Polymeric and Inorganic Nanoparticles
for Environmental Applications
Ju-Young Kim
Ph.D. / Associate Prof.
Department of Advanced Materials Engineering
Kangwon National University, Samcheok, Kangwon 245-711, S.Korea
Nano
Technology
+
Environmental
Technology
““Nanoparticles”
Nanoparticles”
Environmental
Pollution
Monitoring
Removal of
Environmental
Pollutants
Environmental
Friendly
Energy
Systems
: Nanosensor
• Magnetic Nanoparticles
• Ag, Au, Pd, SnO2
• ZnO2, WO3, TiO2
• CdSe
• Carbon Nano Tube
(CNT)
• TiO2 Nanoparticles
• Polymeric Nanoparticles
: Fuel Cell, Li-battery
Solar Cell
• CNT
• Clay Nanoparticles
• Silica Nanoparticles
Nanosensors for Environmental Monitoring
Inorganic Nanoparticles :
‰ Increasing the sensitivity of gas sensors by increasing surface area of
the sensor increases.
‰ Miniaturizing the sensing devices
[Examples]
9 SnO2 (Tin oxide) nanoparticles detecting 3 ppm for CO2, 15ppb for NO2 and O3, and
50 ppb for NO.
9 WO3 (Tungsten Oxide) based gas sensors to detect H2S, N2O and CO. 5 ppm of H2S
9 CNTs-FETs for CO, NH3, NO2, O2, and H2O sensor
9 ZnFe2O4 (Zinc Ferrite) nanoparticles for VOC sensor
9 ZnO nanoparticles for VOC
9 Pd-Polyaniline nanocomposite for methanol sensor
9 Au-decorated SnO2 nanobelt for CO sensor
Just
Just detecting,
detecting,
Not
Not eliminating
eliminating
Applications of TiO2 Photocatalyst
99Only
Onlyfor
forair-purification
air-purification
99It
Itnecessitates
necessitatesaabinder
binderand
anddispersant.
dispersant.
Magnetic Nanoparticles embedded at Polymer Microparticles
for Removal of Transuranic Pollutant
Micron-size Polymer particles
Magnetic Nanoparticles
ƒƒHydrate
HydrateFe(III)
Fe(III)oxides
oxidesor
orHydrated
HydratedFe(III)
Fe(III)oxide
oxidenanoparticles
nanoparticles
embedded
embeddedPolymer
PolymerMicroparticles
Microparticles
99Selectively
Selectivelysorb
sorbdissolved
dissolvedheavy
heavymetal
metallike
likezinc,
zinc,copper
copperor
ormetalloids
metalloidslike
like
arsenic
arsenicoxyacids
oxyacidsor
oroxyanions.
oxyanions.
99Used
Usedonly
onlyin
inbatch
batchor
orfixed
fixedcolumn
columnprocess.
process.
99In-situ
washing
or
flow
through
process
In-situ washing or flow through processisisnot
notpossible.
possible.
Micron-size
Polymer particles
Amphiphilic Organic Nanoparticles for In-situ Removal of
Hydrophobic Pollutants From Soil and Water
Soil
Soil
Soil
Nano-size
Nano-sizeAbsorbent:
Absorbent:Amphiphilic
AmphiphilicNanoparticles
Nanoparticles
99Interfacial
Interfacialactivity
activity
99Solubilizing
Solubilizinghydrophobic
hydrophobicpollutants
pollutants
99 Dispersion
Dispersionstability
stabilityat
ataqueous
aqueousphase
phase
99 Freely
Freelyflowing
flowingthrough
throughsoil
soilpores
pores(much
(muchsmaller
smallerthan
thansoil
soilpores)
pores)
99 Easy
Easyrecovery
recovery
Amphiphilic Nanoparticles
Surfactant micelle
1 – 5 nm
9 Cheaper than ABC
9 a few nm size
9 easily breakable
9 hard to separate
9 strong adsorption
ABC nanoparticle
(Amphiphilic Block Copolymer)
20 – 100 nm
9 too expensive ( $100 – 2,000 / Kg)
9 very complicated synthetic process
9 hard to control hydrophilicity or
hydrophobicity
9 easily breakable
9 Not high molecular weight
Ex) Polystyrene-b-Polyethylene oxide
Polystyrene-b-PVP
NORCOOH(2-norbornene-5,6-dicarboxylic acid)
(MTM)500(NORCOOH)50 block copolymer
Improving efficiency of conventional environmental Process
9 Surfactant-enhanced Desorption Process
9 Micellar-enhanced Ultrafiltration
9 In-situ Surfactant-enhanced Soil Washing Process
9 High and strong sorption onto a soil
9 Easily breakdown (secondary contamination)
9 Very difficult to be separated and recovered
9 Blocked soil pores by newly formed oil emulsion
Schematic
SchematicPresentation
Presentationof
ofAqueous
AqueousPseudophase
Pseudophasecontaining
containingSurfactant
Surfactant
CMC
Surfactant monomer
Surfactant monomer
PAH
Micelle
PAH
Km
Aqueous
Pseudophase
Aqueous
Pseudophase
Soil
Soil
9 At lower or equal to CMC, surfactant can not extract a pollutant because of large
amount adsorption of surfactants onto soil.
9 At higher than CMC, large amount of surfactant are also adsorbed because surfactant
micelles are easily break down.
9 Adsorption of surfactant act as an additional soil contaminants and necessitate
additional washing process.
9 Cheaper than Amphiphilic Block Copolymer
9 Easier process that the synthesis of Amphiphilic Block
Copolymer
9 Lower degree of sorption onto a soil than Surfactant
9 Much lower CMC than surfactant
9 Bigger than Surfactant micelles
A New Type of Polymer Nanoparticle
20 – 100 nm
AmphiphilicPolymer
PolymerNanoparticles
NanoparticlesSynthesized
Synthesized
Amphiphilic
UsingAmphiphilic
AmphiphilicReactive
ReactiveOligomer
Oligomer
Using
Amphiphilic
Amphiphilic
Reactive
Reactive
Oligomer
Oligomer
Nano-dispersion
Amphiphilic
Amphiphilic
Oligomer
Oligomer
Nanoparticles
Nanoparticles
Amphiphilic
Amphiphilic
Crosslinked
Crosslinked
Polymer
Polymer
Nanoparticles
Nanoparticles
Crosslinking Polymerization
9 Cheaper than amphiphilic block copolymer
9 Simpler and easier process than the synthetic process of
amphiphilic block copolymer
9 Easy to vary length and ratio of hydrophilic/hydrophobic
segments
9 20 -100 nm size (Bigger than surfactant micelle)
9 Lower degree of sorption onto a soil
9 Very strong nano-structure owing to chemical cross-linking
9 extremely low cmc and adsorption
Amphiphilic
)
AmphiphilicReactive
ReactiveOligomer:
Oligomer:Urethane
UrethaneAcrylate
AcrylateNonionomer
Nonionomer(UAN
(UAN)
CH3
CH3
NHCOOCH2CH2COO(CH3)=CH2
H2C=(H3C)COOH2CH2CCOONH
NHCOO— CH2CH (CH3)O (CH2CH (CH2) CH2CH (CH3)O)n CH2CH (CH3)OOCNH
COONH
APU Nanoparticles
Hydrophilic segment
Mw = 3450 - 7600
NHCOO— (CH2CH2O CH2CH2O CH2CH2O)nH
Hydrophobic segment
CH3
24 - 80nm
Crosslinked Hydrophobic interior
AmphiphilicReactive
ReactiveOligomer:
Oligomer:Urethane
UrethaneAcrylate
AcrylateAnionomer
Anionomer(UAA)
(UAA)
Amphiphilic
AR
O
CH3
O CHN
O
NHCO
CH3
[
O
R1
O CHN
CH3
O
O
CH3
NHC O CH2C CH2 O CHN
- +
COO H N
O
R2 R2 R2 NHCO
CH3
R1
Mw = 2350 - 8400
H3C O
AR = H2C C C O H2C H2C
,
R2= C2H5
,
R1 =
CH2 4 O
n
Soap-free emulsification of UAA
Average particle size:
40 -85nm
]n
O
O CHN
O
NHC O
RA
Preparation
Preparationof
ofAmphiphilic
AmphiphilicPolymer
PolymerNanoparticles
Nanoparticles
Amphiphilic
Amphiphilic
Oligomer
Oligomer
UAN
UANor
orUAA
UAA
Mixing
Mixingwith
withwater
water
Amphiphilic
AmphiphilicOligomer
OligomerNanoparticles
Nanoparticles
Crosslinking
polymerization
ACPU or APU
Polymer Nanoparticles
Concentration : APU or ACPU nanoparticles in water phase
(10 mg – 100,000mg/L)
Amphiphilic
Amphiphilic
Crosslinked
Crosslinked
Polymer
Polymer
Nanoparticles
Nanoparticles
FE-SEM
FE-SEMimage
imageof
ofUAA
UAAand
andUAN
UANnanoparticles
nanoparticlesdispersed
dispersedat
ataqueous
aqueousphase
phase
UAN
UAA
W. Tungittiplakorn, et al., Environ. Sci. & Technol. 2004, 38, 1605
(Dept. of Civil & Environmental Engineering, Cornell University)
Soil
SoilWashing
WashingEfficiency
Efficiency
Amphiphilic
AmphiphilicPolymeric
PolymericNanoparticles
Nanoparticlesvs.
vs.Surfactants
Surfactants
Surfactants
•Nonionic
•NonionicSurfactant
Surfactant::Triton
TritonX-100
X-100(TX-100)
(TX-100)(CMC
(CMC==110mg/L,
110mg/L,HLB
HLB==13.5)
13.5)
TWIN
TWIN80
80(CMC
(CMC==15.7
15.7mg/L,
mg/L,HLB
HLB==15.0)
15.0)
Brij
Brij30
30(CMC
(CMC==20
20mg/L,
mg/L,HLB
HLB==9.7)
9.7)
••Anionic
AnionicSurfactant
Surfactant::SDS
SDS(CMC
(CMC==2100
2100mg/L)
mg/L)
Amphiphilic Polymeric Nanoparticles
••Amphiphilic
AmphiphilicPolyurethane
PolyurethaneNanoparticles
Nanoparticles
::Anionic
Polyurethane
(ACPU)
Anionic Polyurethane (ACPU)Nanoparticles
Nanoparticles
Nonionic
Polyurethane
(APU)
Nanoparticles
Nonionic Polyurethane (APU) Nanoparticles
Model Medium
9 Soil : Aquifer soil obtained from Newfield, NY
Organic carbon content = 0.049± 0.012%
47.2% of sand = 0.1-0.25mm
47.6% of sand = 0.25-0.5mm
Model Pollutant
9 Model pollutant : phenanthrene (PAH)
(9-14C, 13.1µCi/mol, Sigma Chemical Co)
9 Liquid Scintillation Counter: LS 6800 (Beckmann)
Batch
BatchExperiments
ExperimentsProcedure
Procedurefor
forDetermining
DeterminingDesorption
Desorptionof
ofSorbed
SorbedPAH
PAH
in
the
Presence
of
Surfactants
or
APU
(ACPU)
Nanoparticles
in the Presence of Surfactants or APU (ACPU) Nanoparticles
1mL of PAH
Equilibrated for 24hrs
On rotator shaker
Adding 9mL of TX-100
or APU emulsions
Mixing 24hrs
Centrifugation
(2500rpm, 30min)
1g of aquifer sand
1. Kd = [HOC]s/([HOC]w + [HOC]mic)
= (mol of HOC sorbed/g of solid)/(mol of HOC in aqueous and micellar solution/L)
2. Extraction efficiency = (desorbed amount of phenanthrene)/(sorbed amount of
phenanthrene on aquifer sand) X 100 (%).
Extraction
Extractionefficiency
efficiencyof
ofAPU
APUparticles
particlesand
andTriton
TritonX-100
X-100solution
solution
100
Log (CMC of Triton X-100)
Extraction efficiency(%)
80
60
40
-- APU700-3, -▲- APU 1000
-▼-Triton X-100
20
0
-20
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
Log (Triton X-100 or APU particles dose, mg/L)
Extraction efficiency = (desorbed amount of phenanthrene)/(sorbed amount of
phenanthrene on aquifer sand) X 100 (%).
Extraction
Extractionefficiency
efficiencyof
ofACPU
ACPUparticles
particlesand
andSDS
SDSsolutions
solutions
Extraction Efficiency(% )
100
80
60
ACPU64
ACPU28
40
ACPU55
SDS
20
0
2.0
2.5
3.0
3.5
4.0
4.5
5.0
Log (SDS or ACPU Particle Dose, m g/L)
Soil
Valve
Scintillation vial
Fraction of PAH rem aining in soil colum n
In-situ
In-situextraction
extractionof
ofsorbed
sorbedphenanthrene
phenanthrenefrom
fromsoil
soil
using
ACPU
(APU)
nanoparticles
and
surfactants
using ACPU (APU) nanoparticles and surfactants
Flow rate = 0.01 mL/min
Conc. = 100 mg/L
1.0
0.8
0.6
0.4
Brij30
TW 80
TX100
APU
0.2
0.0
0
2
4
6
8
10
Number of W ashings (Pore Volumes)
Flow rate = 0.01 mL/min
Conc. = 100 mg/L
100
Percent mass PAH remaining in soil column
Percent mass PAH remaining in soil column
In-situ
In-situextraction
extractionof
ofsorbed
sorbedphenanthrene
phenanthrenefrom
fromsoil
soil
Using
ACPU
nanoparticles
and
SDS
solutions
Using ACPU nanoparticles and SDS solutions
80
60
SDS
40
ACPU 55
ACPU 64
20
0
0
2
4
6
8
Number of W ashings (Pore Volumes)
Flow rate = 0.01 mL/min
Conc. = 4000 mg/L
100
80
SDS
ACPU 55
60
ACPU 64
40
20
0
0
2
4
6
8
Number of W ashings (Pore Volumes)
Flow rate = 0.01 mL/min
Conc. = 100 mg/L
1.0
Fraction of PAH rem aining in soil colum n
Fraction of PAH rem aining in soil colum n
In-situ
In-situextraction
extractionof
ofsorbed
sorbedphenanthrene
phenanthrenefrom
fromsoil
soil
Using
APU
nanoparticles
and
nonionic
surfactants
Using APU nanoparticles and nonionic surfactants
0.8
0.6
0.4
Brij30
TW 80
TX100
APU
0.2
0.0
0
2
4
6
8
10
Number of W ashings (Pore Volumes)
Flow rate = 0.01 mL/min
Conc. = 4000 mg/L
1.0
Brij30
TW 80
TX100
APU
0.8
0.6
0.4
0.2
0.0
0
2
4
6
8
10
Num ber of washings (Pore Volum es)
Schematic
SchematicPresentation
Presentationof
ofAqueous
AqueousPseudophase
Pseudophase
Containing
Polymeric
Nanoparticles
Containing Polymeric Nanoparticles
CMC is extremely low !!
Crosslinked APU nano particles
PAH
PAH
Km
Km
Aqueous
Pseudophase
Soil
Soil
9 Polymeric nanoparticles can extract a pollutant at very low concentration because their
extremely low CMC.
9 Adsorption onto soil are very low because of chemically crosslinked strucutre.
MEUF (Micelle-enhanced ultrafiltration)
‰ Very low water solubility but extremely harmful for human
‰ With very small amounts, tremendous volume of water are contaminated
‰ MEUF is one of the most effective process for separating hydrophobic pollutants
(Better than incineration, oxidation, supercritical oxidation process)
Below
CMC
Retentate
Above
Retentate
Feed solution with
pollutant
Surfactant additive
membrane
Surfactant
Permeate
Polyaromatic
Hydrocarbon
(PAH)
Permeate
NEUF (Nanoparticle-enhanced ultrafiltration)
Retentate
Amphiphilic
nanopolymer particle
Polyaromatic
hydrocarbon (PAH)
Membrane
Surfactant
Micelle
Rejectionratio
ratioisisalmost
almost100%!!
100%!!
Rejection
Biggerpore
poresize
sizeof
ofmembrane
membrane
Bigger
Permeate
Dead-end stirred cell filtration system
Pressure Gauge
UF Test Cell
N22
Data recording
Magnetic stirrer
Feed reservoir
Electronic valance
Rejection
Rejection rates
rates of
of ACNP
ACNP and
and SLS
SLS solutions
solutions
110
105
100
90
Rejection rate (%)
Rejection rate (%)
90
80
ANP28
ANP55
ANP64
SLS
70
ANP28
ANP55
ANP64
SLS
75
60
60
45
50
40
0
200
400
600
800
1000
Feed concentration (mg/L)
Fig. 7.The variation of rejection rate of ANP particles
and SLS surfactants with concentration at 2 kgf/㎠.
1200
30
0
1
2
3
4
Pressure (kgf/㎠)
Fig. 8. The variation of rejection rate of ANP particles and
SLS surfactants at different transmembrane pressure,
where the concentration of solutions is 200 mg/L.
‰
-situ amphiphilic
-enhanced Soil
‰In
In-situ
amphiphilicPolymer
PolymerNanoparticle
Nanoparticle-enhanced
SoilWashing
Washingprocess
process
(In
-situ APN
-enhanced Soil
(In-situ
APN-enhanced
SoilWashing
WashingProcess)
Process)
‰
-enhanced Ultrafiltration
‰Amphiphilic
AmphiphilicPolymer
PolymerNanoparticle
Nanoparticle-enhanced
Ultrafiltrationprocess
process
(ANP
-UF Process)
(ANP-UF
Process)
Fusion
FusionTechnology
Technologyof
ofNT
NTand
andET
ET
New
Newenvironmental
environmentalprocess
processcan
canbe
becreated
created
by
byAmphiphilic
AmphiphilicPolymer
PolymerNanoparticles
Nanoparticles
Amphiphilic
AmphiphilicReactive
ReactiveOligomers
Oligomers
(UAN
(UANand
andUAA)
UAA)
Another Applications of Amphiphilic Reactive Oligomer
9
9 Synthesis
Synthesisof
ofNanoparticles
Nanoparticleswith
withmuch
muchcheaper
cheaperprice
price
99 Simple
SimpleProcess
Process
99 Easy
Easyto
toControl
Controlof
ofParticle
ParticleSize
Size
99 Easy
Easyto
toMake
MakeThin
ThinNanocomposite
NanocompositeFilm
Film
‰ Synthesis of Magnetic Nanoparticles Dispersed Polymer Films
‰ Synthesis of CdS and Ag Nanoparticles Dispersed Polymer Films
‰ Synthesis of CdS and Ag Nanoparticles Dispersed at Water and Toluene
‰ Nano-dispersant for Silica and Clay Nanoparticles
‰ Dispersant for Graphite and Carbon Nano Tube (CNT)
TEM Images of Magnetic Nanoparticles Dispersed in PU Films
1000nm
1000nm
UAN NO-Solvent
UANH gel
1000nm
UAND gel
Appearance of PU Films Containing CdS Nanoparticles
Neat UV-cured PU film
Amphiphilic Polymer Lab.
PU film containing
CdS nanoparticles
TEM of Semiconductor nanoparticles dispersed in PU films
PMUA 700-3(3g) + Cd (1%) +THF(1.5g)
Average Particle Diameter : 9.67nm
PMUA 700-3(3g) + Cd (1%) +Methanol(1.5g)
Average Particle Diameter : 8.02nm
Particle Size Distribution
24
22
19
20
15
10
10
5
10
4
4
Particle Number
Particle Number
25
Particle Size Distribution
18
14
12
6
10
5
2
0
0
9.48
9.61
9.67
9.74
Particle Diam eter
9.8
7.94
7.94
8.02
8.05
Particle Diam eter
8.09
TEM of Semiconductor nanoparticles dispersed in PU films
PMUA 700-3(3g) + Cd (1%) +DMAc(1.5g)
Average Particle Diameter : 7.26nm
9 CdS was successfully reduced by sodium
sulfide in a hydrophilic nanodomain.
9 it shows the formation of a stable aggregation
nucleus without agglomerization among
the hydrophilic nanodomains.
9 CdS nanoparticles were successfully dispersed
in polyurethane film and obtained a narrow
particle size distribution
9Solvents of low dielectric constant formed a great
Particle Size Distribution
nanoparticles due to forming larger hydrophilic domai
25
Particle Number
21
20
15
¾ Toluene dielectric constant: 2.38
13
5
¾ THF dielectric constant: 7.6
10
10
2
¾
Methanol dielectric constant: 32.6
7.35
¾
DMAc dielectric constant : 37.8
4
0
7.19
7.23
7.27
7.31
Particle Diam eter
Nano-Silica Powder and Silica Nanoparticles Dispersed in a solvent
Nano-Silica Powder
Silica Nanoparticles dispersed in a solvent
TEM image of Sulfonated Polyimide Containing Silica Nanoparticles
50nm
PEM
PEMmembranes
membranescontaining
containingsilica
silica nanoparticles
nanoparticles
dispersed
dispersedby
byaid
aidof
ofUAN
UAN
99Improved
Improvedchemical
chemicalstability
stability
99Hydrolytic
Hydrolyticstability
stability
99Reduced
methanol
Reduced methanolpermeability
permeability
99Not
Notsacrificing
sacrificingconductivity
conductivity
Dispersion of Carbon Nano Tube Using Amphiphilic Reactive Oligomer
CNT+NMP
(0.05wt% CNT)
After
3 days
UAN+CNT+NMP
(0.05wt% CNT)
Not Polymerized
UAN+CNT+NMP
(0.05wt% CNT)
CNT+NMP
(0.05wt% CNT)
UAN+CNT+NMP
(0.05wt% CNT)