Corrosion Prevention Nanoscience
NanoengineeringMaterialsandTechnologies
Editedby BerdimurodovElyorTukhlievichandChandrabhanVerma
Editors
BerdimurodovElyorTukhlievich FacultyofChemistry
NationalUniversityofUzbekistan
Tashkent100034
Usbekistan
Email:elyor170690@gmail.com
Dr.ChandrabhanVerma DepartmentofChemicalEngineering
KhalifaUniversityofScienceandTechnology
P.O.Box127788
AbuDhabi UnitedArabEmirates
Email:Chandraverma.rs.apc@itbhu.ac.in
ISBN978-3-11-107009-4
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Contents
ListofauthorsVII
NurşahKütük,AslıhanGürbüzer,GamzeTüzün,BurakTüzün
Chapter1
Nanoengineeringandnanoscience:currentandemergingtrends1
OmarDagdag,RajeshHaldhar,Seong-CheolKim,WalidDaoudi, ElyorBerdimurodov,EkeminiD.Akpan,EnoE.Ebenso
Chapter2
Polymernanocomposites:synthesis,modification,propertiesand applications17
ElyorBerdimurodov,KhasanBerdimuradov,IlyosEliboev,LazizbekAzimov, YusufboyRajabov,JaykhunMamatov,BakhtiyorBorikhonov,AbduvaliKholikov, KhamdamAkbarov
Chapter3
Covalentandnoncovalentsurfacefunctionalizationofnanomaterials (forenhancedsolubility,dispersibilityandcorrosionprevention potential)37
AysunAksu,HüseyinFatihÇetinkaya,SerapÇetinkaya, GamzeTüzün,BurakTüzün
Chapter4
MXenesandtheircompositesascorrosionprevention53
Bo-kaiLiao,Zhi-GangLuo,ShanWan,Hao-WeiDeng,Shu-YiJiang,Shuang-JianLi, Jun-JieYang
Chapter5
Quantumdotsincorrosionprevention67
HumiraAssad,AshishKumar
Chapter6
Carbonnanotubes(SWCNTs/MWCNTs)andfunctionalizedcarbonnanotubes incorrosionprevention85
DheerajSinghChauhan
Chapter7
Graphene(Gr)/grapheneoxide(GO)andfunctionalizedGr/GOincorrosion prevention99
DakeshwarkumarVerma,ReemaSahu,SantoshBahadurSingh,BhartiYarda, VikasKumarJain,ShailendraYadav,VikashKande,SharadTiwari, GokulRamNishad,YounusRazaBeg,VandanaMishra,DurgeshSinha Chapter8
Carbondots(CDs)andheteroatom-dopedCDsincorrosionprevention121
MuhammedSafaÇelik,HüseyinFatihÇetinkaya,SerapÇetinkaya,GamzeTüzün, BurakTüzün
Chapter9
Polymericnanoparticlesandtheircompositesincorrosioninhibition135
AmirHosseinJafariMofidabadi,NarimanAlipanah,AliDehghani Chapter10
Organic–inorganichybridnanostructuredmaterialsincorrosion prevention147
ManashProtimMudoi,RhythmKatyal,KhushiBhatt,VidushiSingh, AsmitaChoudhary,SanskritiGupta
Chapter11
Ceramicnanomaterialsincorrosionprevention165
KhasanBerdimuradov,ElyorBerdimurodov,IlyosEliboev,NurbekUmirov, BakhtiyorBorikhonov,AbduvaliKholikov,KhamdamAkbarov
Chapter12
Smart–hybridnanomaterialsincorrosionprevention181
Index195
Listofauthors
NurĹźahKĂĽtĂĽk ChemicalEngineeringDepartment FacultyofEngineering
SivasCumhuriyetUniversity
Sivas
Turkey
AslıhanGürbüzer
PlantandAnimalProductionDepartment TechnicalSciencesVocationalSchoolofSivas SivasCumhuriyetUniversity Sivas Turkey
GamzeTĂĽzĂĽn DepartmentofChemistry FacultyofScience
SivasCumhuriyetUniversity Sivas Turkey
Email:gamzekekul@gmail.com
BurakTĂĽzĂĽn
PlantandAnimalProductionDepartment TechnicalSciencesVocationalSchoolofSivas SivasCumhuriyetUniversity
Sivas
Turkey
OmarDagdag CentreforMaterialsScience CollegeofScience EngineeringandTechnology UniversityofSouthAfrica Johannesburg1710 SouthAfrica
RajeshHaldhar SchoolofChemicalEngineering YeungnamUniversity Gyeongsan38541 RepublicofKorea
https://doi.org/10.1515/9783111071756-203
Seong-CheolKim SchoolofChemicalEngineering YeungnamUniversity Gyeongsan38541 RepublicofKorea
WalidDaoudi LaboratoryofMolecularChemistry MaterialsandEnvironment(LCM2E) DepartmentofChemistry MultidisciplinaryFacultyofNador UniversityMohamedI 60700Nador
Morocco
ElyorBerdimurodov FacultyofChemistry NationalUniversityofUzbekistan Tashkent100034 Uzbekistan
Email:elyor170690@gmail.com
EkeminiD.Akpan CentreforMaterialsScience CollegeofScience EngineeringandTechnology UniversityofSouthAfrica Johannesburg1710 SouthAfrica
EnoE.Ebenso CentreforMaterialsScience CollegeofScience EngineeringandTechnology UniversityofSouthAfrica Johannesburg1710 SouthAfrica
KhasanBerdimuradov FacultyofIndustrialViticultureandFood ProductionTechnology ShahrisabzbranchofTashkentInstituteof ChemicalTechnology Shahrisabz181306 Uzbekistan
IlyosEliboev FacultyofChemistry
NationalUniversityofUzbekistan
Tashkent100034
Uzbekistan
LazizbekAzimov FacultyofChemistry
NationalUniversityofUzbekistan Tashkent100034
Uzbekistan
YusufboyRajabov FacultyofChemistry
NationalUniversityofUzbekistan Tashkent100034
Uzbekistan
JaykhunMamato FacultyofChemistry
NationalUniversityofUzbekistan Tashkent100034
Uzbekistan
BakhtiyorBorikhonov FacultyofChemistry–Biology KarshiStateUniversity Karshi130100
Uzbekistan
AbduvaliKholikov FacultyofChemistry
NationalUniversityofUzbekistan Tashkent100034
Uzbekistan
KhamdamAkbarov FacultyofChemistry
NationalUniversityofUzbekistan Tashkent100034
Uzbekistan
AysunAksu DepartmentofMolecularBiologyandGenetics ScienceFaculty
SivasCumhuriyetUniversity
58140Sivas
Turkey
HüseyinFatihÇetinkaya DepartmentofEnvironmentalEngineering FacultyofEngineering
SivasCumhuriyetUniversity
Sivas
Turkey
SerapÇetinkaya DepartmentofMolecularBiologyandGenetics ScienceFaculty
SivasCumhuriyetUniversity
58140Sivas
Turkey
Email:serapcetinkaya2012@gmail.com
GamzeTĂĽzĂĽn DepartmentofChemistry FacultyofScience
SivasCumhuriyetUniversity
Sivas
Turkey
BurakTĂĽzĂĽn PlantandAnimalProductionDepartment TechnicalSciencesVocationalSchoolofSivas
SivasCumhuriyetUniversity
Sivas
Turkey
Bo-kaiLiao SchoolofChemistryandChemicalEngineering GuangzhouUniversity Guangzhou510006
China and JointInstituteofGuangzhouUniversity& InstituteofCorrosionScienceandTechnology GuangzhouUniversity
Guangzhou510006
China
Email:bokailiao@gzhu.edu.cn
Zhi-GangLuo SchoolofChemistryandChemicalEngineering GuangzhouUniversity
Guangzhou510006
China
ShanWan SchoolofChemistryandChemicalEngineering GuangzhouUniversity
Guangzhou510006
China and
JointInstituteofGuangzhouUniversity& InstituteofCorrosionScienceandTechnology GuangzhouUniversity Guangzhou510006
China
Hao-WeiDeng SchoolofPhysicsandMaterialsScience CenterofAdvancedFunctionalMaterials GuangzhouUniversity Guangzhou510006
China
Shu-YiJiang SchoolofArt&Design GuangdongUniversityofTechnology Guangzhou510062
China
Shuang-JianLi InstituteofNewMaterials GuangdongAcademyofSciences NationalEngineeringLaboratoryofModern MaterialsSurfaceEngineeringTechnology Guangzhou510650
China
Jun-JieYang InstituteofAdvancedWearandCorrosion ResistantandFunctionalMaterials JinanUniversity
Guangzhou510632
China
HumiraAssad DepartmentofChemistry SchoolofChemicalEngineeringandPhysical Sciences LovelyProfessionalUniversity
Punjab
India
AshishKumar
NCE DepartmentofScienceandTechnology
BiharEngineeringUniversity GovernmentofScienceandTechnology GovernmentofBihar
Bihar
India
DheerajSinghChauhan ModernNationalChemicals SecondIndustrialCity Dammam31421
SaudiArabia
Email:dheeraj.chauhan.rs.apc@itbhu.ac.in
DakeshwarkumarVerma DepartmentofChemistry GovernmentDigvijayAutonomousPostgraduate College
Rajnandgaon491441 Chhattisgarh
India
ReemaSahu DepartmentofChemistry GovernmentDigvijayAutonomousPostgraduate College
Rajnandgaon491441
Chhattisgarh
India
SantoshBahadursingh DepartmentofChemistry UniversityofAllahabad Prayagraj211002
UttarPradesh
India
BhartiYarda DepartmentofChemistry GovernmentDigvijayAutonomousPostgraduate College
Rajnandgaon491441
Chhattisgarh
India
VikasKumarJain DepartmentofTechnicalEducationIndravati
Bhawan
NavaRaipur
AtalNagar
Raipur492002
Chhattisgarh
India
ShailendraYadav DepartmentofChemistry
AKSUniversity
Satna Madhyapradesh
India and DepartmentofChemistry GurughasidasCentralUniversity
Bilaspur
Chhattisgarh
India
VikashKande DepartmentofChemistry
GovernmentDigvijayAutonomousPostgraduate College
Rajnandgaon491441
Chhattisgarh
India
SharadTiwari DepartmentofChemistry
GovernmentDigvijayAutonomousPostgraduate College
Rajnandgaon491441
Chhattisgarh
India
GokulRamNishad DepartmentofChemistry
GovernmentDigvijayAutonomousPostgraduate College
Rajnandgaon491441
Chhattisgarh
India
YounusRazaBeg DepartmentofChemistry
GovernmentDigvijayAutonomousPostgraduate College
Rajnandgaon491441
Chhattisgarh
India
VandanaMishra DepartmentofChemistry
GovernmentDigvijayAutonomousPostgraduate College
Rajnandgaon491441
Chhattisgarh
India
DurgeshSinha DepartmentofChemistry
GurughasidasCentralUniversity
Bilaspur
Chhattisgarh
India
MuhammedSafaÇelik
DepartmentofMolecularBiologyandGenetics ScienceFaculty
SivasCumhuriyetUniversity
58140Sivas
Turkey
HüseyinFatihÇetinkaya DepartmentofEnvironmentalEngineering FacultyofEngineering
SivasCumhuriyetUniversity
Sivas
Turkey
SerapÇetinkaya
DepartmentofMolecularBiologyandGenetics ScienceFaculty
SivasCumhuriyetUniversity
58140Sivas
Turkey
GamzeTĂĽzĂĽn DepartmentofChemistry FacultyofScience
SivasCumhuriyetUniversity Sivas
Turkey
BurakTĂĽzĂĽn
PlantandAnimalProductionDepartment TechnicalSciencesVocationalSchoolofSivas SivasCumhuriyetUniversity Sivas Turkey
AmirHosseinJafariMofidabadi DepartmentofChemicalEngineering FacultyofEngineering GolestanUniversity
AliabadKatoul
Iran
NarimanAlipanah DepartmentofSurfaceCoatingsandCorrosion InstituteforColorScienceandTechnology(ICST) P.O.16765-654
Tehran
Iran
AliDehghani DepartmentofChemicalEngineering FacultyofEngineering GolestanUniversity
AliabadKatoul
Iran
Email:dehghaniali1996@gmail.com
ManashProtimMudoi DepartmentofChemicalEngineering IndianInstituteofTechnology Roorkee247667
Uttarakhand
India and DepartmentofChemicalEngineering UniversityofPetroleumandEnergyStudies
Dehradun248007
Uttarakhand,India
Email:mp_mudoi@ch.iitr.ac.in,mpmudoi@ddn. upes.ac.in
RhythmKatyal DepartmentofChemicalEngineering UniversityofPetroleumandEnergyStudies
Dehradun248007
Uttarakhand
India
KhushiBhatt DepartmentofChemicalEngineering UniversityofPetroleumandEnergyStudies
Dehradun248007
Uttarakhand
India
VidushiSingh DepartmentofChemicalEngineering UniversityofPetroleumandEnergyStudies
Dehradun248007
Uttarakhand
India
AsmitaChoudhary DepartmentofChemicalEngineering UniversityofPetroleumandEnergyStudies Dehradun248007
Uttarakhand
India
SanskritiGupta DepartmentofChemicalEngineering UniversityofPetroleumandEnergyStudies
Dehradun248007
Uttarakhand
India
KhasanBerdimuradov FacultyofIndustrialViticultureandFood ProductionTechnology
ShahrisabzbranchofTashkentInstituteof ChemicalTechnology
Shahrisabz181306
Uzbekistan
IlyosEliboev FacultyofChemistry NationalUniversityofUzbekistan Tashkent100034
Uzbekistan
NurbekUmirov
FacultyofChemistry–Biology
KarshiStateUniversity
Karshi130100
Uzbekistan
BakhtiyorBorikhonov
FacultyofChemistry–Biology
KarshiStateUniversity
Karshi130100
Uzbekistan
AbduvaliKholikov FacultyofChemistry
NationalUniversityofUzbekistan Tashkent100034
Uzbekistan
KhamdamAkbarov FacultyofChemistry
NationalUniversityofUzbekistan Tashkent100034
Uzbekistan
Nanoengineeringandnanoscience:current andemergingtrends
Abstract: Thestudyofscienceatthenanoscalehasbecomeoneofthemostimportant researchtopicsinrecentyears.Almostallbranchesofscienceareinterestedinnanotechnology.Metalandmetaloxides,carbonfamilyproducts,polymers,claysandcompositesaresomeofthenanomaterialsused.Despitetheirsmallsize,nanomaterials havedifferentpropertiessuchaslargesurfacearea,differentparticleshapeandsize, porevolume,biocompatibilityandbiodispersibility.Forthisreason,nanotechnology hasalsospreadtotheindustry.Duetotheiruniqueproperties,nanomaterialsare widelyusedinmedical,watertreatment,sensorandenvironmentalapplications.Althoughnanotechnologyresearchhasacceleratedespeciallyinrecentyears,thereare stillmanyunexploredmaterialsandapplicationareas.Theaimofthisstudyistoinvestigatetheadvantagesanddisadvantagesofnanomaterialsandnanotechnologyapplicationsbyexaminingtheirusageareasinscientificandindustrialfields.
Keywords: Nanoparticles,nanotechnology,materials,metaloxides,particlesize
1.1Introduction
Thestudyofnanoscalematerialsandthedevelopmentofassociatedlawsandconceptualinformationconstitutethefieldofscienceknownasnanoscience.Generally,materialssmallerthan100nmareclassifiedasnanomaterials[1].Itsscientificequivalentisa billionthofameter[2].Infact,theexistenceofnanoparticles(NPs)isnotanewphenomenon.Nanoscalematerialshavebeenformedinnatureforcenturies.Someoftheseare thepresenceofeventsthataresourcesofNPssuchasvolcaniceruptionsandfiresand ceramicglazesorstainedglasssilverNPsforcolorpurposes[3].ThescientificdevelopmentofNPsforthefirsttimewasaround50yearsagoforvaccinesandcancertreatment[4].Nanotechnologycannotbelimitedtoanydiscipline.Itisinterdisciplinarywith naturalsciencesandvariousbranchesofengineeringandsciencessuchastoxicology
✶Correspondingauthor:GamzeTüzün, DepartmentofChemistry,FacultyofScience,SivasCumhuriyet University,Sivas,Turkey,e-mail:gamzekekul@gmail.com,http://orcid.org/0000-0002-0420-2043
NurĹźahKĂĽtĂĽk, ChemicalEngineeringDepartment,FacultyofEngineering,SivasCumhuriyetUniversity, Sivas,Turkey
AslıhanGürbüzer,BurakTüzün, PlantandAnimalProductionDepartment,TechnicalSciences VocationalSchoolofSivas,SivasCumhuriyetUniversity,Sivas,Turkey
https://doi.org/10.1515/9783111071756-001
[3].Inrecentyears,nanotechnologyhasbeenusedindifferentdisciplinessuchasengineering,physics,chemistryandmedicine.Itdrawsattentionwithitsdiagnostic,imaging ortherapeuticproperties,especiallyinthebiomedicalfield[5,6].
Thestructuralpropertiesofnanoparticles(NPs)andtheareatobeusedvarydependingontheirpropertiessuchassize,shape,crystallinityandmorphology[7].An importantfeaturethatmakesNPsstandoutisthattheyhavealargersurfaceareacomparedtotherawmaterialsfromwhichtheyaresynthesized.Usingmanyorganicand inorganicelements,NPscanbesynthesizedfromnaturalcomponentssuchaslipids,proteins,polysaccharidesormetalssuchasTi, Ag,Au,ZnandCubyvariousmethods[8,9]. TheuseofNPsinthediagnosisandtreatmentofdiseasessuchascancerrevealstheimportanceofnanotechnologyduetotheirbiocompatibilityandbiodispersibilityproperties [7].AsseeninFigure1.1,aglucosemoleculeis1nminsize,whileawatermoleculeis 0.1nm.Thesedataindicatethatnanomaterialsareatthemolecularsizelevel[10].
1.2Nanomaterials
Nanomaterialswithahighsurface/volumeratioformthebasisofnanotechnologydue totheirmanysuperiorproperties.Researcheshavereportedthatthereareover1,000 nanoproductsduetotheirwideusageareas[11].Today,manymaterialgroupssuchas NPs,nanotubes,nanomembranesandnanofibersareinvestigated[12].NumerousdistinctmetallicNPshaverecentlybeendevelopedandapplied.Titaniumdioxide(TiO2), zincoxide(ZnO),FeO,copperoxide(CuO),bismuthoxide(Bi2O3),silica,mesoporoussilicaandleadoxide(PbO)aresomeofthem[13–15].Zirconiumdioxide(ZrO2),whichis oneoftheimportantindustrialnanomaterials,hasimportantpropertiessuchascatalyticactivity,thermalstabilityandchemicallyinertstructure.Cobaltoxide(Co3O4)is anotherimportantmaterialinmemorystorageunits,catalyticactivityandchemical sensorapplications[16].ZincNPsareanimportantsemiconductorwithoptical,piezoelectricandnontoxicproperties[7,17].SilicaandmesoporoussilicaNPsarenontoxic, biocompatibleandbiodegradablematerials.Thankstoitslargesurfaceareaandpore
Figure1.1: Comparisonoflengthscale109
volume,itcanbeusedindifferentapplicationssuchasdrugrelease,bonetissueengineering,adsorption,biosensorandsolarcell[15].Variousmetallic,carbon,polymeric orcompositeNPsusedinrecentyearsandtheirapplicationareasaregiveninTable1.1.
Carbonisarichandimportantfamilyfornanoscalesystemsandexhibitsbroad functionalitieswithstructuralarrangements[18].sp2 carbonmaterialscangenerally bethoughtofaszero-dimensionalfullerene,one-dimensionalcarbonnanotube(CNT) andtwo-dimensionalgraphene[19].Graphenehasuniqueelectronic,optical,catalytic, mechanicalandmagneticproperties,thermalconductivityandgasbarrierproperties. Thankstotheseproperties,graphenehasusesindifferentapplicationsfromenergy storagetobiomedicalmaterials[20,21].Grapheneoxide(GO)andreducedgraphene oxide(RGO)areknownasseveral-layergrapheneoxidematerials[22].Inaddition, carbon-basednanomaterialssuchasfullereneandCNTareusedindifferentapplicationsfrommedicinetoelectronicssuchasmetalNPs[23].Figure1.2showsthemolecularstructureandshapeoffullerene,CNTandgraphene.
Fullerene (0D) Carbon nanotubes (1D) Graphene (2D)
Figure1.2: Moleculerstructureoffullerene,carbonnanotubesandgraphene.
Table1.1: Differentnanoparticlesandareaofapplications.
Nanoparticles
TiO
TiO
Areaofapplication References
Bonetissueengineering
Antibacterial,larvicidalandanticancereffects
CeO Anticancereffect
ZnO Antifungalactivity
Chitosannanoparticles
Antibacterialactivity
Silane-modifiedFeO Anticorrosion
CuONPs Adsorption
NiONPs Adsorption
Silver Catalyticactivity
CuONPs Photocatalytic,antimicrobialandanticanceractivity[
Fe/Znbimetallic Cytotoxicitystudy [
Mesoporous-orderedsilica(MCM-)Adsorption
ZnO/ZnCrO
Graphene
ZrO/CoO/RGO
PEGlytednanographene
Photocatalyticdegradation
Cytocompatibilityeffect
Electrochemicalsensor [
PhotothermaltherapyTargetedchemotherapy []
]
]
]
]
]
]
]
Inaddition,nano-sizedmaterialsofclayshavecometotheforeinrecentyears. Nanoclayscanbeusedindrugcarriersystems,catalystoradsorbent,foodpackaging indifferentareas.Thenanosizeoftheclayaffectsthethermodynamic,physicaland chemicalpropertiesofthecompositessynthesizedwithpolymers.Itprovidesbenefits suchasincreasingthestabilityofthedrugorincreasingthebiodegradabilityofthe polymerindrugreleaseapplications[33] .Polymernanoparticlescanbeobtained bothfromnaturalpolymersandsyntheticallybysynthesis.Theycanbefunctionalizedwithpolysaccharide,proteinoraminoacidmolecules.Inthisway,theybecome moreeffectivefordrugrelease[34].Polymericnanoparticleswithhighdrugloading capacitycanbeeasilysterilizedanddispersed[35].Poly-hydroxyethylmethacrylate (p(HEMA)),whichcanbesynthesizedinnanosize,isanimportantpolymerinthisfield andisusedinbiomedicalandpharmaceuticalfieldssuchassoftcontactlenses[34]. ChitosanNPs,ontheotherhand,havehighzetapotentialandlargesurfacearea.The useofchitosannanoparticles,whichareusedinthetreatmentofagriculturaldiseases, inmanyareassuchasdrugs,vaccinesandgenereleaseisbeinginvestigated[26].
Nanofibersareveryfineyarnswithadiameterbetween50and500nm,which arelight,porousandhaveahighactivity.Theyareuniquematerialsfordressings, protectiveclothing,membraneandtissueengineering.Theyareobtainedbydifferent methodssuchasphaseseparation,interfacialpolymerization,freeze-dryingsynthesis, especiallyelectrospinningmethod[36].Inaddition,theproductionofnano-basedcellulosefibersandtheirapplicationsincompositematerialshasincreasedinterestdue toimportantpropertiessuchashighstiffness,biodegradabilityandlowweight.The applicationofcellulosenanofibersinpolymerreinforcementisatopicofrecentinterest[37].
Nanocompositeswithorganicorinorganicpropertiesarefunctionalmaterials thatdonotformamixturewitheachotherandcontainorganicandinorganiccomponentsintheirstructures.Complexnanometer-basedstructurescanbeformedfrom them[38].
1.2.1Synthesismethodsandstructureanalyses
Therearetwodifferentapproachestosynthesismethodsinnanotechnology.Oneof themisthe “top-down” approach.Inthisapproach,nano-basedmaterialsaremade usingthesmalleststructures.Thisisphotonicapplicationsinnanoelectricityand nanoengineering.The “bottom-up” approach,ontheotherhand,canbecalledmolecularnanotechnology.Scienceisconcernedwiththeproductionofdifferentnanoparticlesandnanomaterialswithextraordinaryproperties[39].
Withtheincreaseinresearchonthesubject,thesynthesismethodsofnanoparticleshavealsobeendevelopedbyscientists.Greensynthesis,whichhasbecomepopularinrecentyears,isfrequentlypreferredbecauseitisenvironmentallyfriendly,
inexpensive,efficientandeasy.Plant,fruitandvegetableextracts,bacteriaandvarious microorganismsareusedasreducingagents.Variousphytochemicalsubstancessuch aspolyphenols,especiallyinplantextracts,reducemetalionsandprovidenanoparticle synthesis[9].SomeofthecommonlyusedmethodsaregiveninFigure1.3. Aftersynthesis,thechemicalstructureofnanoparticlescanbeanalyzedbytechniquessuchas
– ultravioletspectroscopy(UV/vis),
– Fouriertransformspectroscopy,
– x-raydiffraction,
– energy-dispersiveX-rayspectroscopy.
Propertiessuchassizeandparticleshapeinthemorphologicalstructurecanbedeterminedusing
– scanningelectronmicroscope,
– transmmisonelectronmicroscope(TEM),
– atomicforcemicroscope,
– selectedfieldelectrondiffractiontechniques[9,32,40].
TEMimagesaregivenforsuperparamagneticFe 3 O4 NPsinFigure1.4aandforhydroxyapatiteNPsinFigure1.4b.Whenthemorphologicalstructureofnanoparticlesis examined,itisseenthattheshapeofFe3O4 issphericalandhydroxyapatiteisneedlelike[41].
synthesis methods for the production of metal nanoparticles
Figure1.3: Someofthecommonmethodsusedinmetalnanoparticleproductioninrecentyears.
Some
Sol-jel method
Hydrothermal
Precipitation
Green synthesis
1.3Scopeofapplication
Nanoparticlesobtainedinorganic,inorganic,metalorhybridformhaveverygood electronic,optical,physicalorbiologicalproperties.Therefore,theuseofnanoparticleshasspreadtovariousfieldssuchas[3,30,39,41]
– electronics,
– medicine(controlleddrugdelivery,anticanceractivity,tissuerepair,hemolytic activity),
– biomedical(pharmacy,detecingpathogen,antigendiagnosis),
– catalysis, – fluid,
– agriculture.
Inthissection,popularapplicationsandresearchareasinwhichnanomaterialsare usedtodaywillbeexamined.
1.3.1Medicine,healthandbiomedicalareas
Theuseofnanotechnologyinmedicinehaspavedthewayfortheuseofnanomaterialsforthediagnosisofdiseasesorforvarioustherapeuticpurposes[42].Forexample, cancerisadiseasethathasbeenaffectinghumanbeingsformanyyearsandwhose treatmenthasbeeninvestigated.Canceristheuncontrolleddivisionandproliferation ofcells.Sometimesitcanoccurinacertainorganandsometimesinaspread[43]. Especiallyforcancertreatment,manynanomaterialssuchasAgNPsandTiO2 NPsare usedasdrugdeliverysystemsorfortheirtherapeuticeffects[8,42].
Theuseofnanoparticlesinbonetissueengineeringhasincreasedinrecentyears. Superparamagneticironoxideandhydroxyapatitenanoparticleswereobservedto
Figure1.4: (a)SuperparamagneticFe3O4 nanoparticlesand(b)hydroxyapatite.
improvemineralizationandosteogenicdifferentiationofbonetissue[41].Superparamagneticironoxidenanoparticlesareusedagainstbraintumor.ItisshowninFigure1.5 thatthecompositematerialsynthesizedinsmallnanoscale,modifiedwithsilicananoparticlesandCNTspassesthroughtheblood-brainbarrier(BBB).Eveninalowmagnetic field,nanoparticleshavebeenreportedtoprovideheattodestroytumors.Ithasbeen reportedthatsuperparamagneticironoxide/silica/carbonnanoparticles(earthicles)pass throughtheBBBfromthebloodtothebrainandreachthebraintumor(glioblastoma) andbraincells(astrocyte)[44].
Figure1.5: PassageofsuperparamagneticironoxidenanoparticlesthroughtheBBBandreachingthe brainfromtheblood.
Nanoparticlesarewidelyusedasdrugdeliveryagents.Nanoparticles,whichcanbe usedasbothalubricantandadrugdeliverysystem,areusedinsteadofsurgicalproceduresinjointdiseasessuchasosteoarthritis[45].Nanotechnologicalmethodsare usedinvarioussurgicalprocedures.Therearesensorsusedtoaccuratelydetermine bloodpressureintheballooninflationmethod,whichisatechniqueusedtounclog thearteries[46].
Biocidalpropertiesofvariousnanoparticlesarebeingstudiedtoremovebacteria thatthreatenpublichealth.NiOnanoparticles,asemiconductormaterialwithmagnetic,catalyticandphotocatalyticproperties,areknowntohavesignificantantibacterialpropertiesevenatlowconcentrations.Inaddition,NiO/chitosannanocomposites havereportedsuperiorantibacterialeffectsagainstGram-negative(Escherichiacoli) andGram-positive(Saccharomycescerevisiae and Bacillussubtilis)bacteria[47].ZnO
NPshaveantifungalpropertiesandareeffectiveagainstpathogenssuchas Erythriciumsalmonicolor [17].
Thecosmeticsindustryusesnanotechnologyeffectivelytorealizepeople’sdesire tostaybeautifulandyoung.Forthis,heresolutelypusheshislimits.Nano-basedmaterialsareappliedinvarioushaircareproductssuchasantiagingandskinrejuvenatingcosmetics,sunscreencreamsandsha mpoos.Forexample,nanoemulsionsare usedinshampoo,conditioner,nailpolish,lotionorantiwrinklecreamsbecausethey increaseskinpenetration.Nanoemulsionscandeliveringredientsthatmaybebeneficialfortheskinintotheskindependingontheconcentration[48].
1.3.2Watertreatment
Waterisnonrenewableandavitalresourceforhumansurvival.Duetotheincreasein populationandindustrialization,ithasledtothepollutionofwaters[49].Dyesareimportantpollutantsarisingfromthewastesofsectorssuchasfood,automotive,textileor cosmeticsthatharmhumanhealth[29,50].Asanexampleofthesedyes,methylorange isacarcinogenicazodyeusedinthefoodandtextileindustry[29].Methyleneblue,a cationicdye,isadarkbluedyewithhighwatersolubility.Itcausesvomiting,diarrhea, tachycardia,shortnessofbreathandskinirritationaswellasharmingtheenvironment [9].Evenverysmallconcentrationsofdyescontaminatingwatersystemsarevisible. Duetothecolorationofthewater,photosynthesisisreducedandthereforethewater floraisadverselyaffected.Plants,animals,theenvironmentandhumanhealthare harmedbythepollutionofwater[9,40].InFigure1.6,nanomaterialsusedinwater treatmentandpossiblecontaminantsareshownschematically.
Pollutions:
Organic dyes
– Metal and metal oxide nanoparticles
– Carbon based nanomaterials
– Polymer based nanocomposites
– Clay based nanocomposites
Technics; Adsorption Photocatalytic degradation
Food dyes
Weight metals
Antibiotics
Toxic chemicals
Radioactive waste
Figure1.6: Nanoparticlesusedforcleaningfromwastewaterandtypesofpollutioninwater.
Nanoparticlesarewidelyusedinadsorptionandphotocatalyticdegradationapplicationsforwatertreatment.CuONPswithlargesurfacearea,antibacterialandantifungalpropertiesprovidephotocatalyticdegradationoforganicdyessuchasmethylene blueunderUVlamp[9].Similarly,nanocompositeobtainedbyusingxyloglucan,a biodegradableandnontoxicpolysaccharideandmagneticFe3O4,hasbeenreportedto be99%successfulinremovingcationicdyefromaqueoussolutionwhenusedasa
photocatalyst.Inordertoimprovethephotocatalystactivityandadsorbentproperties ofthesynthesizednanoparticle,thereisaneedtocontinueresearchwithdifferent dyesorpollutants[40].
Mesoporoussilicananoparticles(MSNs)haveuniquestructuralpropertiesdueto thecontrollabilityoftheirporediameters.Theycanalsobefunctionalizedwithdifferentfunctionalgroups.Theyareusedassorbentintheremovalofweightmetalssuch aschromiumduetotheactivesitestheyhave[31].MaterialsformedbyCNTscontainingmetaloxideareamongthealternativesthatcanbeusedtominimizeairpollution andsolvethewatertreatmentproblem[49].
1.3.3Agriculture
Nanotechnologyhasthepowertochangethecourseofthecurrentfoodandagricultureindustry[39].Theeffectiveuseofnanotechnologyinagricultureprovidesbenefitsinareassuchastransportinsoil,displacementinplants,andefficienttargetingof pestswiththeuseofpesticidesatnanoscale,thankstonanomaterials.Newstudies suchascropnutritionandsmartplantsensorsrevealthatnanotechnologycouldbe importantforsustainableagriculture[5 1].Nanobiosensorswillhelpinthefight againstundesirablepathogensintheagricu lturalsector.Itispredictedthatnanostructuredmaterialsthatreducetheamountofdoserequiredforcropplantsandincreasetheactivityofpesticideswillexistinthefuture[39].Zincisbeneficialforplant
Figure1.7: Thepaththatnanofertilizersfollowinthesoilaftertheyaffecttheplant.
growthandametabolicregulatoryelement.Insomeplants,itsdeficiencymayhave consequencessuchasyellowingandshrinkingoftheleaves.ProcessingZnOnanoparticlesintoplantsbyusingtheminbiofertilizersisoneoftheimportantstudies[52]. Scientificreportsreportthatgold,CeO2,ZnO,CuO,FeO,Fe/SiO2,Mg,TiO2 andcalcium nanoparticlesareusedasnanofertilizers.
Theuseofnanobiotechnologyisveryimportantintermsofminimizingagriculturalwasteandsustainabledevelopment[53].Therearestillissuesthatarenotclear. Forexample,copper,silverandzinc-base dnanoparticleshavethepotentialtobe usedaspesticidesandfungicides.However,itisknownhowthispotentialwillaffect thesoilqualityinthelongterm.Thereisaneedfortheformationofnewagricultural modelsandthedevelopmentoftheobtaineddatabyprocessing[51].InFigure1.7,the effectoftheuseofnanofertilizersonplantsandsoilisgivenvisually.
1.3.4Industrialarea
Anotheruseofnanoparticlesisasalubricant.Lubricantshavefunctionssuchasremovingexcessiveheat,preventingfriction,wearandcorrosion,andresistancetodegradation.Ithasbeenreportedtoprovidebenefitssuchasreducingfrictionand increasingbrightness.Propertiesofnanoparticlessuchasconcentration,size,shape andstructureaffecttribologicalpropertieswhenaddedtothelubricant.ThemovementofCNTsinthelubricantmediumisshowninFigure1.8[54].
Figure1.8: Carbonnanoparticlesaslubricant.
Corrosionistheirreversibleself-damageanddestructionofmetal[55].Nanomaterials areuniquematerialsthatcanshowanticorrosivepropertiesduetotheirsurfaceand volumeratios[1].Thesurface/volumeratioofnanoparticlescausesthemtobeeffective
incorrosion.Despitetheirsmallsize,theypreservetheamountofactivesitebyincreasingthesurfaceofagivenmass.Duringinhibition,nanomaterialsaresubjectedtophysicalorchemicalsorptiononthemetalsurface.Thisresultrevealsthestructurethat preventscorrosion[55].Thesolubilityandsorptionabilitiesofnanomaterialsinaqueouselectrolytesareimportantintermsofcorrosion[1].Nanoparticlescanincreasethe corrosionresistanceoforganiccoatingsbyextendingelectrolytepathsduetotheir largesurfacearea.However,ifthenanoparticleagglomerates,itsefficiencyagainstcorrosionmaydecrease[27].Silver,silica,ironandcopper,ZnOandTiO2 nanoparticles haveanticorrosionability[55].
Today,manynanoparticlesareusedtotakeadvantageofthegassensorproperties [56].Volatileorganiccompounds(VOC),knowntobecanserogens,adverselyaffect humanandenvironmentalhealth.Forexample,formaldehyde,polycyclichydrocarbonsandsomeorganicwastegasesarehighlycarcinogenic.Theycanevenleadto deathfromexcessiveinhalation.Variousmetaloxidesemiconductornanoparticlesand carbon-basedmaterialssuchasZnO,SnO2 andWO3 showgassensorproperties[57]. NanocompositesynthesizedusingZnOandpolyanilinehassuperiorsensorproperties forNO2 gas[56].
Nanotechnologyhasmadeprogressinelectronicapplicationsaswellasinallfields. Thankstotheirlargesurfaceareas,theyarecandidatematerialsforflexibleelectronics. Therearemanyusessuchasenergydevices,opticalandelectronicdevices,wearable heatersforthermaltherapy,sensors,softelectronicsandfieldeffecttransistors[58,59]. Copperisanimportantandinexpensivealternativetonoblemetalsforuseinsoftelectroniccircuits.Ithashighelectricalconductivityandiseasilyavailable[59].
1.4Thefutureofnanomaterials
Technologicaldevelopmentsintheworldnowpointtotheexistenceofnanotechnologyandnanoscience.Scientificdatashowthatwhenmicrotechnologyistypedinto theGooglesearchengine,130,000resultsareobtained,whilenanotechnologyiswrittenmorethan20millionsearchresults[60].
Itisexpectedthattheareasaffectedbydevelopingnanoscienceandnanotechnologywillincrease.Wear-resistanttires,nano-basedparticleswiththebestperformanceofpaintpigments,laserswithenhancedperformancewithnewfeatures, nanoparticlestobeusedinmedicinewiththeabilitytodeliverthedrugtothetarget, designsofinnovativebiosensors,productionofnano-basedtrapstoeliminateenvironmentalpollutionaresomeofthem(Figure1.9)[61].
Ascanbeseen,theuseofnanotechnologyandnanomaterialsisasubjectthat developsandcomestotheforeincontemporarylife.Thenumberofnanoparticles andnanocompositessynthesizedbydifferentmethodsisincreasingdaybydayand theirpropertiesarebeingexamined.
Inlinewiththeseresults,
– itisnecessarytounderstandthephysicalandchemicalstructuresofmany nanomaterials;
– itisimportanttochoosetherightapplicationareabyinvestigatingitscytotoxic andantibacterialpropertiesaswellasitselectronicandmagneticproperties;
– inaddition,theefficientandcost-effectivedevelopmentofsynthesismethodsis necessaryforsustainability.
Thefactthatnanotechnologycanbeusedinalmostallfieldsisanindicationthatthe scientificstudiesandindustrialapplicationsonthissubjectwillcontinuerapidly.
Finally,inthenext10years,nanoscien ceandnanotechnologicalapplications havebeenacceptedasthemostpromisingscientificandtechnologicaldevelopment amongthetechnologicalfieldsthatexisttoday.Everycountryintheworldhasmade alargeinvestmentinnanotechnologicalapplications.Nationalgovernmentshavealso ledtotheemergenceoftheNationalNanotechnologyInitiativeduetothefinancing activitiesinEurope.Themajorfutureconsequencesofnanotechnologyonissuessuch asprivacyortheemergenceofacommonlanguagearealarming.Everysocietymust bepreparedforthechangesthatcomewithnanoscienceanditsnanotechnological applications.
Figure1.9: Differentnanomaterialsandapplications.
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about Leila I thought I’d never mention your children to you again.”
“That’s very foolish,” Mills murmured with a slight frown. He thought she was about to attack Leila and he had no intention of listening to criticism of Leila. Alice had made a mess of Leila’s education and he was not interested in anything she might have to say about her. And Alice was richly endowed with that heaven-given wisdom as to the rearing of children which is peculiar to the childless. Mills wished greatly that Alice would go.
“The matter’s delicate—very delicate, Frank. I hesitate——”
“Please, Alice!” he interrupted impatiently. “Either you’ve got something to say or you haven’t!”
At the moment she was not his sister, but a woman who had precipitated herself into a law suit by giving an option on a valuable piece of property and then selling it to a third party, which was stupid and he hated stupidity. He thought she was probably going to say that Leila drank too much, but knowing that Leila had been a pattern of sobriety for months he was prepared to rebuke her sharply for bringing him stale gossip.
“It’s about Shep—Shep and Connie!” said Mrs. Thornberry. “You know how fond I’ve always been of Shep.”
“Yes—yes,” Mills replied, mystified by this opening. “Shep’s doing well and I can’t see but he and Connie are getting on finely. He’s quite surprised me by the way he’s taken hold in the trust company.”
“Oh, Shep’s a dear. But—there’s talk——”
“Oh, yes; there’s talk!” Mills caught her up. “There’s always talk about everyone. I even suppose you and I don’t escape!”
“Well, of course there have been rumors, you know, Frank, that you are considering marrying again.”
“Oh, they’re trying to marry me, are they?” he demanded, in a tone that did not wholly discourage her further confidences.
“I can’t imagine your being so silly. But the impression is abroad that you’re rather interested in that Harden girl. Ridiculous, of course, at
your age! You’d certainly throw your dignity to the winds if you married a girl of Leila’s age, whose people are said to be quite common. They say Dr. Harden used to travel over the country selling patent medicine from a wagon at country fairs and places like that.”
“I question the story. The Doctor’s a very agreeable person, and his wife’s a fine woman. We have had very pleasant neighborly relations. And Millicent is an extraordinary girl—mentally the superior of any girl in town. I’ve been glad of Leila’s intimacy with her; it’s been for Leila’s good.”
“Oh, I dare say they’re all well enough. Of course the marriage would be a big card for the Hardens. You’re a shrewd man, Frank, but it’s just a little too obvious—what you’ve been doing to push those people into our own circle. But the girl’s handsome—there’s no doubt of that.”
“Well, those points are settled, then,” her brother remarked, taking up the ivory paper cutter and slapping his palm with it. Alice was never niggardly with her revelations and he consoled himself with the reflection that she had shown her full hand.
“This other matter,” Mrs. Thornberry continued immediately, “is rather more serious. I came back from California the week after you sailed and I found a good deal of talk going on about Connie.”
“Connie?” Mills repeated and his fingers tightened upon the ivory blade.
“Connie’s not behaving herself as a married woman should. She’s been indulging in a scandalous flirtation—if that’s not too gentle a name for it—with George Whitford.”
“Pshaw, Alice! Whitford’s always run with Shep’s crowd. He’s a sort of fireside pet with all the young married women. George is a fine, manly fellow. I don’t question that he’s been at Shep’s a good deal. Shep’s always liked him particularly. And Connie’s an attractive young woman. Why, George probably makes love to all the women, old and young, he’s thrown with for an hour! You’re borrowing trouble quite unnecessarily, Alice. It’s too bad you have to hear the gossip that’s always going around here; you take it much too seriously.”
“It’s not I who take it seriously; it’s common talk! Shep, poor boy, is so innocent and unsuspecting! George hasn’t a thing to do but fool at his writing. He and Connie have been seen a trifle too often on long excursions to other towns when Shep, no doubt, thought she was golfing. What I’m telling you is gossip, of course; I couldn’t prove anything. But it’s possible sometimes that just a word will save trouble. You must acquit me of any wish to be meddlesome. I like Connie; I’ve always tried to like her for Shep’s sake.”
She was probably not magnifying the extent to which talk about his son’s wife had gone. His old antagonism to Constance, the remembrance of his painful scenes with Shep in his efforts to prevent his marriage, were once more resurgent. Mrs. Thornberry related the episode of the dramatic club play which had, from her story, crystalized and stimulated the tales that had previously been afloat as to Connie’s interest in Whitford. Mills promptly seized upon this to dismiss the whole thing. Things had certainly come to a fine pass when participation in amateur theatricals could give rise to scandal; it merely showed the paucity of substantial material. He was at pains to conceal his chagrin. His pride took refuge behind its fortifications; he would not have his sister, of all persons, suspect that he could be affected by even the mildest insinuation against anyone invested with the sanctity of the Mills name. He told her of having met some old friends of hers in London as he accompanied her to the elevator. But when he regained his room he stood for some time by the window gazing across the town to the blue hills. The patriarchial sense was strong in him; he was the head and master of his house and he would tolerate no scandalous conduct on the part of his daughter-in-law But he must move cautiously The Whitfords were an old family and he had known George’s father very well. With disagreeable insistence the remembrance of his adventure in Laconia came back to him.
III
Several weeks passed in which Mills exercised a discreet vigilance in observing Shep and Connie. Whitford was in town; Mills met him
once and again at Shep’s house, but there were others of the younger element present and there was nothing in Whitford’s conduct to support Mrs. Thornberry’s story. He asked Carroll incidentally about the dramatic club play—as if merely curious as to whether it had been a successful evening, and Carroll’s description of Whitford’s little drama and of Connie’s part in it was void of any hint that it concealed a serious attachment between the chief actors.
The usual social routine of the summer stay-at-homes was progressing in the familiar lazy fashion—country club dances, motor trips, picnics and the like. On his return Mills had called at once upon the Hardens. Millicent’s charms had in nowise diminished in his absence. With everything else satisfactorily determined, there would be no reason why he should not marry Millicent. His sister’s disapproval did not weigh with him at all. But first he must see Leila married, and he still hoped to have Carroll for a son-in-law. Leila had entered into the summer gaieties with her usual zest, accepting the escort of one and another available young man with a new amiability. One evening at the Faraway Country Club Mills saw her dancing with Thomas; but it was for one dance only, and Thomas seemed to be distributing his attentions impartially. A few nights later when they had dined alone at Deer Trail—Leila had suggested that they go there merely to please him—as they sat on the veranda all his hopes that her infatuation for Thomas had passed were rudely shattered.
“Well, Dada,” she began, when he was half through his after-dinner cigar, “it’s nice to be back. It’s a lot more fun being at home in summer. There is something about the old home town and our own country. I guess I’m a pretty good little American.”
“I guess you are,” he assented with a chuckle that expressed his entire satisfaction with her. The veranda was swept fitfully by a breeze warm sweet with the breath of ripening corn. It was something to be owner of some part of the earth; it was good to be alive, master of himself, able to direct and guide the lives of others less fortunately endowed than he with wisdom and power. Leila touched his hand and he clasped and held it on the broad arm of his favorite rocker.
“Dada, what a wonderful time we had on our trip! I was a good little girl—wasn’t I? You know I was trying so hard to be good!”
“You were an angel,” he exclaimed heartily “Our trip will always be one of the happiest memories of my life.”
At once apprehensive, he hoped these approaches concealed nothing more serious than a request for an increase in her allowance or perhaps a new car.
“I want to speak about Freddy Thomas,” she said, freeing her hand and moving her chair the better to command his attention.
“Thomas!” he said as though repeating an unfamiliar name. “I thought you were all done with him.”
“Dada,” she said very gently, “I love Freddy. All the time I was away I was testing myself—honestly and truly trying to forget him. I didn’t hear from him and I didn’t send him even a postcard. But now that I’m back it’s all just the same. We do love each other; he’s the only man in the world that can ever make me happy Please—don’t say no!”
He got up slowly, and walked the length of the veranda and came back to find her leaning against one of the pillars.
“Now, Leila,” he began sharply, “we’ve been all over this, and I thought you realized that a marriage with that man would be a mistake—a grave blunder. He’s playing upon your sympathy—telling you, no doubt, what a great mistake he made in his first venture.”
“I’ve seen him only once since I got back and that was the other night at the club,” she replied patiently. “Freddy’s no cry-baby; you know you couldn’t find a single thing against him except the divorce, and that wasn’t his fault. He’s perfectly willing to answer any questions you want to ask him. Isn’t that fair enough?”
“You expect me to treat with him—listen to his nasty scandal! I’ve told you it won’t do! There’s never been a divorce in our family—nor in your mother’s family! I feel strongly about it. The thing has got too common; it’s taken away all the sanctity of marriage! And that I should welcome as a husband for a young girl like you a man who
has had another wife—a woman who’s still living—keeping his name, I understand—I tell you, Leila, it won’t do! It’s my duty to protect you from such a thing. I have wanted you to take a high position in this community—such a position as your mother held; and can you imagine yourself doing it as the second wife of a man who’s not of our circle, not our kind at all?”
He flung round, took a few quick steps and then returned to the attack.
“I want this matter to be disposed of now. What would our friends think of me if I let you do such a thing? They’d think I’d lost my mind! I tell you it’s not in keeping with our position—with your position as my daughter—to let you make a marriage that would change the whole tone of the family. If you’ll think a little more about this I believe you’ll see just what the step means. I want the best for you. I don’t believe your happiness depends on your marrying this man. I may as well tell you bluntly now that I can never reconcile myself to the idea of your marrying him. I’ve thought it all over in all its aspects. You’ve never had a care nor a worry in your life. When you marry I want you to start even—with a man who’s your equal in the world’s eyes.”
He had delivered this a little oratorically, with a gesture or two, and one might have thought that he was pleased with his phrases. Leila in her simple summer gown, with one hand at her side, the other thrust into the silk sash at her waist, seemed singularly young as she stood with her back to the pillar. The light from the windows, mingled with the starlight and moonlight playing upon her face, made it possible to watch the effect of his words. The effect, if any, was too obscure for his vision. Her eyes apparently were not seeing him at all; he might as well have addressed himself to one of the veranda chairs for any satisfaction he derived from his speech.
It was on his tongue to pile up additional arguments against the marriage; but this unresisting Leila with her back to the pillar exasperated him. And all those months that they had traveled about together, with never a mention of Thomas; when she had even indulged in mild flirtations with men who became their fellow
travelers for a day, she had carried in her heart this determination to marry Thomas. And he, Franklin Mills, had stupidly believed that she was forgetting the man....
He again walked the length of the veranda, and as he retraced his steps she met him by the door.
“Well, Dada, shall we drive in?” she asked, quite as though nothing had happened.
“I suppose we may as well start,” he said and looked at his watch to hide his embarrassment rather than to learn the time.
On the way into town she recurred to incidents of their travels and manifested great interest in changes he proposed making in his conservatories to embrace some ideas he had gathered in England; but she did not refer in any way to Thomas. When they reached home she kissed him good-night and went at once to her room.
The house was stifling from the torrid day and Mills wished himself back at the farm. His chief discomfort was not physical, however; Leila had eluded him, taken refuge in the inconsequential and irrelevant in her own peculiar, capricious fashion. It was not in his nature to discuss his affairs or ask counsel, but he wished there were someone he could talk to.... Millicent might help him in his perplexity. He went out on the lawn and looked across the hedge at the Hardens’, hearing voices and laughter. The mirth was like a mockery.
IV
On the following day Bruce and Millicent drove to the Faraway club for golf. He was unable to detect any signs indicating that Mills’s return had affected Millicent. She spoke of him as she might have spoken of any other neighbor. Bruce wasn’t troubled about Mills when he was with Millicent; it was when he was away from her that he was preyed upon by apprehensions. He could never marry her: but Mills should never marry her. This repeated itself in his mind like
a child’s rigamarole. Their game kept them late and it was after six when they left the club in Bruce’s roadster.
Millicent was beside him; their afternoon together had been unusually enjoyable. He had every reason to believe that she preferred his society to that of any other man she knew. He had taken a route into town that was longer than the one usually followed, and in passing through a small village an exclamation from Millicent caused him to stop the car.
“Wasn’t that Leila and Fred at the gas station?” she asked. “Let’s go back and see.”
Leila saluted them with a wave of the hand. Thomas was speaking to the keeper of the station.
“Hello, children!” Leila greeted them. “Pause and be sociable. What have you been up to?”
“Shooting a little golf,” Millicent answered. “Why didn’t you drop the word that you were going to the club for dinner? You might have had a little company!”
Bruce strolled over to Thomas, who was still conferring with the station keeper. He heard the man answer some question as to the best route to a neighboring town. Thomas seemed a trifle nervous and glanced impatiently toward Leila and Millicent.
“Hello, Bruce,” he said cheerfully, “how’s everything?”
“Skimming!” said Bruce, and they walked back to the car, where Thomas greeted Millicent exuberantly. Leila leaned out and whispered to Bruce:
“We’ll be married in an hour. Don’t tell Millie till you get home!”
“Are you kidding?” Bruce demanded.
“Certainly not!”
“But why do it this way?”
“Oh—it’s simpler and a lot more romantic—that’s all! Tell Millie that everything is all right! Don’t look so scared! All right, Freddy, let’s go!”
Their car was quickly under way and Millicent and Bruce resumed their homeward drive.
“Leila didn’t tell me she was going to the club with Freddy,” remarked Millicent pensively.
“One of those spontaneous things,” Bruce replied carelessly. When they reached the Hardens’ he walked with her to the door.
“That was odd—meeting Leila and Fred,” said Millicent. “Do you think they were really going to the club for supper?”
“They were not going there,” Bruce replied. “They’re on their way to be married.”
“Oh, I’m sorry!” she said and her eyes filled with tears. The privilege of seeing tears in Millicent’s eyes was to Bruce an experience much more important than Leila’s marriage.
“It will be a blow to Mr. Mills,” said Bruce thoughtfully. “Let’s hope he accepts it gracefully.”
Both turned by a common impulse and their eyes rested upon the Mills house beyond the hedge....
The town buzzed for a few days after Leila’s elopement, but in her immediate circle it created no surprise. It was like Leila; she could always be depended upon to do things differently. Mills, receiving the news from Leila by telephone, had himself conveyed the announcement to the newspapers, giving the impression that there had been no objection to the marriage and that the elopement was due to his daughter’s wish to avoid a formal wedding. This had the effect of killing the marriage as material for sensational news. It was not Mills’s way to permit himself to be flashed before his fellow citizens as an outraged and storming father. Old friends who tried to condole with him found their sympathy unwelcome. He personally saw to the packing of the effects Leila telegraphed for to be sent to Pittsburg, where she and her husband, bound for a motor trip through the east, were to pause for a visit with Thomas’s parents.
