Composite Interfaces. Vol. 4. No. 5. pp. 337-354 (1997) © VSP 1997. The role of chemical bonding and surface topography in adhesion between carbon fibers and epoxy matrices L. T. DRZAL,* N. SUGIURA and D. HOOK Departments of Chemical Engineering and Materials Science and Mechanics, Composite Materials and Structures Center, Michigan State University, East Lansing, Michigan 48824-1326, USA Received 3 November 1996: accepted 6 January 1997 Abstract—A series of PAN-based IM6 carbon fibers which were surface treated to different levels with a commercial method were pretreated with compounds representing the constituents encountered in epoxy matrices used in composites. This was done to pre-react any groups on the fiber surface with these com- pounds before composite fabrication in order to determine the effect of chemical bonding on fiber—matrix adhesion. The extent of chemical bonding was quantified using X-ray Photoelectron Spectroscopy (XPS). Chemical bonding between reactive groups in amine cured epoxy matrices and the surface groups present on these IM6 carbon fibers has been determined to be low (1-3%). Pre-reaction with the monofunctional epoxy compound (butyl glycidyl ether) eliminated the possibility of further reaction with the epoxy matrix and the fiber~matrix adhesion that was measured was the lowest value. Pre-reaction with the difunctional amine compound had no measurable effect on adhesion when compared to normal composite fabrication procedures. Pre-reaction with the difunctional epoxy compound however did increase adhesion levels over that attained without any pretreatment encountered in normal composite fabrication methods. These results showed that when compared to physical interactions between the fiber surface and the epoxy ma- trix alone, chemical bonding between the epoxy and the carbon fiber surface could increase the adhesion between fiber and matrix by about 34% while chemical bonding between the amino group and the carbon fiber surface can increase adhesion by about 18%. Quantitative measurements of the fiber surface microtopography were made with scanning twnneling microscopy. A systematic increase in the nanoscale topography (roughness) of the fiber surface was detected with increasing surface treatment, When quantified, it was concluded that surface roughness similarly accounted for a significant increase in fiber-matrix adhesion. Overall, it was concluded that the addition of the surface chemical groups that react with the matrix and are produced during surface treatment are added on a surface that is increasingly rougher. Both effects combine synergistically to increase fiber~ matrix adhesion. Keywords: Adhesion; chemical bonding; carbon fibers; epoxy; interface: fiber—matrix adhesion: fiber topography; roughness. “To whom correspondence should be addressed,1. INTRODUCTION In the course of the development of surface treatments for carbon fibers to improve their adhesion to epoxy matrices, various approaches have been developed which have been proposed to alter the surface chemistry and fiber surface structure simulta- neously. Studies have been published which have established dependencies between fiber—matrix adhesion and surface oxygen content [1, 2], surface acid/base charac- ter [3], chemical bonding [4] and surface roughness [5]. Excellent reviews of this area are available by Donnet and Bansal [6] and Peebles [7]. In each of these studies systematic, well-controlled experiments were conducted using model compounds and conclusions were primarily directed at elucidating one primary mechanism of interac- tion thought to be responsible for all of the adhesion improvement that was detected in these systems. In an electron microscopic investigation of the carbon fiber-epoxy system as a function of the type of electrochemical surface treatment, Guigon [8] found that the external surface microtexture played the most important role. For high strength fiber it was found that the surface texture was on the order of |—-2 nm. Fiber pull-out tests did not correlate with the microtexture determined by transmission electron microscopy however. Harvey et al. [9] investigated anodization as a surface treatment for carbon fibers and fabricated high fiber volume fraction composites with an epoxy matrix. Although the detected significant changes in the oxygen-to-carbon ratios on the sur- faces of these fibers, the interlaminar shear stress measured on the composites did not show a dependency on surface chemical composition, They concluded that mechani- cal keying is the important mechanism although they did not conduct measurements of either fiber surface area or fiber topography. Bader et al. [10] investigated the effect of commercial wet oxidation methods on PAN-based carbon fibers at 0%, 10%, 50% and 100% surface treatment. Oxygen and nitrogen surface concentrations, polar and dispersive components of the fiber surface energy, active site concentration all increased with surface treatment levels. However, the fiber surface area and the active site concentration decreased with surface treatment levels. Single fiber fragmentation tests for measuring fiber—matrix adhesion to epoxy matrices showed that there was a systematic increase in adhesion with surface treatment and most composite mechan- ical properties increased but it was not possible to draw definitive conclusions about the possible mechanisms. A thorough study of the differences in the structural sur- face features of carbon fibers was conducted by Donnet and Qin [11] using scanning tunneling microscopy. Large scale effects detected included an axial ribbon structure that changed with different precursors. At atomic scale resolution, different types of graphitic organization were detected which vary with the Precursor. Quantitative changes in surface area or topography were not made however. Madhukar and Drzal in a series of papers [12-15] compared surface treated with untreated PAN based carbon fibers in an epoxy matrix. Interfacial shear strengths showed increases in fiber—matrix adhesion to epoxy matrices which corresponded with surface chemical changes and increases in composite properties in shear dominated directions. Recently additional studies were conducted [16] on an IM6 carbon fiber surface treated to 20%, 100%, 200% and 600% of commercial anodization levels and also found a systematicincrease in oxygen and nitrogen functionality and fiber surface energy as well as the polar component of the fiber surface free energy. Single fiber fragmentation testing of the adhesion of these fibers to an epoxy matrix showed a corresponding increase in interfacial shear strength. Composites made from the identical fiber and epoxy matrix components, however, showed an increase in shear and transverse properties for 60% fiber volume composites up to the 20% level and then no further increase up to the 600% surface treatment. Mode II fracture toughness, however, increased with all surface treatment levels. Sawada et al. [17] characterized PAN-based carbon fibers with surface oxygen content by XPS and Raman peak intensity ratio, surface acidic groups and active surface area ratio (i.e. the amount of oxygen chemisorption divided by the krypton surface area) and found that the active surface area ratio correlated best with composite interlaminar and transverse tensile strengths. Some variation was noted depending on the fiber precursor. Overall, while both surface functionality and topographical changes have been identified as responsible in some manner for an increase in fiber matrix adhesion, the exact mechanism has not been defined. 2. PREVIOUS RESULTS. Earlier work has shown that there may be an interdependency of mechanisms with changes in adhesion being the net result of the interplay between many factors si- multaneously. Indeed both surface energetic and surface chemical effects have been shown to have an effect on fiber matrix adhesion. The results of the XPS surface analysis for the same series of IM6 fibers with increasing oxidative surface treatment are plotted in Fig. 1 (surface oxygen percentage and surface nitrogen percentage). Surface nitrogen percentages measured by XPS also appear in Fig. 1. The reasons for the initial large increase in surface oxygen with the first surface treatment step 20 5 IM6 Carbon Fibers 16 : } | 4 z x G 12 3z g Z x 3 ° ° - 3 26 * 3s Zz 4 1 0 0 0 100 200 300 400 500 600 Percent Surface Treatment Figure 1. Surface oxygen and nitrogen contents as determined by XPS analysis.(20%) are not entirely clear. The probable explanation rests in the coupling of the surface treatment mechanism with the carbon fiber structure. The native fiber surface present on the IM6-0% is one that has seen the chemical changes and the structural rearrangement of the polyacrylonitrile precursor to a carbon fiber. That surface is removed by the surface treatment leaving behind a defect free surface to which is added surface functional oxygen and nitrogen groups. The sites for these functional groups are most probably at the edges and corners of the crystallites. A linear increase in oxygen content is observed after the 20% surface treatment until 600% and may result from the availability of a more uniform surface on which the sites susceptible to oxygen reaction attachment are generated in a more regular manner than on the untreated fiber after the initial removal of the native fiber surface: 2.1. Surface free energy measurements The surface free energy of the fibers is plotted in Fig. 2. The polar component of the surface free energy increases significantly with increasing surface treatment in the increments from 0% to 20% surface treatment and from 200% to 600%. Negligible change occurs between 20% and 200% surface treatment. The dispersive free energy undergoes little change with increasing surface treatment, aside from small decreases between 0% and 20% and between 200% and 600%, the same increments that produce large increases in the polar component. These changes closely follow the pattern of changes in surface oxygen percentage as determined by the XPS analysis of the surface shown in Fig. 3. Taking the untreated fiber, IM6—0%, as the baseline, increases in surface treatment conditions result in both an increase in surface oxygen as well as an increase in the polar component of o °o 40 30 20 DISPERSIVE IM6 Carbon Fibers Surface Free Energy (mJ/M’) 0 100 200 300 400 500 600 Percent Surface Treatment Figure 2. [M6 carbon fiber surface free energy as determined by polar/dispersive analysis of contact angle data2 POLAR SURFACE FREE ENERGY (mJ/M_ ) a ° IM6 Carbon Fibers [M6 600% 40 30 IM6 100% ms 20% Yb ms 200% 20 0 4 8 12 16 20 SURFACE OXYGEN PERCENTAGE Figure 3. Relationship between surface oxygen content and polar component of fiber surface free energy. the surface free energy. Apparently the surface oxygen groups are also in a molecular state that causes them to act as a ‘polar’ addition to the surface. A similar observation was made with AS and HM carbon fibers earlier [1]. The following model of the fiber surface and its changes with surface treatment emerges from the above surface analyses of IM6 carbon fibers. Before the surface treatment, the IM6 carbon fibers are encased in a thin ‘skin’ of graphitic carbon with a surface mostly composed of unreactive, basal-plane atoms. Some reactive sites exist at the edges of segments of this graphite ‘mosaic’ [6, 18]. With initial oxidative surface treatment, this native surface is etched away exposing subsurface layers and attacking edges and interstices between graphitic basal planes. Further surface treatment continuously erodes this skin, but does not substantially increase the number of available chemisorption sites. It has been reported that oxidation occurs at the corners and edges of graphitic crystallites and not on the basal plane. This results in an approximately linear increase in surface oxygen and nitrogen content as well as a constant value for the surface free energy components. 2.2. Fiber-matrix interfacial shear strength The results of the single fiber fragmentation interfacial shear strength tests show an increase in interfacial shear strength with surface treatment time. As expected, the untreated IM6~—0% fibers showed very poor adhesion, with an interfacial shearstrength (ISS) of 37 MPa. Adhesion improved substantially with the 20% surface treatment, increasing to 66 MPa. Surface treatment to 100% of the nominal value further improved adhesion, but by a smaller amount than for the step from 0% to 20% to 70 MPa. Treatment to 200% again increased adhesion to 86 MPa. Surface treatment at the 600% level increases the interfacial shear strength to still higher levels. The IM6-—600% fiber exhibits ar erfacial shear strength of 115 MPa. This is the highest value measured for this series. 2.3. Relationship between interfacial shear strength and fiber surface properties It has been shown that the increasing amount of oxygen functionalities added to the IM6 fiber surface with increasing surface treatment conditions was linearly related to an increase in the polar component of the surface free energy and the total surface free energy of the fiber surfaces. When these parameters characteristic of the fiber surface are plotted as a function of the interfacial shear strength, a direct relationship can also be seen. Figure 4 is a plot of both the polar component of the surface free energy as well as the surface oxygen percentage as a function of the measured interfacial shear strength. It is obvious that the changes in the surface properties of the fiber strongly affect the measured interfacial shear strength. This result has been reported by Schultz er al. [19] for carbon fibers as well as various matrices. The mechanistic explanation for this dependency is not obvious however. Certainly, the contact angle and therefore the surface energy of the fiber surface is enhanced with the increasing surface treatment time. It is well known that the thermodynamic work SURFACE OXYGEN PERCENTAGE o 2 4 6 6 1 12 14 16 18 20 “0 ™M60% 30 Weak Frictional 20 @ 130 a IM6 Carbon Fibers = 12 E 100 Z Z 0 m% & 80 a 4 1 IM6 100% a M6 20% 60 a Moderate 50 Interfacial 3 5° < by 2 r=) & z o 10 20 30 40 50 2 POLAR SURFACE FREE ENERGY (mJ/™M ) Figure 4. Relationship between carbon fiber surface oxygen content, polar component of the carbon fiber surface free energy and fiber-matrix adhesion as measured by the single fiber fragmentation testof adhesion is strongly related to the measured value of adhesion in situations where the dissipative mechanisms do not play a significant role. However, in this system where the components of the epoxy matrix are potentially reactive with the chemical groups on the carbon fiber surface, it is not clear that the thermodynamic work of adhesion is solely responsible for the measured level of interfacial shear strength. The magnitude of the interfacial free energy changes related to the increases in fiber surface free energy are expected to be small, however, and would not be expected to be a significant factor in increasing the interfacial shear strength. The possibility of chemical reaction between the oxygen groups and the matrix increases as their content increases but a previous study (20] of chemical reaction between surface sites on the 100% surface treated AS4 and the epoxy matrix showed that only a few percent of the surface was involved in chemical bonding with the matrix. Detailed analysis of the fiber surface chemistry shows that the oxygen groups can be both carboxylic acid and phenolic type. Both types could react with components of the epoxy matrix. Figures 5 and 6 illustrate schematically the possible reactions that can take place between these fiber surface groups and either epoxy or amine functionalities. This study was undertaken in order to separate the various factors that contribute to adhesion in this system, namely, the surface energetic factors, the effect of chemical bonding between epoxy matrix and carbon fibers surfaces that occurs as a result of commercial surface treatments, and the surface topographical effects that are the result of the anodization method of surface treatment. Possible reactions between fiber and epoxy resin on | o- H+ CHy-CH- = ——> CHYCH— Fiber Fiber ba oO on Q \ + CikcH- | -C-0-CHy CH OH OH Fiber Fiber Figure 5. Epoxy group reactions possible with oxygen functional groups typically found on carbon fiber surfaces. jw) — br) Fiber Fiber NH; NH; 7 9 oe mC) ve [Ee a) OH Fiber NH, Fiber NH Figure 6. Amine group reactions possible with oxygen functional groups typically found on carbon fiber surfaces.3. EXPERIMENTAL 3.1. Fibers The fibers were MAGNAMITE® type IM6 carbon fiber (Hercules). These are PAN- based high-performance, intermediate-modulus carbon fibers. The tensile strength and modulus of these fibers calculated from the composite laminate data are 4378 MPa and 278 GPa, respectively [21]. These fibers were obtained with five different surface treatments, namely 0%, 20%, 100%, 200% and 600%. 0% was untreated and unsized fiber; 20%, 100%, 200%, and 600% fibers were surface treated to 20%, 100%, 200%, and 600% of their nominal value through an electrolytic anodization process in which the fibers are the electrical anode in a circuit as they are continuously drawn through a solution of electrolyte in water. The voltage in the circuit was maintained constant but the current and time were changed compared with the nominal value used in commercial treatments which is labeled as 100%. These fibers have been the subject of other investigations in which the baseline surface chemistry and effect of surface treatment levels on both fiber—matrix adhesion and composite mechanical properties has been measured and published elsewhere [16]. 3.2. Matrix A standard amine—epoxy thermoset system was selected as the matrix system for this study. A diglycidyl ether of bisphenol-A (EPON 828, Shell Chemical Company) cured with 14.5 parts per hundred by weight of meta-phenylene diamine (m-PDA, Aldrich Chemical Company) was chosen as epoxy matrix material. The epoxy was mixed, debulked under vacuum for 2 min and air-colored for 2 h at 75°C (167°F) and 2 h at 125°C (257°F). The matrix cured in this manner has the tensile modulus 3.6 GPa (525 kpsi) and tensile strength 89.6 MPa (13 kpsi). 3.3. Surface chemical reactants The molecules that were pre-reacted with the carbon fiber surraces were selected to be identical to the molecules present in the matrix. The diglycidyl ether of bisphenol- A (DGEBA) and the m-PDA are the same molecules that were used in the matrix formulation. In addition a monofunctional epoxy, butyl glycidyl ether (BGE) having one reactive epoxy group and one non-reactive butyl group was also used in this study. 3.4. Surface analysis by XPS Data were collected using a Physical Electronics Model 5400 ESCA spectrometer equipped with an Al anode coupled to a toroidal monochrometer (PHI 10-410). Sam- ple analyses were run by using the Al anode source operated at 600 W (15 kV and 40 mA). Data were collected in the fixed analyzer transmission (FAT) mode uti- lizing a 180° hemispherical energy analyzer operated at 89.45 eV for survey scans (0-1000 eV) and 17.9 eV and 35.75 eV for the high resolution narrow energy scans of each element. The portion of the sample analyzed was set through an initiallens assembly (PHI Omni-Focus) and was operated in the large area small solid an- gle mode during analysis. A position-sensitive multi-channel detector was utilized for all data collection. All sample spectra were collected with the stage set at 65° relative to the hemispherical energy analyzer. The instrument was calibrated using Al Ka X-radiation such that the binding energy separation between the Cu 3p3,2 and Cu 2p3)2 was 857.5 0.1 eV and the binding energy of sputter cleaned Ag was 367.9 eV. The signal intensity of sputter cleaned Ag was measured at 40000 counts per second with a full width at half maximum height of 0.65 eV at 17.9 eV pass energy. Instrumental control, data collection, background subtraction, and peak inte- gration were accomplished using an Apollo 3500 Domain Series workstation running version 4.0 of the PHI ESCA series system software. 3.5. Fiber surface chemical reaction An aliquot of fiber was unwound from the spool and inserted into a pyrex chamber. The appropriate chemical reactant (DGEBA or BGE) was added to the chamber to cover the fibers completely. The temperature of the chamber was raised to 125°C for 20 min and then cooled to room temperature. The fibers were then refluxed in acetone in a Soxhlet extractor for 72 h to remove any unreacted DGEBA or BGE. For pre-reaction with m-PDA, a similar procedure was followed except that the m-PDA was dissolved in acetone and the mixture was added to the fibers and kept at 125°C for 20 min. The fibers were then cooled and refluxed in acetone for 48 h. Blank runs were also made with pure acetone for identical times following identical procedures to establish a baseline fiber chemistry and to determine whether surface contamination was interfering with the chemical reaction of the groups to the surface in the as- received case. The as-received fibers surface chemistry was identical to the acetone- washed fiber surface chemistry. 3.6. Fiber-matrix adhesion measurement The fiber—matrix interfacial shear strength for the six different fiber surface modi- fications were determined by the single fiber fragmentation test. This technique is described in detail elsewhere. Epoxy samples having a single fiber embedded cen- trally in a tensile dogbone coupon were prepared for each fiber type. Single fiber samples having the various levels of surface treatment (i.e. 0%, 20%, 100%, 200% and 600%) that were either as-received; treated with pure acetone, pre-reacted with m-PDA, pre-reacted with BGE or pre-reacted with DGEBA were mounted in a load- ing jig and loaded in tension. The applied tensile stresses are transferred from the matrix to the embedded fiber through the interface. The strength of the interface and the fracture strength of embedded fiber determine the length of the fiber fragments obtained. The lengths of fiber fragments were measured and the IFSS was calculated from the distribution of fragments lengths according to equation: t= Hr a =):where oy is fiber tensile strength, a and f are the Weibull shape and scale parameters, respectively, and I is the Gamma function. 3.7. Scanning tunneling microscopy A Nanoscope-III scanning tunneling microscope was used to characterize the fiber surface topography. Single fibers were mounted with conductive paint to a metallic substrate and scanned transverse to the fiber axis. Replicate runs were made and representative data were selected for each fiber. The surface roughness factor and surface area were computed using the internal algorithm in the Nanoscope-III. Data were selected a various image sizes ranging from 100 x 100 nm to 800 x 800 nm in order to make sure that possible artifacts due to image size did not exist. 4. RESULTS AND DISCUSSION 4.1. Pre-reaction with surface chemical groups XPS analysis of the IM6 fibers surfaces was carried out after exposure and reaction with pure acetone, an acetone m-PDA mixture, DGEBA and BGE. The acetone- washed fiber surface was very similar in surface chemical composition to the as- received carbon fiber surface and was taken as the baseline for comparison. The untreated (0%) IM6 carbon fiber surface was not included in the comparison since it has been shown previously that the 0% surface contains a defect structure that is removed during surface treatment. Interfacial failure always takes place within this defect layer making surface chemical effects unimportant. For the other fibers treated from 20% to 600% and exposed to the epoxy or amino- functional molecules, chemical reaction with the fiber surface was detected in all cases. A summary of these results is listed in Table 1. The oxygen-to-nitrogen atomic ratios have been calculated as a marker to detect chemical bonding. The usual accuracy of these measurements is about +0.1. Using the acetone-washed fiber as a baseline, it can be seen that all three molecules have chemically reacted with the fiber surface and remain there even after the prolonged exposure of refluxing acetone. The average higher ratio for both the BGE and DGEBA indicate that the epoxy has reacted with the carbon fiber surface. The same surface sites would be expected to react with the DGEBA also. The higher O/N ratio for the DGEBA reacted fiber surface is due to the presence of twice the number of oxygen atomics in the DGEBA compared to the Table 1. Oxygen/nitrogen atomic ratios (45%) as determined by XPS analysis of treated IM6 carbon fibers Fiber ‘Acetone wash BGE DGEBA m-PDA 20% S.T 29 26 37 14 100% S.1. 3.1 34 37 24 200% S.T. 32 36 35 16 600% S.T. 3.2 43 38 19BGE. The increase in nitrogen causes a lowering of the O/N ratio since two nitrogen atoms are added to the carbon fiber surface at each reactive site but additional oxygen is not added. Overall it is estimated that |-3% chemical bonds are formed on each surface with each reactant. It would be expected that a similar amount of chemical bonding would take place in the solid state when a composite is fabricated from these carbon fibers and this epoxy matrix. 4.2. Effect of chemical bonding on fiber-matrix adhesion The measurement of fiber—matrix adhesion was conducted using the single fiber fragmentation test on fibers that had been pre-reacted with these molecules. Results are tabulated in Table 2 and plotted in Fig. 7 as interfacial shear strength (IFSS) versus percent surface treatment. It can be seen from the figure that there is a systematic increase in fiber—matrix adhesion as measured by the interfacial shear strength (IFSS) with increasing levels of fiber surface treatment for each pre-reacted fiber surface. The as-received and acetone-washed carbon fiber surfaces showed no difference in adhesion compared to each other, This baseline case represents what is encountered in the fabrication of composite materials with these IM6 fibers and matrix. Some chemical bonding undoubtedly does take place. All IM6 carbon fiber surfaces treated with butyl glycidyl ether (BGE) had lower val- ues of adhesion as measured by IFSS than the baseline as-received or acetone-washed fiber surfaces. This is a direct result of the chemical blocking of the fiber reactive sites with the BGE and the prevention of additional reaction with the epoxy—amine matrix during sample fabrication. The epoxy group on the BGE will react with the fiber surface but the butyl group is unreactive to any other chemical environment encountered in the matrix because it is a saturated hydrocarbon. The value of IFSS for the BGE pre-reacted carbon fiber surface represent the level of adhesion that can be attained without any chemical bonding between fiber and matrix. The results for the m-PDA-treated fiber are surprising because they do not show any difference between the acetone-washed or as-received cases and the m-PDA-treated fibers, even though chemical bonding has been detected. The extent of chemical bonding of the amine to the fiber surface is of the same order of magnitude as the epoxy groups. This could be interpreted as indicating that in the case of the normal fiber surface coming into contact with the epoxy—amine matrix during composite fabrication, the amine will preferentially react with the fiber surface in place of the epoxy groups. Amines are known for their reactivity with a variety of chemicals and this hypothesis is reasonable. Pre-reaction with amine does not improve adhesion over what can take place conventionally but is greater than the level of chemical bonding that can take place with the totally unreactive BGE treated fiber surface. The 18% increase in IFSS of the amine pre-reacted surface over the BGE reacted surface represents the adhesion increase due to chemical bonding of the amine to the carbon fiber surface. The results for the DGEBA pre-reacted carbon fiber surfaces show the highest values of IFSS. The DGEBA molecule like the m-PDA is difunctional and can react in a similar fashion at either end. The higher level of adhesion obtained with this moleculeTable 2. Interfacial shear strength (MPa) of IM6 carbon fibers to epoxy after fiber pretreatment with model epoxy compounds Fiber As rec'd Acetone wash BGE DGEBA m-PDA 20% S.T. 63 +6 6249 S449 7411 6644 100% S.T. RT Th 12 6446 8347 T2£8 Wts 7549 6411 8044 TO+8 S 1009 9549 82410 U4 13 9749 © As Received & Acetone Washed Q BGE © DGEBA (Epon 828) 7 mPDA Interfacial Shear Strength (MPa) © 100 200 300 400 500 600 700 Surface Treatment Level (%) Figure 7. Interfacial shear strength of [M6 carbon fibers in epoxy matrix after fiber pretreatment with model epoxy compounds. suggests that it can chemically tie into the bulk epoxy matrix in a more efficient manner than the m-PDA molecule can and therefore it produces higher levels of adhesion. This may be due to the longer length of the molecule or to a greater extent of chemical bonding than the amine. In either case, the 32% increase in IFSS attained by pre- treating the carbon fiber surface with the DGEBA represents the increase in adhesion due to chemical bonding of the epoxy groups to the carbon fiber surface. It should be noted that if interfacial chemical bonding between fiber and matrix was the sole mechanism responsible for the observed changes in IFSS measured for these IM6 fibers as a function of surface treatment, the change in IFSS should be constant (i.e. a straight line rather than an upwardly sloping one) with increasing levels of surface treatment for the data plotted in Fig. 7. That is, once all of the sites had been reacted with the chemical pre-treatments, regardless of surface treatment levels, the IFSS should be constant and the same for each fiber surface. The constant positive slope indicates that another change may be taking place with surface treatment. The most probable cause for such a change is an increase in microscale surface roughness (or surface area) with extent of surface treatment. It is well known that such microscale topographical changes are responsible for increased adhesion to metal oxides for example.4.3. Fiber surface topography Representative STM images for the 0%, 20%, 100% and 600% IM6 carbon fiber surfaces are shown in Figs 8-11. The images are shown at the same magnification in the x, y and z directions and with the fiber axis in the same orientation, i.e. in the direction from upper left to lower right. It is apparent that there is a detectable change in the surface roughness of the carbon fibers with increasing levels of surface treatment. The line scan shown at the front of each image is a good representation of the features of each. The 0% surface treated fiber has a surface that has topo- graphical features that vary with a periodicity of about 50 nm. After the 20% surface treatment, the surface appears to be much smoother. With increasing levels of surface treatment to 100% and 600%, the fiber surfaces start to show increasing amounts of topographical variation but with a lower periodicity of 25 nm. The STM has the capability of quantifying the topography and surface area of each image with its sophisticated data collection and processing software. Scanning tunneling microscopy results for the IM6 fibers as a function of surface treatment level for 100 x 100 nm images as well as for 800 x 800 nm images were obtained and are plotted in Fig. 12. Both the mean roughness in nm and the change in surface area over a flat surface with the same overall dimensions were determined. Although the absolute values of the mean roughness and surface area change are not identical for each image size, the relative changes taking place with surface treatment level X 20.000 nm/div Z 15.000 nm/div Figure 8. 100 nm x 100 nm STM image of 0% surface weated IM6 carbon fiber with 15 nm z axis magnification.X 20.000 nm/div Z 15.000 nw/div Figure 9. 100 nm x 100 nm STM image of 20% surface treated IM6 carbon fiber with 15 nm z axis magnification. X 20.000 nu/div Z 15.000 nw/div Figure 10. 100 am x 100 nm STM image of 100% surface treated IM6 carbon fiber with 15 nm z axis magnification.X 20.000 nm/div 2 15.000 nw/div Figure 11. 100 nm x 100 nm STM image of 600% surface treated IM6 carbon fiber with 15 nm z axis magnification. are the same. These results show that the surface area and mean roughness (asperity height) of the carbon fibers decreases after the first surface treatment level of 20%. Even after the 100% surface treatment, the surface area and asperity height is low. Increasing the surface treatment levels to 200% and 600% causes the surface area and asperity height to increase substantially. This type of change is to be expected since it is known that the anodic type of surface treatments involve a surface etching as well as functionalization of the surface. Figure 13 is a replot of the data first displayed in Fig. 7 but now corrected for the change in surface area and mean roughness for each fiber. This is accomplished by determining the difference in IFSS for each fiber compared to the same fiber in the acetone-washed state and then dividing by this value to determine the percent change. In the previous plot of Fig. 7, all of the results were plotted on an absolute basis whereas here the change in surface area that accompanies the increasing levels of surface treatment is taken into account. This has the effect of separating the differences in IFSS attributable to chemical bonding from the differences due to changes in surface area and mean roughness. When the data are replotted in this manner, it is clear that the changes in adhesion brought about by the chemical bonding add to those that are due to purely surface energetic interactions and are relatively constant throughout the range of carbon fiber surface treatments used in this study. The pretreatment of all of the carbon fibers with BGE uses up all of the reactive surface groups and prevents any chemical interactionSTM Image Surface Area and Roughness Analysis of IM6 Carbon Fibers 100om x 100nm 800nm x 800nm 2S Roughness (nm) 6 O surf Area (%) © Roughness (nm) O surf Area (%) Mean Roughness (nm) (%) eseoingy oney vary so¥jIng Mean Roughness (nm) (%) esearou] oney vary aoeIng 9 100 200 300 400 500 600 700 © 100 200 300 400 500 600 700 Surface Treatment Level (%) Surface Treatment Level (%) Figure 12. Surface roughness and surface area characterization results from 100 nm x 100 nm and 800 nm x 800 nm STM images. IMG Carbon Fibers ‘Op 2 ____2 DGEBA (Epon 828) Percent Difference in IFSS/IFSS(acetone) (%) 9 100 200 300 400 500 600 700 Surface Treatment Level (%) Figure 13. Percent change in IFSS attributable to chemical bonding between the IM6 carbon fibers surface groups and epoxy matrix.with the epoxy. Therefore the BGE line in Fig. 13 represents the adhesion as measured by ILSS that is due to van der Waals interactions, i.e. the work of adhesion alone. The m-PDA-treated carbon fibers surfaces exhibit an 18% increase in adhesion over the BGE-treated fibers which is due to chemical bonds forming between the carbon fiber surface and m-PDA which then reacts with the epoxy groups in the matrix. In the case where the fibers are pretreated with DGEBA the IFSS increases about 16% over the m-PDA-treated fibers but about 32% over the BGE-treated fiber. This means that if the BGE-treated fiber represents the conditions of adhesion without any chemical bonding, the effect of chemical bonding through the 1-3% amine groups can increase adhesion about 18% whereas chemical bonding through epoxy groups can increase adhesion about 32%. The results of this study show that adhesion as measure by IFSS between carbon fibers and epoxy matrices consist of three interacting mechanisms, namely, surface energetic interactions, chemical bonding and increases in fiber surface topography. The 1-3% oxygen and nitrogen chemical groups that chemically bond to the epoxy matrix are added simultaneously with an increase in surface roughness as a result of surface treatment. Indeed, it is the increase in surface roughness that causes the IFSS results in Fig. 7 to increase with surface treatment rather than remain constant. Both surface chemical bonding and an increase in surface roughness contribute to increasing fiber—matrix adhesion with fiber surface treatment. 5. CONCLUSIONS Experiments with reactive molecules having epoxy or amine groups were carried out on a series of IM6 carbon fibers produced with increasing amounts of surface treatment levels. Chemical bonding between reactive groups in amine cured epoxy matrices and the surface groups present on IM6 carbon fibers as a result of commercial surface treatments has been detected. It was found that the level of chemical bonding increases with surface treatment levels although the absolute amount of chemical bonding is low (1-3%). Interfacial shear strength measurements conducted on these carbon fibers that had been pre-reacted with amino or epoxy functional groups allowed the differentiation between possible reactions to be made. It was found that reaction with monofunctional epoxy groups having hydrocarbon functionalities blocked the surface from further reaction and reduced the adhesion that could be attained to its lowest value. Therefore, the BGE-treated fiber represents the adhesion as measured by ILSS that is due to van der Waals interactions, i.e. the work of adhesion alone. Chemical bonding between epoxy and the carbon fiber surface increases the adhesion between fiber and matrix by about 34% while chemical bonding between the amino group and the carbon fiber surface was responsible for an increase in adhesion of about 18%. Quantitative measurements of the fiber surface microtopography made with scanning tunneling microscopy show an increase in roughness with increasing surface treatment. It was concluded that surface roughness also accounted for a significant increase in fiber—matrix adhesion.REFERENCES 1. L. T. Drzal. M. J. Rich and P. F. Lloyd. J. Adhesion 16, 1 (1982). 2. J. Harvey, C. Kozlowski and P, M. A. Sherwood, J. Mater: Sci. 22, 1585%1987). 3. J. Schultz and L. Lavielle, Inverse gas chromatography, in: ACS Sympositm Series 391, D. R. Lloyd, T.C. Ward and H. P. Schrieber (Eds), p. 185. American Chemistry Society, Washington, DC (1989). 4. E. Fitzer and R. Weiss, Carbon 25, 455 (1987). 5. W. P. Hoffman, Carbon 30, 315 (1992). 6.4. B. 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