Continuous InkJet (CIJ) printing is a common 2-Dimensional printing technique that creates jets of ink that breakup into drops as they are propelled towards a substrate to create a print. Inkjet printing has been used not only to print on paper, but to manufacture a variety of devices including OLEDs, solar cells and microfluidic devices. In many cases, the ‘ink’ consists of a polymer dissolved in a volatile solvent. As this ink is sprayed on to the substrate, the solvent evaporates, leaving the polymer behind as the print. The addition of the polymer alters the physics of the problem significantly enough that it varies greatly from jetting only a fluid with nothing dissolved in it. Polymers impart viscoelasticity to the solution, creating ink jets that are long-lived and difficult to break into droplets. In order to maintain the formation of drops in a repeatable, uniform fashion, a disturbance of known magnitude is imposed upon the jet. While jetting a liquid with no additives in it, this disturbance governed jet breakup leads to the formation of satellite drops, smaller drops of fluid in-between the main jet drops. Satellite drops are an undesirable occurrence in inkjet printing because of their unpredictable behavior and potential to affect the quality of the print. However, the addition of polymers to the liquid can control and potentially suppress the formation of these satellite drops, greatly improving the print quality. The elasticity of iv the polymer and its ability to influence the jet behavior and formation of satellite drops is highly dependent on multiple factors including the backbone rigidity, molecular weight and the concentration in which it is present in the fluid. Strongly viscoelastic effects have a marked effect on the jet and their presence can be quantified quite easily. However, some polymers show weak viscoelastic behavior while present in the ink fluids and may or may not affect the jetting process. The objective of this study is to examine such a class of polymeric fluids that are weakly viscoelastic in the context of inkjet printing and satellite drop formation. Firstly, the fluids are tested in an extensional rheology setup called Capillary Breakup Extensional Rheometry – Drop-on-Substrate (CaBER-DoS) to quantify their extensional properties. Then, they are tested in an emulated inkjet printing setup. The goal is to quantify the impact of the aforementioned factors on jetting and using satellite drop behavior as a guiding metric to understanding viscoelastic behavior in inkjet printing fluids.

Nanocellulosics, often found in the form of cellulose nanocrystals (CNCs) and nanofibrillated cellulose (NFCs), provide promise as rheological modifiers and reinforcement fillers for composite materials. The biological origin of CNCs promises a bio-renewable resource with the potential to expedite degradation times compared to synthetic polymer species. Additionally, the surface functional groups provide a route for both hydrogen bonding and further chemical modification. While much research is currently investigating the possible uses of these materials, they offer limited aid if their use is not scalable to industrial processing techniques. Common processing techniques such as injection molding subject materials to high temperatures and strain rates upwards of 100000 s-1. Thermal stability is a known challenge that can be increased via chemical modifications, but little is known about the effects of high or extended shear stresses typical of those experienced during typical polymer processing. High shear rates, which proportionally result in high shear stresses, have the potential to influence the alignment, degradation, and overall usability of these materials when employed in consumer applications. In this work, we investigate the rheology and processing of aqueous CNC suspensions at concentrations up to 12.1 wt% and of aqueous NFC suspensions at concentrations up to 20 wt% under capillary shear stresses. Traditional capillary rheology corrections, including the Weissenberg-Rabinowitsch-Mooney (WRM) correction for non-Newtonian fluids, and the Bagley correction for entrance pressure effects, have been applied to determine the true rheological behaviors of these suspensions. Additional analysis using atomic force microscopy (AFM), wide-angle x-ray scattering (WAXS), and conductometric titration assist identification of morphological and chemical changes that affect the CNMs after they have been subjected to industry-relevant shear rates. These studies demonstrate that processing conditions can significantly affect the size and shape of the post-processed nanomaterials by fracturing the CNCs and unwinding the larger bundles of the NFCs. Given the importance of the final aspect ratio of filler and reinforcement materials, the impact of this discovery will substantially influence how these materials are used and processed to create consumer products. / Doctor of Philosophy / As the world struggles with the problem of plastic waste and climate change, it is important to develop biologically friendly solutions to combat these issues. Filler materials such as carbon fibers and glass fibers can help create lightweight materials for cars and transportation containers. However, carbon fibers can be hazardous and expensive to obtain. Glass fibers offer a more cost-effective option, but they often break during processing and are heavy in comparison to carbon fibers. Cellulose nanomaterials (CNMs) can provide a lightweight and more bio-friendly alternative to these fillers. These CNMs can come from a wide variety of sources, such as hardwood trees, bacteria, or tunicates (a type of marine animal). This makes them abundantly available, relatively cheap to produce, and easy for the environment to break down fully. Using these as fillers instead of glass fibers, carbon fibers or other materials could help reduce much of our waste, but we need to be able to process them in the same ways we currently handle other composite materials. This work focuses on characterizing the effect of high-speed flows and the forces those flows put on the cellulose nanomaterials. The following document will show that the smaller, more rigid, cellulose nanocrystals (CNCs) often break under these stresses, while the longer nanofibrillated cellulose (NFCs) unwind and disperse.

A major problem faced by the petroleum industry is the deposition of wax during the pumping of waxy crude oils. This precipitation occurs at “normal” temperature, typically 20-30°C in Libya. It could occur during the journey from well to terminal through hundreds of miles of pipelines. This kind of transportation is expensive in terms of pumping costs. The pumping has to be continuous; otherwise wax can build up in the pipeline, reducing the pumping or even stopping it. The property that defines this characteristic is the yield stress which depends on wax concentration and cooling rate. The build-up of paraffin and asphaltenes can lead to serious problems in formation, tanks, and pipelines. Blockages can be expensive and time-consuming to deal with; this is precisely the topic of this research. For this research, model and real waxy crude oils are formulated and their rheology systematically measured under various cooling rates to determine the yield stress. A pipeline loop has been designed to measure the start-up pressure of stagnant oil which has been allowed to precipitate wax. The start-up pressure and the thickness of deposited wax are used in a simple mathematical model to calculate the yield stress. This research thus provides two independent means of predicting the yield stress. This research studied three different waxy crude oils. An MCR-301 Anton Paar rheometer was used to measure the rheology of the oils, and a pipeline rig was used to obtain the start-up pressure to calculate the yield stress of each type of oil after different stoppage times. Also, the thickness of the precipitated wax is measured to calculate the yield stress precisely. The data show that the layer thickness has significant effect on the yield stress and start-up pressures and corresponding yield flow stresses have been found to underpin the crystallisation process of the wax and slow cooling rate produce stronger structures requiring higher stresses to fracture and induce flow. Also, longer shutdown times make these structures even stronger and therefore require even larger stresses for flow to commence.

Yes / Melt blending of polyolefin/carbon nanotube (CNT) composites always leads to serious agglomeration of CNTs and hence inferior properties. Thus, well-dispersed CNTs within matrix are urgently required during processing. In this work, effective breakage of CNT agglomerates was achieved by solid-phase die drawing at a temperature below but near to the melting temperature of the matrix. Experimental results indicate that the incurred extensional stress provides a high orientation degree on the polypropylene (PP) matrix and consequently helps rupture CNT agglomerates, leading to improved alternating current（AC） conductivity by ~5–6 orders in magnitude. The reduced agglomerate ratio, the altered CNT networks (3D→2D), and the improved interfacial morphology between CNT and matrix are suggested to be responsible for the viscoelasticity variation of the composite melt and the improved property of PP/multiwalled CNTs (MWCNTs) composite. The initial loss of tensile ductility by the incorporation of MWCNTs is recovered by nearly 100%, which was attributed to the low agglomeration rate and improved interfacial morphology. This article provided the potential inspiration for the melt blending of polymer melt and CNTs. / China Scholarship Council. Grant Number: 201806465028

published_or_final_version / abstract / Civil Engineering / Doctoral / Doctor of Philosophy

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