Composites: Part A 31 (2000) 959968 www.elsevier.

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Complete system monitoring of polymer matrix composites

F.J. Johnson a, W.M. Cross a, D.A. Boyles b, J.J. Kellar a,*
a

Department of Materials and Metallurgical Engineering, South Dakota School of Mines and Technology, Rapid City, SD 57701-3995, USA b Department of Chemistry and Chemical Engineering, South Dakota School of Mines and Technology, Rapid City, SD 57701-3995, USA Received 20 July 1999; received in revised form 6 February 2000; accepted 23 February 2000

Abstract In situ, real time analysis of the chemical interactions occurring within the interphase of berglass ber-reinforced polymer matrix composites (PMCs) has been accomplished through utilization of ber optic sensors. The ber size, as well as the composition of the thin cladding, closely approximates industrial berglass bers, which allows the bers to function simultaneously as model ber-reinforcements and evanescent wave sensors. Using this sensor technology, the current research has shown that reactions occurring between the ber surface, adsorbed silane coupling agent, and polymer can be monitored using FT-NIR spectroscopy. Two PMC systems have been chosen to demonstrate the ability to monitor complex interphase chemistry in situ and in real time. 2000 Elsevier Science Ltd. All rights reserved.
Keyword: Interphase

1. Introduction The region adjacent brous reinforcements in polymer matrix composites (PMCs), referred to as the interphase, is thought to have properties unlike those of either the matrix or the reinforcement [1]. Therefore, a need exists for an improved understanding of the chemical interactions and mechanical properties of this region. With regard to the former, molecular-level monitoring of PMC interfacial reactions involving bers, adsorbed species (such as silane coupling agents), and a polymer matrix (monomer and curing agent), has recently been accomplished in our laboratories [2]. Previously, such analyses were considered nearly impossible for a number of reasons. First, few analytical methods are available that allow in situ measurements in such a relatively small, highly localized region. Evidencing the small scales involved, recent atomic force microscopy measurements have shown that for a carbon ber-reinforced polyphenylene sulde system, the interphase region is on the order of 2080 nm [3]. Similarly, recent nano-indentation and atomic force microscopy (phase imaging) results from our laboratories (see Fig. 1) suggest the existence of a modulus gradient throughout the interphase region adjacent glass bers in an epoxy matrix; this gradient is less than 1mm in thickness [4]. Second, given the relatively low concentration of the adsorbed coupling agent (usually submonolayer to several monolayers of adsorbed material) in
* Corresponding author. Tel.: 1-605-394-2341; fax: 1-605-3943369.

relation to the monomer and curing agent concentrations, discriminating between distinct signals from each constituent is difcult. For this reason, most analytical methods do not have adequate sensitivity for the detection of coupling agent reactivity concurrently with monomer/curing agent reactivity. Infrared evanescent wave spectroscopy, alternately called attenuated total reectance spectroscopy, has proven capable of monitoring various aspects of interphase chemistry. For example, numerous researchers have employed this method to monitor monomer and/or curing agent reactivity, utilizing a high refractive index crystal or ber to allow propagation of the evanescent wave into the polymer phase [510]. Use of a high refractive index substrate is necessary because the evanescent wave sampling method requires the refractive index of the sample (in this case the polymer) be less than that of the material in which internal reection occurs (crystal or ber). For example, Connell et al. [10] used fused silica glass bers as evanescent wave sensors to monitor the organofunctional reactivity of an amino-silane with a partially uorinated epoxy monomer. The uorination of the epoxy lowered the monomer refractive index, allowing the use of the relatively low refractive index fused quartz ber as an evanescent wave sensor [10]. Such an approach works well for analysis of monomer and/or curing agent reactivity. However, monitoring of adsorbed coupling agent reactivity concurrently with monomer/curing agent reactivity via evanescent wave analysis is problematic. Specically, the high refractive

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Fig. 1. Image of a DJ ber with nano-indentations in the interphase region.

index materials commonly employed (high lead content oxides, sapphire, chalcogenide or selenide glasses) do not mimic the substrate chemistry of oxide glasses used industrially. The composition of the ber is relevant because previous work indicates that substrate effects can signicantly inuence composite properties [11,12]. For example, previous work suggests that quartz exhibits much different bonding characteristics when exposed to a silane coupling agent than either glass or alumina [11]. Furthermore, because sapphire, chalcogenide or selenide bers (traditional high refractive index bers used for evanescent wave analysis) are not used as reinforcements for polymer matrix composites, their utilization, from a substrate-specic surface chemistry perspective, can be considered irrelevant. Substrate-specic interactions are important when considering the mechanisms associated with coupling agents; i.e. silane coupling agents can be represented by the general structure X3SiRY, where X is a readily hydrolyzable functional group, and Y an organofunctional group [1,13]. These compounds, when applied as surface treatments to the reinforcement, have been widely recognized to improve overall strength and modulus, as well as hygrothermal stability of glass ber-reinforced polymer matrix composite. With regard to silane coupling agent chemistry, the earliest molecular rationale for coupling agent performance was predicated on several seemingly logical assumptions, including: 1. a chemical reaction of the organofunctional group, Y, with reactive organic functionality of the resin (e.g. reaction of the amino moiety of aminofunctional silanes with the oxirane ring of epoxy resins); 2. condensation/oligerimerization between adjacent adsorbed silanol groups; and 3. the chemisorption of the coupling agent (through condensation of silanol groups with surface hydroxyl groups) to the glass surface. Numerous studies with organofunctional silanes have

demonstrated that assumptions (2) and (3) are correct [1215]. However, direct in situ evidence of organofunctional reactivity, as specied in (1) above, has been elusive due to the sampling problems delineated previously. Assumption (1) serves as the basis for the chemical bonding theory, as described by Plueddemann [13] and Ishida [16]. Plueddemann [13] suggests that the X groups of the silane are hydrolyzed in water, after which the OH groups react with the hydrated glass surface, forming a chemisorbed layer of silane via SiOSi bonds. Coupled with the reaction in (1), the silane can be said to have formed a chemical bridge between the matrix and the reinforcement. In addition, Ishida [16] describes the existence of physically adsorbed (physisorbed) silane molecules in the outermost layers of the silane interphase. These molecules are held in place through weak van der Waals forces, as well as through hydrogen bonding to adjacent OH groups on the silanols [16]. An analysis of the chemical reactions occurring at the interphase is necessary to determine the efcacy of these theories. Such an analysis should ultimately lead to improved understanding and/or modication of the behaviors and properties of glass ber-reinforced PMCs. Ideally, to monitor the interphase chemistry of an oxide berglass PMC via evanescent wave spectroscopy, an internal reection element (IRE) possessing surface chemical properties closely approximating those of berglass should be employed. However, most silicon-based oxide glasses have refractive indices in the range 1.451.51 [17], which are lower than those of most polymers; therefore, evanescent wave sensing of polymer chemistry through such glass IREs cannot occur. Thus, monitoring complete interphase chemistry (coupling agent/monomer/curing agent) by utilization of common oxide glasses and evanescent wave spectroscopy would seem to be impossible. In fact, due to sensitivity problems associated with adsorbed silane coupling agent monolayers, investigations of their reactivity have been limited. A noteworthy exception is the work of Nishio et al. [14], which involved the chemisorption and oligimerization of the silane headgroup

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Fig. 2. General chemical structures of complete composite system components.

to a soda-lime glass microscope slide. The slide served as both substrate and internal reection element; however, only glass/silane reactivity was monitored (items 2 and 3 given earlier), i.e. no monitoring of polymer interphase chemistry was reported. Presumably, interphase analysis (with the polymer present) was not performed in this study, due to the aforementioned refractive index problem. Another example of interphase analysis is the work of Johnson et al. [2], who used thin-clad optical bers to perform a qualitative analysis of an adsorbed silane coupling agent/epoxy-amine polymer system. The bers, obtained from Dolan-Jenner, Inc. (DJ), consisted of 25mm diameter int-glass core with an 1-mm thick sodalime cladding. Thus, the diameter of the DJ bers was close to that of industrial berglass bers. In addition, these bers were advantageous as internal reection elements because the high refractive index int glass core n 1:62 allowed evanescent wave sensing, while the soda-lime cladding (which serves as the substrate) was thin enough to allow extension of the evanescent wave into the polymer phase [18]. Furthermore, the composition of the cladding was 74% SiO2 (with other oxides), which is similar to industrial E-glass bers commonly used in berglass reinforced PMCs. The ber sensors were used in both a silane/epoxy/amine system and silane/epoxy/aniline system. This work illustrated the utility of the DJ bers to allow simultaneous monitoring of the silane and epoxy/ hardener reactivity, a feat of which most analytical methods

have not proven capable. However, in each epoxy/hardener system examined, the primary NIR amino band of the hardener either masked or overlapped that of the adsorbed silane [2]. Therefore, research efforts herein were directed toward development of a system in which the relevant NIR amino bands of the adsorbed silane and the hardener, as well as a band attributable to the epoxy, could be monitored simultaneously without any overlap or masking of the individual bands. In addition, a polyester polymer/silane system was examined, to illustrate the ability of the ber sensors to monitor multiple PMC systems in a complete manner.

2. Experimental The DJ bers were tested as evanescent wave sensors through a number of experiments, which were performed on bundles of approximately 250350 bers. Each experiment was monitored in the near-infrared (NIR) using a Biorad Digilab FTS-40A Fourier transform infrared (FT-IR) spectrometer. Complete experimental details can be found elsewhere [2]. Initially, optimum ber bundle thickness and length were established to maximize sensitivity. Bundles of DJ bers from 10 to 30 in. in length and 100450 bers (per bundle) were examined. A back-ground single-beam spectrum (1024 scans) was collected, after which the bundles

962 Table 1 Relevant NIR bands for PMC cure monitoring Constitutent g-Aminopropyltrimethoxysilane (g-APS) Epon 828 Methyl-5-norbornene-2,3-dicarboxylic anhydride (NMA) Imidazole Polyester monomer/styrene mixture Methyl ethyl ketone peroxide (MEKP)

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Relevant bands 4930 cm 1 4530 cm 1 4830 cm 1 None present 4493, 4721, 6137 cm 1 4783 cm 1

were placed in aqueous 5 wt% g-aminopropyltrimethoxysilane (g-APS) solution for 1 h, dried at 75C for 1 h, and immersed in Epon 828 (Shell Chemical Co.). The variables examined in the optimization process included length of the transparent region (i.e. the wavelength region over which the NIR signal is not absorbed by the bers) and noise, especially near the wavelength region where the ber bundles are no longer transparent. Previous X-ray photoelectron spectroscopic (XPS) analyses indicated signicant contamination on the surface of the as-received bers [19]. Therefore, prior to complete composite monitoring, the ber bundles were rst cleaned for approximately 1015 min in NoChromix, a sulfuric acid-based cleaning solution, to remove contaminants. The bundles were then rinsed several times with distilled water. The clean bers were dried for 1 h at 75C, then cooled to room temperature over approximately 1 h. The curing agent chosen for the Epon 828 epoxy system was methyl-5-norbornene-2,3-dicarboxylic anhydride (NMA, Aldrich Chemical Company, Inc.), with 0.5% imidazole initiator (Avocado Research Chemicals, Ltd.). The second polymer matrix was a polyester monomer/styrene mixture with a methyl ethyl ketone peroxide (MEKP) initiator (Dynatron/Bondo corp.). The coupling agent used in both systems was g-APS; these systems are both of industrial relevance [20]. The formulae of the constituents of these systems are shown in Fig. 2. The concentration of g-APS in aqueous solution treatment of the DJ bers was either 1 or 2 wt%. Once the ber optimization process (number/length) was completed, clean ber bundles were used to collect spectra of the individual neat constituents on the bers. A background spectrum of each clean bundle was collected (resolution 16 cm 1, 1024 scans). The spectra were collected by ratioing 512 co-added scans against the background spectrum. The bers were immersed in the desired constituent and a spectrum collected at room temperature. A spectrum of powdered imidazole was obtained through diffuse reectance FT-IR (DRIFT) spectroscopy. The remaining bundles were treated with silane and then placed in either the epoxy or the polyester system and subjected to cure monitoring. The ber bundles used with the epoxy system were immersed in an aqueous 1-wt% g-APS solution at room temperature for 1 h, dried at approximately 115C for 1 h, and cooled to 93C. A spectrum of the adsorbed silane on

the dried bers was then collected. The treated bers were placed in a 100:90 Epon 828/NMA mixture, with 0.5% imidazole added as an initiator. The mixture was contained in an insulated aluminum curing cell, and maintained at 93C using a Harrick Scientic temperature controller. After 1 h, the temperature was increased over a period of approximately 10 min to 115C. The spectra were then collected every 20 min for 2 h. After approximately 17 h, a nal spectrum of the cured composite was collected at 115C. The ber bundles used with the polyester system were treated with an aqueous 2-wt% g-APS solution for 1 h, dried at approximately 115C for 1 h, and cooled to room temperature over 12 h. A spectrum of the adsorbed silane on the dried bers was collected, after which the bundles were placed in 3 oz of a polyester monomer/styrene mixture with 2 ml MEKP initiator added, and cured at room temperature. The spectra were collected every 10 min over the rst two hours; the polymer was cured for approximately 17 h, after which a nal spectrum was collected.

3. Results and discussion With respect to transparent region versus ber bundle length, lengths approximating 30 in. were found to provide a shorter region of transparency than those of shorter lengths, as the IR light was lost through the length of the bers. Of particular importance is the loss of signal around the lower energy end of the spectrum; i.e. signal loss occurred prior to 4600 cm 1. Since the desired epoxy band for cure monitoring, given in Table 1, is at 4530 cm 1, lack of a signal in this region makes monitoring of the band nearly impossible. Conversely, those bundles with lengths approximating 10 in. provided sufcient signal for monitoring of all desired bands. When comparing signal intensity versus ber bundle length, longer bundles were found to have lower signal intensities than shorter bundles. However, the high signal intensity around 4530 cm 1 in 10-in. bundles resulted in large absorbance values of the epoxy band; this high absorbance often tended to dwarf the relevant silane band occurring at 4930 cm 1. Based on these observations, the optimum ber bundle length was determined to be 24 in. Sensing region length was not found to have a relationship to bundle thickness. However, the signal-to-noise ratio tended to increase with thickness. Specically, bundles of 100 bers or less had low signal intensities, so that monitoring changes associated with bands related to curing reactions was difcult. Bundles containing 450 bers had high signal intensities, but once again the resulting absorbance of the relevant epoxy band tended to dwarf that of the relevant g-APS band. Therefore, bundles of 300350 bers were chosen as the optimum quantity. Table 1 lists the relevant bands for each constituent in the

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Fig. 3. 1 wt% gamma-APS absorbed on DJ bers.

PMC systems analyzed. A spectrum of adsorbed g-APS (1 wt% solution) on the DJ bers is shown in Fig. 3. The band at 4930 cm 1 can be attributed to the NH2 bendingstretching combination of the g-APS [14]. Individual spectra of Epon 828, NMA, imidazole, polyester resin, and MEKP initiator are shown in Figs. 48.

In Fig. 4 (Epon 828), the band at 4530 cm 1 can be attributed to the CH2 bendingstretching combination of the epoxide ring; this band should decrease with curing of the polymer [2123]. The band at 4830 cm 1 in Fig. 5 (NMA) is used for identication of the presence of the curing agent. In Fig. 7, the bands at 4493 and 4721 cm 1

Fig. 4. Spectrum of Epon 828.

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Fig. 5. Spectrum of methyl-5-norbornene-2,3-dicarboxylic anhydride.

are assigned to HCyCH bendingstretching combination of the polyester monomer, and the band at 6137 cm 1 is the rst overtone of the CH stretching of the yCH2 of the styrene [24]. Because the reaction of styrene with the polyester results in the elimination of the double bonds [25], these bands were used to monitor the reactivity of the

mixture. The band at 4783 cm 1 in Fig. 8 is used to monitor the reactivity of the MEKP initiator. Figs. 9 and 10 are spectra of the complete epoxy system at 93C (initial) and 115C (nal), respectively. In Fig. 9, the bands at 4930 cm 1 (g-APS), 4830 cm 1 (NMA), and 4530 cm 1 (Epon 828) are clearly visible; i.e. none of the

Fig. 6. DRIFT spectrum of imidazole initiator.

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Fig. 7. NIR spectrum of polyester monomer/styrene mixture.

bands are overlapping or masking the others. The bands at 4530 and 4830 cm 1 are seen to decrease considerably after curing. This decrease is assumed to be due to the reaction of the epoxy and curing agent. The band at 4930 cm 1 does not observably decrease, suggesting little reaction has occurred

between the g-APS and the polymer constituents. Regarding the spectrum of the imidazole initiator in Fig. 6, no bands are visible in the regions where the aforementioned constituent bands are present; therefore, the initiator should not interfere with monitoring of the epoxy PMC system.

Fig. 8. NIR spectrum of MEKP initiator.

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Fig. 9. Spectrum of complete epoxy system before curing.

Figs. 11 and 12 are spectra of the complete polyester system before and after curing, respectively. Again, Fig. 11 clearly shows the amino band of the g-APS at 4930 cm 1. In addition, the bands at 4493, 4721, and 6137 cm 1, all of which can be attributed to the polyester monomer mixture, are also present. The band at 4783 cm 1,

which identies the presence of the MEKP initiator, is small, due to the small quantity used. In Fig. 12, this band, as well as the relevant polyester bands, has decreased signicantly. As with the epoxy system, the relevant g-APS band is still present, suggesting a lack of silane organofunctional reactivity with the polymer.

Fig. 10. Spectrum of complete epoxy system after curing.

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Fig. 11. Spectrum of complete polyester system before curing.

As discussed previously, in situ analysis of a complete composite system has hitherto not been reported. The resultant ability to differentiate the individual components is signicant because the reactivity of these constituents can now be monitored using NIR evanescent wave spectro-

scopy, both in situ and in real time. Ultimately, using this approach, a more complete understanding of the chemical reactivity at the interphase can therefore be established, and, more specically, the degree of organofunctional silane reactivity determined. Furthermore, this approach will

Fig. 12. Spectrum of complete polyester system after curing.

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allow the role of silane treatments on bulk polymer curing to be ascertained. 4. Conclusions

and CMS-9900383. The authors would also like to thank Mr Travis Downing for providing the Hysitron image.

References Previous work in our laboratories has resulted in the development of a system that utilizes a thin-clad optical ber bundle as an FT-NIR evanescent wave sensor. The system approximates those of industrial berglass-reinforced composites. Study of the reactivity of coupling agent, polymeric monomer, and hardener requires that each constituent have an NIR reactive band separate from the reactive bands of the other system components. Therefore, a system was established whereby each constituent was discernable. Specically, the hardener, methyl-5-norbornene-2,3-dicarboxylic anhydride, was chosen to combine with the bisphenol-A epoxy and aminosilane coupling agent. Subsequent FT-NIR evanescent wave examination showed each constituent was separate and discernable from the others. In addition, another complete polymer system consisting of an aminosilane coupling agent, polyester monomer mixture, and MEKP initiator, was monitored, to illustrate the ability of the ber sensors to be used in a variety of PMC systems. The signicance of these results rests in the ability to monitor the reactivity of complete composite systems, both in situ and in real time. This system is the rst to not only approximate that of a real composite (berglass-reinforced polymer), but to allow for analysis of the reactivity of each constituent during the curing process; this is an important rst step in the development of an understanding of the chemical reactivity within the interphase region, which is important industrially for engineered modication of reinforcements which maximize the desired properties at the interphase within a composite system. Future work will entail system monitoring at aqueous silane treatments of less than 1 wt% (such as 0.5 wt%), which would more closely approximate concentrations employed industrially. In addition, an investigation of organofunctional reactivity will be conducted to determine potential silane reactivity. Acknowledgements Support for this work was provided by the National Science Foundation (NSF) under Grants # CMS-9453467
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