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Enhancing the multi-functional properties of renewable lignin carbon fibers via defining the structure–property relationship using different biomass feedstocks

Lignin has been explored extensively as a renewable precursor for carbon materials, considering its abundance as a major component of plant cell walls and its sustainability as a byproduct of both lignocellulosic biorefinery and the paper-making industry. Despite the extensive efforts to define the process–property relationship, it remains largely unknown how lignin biosynthesis and its chemistry would impact the resultant carbon fiber properties, for both mechanical and electroconductive performances. Such inadequate understanding fundamentally limits feedstock design and selection to improve carbon fiber properties toward broader commercial applications. Using lignin from a broad range of biomass feedstocks for carbon fiber manufacturing, we have fundamentally explored the structure–function relationship between lignin chemistry and carbon fiber performance. Specifically, lignin extracted from hardwood (sugar maple), softwood (loblolly pine and red cedar), and herbaceous plants (corn stover and switchgrass) was used for carbon fiber manufacturing, considering the very different lignin structures from these feedstocks. Linear regression models were established to define the relationship between carbon fiber mechanical properties and lignin structural characteristics. The results highlighted that the content of β-O-4 linkages correlates significantly with the tensile strength and elastic modulus of lignin carbon fibers, indicating that more linear β-O-4 linkages would promote the carbon fiber mechanical performance. Moreover, electroconductive properties are essential for broader energy device application of lignin-based carbon fibers, yet the mechanisms controlling their electroconductivity are largely unknown. Furthermore, we hereby demonstrated that a higher β-O-4 content also promotes the electroconductivity of lignin carbon fibers. Microstructure analysis further revealed that the crystallite size and content of the pre-graphitic turbostratic carbon structure in lignin-based carbon fibers were enhanced as the β-O-4 linkages increased. The content of β-O-4 linkages has shown a strong correlation with the crystallite content in a linear regression model. This study thus revealed the underlying mechanisms regarding how the lignin structure in planta defines the resultant carbon fiber properties. Moreover, the study also highlighted the correlation between the mechanical and electroconductive properties of lignin-based carbon fibers, both of which were defined by the lignin structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Integrated fiber-mirror ion trap for strong ion-cavity coupling

We present and characterize fiber mirrors and a miniaturized ion-trap design developed to integrate a fiber-based Fabry-Perot cavity (FFPC) with a linear Paul trap for use in cavity-QED experiments with trapped ions. Our fiber-mirror fabrication process not only enables the construction of FFPCs with small mode volumes, but also allows us to minimize the influence of the dielectric fiber mirrors on the trapped-ion pseudopotential. We discuss the effect of clipping losses for long FFPCs and the effect of angular and lateral displacements on the coupling efficiencies between cavity and fiber. Optical profilometry allows us to determine the radii of curvature and ellipticities of the fiber mirrors. From finesse measurements, we infer a single-atom cooperativity of up to 12 for FFPCs longer than 200 μm in length; comparison to cavities constructed with reference substrate mirrors produced in the same coating run indicates that our FFPCs have similar scattering losses. We characterize the birefringence of our fiber mirrors, finding that careful fiber-mirror selection enables us to construct FFPCs with degenerate polarization modes. As FFPCs are novel devices, we describe procedures developed for handling, aligning, and cleaning them. We discuss experiments to anneal fiber mirrors and explore the influence of the atmosphere under which annealing occurs on coating losses, finding that annealing under vacuum increases the losses for our reference substrate mirrors. X-ray photoelectron spectroscopy measurements indicate that these losses may be attributable to oxygen depletion in the mirror coating. Special design considerations enable us to introduce a FFPC into a trapped ion setup. Our unique linear Paul trap design provides clearance for such a cavity and is miniaturized to shield trapped ions from the dielectric fiber mirrors. We numerically calculate the trap potential in the absence of fibers. In the experiment additional electrodes can be used to compensate distortions of the potential due to the fibers. Home-built fiber feedthroughs connect the FFPC to external optics, and an integrated nanopositioning system affords the possibility of retracting or realigning the cavity without breaking vacuum.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Use of polypropylene fibers coated with nano-silica particles into a cementitious mortar

Fiber reinforced cementitious composite (FRCC) materials have been widely used during last decades in order to overcome some of traditional cementitious materials issues: brittle behaviour, fire resistance, cover spalling, impact strength. For composite materials, fiber/matrix bond plays an important role because by increasing fiber/matrix interactions is possible to increase the behaviour of the entire material. In this study, in order to improve fiber to matrix adhesion, two chemical treatments of polypropylene fibers were investigated: alkaline hydrolysis and nano-silica sol-gel particles deposition. Treatmtents effect on fibers morphology and mechanical properties was investigated by scanning electron microscopy (SEM) and tensile tests. SEM investigations report the presence of spherical nano-silica particles on fiber surface, in the case of sol-gel process, while alkaline hydrolysis leads to an increase of fibers roughness. Both treatments have negligible influence on fibers mechanical properties confirming the possibility of their use in a cementitious mortar. Pullout tests were carried out considering three embedded length of fibers in mortar samples (10, 20 and 30 mm, respectively) showing an increase of pullout energy for treated fibers. The influence on fiber reinforced mortar mechanical properties was investigated by three-point flexural tests on prismatic specimens considering two fibers length (15 and 30 mm) and two fibers volume fractions (0.50 and 1.00 %). A general increase of flexural strength over the reference mix was achieved and an overall better behaviour is recognizable for mortars containing treated fibers.

36 MATERIALS SCIENCE↗

Embedded metallized optical fibers for high temperature applications

Embedding fiber optics in metal components could enable new capabilities such as active monitoring of spatially distributed strain. Ultrasonic additive manufacturing is a suitable technique for embedding fiber optics because it allows fibers to be embedded in metals without melting and without the use of epoxy. However, for harsh environments that could have high temperatures or high radiation doses, traditional polymer-coated fibers cannot survive for extended periods of time. This work demonstrates successful embedding of commercially available copper-, nickel-, and aluminum-coated fibers into aluminum without any observable damage to the fiber. Copper-coated fibers embedded in copper show adequate light transmission, although residual strain could not be resolved. With further processing improvements, fibers embedded in copper or other high-temperature materials could enable even higher temperature operation. Optical transmission and spatially distributed strain were measured in the fibers embedded in aluminum. Measurements were taken after embedding and during heating to temperatures greater than 500 °C. Within the embedded region, both the copper- and aluminum-coated fibers showed strain that matched the expected strain in the surrounding aluminum matrix during heating. This suggests a strong interfacial bond strength that exceeds the maximum estimated fiber strain of 1.2% (871 MPa tensile stress). Furthermore this demonstration of embedded fibers that can survive high temperatures and remain bonded to the metal matrix is the first step toward embedded fiber optic sensors for harsh environment applications.

36 MATERIALS SCIENCE↗

TH-C-17A-08: Monte Carlo Based Design of Efficient Scintillating Fiber Dosimeters

Purpose: To accurately predict Cherenkov radiation generation in scintillating fiber dosimeters. Quantifying Cherenkov radiation provides a method for optimizing fiber dimensions, orientation, optical filters, and photodiode spectral sensitivity to achieve efficient real time imaging dosimeter designs. Methods: We develop in-house Monte Carlo simulation software to model polymer scintillation fibers' fluorescence and Cherenkov emission in megavoltage clinical beams. The model computes emissions using generation probabilities, wavelength sampling, fiber photon capture, and fiber transport efficiency and incorporates the fiber's index of refraction, optical attenuation in the Cherenkov and visible spectrum and fiber dimensions. Detector component selection based on parameters such as silicon photomultiplier efficiency and optical coupling filters separates Cherenkov radiation from the dose-proportional scintillating emissions. The computation uses spectral and geometrical separation of Cherenkov radiation, however other filtering techniques can expand the model. Results: We compute Cherenkov generation per electron and fiber capture and transmission of those photons toward the detector with incident electron beam angle dependence. The model accounts for beam obliquity and nonperpendicular electron fiber impingement, which increases Cherenkov emission and trapping. The rotational angle around square fibers shows trapping efficiency variation from the normally incident minimum to a maximum at 45 degrees rotation. For rotation in the plane formed by the fiber axis and its surface normal, trapping efficiency increases with angle from the normal. The Cherenkov spectrum follows the theoretical curve from 300nm to 800nm, the wavelength range of interest defined by silicon photomultiplier and photodiode spectral efficiency. Conclusion: We are able to compute Cherenkov generation in realistic real time scintillating fiber dosimeter geometries. Design parameters incorporate fiber dimensions, orientations, several types of detector spectral response, optical coupling filters and light transport. We can vary these parameters to design and optimize high efficiency real time dosimeters capable of enhancing external beam patient safety and treatment accuracy. This research was supported in part by a GAANN Fellowship from the Department of Education.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Optimized Carbon Fiber Intermediate Development to Enable High-Volume Manufacturing of Lightweight Automotive Composites

The ongoing pursuit of improved fuel economy and reduced greenhouse gas emissions has resulted in sustained interest for lightweight materials technologies. In this context, carbon fiber composites have captured the imagination of automotive engineers due to the potential to achieve substantial mass reduction when compared to traditional steel construction. That stated, the use of carbon fiber composites in automotive has been limited for the most part to premium supercars and other derivative platforms. In these cases, manufacturing costs are less of an obstacle to implementation, and the performance benefits of carbon fiber have enabled production of structures offering more than 50% weight savings. In practice, translating these low-volume demonstrations onto high-volume vehicle platforms has remained challenging. This can be attributed to several factors, with the absence of suitable high throughput production methodologies being a key impediment. To date, structural, crash critical components have relied upon manufacturing techniques born out of the aerospace industry. This has created a disconnect between automotive production systems that are accustomed to manufacturing multiple parts per minute and the aerospace technologies that have cycle times in the order of hours. Consequently, the focus of this project is the development of manufacturing process technology for carbon fiber composites that can support a mainstream vehicle program at an assumed throughput of 100,000 vehicles per year. In practice, this translates to a part-to-part cycle time of less than 3 minutes. Project participation included contributions from a broad range of academic, industrial and national lab partners. The primary scope of work, being the development of new carbon fiber epoxy compounds that are stable at room temperature and suited to high throughput automated processing. For project management, the work streams were divided into six key areas, with the lead organization in parentheses. • Carbon fiber/epoxy materials formulation development and scale up (Dow) • Simulation of discontinuous near isotropic meso-structure intermediates (Purdue) • Simulation of mechanical performance of compression molded components (Purdue) • Meso-Scale morphological analysis and correlation with structural performance (UTK) • Paint and adhesion durability analysis (MSU) • Demonstrator part design, prototype production, and validation testing (Ford). The primary goal at the commencement of the project was development of a chopped carbon fiber sheet molding compound (SMC) that offered a three times improvement in tensile modulus over a comparable glass-based SMC. In addition to meeting mechanical performance targets, the resin kinetics were modified to achieve a processing cycle time of less than 3 minutes. Other critical-to-quality (CTQ) specifications were also stipulated to account for a broad range of materials and processing characteristics. To achieve the above, staff scientists at Dow Chemical created an extensive series of new epoxy blends for testing and validation. Throughout this development, a key challenge was attaining material performance goals without impacting processing behavior and paintability of finished components. The latter required a new internal mold release system being developed by Dow that was designed to complement the kinetics of the rapid cure epoxy. As a complement to work studies at the industrial partners, the teams from academia executed a series of analytical and experimental studies to investigate potential factors influencing CF-SMC performance. Unit cell models were developed to capture the meso-scale representations of the fiber matrix architecture. Results of this analysis and subsequent morphological investigations led to the design of a novel composite derivative comprising carbon fiber platelets embedded in an epoxy matrix; the platelet size and aspect ratio playing significant role in final composite properties. This approach was a departure from previous research in CF-SMC development whereby bulk filamentization or disassembly of the carbon fiber rovings had been considered the most effective means of achieving both fiber wet through and wet-out. As the course of the academia studies progressed, the aspect ratio of the fiber constituents was further optimized before finalizing material attributes and processing conditions. For the purposes of technology validation, the Ford team led a work stream devoted to the design, fabrication and testing of demonstration components. The carbon fiber SMC material has the potential to displace numerous stampings and castings on an automotive structure but ultimately vehicle closure applications were selected to showcase the abilities of the CF-SMC to achieve both mass reduction and business case for large complex structures. Using target properties established by the Dow staff scientists, the complete closure system for a full-size sedan decklid and a mid-size wagon liftgate were engineered. Prototypes for both applications were fabricated using production representative processing methods to allow for physical testing and performance validation of the CF-SMC structures. Following completion of a testing program that concluded with a FMVSS301 55 mph offset rear crash, the CF-SMC formulation was declared by the Ford team to have met all engineering requirements. To summarize, the joint development activities during this project led to significant technical breakthroughs and achievement of all milestones. The result was the development of a novel, tack-free carbon fiber molding compound that is suited to automated processing. This combined room temperature stability, fast cure kinetics, and internal mold release system facilitates cycle times that are conducive to high-volume production. The VORAFUSE M6400 successfully passed technology validation at Ford and is now eligible for consideration on future production commercial vehicle programs.

36 MATERIALS SCIENCE↗

Fiber-type susceptibility to eccentric contraction-induced damage of hindlimb-unloaded rat AL muscles

Slow oxidative (SO) fibers of the adductor longus (AL) were predominantly damaged during voluntary reloading of hindlimb unloaded (HU) rats and appeared explainable by preferential SO fiber recruitment. The present study assessed damage after eliminating the variable of voluntary recruitment by tetanically activating all fibers in situ through the motor nerve while applying eccentric (lengthening) or isometric contractions. Muscles were aldehyde fixed and resin embedded, and semithin sections were cut. Sarcomere lesions were quantified in toluidine blue-stained sections. Fibers were typed in serial sections immunostained with antifast myosin and antitotal myosin (which highlights slow fibers). Both isometric and eccentric paradigms caused fatigue. Lesions occurred only in eccentrically contracted control and HU muscles. Fatigue did not cause lesions. HU increased damage because lesioned- fiber percentages within fiber types and lesion sizes were greater than control. Fast oxidative glycolytic (FOG) fibers were predominantly damaged. In no case did damaged SO fibers predominate. Thus, when FOG, SO, and hybrid fibers are actively lengthened in chronically unloaded muscle, FOG fibers are intrinsically more susceptible to damage than SO fibers. Damaged hybrid-fiber proportions ranged between these extremes.

Non-NASA Center↗

Predictive Engineering Tools for Injection-Molded Long-Carbon-Fiber Thermoplastic Composites - FY 2016 First Quarterly Report

During the first quarter of FY 2016, the following technical progress has been made toward project milestones: 1) Virginia Tech completed fiber orientation (FO) measurements for the samples taken at Locations A, B, C and D (Figure 1) from the 30wt% LCF/PP and 30wt% LCF/PA66 ribbed and non-ribbed complex parts using Virginia Tech’s established procedure. Virginia Tech delivered to PNNL all the measured fiber orientation data for validating ASMI fiber orientation predictions. 2)Virginia Tech performed fiber length distribution (FLD) measurements for the samples taken at Locations A, B, C and D from these complex parts using Virginia Tech’s established procedure. Virginia also re-assessed previous data and measured fiber length distributions in the corresponding nozzle purging materials and delivered to PNNL all the measured length data for validating ASMI fiber length predictions. 3)Based on measured fiber orientation data, Autodesk identified the parameters of the anisotropic rotary diffusion reduced strain closure (ARD-RSC) model [1] and provided PNNL with the values of these parameters that were used in ASMI analyses of the complex parts. 4) Magna provided Virginia Tech with additional samples cut out from the 30wt% LCF/PP and 30wt% LCF/PA66 ribbed parts (Figure 1) for fiber length and orientation measurements. 5) In discussion with Autodesk, PNNL performed 3D ASMI analyses of the 30wt% LCF/PP and 30wt% LCF/PA66 ribbed and non-ribbed complex parts to predict fiber orientations and length distributions in these parts. The issues observed through the analyses regarding fiber orientation distributions profiles and abnormal length distributions were reported to Autodesk. Autodesk is working to resolve these issues. 6) PNNL completed 3D ASMI analyses of the complex parts and compared predicted fiber orientation results at Locations A, B, and C on the non-ribbed parts, and at Locations A, B, C and D on the ribbed parts with the corresponding measured data. PNNL also evaluated the within-15%-agreement criterion using the principal tensile and flexural moduli computed based on predicted vs. measured fiber orientation results. 7) PNNL developed and discussed with Toyota, Magna and PlastiComp a method to perform weight and cost reduction for making the 30wt% LCF/PA66 ribbed part through comparative three-point bending simulations of this part and of similar parts in steel.

36 MATERIALS SCIENCE↗

Tensile performance of sustainable Strain-Hardening Cementitious Composites with hybrid PVA and recycled PET fibers

Highlights: • SHCCs with hybrid PVA/PET fibers are theoretically and experimentally studied. • A semi-empirical way to predict strain capacity of hybrid-fiber SHCCs is proposed. • The impacts of PET fiber surface treatment and curing time are explored. • SHCCs achieve satisfactory performance even 50% PVA fibers are replaced by PET fibers. • Using PET fibers in SHCCs effectively reduces material cost and environmental impact. - Abstract: Strain-Hardening Cementitious Composite (SHCC) is a type of advanced construction material that can enhance the resiliency and durability of structures. However, the high cost of the constituents limits the wide application of SHCCs. To reduce the material cost and improve the sustainability, this study explores the potential of replacing commonly-used polyvinyl alcohol (PVA) fibers by recycled polyethylene terephthalate (PET) fibers. The potential of fiber hybridization was first evaluated using micromechanical modeling, and the ultimate tensile strain of hybrid-fiber SHCCs was estimated using a semi-empirical method. Then the tensile performance of SHCCs after standard curing and accelerated aging was experimentally evaluated, and the crack pattern development with increasing tensile strain was recorded. Satisfactory mechanical performance can be achieved even when 50% of PVA fibers are replaced by recycled PET fibers with surface treatment. In addition, using recycled PET fibers in SHCCs can significantly reduce the material cost and environmental impact.

36 MATERIALS SCIENCE↗

The preparation and properties of polyurethane foams reinforced with bamboo fiber sources in China

Abstract Polyurethane (PU) foams reinforced with bamboo fiber sources in China, i.e. , bamboo fiber, bamboo α -cellulose fiber, and bamboo nanocellulose fiber, were prepared and their physico-mechanical properties were analyzed in this work. The bamboo fiber sources and PU foams were characterized by Fourier transform infrared spectroscopy (FTIR), Scanning electron microscope (SEM), Thermal gravimetric analysis (TGA) and universal compression testing. The results indicated that the hydroxyl groups on the fiber surfaces were enhanced by removing non-celluloses in the preparation of α -cellulose and nanocellulose. With the addition of small particle size α -cellulose and nanocellulose, the cell sizes of PU foams were reduced due to more nucleating agents being introduced. The FTIR spectra confirmed that the bamboo fiber sources were involved in the foaming reaction. The PU foams with bamboo fiber sources had a higher thermal stability than neat foam, and they were satisfactory enough to be used as insulation. PU foams reinforced with 5% bamboo fiber, 3% α -cellulose fiber and 3% nanocellulose fiber had better physico-mechanical performance than other foams. The reinforcement performance of 3% bamboo α -cellulose fiber on PU foam was comparable with that of high-cost nanocellulose. Accordingly, bamboo α -cellulose fiber was demonstrated to be a promising candidate to reinforce PU foam, which could be used in the reinforcement of foam insulation.

Qiu, Chongpeng↗

Extending the Gutowski model to kidney-bean and elliptically shaped fibers

Efforts by manufacturers to produce more cost-effective carbon fibers have resulted in fibers with irregular cross-section often referred to as kidney-bean shaped fibers. In this research, compaction experiments were performed with a modified laser light section method to evaluate the compaction behavior of kidney-bean shaped carbon fibers. The kidney-bean shaped fibers followed a different compaction behavior compared to the Gutowski model for circular fibers. Additionally, these fibers required an order of magnitude larger force to compact than circular fibers to achieve similar fiber volume fraction, which has implications in infiltration and consolidation efficiency for composites manufacturing. A shape correction factor based on the fiber cross-sectional aspect ratio was proposed to extend the Gutowski model to fibers with irregular cross-sectional shapes. The modified Gutowski model provided an appropriate order of magnitude fit for the kidney-bean fibers. Furthermore, this modification to the Gutowski model recovered the original solution for circular fibers (cross-sectional aspect ratio = 1).

Materials Science↗

Study of high resistance inorganic coatings on graphite fibers

Coatings made of boron, silicon carbide, silica, and silica-like materials were studied to determine their ability to increase resistance of graphite fibers. The most promising results were attained by chemical vapor depositing silicon carbide on graphite fiber followed by oxidation, and drawing graphite fiber through ethyl silicate followed by appropriate heat treatments. In the silicon carbide coating studies, no degradation of the graphite fibers was observed and resistance values as high as three orders of magnitude higher than that of the uncoated fiber was attained. The strength of a composite fabricated from the coated fiber had a strength which compared favorably with those of composites prepared from uncoated fiber. For the silica-like coated fiber prepared by drawing the graphite fiber through an ethyl silicate solution followed by heating, coated fiber resistances about an order of magnitude greater than that of the uncoated fiber were attained. Composites prepared using these fibers had flexural strengths comparable with those prepared using uncoated fibers, but the shear strengths were lower.

Galasso, F. S.↗

Effect of fiber reinforcements on thermo-oxidative stability and mechanical properties of polymer matrix composites

A number of studies have investigated the thermo-oxidative behavior of polymer matrix composites. Two significant observations have been made from these research efforts: (1) fiber reinforcement has a significant effect on composite thermal stability; and (2) geometric effects must be considered when evaluating thermal aging data. A compilation of some results from these studies is presented, and this information shows the influence of the reinforcement fibers on the oxidative degradation of various polymer matrix composites. The polyimide PMR-15 was the matrix material that was used in these studies. The control composite material was reinforced with Celion 6000 graphite fiber. T-40R graphite fibers, along with some very stable ceramic fibers were selected as reinforcing fibers because of their high thermal stability. The ceramic fibers were Nicalon (silicon carbide) and Nextel 312 (alumina-silica-boron oxide). The mechanical properties of the two graphite fiber composites were significantly different, probably owing to variations in interfacial bonding between the fibers and the polyimide matrix. The Celion 6000/PMR-15 bond is very tight but the T-40/PMR-15 bond is less tight. Three oxidation mechanisms were observed: (1) the preferential oxidation of the Celion 6000 fiber ends at cut surfaces, leaving a surface of matrix material with holes where the fiber ends were originally situated; (2) preferential oxidation of the composite matrix; and (3) interfacial degradation by oxidation. The latter two mechanisms were also observed on fiber end cut surfaces. The fiber and interface attacks appeared to initiate interfiber cracking along these surfaces.

Bowles, Kenneth J.↗

Collection of Light From an Optical Fiber With a Numerical Aperture Greater Than One

In an optical fiber having NA greater than 1, light may be internally reflected when it strikes the fiber end at a fiber-air interface. This problem may be overcome by modification of the fiber by reverse tapering the core. Light is redirected by the taper to strike the interface at an angle closer to normal. This allows light to exit the fiber end that would by internally reflected in an untapered fiber of NA greater than 1. The novelty of the present invention lies in the tapering of the fiber core for increased through transmission of light. Prior art devices have made use of fiber tapers to achieve mode control or fiber coupling. The problem of internal reflection has not been addressed as it is one that is not as important in fibers having NA less than 1, which are more common. In chemical sensing it is advantageous to make use of fibers having higher NA due to an increased sensitivity. However the advantages in sensitivity are diminished due to the loss of signal at the fiber-air interface. The present invention overcomes the problem of loss at the interface, thus facilitating the use of high NA fibers for chemical sensing.

Egalon, Claudio O.↗

Mechanical, Chemical and Microstructural Characterization of Monazite-Coated Silicon Carbide Fibers

Tensile strengths of as-received Hi-Nicalon and Sylramic fibers and those having monazite surface coatings, deposited by atmospheric pressure chemical vapor deposition, were measured at room temperature and the Weibull statistical parameters determined. The average tensile strengths of uncoated Hi-Nicalon and Sylramic fibers were 3.19 +/- 0.73 and 2.78 +/- 0.53 GPa with a Weibull modulus of 5.41 and 5.52, respectively. The monazite-coated Hi-Nicalon and Sylramic fibers showed strength loss of approx. 10 and 15 percent, respectively, compared with the as-received fibers. The elemental compositions of the fibers and the coatings were analyzed using scanning Auger microprobe and energy dispersive X-ray spectroscopy. The LaPO4 coating on Hi-Nicalon fibers was approximately stoichiometric and about 50 nm thick. The coating on the Sylramic fibers extended to a depth of about 100 to 150 nm. The coating may have been stoichiometric LaPO4 in the first 30 to 40 nm of the layer. However, the surface roughness of Sylramic fiber made this profile somewhat difficult to interpret. Microstructural analyses of the fibers and the coatings were done by scanning electron microscopy, transmission electron microscopy, and selected area electron diffraction. Hi-Nicalon fiber consists of fine beta-SiC nanocrystals ranging in size from 1 to 30 mn embedded in an amorphous matrix. Sylramic is a polycrystalline stoichiometric silicon carbide fiber consisting of submicron beta-SiC crystallites ranging from 100 to 300 nm. Small amount of TiB2 nanocrystallites (approx. 50 nm) are also present. The LaPO4 coating on Hi-Nicalon fibers consisted of a chain of peanut shape particles having monazite-(La) structure. The coating on Sylramic fibers consisted of two layers. The inner layer was a chain of peanut shape particles having monazite-(La) structure. The outer layer was comprised of much smaller particles with a microcrystalline structure.

Bansal, N. P.↗

Improved Phase-Mask Fabrication of Fiber Bragg Gratings

An improved method of fabrication of Bragg gratings in optical fibers combines the best features of two prior methods: one that involves the use of a phase mask and one that involves interference between the two coherent laser beams. The improved method affords flexibility for tailoring Bragg wavelengths and bandwidths over wide ranges. A Bragg grating in an optical fiber is a periodic longitudinal variation in the index of refraction of the fiber core. The spatial period (Bragg wavelength) is chosen to obtain enhanced reflection of light of a given wavelength that would otherwise propagate relatively unimpeded along the core. Optionally, the spatial period of the index modulation can be made to vary gradually along the grating (such a grating is said to be chirped ) in order to obtain enhanced reflection across a wavelength band, the width of which is determined by the difference between the maximum and minimum Bragg wavelengths. In the present method as in both prior methods, a Bragg grating is formed by exposing an optical fiber to an ultraviolet-light interference field. The Bragg grating coincides with the pattern of exposure of the fiber core to ultraviolet light; in other words, the Bragg grating coincides with the interference fringes. Hence, the problem of tailoring the Bragg wavelength and bandwidth is largely one of tailoring the interference pattern and the placement of the fiber in the interference pattern. In the prior two-beam interferometric method, a single laser beam is split into two beams, which are subsequently recombined to produce an interference pattern at the location of an optical fiber. In the prior phase-mask method, a phase mask is used to diffract a laser beam mainly into two first orders, the interference between which creates the pattern to which an optical fiber is exposed. The prior two-beam interferometric method offers the advantage that the period of the interference pattern can be adjusted to produce gratings over a wide range of Bragg wavelengths, but offers the disadvantage that success depends on precise alignment and high mechanical stability. The prior phase-mask method affords the advantages of compactness of equipment and relative insensitivity to both misalignment and vibration, but does not afford adjustability of the Bragg wavelength. The present method affords both the flexibility of the prior two-beam interferometric method and the compactness and stability of the prior phase-mask method. In this method (see figure), a laser beam propagating along the x axis is normally incident on a phase mask that lies in the (y,z) plane. The phase of light propagating through the mask is modulated with a spatial periodicity, p, along the y axis chosen to diffract the laser light primarily to first order at the angle . (The zero-order laser light propagating along the x axis can be used for alignment and thereafter suppressed during exposure of the fiber.) The diffracted light passes through a concave cylindrical lens, which converts the flat diffracted wave fronts to cylindrical ones, as though the light emanated from a line source. Then two parallel flat mirrors recombine the diffracted beams to form an interference field equivalent to that of two coherent line sources at positions A and B (virtual sources). The interference pattern is a known function of the parameters of the apparatus and of position (x,y) in the interference field. Hence, the tilt, wavelength, and chirp of the Bragg grating can be chosen through suitable adjustments of the apparatus and/or of the position and orientation of the optical fiber. In particular, the Bragg wavelength can be adjusted by moving the fiber along the x axis, and the bandwidth can be modified over a wide range by changing the fiber tilt angle or by moving the phase mask and/or the fiber. Alignment is easy because the zero-order beam defines the x axis. The interference is relatively stable and insensitive to the mechanical vibration because of the gh symmetry and compactness of the apparatus, the fixed positions of the mirrors and lens, and the consequent fixed positions of the two virtual line sources, which are independent of the translations of the phase mask and the laser relative to the lens.

Grant, Joseph↗

Manufacturing of Nanocomposite Carbon Fibers and Composite Cylinders

Pitch-based nanocomposite carbon fibers were prepared with various percentages of carbon nanofibers (CNFs), and the fibers were used for manufacturing composite structures. Experimental results show that these nanocomposite carbon fibers exhibit improved structural and electrical conductivity properties as compared to unreinforced carbon fibers. Composite panels fabricated from these nanocomposite carbon fibers and an epoxy system also show the same properties transformed from the fibers. Single-fiber testing per ASTM C1557 standard indicates that the nanocomposite carbon fiber has a tensile modulus of 110% higher, and a tensile strength 17.7% times higher, than the conventional carbon fiber manufactured from pitch. Also, the electrical resistance of the carbon fiber carbonized at 900 C was reduced from 4.8 to 2.2 ohm/cm. The manufacturing of the nanocomposite carbon fiber was based on an extrusion, non-solvent process. The precursor fibers were then carbonized and graphitized. The resultant fibers are continuous.

Tan, Seng↗

Hemp fiber reinforced dual dynamic network vitrimer biocomposites with direct incorporation of amino silane

Natural fiber composites are inexpensive and renewable alternatives to traditional fiber reinforced polymers (FRPs). However, existing natural fiber composites primarily rely on petrochemical based thermosetting matrices, which are difficult to recycle due to their stable crosslinked network structures. To address this challenge, it is desirable to develop natural fiber composites with inherently recyclable biobased matrices. In this study, we developed a dual dynamic network vitrimer matrix from hempseed oil and limonene derivatives and demonstrated its application in hemp fiber reinforced composites. To improve the weak interface between hemp fiber and the polymer matrix, a common challenge in the realm of natural fiber composites, we directly incorporated amino silane into the vitrimer matrix. The amino silane participated in the polymer network, increasing the crosslink density and toughening the matrix, as evidenced by a significantly improved impact strength from 3.5 kJ/m 2 to 10.3 kJ/m 2 . Moreover, the incorporation of amino silane resulted in a lower water absorption by 11% in 7-day soaking for the composites, demonstrating improved fiber/matrix interfacial interaction. Furthermore, our biobased vitrimer matrix exhibits both imine and hydroxy-ester dynamic bonds, which enable the recycling of the biocomposite through a mild and cost-effective aminolysis process (100°C, 3h, ambient pressure). The decomposed polymer matrix was successfully reused as a polyol for polyurethane adhesives, and the surface morphology of recovered hemp fibers was analyzed and compared with that of the original fibers. Furthermore, these findings will help broaden the use of vitrimers for practical natural fiber composite applications, raise awareness of the problem of recycling natural fiber composite waste, and shed light on the interfacial challenge of natural fiber reinforced vitrimer composites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗