Process-structure-property relationships in material extrusion additive manufacturing (MEAM) are complex, non-linear, and poorly understood. Without proper characterization of the effects of each processing parameter, products produced through fused filament fabrication (FFF) and other MEAM processes may not successfully reach the material properties required of the usage environment. The two aims of this thesis were to first use an informatics approach to design a workflow that would ensure the collection of high pedigree data from each stage of the printing process; second, to apply the workflow, in conjunction with a design of experiments (DOE), to investigate FFF processing parameters. Environmental, material, and print conditions that may impact performance were monitored to ensure that relevant data was collected in a consistent manner. Acrylonitrile butadiene styrene (ABS) filament was used to print ASTM D638 Type V tensile bars. MakerBot Replicator 2X, Ultimaker 3, and Zortrax M200 were used to fabricate the tensile bars. Data was analyzed using multivariate statistical techniques, including principal component analysis (PCA). The magnitude of effect of layer thickness, extrusion temperature, print speed, and print bed temperature on the tensile properties of the final print were determined. Other characterization techniques used in this thesis included: differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and scanning electron microscopy (SEM). The results demonstrated that printer selection is incredibly important and changes the effects of print parameters; moreover, further investigation is needed to determine the sources of these differences.

The overall goal of this work is to expand the materials library for the fused filament fabrication (FFF) material extrusion additive manufacturing (AM) process through innovations in the FFF process, post-process, and polymer composition. This research was conducted at two opposing ends of the FFF-processing temperature: low processing temperature (<100 °C) for pharmaceutical applications and high processing temperatures (>300 °C) for high-performance structural polymer applications. Both applications lie outside the typical range for FFF (190-260 °C). To achieve these goals, both the material and process were modified. Due to the low processing temperature requirements for pharmaceutical active ingredients, a water-soluble, low melting temperature material (sulfonated poly(ethylene glycol)) series was used to explore how different counterions affect FFF processing. The strong ionic interaction within poly(PEG8k-co-CaSIP) resulted in the best print quality due to the higher viscosity (105 Pa∙s) allowing the material to hold shape in the melt and the high-nucleation producing small spherulites mitigating the layer warping. Fillers were then explored to observe if an ionic filler would produce a similar effect. The ionic filler (calcium chloride) in poly(PEG8k-co-NaSIP) altered the crystallization kinetics, by increasing the nucleation density and viscosity, resulting in improved printability of the semi-crystalline polymer. A methodology for embedding liquids and powders into thin-walled capsules was developed for the incorporation of low-temperature active ingredients into water-soluble materials that uses a higher processing temperature than the actives are compatible with. By tuning the thickness of the printed walls, the time of internal liquid release was controlled during dissolution. This technique was used to enable the release of multiple liquids and powders at different times during dissolution. To enable the printing of high-temperature, high-performance polymers, an inverted desktop-scale heated chamber with the capability of reaching over 300 °C was developed for FFF. The design was integrated onto a FFF machine and was used to successfully print polyphenylsulfone which resulted in a 48% increase in tensile strength (at 200 °C) when compared to printing at room temperature. Finally, the effects of thermal processing conditions for printing ULTEM® 1010 were studied by independently varying the i) nozzle temperature, ii) environment temperature, and iii) post-processing conditions. The nozzle temperature primarily enables flow through the nozzle and needs to be set to at least 360 °C to prevent under extrusion. The environment temperature limits the part warping, as it approaches Tg (217 °C), and improves the layer bonding by decreasing the rate of cooling that allows more time for polymer chain entanglement. Post-processing for a longer time above Tg (18 hrs at 260 °C) promotes further entanglement, which increases the part strength (50% increase in yield strength); however, the part is susceptible to deformation. A post-processing technique was developed to preserve the parts' shape by packing solid parts into powdered salt. / Doctor of Philosophy / Fused filament fabrication (FFF) is the most widely used additive manufacturing (also referred to as 3D printing) process in industry, education, and for hobbyists. However, there is a limited number of materials available for FFF, which limits the potential of using FFF to solve engineering problems. This work focuses on material and machine modifications to enable FFF for use in both pharmaceutical and structural applications. Specifically, many pharmaceutical active ingredients require processing temperatures lower than what FFF typically uses. A low-temperature water-soluble material was altered by incorporating salt ions and ionic fillers separately. The differences in the printability were directly correlated to the measured variations in the viscosity and crystallization material properties. Alternatively, a technique is presented to embed liquids and powders into thin-walled, water-soluble printed parts that are processed using typical FFF temperatures, where the embedded material remains cool. The release time of the embedded material during dissolution is controlled by the thickness of the capsule structure. For structural applications, a machine was developed to allow for the processing of high-performance, high-temperature polymers on a desktop-scale system. This system uses an inverted heated chamber that uses natural convection to be able to heat the air around the part and not the electric components of the machine. The heated environment allows the part to remain at a higher temperature for a longer time, which enables a better bond between printed layers to achieve high-strength printed parts using high-performance materials. This machine was used to characterize the thermal processing effect for printing the high-performance polymer ULTEM® 1010. The nozzle temperature, environment temperature, and post-processing were tested where i) a higher nozzle temperature (360 °C) increases strength and prevents under extrusion, ii) a higher environment temperature (≥200 °C) increases the strength by slowing cooling and decreases warping by limiting the amount of shrinkage the occurs during printing, and iii) post-processing in powdered salt (18 hrs at 260 °C) increases part strength (50%) by allowing the printed roads to fuse.

Yes / In recent years 3D printing has gained popularity amongst industry professionals and hobbyists alike, with many new types of Fused Filament Fabrication (FFF) apparatus types becoming available on the market. A massively overlooked component of FFF is the requirement for a simple method to calculate the geometries of polymer depositions extruded during the FFF process. Manufacturers have so far achieved adequate methods to calculate tool-paths through so called slicer software packages which calculate the required velocities of extrusion from prior knowledge and data. Presented here is a method for obtaining a series of equations for predicting height, width and cross-sectional area values for given processing parameters within the FFF process for initial laydown on to a glass surface.

Consumer additive manufacturing (3D printing) has rapidly grown over the last decade. While the technology for the most common type, Fused Filament Fabrication (FFF), has systematically improved and sales have increased, fundamentally, the capabilities of the machines have remained the same. FFF printers are still limited to depositing layers onto a flat build plate. This makes it difficult to combine consumer AM with other objects. While consumer AM promises to allow us to customize our world, the reality has fallen short. The ability to directly modify existing objects presents numerous possibilities to the consumer: personalization, adding functionality, improving functionality, repair, and novel multi-material manufacturing processes. Indeed, similar goals for industrial manufacturing drove the research and development of technologies like direct write and directed energy deposition which can deposit layers onto uneven surfaces. Replicating these capabilities on consumer 3-axis FFF machines is difficult mainly due to issues with reliability, repeatability, and quality. This thesis proposes, demonstrates, and tests a method for scanning and printing dimensionally-accurate (unwarped) digital forms onto physical objects using a modified consumer-grade 3D printer. It then provides an analysis of the machine design considerations and critical process parameters. / Master of Science / Consumer additive manufacturing (3D printing) has rapidly grown over the last decade. While the technology for the most common type, Fused Filament Fabrication (FFF), has systematically improved and sales have increased, fundamentally, the capabilities of the machines have remained the same. FFF printers are still limited to depositing layers onto a flat build plate. This makes it difficult to combine consumer AM with other objects. While consumer AM promises to allow us to customize our world, the reality has fallen short. The ability to directly modify existing objects presents numerous possibilities to the consumer: personalization, adding functionality, improving functionality, repair, and novel multi-material manufacturing processes. Indeed, similar goals for industrial manufacturing drove the research and development of technologies like direct write and directed energy deposition which can deposit layers onto uneven surfaces. Replicating these capabilities on consumer 3-axis FFF machines is difficult mainly due to issues with reliability, repeatability, and quality. This thesis proposes, demonstrates, and tests a method for scanning and printing dimensionally-accurate (unwarped) digital forms onto physical objects using a modified consumer-grade 3D printer. It then provides an analysis of the machine design considerations and critical process parameters.

Filament-based material extrusion additive manufacturing (MEAM) is an established technique in additive manufacturing (AM). However, semicrystalline polymers, such as polypropylene (PP), have limited commercial use in MEAM processes in the past due to their rapid crystallization kinetics and the subsequent effect on the integrity of the generated structures. The rapid crystallization of PP can be controlled by formulating blends of PP with hydrocarbon resins to enable longer re-entanglement times for interlayer adhesion. While the topic of formulating PP blends/composites with other materials to improve the printability has been investigated, variation in properties of commercial PP grades, of similar molecular weight (MW) and molecular weight distribution (MWD), on printability is still to be investigated. Those commercial PP grades can have wide variation in properties such as Melt Flow Index (MFI), additive content, and polymer architecture which can impact material properties relevant to printability. To investigate the effect of properties of commercial PP on their printability and mechanical performance, different commercial PP grades, with different properties, are blended with a fixed loading of hydrogenated resins, and the consequent effects on the mechanical properties of MEAM generated PP structures are studied via mechanical analysis. Tensile strength and the extent of interlayer adhesion in the 3D printed blends are characterized through rheological measurements. These measurements emphasize the importance of the relative location of the storage/loss modulus crossover point via small oscillatory frequency sweeps. We specifically show that a relatively higher crossover frequency will correlate with improved interlayer adhesion and reduced warpage in printed structures. However, this improvement is accompanied by a tradeoff, resulting in inferior tensile strength and an increased degree of print orientation anisotropy. / Master of Science / Additive Manufacturing (AM), commonly known as 3D printing, is a transformative technology with high potential to revolutionize the manufacturing landscape. Polymers are widely used in AM for various applications. As a result, extensive research is conducted to enhance the printability and properties of printed polymer structures. Polypropylene (PP) exhibits desirable mechanical, optical, and chemical properties that make its use in AM attractive. Despite this potential, optimizing the use of PP in 3D printing remains challenging. Consequently, extensive research is underway to improve the printability of PP. However, the effects of including additives to enhance the properties of commercial PP grades are often overlooked. We demonstrate that the choice of commercial PP grade is crucial to the mechanical and structural properties of structures generated via AM. This was established by developing a systematic experimental procedure to assess the printability of various PP grades and to measure their key mechanical and structural properties.

Yes / Designing and manufacturing functional parts with enhanced mechanical property is a major goal of fused filament fabrication (FFF) for polymeric elastomers, which exhibits major advantages in producing such parts with a range of structures. But the unsatisfactory mechanical performance constrains greatly its real application and there is yet no consensus in the mechanical characterization of printed samples. This work takes the nozzle height as the considered factor and tests the tensile property of FFF-printed thermoplastic polyurethane (TPU). Rheological property of the TPU melt, represented here by die swell behavior and shear viscosity, were measured initially to obtain a preliminary assessment of the material suitability and an optimization of melt extrusion conditions for FFF processing. Then correlation between the cross-section profile of deposited bead and the tensile performance of printed sample were evaluated. Both the shape of deposited bead and the bonding strength of two adjacent beads are emphasized when explaining the measured tensile strength. The significance of molecular permeation efficiency at bead-bead interfaces, and bonding-releasing patterns between adjacent beads to the tensile failure of printed objects is discussed. / The support provided by China Scholarship Council (CSC, 201806465028) for Xiang Lin during his academic visit in University of Bradford is acknowledged.

Denna rapport detaljerar ett examensarbete där användbarheten på en lokalt skapad 3D-skrivare förbättrats i syfte av att tillåta skrivarens användning av studenter på KTH Södertälje. Skrivarens har ursprungligen byggts för att agera som ett pågående projekt som kan återupptas som examensarbete, varav detta är det tredje. Skrivaren i fråga är en FFF-skrivare i ”box” stil med utskriftsvolymen 400 x 400 x 375 mm. Vid projektstart är skrivaren i nominellt användbart skick men saknar dokumentation, processrutiner och användbara slicerprofiler. Skrivaren besitter även hårdvaran för att tillåta utskrifter med två material men denna funktion har aldrig implementerats. Framtagningen av slicerprofiler har tagit upp majoriteten av arbetet och har utförts genom iterativ testning där inställningar modifieras och testas, vartefter positiva ändringar implementeras för att gradvis eliminera defekter och minska haveririsk. Projektet har levererat en full slicerprofil som tillåter pålitliga utskrifter med två olika PLA-filament samt en användarmanual till skrivaren. Utöver användarverktygen så detaljeras även de reparationsarbeten och hårdvaruändringar som gjorts. Profil, manual, rådata och filer för utskrivna komponenter är tillgängliga i en projektmapp som kan hittas från en länk i början av kapitel 4. / This report details a thesis project for getting a 3D-printer internally built at KTH Södertälje into a state where it can be used by other students for unrelated projects. The printer acts as an ongoing project that can be used for thesis work, with this project in particular being the third in line. The printer in question is an FFF-printer with the ”box” configuration and a print volume of 400 x 400 x 375 mm. At project start, the printer is nominally in working condition but lacks any documentation for proper handling and slicer settings. Additionally, its multi-material function has never been successfully implemented. Adjustment of slicer settings is done using iterative testing, wherein settings are modified and tested, with positive changes being integrated and negative changes discarded with the intent of removing defects and minimizing risk of print failure. The project has delivered a slicer profile for Cura capable of reliably printing with two different PLA filaments as well as a user manual. Hardware upgrades and repair work has also been detailed. The profile, user manual, raw data and object files for upgrades and spares can be found through a link in the beginning of chapter 4.

<div>From its advent in the 1980s until the 2000s, many of the advances in additive manufacturing (AM) technology were primarily focused on the development of various 3D printing techniques. During the 2000s, AM came to a juncture where these processes were well developed and could be used effectively for rapid prototyping purposes; however, the ability to produce functional components that could reliably perform in a given system had not been fully achieved. The primary focus of AM research since this juncture has been to transition AM from a rapid prototyping technique to a legitimate means of mass manufacturing end-use products. In order to make this happen, two significant areas of research needed to be advanced. The first area focused on advancing the limited selection and functionality of the materials being used for AM. The second area focused on the characterization of the end-use products comprised of these new materials.</div><div><br></div><div>The primary goals of the work described in this document are to substantially further the field of the additive manufacturing by developing new functional materials and subsequently characterizing the resultant printed components. The primary focus of the first two chapters (Chapters 2 and 3) is to further characterize an energetic material system comprising of aluminum (Al) particles embedded in a polyvinylidene fluoride (PVDF) binder, which has been shown to be compatible with AM. This material system has the ability to be implemented as a lightweight multifunctional energetic structural material (MESM); however, significant characterization of its structural energetic properties is needed to ensure reliable MESM performance. First, variations of a previously demonstrated Al/PVDF filament were investigated in order to determine the effect of material constituents on the structural energetic properties of the material. Seven different Al/PVDF formulations, with various particle loadings and particle sizes, were considered. The modulus of elasticity and ultimate strength for the seven formulations were obtained via quasi-static tensile testing of 3D printed dogbones. The energetic performance was quantified via burning rate measurements and differential scanning calorimetry (DSC) of 3D printed samples. Next, variations in the AM process were made and the effect of print direction on the same properties was determined. Once viable MESM performance was quantified, representative structural elements were printed in order to demonstrate the ability to create structural energetic elements. During quasi-static tensile testing, it was observed that aligning the load direction perpendicular to the print direction of the component resulted in inferior mechanical properties. This reduction in mechanical properties can be attributed to the lack of continuity at material interfaces, a well studied phenomena in AM.</div><div><br></div><div>This phenomena is the primary focus of the next two chapters (Chapters 4 and 5), which investigate the polymer healing process as it pertains to fusion-based material extrusion additive manufacturing, also known as fused filament fabrication (FFF). In the context of the FFF process, the extent of the polymer healing, or lack thereof, at the layer interface is known to be thermally driven. Chapter 4 quantifies the relationship between the reduction in mechanical properties and the temperature of the previously deposited layer at the time the subsequent layer is deposited. This relationship gives insight into which parameters should be closely monitored during the FFF process. The following chapter investigates incorporating plasma surface treatment as a means to improve the reduced mechanical properties seen in Chapter 3 and 4. As plasma surface modification can affect various stages of the polymer healing process, a variety of experiments were completed to determine which mechanisms of the plasma treatment were significantly affecting the mechanical properties of the FFF components. The thermal history was analyzed and it was hypothesized that enhanced diffusion at the layer interface was not a significant contributor to, but a rather a detractor from, the improved mechanical properties in this system. A variety of tests investigating how the plasma treatment was affecting the wettability of the surface were performed and all of the tests indicated that the wettability was increased during treatment and was likely the driving mechanism causing the improvement seen in the mechanical properties. These tests give some initial insight into how to successfully pair plasma treatment capabilities with FFF systems and give insights into how that plasma treatment can affect the polymer healing process in FFF applications.</div>

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