Observations of Microdrop Decan and Oil on Mica Surface by AFM and VSI.
Ueda, A.1, Kunieda, M.1, Fukunaka, Y.1, Liang, Y.1, Matsuoka, T.1 and Okatsu, K.2
1 Kyoto University2 The Technology and Research Center, Oil, Gas and Metals National Corporation (JOGMEC)
-Background “EOR⇔NANO”-
High recovery=EOR (Enhanced Oil Recovery)
⇒ Viscosity, Fluidity, Substitution efficiency…
micro-phenomena controls the wettability (contact angle, surface tension)
in oil-mineral-fluid
quartzquartz carbonatecarbonate clayclay rockrock
OilOil
quartzquartz carbonatecarbonate clayclay
Sea waterSea water
quartzquartz carbonatecarbonate
Sea waterSea water ＋＋chemicalchemical
brine
Water-oil-rock (Enhanced oil recovery)
lv
slsv
Vapor/fluid
solid
liquid Ylvslsv cos（ Young’s equation ）
clayclay
Oil
Mineral
Brine
Oil
Mineral
Brine
Brine
Oil
Oil
Mineral
MD
Ab initio
Calculations Experiment
+
Contact angle(macro)
Mineral
Oil
Brine
Mica/Quartz
・Light oil・Heavy oil・Crude oil
Analyses of oil-water-mineral interface
Flow test (lab)
Flow test (Field)
Zeta potential
Experiments
Oil
Contact angle(nano)+Force
Comparison of computational and experimental results
5
5
Force curve
AFMInterface equilibrium
Contact angle
Force curve
ζ potential
MD
Fluidity
LBMContact angle under low P,T
Contact angle under high P,T
VSI
ζ potential
Experiment Simulation
yes
Wettability
Salinity
electric double layerDLVO
Adhesion, cohesion
Contact angle
Contact angle
Geochemical behavior in pore and fracture
OIL-PAC
The previous results presented in 2008 （北京）
Contact angle vs Salinity of brine
20
30
40
50
60
70
0 10 20 30
Oil volume μ L（ ）
Con
tact
ang
le（○
） Distilled water
Sea water
Cruide oil Higashi-Niigata
Locality Niigata
Density(g/cm3) 0.784
API 49.0
Velosity(30℃) 1.2
Observation of oil droplet on mica by AFM
(Oil diameter ;400nm)
1
Sapphire disc
Petroleum droplet
VSI measurement
~4.2
Observation of oil droplet by VSI (Vertical Scanning Interferometry) in distilled water at 25℃ and 1 atm
9
CCD cameraPC
Laser/White light
= 532 nm
Piezo actuator
Phase shift interferometry
Thin section sample
The results in 2009(A preliminary report)
Macro analyses
R
h
2
Decane
H2O droplet
R
h2arctan2
θ/2 method
R = 159 μmh = 20 μm
Θ= 28.2°
C10H22
0.7g/cm3
mica
H2O droplet
Decane
Naturally deposition for 1 hour
Cleanup mica surface with water
Make Mica cleavage
Splash by air compressor
Soak mica in Decane for 1 day
Mica preparation
Contact angle measurement
Small emulsion(~10 micro m)
Large emulsion(10 micro m~)
Decane
H2O
Ultrasonic bath
Magnetic stirrer
Sample preparation for micro droplet
dw
Cantilever: k=0.01Pressure: 2.5nNScan rate: 0.5Hz
1μm×1μm
21
hhn
Rrms
Root mean square Roughness
Roughness; 0.75nm
⇒ smooth surface in nanoscale
Mica surface in decan (AFM)
5μm×5μm
Rms roughness; 0.32nm
Cantilever: k=0.01Pressure: 2.5nNScan rate: 0.5Hz
H2O droplet
Water droplet in decan (AFM)
R=2.109 micro mH=92.25 nano mContact angle
12.7 degree (θ/2 method)
Contact angle of water droplet in decan
5μm×5μm
R
h
2
θ/2 method
R
h2arctan2
Contact angle of water droplet in decan on mica surface (f=2.5nN)
Cantilever: k=0.01Pressure: 2.5nNScan rate: 0.5Hz
Effect of cantilever pressure on contact angle
Is it a real contact angle?
R~10 micro mh=456.6 nano mContact angle= 10.7°
F=2.5nN
Cantilever: k=0. 1Pressure: 25nNScan rate: 0.5Hz
F=25nN
×
Contact angle of water droplet in decan on mica surface
C.Pressure(low)
C.Pressure(high)
Error signalTopography
Effects of scanning pressure
Real surfaceApparent surface
cantilever
F=25nN
AA=15.4 micro m
(Differential calculus)
Effects of scanning pressure
cantilever
Force curve near water droplet
ApproachRetract
Decan on mica surface In H2O droplet
Approach
Retract
＊
Correction of contact angle
Error signal⇒ contact angle correctionForce curve⇒ height correction
RlvY
coscos
degree1.26
N1097.2 9
Y
N/m053.0lv
Contact angle vs. oil size (AFM)
Modified Young’s equation
Similar value to the observed one in macro scale
Waterchiller
Optical bench
Peltiercooler
HEPA filter
VSI optics(RSI, MM5500)
Wind shield(metal frame)
Active stage
Air-conditionerAmbient: 22± 0.5 ℃<40 % humidity
Air
Vertical Scan Interferometry (VSI)
= 520 nm
fluid
20x
20xreferencemirror
compensator
PZT scanning
interferogram
beam-splitter
mica substrate
lens
lens
stage unit for reference mirror
lens
Vertical Scanning Interferometer HT-HP cell and In-situ optics
x’x
0
500
1000
1500
2000
2500
3000
0 50 100 150 200
Distance (µm)
x-x’ profile
p1 p2
He
igh
t (n
m)
20µm
（２２℃、40µl/min）
CVD diamondsubstrate
Cell body(titanium)w/ heater
Sample holder(titanium)
Calcite substrateSapphire substrate(cell window)
VSI
PTFE + metal coilseal
Gold wire(spacer)
Reaction cell for high T and P (~200℃, ~20MPa)
Width ： 9.9μmHeight ： 0.52μm
Contact angle ＝ 12.0°
Water droplet in decan (VSI)
27
hydrophilic no hydrophilic
5nm
α-Quartz
HexaneCH3(CH2)4CH3
H2O
Thank for your attention.
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