Int. J.

Adhesion and Adhesives 17 (1997) 121-126

ELSEVIER

~!;)1997 Elsevier Science Limited Printed in Great Britain. All rights reserved 0143-7496/97/$17.00 PII: SO143--7496(96)00042-5

Spectroscopic and mechanical evidence of the influence of the substrate on an anaerobic adhesive cure
B. George a*, F. Touyeras a, Y. Grohens b and J. Vebrel a alut Chimie, 30, Avenue de I'Observatoire BP1559 25009 Besancon, France blnstitut de Chimie des Surfaces et Interfaces-CNRS, 15, Rue Jean Starcky BP2478 68057, Mulhouse, France (Accepted 5 November 1996)

The catalytic effect of different substrates-steel, aluminium and copper-on the curing reaction of a standard anaerobic adhesive is investigated by infrared microscopy in reflection mode. Thus, kinetics of the cure reaction, studied from the decrease of the carbon-carbon double bonds absorption peak, are quite different depending on the substrate under investigation. Among the studied metals, copper has been found as the most reactive surface. The assumed role of saccharine contained in the anaerobic adhesive which is able to oxidise metals into ions will be highlighted. Finally, an attempt will be made to correlate the kinetic results with the mechanical performances of the adhesive joint measured by a single lap shearing test. Thus, fast curing reaction of the anaerobic adhesive on a surface such as copper leads to poor maximal strain while lower surface reactivity may provide better mechanical performances of the adhesive joints. 1997 Elsevier Science Ltd
(Keywords: adhesive; anaerobic; metallic catalysis; spectroscopy; shearing test)

INTRODUCTION For these two last decades, the use of structural adhesives in industry developed increasingly because of their advantages: lowering of production costs, lightness of structures, ease of application and occurrence of corrosion limited comparatively to the more usual ways of joining pieces (welding, bolting, clinching). The anaerobic adhesives merely used in automotive industry 1 have some other interesting properties: they can cure via a redox radical mechanism at room temperature as soon as oxygen is removed. So these one-part systems based on acrylic monomers cure very quickly when confined between the materials to be bonded (commonly metals) 2' 3. The catalytic decomposition of initiator molecules by metallic cations, arising from substrates, provides free radicals able to induce the reaction. This catalysed reaction requires about four times less energy (1015kcal/mol) than a thermally induced reaction. As initiation generally proceeds through the decomposition of an hydroperoxide, such as cumene hydroperoxide 4, the following relations can be written:
ROOH + M e "+ ~ R O + M e ("+1~+ + O H

ROOH

+ M e ('+11+ --+ R O 0 + M e "+ + H +

(b)

(a)

*Correspondence to: Iut Chimie, 30, Avenue de l'Observatoire BP1559 25009 Besancon (France)

The reaction (b) produces radicals which are less efficient on the initiation stage than the RO radicals 5. Nevertheless, this reaction is crucial to regenerate the cations at their lower oxidation state. Indeed, this regeneration is essential to maintain the initiation rate at a high level in formulations where an inhibiting system is present. Consequently, in order to ensure the continuous reduction of cations to their lower oxidation state, a synergistic accelerating system has to be employed 6. Thus, a charge-transfer complex between constituents of the accelerating system, in the presence of metallic ions, has been proposed by Okamoto 7, Beaunez et al. 4 and Dournel 8. Besides, Wellmann et al. 9 have achieved the isolation of a new compound, aminal, which results from the reaction of saccharin and N,N-dimethyl-p-toluidine. Whatever the accounted assumption, the synergistic effect of the catalytic system mainly affects the relation (2) by providing species which are strong reductants towards the hydroperoxide. Furthermore, Yang et al. 10. 11 have shown, using F T - I R , that the nature of the substrate, as well as the surface treatment, greatly influence the cure rate but also the final cure degree of an anaerobic adhesive. Thus copper has been found to be the most active surface for initiating the polymerisation. In this work, F T - I R microscopy will be shown as a powerful tool for investigating the adhesive/substrate

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Influence of substrate on anaerobic adhesive: B. George et al.

interface. Moreover, absorption spectroscopy will be useful for probing the availability of the surface metallic ions and the mechanical performances will be investigated through a single lap shearing test. This work will not focus on the chemistry of the anaerobic adhesive cure which is well documented in the literature cited above. Therefore, the originality of our work will be of the search for relations between the reactivity of the adhesive formulation and the availability of the surface cations and also between this reactivity and the mechanical performances of the joints. 500mPa.s. at 25C and a density of 1.14 as provided by the supplier. Three metallic active substrates, steel, aluminium and copper, have been supplied from Goodfellow and their compositions are given in Table 1. These substrates are polished, in order to have a roughness of the same order. This roughness checked by profilometry has provided values ranging from 4 to 5,5/~m. The surfaces are then degreased by dipping the lamellas in a trichloroethane ultrasonic bath. After 10 minutes, they are rinsed with distilled water and acetone, then dried at room temperature and stored in a dessicator under vacuum.
Techniques Materials

EXPERIMENTAL

A standard anaerobic adhesive, used in the automotive industry, is chosen from a large range of commercially available products. Thus, Loctite 648, purchased from Loctite Corporation, is mainly composed by a dimethacrylic ester, an initiator, accelerators and stabilizers. This formulation is more specifically made of a urethane modified dimethacrylate prepolymer which formula is:
O2C = C(CH3) - CO0 -R - CO - NH-

(CO2)n - N H -

CO CH2

(CH2)n - COO - (CH3)C=

Where R is the polyol structure resulting from the reaction with an isocyanatoalkyl methacrylate~2. Size exclusion chromatography, performed on this anaerobic adhesive, has provided the ester methacrylate molecular weight that are: Mn=474, Mw = 1022g/mol and polydispersity=2,14. These results show that the monomer cited above is prepolymerised which leads to this polydispersity. The initiator commonly used is cumene hydroperoxide. The accelerating system is made of a tertiary aryl alkylamine, such as N,N dimethyl-p-toluidine13, coupled with saccharin, also named orthobenzosulfimid acid. Finally, the free radical stabilizer is generally quinone, and more precisely 1,4 benzoquinone 14 which acts, in the presence of oxygen, as radical scavenger 15. The main physicochemical characteristics are a superficial energy (7) of 37,16mJ/mm 2 as determined with a LAUDA liquid tensiometer, a viscosity of
Table 1

The apparatus used was a Fourier Transform Infrared Spectrometer connected to an optical microscope (MAGNA IR spectrometer 550, NICOLET, fitted with software OMNIC). 200 scans were collected in order to improve the signal to noise ratio. For the studies of the cure of the bulk adhesive, a 10#m thick adhesive film was held between two lamellas of KBr. The spectra were recorded in transmission mode at regular intervals of time. The studies of the cure of the adhesive at a surface were performed by applying a thin layer (3050/tin) on the different metallic substrates and left standing at room temperature. The infrared spectra were recorded in reflection microscopy and the spectrum of a metallic sample, without adhesive, was used as a reference. The polymerization reaction was studied by following the variations of intensity of the absorption peaks corresponding to the stretching of double bonds C = 0 and C = C. For our purpose, the degree of cure was calculated at different intervals of time using the following equation: c~= [(A0- A , ) / A o ] x 100 (1)

where A0 is the ratio of the area of the peak around 1640 cm -l (C = C stretching band) by the area of the peak around 1720 cm-1 (C = 0 stretching band) at time t = 0 (time required for the recording of the first spectrum, chosen as reference time) and At the ratio of the areas of the same two peaks at time t. In order to study the influence of saccharin on the

Characteristics of metallic substrates (copper, steel and aluminium) used in that study Copper of high level of purity (99,99%) Co Pb Sn < 0,0001 A1 0,015 0,004 Mg 0,5 1 < 0,0001 Steel XC 38 Si 0,1 0,4 < 0,0001 S 0,020 0,040 Ti <0,2

A1 < 0,0001 C 0,34 0,42 Fe <0,5

P < 0,0001 Mn 0,5 0,8 Si 0,3 0,8

Si < 0,0001 Cu < 0,4

Cr < 0,0001 Ti < 0,01

Ni < 0,0001 P < 0,03

Zn < 0,0001

Fe 0,001

Cu 3,5 4,5

Zn <0,1

Aluminium A-U4G Mn 0,3 0,8

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Influence of substrate on anaerobic adhesive: B. George et al.

metallic surfaces, samples of the three metals were degreased, as explained above, and then immersed in ethanolic solutions of saccharine at different concentrations. Samples immersed in ethanol without saccharine were used as references. The concentration of metallic ions in solution was determined by means of atomic absorption spectrometer Perkin Elmer 3100 or ionic chromatograph Waters as a function of time. Mechanical performances of the adhesive were tested on the three metallic substrates. The joint was made of two lamellas, which dimensions are 5 0 x l 0 x l 0 m m . The samples were maintained under pressure, 10kg/ cm 2 applied for 3 hours, and stored for 24 hours which was time required to reach the final resistance. The single lap shearing test is carried out by compression at a constant speed of 2 m m / m i n on an I N S T R O N 1121 compression device fitted with a measuring cell. The maximal resistance for this type of sollicitation ~bmoyis defined in equation 2 as qSmoy = F,~,x/A (2) the C = C band, at 1640cm I, is visible as well as a weak decrease of the carbonyl band, at 1720cm 1, used as an internal standard. This decrease of the carbonyl band can be ascribed to a slight spreading of the adhesive layer on the KBr windows during the cure, but also to a rearrangement of the absorption frequencies due to a loss of conjugation of the carbonyl bonds and the disappearing double bonds ~. However this phenomena does not seem to disrupt the obtained results. Figure 2 shows the evolution of the degree of cure of the anaerobic adhesive, in anaerobic conditions, as a function of time. The first part, of the curve recorded at 20C typically represents the reaction of polymerization in presence of inhibitive species which is called the induction period. Firstly, the active free radicals, due to the decomposition of the cumene hydroperoxide, are consumed at a finite rate by the pbenzoquinone molecules so that the initiation phase is completely hindered. Indeed, the inhibitors are known to be very efficient at r o o m temperature in the presence of oxygen ]5. Therefore, oxygen and inhibitor contained in our formulation can react with the free radicals able to be generated to form inactive radicals as shown in the following equations. R" + 02 =,, ROO" 80 70 =~ 60
P -,E 50 o
ii B

40

.Q
~ 20

0"~

i'::"
ooo

I ~

.....

~ _ _

50

100

150

Time (rain)
Figure 2 Degree of cure of the anaerobic adhesive during curing

reaction in anaerobic media at 65C, 50C, 35C, O 35C (in presence of oxygen), 20C.

where Fm,x is the charge applied expressed in N and A the surface of the bond. The samples were observed after rupture with a classical optical microscope in reflection (LEICA metallux 3) coupled with a colour video printer in order to define the faces of the rupture.

RESULTS AND DISCUSSION The infrared spectra obtained from the transmission measurements are shown in Figure 1. The decrease of
1.4

1.2

0.8

0 ,1~ 0.6

<

0.4

o,2j
0 1799 ---+-1761
I - -

O=:=~O

R"

R
1722 1684 1645 1606

Wavenumber (cm-1)
Figure I FT IR spectra o f an anaerobic adhesive during curing reaction at 35'~C in anaerobic conditions. The time is ranging from 0 to 60rain with an interval of 10min for each spectrum.

Thus, as long as p-benzoquinone can act as a radical scavenger by stabilizing the resultant free radicals, the initiating stage of the reaction remains at a very low rate. As soon as the inhibitor molecules became, for most of them, involved in chemical bonds with the first

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Influence of substrate on anaerobic adhesive: B. George et al.

free radicals, the polymerisation can proceed at a normal rate. Thus, about 50-75 minutes are necessary to consume the inhibitor at room temperature. Moreover, after that period, kinetics of the cure, characterised by the fast increase of ~, seems to be relatively unaffected by the very long induction period. This induction period decreases at higher temperature. The assumption of a higher rate of reaction of the free radicals with the inhibitors can be made. However, the assumption of a higher reactivity of the resultant radicals, towards the double bonds, at temperatures higher than room temperature, is also valuable. To go ahead in the kinetic treatment of this cure reaction, the order of the overall reaction of consumption of the vinyl functional groups ( > C - C < ) must be calculated. Therefore, the van't H o f f relation, in which the order of the reaction m is the slope of the straight line defined by equation 3 is applied. In v = A + m.ln(1 - c~) (3)

-0.2 .'~ -0.4 -0.6

-a -0.8

-1.2

20

40

60

T i m e (rain)
Figure 3 In (1-~t) plotted as a function of time. The slope is ascribed to the rate constant k. 65C, 50C, 35C.

70 60

gsoE ,o i
a 20 4

where v - r e a c t i o n rate, A = c o n s t a n t , r e = o r d e r of reaction, c~= degree of cure. This treatment leads to orders of 4 to 11 which are nearly equivalent to those calculated by Beaunez et al., 4 which are 3.5 for the propagation process and 5 for the initiation process. These reaction orders tend to decrease as temperature increases. In fact, these very high values may originate in the complex nature and the number of chemical species involved in the cure reactions. Unfortunately, these results do not allow the calculation of Arrhenius kinetic parameters such as activation energies. However, stating that the beginning of the reaction is of kinetic order 1 allows the calculation of the rate constants k. This can be done, by plotting ln(l - ~ ) as a function of time, the slope of the resulting curve provides the k value as shown on F i g u ~~ 3. The rate constants are, for the anaerobic cure, 1.2710 -2, 2.2210 -2 and 3.1810-2min -I at 35, 50 and 65C, respectively. Furthermore, the rate constants calculated, in aerobic conditions on metallic substrates, are 6.210 -3, 7.210 3 and 1.41xl0-2min i for aluminium, steel and copper respectively. The surface activity for the cure of the adhesive is then in the order copper > steel > aluminium. Moreover, the rate constant, of the aerobic cure of the adhesive, on copper is in the same order of magnitude as those obtained, for the cure of the bulk adhesive, in anaerobic conditions. Besides, at room temperature, we note that the reaction is only 55% completed after 3 hours and 65% after 16 hours. One hour of cure, in anaerobic conditions, allow the adhesive to reach a conversion rate of 42, 50 and 65, respectively at 35, 50 and 65C. Whatever the temperature, the system can not easily proceed further because, at these degrees of cure, the whole system is 'frozen' in a finite configuration which probably hinder the motions of macromolecular chains. I R microscopy has been used to follow the cure of the anaerobic adhesive on the metallic substrates. The results obtained are represented on Figure 4. The induction period, which was very important without

0;
0

I -

50

100 Time (min)

150

200

Figure 4 Degree of cure of the anaerobic adhesive depending on metallic catalysis. copper, aluminium AU-4G, steel XC 38.

any metallic contact, is no more visible and the degree of cure (c0 increases significantly until a threshold is reached which corresponds to the m a x i m u m value of conversion rate the system can achieve. Thus, the substrates increase the cure rate of the adhesive at the same level that the lack of oxygen does. This phenomena can be ascribed to the accelerating system which allows, in the presence of metallic cations, a synergistic speed up of the cure rate 5. Metallic ions are assumed to be complexed by the accelerator molecules and to catalyse, in such a state, the decomposition of the peroxide 16. It is noteworthy that the degree of cure is also largely dependent upon the nature of substrates as shown on Table 2. Indeed, copper is much more active than the two other substrates (1,5 times compared to steel and 2,5 times to aluminium) as already mentioned in the literature ~. Two different assumptions can be made according to the previous results. The first one is that the complexion of the three metallic ions leads to a
Table 2 Substrate Copper Steel XC38 Aluminium AU4G values of conversion rates depending on type of metals Conversion rate at t 59 1 381 244-1 150min (%)

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Influence of substrate on anaerobic adhesive: B. George e t al.

different catalytic activity. Thus, it has been shown by Yang m that this catalytic activity appears to be related to the redox potential of the metals in various oxidation states. The table of the redox potentials, taking into account the highest redox potential of the three studied metals, provides values which are 0.77, 0.52 and - 1 . 6 6 for the redox couples Fe2+/Fe, Cu +/ Cu and A I 3 + / A I , respectively 17. This order in the redox potentials can not be directly linked to the order of reactivity of the three surfaces which is Cu > Fe > A1. A second assumption, taking into account the availability of the surface ions is then formulated. Thus, the influence of the orthobenzosulfimid acid (i.e. saccharine) which is a constituent of the accelerating system of the adhesive was investigated. Indeed, some authors (', have shown that saccharine is able to oxidise metals throughout the oxidised layer and generate metallic ions because of its acidic character as follows.
Oxidation of metals by saccharin

Me

~,.

MeX~,nH20
x

-SO2
where M e = metal

Therefore, metallic ions formed, decompose the initiator and produce free radicals via a redox process. Polymerisation can then begin through a free radical mechanism. Figure 5 shows the results of atomic absorption spectroscopy and ionic chromatography performed on 10 2M ethanolic solutions of saccharin which have been brought into contact with the three metallic surfaces for 180 minutes. The pH of such a solution is 2.6 i.e. a bit more acidic than the commercial formulation which pH is about 3.6. Such an acid strength is, of course, expected to have a corrosive action on the metals. For all substrates immersed in pure ethanol, no ion concentration can be determined because the solvent does not oxidise copper, steel and aluminium for this interval of time. However, for solutions containing saccharin, a concentration of metallic ions can be detected. It can
3.5 :
!

"-"
E

3 2.5
2

be observed that copper ions are more rapidly available than iron ions or A13+ (as measured by ionic chromatography) when the substrate is allowed to interact with the solution. Indeed, the acidic character of saccharine oxidises the substrates in the following order C u > s t e e l XC38-_aluminium AU4G. This sensitivity to the oxidation, which increases the availability of ions at the surface, greatly affects the cure speed of anaerobic formulations. This may be one of the main reasons why the curing rate is much greater on copper than on steel and aluminium. Does any correlation exist between kinetics of polymerization and the mechanical performances? By observing the results from Table 3, we note that the maximal strain ~ recorded in the case of copper is very low (3,92 MPa only) and the rupture is 100% cohesive type in the adhesive. Very fast curing kinetics result in the formation of a polymer network not homogeneous all along the bondline: at the interface adhesive/metal, the reaction is favoured and the polymer is formed of very short macromolecular chains tightly crosslinked. In the joint itself, the density of network decreases slightly since movements of chains is progressively hindered. The strains r recorded for the samples with steel and aluminium are nearly of the same order (11,54 and 9,23MPa, respectively) and about twice greater than the value concerning copper samples. Since the curing reaction proceeds slower on these two substrates, we can assume that a more homogeneous polymer network with a lower crosslinking density is achieved. Our assumption can be related to the Figure6. The photographs ( G - 7 0 times) which represent the surface of the adhesive after the test was performed highlight different types of rupture. On copper, the rupture appears to be brittle whereas on aluminium or steel, the rupture is more ductile, indeed the density of ripples in the testing direction is much more greater for the former case compared to the latter. Polymer cured on aluminium and steel samples can store more energy before rupture because its network is flexible. Consequently, the rupture occurs in the zone of elastic deformation for copper samples and in plastic zone for aluminium or steel samples respectively as shown on Figure 7. We saw that very fast kinetics of polymerization do not induce very high mechanical performances but the contrary is not necessarily true. As a matter of fact, the higher performances are recorded for steel for which the reaction of polymerization proceeds nevertheless

0 m

.o 1.5
1 E '-'0.5
0 --

" 1~

Table 3 Mechanical performances of the adhesive no metallic substrates.F= strength applied, A = adhesion area, r = maximal strain
l |
~

I
~

,
-~ I

Fmean (daN)

A(cm2)

r(Mpa)

50
Time

100
(rain)

150

200
Copper Steel XC38 Aluminium AU4G 113.5i4.0 202.0-1-5.4 219.0~26.2 2.88 1.75 2.37 3.94 11.54 9.23

Type of rupture (% cohesive) 100 (in adhesive) 70 60

Oxidising action of an ethanolic solution of saccharin 10-2M on copper, aluminium AU-4G, steel XC38, (x corresponds to references)
Figure 5

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Influence of substrate on anaerobic adhesive: B. George et al.

adhesive / copper

250

200
Z

.~ 150

i1

100

50

t
0.1 0.2 0.3 0.4

adhesive / aluminium A U4G

Deformation (ram)
Figure 7 Strains recorded as a function of the relative deformation.at copper, aluminium AU-4G, steel XC38.

adhesives. From the results provided by this technique and a shearing single-lap test, the role of metallic catalysis on curing kinetics of a same anaerobic adhesive applied on copper, steel and aluminium has been highlighted. Our results seem to show that a tight relationship exists between cohesive properties and kinetics of polymerization which is dependent upon interactions between formulation and substrates. A (too) fast reaction results in samples with poor mechanical properties (case of copper).

adhesive / steel XC38

REFERENCES
1 2 3 4 5 Gross, A. and Hennemann, O.D. Adh{&ion 1992, 36(9), 3 5 38. Stamper, D.J. British Polymer Journal 1983, 15, 34 39. Hartshorn, S.R., in Structural adhesives, chapter 7, New York and London, Plenum Press, 1986. Beaunez, P., Helary, G. and Sauvet, G. J. Polym. Sci., Polvm. Chem. 1994, 32, 1459. Odian, G., in Principles of Polymerization+ 2nd ed., Wiley, New York, 1981. Yang, D.B. Applied spectroscopy 1993, 47(9), 1425 1429. Okamoto, Y. J. Adhesion 1990, 32, 227. DourneL P., Thesis of the Bordeaux 1 University, 1990. Wellman, S. Brockmann, H. Int. J. Adhesion Adhesives 1994, 14+ 47. Yang, D.B.J. Adhesion 1993, 43, 273. Yang, D.B., Wolf, D., Wakamatsu, T. and Holmes, M. J.Adhesion Sci. Technol. 1995, 9, 1369. Rich, R.D., in Handbook of Adhesive Technology, M. Dekker, New York, 1994. Lal, J., US patent 2,833,753 (1955) and Yang, D.B., (Loctite), US patent 5, 126,416 (1992). Krieble, V.K., (Loctite), US patent 3+218,305, (1965).. Alger, M.S.. in Polymer Science Dictionary, Elsevier, London. t 990. Humphreys, R.W.R., in Adhesive Chemistry, Plenum Press, New York, 1984. CRC Handbook of Chemistry and Physics, 66TM Edition, CRC press, Florida, 1986.

Figure 6 Profiles of rupture for the adhesive cured on the three

substrates.

6 7 8 9 10 11 12 13 14 15 16 17

faster than on aluminium. Besides, the type of rupture (% of cohesion) shows that adherence on steel is higher than on aluminium. It is possible that the superficial characteristics of substrates as surface energy for example have to be taken into account in order to explain these differences. CONCLUSION The infrared microscopy appeared to be a valuable technique to analyse the polymerization of

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