Applications Of Nanotechnology In Geotechnical Engineering .
Applications of Nanotechnology in Geotechnical EngineeringbyXianglei ZhengA Dissertation Presented in Partial Fulfillmentof the Requirements for the DegreeDoctor of PhilosophyApproved September 2016 by theGraduate Supervisory Committee:Jaewon Jang, ChairClaudia ZapataEdward KavazanjianARIZONA STATE UNIVERSITYDecember 2016
ABSTRACTNanotechnology has been applied to many areas such as medicine, manufacturing,catalysis, food, cosmetics, and energy since the beginning 21st century. However, theapplication of nanotechnology to geotechnical engineering has not received much attention.This research explored the technical benefits and the feasibility of applying nanoparticlesin geotechnical engineering. Specific studies were conducted by utilizing high-pressuredevices, axisymmetric drop shape analysis (ADSA), microfluidics, time-lapse technology,Atomic Force Microscopy (AFM) to develop experiments. The effects of nanoparticle onmodifying interfacial tension, wettability, viscosity, sweep efficiency and surface attractionforces were investigated. The results show that nanoparticles mixed in water cansignificantly reduce the interfacial tension of water in CO2 in the applications of nanofluidCO2 flow in sediments; nanoparticle stabilized foam can be applied to isolate contaminantsfrom clean soils in groundwater/soil remediation, as well as in CO2 geologicalsequestration or enhanced oil/gas recovery to dramatically improve the sweep efficiency;nanoparticle coatings are capable to increase the surface adhesion force so as to capturemigrating fine particles to help prevent clogging near wellbore or in granular filter in theapplications of oil and gas recovery, geological CO2 sequestration, geothermal recovery,contaminant transport, groundwater flow, and stormwater management system.i
DEDICATIONThis dissertation is dedicated to my family, especially to my wife, Wei Yan, andmy son, Aaron Zheng. Without their support, I could not have done this work.ii
ACKNOWLEDGMENTSI would like to thank the committee and all the people who take part in myresearch projects for the valuable supports and suggestions.I am very grateful to my advisor, Dr. Jaewon Jang, for his support and guidancethroughout my five years’ research. I could not have finished my research without hishelp.I would like to thank Dr. Francois Perreault at Arizona State University, Dr.McElmurry at Wayne State University, and the Center for Solid State Science at ArizonaState University for the support to use the nanoparticle and fine measurement devices.I would also like to thank Dr. Taesup Yun at Yonsei University, Seoul for thesupport on the analysis of CO2 sweep efficiency.iii
TABLE OF CONTENTSPageLIST OF TABLES . viiLIST OF FIGURES . viiiCHAPTER1.Introduction . 11.1.Background and Objective . 11.2.Organization of Dissertation . 22.Literature Review. 43.Interfacial Tension and Contact Angle of CO2 –Water/Nanofluid-Quartz System . 143.1.Introduction . 143.2.Experimental Details . 183.2.1.Material and Experimental Configuration. . 183.2.2.Experimental Procedure . 193.3.3.3.1.IFT and CA of Pure Water-CO2-quartz System . 223.3.2.Effects of Nanoparticles on IFT and CA. . 243.3.3.Equilibration Time . 273.4.4.Results and Discussion . 22Conclusions . 28Nanoparticles Stabilized Air Foam Used as a Barrier in Porous Media . 304.1.Introduction . 304.2.Background - Literature Review . 314.3.Experimental Details . 33iv
CHAPTERPage4.3.1.Nanoparticles and Surfactants. 334.3.2.Foam Generation and Stability. . 354.3.3.Viscosity Measurement. . 354.3.4.Breakthrough Pressure Measurement - Micromodel. . 374.3.5.Breakthrough Pressure and Hydraulic Conductivity - Sand Column . 384.4.Results and Discussion . 404.4.1.Stability . 404.4.2.Bubble Size Distribution . 434.4.3.Effects of Time and Nanoparticle Concentration on Foam Viscosity. . 444.4.4.Breakthrough Pressure in Foam-Saturated Micromodel. 464.4.5.Breakthrough Pressure and Hydraulic Conductivity of Foam-filled SandColumns. . 464.5.5.Conclusions . 48Effects of Nanoparticles on CO2 Invading Brine Saturated Microfluidic Chips . 505.1.Introduction . 505.2.Interfacial Tension and Contact Angle (wettability) . 555.2.1.Experimental Details . 555.2.2.Results and Analyses - Interfacial Tension, Contact Angle, and WettabilityChange . 575.3.Gaseous, Liquid, and Supercritical CO2 Injection . 595.3.1.Experimental Details . 595.3.2.Results and Analyses - Displacement Efficiency . 61v
CHAPTER5.4.Experimental Details . 645.4.2.Results and Analyses - Foam Viscosity and Displacement Efficiency . 66Conclusion . 68Nanoparticle-coated Surface to Capture Migrating Fine Particles . 706.1.Introduction . 706.2.Backgrounds – Fines Migration . 716.3.Experimental Details . 746.3.1.Nanoparticles and Surface Coating Procedure . 746.3.2.Surface Topography and Surface Force Measurement . 756.3.3.Sand Column Test for Fines Adsorption Efficiency . 756.4.Results and Analyses . 776.4.1.Surface Image and Surface Forces . 776.4.2.Fines Adsorption to the Nanoparticle-coated Sands . 836.5.7.CO2 - water Foam Injection . 645.4.1.5.5.6.PageConclusions . 87Conclusion . 887.1.Summaries. 887.2.Future Study . 90References . 92vi
LIST OF TABLESTablePage2-1. The Effect of Nanoparticles on Interfacial Tension. (EG: Ethylene Glycol, G:Glycerol, SU: Sulphanole, S: Surfactant) . 52-2. The Effect of Nanoparticles on Contact Angle. . 62-3. The Effect of Nanoparticles on Thermal Conductivity. . 74-1. Fluids for Generating Air Foams. . 345-1. Physical and Interfacial Properties of Fluids Used in This Study. . 546-1. The Volumetric Concentration of Nanoparticles in the Influent and Effluent. . 84vii
LIST OF FIGURESFigurePage3-1. IFT and CA for Fluid-liquid-substrate System. . 163-2. Experimental Configuration for IFT and CA Tests at High-pressures. . 193-3. IFT and CA of Water Pressurized with CO2. . 223-4. IFT and CA of Pure Water and Nanofluids Pressurized with CO2. . 253-5. The Effect of Nanoparticle Concentration on IFT. 263-6. Equilibration Time for Al2O3 Nanofluid. . 284-1. Experimental Configurations of Viscosity and Breakthrough Pressure Measurement. 394-2. Foam Stability as a Function of Time. . 414-3. Coalescence of Air Bubbles In between Two Microscope Slides. . 424-4. Properties of Foam as a Function of Time. . 454-5. Breakthrough Pressure and Hydraulic Conductivity of Sand Filled with Foam.(estimated foam saturation 92%). . 475-1. Fluid Invasion Pattern: Displacement Boundary and Efficiency. . 535-2. A Brine Droplet on a Quartz Substrate Surrounded by CO2. . 585-3. Experimental Configurations for CO2 Invasion into a Brine-saturated MicrofluidicChip. . 605-4. Distribution of CO2 and Saline Water (blue) in the Microfluidic Chip after CO2Breakthrough. 625-5. The Saturation of CO2 in the Microfluidic Chip. . 63viii
FigurePage5-6. Experimental Configurations for Nanoparticle-stabilized CO2-water FoamGeneration and Foam Invasion into a Brine-saturated Microfluidic Chip. . 655-7. The Invasion of CO2-water Foam into a Brine-saturated Microfluidic Chip. . 676-1. Experimental Configuration of Sand Column Test for Fines Adsorption. . 766-2. Surface Topology Obtained by AFM for Clean and Nanoparticle-coated Surfaces. 786-3. Force Profiles Measured between the Surface and the Tip of AFM Probe. . 796-4. Adhesion Forces Measured in Air. . 816-5. Attraction Forces and Adhesion Forces in Air and Water. 826-6. Particle Size Distribution of the Kaolinite in the Influent (black), and 1st (red), 2nd(blue), and 3rd (green) Effluents. . 856-7. Fines Adsorption Efficiency of the Clean and Nanoparticle-coated Sand Columns. 86ix
1. Introduction1.1. Background and ObjectiveNanotechnology has been rapidly developing during the past two decades. NationalNanotechnology Initiative (NNI) in 2007 defined the term “nanotechnology” as theunderstanding and control of matter at dimensions of roughly 1 to 100 nanometers, whereunique phenomena enable novel applications. In 2000, the US government recognized that“nanotechnology can have a profound impact on our economy and society in the early 21stcentury, perhaps comparable to that of information technology or of cellular, genetic andmolecular biology”. Since then, research on nanotechnology boomed in many fields suchas medicine, manufacturing, catalysis, food, energy, and cosmetics. Up to date, greatbenefits have been obtained from the nanotechnology applications. For example,nanotechnology has been applied to diagnose disease and treat different cancers inmedicine. There are over 50 cancer-targeting drugs based on nanotechnology have been inclinical trials in the United States [Roco et al., 2011]. Nanoscale semiconductor processorsand memories have been widely used in electronic devices [S K Kim et al., 2010]. Foodindustry utilizes nanoparticles as antimicrobial food packaging materials to keep food freshand extend the storage time [Rashidi and Khosravi-Darani, 2011]. Around 30–40% ofthe U.S. oil and chemical industries deal with nanostructured materials [Roco et al., 2011].However, the application of nanotechnology in geotechnical engineering has notreceived much attention. Nanoparticles can be used to modify the properties of fluids andsediment in many applications such as CO2 geological sequestration, oil/gas-watermultiphase flow in porous media, non-aqueous phase liquid (NAPL) remediation in soil,1
the mitigation strategy for fines migration, and deep geothermal recovery. For example,nanoparticles are able to modify fluid flow, interfacial tension, viscosity, wettability, poresize distribution, which are key factors in many applications. Ordinarily, flowrate is theonly factor that can be controlled in operation. Sometimes, alkaline and surfactants areapplied to modify the interfacial tension and wettability to improve the productivity inpetroleum engineering. However, the surfactants are ineffective in modifying the surfaceproperties under harsh conditions such as high pressure and temperature conditions.Nanoparticles, on the contrast, can stably modify the properties under harsh environment,which will bring more benefits.The objective of this research is to explore the technical feasibility of nanoparticleapplication to geotechnical engineering. In this study, the effects of nanoparticles on themodification of interfacial tension, wettability, viscosity, and the surface attraction forcewill be investigated for the applications to groundwater and soil remediation, CO2geological sequestration, fines migration, and enhanced oil/gas recovery.1.2. Organization of DissertationThis research puts the emphasis on the fluid and sediment surface modification bynanoparticles and the applications to Geotechnical engineering. Specific studies in eachchapter are summarized below.Chapter 2 documents the previous studies on nanotechnology that potentiallybenefit to the geotechnical engineering projects.Chapter 3 reports the effects of nanoparticles on interfacial tension and contactangle in a CO2-nanofluids-quartz system. The interfacial tension and contact angle aremeasured within a high-pressure resistant device at the equilibrium condition.2
Chapter 4 studies the nanoparticle-stabilized air-water foams and the effects on thebreakthrough pressure and hydraulic conductivity of a porous medium. Several types ofnanoparticles are investigated. This chapter investigates the stability and viscosity ofnanoparticle-stabilized air-water foam and explores the applications in groundwater/soilremediation.Chapter 5 investigates the CO2 injection efficiency into a brine-saturatedmicrofluidic chip based on the techniques developed in the Chapter 4 and the improvementby the presence of nanoparticles, for the potential application to geological CO2sequestration, CO2-enhanced oil recovery, and CH4-CO2 replacement in gas hydratereservoir.Chapter 6 discusses the effects of fines fixation by nanoparticle-coated sandcolumns. The adhesion force and attraction force of nanoparticle-coated surfaces aremeasured, and a core-scale experiment is performed for the fines adsorption efficiency.The results help better understand the mechanism of fines fixation by porous media.Chapter 7 summarized the main points of the specific studies and suggests thefuture studies.3
2. Literature ReviewNanoparticles are around two orders of magnitude smaller than colloid particles.Due to the small size, nanoparticles can migrate through pore throat in reservoir sediments[Tiantian Zhang et al., 2009b]. And nanoparticles can be functionalized to have specificmechanical, thermal, electrical, optical, magnetic, and chemical properties [Krishnamoorti,2006]. Nanoparticles have been studied for applications such as (1) modification ofinterfacial tension (IFT), contact angle (CA), viscosity, and thermal conductivity [H Fanand Striolo, 2012; Maghzi et al., 2011; 2013; Rana et al., 2012; L Q Wang and Fan, 2011],(2) fixation of migrating fine particles by coating proppants’ surface [Masoudeh Ahmadiet al., 2011; Ali Habibi et al., 2011; Tianping Huang et al., 2008], (3) stabilization ofemulsion and foam [Adkins et al., 2010b; Binks et al., 2008; DiCarlo et al., 2011; Nguyenet al., 2014], and (4) fluid mobility control for better sweeping efficiency [T P Huang andClark, 2015; Ponnapati et al., 2011; Zeyghami et al., 2014].Nanoparticles in fluid alter IFT and CA as shown in Table 2-1 and Table 2-2. Asthe concentration of nanoparticle in fluid increases, the IFT decreases. At a given particleweight concentration, IFT of the fluid including smaller size nanoparticles is lower thanthat of the fluid including bigger size of nanoparticles. Possible reason of the reduction inIFT is the alignment of nanoparticles at the interface. Hydrophobic nanoparticles make theinterface to curve towards the water [Aminzadeh et al., 2012; Binks and Horozov, 2006; T.Zhang et al., 2009].Coating is an efficient way to change the surface wettability. The development of4
nanotechnology provides a convenient and effective way for the coating. The coating layercan be completed by spraying [Ogihara et al., 2015; Y F Zhang et al., 2014], plasmairradiation [Park et al., 2013; Takata et al., 2009], boiling induced precipitation [Hegde etal., 2012], etc. Super hydrophilic and super hydrophobic surfaces have been created bycoating a layer of nanoparticles on solid surfaces [Fleming and Zou, 2013
Chapter 2 documents the previous studies on nanotechnology that potentially benefit to the geotechnical engineering projects. Chapter 3 reports the effects of nanoparticles on interfacial tension and contact angle in a CO 2-nanofluids-quartz system. The interfacial tension and contact angle are
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