Adhesion Characterization and Enhancement between Polyimide-Silica Composite and Nodulated Copper for Applications in Next-Generation Microelectronics.

As the need for high-speed electronics continues to rise rapidly, printed wiring board (PWB) requirements become ever-more demanding. A typical PWB is fabricated by bonding dielectric films such as polyimide to electrically conductive copper foil such as rolled annealed (RA) copper and is expected to become thinner, flexible, durable, and compatible with high-frequency 5G performance. Polyimide films inherently feature a higher coefficient of thermal expansion (CTE) than copper foils; this mismatch causes residual thermal stresses. To attenuate the mismatch, silica nanoparticles may be used to reduce the CTE of PI. A nodulated copper surface can be used to enhance the Cu/PI adhesion by additional bonding mechanisms that could include a type of mechanical bonding, which is a focus of this study. In this investigation, a 90° peel test was used to measure the peel strength in copper/polyimide/copper laminates containing nodulated copper and polyimide reinforced with 0, 20, and 40 wt % silica nanoparticles. The influence of silica nanoparticles on the peel strength was quantitatively evaluated. Laminates incorporating polyimide films lacking silica nanoparticles had a ∼3.75× higher peel strength compared with laminates reinforced with 40% silica. Their failure surfaces were analyzed by using scanning electron microscopy (SEM), energy-dispersive X-ray analysis (EDX), and X-ray photoelectron spectroscopy to identify the mode of failure and to understand bonding mechanisms. The key bonding mechanism, mechanical interlocking, was achieved when the polyimide surrounded or engulfed the copper nodules when the laminate was created. Post-testing failure surface analysis revealed the presence of copper on the polyimide side and polyimide on the copper side, indicating mixed mode failure. An analytical model was developed to determine the impact of applied pressure, temperature, and time on the polyimide penetration and mechanical interlocking around the copper nodules. The model was validated by measuring the peel strength on another set of specimens fabricated using increased temperature and pressure that showed a 3× increase in peel strength compared to lower temperature/pressure processing conditions. This enhanced adhesion resulted from the lower polymer material viscosity at higher temperatures, which fosters deeper and more complete penetration around the copper nodules during processing at higher pressures for longer durations. The methodology of combining peel testing, viscosity and CTE measurement, SEM/EDX, surface chemical analysis, and penetration depth calculation developed herein enables the calculation of the desired processing parameters to enhance functionality and improve adhesion.

Rapid Nanowelding of Carbon Coatings onto Glass Fibers by Electrothermal Shock.

With the rapid development of nanomanufacturing, scaling up of nanomaterials requires advanced manufacturing technology to composite nanomaterials with disparate materials (ceramics, metals, and polymers) to achieve hybrid properties and coupling performances for practical applications. Attempts to assemble nanomaterials onto macroscopic materials are often accompanied by the loss of exceptional nanoscale properties during the fabrication process, which is mainly due to the poor contacts between carbon nanomaterials and macroscopic bulk materials. In this work, we proposed a novel cross-scale manufacturing concept to process disparate materials in different length scales and successfully demonstrated an electrothermal shock approach to process the nanoscale material (e.g., carbon nanotubes) and macroscale (e.g., glass fiber) with good bonding and excellent mechanical property for emerging applications. The excellent performance and potentially lower cost of the electrothermal shock technology offers a continuous, ultrafast, energy-efficient, and roll-to-roll process as a promising heating solution for cross-scale manufacturing.

Hierarchical Composites with Electrophoretically Deposited Carbon Nanotubes for In Situ Sensing of Deformation and Damage.

As composites are used increasingly in structural components, novel techniques for detecting micro-scale damage are required. Their nanoscale size and high aspect ratio allow carbon nanotubes to create electrically conductive pathways that enable sensing. In this work, carbon nanotubes are deposited onto glass fabric using electrophoretic deposition to create hierarchical composites. Polyethylenimine functionalized carbon nanotubes are deposited from an aqueous dispersion using an electric field. Symmetric cross-ply composites are investigated as a model system to demonstrate the ability to detect incipient damage and transverse microcracks. The specimens are subjected to tensile loading, and a resistance increase is observed because of two key mechanisms-a reversible change in nanotube-nanotube tunneling gaps due to elastic straining of the network and a permanent severing of paths in the conducting network due to formation of transverse cracks in the 90° plies. By analyzing the electrical response, the damage state can be identified. Acoustic emission sensors are used to validate the results. The strength and Young's modulus of the composites with integrated carbon nanotubes are similar to the control specimens. Crack density measurements using edge replication reveal that transverse cracking can be suppressed, demonstrating multi-functionality with improved damage tolerance and integrated sensing.

Multiscale Polymer Dynamics in Hierarchical Carbon Nanotube Grafted Glass Fiber Reinforced Composites.

Carbon nanotube (CNT) grafted glass fiber reinforced epoxy nanocomposites (GFRP) present a range of stiffnesses (MPa to GPa) and length scales (µm to nm) at the fiber-matrix interface. The contribution of functionalized CNT networks to the local and bulk polymer dynamics is studied here by using a combination of torsion dynamical mechanical thermal analysis (DMTA), positron annihilation lifetime spectroscopy (PALS), and neutron scattering (NS) measurements. DMTA measurements highlight a reduction in the storage modulus (G') in the rubbery region and an asymmetric broadening of the loss modulus (G″) peak in the α-transition region. NS measurements show a suppressed hydrogen mean-square displacement (MSD) in the presence of glass fibers but a higher hydrogen MSD after grafting functionalized CNTs onto fiber surfaces. PALS measurements show greater free volume characteristics in the presence of the functionalized CNT modified composites, supporting the view that these interface layers increase polymer mobility. While NS and DMTA are sensitive to different modes of chain dynamics, the localization of functionalized nanotubes at the fiber interface is found to affect the distribution of polymer relaxation modes without significantly altering the thermally activated relaxation processes.

Thin and Flexible Carbon Nanotube-Based Pressure Sensors with Ultrawide Sensing Range.

A scalable electrophoretic deposition (EPD) approach is used to create novel thin, flexible, and lightweight carbon nanotube-based textile pressure sensors. The pressure sensors can be produced using an extensive variety of natural and synthetic fibers. These piezoresistive sensors are sensitive to pressures ranging from the tactile range (<10 kPa), the body weight range (∼500 kPa), and very high pressures (∼40 MPa). The EPD technique enables the creation of a uniform carbon nanotube-based nanocomposite coating, in the range of 250-750 nm thick, of polyethyleneimine (PEI) functionalized carbon nanotubes on nonconductive fibers. In this work, nonwoven aramid fibers are coated by EPD onto a backing electrode followed by film formation onto the fibers creating a conductive network. The electrically conductive nanocomposite coating is firmly bonded to the fiber surface and shows piezoresistive electrical/mechanical coupling. The pressure sensor displays a large in-plane change in electrical conductivity with applied out-of-plane pressure. In-plane conductivity change results from fiber/fiber contact as well as the formation of a sponge-like piezoresistive nanocomposite "interphase" between the fibers. The resilience of the nanocomposite interphase enables sensing of high pressures without permanent changes to the sensor response, showing high repeatability.