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Chemistry ofChemistry of absorbatesabsorbates foundfound
from the salvaged ROK navy shipfrom the salvaged ROK navy shipCheonanCheonan and torpedo fragmentsand torpedo fragments
Panseok YangPanseok Yang
Department of Geological SciencesDepartment of Geological SciencesUniversity of ManitobaUniversity of Manitoba
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Overview of underwater explosionOverview of underwater explosion
Summary ofSummary of JIGJIGss investigation of theinvestigation of theadsorbatesadsorbates
YangYangs results and interpretations results and interpretationSeismic evidenceSeismic evidence
A possible cause of the sinking ofA possible cause of the sinking ofCheonanCheonan
Outlines of the talkOutlines of the talk
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Underwater explosion and shock wavesUnderwater explosion and shock waves
water
Detonation wave
Explosive material/
water boundary
Gases
Unreacted material
Torpedo fragments Dense superheated gaseousproducts, 2-4 million PSI (138-
276 kbar) pressure and a fewthousands degree temperature
Chemical explosions withindetonation wave which travelsat a supersonic speed followedby physical explosions byshock waves and bubble pulses
Can the torpedo fragmentswithstand shockwaves andremain within the expandingbubble?
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Bubble pulses and water jetBubble pulses and water jet
Water surface orShip-water boundary
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A torpedo test on Australian navy shipA torpedo test on Australian navy ship
Shock wave Water jet
Gases + Al oxide
Al oxide and diesel oilin the water but notmuch unreactedexplosives
Unknown source
Fractured keel
StationedAmmunitions and fuelswere most likely removed
Aftermath of an UNDEXStrong smell of oilNo smell of explosives
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Settling speed of AlSettling speed of Al22OO
33particlesparticles
40 m
1 m dia. Al2O3
Current: 5.7 km/hr
Torpedo propeller
2)(92 gRv fps
s: settling speed
p
: density of Al2
O3
f: density of seawater: dynamic viscosity of seawaterg: gravitational accelerationR: particle radius
Sea floor
Water surface
Assuming no current, it takes 7.2 hrto reach the sea floor located 40 m below.Under the current speed of 5.7 km/hr,aluminum oxide particles with 1 mdiameter would have drifted 41 km awayfrom the origin.
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Diesel fuelDiesel fuel--clay mineral/Alclay mineral/Al22OO33 interactionsinteractions
Forms oil-seawater-clay mineral/Al2O3flocculated emulsionSubject tobiodegradationPositively buoyant
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Bubble oscillationsBubble oscillations
Water jet of Cheonan ~1.1 sec
Webster, 2007
300 lb TNT (136 kg)
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High explosivesHigh explosives: C: C--HH--OO--NN--Al systemAl system
Solid residues: Al2O3, nano-diamond and/or graphite, and
unreacted explosive materials including Al powder
2N(g) + 2Al(s) = 2AlN(s)
JIG
JIG: amorphous Al2O3 by rapid quenching by seawaterSulfur is not in the system
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SongSongs heat transfer models heat transfer model
Did not take account of Al explosions
Aluminum is added to prolong and to increase bubble size
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Solid explosion productsSolid explosion products
S. D. Gilev and V. F. Anisichkin, 2006Combustion, Explosion, and Shock Waves,Vol. 42, No. 1, pp. 107115
Round, a few tens micronsaluminum oxide balls and
sub micron or lessdiamond
Unreacted Al cores(appear as voids afteracid treatment) coatedwith aluminum oxide
Close-up of aluminum oxide coatings
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Aluminum oxide: AlAluminum oxide: Al
22OO
33
Corundum
Ruby
Sapphire
Alumina
AluminaAl2O3
BoehemiteAlO(OH)
Aluminum hydroxide
Al(OH)3
T
(Dehydration)
crystalline crystalline
crystalline amorphous
Used as gemstone, abrasive, andcatalyst because of physical-chemical resistance
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Carbon polymorphsCarbon polymorphs
Cheonan carbon: hydro carbon (CH, CH2, CH3 etc) as in petroleum products
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The occurrence ofThe occurrence of adsorbatesadsorbates
Under the deck
Abundant in stagnant areas and
commonly associated with Alalloys
JIG
unknown unknown
Absorbates under themetal cover?
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ContinuedContinued
JIG
Underwater explosion experiment
Holding the key but was
not available (limitedquantity)
Not analyzed
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Explosive residuesExplosive residues
Found even in sand but not from the torpedo fragments
JIG
graphite
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JIGJIGss EDS resultsEDS results
JIG interpreted it as a mixture of four different compounds (aluminum oxide, elemental carbon and sulfur, and water)
= =
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JIGJIGss TGA/DTATGA/DTA results and conclusionsresults and conclusions
Continuous decreases in oxygen
Sulfur remains constant up to 600 CThermal decomposition of aluminum sulfate (Al2(SO4)3)occurs at 760 C
Going through phase changes
JIGs conclusion:
Ship = Torpedo fragmentsDid not discuss the meaning of variations
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EDS simulationsEDS simulations
Aluminum hydroxideAl(OH)3
BoehmiteAlO(OH)
Aluminum oxideAl2O3
BasaluminiteAl4(SO4)OH10 5H2O
OAl
S
O
Al
O
Al O Al
AlxOy = Al2O3
X-ray energy (keV)
X-rayintensities(cps)
JIG
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EDS spectrum ofEDS spectrum of wetwet AlAl22OO
33
JIG
O
Al
50 nm alumina
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Nature News,Nature News, volvol 466 July 2010466 July 2010
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SamplingSampling
J. Roh
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Corroded and then adsorbed?Corroded and then adsorbed?Corroded fishing boat propellerCheonan torpedo propeller
White materials below the paint
adsorbates
absorbates
corrosion?
corrosion?Unknown source
Corrosion products underseawater: aluminum hydroxide[Al(OH)3]
This warrants chemical
analyses on the white materialsbelow the paint
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Precipitation vs. adsorptionPrecipitation vs. adsorption
JIG
Stagnant water
clean
clean
Smokestack
unknown
water jet
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SEM, BSE, and TEMSEM, BSE, and TEM
K. Jeong
K. JeongJIG
These textures point to precipitation
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XX--ray mappingray mapping
Detrital Al-silicate
Gypsum
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Quantitative analyses usingQuantitative analyses using
an electron microprobean electron microprobe
Matches with the molecular
formula of basaluminiteAl4(SO4)(Cl0.5OH9.5) 5H2O
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MMicroicro--RamanRaman and FTand FT--IRIR
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Carbon isotopesCarbon isotopesCarbons from diesel fuels of Cheonan
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Natural occurrence ofNatural occurrence of basaluminitebasaluminite
Rio Tinto Mine, Brazil
Sulfide oxidation of pyrite (FeS2)Sulfates and sulfuric acidDissolution of Al from adjacent rocksPrecipitation of basaluminite
Natural basaluminite
Inside the smokestack Propeller
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Precipitation conditions of amorphousPrecipitation conditions of amorphous basaluminitebasaluminite
Amonette et al, 2003
basaluminite
alunogen
Aluminumhydroxide
gibbsite
pH ranges of seawater
Basaluminitecannot be formed
under seawater,requiring moreacidicenvironments
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Ingredients ofIngredients of basaluminitebasaluminite formationformation
JIG p. 61
JIG p. 106
Diesel fuel (bacteria food)Water (seeding bacteria)
Acids (byproducts of dieselbiodegradation)Clay suspensions (Al sources)
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Biodegradation of diesel fuelBiodegradation of diesel fuel
Massive micro-biological populationsCorrosion products (e.g. H2S) by sulfate reducing bacteriaDeterioration of fuel quality
Organic acid accumulationSludge formation
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Dissolution of clay mineralsDissolution of clay minerals
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Evidence of corrosion by dieselEvidence of corrosion by diesel
biodegradation?biodegradation?
unknown
JIG JIG
Water within the vesselenriched in dissolvedmetals
Enhance corrosion in the dotted areas?
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Conclusions and suggestionsConclusions and suggestions
Evidences of underwater explosion such as AlEvidences of underwater explosion such as Al22OO33 andandnanonano--diamond/graphite were not found from the torpedodiamond/graphite were not found from the torpedo
fragments and the ship.fragments and the ship.The white substance is amorphousThe white substance is amorphous basaluminitebasaluminiteprecipitated under more acidic environments thanprecipitated under more acidic environments thanseawater.seawater.
Localized acidic environments can be formed by theLocalized acidic environments can be formed by thebiodegradation of the diesel fuels within the fuel tanks.biodegradation of the diesel fuels within the fuel tanks.
The white substance should not be presented as anThe white substance should not be presented as anevidence of underwater torpedo explosion.evidence of underwater torpedo explosion.
Redo underwater explosion experimentsRedo underwater explosion experiments
Oxygen isotope studyOxygen isotope study
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Seismology and explosionSeismology and explosion
Rogers and Kopper
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KIGAM seismic and sound wave dataKIGAM seismic and sound wave data
Lee, H.
Seismic waves, magnitude = 1.5
Sound wavesTwo peaks with a 1.1 sec intervalFirst peak = shock waveSecond peak = water jet
The interval was used to estimateexplosive power
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CheonanCheonan signalssignals
Hong, 2011
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Kursk signalsKursk signals
Russian Nuclear submarinesank in August, 2000
Rogers and Kopper
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Bubble pulse frequencyBubble pulse frequency
Spacing: function of yield and depth of detonationKursk: 1.45 Hz = 5,000 Kg TNT at 90 meterJIG: 0.91 Hz (1.1 sec) from sound wave = 250-300
Kg TNT at 10 meter
Hong (2011): fundamental frequency of 8.5 Hz andmultiples representing reverberation of watercolumn at 44 meter. No second period of
bubble oscillation.
Detonation depth and yield are questionable.
Kursk
Cheonan
9.1 8.3 8.6
8.5 17.726
34.6
Rogers and Kopper
1.45
KurskHong, 2011 Cheonanham
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My speculation on the sinking ofMy speculation on the sinking of CheonanCheonan
Human torpedo
Illustration from Joongang-Ilbo
= Russian investigators conclusions
Damages similar to a torpedo explosionConsistent with no sonar activities detected beforeand after the explosion
Collision with objects
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AcknowledgementsAcknowledgements
CongresswomenCongresswomen JeongJeong--HeeHee Lee, providingLee, providing CheonanCheonansamplessamples
ReporterReporter JongJong--MyunMyun RohRoh, arranging the investigation, arranging the investigationand presenting the preliminary results at the Nationaland presenting the preliminary results at the NationalAssembly of KoreaAssembly of Korea
Dr.Dr. RavinderRavinder Sidhu, Electron microprobe, EDS and SEMSidhu, Electron microprobe, EDS and SEM
Dr.Dr. YassirYassir Abdu, FTAbdu, FT--IR and Raman SpectroscopyIR and Raman SpectroscopyDr. S.Dr. S. ChaerunChaerun, biodegradation and clay minerals, biodegradation and clay minerals
Neil Ball, XRD analysesNeil Ball, XRD analyses
Misuk Yun, carbon isotope analysesMisuk Yun, carbon isotope analysesDrs.Drs. SeunghunSeunghun Lee and JaeLee and Jae--JungJung SuhSuh, constructive, constructivediscussionsdiscussions
Members of BRIC, critical and valuable discussions overMembers of BRIC, critical and valuable discussions over
many sleepless nightsmany sleepless nights