CARBON FIBERS SURFACE AND ITS EFFECTS ON AN INTERPHASE FORMATION FOR ULTIMATE ADHESIONRELATED PERFORMANCES

Felix N. Nguyen1, Yoshifumi Nakayama2, Daigo Kobayashi2, Toshiya Kamae2, Kenichi Yoshioka1
1

Toray Composites (America), Inc., 19002 50th Ave E, Tacoma, Washington 98446, USA 2 Toray Industries, Inc., 1515, Tsutsui, Masaki-cho, Iyogun, Ehime 791-3193, JAPAN

ABSTRACT
Adhesion between a carbon fiber and a resin matrix has been documented to substantially affect adhesion-related mechanical properties of carbon fiber reinforced polymer composite (CFRP) such as tensile, flexural, and fracture toughness. Adhesion strength generally relies on the formation of an interphase between the carbon fiber and the resin matrix, and chemical interactions within this interphase. Nanostructures on the fibers surface, chemical functionalities introduced by a surface treatment, and a reactive sizing material with both the fibers surface and the resin are essentially critical factors. This paper discusses the uniqueness of an intermediate modulus (IM) and high modulus (HM) carbon fiber, their surface chemistry and sizing chemistry that altogether improve adhesion strength substantially. Furthermore, when all factors involved in the formation of the interphase were fully optimized, a tensile strength of CFRP normalized to fiber strength and fiber volume fraction could approach 100%. This remarkable breakthrough is being further developed for all CFRP systems at Toray Composites (America) Inc.

1. INTRODUCTION
When bonding carbon fibers together by a resin matrix to create a fiber reinforced polymer composite (CFRP), functional groups on the fibers surface is very critical. In addition, the bond has to be durable as subjected to environmental and/or hostile conditions. Bond strength or force per unit of interfacial area required to separate the (cured) resin from the fiber that were in contact is a measure of adhesion. Maximum adhesion is obtained when a cohesive failure of either the resin or the fiber or both, as opposed to an adhesive failure between the fiber and the resin, is mainly observed. To make a strong bond, firstly oxygen functional groups on the pristine fibers surface must be introduced; secondly an adhesion promoter is selected such that one end could covalently bond to the oxygen functional groups while the other end can promote chemical interactions with the functional groups in the resin. Essentially, the adhesion promoter acts as a bridge connecting the fiber to the bulk resin during curing. A surface treatment such as plasma, UV, corona discharge, wet electro-chemical treatments is often used to introduce oxygen functional groups. Selection of a type of surface treatment as well as a level of surface treatment depends on the surface structure of the pristine fiber, determined from a precursor type, a spinning process and a

carbonization temperature. A successful surface treatment should provide a uniform distribution of the oxygen functional groups on the surface without damaging the fiber and weakening it. The adhesion promoter material often called a sizing material or simply sizing or size or in other context it might be called a surface finish. The sizing can be as simple as a silane or a polymer to as complicated as a mixture of appropriate components to achieve adhesion-related properties of the composite. Normally, the sizing is coated onto fibers via a wet chemical process which is in-line with the surface treatment process. Finally, the sized fibers are impregnated with the resin, and the resulting composite is cured. Selection of a right curing method is also important. A common method is to use an autoclave to produce the highest bonding quality. Yet, other methods such as a thermal oven, a microwave oven, a UV light, or an electron beam could also be used, but voids might be found in the composite and thus its performances are lower. Ultimately, to achieve the strong bond, there certainly cannot be voids at the interface between the fiber and the resin, i.e., there is sufficient molecular contact between them upon cured. Often, this interface is considered as a volumetric region or an interphase. The interphase can extend from the fibers surface a few nanometers up to several tens of micrometers, depending on the chemical composition on the sized fibers surface, chemical interactions between the fiber and the bulk resin, and other chemical moieties migrating to the interface during curing [1]. The interphase; therefore, has a very unique composition, and its properties are far different from those of the fibers surface and the bulk resin. Moreover, existence of high stress concentrations in the interphase due to the modulus mismatch between the fiber and the resin often makes it vulnerable to crack initiation. Such high stress concentrations could be intensified by chemical embrittlement of the resin induced by the fiber, and local residual stress due to the thermal expansion coefficient difference such that when a load is applied, a catastrophic failure of the composite can be observed. As a result, an advanced interphase is critical to realize the maximum potential of carbon fibers in the composite. The present paper introduces an innovative design methodology from Toray for such an advanced engineering interphase (AEI) such that the resulting composite could reach a tensile strength of 100% when normalized to strength of the carbon fiber and fiber volume (100% translation). The requirements for a stable carbon fibers surface and consistent surface chemical functionalities as well as a stable sizing material for promoting a desired adhesion between the fiber and a model resin are discussed.

2. EXPERIMENTATION
2.1. Materials All PAN-based model carbon fibers were provided by Toray Industries, Inc. (Japan). An intermediate modulus carbon fiber designated IM and a high modulus carbon fiber designated HM were used for the study. A simple bisphenol-A epoxy resin system, R1, was used to study the adhesion of the fibers to the resin while a model aerospace-grade resin, R2, was used to examine tensile strength of the fiber composites.

2.2. Methods 2.2.1. Surface Topography A JEOL 7500F SEM equipped with a gentle beam technology and a Hitachi S-4800 SEM equipped with a deceleration beam technology both were used to examine and compare the nanostructures on the fibers surfaces. Individual fibers were gently placed on an electrical tape glued to an aluminum mount (also called stud or stub), and inserted into a sample stage in the machine. When a negative bias voltage was applied to the stage the primary electron beam was slowed down, and hitting the surface at a desired energy; thus surface structures is preserved without damaging the surface. The secondary electron beam generated from the surface is then accelerated to the detector. The sample was observed between 1-3mm working distance, and an accelerating voltage of less than 1kV was used. A SPI 3800N AFM from SII NanoTechnology Inc. was used to examine surface topography of the fibers. Individual fibers were laid flat at least one fiber distance away from one another on a clean silicon wafer. One end of each fiber was taped onto the wafer to keep them secure. Tapping mode was performed with a silicon cantilever (SI-DF20) having a tip radius of 10nm and a catalog spring constant of 12N/m. After the laser was aligned, the tip was set onto the fiber such that it was parallel to the fibers axis. The scan direction was perpendicular to the fibers axis and at a speed of 1Hz. 2.2.2. Surface chemistry Pristine IM and HM were oxidized by a proprietary wet chemistry method to introduce a desired amount of oxygen functional groups onto their surfaces. An x-ray photoelectron spectroscopy (XPS) technique was used to document a change in surface chemistry of the fibers. Several conditions of an proprietary surface treatment method were performed. A Witec Alpha300 equipped with a digital pulse forced mode (AFM-DPFM), and a Veeco (now Bruker) Dimension Icon with PeakForce QNM were used to map an adhesion force between the tip and a location on the carbon fibers surface. A description of PFM method was described by Marti et al. [2-3] while details of PeakForce QNM can be found from the manufacturers website. When added to an AFM System, the PFM extends the capabilities of the microscope beyond simply measuring topography to include the investigation of all properties described by pulsed force and forcedistance curves. In addition to adhesion, other properties such as local stiffness, viscosity, energy dissipation, contact-time, long range forces and many more can be analyzed and imaged simultaneously along with topography. Yet, they are not in the scope of this study. The electronics of PeakForce QNM is essentially similar to PFM. The electronics of the DPFM include a high speed data-acquisition system, a freely programmable modulation generator and a real-time data evaluation module. With the storage of the complete measurement, extensive post-processing data evaluation can be easily performed. The aforementioned procedure in Section 2.2.1 was used to prepare samples and align the tip onto a fibers surface. Once a suitable applied load (set point) on the surface was found to obtain a stable a force-curve as shown in Figure 4, as the tip was rastered across the fibers surface, an

adhesion map along with a topography image with either 256 or 512 data points per line was captured. Detailed operation of AFM-PFM can be referred to the manufacturers manual. 2.2.2. Sizing Application Oxidized fibers were coated with an epoxy compatible sizing material to promote adhesion between the fibers and resins R1 and R2. The fibers are called sized fibers. 2.2.3. Mechanical Tests An adhesion test was carried out using the procedure described by Rao et al. [4] in which a fiber embedded in the resin R1 was subjected to a unidirectional tensile load until the fiber no longer produced shorter fragments. Interfacial shear strength was determined from the strength of the fiber, the averaged critical fragment length and the fibers diameter. The specimens were made by hand-picking either pristine, oxidized or sized fibers and securely placing them into a rubber mold with eight cavities such that one fiber per cavity was allowed, impregnating resin R1 onto the fiber and curing the mold in an oven at 75 C for 2 hr followed by 125 C for 2 hr. Tensile test was carried out according to ASTM D 3039 on 6-zero ply UD specimens. The specimens were made as follows. Resin R2 was first casted into a thin film using a knife coater onto a release paper. The film was consolidated onto a bed of sized fibers on both sides by heat and compaction pressure. A UD prepreg having a carbon fiber area weight of about 190g/m2 and a resin content of about 35% was obtained. The prepregs were cut and hand laid up. Panels were cured in an autoclave at 180C for 2 hr with a ramp rate of 1.7C/min and a pressure of 0.59 MPa.

3. RESULTS
3.1. Surface Topography and Chemistry Figure 1 shows the topography images of a HM fiber from both SEM (right) and AFM (left). Both JEOL and Hitachi machines were fine-tuned to capture highest quality images. Similar nanofeatures were found from both machines. From the SEM image nanofeatures (ribbons) having basal planes (hills) and crevasses (valleys) were clearly shown. Each hill can be resolved from one another and having a width of about 10nm. These nanofeatures are consistently found on the surface of all HM fibers. Note that no sputter coating with a metal was used to preserve the surfaces nanofeatures. To get such a clear and crisp image with minimal to none charging due to accumulation of secondary electrons around the contact point between the primary electron beam and the surface, a low accelerating voltage of about 0.5kV, an optimal working distance about 2mm on top of the good sample preparation technique were found. Similar nanofeatures were observed with AFM. The features seen in SEM appeared to be fatter as their sizes were determined by the tip radius. Care should be taken to interpret AFM images to avoid artifacts. Yet, the general shape of these features was shown similar to that from SEM image. Hills and valleys were clearly resolved as well. The good sample preparation technique combined with an optimal set of operating conditions allowed consistently high-quality images

along the fibers to be captured. It was noted that noise could be introduced if one fiber was on top of another, or the fiber was on top of some debris when the silicon wafers surface was not sufficiently cleaned. No attempt was to measure the depth of hills by SEM, but apparently it was in the order of nanometers. Nevertheless, an averaged surface roughness could be determined by AFM. Figure 2 shows typical nanofeatures on the surface of an IM fiber. Both SEM and AFM images were taken and compared to those of the HM fiber. Nanofeatures as shown were found on all locations along the IM fibers, indicating a uniformity of the fibers surface. From the SEM image the depth of hills were shallower, and hence the averaged surface roughness (Ra) determined from AFM was much lower. Note that due to the curvature of fiber, each location of the fiber might have been included this curvature effect. Therefore, AFM images were flattened to a second order to remove tilt and bow, and re-center the image so that an averaged value of roughness could be used to compare all fibers relatively, especially among the oxidized fibers with several levels of surface treatment.

Figure 1 Topography images from AFM and SEM techniques for an HM fiber. The scale bar for SEM is 200nm with 10 increments. Clearly individual basal planes and crevasses were resolved.

Figure 2 Topography images from AFM and SEM techniques for an HM (left) and an IM (right) fiber. Averaged surface roughness (Ra) measured by AFM is a relative value to minimize curvature effect of the fibers. Figure 3 shows the effect of surface treatment level on surface roughness and surface chemistry of HM carbon fibers. Apparently, increasing level of surface treatment than 100% changed surface roughness marginally. In fact, even at the highest level of surface treatment of 400%, the surface examined by SEM was just like the pristine fibers that were never oxidized. This indicates a very stable surface for the HM fibers. Similarly, a stable surface was also found for the IM fibers. Yet, no higher level of surface treatment than 100% was performed for this IM fiber because the amount of oxygen functional groups was determined to be more than sufficient to anchor the sizing material. As shown, for both fibers the level of oxygen to carbon (O/C) determined by a XPS method reached 100% for the HM fiber and 150% for the IM fiber. A higher O/C level was obtained for the HM fiber as a level of surface treatment exceeded 100%. At 400% level of surface treatment, 200% O/C level was resulted without damaging the surface.

Figure 3 Effects of surface treatment levels on surface roughness and surface chemistry. While a substantial increase in surface functional groups with increasing surface treatment level, a modest increase in relative surface roughness was observed.

3.2. Surface Chemistry Mapping Oxygen functional groups on a fibers surface is critical to allow an adhesion promoter or a sizing material to act as a bridge connecting the fiber to the bulk resin. The pristine fiber is typically inert as all functional groups were removed during a carbonization process. To promote oxygen functional groups on the surface, the surface is needed to be oxidized. Since the alignment of graphitic crystallites are different between intermediate and high modulus fibers [5], a level of surface treatment has to be optimized to achieve a desired density of these functional groups on each type of fibers. The total amount of these functional groups can be determined through an XPS method or an acid/base titration method. A general idea on uniformity and distribution of these functional groups on the surface could be accessed through a degree of variation of average values from many XPS measurements. Yet, it is very expensive and time consuming, but might not represent the whole lot of carbon fibers, if a stable surface does not exist. Here in this paper an attempt was made to investigate the spatial distribution of the surface functional groups on the IM and HM fibers with different levels of O/C through a mapping technique of adhesion force between an AFM tip and the surface by a pulse forced mode (PFM). Chemical force microscopy (CFM) with point-by-point measurement between an AFM tip and a flat surface has been studied extensively [6]. Yet, AFM-PFM is much less time consuming compared CFM as hundreds of thousands of data points can be obtained very quickly by a raster method of the tip across the surface. This AFM-PFM method has been used extensively on a flat surface [2-3, 7], but to our knowledge it has not been used on a curved surface of carbon fibers.

Figure 4 Schematic of AFM-PFM for one cycle. Adhesion force is determined as F =-kx, where x is a snap-off distance and k is the spring constant of the cantilever Figure 4 discusses the mechanism of the PFM. The electronics introduce a sinusoidal modulation to the z-piezo of the AFM with an amplitude of typically 10-500 nm at a userselectable frequency between 100 Hz and 2 kHz (which is far below the resonance frequency of the cantilever). As the AFM tip approaches the surface it will snapped into the surface (A). A load called a set point is applied to push the tip further into the surface. Once the max forced is reached (B), the tip is retracted and up to a point it will snap off the surface (C). After free oscillation is damped toward the baseline, the cycle starts gain. If the spring constant k of the cantilever and the snap off distance x are known, the local adhesion force underneath the tip could be calculated. Therefore, a relative distribution of adhesion on the fibers surface could be represented. Since this is a dynamic mechanical method, many variables are needed to be controlled to quantify adhesion for a meaningful comparison among surfaces. Operating parameter such as set point, sample geometry such as fiber curvature and the tip characteristic such as spring constant are determined to be critical factors and needed to be carefully controlled. Environmental factor such as humidity above 40% is also a critical factor [8]. Yet, the measurement was attempted in a semi-controlled atmosphere with less than 40% humidity. Once a stable set point was found for the interrogated fibers surface, and a curvature length of 500nm with respect to the fibers axis to minimize curvature effect was set, many scans of 0.5umx0.5um were captured from both Witec and Veeco machines to examine, and verify the effects of spring constant on adhesion. Essentially individual tips having an experimentally calibrated value of less than 5% of the averaged was needed for a reasonably meaningful comparison of the averaged adhesion among fibers.

(A) Pristine HM

(B) Oxidized HM Figure 5 Topography and adhesion map of HM fibers. Image size is 0.5umx5um. Scan direction is 90deg to the fibers axis. Silicon tips from NanoSensors (PPP-CONTR with k=0.1N/m) was used. Spring constants were experimentally calibrated to be 0.075N/m for both fibers. Finer adhesion features were found on the oxidized IM fiber (200% surface treated, O/C=110%) than the pristine, indicating that the fiber was uniformly surface treated. Figures 5-6 show an example of the adhesion map and topography image of 0.5umx5um of the pristine and oxidized HM (200% surface treated), and the pristine and oxidized IM fibers (100% surface treated), respectively, from the Witec AFM-DPFM. Such long scans were needed to obtain a statistically meaningful averaged adhesion value. Unfortunately, long scan option was available in the Witec machine only though the Veeco machine gave a better resolution, less total scanning and analyzing time per image, and easier to operate. As shown, a good distribution of adhesion values implies a good distribution of functional groups on the fiber surface. Finer adhesion features on both oxidized IM and HM fibers compared to the pristines indicate that these fibers were uniformly oxidized. Yet, care should be taken when further interpreting these results as the tip radius was about similar size as the nanofeatures on the fibers surfaces. Since more functional groups were found on the oxidized fiber surface, its averaged adhesion was

higher than the corresponding pristine fiber. Also, note that the increase in the averaged adhesion value of the IM fiber when it was oxidized was higher than that of the HM fiber. This was expected as generally it was more difficult to introduce oxygen functional groups onto a high modulus carbon fiber.

(A) Pristine IM

(B) Oxidized HM Figure 6 Topography and adhesion map of IM fibers. Image size is 0.5umx5um. Scan direction is 90deg to the fibers axis. Silicon tips from NanoSensors (PPP-CONTR with k=0.1N/m) was used. Spring constants were experimentally calibrated to be 0.076N/m and 0.074N/m for the pristine and oxidized, respectively. Finer adhesion features were found on the oxidized IM fiber (100% surface treated, O/C=150%) than the pristine, indicating that the fiber was uniformly surface treated.

3.3. Adhesion-related Properties VS. Surface Chemistry

Figure 7 Effects of surface chemistry on adhesion between fibers and resin R1. Optimal surface treatment levels are to achieve well-balanced adhesion-related properties in CFRP.

Figure 8 Percent translation of CFRPs tensile strength (TS) to tow strength of carbon fiber for HM and IM fibers with and without an AEI. AEI was introduced by optimizing the resin R2 for maximum interactions with the carbon fibers surface. Figure 7 shows the effect of O/C level on adhesion determined from interfacial shear strength (IFSS) of the fibers on the resin R1. In the case of HM fiber, a significant increase was observed with increasing O/C level. However, up to a certain amount of O/C, IFSS was leveled off, implying that a higher O/C level was not necessary to achieve a higher IFSS. This also indicates that an excessive level of surface treatment was not needed, and certainly surface damages could be minimized. Interestingly enough that IFSS of corresponding sized fibers followed the same trend, and there was an apparent constant increase in IFFS from the oxidized to the sized fiber cases. This result implies that one could quickly determine if a desired level of adhesion between the sized fibers to the resin R1 could be achieved by screening O/C level or a level of

surface treatment. SFFT then could be used to confirm the screening results. Note that in this study, SEM was also used to examine the sized fibers surfaces. Yet, no difference between the pristine surface and sized fibers surface, indicating a uniform layer of a few nanometers of the sizing material might be coated on the oxidized fibers. No attempts to determine the real thickness of this layer as well as to map adhesion on these sized fibers were performed. In the case of IM fiber similar tendencies were achieved in that higher IFSS was found for both oxidized and sized fiber than the pristine case. Yet, IFSS of the sized IM fiber case was found more than twice than the sized HM fiber, though the O/C level of these fibers were similar. Typically a HM fiber has about 20% lower strength than an IM fiber. Therefore, such significant difference in IFSS could involve other factors such as the type of functional groups on each fiber, their distribution, and more importantly the chemical interactions among the sizing material, the surface functional groups and the resin R1. In other words, the interphase in the IM and HM cases might be different. After examined the fracture surface of tensile strength specimens with SEM, it was found that cohesive failure occurred for the IM case, but interfacial failure for the HM case. Essentially, an interfacial layer could have formed in both cases. Yet, it retained in the IM case, but came off in the HM case. Nevertheless when tensile strength of IMCFRP and HMCFRP were normalized to strength of the corresponding carbon fiber and fiber volume (% translation), a translation of about 75% was found for both IMCFRP and HMCFRP (Figure 8). This indicates that a sufficient adhesion might have been achieved in the HMCFRP. To further reinforce the interfacial layer so that it could be retained in the HMCFRP system after fractured, an advanced engineering interphase (AEI) was introduced by further optimizing the resin R2 system for maximum interactions with the fibers surface. That resulted in about 10% increase in translation, and cohesive failure finally occurred. A similar optimization performed on the IMCFRP system remarkably yielded almost 100% translation, which is far beyond the current state of the art allowing the highest value between 80-90%.

4. CONCLUSIONS
The present study has shown unique surface nanofeatures of IM and HM fibers examined by both SEM and AFM techniques. Both fibers were shown to have a very stable surface. A surface treatment while produced more than sufficient amount of O/C level for an interphase formation with the sizing material and the resin, surface roughness changed marginally only. AFM-PFM technique showed that finer adhesion features were found when HM and IM fibers were oxidized at 200% and 100% level, respectively. This implies that a uniform distribution of oxygen functional groups on the oxidized fibers surfaces might be achieved. A unique and stable carbon fiber surface, a sufficient amount and uniform distribution of functional groups, a uniform layer of the sizing material coated on the oxidized fiber, and an optimized resin aerospace-grade system altogether contribute to a successful AEI that allowed TS of IMCFRP to approach a translation of 100% strength of the IM fibers. The AEI also changed interfacial failure mode in HMCFRP to cohesive failure of the resin. Yet, more work is being conducted at Toray Composites (America) Inc. to increase the translation of HMCFRP to 90% or higher.

5. ACKNOWLEDEMENTS
Helpful discussions and supports by Prof. D. Eric Aston and Dr. Jamie M.F. Jabal of University of Idaho, Department of Chemical and Materials Engineering, Moscow, ID are gratefully acknowledged. The authors also would like to thank Surface Analysis Recharge Center (SARC) of University of Washington, Department of Bioengineering, Seattle, WA for the use of AFM facility.

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