, which can be applied during frictional tests, covers the mili-Newton scale (11000 mN). Standard frictional pairs are a at surface covered by a thin lm and a ceramic or metallic ball of 15 mm diameter as a counterbody.

2.4. Preparation of hybrid composites The TA materials were modied by triazine derivatives, according to the scheme of reactions shown in gure 2. Abbreviations of hybrid composites used in this paper are presented in table 2. The general procedure of synthesis of these materials was as follows. The TA material on silicon pre-heated at 80 C (2 h) was put into the 1% (0.2 g) THF (or toluene) solution of the triazine modier in a round ask. After that, the molar

Table 1. Triazine surface modiers. R Groups Abbreviation CDMT C8T BzT CF3T FCDMT TPhT PhF5 Name (-1,3,5-triazine) 2-chloro-4,6-dimetoxy2-chloro-4,6-dioctyloxy2-chloro-4,6-dibenzyloxy2-chloro-4,6-bis (2,2,2-triuoro)ethoxy2-chloro-4,6-bis- (1H,1H-peruorononyl-1-oxy)2,4,6-trifenoxy2,4,6-tris(pentauorofenoxy)-

OR

N
Cl or RO

N N
OR

CH3 (CH2)7CH3 CH2-Ar CH2CF3 CH2(CF2)7CF3 Ar Ar-F5

M. Mizerski et al./Friction properties of triazine composites

121

OC2H5 H5C2O Si OC2H5 OC2H5

hydrolysis

- 4 C H OH
2 5

4 H2 O

OH HO Si OH OH

condensation
Si
4 H5 C2 O

O
O

OC2H5 Si OC2H5 OC2H5

O O

TEOS thin film (SILICA)

O H2 N Si O O *

2
H2 N
Si

OC2H5 OC2H5 OC2H5

hydrolysis

3 H2 O 3 C2H5OH

H2 N

Si

OH OH OH

condensation
OC2H5 Si OC2H5 OC2H5

3 H2 N

2. 1.

APS thin film (AMINOSILICA)

Aminosilica APS Silica TEOS Silicon Wafer

TA material Figure 1. Preparation of the TA material.

O-R
O-R N
NH2

1. N(iPr)2(Et) , THF or Toluene - HN+(iPr)2(Et)Cl-

N
N H

N N
O-R

RO or Cl N

N O-R

2. Soxhlett reflux THF or Toluene12-24h

TA material

triazine modifier

TA-m Anisotropic composites (RO- FUNCTIONALLY GRADIENT GROUP)

Figure 2. General procedure of synthesis of TA-modied triazine hybrid composites.

Table 2. Abbreviations used for the composite materials. No. Composite TA-m abbreviations TA-CDMT TA-C8T TA-BzT TA-TPhT TA-CF3T TA-FCDMT TA-PhF5T Triazine modiers abbreviations CDMT C8T BzT TPhT CF3T FCDMT PhF5T

The reaction process was controlled by 4-(4-nitrobenzyl) pyridine colorful test [10]. The mechanism of this colorful reaction is presented below in gure 3.

1 2 3 4 5 6 7

2.5. Microtribological measurements (Microfriction) The friction coecients were determined in a ballat disk conguration of sample frictional contact. The ball was made of zirconia, stabilized by yttrium oxide (ZrO2 97%, Y2O3 3%), and had a 3 mm diameter. The reciprocating movement was used, at the speed of 420 lm/s, on 20 mm distances. The load applied was in the range from 10 to 80 mN. All the friction tests were conducted at room temperature. The friction coecient was calculated from an average value of full distance, excluding start and end points, where the speed is not stable.

equivalent of DIPEA was added (depending on the molecular weight of the triazine derivative). The whole sample was then reuxed with the solvent (bp temperature). After 24 h, the modication process was nished. The sample of TA-modied composites was washed with some portion of solvent, and ultrasonicated for 10 min. Finally, the prepared sample was reuxed with the adequate solvent, using a Soxhlett extractor, for 612 h. The scheme of the process of preparation of the TA-m composites (hybrid composites TA-modied) is shown in gure 2. The increase of the hydrophobicity after the modication of aminosilica surface allowed to resolve the problem of the spontaneous reaction of amine groups with the environmental vapor and CO2.

2.6. Nanotribological measurements (Nanofriction) The AFM/LFM measurements were carried out in the contact mode, with direct recording of topography and friction images. All of the AFM/LFM measurements were of a relative character. The method of determination the relative friction coecient is shown in gure 4.

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4NBP
O O N
+

M. Mizerski et al./Friction properties of triazine composites

OR,OAr,Cl N OR,OAr,Cl

O
N

CH2

Cl N

N O

CH2

N N N OR,OAr,Cl

Cl

OR,OAr,Cl

+ 4NBP - 4NBP*HCl
OR,OAr,Cl

O N O

CH

N
N

N OR,OAr,Cl

Figure 3. General procedure of 4NBP-test.

3,5 3

TA-PhF5T

y = 0,1444x +1,8402

Normal Force [nA]

2,5 2
1,5

1
0,5

y = ax + b a - Relative Friction Coefficient

-1

Friction Force [a.u.]

Figure 5. IR Spectra of the TA material (dotted) and TA-CF3T hybrid composites (black).

Figure 4. Determination of the relative friction coecient for the TA-PhF5T composite.

3. Results and discussion 3.1. FTIR Analysis of hybrid composites The analysis of silica/aminosilica (TA) and hybrid composites was performed to conrm their structures. Figure 5 shows typical FTIR spectra (TA-CF3T hybrid) of the TA surface, modied by 2-chloro)4,6-bis(2,2, 2-triuoroethoxy)-1,3,5-triazine (CF3T), including the spectrum of unmodied TA, for comparison. The FT-IR spectra of remaining hybrid materials are summarized below as the observed frequencies of the absorption bands with qualitative intensities and their corresponding groups. TA (silica/aminosilica): (IR, cm)1) 3368, 3286 (w, NH); 2929, 2863 (s, CH); 1589 (m, NH); 1391 (w, CH, CH2Si); 1219, 1148, 1039 (vs, SiOSi, SiO). The remaining parts of the spectra were conrmed apart from SiO bonds and CH (str aminopropyl chain that existed on every spectrum. TA-CDMT: 3283 (m, NH-triazine); 1618 (m, def, NH-triazine); 1584 (s, C=N triazine); 1535, 1505, 1419 (s, s, m, triazine ring); 806 (s, def, triazine ring). TA-TPhT: 3277 (m, NH-triazine): 3058, 3030 (m, CH, C6H5O); 1663 (s, C=C, C6H5O); 1603 (s, combined, NH-triazine def, C=N triazine); 1517, 1495, 1451, 1347 (s, s, s, s triazine ring); 1410 (m, combined triazine and benzene ring); 803 (s, def, triazine ring).

TA-C8T: 3288 (m, NH-triazine); 1618 (s, def, NH-triazine); 1578 (s, C=N triazine); 1533, 1477, 1433 (s, s, s, triazine ring); 1406 (s, combined triazine ring, CH [C8H17O]); 807 (s, def, triazine ring). TA-BzT: 3245 (n, NH-triazine); 3094, 3020, 3001 (m, CH, CH2C6H5); 1612 (s, combined, C =N triazine, C=C benzyl); 1511, 1410, 1337 (s, s, s, triazine ring); 1466 (s, combined triazine ring, benzyl C=C); 807 (s, def, triazine ring). TA-CF3T: 3273 (m, NH-triazine); 1616 (m, def, NHtriazine); 1554, 1472, 1333 (s, s, s, triazine ring); 1410 (s, combined CF [CF3CH2] and triazine ring); 1397 (s, CF CF3CH2); 803 (s, def, triazine ring) presented as an example in gure 5. TA-FCDMT: 3292 (m, NH-triazine); 1610 (m, def, NH-triazine); 1589 (s, C=N triazine); 1544, 1470 (s, s, triazine ring); 1413 (s, combined CF [C8F17CH2] and triazine ring); 1350 (s, CF [C8F17CH2]); 807 (s, def, triazine ring). TA-PhF5T: 3240 (m, NH-triazine); 1627 (s, combined NH-triazine, def and C =C [C6F5]); 1595 (s, C=N triazine); 1578, 1529, 1340 (s, s, s, triazine ring); 1385, 1312 (s, m, CF [C6F5O]); 825 (s, def, triazine ring). In our recent studies [7,8], the Secondary Ion Mass Spectrometry (SIMS) was also used as an alternative method for conrmation of molecules structures. For example, table 3 contains data for aminosilica hybrid APS-CF3T (aminosilica thin lm, on a silicon-modied

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Table 3. Results the ToF-SIMS analysis of aminosilica coating (APS) modied CF3T triazine [2-chloro-4,6-bis(2,2,2-triuoroethoxy)-1,3,5-triazine]. Ion fragment Ion type m/z APS (aminosilica coating) lot of counts APS-CF3T (aminosilica hybrid) lot of counts Positive mode 3370 14 806 30 676 5200 4800 3600 6400 28 394 Negative mode 21 600 7340 107 400 83 286 6200 110 154 4800 17 660

Positive mode CH2NH2 C3N3H3 C3N3H2 CF3 CF CF3CH2 CH2F CH2O F CN HCN CNO C2N2O H2C2N2O P P P P P P P N N N N N N N 30.05 81.03 67.02 69.01 31.01 83.02 33.03 30.02 19.00 26.02 27.03 42.02 68.00 70.02 7979

Negative mode 2050 60 484 73 038 807 2200

uorinated triazine derivative CF3T). Both mono(previously investigated) and bi-layered materials (in this work) were modied in the same way. In consequence, they had a similar chemical constitution of the modied surfaces. In addition, the results of the SIMS analysis would not dier much. Therefore it was not advisable to analyze the bi-layered hybrids. The FTIR and the ToF-SIMS analysis provides a clear evidence of chemical reactions between amine group of TA and triazine derivatives on the surface.

3.2. Microfrictional properties The results of microfrictional measurements of seven hybrid composites are presented in gures 6 and 7. They show that all of them have lower values of friction coecients, in comparison to the TA material. The aminosilica forms low-hardness coatings (soft). It allows resolving this problem by surface modication. The
TA-CDMT TA-BzT TA-TPhT TA TA-C8T

coating hardness should grow up undoubtedly. It is supposed to be true, because the dierences between the frictional properties of modied and non-modied materials are much more signicant. This reinforcing capability could be also attributed to the character of the substitution in the triazine ring. The results clearly show the dierences in frictional performance of composite materials. The increasing length of the carbon chain from short (TA-CDMT, TA-CF3T) to long (TA-C8T, TAFCDMT), results in the signicant decrease of friction coecient values. The reason for such behavior may arise from the reinforcement of the condensed layer by cohesion forces, formed between long carbon chains (CH2)7CH3 and CH2(CF2)7CF3, as in the example of TA-C8T, shown in gure 8(a). TA-C8T and TA-FCDMT are most eective in the reduction of friction, among all prepared composites. Their values of the friction coecient, in the whole range of loads, are 0.11 and 0.14, respectively. The reinforcing eciency is
TA TA-FCDMT TA-CF3T TA-PhF5T

0,35 Friction coefficient 0,30 0,25 0,20 0,15 0,10 0,05 0,00 0,0 10,0

0,35
Friction coefficient

0,30 0,25 0,20 0,15 0,10 0,05 0,00

0,0 10,0 2,00 30,0 40,0 50,0 60,0 70,0 80,0 90,0

20,0

30,0

40,0

50,0

60,0

70,0

80,0

90,0

Load [mN] Figure 6. The eect of load on the friction coecient for nonuorinated composites in the micro-scale.

Load [mN] Figure 7. The eect of load on the friction coecient for uorinated composites in the micro-scale.

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M. Mizerski et al./Friction properties of triazine composites

F O N N O O N N NH N OO N NH N N OO N NH N N O O N NH NH2 N N O N NH NH2 F O N O N N NH NH2 NH2 F

F O F N N O

F F F NH2 NH2

N F NH

Figure 8. The general idea of: (a) a long hydro-carbon chain protective coating, presented by the TA-C8T hybrid composite. (b) The steric compression in the TA-TPhT hybrid composite. (c) The steric compression in the TA-PhF5T hybrid composite.

higher for TA-C8T, replacing the hydrogen atoms in the hydrocarbon chain (TA-C8T) with the uorine ones (TA-FCDMT) decreases the antifriction action. The friction performances of short-chain hybrids (TA-CDMT, TA-CF3T) are nearly the same. The composite materials including phenyl groups give higher values of friction coecient than other composites. It can be explained by the steric eect of (TA-TPhT and TA-BzT) molecules, which decreases the antifrictional properties. The steric compression causes that not all of the amine groups participate in the reaction of modication, as it is presented in gure 8(b). This may suggest that higher values of friction coecient should have been observed for uorinated aromatic ring like PhF5T (nanocomposite TA-PhF5T) (gure 8(c)). In the microtribological tests, the friction coecient values for TA-PhF5T composites are nearly the same as for non-substituted aromatic composites TA-TPhT and TA-BzT. Probably, there exists a combination of at least two opposite eects. On the one hand, the steric eect causes the rise of friction coecient. On the other hand, the uorine electron withdrawing substituents are well known for their inuence on reduction of friction. The net result of these competitive eects is that the friction coecient of TA-PhF5 is not lower. Generally, alkoxytriazines are better surface modiers than aryloxytriazines in microfriction conditions. The order of improvement in the antifrictional activity in the microscale is: C8T > FCDMT > CDMT CF3T > BzT TPhT PhF5T: Although this paper does not present results of wear resistance tests of triazine-containing hybrid composites, it is supposed that the modication of aminosilica surface improves antiwear performance in comparison to starting bi-layer silica/aminosilica coating. Long carbon chain- and aromatic-containing (especially fully uorinated) materials (i.e. composites, lubricants), are wellknown and used in tribology. Mostly, they cause improvement of frictional and antiwear performance of materials. It is believed that the eect of such groups

into aminosilica surface should be nearly the same among all of testing hybrids, TA-C8T, TA-FCDMT, TA-PhF5T are expected to have the best wear resistance characteristic.

3.3. AFM studies The topographies of surfaces before and after the modication are shown in gure 9. It can be clearly seen that modication of the surface occurs. The results of nanofriction tests are given in gures 10 and 11. As noted before, the presented values of friction coecients obtained in nanofriction conditions are in arbitrary units, allowing us only to derive tendencies in friction coecients and to compare the investigated materials. A higher antifriction eciency was observed for the carbon-chain substituted nanocomposites: TA-C8T and TA-CDMT, and fully substituted by uorine atoms methyl and phenyl rings: TA-CF3T and TA-PhF5T. These results correspond well with the results of the microscale measurements. The inuence of the steric and the electronic character of triazine substituents is dierent than that observed in the microscale. For the chain-containg hybrid composites (TA-CDMT, TA-C8T, TA-CF3T, and TA-FCDMT) the steric eects have no signicant inuence. However, the electronic character is of fundamental meaning again. The full rearrangement of (CH2)8-H chain (TA-C8T) to (CF2)8F (TA-FCDMT) causes that the relative friction coecient increases signicantly. Despite the uorine carbons chain presence, which should give antifriction protective layer, the extremely strong withdrawing eect in the nanoscale may be responsible for the high increase of the relative friction coecient observed. On other hand, when hydrogen atoms in aromatic ring are replaced (TA-TPhT) with a fully uorinated ring, the friction coecient decreases. For the hybrids contain aromatic ring (TA-TPhT, TA-BzT, and TA-PhF5T), the steric eect is important, but the character of the substitution of the aromatic ring is of much higher importance, especially when the

M. Mizerski et al./Friction properties of triazine composites

125

Figure 9. AFM topography images (5 5 lm2) of the starting material and hybrid composites: TA (A), TA-BzT (b), TA-PhF5T (c).

aromatic ring is fully substituted with electron withdrawing uorine atoms. Hence, the increase in friction coecient is normally observed in the case of (TA-TPhT, and TA-BzT). The dierence between TA-TPhT and TA-BzT composites can be explained by the stiness of the surface structure. It is known that if the thin layer is formed on a surface, it has an almost completely ordered character. A less ordered layer should possess better friction properties in the nanoscale [1113], if only the previously described conditions are realized (aromatics substituents character).

3.4. Comparison of micro and nanoscale results For comparison purposes, the friction coecient of a given sample, measured in the microscale, was calculated as the average over the full range measurements results, presented in gures 6 and 7. Such a calculation was justied, because in the full range of the applied loads, the friction coecient varied insignicantly. With this approach, a similarity between friction results in the micro and nanoscale can be seen. Such correlation was found for the group of non-uorine hybrid composites, as shown in gure 12. It can be said that the friction

0,350

0,350

Relative Friction Coefficient

0,300 0,250 0,200 0,150 0,100 0,050 0,000 TA TA-C8T TA-CDMT TA-BzT TA-TPhT

Relative Friction Coefficient

0,300 0,250 0,200 0,150 0,100 0,050 0,000 TA TA-CF3T TA-PhF5T TA-FCDMT

Composite Materials TA-m (Series A)

Figure 10. The results of the nanofriction tests for non-uorinated hybrid composites.

Composite Materials TA-m (Series B) Figure 11. The results of the nanofriction tests for non-uorinated hybrid composites. Fluorinated hybrid composites.

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Microfriction 0,35 0,30

M. Mizerski et al./Friction properties of triazine composites

Nanofriction [a.u.]

Friction Coefficient

0,25 0,20 0,15 0,10 0,05 0,00 TA TA-CDMT TA-C8T TA-BzT TA-TPhT

In the nanoscale, the highest reinforcement eciency was observed for the non-uorinated carbon chain substituted composites, like silica/aminosilica-dioctyloxytriazine (TA-C8T). The character of the substitution is much more important than the steric eect, if only the aromatic ring is fully substituted, especially by electron withdrawing substituents. For the group of non-uorine hybrid composites, a correlation was found between friction results in the micro and nanoscale.

Acknowledgments This work was supported by the State Committee of Science Grants 4 T09B 071 24 and 4 T07B 03626. The authors would also like to thank Prof. Z. Kaminski from the Institute of Organic Chemistry at the Technical University of Lodz, for help with synthesis of triazine derivatives.

Composite Materials TA-m

Figure 12. Comparison micro and Nanofriction results for TA-m composites.

protection behavior of non-uorine triazine modiers is similar in the micro and nanoscale, despite the dierent scale eects, mutual interactions, forces character, etc. The signicant dierence in the inuence of electron withdrawing substituents (uorine) did not allow us to present a convincing proof to point the correlation between the micro and nanoscale measurements for uorine hybrid composites.

References
[1] G.J. Brinker and G.W. Scherer, Sol-Gel Science. The Physics and Chemistry of Sol-Gel Processing (Academic Press, San Diego, 1990). [2] R. Holmes-Farley and L.C. Yanyo, J. Adhesion Sci. Technol. 5 (1991) 131. [3] J.M.E. Quirke, Comprehensive Heterocyclic Chemistry I, Vol 3, Part 2B. Six Membered Rings, Section 2.20 1,3,5-triazines (Pergamon Press, Oxford, 1982). [4] D. Bartholomew, Comprehensive Heterocyclic Chemistry II Review of Literature 19821995, Vol 6, Section 6.12 1,3,5-triazines (Pergamon Press, Oxford, 1995). [5] C. Pawlowski and J.E. Dunbar US Pat. 5,032,301 (1991). [6] T. Dekura, US Pat. 5,034,525 (1991). [7] M. Mizerski, G. Celichowski and J. Kolesinska, Tribologia 35(5)(2004) 195. [8] M. Mizerski, Synthesis and tribological studies of hybrid nanocomposites Ph.D thesis, University of Lodz, 2004. [9] E.F. Vansant, P. Van der Voort and K.C. Vrancken, in: Studies in Surface Science and Catalysis Vol 93 (Elsevier Science B.V., Amsterdam, 1995). [10] C.R. Turner, Analyst 99 (1974) 431. [11] B. Bhushan, Handbook of Micro/Nanotribology (CRC Press, Boca Raton, FL, 2001). [12] B. Bhushan, J.N. Israelachvili and U. Landman, Nature 374 (1995) 607. [13] B. Person, Sliding Friction, Springer Series in Nanoscience and Technology (Springer, Heidelberg, 1998).

4. Conclusions From the presented work, it can be concluded that the aryloxy- and alkoxy-triazines are good surface modiers. In most cases, the use of 2-chloro-4,6-dioctyloxy-1,3,5triazine lead to the formation of the best hybrid composite. In the microscale, if the carbon chain is longer (independently of the carbon chain character uorinated or non-uorinated), a greater decrease in the friction coecient was observed. The strong inuence of the steric eect resulted in slightly worse properties of the aromatic-containing hybrids, in comparison to the others. The electron withdrawing substituents, like uorine, can compensate for this eect, though. The order of improving the microfrictional activity, depending on the kind of the triazine ring substitution, is: noctyloxy ! 1H; 1Hperfluorononyl1oxy ! methoxy 2; 2; 2trifluoroethoxy ! benzyloxy phenoxy pentafluorofenoxy :