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Effects of Microcrystallinity on Physical Aging and Environmental Stress Cracking of Poly (ethylene terephthalate) (PET)Zhou, Hongxia 05 October 2005 (has links)
No description available.
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LBIC Measurements on Busbarless Crystalline Silicon Solar CellsArvidsson, Saga January 2022 (has links)
The importance of further research in the field of solar cells is crucial for the transition to cleaner energy. The aim of this project is to design and manufacture a contact system that can measure busbarless solar cells with an LBIC-system. In this project mono-crystalline busbarless solar cells were utilized, busbarless solar cells only have small fingers that go vertically. When an incident photon hits the solar cell it can be absorbed by the bulk material, by the pn-junction an electrical field will set the electrons in motion so an electrical current can be harvested. LBIC, which stands for light beam induced current is a technique to spatially map the quantum efficiency of a solar cell, there is also an availability to make phasemeasurements. There are two different quantum efficiencies, External quantum efficiency (EQE) and Internal quantum efficiency (IQE). The phase measurement of the LBIC shows how much resistance exists between the point of current-generation and the contacts where the current is collected. A contact system with a comb-like figure of phosphor bronze was manufactured and mounted on to the LBIC-machine. Several measurements were executed on two solar cells. This new contact system can measure busbarless solar cells, with a good connection to almost all the fingers on the solar cell. The lack of contact with some fingers seemed to not affect the end result too much. It isn’t vital to have contact with all fingers to get a decent LBIC-mapping. / Vikten av ytterligare forskning inom området solceller är avgörande för omställningen till renare energi. Syftet med detta projekt är att designa och tillverka ett kontaktsystem som kan mäta solceller utan busbars med ett LBIC-system. I detta projekt användes monokristallina solceller utan busbars, solceller utan busbars har endast smala fingrar som går vertikalt. När en infallande foton träffar solcellen kan den absorberas av bulkmaterialet, vid pn-övergången kommer ett elektriskt fält att sätta elektronerna i rörelse så att en elektriskström kan samlas in. LBIC, som står för light beam induced current är en teknik för att rumsligt kartlägga kvantverkningsgraden för en solcell, det finns även en möjlighet att göra fasmätningar. Det finns två olika kvanteffektiviteter, Extern kvanteffektivitet (EQE) och Intern kvanteffektivitet (IQE). Fasmätningen av LBIC visar hur mycket motstånd som finns mellan punkten för strömgenerering och kontakterna där strömmen samlas. Ett kontaktsystem med en kamliknande figur gjord av fosforbrons tillverkades och monterades på LBIC-maskinen. Flera mätningar utfördes på två solceller. Detta nya kontaktsystemet kan mäta solceller utan busbars, med bra anslutning till nästan alla fingrar på solcellen. Bristen på kontakt med enskilda fingrar verkade inte påverka slutresultatet alltför mycket. Det är alltså då inte nödvändigt att ha kontakt med alla fingrar för att få en anständig LBIC-mätning.
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Dilatancy : further studies in crystalline rockHadley, Kate Hill January 1975 (has links)
Thesis. 1975. Ph.D.--Massachusetts Institute of Technology. Dept. of Earth and Planetary Sciences. / Bibliography: leaves 190-202. / by Kate Hadley. / Ph.D.
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Process/Structure/Property Relationships of Semi-Crystalline Polymers in Material Extrusion Additive ManufacturingLin, Yifeng 14 March 2024 (has links)
Material Extrusion additive manufacturing (MEX) represents the most widely implemented form of additive manufacturing due to its high performance-cost ratio and robustness. Being an extrusion process in its essence, this process enables the free form fabrication of a wide range of thermoplastic materials. However, in most typical MEX processes, only amorphous polymers are being used as feedstock material owing to their smaller dimensional shrinkage during cooling and well-stablished process/structure/property (P/S/P) relationship. Semi-crystalline polymers, with their crystalline nature, possess unique properties such as enhanced mechanical properties and improved chemical resistance. However, due to the inherent processing challenges in MEX of semi-crystalline polymers, the P/S/P relationships are much less established, thus limits the application of semi-crystalline polymers in MEX.
The overall aim of this thesis is to advance the understanding of P/S/P relationship of semi-crystalline polymers in MEX. This is accomplished through both experimental and simulation-based research. With a typical commodity semi-crystalline polymer, Poly (ethylene terephthalate) (PET), selected as the benchmark material.
First, we experimentally explored the MEX printing of both neat and glass fiber (GF) reinforced recycled PET (rPET). Excellent MEX printability were shown for both neat and composite materials, with GF reinforced parts showing a significant improved mechanical property. Notably, a gradient of crystallinity induced by a different toolpathing time was highlighted.
In the second project, to further investigate the impact of MEX parameter on crystallinity and mechanical properties, a series of benchmark parts were printed with neat PET and analyzed. The effect of part design and MEX parameter on thermal history during printing was revealed though a comparative analysis of IR thermography. Subsequent Raman spectroscopy and mechanical test indicated that crystallinity developed during the MEX process can adversely affects the interlayer adhesion.
In the third project, a 3D heat transfer model was developed to simulate and understand the thermal history of MEX feedstock material during printing, this model is then thoroughly validated against the experimental IR thermography data. While good prediction accuracy was shown for some scenarios, the research identified and discussed several unreported challenges that significantly affect the model's prediction performance in certain conditions.
In the fourth project, we employed a non-isothermal crystallization model to directly predict the development of crystallinity based on given temperature profiles, whether monitored experimentally or predicted by the heat transfer model. The research documented notable discrepancies between the model's predictions and actual crystallinity measurements, and the potential source of the error was addressed.
In summary, this thesis explored the MEX printing of semi-crystalline polymer and its fiber reinforced composite. The influence of MEX parameters and part designs on the printed part's thermal history, crystallinity and mechanical performance was then thoroughly investigated. A heat transfer model and a non-isothermal crystallization model were constructed and employed. With rigorous validation against experimental data, previously unreported challenges in MEX thermal and crystallization modeling was highlighted. Overall, this thesis deepens the understanding of current semi-crystalline polymer's P/S/P relationship in MEX, and offers insights for the optimization and future research in the field of both experiment and simulation of MEX. / Doctor of Philosophy / Material extrusion additive manufacturing (MEX), also known as fused filament fabrication (FFF), is a popular form of 3D printing known for its cost-effectiveness and versatility in creating objects from plastic materials. Traditionally, MEX utilizes amorphous polymers because they are less prone to shrinkage and thus easier to print. However, semi-crystalline polymers, offer enhanced strength and chemicals resistance, yet they pose significant challenges in printing due to a limited understanding of their process/structure/property (P/S/P) relationships in MEX.
This research aims to improve our understanding of P/S/P relationships of semi-crystalline polymers in MEX. The study utilizes a typical semi-crystalline polymer, Poly (ethylene terephthalate) (PET), as the benchmark material.
The study begins with the exploration of the MEX printing of recycled PET (rPET) and its glass fiber composite, finding that with appropriate MEX parameters, both feedstocks are highly printable, and the incorporation of glass fibers substantially increased the strength of the printed parts.
Subsequently, a comprehensive investigation regarding the intricate relationship between crystallinity development, mechanical properties, and the MEX printing process is conducted. Our research revealed that the MEX process and the design of the part both considerably affect the crystallinity of the final part, thereby influencing its mechanical properties.
In the third chapter, a 3D heat transfer model is constructed to better understand and predict the temperature evolution of materials during MEX printing. Most importantly, the modeling results are rigorously validated against experimental data, showing promising results. However, it also reveals challenges in precisely predicting the temperature of parts under certain conditions.
The research then evaluates the applicability of Nakamura non-isothermal crystallization model for MEX printing scenarios. It is found that this model underestimates crystallinity in MEX, primarily because it does not account for shear-induced crystallization, a critical factor in the process. This finding underscores the necessity for more advanced models that can effectively capture the complex dynamics of MEX.
In summary, this dissertation significantly enhances our understanding of the behavior of semi-crystalline polymers in MEX printing. It sheds light on the complex relationship between the printing process, the structure of the material, and the final properties of the printed object. This work not only advances our knowledge in 3D printing but also paves the way for more sophisticated modeling approaches, optimizing the MEX process and expanding its potential applications.
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Multiple Wave Scattering and Calculated Effective Stiffness and Wave Properties in Unidirectional Fiber-Reinforced CompositesLiu, Wenlung 05 August 1997 (has links)
Analytic methods of elastic wave scattering in fiber-reinforced composite materials are investigated in this study to calculate the effective static stiffness (axial shear modulus, m) and wave properties (axially shear wave speed, B and attenuation, Y) in composites. For simplicity only out-of-plane shear waves are modeled propagating in a plane transverse to the fiber axis. Statistical averaging of a spatially random distribution of fibers is performed and a simultaneous system of linear equations are obtained from which the effective global wave numbers are numerically calculated. The wave numbers, K=Re(K)+iIm(K), are complex numbers where the real parts are used to compute the effective axial shear static stiffness and wave speed; the imaginary parts are used to compute the effective axial shear wave attenuation in composites.
Three major parts of this study are presented. The first part is the discussion of multiple scattering phenomena in a successive-events scattering approach. The successive-events scattering approach is proven to be mathematically exact by comparing the results obtained by the many-bodies-single-event approach. Scattering cross-section is computed and comparison of the first five scattering orders is made. Furthermore, the ubiquitous quasi-crystalline approximation theorem is given a justifiable foundation in the fiber-matrix composite context. The second part is to calculate m, B and Y for fiber-reinforced composites with interfacial layers between fibers and matrix. The material properties of the layers are assumed to be either linearly or exponentially distributed between the fibers and matrix. A concise formula is obtained where parameters can be computed using a computationally easy-to-program determinant of a square matrix. The numerical computations show, among other things, that the smoother (more divisional layers), or thinner, the interfacial region the less damped are the composite materials. Additionally composites with exponential order distribution of the interfacial region are more damped than the linear distribution ones. The third part is to calculate m, B and Y for fiber-reinforced composites with interfacial cracks. The procedures and computational techniques are similar to those in the second part except that the singularity near the crack tip needs the Chebychev function as a series expansion to be adopted in the computation.
Both the interfacial layers and interfacial crack cases are analyzed in the low frequency range. The analytic results show that waves in both cases are attenuated and non-dispersive in the low frequency range. The composites with interfacial layers are transversely isotropic, while composites with interfacial cracks are generally transversely anisotropic. / Ph. D.
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Generation of Recyclable Liquid Crystalline Polymer Reinforced Composites for Use in Conventional and Additive Manufacturing ProcessesChen, Tianran 21 May 2021 (has links)
The application of glass fiber reinforced composites has grown rapidly due to their high strength-to-weight ratio, low cost, and chemical resistance. However, the increasing demand for fiber reinforced composites results in the generation of more composite wastes. Mechanical recycling is a cost-effective and environmentally-friendly recycling method, but the loss in the quality of recycled glass or carbon fiber composite hinders the wide-spread use of this recycling method. It is important to develop novel composite materials with higher recyclability. Thermotropic liquid crystalline polymers (TLCPs) are high-performance engineering thermoplastics, which have comparable mechanical performance to that of glass fiber. The TLCP reinforced composites, called in situ composites, can form the reinforcing TLCP fibrils during processing avoiding the fiber breakage problem.
The first part of this dissertation is to study the influence of mechanical recycling on the properties of injection molded TLCP and glass fiber (GF) reinforced polypropylene (PP). The processing temperature of the injection molding process was optimized using a differential scanning calorimeter (DSC) and a rheometer to minimize the thermal degradation of PP. The TLCP and GF reinforced PP materials were mechanically recycled up to three times by repeated injection molding and grinding. The mechanical recycling had almost no influence on the mechanical, thermal, and thermo-mechanical properties of TLCP/PP because of the regeneration of TLCP fibrils during the mold filling process. On the other hand, glass fiber/PP composites decreased 30% in tensile strength and 5% in tensile modulus after three reprocessing cycles. The micro-mechanical modeling demonstrated the deterioration in mechanical properties of GF/PP was mainly attributed to the fiber breakage that occurred during compounding and grinding.
The second part of this dissertation is concerned with the development of recyclable and light weight hybrid composites through the use of TLCP and glass fiber. Rheological tests were used to determine the optimal processing temperature of the injection molding process. At this processing temperature, the thermal degradation of matrix material was mitigated and the processability of the hybrid composite was improved. The best formulation of TLCP and glass fiber in the composite was determined giving rise to the generation of a recyclable hybrid composite with low melt viscosity, low mechanical anisotropy, and improved mechanical properties.
Finally, TLCP reinforced polyamide composites were utilized in an additive manufacturing application. The method of selecting the processing temperature to blend TLCP and polyamide in the dual extrusion process was devised using rheological analyses to take advantage of the supercooling behavior of TLCP and minimize the thermal degradation of the matrix polymer. The composite filament prepared by dual extrusion was printed and the printing temperature of the composite filament that led to the highest mechanical properties was determined. Although the tensile strength of the TLCP composite was lower than the glass fiber or carbon fiber composites, the tensile modulus of 3D printed 60 wt% TLCP reinforced polyamide was comparable to traditional glass or carbon fiber reinforced composites in 3D printing. / Doctor of Philosophy / The large demand for high performance and light weight composite materials in various industries (e.g., automotive, aerospace, and construction) has resulted in accumulation of composite wastes in the environment. Reuse and recycling of fiber reinforced composites are beneficial from the environmental and economical point of view. However, mechanical recycling deteriorates the quality of traditional fiber reinforced composite (e.g., glass fiber and carbon fiber). There is a need to develop novel composites with greater recyclability and high-performance.
Thermotropic liquid crystalline polymers (TLCP) are attractive high performance materials because of their excellent mechanical properties and light weight. The goal of this work is to generate recyclable thermotropic liquid crystalline polymer (TLCP) reinforced composites for use in injection molding and 3D printing. In the first part of this work, a novel recyclable TLCP reinforced composite was generated using the grinding and injection molding. Recycled TLCP composites were as strong as the virgin TLCP composites, and the mechanical properties of TLCP composites were found to be competitive with the glass fiber reinforced counterparts. In the second part, a hybrid TLCP and glass fiber reinforced composite with great recyclability and excellent processability was developed. The processing conditions of injection molding were optimized by rheological tests to mitigate fiber breakage and improve the processability. Finally, a high performance and light weight TLCP reinforced composite filament was generated using the dual extrusion process which allowed the processing of two polymers with different processing temperatures. This composite filament could be directly 3D printed using a benchtop 3D printer. The mechanical properties of 3D printed TLCP composites could rival 3D printed traditional fiber composites but with the potential to have a wider range of processing shapes.
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Lens calcium homeostasis and selenite cataractWang, Zaiqi 04 May 2006 (has links)
A 3- to 5-fold increase in Ca2+ accompanies cataract formation induced by selenite. The mechanism of selenite cataractogenesis involves calcium activation of calpain with subsequent proteolysis within the lens nucleus. This study was undertaken to investigate the biochemical mechanisms that lead to calcium accumulation in these circumstances. The components responsible for rat lens calcium regulation were defined by using either lens membrane vesicle preparations or intact lenses. Both Na+ gradient-dependent Ca2+ uptake and efflux occurred in lens membrane vesicles. Experiments with intact lenses showed that Na + ICa2 + exchange plays an important role in lens calcium regulation. ATP-dependent Ca2+ uptake and Ca2+ -dependent ATP hydrolytic activity have been characterized in lens membrane vesicles. Therefore, both Ca2+ -ATPase and Na + ICa2+ exchange participate in rat lens calcium regulation. Calcium accumulation in lenses treated by selenite may result from either increased influx (via non-selective cation channel), decreased efflux (via Ca2 +-ATPase and Na+ ICa 2+ exchange) or both. The selenite effects on the different components involved in lens calcium regulation were tested. / Ph. D.
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Improved Properties of Poly (Lactic Acid) with Incorporation of Carbon Hybrid NanostructureKim, Junseok 01 July 2016 (has links)
Poly(lactic acid) is biodegradable polymer derived from renewable resources and non-toxic, which has become most interested polymer to substitute petroleum-based polymer. However, it has low glass transition temperature and poor gas barrier properties to restrict the application on hot contents packaging and long-term food packaging. The objectives of this research are: (a) to reduce coagulation of graphene oxide/single-walled carbon nanotube (GOCNT) nanocomposite in poly(lactic acid) matrix and (b) to improve mechanical strength and oxygen barrier property, which extend the application of poly(lactic acid).
Graphene oxide has been found to have relatively even dispersion in poly(lactic acid) matrix while its own coagulation has become significant draw back for properties of nanocomposite such as gas barrier, mechanical properties and thermo stability as well as crystallinity. Here, single-walled carbon nanotube was hybrid with graphene oxide to reduce irreversible coagulation by preventing van der Waals of graphene oxide. Mass ratio of graphene oxide and carbon nanotube was determined as 3:1 at presenting greatest performance of preventing coagulation. Four different weight percentage of GOCNT nanocomposite, which are 0.05, 0.2, 0.3 and 0.4 weight percent, were composited with poly(lactic acid) by solution blending method. FESEM morphology determined minor coagulation of GOCNT nanocomopsite for different weight percentage composites. Insignificant crystallinity change was observed in DSC and XRD data. At 0.4 weight percent, it prevented most of UV-B light but was least transparent. GOCNT nanocomposite weight percent was linearly related to ultimate tensile strength of nanocomposite film. The greatest ultimate tensile strength was found at 0.4 weight percent which is 175% stronger than neat poly(lactic acid) film. Oxygen barrier property was improved as GOCNT weight percent increased. 66.57% of oxygen transmission rate was reduced at 0.4 weight percent compared to neat poly(lactic acid). The enhanced oxygen barrier property was ascribed to the outstanding impermeability of hybrid structure GOCNT as well as the strong interfacial adhesion of GOCNT and poly(lactic acid) rather than change of crystallinity. Such a small amount of GOCNT nanocomposite improved mechanical strength and oxygen barrier property while there were no significant change of crystallinity and thermal behavior found. / Master of Science
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Generation of Thermotropic Liquid Crystalline Polymer (TLCP)-Thermoplastic Composite Filaments and Their Processing in Fused Filament Fabrication (FFF)Ansari, Mubashir Qamar 11 March 2019 (has links)
One of the major limitations in Fused Filament Fabrication (FFF), a form of additive manufacturing, is the lack of composites with superior mechanical properties. Traditionally, carbon and glass fibers are widely used to improve the physical properties of polymeric matrices. However, the blending methods lead to fiber breakage, preventing generation of long fiber reinforced filaments essential for printing load-bearing components. Our approach to improve tensile properties of the printed parts was to use in-situ composites to avoid fiber breakage during filament generation. In the filaments generated, we used thermotropic liquid crystalline polymers (TLCPs) to reinforce acrylonitrile butadiene styrene (ABS) and a high performance thermoplastic, polyphenylene sulfide (PPS). The TLCPs are composed of rod-like monomers which are highly aligned under extensional kinematics imparting excellent one-dimensional tensile properties. The tensile strength and modulus of the 40 wt.% TLCP/ABS filaments was improved by 7 and 20 times, respectively. On the other hand, the 67 wt.% TLCP/PPS filament tensile strength and modulus were improved by 2 and 12 times, respectively.
The filaments were generated using dual extrusion technology to produce nearly continuously reinforced filaments and to avoid matrix degradation. Rheological tests were taken advantage of to determine the processing conditions. Dual extrusion technology allowed plasticating the matrix and the reinforcing polymer separately in different extruders. Then continuous streams of TLCP were injected below the TLCP melting temperature into the matrix polymer to avoid matrix degradation. The blend was then passed through a series of static mixers, subdividing the layers into finer streams, eventually leading to nearly continuous fibrils which were an order of magnitude lower in diameter than those of the carbon and glass fibers.
The composite filaments were printed below the melting temperature of the TLCPs, and the conditions were determined to avoid the relaxation of the order in the TLCPs. On printing, a matrix-like printing performance was obtained, such that the printer was able to take sharp turns in comparison with the traditionally used fibers. Moreover, the filaments led to a significant improvement in the tensile properties on using in FFF and other conventional technologies such as injection and compression molding. / Doctor of Philosophy / In this work two thermoplastic matrices, acrylonitrile butadiene styrene (ABS) and polyphenylene sulfide (PPS), were reinforced with higher melting thermoplastics of superior properties called thermotropic liquid crystalline polymers (TLCPs). This was done so that the resulting filaments could be 3D-printed without melting the TLCPs. The goal of this work was to generate nearly continuous reinforcement in the filaments and to avoid matrix degradation, and, hence, a technology called dual extrusion technology was used for the filament generation. The temperatures required for filament generation were determined using rheology, which involves the study of flow behavior of complex fluids.
Dual extrusion technology allows processing of the constituent polymers separately at different temperatures, followed by a continuous injection of multiple TLCP-streams into the matrix polymers. In addition, the use of static mixers (metallic components kept in the path of flow to striate incoming streams) leads to further divisions of the TLCP-streams which are eventually drawn by pulling to orient the TLCP phase. The resulting filaments exhibited specific properties (normalized tensile properties) higher than aluminum and contained fibers that were nearly continuous, highly oriented, and an order in magnitude lower in diameter than those of carbon and glass fiber, which are commonly used reinforcements. High alignment and lower fiber diameter are essential for printing smoother printed parts.
The filaments were intended to be printed without melting the TLCPs. However, previous studies involving the use of TLCP reinforced composites in conventional technologies have reported the occurrence of orientation relaxation on postprocessing, which decreases their tensile v properties. Therefore, temperatures required for 3D printing were determined using compression molding to retain filament properties on printing to the maximum extent. On printing using an unmodified 3D printer, parts were printed by taking 180º turns during material deposition. Contrarily, the use of continuous carbon fibers required a modified 3D printer to allow impregnation during 3D printing. Moreover, the performance comparison showed that the continuous carbon fibers could not be deposited in tighter loops. The properties of the printed parts were higher than those obtained on using short fibers and approaching those of the continuous fiber composites.
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In-Situ Monitoring and Simulations of the Non-Isothermal Crystallization of FFF Printed MaterialsAnderegg, David Alexander 15 January 2019 (has links)
This thesis is concerned with the development of methods and models to aid in optimization and development of new materials for Fused Filament Fabrication (FFF). We demonstrate a novel FFF nozzle design to enable the first measurements of in-situ rheology inside FFF nozzles, which is critical for part performance by ensuring that the polymer extrudate is flowing at an appropriate temperature and flow rate during the part build process. Testing was performed using Acrylonitrile butadiene styrene filament and a modified Monoprice Maker Select 3D printer. Tests using the default temperature control settings of the printer showed an 11 °C drop in temperature and significant fluctuations in pressure, during printing and while idle, of ± 2 °C and +/-14 kPa. These deviations were eliminated at lower flow rates with a properly calibrated proportional–integral–derivative (PID) system. At high flow rates, drops in temperature as high as 6.5 °C were observed even with a properly calibrated PID, providing critical input to the impact of flow rate and PID calibration on polymer melt temperature inside FFF nozzles. Pressure readings ranging from 140-6900 kPa were measured over the range of filament feed rates and corresponding extrusion flow rates. Theoretical predictions of pressure profiles, assuming a powerlaw fluid model, matched well with experimental results. Our nozzle prototype succeeded in measuring internal conditions of FFF nozzles for the first time, thereby providing several important insights into the printing process which are vital for monitoring and improving FFF printed parts.
Furthermore, finite difference simulations based on first principles analysis are presented which are capable of quantifying the effect of processing conditions on the properties of semicrystalline parts made by FFF. Each layer was modelled as a rectangular cross section which was broken down into smaller elements for modelling. Crystallinity of each element was calculated using a parallel Avrami model which accounts for changes in crystallization rate due to temperature and multiple crystallization mechanisms. The amount of polymer diffusion, also referred to as the degree of healing, was calculated using a novel incremental diffusion model which accounted for not only changes in reptation time due to temperature but also restrictions to healing due to crystallinity. To the authors knowledge, this is the first healing model capable of accounting for the effect of crystallinity on healing and is relevant to any process involving healing of crystalline interfaces; not just FFF. Cumulative shear stresses between each layer and at the bottom of the part were also calculated for the first time using a force balance model by assuming constant shear strain throughout each layer. Simulations were performed using typical printing conditions for polyether ether ketone. In the first layer of a 24 layer part, the average degree of crystallinity, healing, and shear stress were 25.0%, 53.8% and 19.4 MPa respectively. The degree of crystallinity and healing at layer 22 (which represented the steady state values) were 18.4-25.0% and 51.4% respectively. When crystallinity was not accounted for, varying the printing parameters and material properties supported the use of high temperatures and specific heat in addition to a low printing speed, heat transfer coefficient, and thermal conductivity to maximize part properties. These conditions also supported crystallization, however, which led to a simultaneous reduction in the part properties when crystallinity was taken into account. These contradictory effects will need to be considered when optimizing the printing parameters, though the optimal balance will be highly dependent on the material used and the limitations of the printer.
Experimental validation of the accuracy of the heat transfer and polymer diffusion models was performed using an amorphous polymer (polyether imide). Single road wide parts were printed at various nozzle temperatures, bed temperatures, and printing speeds and the results were compared to the simulated results. The predicted shear stress in the bottom of the part ranged from 2.3-3.8 MPa and correlated to warpages at the corners of each part of 1.2-2.4 mm. A linear increase in warpage with predicted shear stress was observed supporting the shear stress model. Predicted degrees of healing ranged from 2-90% but the experimental results ranged from 15-36%. Results of the healing model underpredicted strength at low printing speeds and over predicted strength at high printing speeds. The experimental validations showed the capabilities of the models, but the effect of printing speed will need to be investigated further to improve the accuracy of the healing model. / MS / This thesis is concerned with the development of methods and models to aid in optimizing a type of 3D printing known as Fused Filament Fabrication (FFF). We demonstrate a novel FFF nozzle design to enable the first measurements of the temperature and pressure within FFF nozzles, which is critical for ensuring that the printer is printing at the appropriate temperature and flow rate. Testing was performed using a material known as Acrylonitrile butadiene styrene and a modified Monoprice Maker Select 3D printer. Tests using the default temperature control settings of the printer showed an 11 °C drop in temperature and significant fluctuations in pressure, during printing and while idle, of ± 2 °C and +/-14 kPa. These deviations were eliminated at lower flow rates with a properly calibrated temperature control system. At high flow rates, drops in temperature as high as 6.5 °C were observed even with a properly calibrated temperature control system, providing critical input to the impact of flow rate and temperature control calibration on the temperature of the polymer melt inside FFF nozzles. Pressure readings ranging from 140-6900 kPa were measured over the range of extrusion flow rates tested. Theoretical predictions of the pressure within the nozzles matched well with the experimental results. Our nozzle prototype succeeded in measuring internal conditions of FFF nozzles for the first time, thereby providing several important insights into the printing process which are vital for monitoring and improving FFF printed parts.
Furthermore, simulations of the FFF process are presented which can quantify the effect of processing conditions on the properties of FFF parts made from materials which can crystallize. Each layer was modelled as a rectangular cross section which was broken down into smaller elements for modelling. Crystallinity of each element was calculated using a model which can account for changes in the rate of crystallization due to temperature as well as multiple types of crystallization. The strength of the interlayer bonds was calculated using a novel model which accounts for the effects of temperature and crystallinity. To the authors knowledge, this is the first bonding model capable of accounting for the effect of crystallinity on bonding and is relevant to any process involving bonding of crystalline materials; not just FFF. The shear stress between each layer and at the bottom of the part was also calculated for the first time by balancing thermal and shear stresses of each layer. Simulations were performed using typical printing conditions for a high performance polymer (polyether ether ketone). In the first layer of a 24 layer part, the average amount of crystallinity, bonding, and shear stress were 25.0%, 53.8% and 19.4 MPa respectively. The degree of crystallinity and healing at layer 22 (which represented the majority of the part) were 18.4-25.0% and 51.4% respectively. When crystallinity was not accounted for, varying the printing parameters and material properties supported the use of high temperatures and specific heat in addition to a low printing speed, heat transfer coefficient, and thermal conductivity to maximize part properties. These conditions also supported crystallization, however, which led to a simultaneous reduction in the part properties when crystallinity was considered. These contradictory effects will need to be considered when optimizing the printing parameters, though the optimal balance will be highly dependent on the material used and the limitations of the printer.
Experimental validation of the accuracy of the heat transfer and bonding models was performed using an amorphous polymer (polyether imide). Single road wide parts were printed at various nozzle temperatures, bed temperatures, and printing speeds and the results were compared to the simulated results. The predicted shear stress in the bottom of the part ranged from 2.3-3.8 MPa and correlated to the corners of each part peeling 1.2-2.4 mm from the printer. A linear increase in the experimental peeling with predicted shear stress was observed, supporting the shear stress model. Predicted bonding ranged from 2-90% of the strength of the material, but the experimental results ranged from 15-36%. Results of the bonding model underpredicted strength at low printing speeds and over predicted strength at high printing speeds. The experimental validations showed the capabilities of the models, but the effect of printing speed will need to be investigated further to improve the accuracy of the bonding model.
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