ISU ME REU

NSF-REU Site: Microscale Sensing, Imaging and Actuation Mechanical Engineering Department, Iowa State University, Ames IA

ALUMINUM CARBON-NANOTUBE COMPOSITES VIA COLD ROLL BONDING

Dr. Gap-Yong Kim Mentor Ames, IA, USA Mina Bastwros Graduate Mentor Ames, IA, USA

Caleb Messmer Undergraduate Researcher Huntingburg, IN, USA

INTRODUCTION AND OBJECTIVES Strong, lightweight materials are desirable in numerous engineering applications today. Aerospace, automotive, sports equipment and many other industries have an ever-present need for advanced materials. Carbon nanotubes (CNTs) exceptional mechanical properties [1] have drawn attention in recent years and made them an interesting candidate in advanced material development for lightweight composite applications. In the current study, we seek to synthesize aluminum-carbon nanotube (Al-CNT) composites that meet these criteria, through novel techniques. Using CNTs as reinforcement in metal composites creates an increase in mechanical properties unachievable in the metals alone [2]. One of the major challenges in making composites with nano-constituents is dispersion of the particles or fibers within the matrix phase. Because of the van der Waals force, CNTs are difficult to disperse. To date, ball milling [3] [4] [5], powder metallurgy [6] [7] [8], thermal spraying [9] [10] [11], melt processing [12], and others [13], have been used to integrate CNTs into an aluminum matrix. Most techniques investigated thus far include some method of heat treatment within the forming process [7]. Because processes that require high temperature may cause secondary reactions between the aluminum and CNTs [6] resulting in formation of undesirable compounds, we wish to examine methods that do not require heat during formation. Our study investigates cold roll bonding (CRB), which is achievable at room temperature. CRB joins surfaces through a phenomenon known as cold welding. CRB, sometimes referred to as cold forming [14], has been around since the 1940s. Saito developed accumulative roll bonding (ARB) in the 1990s [15], which takes advantage of the fact that CRB is reiterative. This means a single specimen can be processed multiple times, until the metal deformation exceeds strength gained [15]. Furthermore, ARB is very practical in mass production settings. In comparison with other methods, ARB is rudimentary and can be easily automated [14].

There have been numerous studies completed using CRB and ARB to fabricate metal composites with reinforcing particles or fibers. For instance, aluminum matrix composites reinforced with both tungsten carbide (Al-WC) and nano-sized SiO2 particles (Al-SiO2) have been successfully produced via cold forming processes [16] [17]. Other lightweight metals, such as titanium and copper, have also been used to form composites i.e. titanium-titanium palladium fiber composites (Ti-TiPd) [18] and copper/single-walled carbon nanotubes composites (Cu-SWCNT) [19]. These studies translate to our research and elucidate the fact that CRB and ARB are viable processes in the formation of metal composites with reinforcing particles. Our experiment will expand upon the previous research on Al-CNT composites [2] [20] by investigating sheet patterning of the specimen surfaces, CNTs effect bond quality, and multiple layered composite structures. Research on the mechanical properties of Al-CNT composites was developed by Lahiri et al [2]. The primary purpose of our research is to synthesize Al-CNT composite panels and to understand how the different surface preparations and roll bonding procedures affect this process. MATERIALS AND METHODS Materials Aluminum alloy 1100 (AA1100) was used to form the metal matrix in this study. AA1100 consists of a minimum of 99% pure aluminum, with silicon (Si) and iron (Fe) being the primary constituents of the remaining 1%. The CNTs in this experiment were ultrasonically agitated in an ethanol suspension at 0.1% volume. This was done using a Fisher Scientific ultrasonic agitator for two hours prior to application. Surface Preparation The as-received sheet material was cut into strips to test the multiple parameters governing roll bonding. The area of each

Surface preparation and CNT application Aluminum

CNTs

Cut and Repeat

Roll Bonding

Fig. 1: Schematic of composite fabrication via ARB

Fig. 2: Processed specimen with severe edge deformation

strip was 44 x 18 mm2 (1mm2) with an average thickness of 1.0 mm (0.1mm). The strips were then manually pressed flat to increase the contact area between the sheets and aid in alignment of the strips. Once flattened, the surface of each specimen was degreased with ethanol and thoroughly sanded with 80-grit sandpaper. This method of degreasing and scratching has been proven as the most effective in surface preparation of coldwelded composites [21]. Half of the specimens tested also underwent knurling to investigate the effects of sheet patterning in roll bonding. The knurling apparatus, fabricated in-house, applied a pattern of indentations approximately 400-m apart perpendicular to the longitudinal axis of the sheet. The samples were then degreased with ethanol once more to eliminate any surface contaminants acquired via sanding or knurling to ensure a clean surface during CNT spraying. The surface of each specimen was covered with the 0.1% volume CNT suspension using a Sono-Tek ExactaCoat spraying machine. An ultrasonic nozzle sprayed at a rate of 0.25 mL/min and a speed of 10 mm/s. The suspension sprayed over the entire surface of each specimen four times. A hot plate set to approximately 350C heated the specimens during spraying to evaporate the ethanol from the surface leaving only CNTs. Roll bonding The prepared specimens were stacked creating an initial thickness of ~2 mm and ARBed using a Durston DRM 130 Manual Rolling Mill. After the first pass, each bonded pair was approximately 500 m thick, a reduction in thickness of 75%. The specimens were cut into four pieces for the following passes to maintain a final thickness of ~500 m. Thus, the number of sheets bonded per rolling cycle increases by a magnitude of four for each pass after the initial pass. Each composite underwent a total reduction in thickness of ~75%. Fig. 1 above diagrams this process.

After each rolling bonding cycle, some level of edge deformation was present. Some specimens, especially those undergoing multiple rolling passes, the deformation can be quite severe. Fig.2 above shows a sample that became severely deformed after 2 cycles. Removal of these deformations is necessary to ensure bonding in subsequent passes. Additionally, annealing post-bonding was used to recover the ductility lost to work hardening, and thus aid bonding. Interfacial Bond Inspection To inspect interfacial bonding, the composites were cut, molded, and polished. A Ukam Industrial Precision Diamond Saw was used to cut the specimens in both the longitudinal and transverse planes. The samples were then placed in an acrylic mold and polished with a Ukam Industrial Diamond Polishing Machine. Well-polished samples were inspected using an Amscope optical microscope fitted with an eyepiece camera. Theoretical Model The total sheets bonded increased by a magnitude of four for each cycle after the first initial pass. The number of individual layers in the composite per rolling pass can be calculated using the following equation. = 221 (1)

where equals the number of layers and equals the number of passes. This shows how specimens of 8, 32 and 128 were formed using two, three and four rolling passes, respectively. Assuming each layer condenses uniformly at 75%, each sheet becomes 0.25 times as thick as the previous cycle. Recall that the initial thickness is ~1 mm. Equation (2) below evaluates the thickness of each individual layer in relation to the number of passes the specimen has undergone.

 = ( ) 0.25 = 1 0.25 = (0.25 ) where equals the single layer thickness and equals the number of passes. By multiplying the individual layer thickness by the number of layers gives the final thickness. = [(221 ) (0.25 )] ln = (2n 1)ln(2) + (n)ln(0.25) ln = [2 ln(2) + ln(0.25)] ln(2) ln = ln(2) = .

(2)

(a)

(3)

The derivation in (3) above proves that the specimen always reaches a final thickness of 0.5 mm (500 m) for any number of passes. RESULTS Highly Layered Composites Using the ARB process, numerous 2, 8 and 32-layered composite panels were formed, along with a 128-layered specimen. As shown by (1), the 128-sheet composite was formed in just four rolling passes. Highly layered composites are beneficial because additional layers equate to more interfaces available for CNT application, which ultimately leads to a higher level of CNTs within the composite. High levels of CNTs compound the mechanical strengthening of aluminum gained by roll bonding alone [2] [22]. The number of sheets was limited in our experiment primarily by the loss of material do to edge deformation removal. For instance, the 128-sheet specimens volume changed from ~2006 mm3 to ~1333 mm3 after four passes, a 66.5% decrease in volume. The removal of deformations is necessary to ensure subsequent bonding passes are successful. Bonding Parameters The reduction percentage needed to bond specimens varies directly with initial sheet thickness. Specimens of initial thickness of approximately 0.2 mm were successfully bonded, but a reduction percentage of 85-90% was needed to create a full bond. In contrast, 1 mm thick specimens needed only 75% reduction to bond. Sheets less than 0.2 mm were not successfully bonded. Al-CNT composites bonded successfully at a rate of 65%, with specimens containing double the CNTs accounting for 75% of the failures. In contrast, non-sprayed specimens bonded 85% of the time. Though there are many parameters that govern cold-welding, the additional of CNTs has a markedly negative affect on the rate of successful bonding. Other factors, such as rolling speed and specimen width or length, had decidedly less effect on the rate of successful bonding.

(b)

Fig. 3: Optical micrograph of knurling (a) on the surface of a sheet and (b) after bonding

Knurling Knurling creates spaces between the layers of the composite in which the metal matrix can flow and allows for the addition of higher levels of CNTs. Specimens that were both sanded and knurled bonded at the same rate as specimens that were only sanded; the effect of knurling on bond quality is negligible in comparison to other parameters. However, knurling must be used in addition to sanding, because sheets that are only knurled will not effectively bond. Fig. 3 above shows optical micrographs of knurling before and after bonding. Our process used a knurling pattern that made indentations orthogonal to the longitudinal plane. A variety of patterns could be applied in the same way depending on the application.

procedure in the ARB process, but a preferred one i.e. multiple 32-sheet specimens were produced without the use of annealing. Fig. 4 above shows one such specimen The heat from annealing can have undesirable secondary effects on the CNTs. Additionally, annealing becomes increasingly detrimental to the composites as the number of sheets increases. Any air trapped within the bonded sheets expands when heated and forms bubbles that detract from the bond quality. This issue is compounded when annealing is used in conjunction with knurling. Interfacial Bonding Fig. 5 below shows cross-sectional images of composites with different sheet counts. These images show the diminishing size of the visible bonding regions between sheets as the number of passes increases. For the 8 and 32-sheet specimens, only some of the separations between sheets are visible. At 128-sheets, a single bond region is visible at the highest magnification. Distinct layers are more readily seen at the edges of the specimen because rolling pressure distributes more uniformly in the middle of the composites. All specimens that reached
Fig. 5: Optical micrographs of interfacial bonding between (a) 2 sheets, (b) 8 sheets, (c) 32 sheets, and (d) 128 sheets.

Fig. 4: Optical micrograph of a 32-sheet composite processed without annealing

Annealing Ductility lost to work hardening throughout the ARB process was recovered through annealing. The increase in ductility decreases the threshold strain [20] and thus, the required rolling pressure. However, annealing is not a necessary

(a)

(b)

(c)

(d)

this stage were fully bonded. A specimen was deemed fully bonded if no sheets could be separated from the composite using a sharp edge. If separation was present in a portion of the specimen after deformations had been removed, it was considered a pseudo-bonded specimen. CONCLUSIONS AND OUTLOOK This study has shown that accumulative roll bonding can be used to create multilayered Al-CNT composite panels. The process was effective in producing a composite consisting of 128 sheets in four rolling passes. Additionally, knurling was proven as a viable surface preparation within the accumulative roll bonding process. Furthermore, it was verified that Al-CNT composites of at least 32-sheets can be formed without the use of heat treatment. This fact, in conjunction with the relative simplicity of the ARB process, shows that this process is a viable option in composite mass production. Outlook Further research on composites consisting of a very high number of layers could improve the understanding of how CNTs react within highly condensed composites. Additionally, investigation of the maximum amount of CNTs that can be added to a composite, while maintaining cold-welding bond strength, should be established. Both of these topics along with the research done in this study could lead to a better understanding of the mechanical strength limits of Al-CNT composites. ETHICAL IMPLICATIONS AND CONSIDERATIONS Ethical considerations involving Al-CNT composites can be focused primarily on carbon-nanotubes, as aluminum is a relatively innocuous material, better understood than CNTs. Additionally, high-level production of CNTs has only been realized fairly recently. Therefore, the effects of CNTs on people should be researched thoroughly before they are used, especially in mass production applications. The very small size of nanoparticles means they are difcult or even impossible to lter, which can present many challenges in the area of health and safety. Their size also allows them to enter the body in a variety of ways. Once in the body, nanoparticles may be able to migrate freely, even scaling the blood-brain barrier [23]. It has been shown experimentally that CNTs are capable of inducing inammation, epithelioid granulomas, brosis, and biochemical toxicity changes in the lungs that might impair pulmonary functions of lab rats [24]. Because of these findings, CNTs have been likened to asbestos fibers. However, it is believed that they cannot escape into the air as individual bers like asbestos [23]. In addition, the problem of human inhalation can be greatly reduced by the use of spraying machines and proper ventilation. Nevertheless, the impact CNTs on health and safety should be fully explicated before they are used consistently in industry.

ACKNOWLEDGMENTS I would like to thank my mentor Dr. Kim and my graduate mentor Mina Bastwros for leading me throughout this study and teaching me a great deal this summer. I would also like to commend Can Zhu and Jie Wang for their help in the lab. Finally, I would like to acknowledge Amy Carver, Kristi Korkowski, Dr. Sundararajan, Dr. Shrotriya, and everyone involved in the Iowa State MoSAIc program for making this a great experience. REFERENCES
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