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Transcript of Predicting the Fraction of Mixing Between Latex Particles · PDF filePy-PBMA-Latex-2 1.8 120...
PredictingtheFractionofMixingBetweenLatexParticles
RemiCasierProfs.JeanDuhamelandMarioGauthier
DepartmentofChemistry,UniversityofWaterloo,Waterloo,Ontario
1
• Latex:
o Stabledispersionofpolymerparticlesinanaqueoussolution
• Applications:
o Products:glovesandtires
o Additives:adhesivesandpapercoatings
o Films:paintsandcoatings
2
Introduction
Tiretread,<http://mrg.bz/q7fSMj>.
Paintedboards,<http://mrg.bz/q7fSMj>.
Film FormationfromaLatexDispersion
3
• Theminimumfilmformationtemperature(MFT)mustbereachedbeforepolymerchainscaninterdiffuse (MFT≈Tg)1
• Interparticlepolymerdiffusion(IPD)duringthecoalescenceoflatexparticlesproducesahomogeneousfilm
• MechanicalpropertiesarehighlydependentontheextentofIPD2
1. Zhao,C.,Wang,Y.,Hruska,Z.,Winnik,M.MolecularAspectsofLatexFilmFormation:AnEnergy-TransferStudy;Macromolecules 1990,23,4082-4087.
2. Gauthier,C.;Guyot,A.;Perez,J.;Sindt,O.FilmFormationandMechanicalBehaviorofPolymerLaticies.FilmFormationinWaterborneCoatings, Chapter10, 1996, 163-178.Washington,DC:AmericanChemicalSociety.
• GoodMechanicalProperties
• PoorMechanicalProperties
T>MFTT>MFT
Stage1:WaterEvaporation
Stage2:ParticleDeformation
Stage3:Coalescence
T>MFT
SmallAngleNeutronScattering(SANS)
• Deuteratedpolymersareexpensive• Requiresaneutronsource• Smallparticlesonly
FluorescenceResonanceEnergyTransfer(FRET)
• Bothlatexesmustbelabeledwithdyes• Requirestime-resolvedfluorescence
4
QuantificationofIPD
D
D DD
DDA
AAA D
AA
AIPD
IPD
ProbingIPD:
PyreneExcimerFluorescence(PEF)
5
• Asimplermethodtoprobethedegreeofinterparticlepolymerdiffusion(IPD)inlatexfilms1
• Usingafluorescently-labeledlatexwithanemissionthatchangesdependingonthedegreeofIPD
• Asinglefluorophorepyrene(Py)canbeused• Onlyonefluorescently-labeledlatexisrequired
• Steady-statefluorescencecanbeused
1. Casier,R.;Gauthier,M.;Duhamel,J.UsingPyreneExcimerFluorescencetoProbePolymerDiffusioninLatexFilms.Macromolecules 2017,50,1635–1644.
PyreneFluorescence
0.0
0.2
0.4
0.6
0.8
1.0
350 400 450 500 550 600
Fluo
.Int.(a.u.)
Wavelength(nm)
IM
IEExcimer
Monomer
IE/IM – ameasureoftheamountofexcimerformed
6
* *( ) ( )h hPy Py Py Py PyPy PyPyn n+ ¾¾® + ¾¾® ¬¾¾MonomerEmission ExcimerEmission
7
InterparticlePolymerDiffusionusingPEF
t=0 t˃0
•HighCpy •LowCPy
•Lotsofexcimerformation •Littleexcimerformation
•HighIE/IM ratio •LowIE/IM ratio
PyPyPy
Py Py
PyPy
Py
PyPy
Py
PyPy
Py
Py
Py
Py
Py Py
Py
Py
8
PyreneLabeledLatex
PyEG3MA
• Hydrophobicityofthemonomerwascontrolledbyvaryingthelengthoftheoligo(ethyleneglycol)unit
OO
O
3
• Semi-batchemulsionprocess
• Copolymerizedwithn-butylmethacrylate(BMA)toyieldapoly(n-butylmethacrylate)randomlylabeledwithpyrene(Py-PBMA)
Py-PBMALatex
x 1-x
9
Sample PyLM PyLMIncorporated
(mol%)
ParticleSize(nm)
PSD Mw(kg/mol)
Ð
Py-PBMA-Latex-1 PyEG3MA 1.9 118 1.04 820 1.9
Py-PBMA-Latex-2 PyEG3MA 1.8 120 1.04 360 1.8
GPC:Py-PBMA-Latex-1
• Afilmwaspreparedfromamixtureof5wt%Py-PBMA-latexin95wt%PBMA-latex
10
FilmPreparationandAnnealing
Film LatexLatexPyrene
Content (mol%)
ParticleSize
(nm)PSD
Mw
(kg/mol)Đ
Weight
Fraction
1Py-PBMA-Latex-1 1.9 118 1.04 820 1.9 0.05
PBMA-Latex-1 0 95 1.04 1,000 2.0 0.95
2Py-PBMA-Latex-2 1.8 120 1.04 360 1.8 0.05
PBMA-Latex-2 0 119 1.04 320 1.7 0.95
···1)Anneal2)Freeze
1)Anneal2)Freeze
FluorescenceMeasurements FluorescenceMeasurements FluorescenceMeasurements
1)Anneal2)Freeze
0.0
0.2
0.4
0.6
0.8
1.0
1.2
350 400 450 500 550 600
Flu
ores
cenc
e In
tens
ity (a
.u.)
Wavelength (nm)
0
0.01
0.02
0.03
0.04
0.05
500 510 520 530
11
Steady-StateFluorescence:Film1
Annealing Time (min.)
IE/IM
0 0.1325 0.10110 0.08560 0.07t∞ 0.04
IncreasingAnnealingTime
Tan=102°C
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
0 200 400 600 800
f m(a
.u.)
Annealing Time (min.)
FractionofMixing
12
𝑓" 𝑡 =
𝐼&𝐼' ())
− 𝐼&𝐼' (),-)
𝐼&𝐼' ().)
− 𝐼&𝐼' (),-)
Film1:Mw =820kg/mol Film2:Mw =360kg/mol
119 °C
112 °C111 °C
119 °C 112 °C111 °C 102 °C
88 °C
84 °C
75 °C
98 °C94 °C
102 °C
88 °C84 °C
75 °C
98 °C94 °C
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
0 200 400 600 800
f m(a
.u.)
Annealing Time (min.)
FractionofMixing:LinearTrend
13
Film1:Mw =820kg/mol Film2:Mw =360kg/mol
0.00.10.20.30.40.50.60.70.80.91.0
1 10 100 1000 10000f m
(a.u
.)
Annealing Time (min.)
0.00.10.20.30.40.50.60.70.80.91.0
1 10 100 1000 10000
f m(a
.u.)
Annealing Time (min.)
( ) ( ) ( ), ln( )m an anf T t A T t B T= × +
119 °C
75 °C
119 °C
75 °C
-0.1
0.0
0.1
0.2
0.3
0.4
0.5
0.6
340 360 380 400
A(T
) (K
-1)
Annealing Temperature (K)
fm:SlopesandIntercepts
14
( ) ( ) ( ), ln( )m an anf T t A T t B T= +
( ) ( ) ( ) ( )4 3, 6.71 10 0.184 ln 7.74 10 2.65m an anf T t T t T- -= ´ - + ´ -
( ) ( ) ( ) ( )4 2, 0.172 10 0.144 ln 1.16 10 4.05m an anf T t T t T- -= - ´ + + ´ -
-0.1
0.0
0.1
0.2
0.3
0.4
0.5
0.6
340 360 380 400
B(T
)
Annealing Temperature (K)
Film1
Film 2
Film1
Film 2
Film1:
Film 2:
Predictingfm:TimeandTemperature
15
0.00.10.20.30.40.50.60.70.80.91.0
1 10 100 1000 10000
f m(a
.u.)
Annealing Time (min.)
0.00.10.20.30.40.50.60.70.80.91.0
1 10 100 1000 10000
f m(a
.u.)
Annealing Time (min.)
Film1:Mw =820kg/mol Film2:Mw =360kg/mol
( ) ( ) ( )
( )
4
3
, 6.71 10 0.184 ln
7.74 10 2.65
m an anf T t T t
T
-
-
= ´ -
+ ´ -
( ) ( ) ( )
( )
4
2
, 0.172 10 0.144 ln
1.16 10 4.05
m an anf T t T t
T
-
-
= - ´ +
+ ´ -
119 °C
75 °C
119 °C
75 °C
Applications
16
( ) ( ) ( ), ln( )m an anf T t A T t B T= +( )
( )exp
desiredm
an
f B Tt
A Tæ ö-
= ç ÷ç ÷è ø
• Theproperties ofafilmaredirectlyrelatedtotheextentofcoalescence1
1. Gauthier,C.;Guyot,A.;Perez,J.;Sindt,O.FilmFormationandMechanicalBehaviorofPolymerLaticies.FilmFormationinWaterborneCoatings, Chapter10, 1996, 163-178.Washington,DC:AmericanChemicalSociety.
• Predictthecoalescencetimerequiredtoreachaspecificfm.
Example:• Abrasionresistance
• Mechanicallyrobust• Lowfm ≈0.4
• Film1(102°C)tan =34min.• Corrosionresistance
• Void-free• Highfm ≈ 0.95
• Film1(102°C)tan =3months
T>MFT
H2O
H2O
H2OH2O
OnsetTimeforDiffusion
17
0.0001
0.001
0.01
0.1
1
10
2.5 2.6 2.7 2.8 2.9
t an(f
m=
0) (m
in.)
1000·T-1 (K-1)
Film1(Mw =820kg/mol):Ea =109± 13kJ/mol
Film2(Mw =360kg/mol):Ea =169± 21kJ/mol
Film1
Film 2
WhydothechainsinFilm1flowsooner?
0.0
0.2
0.4
0.6
0.8
1.0
0.01 10 10000
f m(a
.u.)
tan (min.)
ReleaseofStrainT>MFT
FutureWork
Probethediffusionbetweenasymmetriclatexnanoparticles:
•Particlesize•Molecularweight•PolymerType•PlasticizerContent
Increasepyrenemonomerincorporationtoenhanceexcimerformation18
Py
Py
Py
PyPy
Py
Py
Py
Zehou You:PosterSession
Supervisors:Prof.JeanDuhamelProf.MarioGauthier
AllmembersoftheDuhamelandGauthiergroups.
Thankyouforyourattention!
19
Acknowledgements
WhyUsePyreneExcimerFormation?
21
Requirement FRET PyreneExcimerFormation
InstrumentationTime-resolvedfluorometer
(complex andexpensive)
Steady-statefluorometer
(simpleandinexpensive)
DataAcquisition ~10minutesperdecay ~30secondsperspectrum
FluorescenceAnalysisDecaymustbemodeled,fitted,and
thenintegratedIE/IM ratio
Fluorescently-LabeledLatex2
(donorlabeled,acceptorlabeled)
1
(pyrenelabeled)
Film Composition 100wt%labeled-latex≤5wt%labeled-latex
≥95wt%native-latex
LatexNanoparticles Symmetrical SymmetricalorAsymmetrical