2016 VTO Annual Merit Review Presentations Lightweight Materials [Slides]
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The quest for converting lignin into high-value products has been continuously pursued in the past few decades. In its native form, lignin is a group of heterogeneous polymers comprised of phenylpropanoids. The major commercial lignin streams, including Kraft lignin, lignosulfonates, soda lignin and organosolv lignin, are produced from industrial processes including the paper and pulping industry and emerging lignocellulosic biorefineries. Although lignin has been viewed as a low-cost and renewable feedstock to replace petroleum-based materials, its utilization in polymeric materials has been suppressed due to the low reactivity and inherent physicochemical properties of lignin. Hence, various lignin modification strategies have been developed to overcome these problems. Herein, we review recent progress made in the utilization of functionalized lignins in commodity polymers including thermoset resins, blends/composites, grafted functionalized copolymers and carbon fiber precursors. In the synthesis of thermoset resins such as polyurethane, phenol-formaldehyde and epoxy, they are covalently incorporated into the polymer matrix, and the discussion is focused on chemical modifications improving the reactivity of technical lignins. In blends/composites, functionalization of technical lignins is based upon tuning the intermolecular forces between polymer components. In addition, grafted functional polymers have expanded the utilization of lignin-based copolymers to biomedical materials and value-added additives. Different modification approaches have also been applied to facilitate the application of lignin as carbon fiber precursors, heavy metal adsorbents and nanoparticles. These emerging fields will create new opportunities in cost-effectively integrating the lignin valorization into lignocellulosic biorefineries.
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Recycled carbon fiber has historically proven challenging to integrate into composite manufacturing due in no small part to the low-density, randomly oriented, discontinuous fiber format that results from typical recycling. Discontinuous fiber requires the use of alternative technologies than those traditionally applied to continuous fiber (e.g., hand lay-up, winding). Extrusion compounding is one such applicable technology, but material transfer into the system requires alternative feeding equipment or the use of an altered procedure as trialed in this research. In this study, an injection molding compound for automotive applications was prepared with recycled carbon fiber and compared against an existing commercial compound. Input fibers and molded compound were evaluated for mechanical performance, while relevant variables such as compounded fiber alignment and aspect ratio were compared to the existing baseline material to confirm a like-for-like composite material structure. Overall, analysis indicates that recycled fiber performs similarly to virgin fiber reinforcement, demonstrating that recycled fiber may be a viable drop-in replacement for short-fiber discontinuous applications.
Engineered Cementitious Composites (ECC) have demonstrated superior mechanical and durability performance than conventional concrete. In the micromechanical reinforcing system of ECC, fibers play a pivotal role in establishing the ultrahigh tensile ductility and autogenous crack width control. This article reviews the state-of-the-art of discontinuous micro-fibers as intrinsic reinforcement of ECC regarding technical performance as well as environmental and economic impacts. Mechanical properties of ECC made with different micro-fibers, man-made or natural, and their embodied energy, emissions and material cost, are comprehensively surveyed. Further, studies on fiber hybridization are discussed regarding the combination of different types of fibers to form synergetic reinforcements that mitigate total material cost, and potentially enhance the composite performance. Lastly, recommendations on fiber selections are highlighted and directions for future research are suggested.
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Light-weight construction, design freedom, integration of functions, and compelling cost element are desired by Original Equipment Manufacturers (OEMs) and their suppliers. The emergence of overmolding of continuous-discontinuous reinforcement enables design freedom and ability to tailor stiffness, strength, and damage tolerance for structural applications. In this work, long fiber thermoplastics (LFT) are overmolded with continuous fiber-reinforced thermoplastic (CFRTP) tape are combined using extrusion compression molding process to evaluate the structural performance. The CFRTP tape overmolded LFT samples were characterized using nondestructive and destructive techniques to track fiber alignment, fiber distribution, manufacturing defects, interfacial bonding of the tape – LFT and effect of CFRTP tape on LFT. Mode 1 fracture toughness, G 1c for tape overmolded LFT was higher by 25–30% compared to literature reported G 1c . This response was attributed to excellent fiber distribution, good fiber wetting, and absence of voids at the interface. Three-point bend test indicated that CFRTP tape overmolded LFT composites were better able to resist damage under the bending load compared to constituent LFT composite. Flexural strength of the overmolded composite was higher by 119–142%, and modulus higher by 77–65% compared to constituent LFT composite. Simulated flexural results accurately represents the mechanical behavior of composites. Here, the penetration energy of tape overmolded LFT composites determined by LVI test was in the range of 27.66–30.15 J, which is significantly higher than constituent LFT composite, 7.76 J. CFRTP tape overmolded LFT composite exhibits progressive fiber fracture, matrix cracking, and interfacial debonding failure, whereas, constituent LFT composite showed catastrophic fiber fracture.
Here, large-scale multimaterial preforms produced by additive manufacturing (AM) underwent compression molding (CM) to produce high-performance thermoplastic composites reinforced with short carbon fibers. AM and CM techniques were integrated to control the fiber orientation (microstructure) and to reduce void content for the improved mechanical performance of the composite. The new integrated manufacturing technique is termed “additive manufacturing-compression molding” (AM-CM). For the present study, the most common materials were used for large-scale printing, i.e., acrylonitrile butadiene styrene (ABS), carbon fiber (CF)–filled ABS (CF/ABS) and glass fiber (GF)–filled ABS (GF/ABS). Three different manufacturing processes; (a) AM (b) extrusion compression molding (ECM), and (c) AM-CM were used to prepare four different panel configurations: (1) neat ABS, (2) CF/ABS, (3) overmold (CF/ABS over neat ABS), and (4) sandwich (neat ABS between two CF/ABS layers). The mechanical properties (tensile and flexural strength and modulus, and Izod impact energy) of samples prepared via all three manufacturing processes were compared. X-ray microcomputer tomography was employed to evaluate the fiber orientation distribution and the volumetric porosity content. The preform maintained high fiber alignment (≈ 82% of fibers within the range of 0–20° in the deposition direction), and the volumetric porosity was reduced by 50% from 3.79% to 1.91% after compression. The alignment of long pores along the deposition direction was also observed. The mechanical properties are discussed with correlation to the fiber alignment and void content in the samples. CF/ABS samples prepared by AM-CM showed significant improvement of 11.15%, 35.27%, 28.6%, and 74.3% in the tensile strength, tensile modulus, flexural strength, and flexural modulus, respectively, when compared with samples prepared by ECM. Unique aspects of this study are the demonstration of large-scale multimaterial AM and the use of multimaterials as preforms to make high-performance composites.
In order to prolong the service life of fiber-reinforced polymer composites, the implementation of self-healing ability with the micro-encapsulated healing agent has been extensively studied. However, such microcapsule-based self-healing composites typically suffer from degraded mechanical properties due to the liquid-phase inclusions, thereby limiting their proliferation. Here, in this study, a low-melting-point alloy is utilized as the particulate inclusions of carbon fiber/epoxy laminated composites. Field's Metal particles (melting point: 62 °C) are distributed between woven carbon fiber preforms followed by the resin impregnation to realize laminated composites with a Field's Metal-enhanced interlayer(s). The resulting laminated composites demonstrate the autonomic repair of interlaminar failure with a 40 % of healing efficiency. Most of all, the mechanical properties of these self-healing laminated composites are comparable to the conventional laminated composites attributed to the rigid inclusions that can be compressed to increase the fiber volume. Since the Field's Metal particle inclusions can bestow polymer composites with self-healing ability and the potential increase in mechanical properties, Field's Metal-enhanced fiber-reinforced polymer composites are expected to unlock the practical utility of self-healing composites.
Self-reinforced composites (SRCs) consist of reinforcing fibers and a base matrix made of the same thermoplastic polymer, offering lightweight, recyclability, and sustainability benefits. However, limited research exists on composites where the reinforcing thermoplastic polymer fibers differ from the base thermoplastic matrix. Here, this study focuses on investigating the mechanical behavior of such composites and exploring different surface modification methods to enhance the fiber/matrix interfacial bonding using polypropylene fibers and a polyethylene matrix as an example. It is shown that surface treatment with a commercial adhesion promoter containing n-butyl acetate significantly improves the interfacial shear strength between polypropylene fibers and the polyethylene matrix, increasing it by 145% compared to other methods investigated. Additionally, increasing the length of the embedded polymer fiber in the matrix leads to a notable increase in specific interfacial energy. Consequently, the thermoplastic polymer-fiber-reinforced polymers (PFRPs) using surface-treated woven polypropylene fabrics and a polyethylene matrix exhibit a 20% higher tensile strength and a 65% higher toughness compared to non-treated PFRPs. This study also shows that specific mechanical properties (normalized by the composite density) of the investigated woven PFRPs are similar to those of non-treated SRCs under uni-axial tension. Particularly, their ductility outperforms carbon-/glass-/aramid-fiber-reinforced polymers by at least 6 times at a same fiber volume fraction. The investigation of such composites and the exploration of surface modification methods present important progress in the field of thermoplastic PFRPs, which serve as a solution for addressing concerns related to recyclability and sustainability.
Hybrid fiber-reinforced polymer composites (HFRPs) are multifunctional materials that bear more than one characteristic benefit. In this study, hybrid cellulose fibers, e.g., pulp fiber (PF) and cellulose nanofibril (CNF), were used for reinforcing poly(lactic acid) (PLA). A synergistic approach was applied to disperse CNF. The low-surface-tension solvent (ethanol), together with PF templating, assisted the dispersion of CNF in PLA. The HFRP achieved a higher tensile strength (∼70 MPa, 29% increase from PLA) and modulus (∼7 GPa, 46% increase from PLA), as well as a higher heat deflection temperature (∼60℃, 6℃ increase compared to neat PLA), compared to single-reinforcement FRPs. Additionally, the formulation was demonstrated to be potentially suitable for large-scale additive manufacturing.
Fiber-reinforced polymer composites have been highlighted as ideal candidates for structural applications in marine renewable energy devices, such as tidal turbines and wave energy converters. It is well understood that harsh marine environments can cause strength degradation of composite laminates, which has been extensively researched at the coupon scale; however, no research has investigated how this translates into larger-scale composite structures. This paper presents a subcomponent-scale study which investigates the effects of hygrothermal aging and subsequent static and fatigue characterization of thick composite T-bolt connections as part of a large, multilaboratory materials research effort. Of the glass-reinforced epoxy and vinylester-epoxy matrix composites tested, both showed measurable static strength degradation (4–36%) after being hygrothermally aged, even though the composite specimens were only partially saturated with water. Under tension–tension fatigue loading, the epoxy specimens performed very well in their dry states but exhibited significant degradation after hygrothermal aging. In comparison, the vinylester-epoxy specimens had much shorter fatigue lives in their dry states but exhibited no degradation after hygrothermal aging. Overall, this research demonstrates that hygrothermal aging can have significant effects on the ultimate strengths and fatigue lives of even partially saturated thick composite T-bolt connections, indicating that degradation of the outer plies on thick composite laminates can have pronounced effects on the whole structure. It discusses the challenges of building an understanding of the effects of harsh marine environments in large-scale composite structures.
The objective of this research is to demonstrate the versatility of a dip coating process for the efficient integration of piezoelectric barium titanate (BaTiO3) microparticles on a wide variety of fibers to design passive self-sensing composites. The microparticles were deposited on glass, aramid, and basalt fiber weaves through the proposed dip coating technique. A computational framework is established to predict the deposition thickness on the fiber surfaces from the given microparticle concentration, size, coating velocity, and coating fluid viscosity. The deposition quality assessment was performed through scanning electron microscope imaging and subsequent image analysis. BaTiO3-coated fibers were directly used in composite preparation. After fabrication, the BaTiO3-enhanced composites were subjected to high-voltage poling. Finally, their passive self-sensing properties were characterized through experimental studies. The results show the adaptability of the proposed coating process to integrate BaTiO3 microparticles within different types of fiber-reinforced composites enabling passive self-sensing to attain subsurface damage characterization.
The rapid growth of the carbon fiber-reinforced polymer (CFRP) composite market has driven researchers to find value-added applications for outdated prepregs, manufacturing scraps, and end-of-life components. Currently, most CFRP waste is incinerated or landfilled, which squanders its residual value and burdens the environment. Various mechanical, thermal, and chemical approaches have been attempted to recover the carbon fiber, polymer matrix, or both. However, these current practices are often costly, energy-intensive, and generate secondary waste and pollution. To address these shortcomings, this project aims to develop a viable and sustainable chemical recycling technology for CFRP waste that can efficiently and cost-effectively decompose the polymer matrix and manufacture new recyclable composites from both the recovered carbon fiber (rCF) and decomposed matrix polymer (DMP).
This work focuses on the simultaneous determination of the elastic constants and the fiber orientation state for a short fiber-reinforced polymer composite by performing a minimum of experimental tests. Here we introduce a methodology that enables the inverse determination of fiber orientation state and the in-situ polymer properties by performing tensile tests at the composite coupon level. We demonstrate the approach for the extrusion deposition additive manufacturing (EDAM) process to illustrate one application of the methodology, but the development is such that it can be applied to short fiber-reinforced polymer (SFRP) systems processed via other methods. Currently, developing composites additive manufacturing digital twins require extensive material characterization. In particular, the mechanical characterization of the orthotropic elastic properties of a composite involves extensive sample preparation and testing, therefore the elasticity tensor is generally populated using a micromechanics model. This, however, requires measuring the fiber orientation state in addition to knowing the constituent material properties. Experimentally measuring the fiber orientation state can be tedious and time consuming. Further, optical methods are limited to resolving the orientation of cylindrical fibers or cluster of non-cylindrical fibers, and computed tomography (CT) methods scan regions of volume that are much smaller than a full printed bead. Therefore, we propose a methodology, accelerated by machine learning, to identify the anisotropic mechanical properties and fiber orientation state at the same time. Early results show that inference of the fiber orientation and composite properties is possible with as few as three tensile tests. Our results show that a combination of the choice of the micromechanics model and reliable set of experiments can yield the nine elastic constants, as well as, the fiber orientation state.
The Big Area Additive Manufacturing (BAAM) system has been used to print large-scale parts, such as automotive structures and molds for tooling, with fiber-reinforced polymer composites. Incorporating reinforcing fibers in printed parts is commonly used to increase stiffness and strength, but it also introduces significant anisotropy in the thermomechanical performance, which can lead to distortion and warping during thermal cycling. Characterizing and understanding how a printed tool distorts is crucial to maintaining tolerances and avoiding part failure. This study uses digital image correlation (DIC) to measure the coefficient of thermal expansion (CTE) of a printed part from room temperature and to a known steady state temperature. The samples were printed with carbon fiber reinforced acrylonitrile butadiene styrene (CF-ABS). Various nozzle geometries were evaluated in this study with the intent of minimizing the thermal- induced distortion experienced by printed parts.
Vehicle lightweighting is an essential component to the automotive industry to improve fuel economy of internal combustion engine (ICE) vehicles to meet ever improving emission standards and to improve the range of electric vehicles (EV). Composite materials offer high specific modulus and specific strength, which makes them appealing for these light weighting efforts. Sheet molding compounds (SMC) are particularly interesting from an automotive perspective because of the relatively low cost and high volume of producing SMC parts. Traditionally, composite materials for automotive application are glass fiber reinforced because of the attractive price - performance ratio, but basalt fibers are a cost and recycling competitive reinforcement alternative in this market. The aim of this project was to examine the feasibility of utilizing basalt fiber for automotive applications. More specifically, an effort was made to examine different fiber sizings on basalt fiber combined with vinyl-ester (VE) resin, and their performance as part of an SMC process. In addition to offering vehicle lightweighting with fiber reinforced polymer composites, basalt fiber is a fully recyclable material and thus supports the IACMI technical goal of: Demonstrate that the technology is capable at a sufficient scale for >80% recyclability or reuse of fiber reinforced polymer composites in five years into useful components with projected cost and quality at commercial scale competitive with virgin materials on a pathway to 95% recyclability or reuse starting in ten years. Three different fiber sizings were applied to a continuous roving of basalt fiber and compared to a traditional Electrical/Chemical Resistance (E-CR) glass fiber that is typically used in these types of applications. Fiber tows were examined for Loss on Ignition percentage (LOI%), Tex, and tow strength. Some sizings clearly outperformed others, and the ability to process these fibers on a pilot scale SMC line was demonstrated. A test plan for the manufacturing and mechanical testing of SMC panels was developed. This work continues outside the time frame allocated for this project. When this work is completed, it will be added to this report and posted as Appendix C. Glass fiber reinforced SMC materials have already proven feasible as a light weighting method for traditionally steel parts like the Volkswagen (VW) Atlas lift-gate (Figure 1); this project team is seeking the feasibility of basalt fiber as a drop-in replacement for glass fiber reinforced SMC. Sizing development for basalt fibers has proven that the mechanical properties are better than E-glass and closer to S-glass, which makes it an interesting material for SMC applications. Better mechanical properties translate to less material needed to achieve load case requirement for target applications. The business case has already been demonstrated for 100,000 parts per year of glass fiber reinforced SMC Atlas lift-gates compared to traditional steel manufacturing processes. Reduced overhead and assembly costs are offset by glass fiber SMC higher cost per kg beyond 100,000 parts per year, which is still a relatively low volume for the automotive industry. For basalt fiber reinforced SMC to become feasible for automotive applications, the price-performance ratio has to be precisely determined. Based on the mechanical performance it is possible to establish a range of applications and technical solutions in which the potential of basalt SMC can be utilized, while the price of the material can be used to compile the business case for such applications. Based on these business cases and the sustainability indicators, glass fiber reinforcement (or other) materials can be directly substituted. Volkswagen’s commitment to reducing carbon emissions cannot be understated. Basalt fiber shows promise of reducing the carbon footprint in SMC materials, especially if sizing optimizations can be made with thermoplastic based SMC. To fully realize the value of basalt fiber reinforced materials, a lifecycle cost analysis should be performed on basalt’s production and recycling, and then compared against E-glass. From this assessment, a true judgement can be made on the commercialization potential of this material. Figure 1. Example of Fiber Reinforced Polymer Composite Liftgate As a conclusion, we can state that Mafic basalt fiber is not a direct replacement for E-glass or E-CR glass based on price, but should be considered a technical solution when E-glass does not provide adequate performance in a composite design and S-glass, aramid and carbon fibers are too costly. Mafic basalt fiber can be placed on the high-performance fiber spectrum next to S-glass for performance but at one third the price. It should be considered for more technically challenging structural designs wherein the performance can demonstrate 20-25% performance enhancement over E-glass to elicit more strength or a weight reduction. Both Michelman and Mafic produce thermoplastic sizings which, in combination with Nylon and polypropylene resin and fibers, can further advance high speed composite implementations while maintaining an eco-friendly manufacturing process.
Additive Manufacturing (AM) of carbon fiber (CF) reinforced composite has received growing attention because of the design flexibility, superior mechanical properties, improved thermal properties, and weight reduction. Autoclave tooling was proven to be a successful application for large scale AM technology. The capital cost, and cost associated with heating, and cycle time in a conventional autoclave process is relatively high. Thus, an innovative design of AM mold with an efficient heating scheme is essential. This study represents an innovative method of the resistive heating of composite molds which does not require a room size oven for heating during the curing processing. Therefore, it has the potential to reduce the operating cost drastically. For the design validation and feasibility study, we performed a numerical analysis of the wire embedded and AM mold parts. The goal of this study is to determine and optimize the thermal behavior of the printed mold with embedded wire technology. It is anticipated that the larger distance between the embedded wires along the printing direction (z-direction) increase the cold spot, on the other hand, a close distance of the wire can create the unwanted localize heating, thus melting. Constant thermal properties of the 20 wt.% short CF reinforced acrylonitrile butadiene styrene (ABS) was used for the simulation purpose. Thermal characterization was set to 100°C to avoid the thermal deformation or bulging on the part surface.