AMML Modeling of CNT based composites N. Chandra and C. Shet FAMU-FSU College of Engineering, Florida State University, Tallahassee, FL 32310

AMML Answer: Currently NO!!! Parallel model Upper Bound Series model Lower Bound

AMML Interface Properties affected Fatigue/FractureThermal/electronic/magnetic Factors affecting interfacial properties Trans. & long. Stiffness/strength Interfacial chemistry Mechanical effects Origin: Chemical reaction during thermal-mechanical Processing and service conditions, e.g. Aging, Coatings, Exposures at high temp.. Issues: Chemistry and architecture effects on mechanical properties. Approach: Analyze the effect of size of reaction zone and chemical bond strength (e.g. SCS-6/Ti matrix and SCS-6/Ti matrix ) Residual stress Origin: CTE mismatch between fiber and matrix. Issues: Significantly affects the state of stress at interface and hence fracture process Approach: Isolate the effects of residual stress state by plastic straining of specimen; and validate with numerical models. Asperities Origin: Surface irregularities inherent in the interface Issues: Affects interface fracture process through mechanical loading and friction Approach: Incorporate roughness effects in the interface model; Study effect of generating surface roughness using: Sinusoidal functions and fractal approach; Use push-back test data and measured roughness profile of push-out fibers for the model. Metal/ ceramic/ polymer CNTs H. Li and N. Chandra, International Journal of Plasticity, 19, , (2003).

AMML Functionalized Nanotubes Change in hybridization (SP2 to SP3) Experimental reports of different chemical attachments Application in composites, medicine, sensors Functionalized CNT are possibly fibers in composites How do fiber properties differ with chemical modification of surface?

AMML Functionalized nanotubes Increase in stiffness observed by functionalizing Stiffness increase is more for higher number of chemical attachments Stiffness increase higher for longer chemical attachments Vinyl and Butyl Hydrocarbons T=77K and 3000K Lutsko stress N. Chandra, S. Namilae, Physical Review B, 69 (9), 09141, (2004)

AMML Increased radius of curvature at the attachment because of change in hybridization Radius of curvature lowered in adjoining area Sp3 Hybridization here Radius variation

AMML Evolution of defects in functionalized CNT Defects Evolve at much lower strain of 6.5 % in CNT with chemical attachments Onset of plastic deformation at lower strain. Reduced fracture strain

AMML Different Fracture Mechanisms Fracture Behavior Different Fracture happens by formation of defects, coalescence of defects and final separation of damaged region in defect free CNT In Functionalized CNT it happens in a brittle manner by breaking of bonds S. Namilae, N. Chandra, Chemical Physics Letters, 387, 4-6, , (2004)

AMML Interfacial shear Typical interface shear force pattern. Note zero force after Failure (separation of chemical attachment) After Failure Max load 250,000 steps Interfacial shear measured as reaction force of fixed atoms

AMML Matrix Debonding and Rebonding Energy for debonding of chemical attachment 3eV Strain energy in force-displacement plot 20 ± 4 eV Energy increase due to debonding-rebonding Matrix

AMML Interfaces are modeled as cohesive zones using a potential function are work of normal and tangential separation are normal and tangential displacement jump The interfacial tractions are given by Interfacial traction-displacement relationship are obtained using molecular dynamics simulation based on EAM functions 1.X.P. Xu and A Needleman, Modelling Simul. Mater. Sci. Eng.I (1993) N. Chandra and P.Dang, J of Mater. Sci., 34 (1999) Grain boundary interface Mechanics of Interfaces in Composites Atomic Simulations Reference Formulations

AMML Debonding and Rebonding of Interfaces Rebonding Debonding Failure

AMML Prelude 2 Cohesive Zone Model CZM is represented by traction-displacement jump curves to model the separating surfaces Advantages  CZM can create new surfaces.  Maintains continuity conditions mathematically, despite the physical separation.  CZM represents physics of the fracture process at the atomic scale.  Eliminates singularity of stress and limits it to the cohesive strength of the the material.  It is an ideal framework to model strength, stiffness and failure in an integrated manner. N. Chandra et.al, Int. J. Solids Structures, 37, , (2002).

AMML Finite element simulation: Composite stiffness

AMML Fig. Shear lag model for aligned short fiber composites. (a) representative short fiber (b) unit cell for analysis (a) (b) Shear Lag Model * Prelude 1 The governing DE Whose solution is given by Where Disadvantages The interface stiffness is dependent on Young’s modulus of matrix and fiber, hence it may not represent exact interface property. k remains invariant with deformation Cannot model imperfect interfaces * Original model developed by Cox [1] and Kelly [2] [1] Cox, H.L., J. Appl. Phys. 1952; Vol. 3: p. 72 [2] Kelly, A., Strong Soilids, 2 nd Ed., Oxford University Press, 1973, Chap. 5.

Modified Shear lag Model The governing DE If the interface between fiber and matrix is represented by cohesive zone, then Evaluating constants by using boundary conditions, stresses in fiber is given by

AMML Comparison between Original and Modified Shear Lag Model Variation of stress-strain response in the elastic limit with respect to parameter  The parameter  defined by defines the interface strength in two models through variable k. In original model In modified model interface stiffness is given by slope of traction-displacement curve given by In original model k is invariant with loading and it cannot be varied In modified model k can be varied to represent a range of values from perfect to zero bonding

Comparison with Experimental Result The average stress in fiber and matrix far a applied strain  is given by Then by rule of mixture the stress in composites can be obtained as Fig. A typical traction-displacement curve used for interface between SiC fiber and 6061-Al matrix For SiC-6061-T6-Al composite interface is modeled by CZM model given by With N=5, and k 0 = 1, k 1 = 10, k 2 = -36, k 3 = 72, k 4 = -59, k 5 = 12. Taking  max = 1.8  y, where  y is yield stress of matrix and  max =0.06  c

Fig.. Comparison of experimental [1] stress-strain curve for Sic/6061-T6-Al composite with stress-strain curves predicted from original shear lag model and CZM based Shear lag model. [1] Dunn, M.L. and Ledbetter, H., Elastic-plastic behavior of textured short-fiber composites, Acta mater. 1997; 45(8): The constitutive behavior of 6061-T6 Al matrix [21] can be represented by Comparison (contd.) yield stress =250 MPa, and hardening parameters h = 173 MPa, n = Young’s modulus of matrix is 76.4 GPa. Young’s modulus of SiC fiber is E f of 423 GPa Result comparison EcEc (GPa) Failure Strength (MPa) Variable Original Modified Experiment

FEAModel The CNT is modeled as a hollow tube with a length of 200, outer radius of 6.98 and thickness of 0.4. CNT modeled using 1596 axi-symmetric elements. Matrix modeled using axi-symmetric elements. Interface modeled using node axisymmetric CZ elements with zero thickness Comparison with Numerical Results Fig. (a) Finite element mesh of a quarter portion of unit model (b) a enlarged portion of the mesh near the curved cap of CNT

AMML Longitudinal Stress in fiber at different strain level Interface strength = 5000 MPa Interface strength = 50 MPa

AMML Shear Stress in fiber at different strain level Interface strength = 5000 MPa Interface strength = 50 MPa

AMML Table : Variation of Young’s modulus of the composite with matrix young’s modulus, volume fraction and interface strength Effect of interface strength on stiffness of Composites Young’s Modulus (stiffness) of the composite not only increases with matrix stiffness and fiber volume fraction, but also with interface strength

AMML Conclusion 1.The critical bond length or ineffective fiber length is affected by interface strength. Lower the interface strength higher is the ineffective length. 2.In addition to volume fraction and matrix stiffness, interface property, length and diameter of the fiber also affects elastic modulus of composites. 3.Stiffness and yield strength of the composite increases with increase in interface strength. 4.In order to exploit the superior properties of the fiber in developing super strong composites, interfaces need to be engineered to have higher interface strength.

Critical Bond Length l/2 Table 1. Critical bond lengths for short fibers of length 200 and for different interface strengths and interface displacement parameter  max1 value 0.15.

Critical bond length varies with interface property (Cohesive zone parameters (  max,  max1 ) When the external diameter of a solid fiber is the same as that of a hollow fiber, then, for any given length the load carried by solid fiber is more than that of hollow fiber. Thus, it requires a longer critical bond length to transfer the load At higher  max1 the longitudinal fiber stress when the matrix begins to yield is lower, hence critical bond length reduces For solid cylindrical fibers, at low interface strength of 50 MPa, when the fiber length is 600 and above, the critical bond length on each end of the fiber exceeds semi-fiber length for some values  max1 tending the fiber ineffective in transferring the load interface strength is 5000MPa Variation of Critical Bond Length with interface property interface strength is 50MPa

Effect of interface strength on strength of Composites Table Yield strength (in MPa) of composites for different volume fraction and interface strength Fiber volume fraction = 0.02 Fiber volume fraction = 0.05 Yield strength (when matrix yields) of the composite increases with fiber volume fraction (and matrix stiffness) but also with interface strength With higher interface strength hardening modulus and post yield strength increases considerably

Effect of interface displacement parameter  max1 on strength and stiffness Fig. Variation of stiffness of composite material with interface displacement parameter  max1 for different interface strengths. Fig. Variation of yield strength of the composite material with interface displacement parameter  max1 for different interface strengths. As the slope of T-  curve decreases (with increase in  max1 ), the overall interface property is weakened and hence the stiffness and strength reduces with increasing values of  max1. When the interface strength is 50 MPa and fiber length is small the young’s modulus and yield strength of the composite material reaches a limiting value of that of matrix material.

Effect of length of the fiber on strength and stiffness Fig. Variation of yield strength of the composite material with different fiber lengths and different interface strengths Fig. Variation of Young’s modulus of the composite material with different fiber lengths and for different interface strengths For a given volume fraction the composite material can attain optimum values for mechanical properties irrespective of interface strength. For composites with stronger interface the optimum possible values can be obtained with smaller fiber length With low interface strength longer fiber lengths are required to obtain higher composite properties. During processing it is difficult to maintain longer CNT fiber straigth.

AMML Objective To develop an analytical model that can predict the mechanical properties of short-fiber composites with imperfect interfaces. To study the effect of interface bond strength on critical bond length l c To study the effect of bond strength on mechanical properties of composites. Approach To model the interface as cohesive zones, which facilitates to introduce a range of interface properties varying from zero binding to perfect binding