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At least 91 records · Page 5

Application of entropy and signal energy for ultrasound-based classification of three-dimensional printed polyetherketoneketone components

This paper describes a preliminary method for the classification of annealed and unannealed polyetherketoneketone (PEKK) components manufactured using a material extrusion three-dimensional (3D) printing process. PEKK is representative of a class of high-performance thermoplastics that are increasingly employed as feedstocks for use in 3D printing. PEKK components may be used continuously at elevated temperatures, are chemically resistant, and able to withstand large mechanical loads. These properties render PEKK suitable as a metal component replacement in aerospace applications, high-temperature industrial applications, and surgical implants. The structure of PEKK is semi-crystalline with the specific crystallinity correlating to the final properties during application, making determination of this property crucial. This study compares three different signal processing techniques intended to distinguish annealed (high crystallinity) from unannealed (low crystallinity) components using backscattered ultrasound. The first is energy-based and is unable to detect annealing. The second two are based on different entropies of the backscattered signal: a limiting form of Renyi's entropy and a limiting form of joint entropy. The joint entropy values for the annealed and unannealed specimens fall into two non-overlapping intervals and have a statistical separation of two standard deviations.

36 MATERIALS SCIENCE↗

Effects of processing temperature, pressure, and fiber volume fraction on mechanical and morphological behaviors of fully-recyclable uni-directional thermoplastic polymer-fiber-reinforced polymers

This work explores a type of composite called thermoplastic polymer-fiber-reinforced polymers (PFRPs), often referred to as self-reinforced composites (SRCs). A representative PFRP was exemplified using unidirectional (UD) ultra-high-molecular-weight polyethylene (UHMWPE) fibers embedded in a high-density polyethylene (HDPE) matrix. The effects of compression molding temperature and pressure on the mechanical and morphological behaviors of the filament-wound PFRPs with various fiber volume fractions (V f ) were experimentally investigated. The results elucidate the evolution of morphologies and tensile properties of the PFRPs due to thermal melting, fiber misalignment from pressure, and (V f )-induced structural variance, which has not been comprehensively reported yet. The highest specific tensile strength and modulus of the PFRP laminae reach 600 MPa/(g/cm 3 ) and 31 GPa/(g/cm 3 ), respectively. These properties are comparable to glass-/aramid-fiber-reinforced polymers (GFRPs, GFRTPs, AFRPs, and AFRTPs), with PFRPs exhibiting better ductility (specific strain at peak load ≈ 4%/(g/cm 3 )) than other common polymer composites. The motivation for this work was the high recyclability of PFRPs, which can be recycled by melting both the fibers and the matrix, and then reshaped them for re-manufacturing composites to maximize the efficiency in material reuse. This process simplifies the implementation of closed-loop recycling, re-manufacturing, and reuse to support sustainability in composites. This work aims to contribute to advancing thermoplastic PFRPs for their potential applications in various industries.

36 MATERIALS SCIENCE↗

Linking thermoset ink rheology to the stability of 3D-printed structures

Thermoset polymer composites show promise for additive manufacturing (AM) applications to address some of the limitations of the more widely used thermoplastic feedstock materials. Thermosets offer attractive mechanical properties while providing excellent interlayer bonding, high thermal and chemical stability, and reduced energy consumption as a result of deposition at room temperature. However, since thermoset resins rely on a crosslinking reaction to solidify, rather than quickly cooling like thermoplastics, viscoelastic properties must be relied upon to maintain deposited shape after deposition until crosslinking can occur. This fact has not impeded development and characterization of new thermoset feedstocks on the small scale, but recent efforts to increase scale of thermoset printing have highlighted issues with structural stability under self-weight. This study addresses issues of self-weight by investigating the mechanisms that cause collapse of tall, thin printed walls. Using nanoclay- and fumed silica-filled epoxy feedstocks, this work compares the collapse height for printed walls to stability models based on yielding and buckling mechanics. Inputs for these models – shear yield stress and storage modulus – were taken directly from parallel plate rheometry measurements. Model predictions were found to be in good agreement with experimental results, where both yielding and buckling behavior were observed, provided the rheological properties after a shear excursion were used as inputs. This work establishes a direct link between basic rheological properties of the feedstock, geometry of the printed object, and achievable height. Overall, the results presented highlight the importance of understanding recovery behavior in thermoset feedstocks and provide valuable guidance on the development of more effective direct-ink writing feedstock materials.

36 MATERIALS SCIENCE↗

Predictive Modeling of Fast-Curing Thermosets in Nozzle-Based Extrusion

This work presents an approach to modeling the dynamic spreading and curing behavior of thermosets in nozzle-based extrusions. Thermosets cover a wide range of materials, some of which permit low-temperature processing with subsequent high-temperature and high-strength working properties. Extruding thermosets may overcome the limited working temperatures and strengths of conventional thermoplastic materials used in additive manufacturing. This project aims to produce technology for the fabrication of thermoset-based structures leveraging advances made in nozzle-based extrusion, such as fused deposition modeling (FDM), material jetting, and direct writing. Understanding the synergistic interactions between spreading and fast curing of extruded thermosetting materials will provide essential insights for applications that require accurate dimensional controls, such as additive manufacturing [1], [2] and centrifugal coating/forming [3]. Two types of thermally curing thermosets -- one being a soft silicone (Ecoflex 0050) and the other being a toughened epoxy (G/Flex) -- served as the test materials in this work to obtain models for cure kinetics and viscosity. The developed models align with extensive measurements made with differential scanning calorimetry (DSC) and rheology. DSC monitors the change in the heat of reaction, which reflects the rate and degree of cure at different crosslinking stages. Rheology measures the change in complex viscosity, shear moduli, yield stress, and other properties dictated by chemical composition. By combining DSC and rheological measurements, it is possible to establish a set of models profiling the cure kinetics and chemorheology without prior knowledge of chemical composition, which is usually necessary for sophisticated mechanistic modeling. In this work, we conducted both isothermal and dynamic measurements with both DSC and rheology. With the developed models, numerical simulations yielded predictions of diameter and height of droplets, along with width and height of extruded lines cured at varied temperatures. Experimental results carried out on a goniometric platform and a nozzle-based 3D printer showed agreement with the numerical simulations. Finally, this presentation will show how the models are adaptable to the planning of tool paths and designs in additive manufacturing.

Xie, Jingjin↗

Preparing thermoplastic aromatic polyimides

Method prepares aromatic polyimides with significantly reduced glass-transition temperatures and without accompanying loss of high-level thermo-oxidative stability which has been typical. This has been made possible by use of diamine monomers with specific stereoisomeric features.

Bell, V. L.↗

Test methods and design allowables for fibrous composites. Volume 2

Topics discussed include extreme/hostile environment testing, establishing design allowables, and property/behavior specific testing. Papers are presented on environmental effects on the high strain rate properties of graphite/epoxy composite, the low-temperature performance of short-fiber reinforced thermoplastics, the abrasive wear behavior of unidirectional and woven graphite fiber/PEEK, test methods for determining design allowables for fiber reinforced composites, and statistical methods for calculating material allowables for MIL-HDBK-17. Attention is also given to a test method to measure the response of composite materials under reversed cyclic loads, a through-the-thickness strength specimen for composites, the use of torsion tubes to measure in-plane shear properties of filament-wound composites, the influlence of test fixture design on the Iosipescu shear test for fiber composite materials, and a method for monitoring in-plane shear modulus in fatigue testing of composites.

Chamis, Christos C.↗

STPI/LARC: A 200 deg C polyimide adhesive

A copolyimide, STPI/LARC, was prepared from the reaction of 3,3'4'benzophenonetetracarboxylic dianhydride (BTDA), equimolar quantities of m-phenylenediamine and 4,4'-oxydianiline, and a small amount of phthalic anhydride to control the molecular weight. The processability and adhesive properties of STPI/LARC were compared to those of a commercially available form of LARC-TPI. LARC-TPI, a thermoplastic polyimide, from the reaction of BTDA and 3,3'-diaminobenzophenone, had previously shown promise as a high temperature structural adhesive. Lap shear specimens were fabricated using adhesive tape prepared from each of the two polymers. Lap shear tests were performed at room temperature, 177 C, and 204 C before and after exposure to a 72-hour water-boil and to aging at 204 C.

Progar, D. J.↗

A thermoplastic copolyimide

A copolyimide, STPI/LARC, was prepared from the reaction of 3,3'4,4'-benzophenonetetracarboxylic dianhydride (BTDA), equimolar quantities of m-phenylenediamine and 4,4'-oxydianiline, and a small amount of phthalic anhydride to control the molecular weight. The processability and adhesive properties of STPI/LARC were compared to those of a commercially available form of LARC-TPI. LARC-TPI, a thermoplastic polyimide, from the reaction of BTDA and 3,3'-diaminobenzophenone, had previously shown promise as a high temperature structural adhesive. Lap shear specimens were fabricated using adhesive tape prepared from each of the two polymers. Lap shear tests were performed at room temperature, 177 C, and 204 C before and after exposure to a 72-hour water-boil and to aging at 204 C.

Progar, D. J.↗

Aromatic Diamines and Polyimides Based on 4,4'-Bis-(4-Aminophenoxy)-2,2' or 2,2',6,6'- Substituted Biphenyl

This invention relates the novel diamines. the polyimide oligomers and the polyimides derived therefrom and to the method of preparing the diamines, oligomers and the polyimides. The thermoplastic polyimides derived from the aromatic diamines of this invention are characterized as having a high glass transition temperature. good mechanical properties and improved processability in the manufacture of adhesives. electronic and composite materials for use in the automotive and aerospace industry. The distinction of the novel aromatic diamines of this invention is the 2.2',6.6substituted biphenyl radicals which exhibit noncoplanar conformation that enhances the solubility of the diamine as well as the processability of the polyimides. while retaining a relatively high glass transition temperature and improved mechanical properties at useful temperature ranges.

Chuang, Chun-Hua K.↗

Aromatic Diamines and Polyimides Based on 4,4'-Bis-(4-Aminophenoxy)-2,2' or 2,2',6,6'- Substituted Biphenyl

This invention relates the novel diamines, the polyimide oligomers and the polyimides derived therefrom and to the method of preparing the diamines, oligomers and the polyimides. The thermoplastic polyimides derived from the aromatic diamines of this invention are characterized as having a high glass transition temperature, good mechanical properties and improved processability in the manufacture of adhesives, electronic and composite materials for use in the automotive and aerospace industry. The distinction of the novel aromatic diamines of this invention is the 2,2',6,6'-substituted biphenyl radicals which exhibit noncoplanar conformation that enhances the solubility of the diamine as well as the processability of the polyimides, while retaining a relatively high glass transition temperature and improved mechanical properties at useful temperature ranges.

Chun-Hua K Chuang↗

Use of Guided Acoustic Waves to Assess the Effects of Thermal-Mechanical Cycling on Composite Stiffness

The introduction of new, advanced composite materials into aviation systems requires it thorough understanding of the long-term effects of combined thermal and mechanical loading. As part of a study to evaluate the effects of thermal-mechanical cycling, it guided acoustic (Lamb) wave measurement system was used to measure the bending and out-of-plane stiffness coefficients of composite laminates undergoing thermal-mechanical loading. The system uses a pulse/receive technique that excites an antisymmetric Lamb mode and measures the time-of-flight over a wide frequency range. Given the material density and plate thickness, the bending and out-of-plane shear stiffnesses are calculated from a reconstruction of the velocity dispersion curve. A series of 16 and 32-ply composite laminates were subjected to it thermal-mechanical loading profile in load frames equipped with special environmental chambers. The composite systems studied were it graphite fiber reinforced amorphous thermoplastic polyimide and it graphite fiber reinforced bismaleimide thermoset. The samples were exposed to both high and low temperature extremes its well as high and low strain profiles. The bending and out-of-plane stiffnesses for composite sample that have undergone over 6,000 cycles of thermal-mechanical loading are reported. The Lamb wave generated elastic stiffness results have shown decreases of up to 20% at 4,936 loading cycles for the graphite/thermoplastic samples and up to 64% at 4,706 loading cycles for the graphite/thermoset samples.

Seale, Michael D.↗

Polyimides based on 4,4'-bis (4-aminophenoxy)-2,2'or 2,2', 6,6'-substituted biphenyl

This invention relates the novel diamines, the polyimide oligomers and the polyimides derived therefrom and to the method of preparing the diamines, oligomers and the polyimides. The thermoplastic polyimides derived from the aromatic diamines of this invention are characterized as having a high glass transition temperature, good mechanical properties and improved processability in the manufacture of adhesives, electronic and composite materials for use in the automotive and aerospace industry. The distinction of the novel aromatic diamines of this invention is the 2,2',6,6'-substituted biphenyl radicals which exhibit noncoplanar conformation that enhances the solubility of the diamine as well as the processability of the polyimides, while retaining a realatively high glass transition temperature and improved mechanical properties at useful temperature ranges.

Chuang, Chun-Hua K.↗

Additive Manufacturing of Poly(phenylene Sulfide) Aerogels via Simultaneous Material Extrusion and Thermally Induced Phase Separation

Abstract Additive manufacturing (AM) of aerogels increases the achievable geometric complexity, and affords fabrication of hierarchically porous structures. In this work, a custom heated material extrusion (MEX) device prints aerogels of poly(phenylene sulfide) (PPS), an engineering thermoplastic, via in situ thermally induced phase separation (TIPS). First, pre‐prepared solid gel inks are dissolved at high temperatures in the heated extruder barrel to form a homogeneous polymer solution. Solutions are then extruded onto a room‐temperature substrate, where printed roads maintain their bead shape and rapidly solidify via TIPS, thus enabling layer‐wise MEX AM. Printed gels are converted to aerogels via postprocessing solvent exchange and freeze‐drying. This work explores the effect of ink composition on printed aerogel morphology and thermomechanical properties. Scanning electron microscopy micrographs reveal complex hierarchical microstructures that are compositionally dependent. Printed aerogels demonstrate tailorable porosities (50.0–74.8%) and densities (0.345–0.684 g cm −3 ), which align well with cast aerogel analogs. Differential scanning calorimetry thermograms indicate printed aerogels are highly crystalline (≈43%), suggesting that printing does not inhibit the solidification process occurring during TIPS (polymer crystallization). Uniaxial compression testing reveals that compositionally dependent microstructure governs aerogel mechanical behavior, with compressive moduli ranging from 33.0 to 106.5 MPa.

Chemistry↗

Evaluation of Ti-6Al-4V surface treatments for use with a polyphenylquinoxaline adhesive

Three surface treatments for Ti-6Al-4V adherends were evaluated using a thermoplastic polymer monoether polyphenylquinoxaline, MEPPQ, which had been shown in previous studies to have good potential as a high temperature adhesive for aerospace applications. Initial results based on long term thermal exposure at 232 C (450 F) using the phosphate-fluoride (PF) and chromic acid anodized (CAA) treatments with MEPPQ adhesive were not encouraging. A significant improvement in strength retention and a change in failure mode (cohesive) at 232 C (450F) was found for the SHA treated specimens compared to the PF and CAA treatments. Although an improvement in long term thermal durability was obtained with the SHA treatment of Ti-6Al-4V, an improved surface treatment with better long term durability is still required for aerospace applications.

Progar, D. J.↗

Evaluation of Ti-6Al-4V surface treatments for use with a polyphenylquinoxaline adhesive

Three surface treatments for Ti-6Al-4V adherends were evaluated using a thermoplastic polymer monoether polyphenylquinoxaline, MEPPQ, which had been shown in previous studies to have good potential as a high temperature adhesive for aerospace applications. Initial results based on long term thermal exposure at 232 C (450 F) using the phosphate-fluoride (PF) and chromic acid anodized (CAA) treatments with MEPPQ adhesive were not encouraging. A significant improvement in strength retention and a change in failure mode (cohesive) at 232 C (450 F) was found for the SHA treated specimens compared to the PF and CAA treatments. Although an improvement in long term thermal durability was obtained with the SHA treatment of Ti-6Al-4V, an improved surface treatment with better long term durability is still required for aerospace applications.

Progar, Donald J.↗

Polymer powder prepregging: Scoping study

Early on, it was found that NEAT LARC-TPI thermoplastic polyimide powder behaved elastoplastically at pressures to 20 ksi and temperatures to 260 degrees celcius (below MP). At high resin assay, resin powder could be continuously cold-flowed around individual carbon fibers in a metal rolling mill. At low resin assay (2:1, C:TPI), fiber breakage was prohibitive. Thus, although processing of TPI below MP would be quite unique, it appears that the polymer must be melted and flowed to produce low resin assay prepreg. Fiber tow was spread to 75 mm using a venturi slot tunnel. This allowed intimate powder/fiber interaction. Two techniques were examined for getting room temperature powder onto the room temperature fiber surface. Electrostatic powder coating allows the charged powder to cling tenaciously to the fiber, even while heated with a hot air gun to above its melt temperature. A variant of the wet slurry coating process was also explored. The carbon fibers are first wetted with water. Then dry powder is sprinkled onto the wet tow and doctor-rolled between the fibers. The wet structure is then taken onto a heated roll, with hot air guns drying and sinter-melting the powder onto the fiber surfaces. In both cases SEM shows individual fibers coated with powder particles that have melted in place and flowed along the fiber surface via surface tension.

Throne, James L.↗

Engineering the Novel Extremophile Alga Chlamydomonas pacifica for High Lipid and High Starch Production as a Path to Developing Commercially Relevant Strains

Microalgae offer a compelling platform for the production of commodity products, due to their superior photosynthetic efficiency, adaptability to nonarable lands and nonpotable water, and their capacity to produce a versatile array of bioproducts, including biofuels and biomaterials. However, the scalability of microalgae as a bioresource has been hindered by challenges such as costly biomass production related to vulnerability to pond crashes during large-scale cultivation. This study presents a pipeline for the genetic engineering and pilot-scale production of biodiesel and thermoplastic polyurethane precursors in the extremophile species Chlamydomonas pacifica. This extremophile microalga exhibits exceptional resilience to high pH (>11.5), high salinity (up to 2% NaCl), and elevated temperatures (up to 42 °C). Initially, we evolved this strain to also have a high tolerance to high light intensity (>2000 μE/m 2 /s) through mutagenesis, breeding, and selection. We subsequently genetically engineered C. pacifica to significantly enhance lipid production by 28% and starch accumulation by 27%, all without affecting its growth rate. We demonstrated the scalability of these engineered strains by cultivating them in pilot-scale raceway ponds and converting the resulting biomass into biodiesel and thermoplastic polyurethanes. This study showcases the complete cycle of transforming a newly discovered species into a commercially relevant commodity production strain. This research underscores the potential of extremophile algae, including C. pacifica, as a key species for the burgeoning sustainable bioeconomy, offering a viable path forward in mitigating environmental challenges and supporting global bioproduct demands.

59 BASIC BIOLOGICAL SCIENCES↗

A thermoplastic polyimidesulfone

A polymer system has been prepared which has the excellent thermoplastic properties generally associated with polysulfones, and the solvent resistance and thermal stability of aromatic polyimides. This material, with improved processability over the base polyimide, can be processed in the 260-325 C range in such a manner as to yield high quality, tough unfilled moldings; strong, high-temperature-resistant adhesive bonds; and well consolidated, graphite-fiber-reinforced moldings (composities). The unfilled moldings have physical properties that are similar to aromatic polysulfones which demonstrates the potential as an engineering thermoplastic. The adhesive bonds exhibit excellent retention of initial strength levels even after thermal aging for 5000 hours at 232 C. The graphite-fiber-reinforced moldings have mechanical properties which makes this polymer attractive for the fabrication of structural composites.

St.clair, T. L.↗