Chemistry of absorbates found from the salvaged ROK navy ship Cheonan and torpedo fragments

Panseok Yang Department of Geological Sciences University of Manitoba

Outlines of the talk

Overview of underwater explosion Summary of JIGs investigation of the adsorbates Yangs results and interpretation Seismic evidence A possible cause of the sinking of Cheonan

Underwater explosion and shock waves

Torpedo fragments Detonation wave

Dense superheated gaseous products, 2-4 million PSI (138276 kbar) pressure and a few thousands degree temperature Chemical explosions within detonation wave which travels at a supersonic speed followed by physical explosions by shock waves and bubble pulses Can the torpedo fragments withstand shockwaves and remain within the expanding bubble?

Gases

Unreacted material water

Explosive material/ water boundary

Bubble pulses and water jet

Water surface or Ship-water boundary

A torpedo test on Australian navy ship

Stationed Ammunitions and fuels were most likely removed Fractured keel

Shock wave

Water jet Gases + Al oxide

Strong smell of oil No smell of explosives

Al oxide and diesel oil in the water but not much unreacted explosives

Aftermath of an UNDEX

Unknown source

Settling speed of Al2O3 particles

Water surface 1 m dia. Al2O3

2 ( p f ) 2 vs gR 9
s: settling speed p: density of Al2O3 f: density of seawater : dynamic viscosity of seawater g: gravitational acceleration R: particle radius Assuming no current, it takes 7.2 hr to reach the sea floor located 40 m below. Under the current speed of 5.7 km/hr, aluminum oxide particles with 1 m diameter would have drifted 41 km away from the origin.

40 m

Current: 5.7 km/hr

Sea floor Torpedo propeller

Diesel fuel-clay mineral/Al2O3 interactions

Forms oil-seawaterclay mineral/Al2O3 flocculated emulsion Subject to biodegradation Positively buoyant

Shock wave profiles with distance

(2,390 kg/cm2)

Distance to torpedo propeller 6 m = 3.2 ft Distance to keel 3 m = 1.5 ft

JIG

(136 kg)

Webster, 2007

Bubble oscillations
300 lb TNT (136 kg)

Water jet of Cheonan ~1.1 sec

Webster, 2007

High explosives: C-H-O-N-Al system

JIG

2N(g) + 2Al(s) = 2AlN(s)

JIG: amorphous Al2O3 by rapid quenching by seawater Sulfur is not in the system

Solid residues: Al2O3, nano-diamond and/or graphite, and unreacted explosive materials including Al powder

Songs heat transfer model

Did not take account of Al explosions Aluminum is added to prolong and to increase bubble size

Solid explosion products

Round, a few tens microns aluminum oxide balls and sub micron or less diamond

Unreacted Al cores (appear as voids after acid treatment) coated with aluminum oxide Close-up of aluminum oxide coatings

S. D. Gilev and V. F. Anisichkin, 2006 Combustion, Explosion, and Shock Waves, Vol. 42, No. 1, pp. 107115

Aluminum oxide: Al2O3

crystalline crystalline Used as gemstone, abrasive, and catalyst because of physicalchemical resistance

(Dehydration)

Alumina Al2O3 Boehemite AlO(OH) Aluminum hydroxide Al(OH)3

Corundum
crystalline amorphous

Sapphire

Ruby

Alumina

Carbon polymorphs

Cheonan carbon: hydro carbon (CH, CH2, CH3 etc) as in petroleum products

The occurrence of adsorbates

Abundant in stagnant areas and commonly associated with Al alloys

JIG

Absorbates under the metal cover?

unknown

Under the deck

unknown

Continued

Not analyzed

JIG Underwater explosion experiment

Holding the key but was not available (limited quantity)

Explosive residues

graphite

JIG

Found even in sand but not from the torpedo fragments

JIGs EDS results

JIG interpreted it as a mixture of four different compounds (aluminum oxide, elemental carbon and sulfur, and water)

JIGs TGA/DTA results and conclusions

Continuous decreases in oxygen Sulfur remains constant up to 600 C Thermal decomposition of aluminum sulfate (Al2(SO4)3)occurs at 760 C

JIGs conclusion: Ship = Torpedo fragments Did not discuss the meaning of variations
Going through phase changes

EDS simulations
JIG

AlxOy = Al2O3

Aluminum hydroxide Al(OH)3

Boehmite AlO(OH)

Aluminum oxide Al2O3

Basaluminite Al4(SO4)OH10 5H2O

X-ray intensities (cps)

Al

Al

Al

Al

O O S

X-ray energy (keV)

EDS spectrum of wet Al2O3

JIG

50 nm alumina

Al

Nature News, vol 466 July 2010

Sampling

J. Roh

Corroded and then adsorbed?

Cheonan torpedo propeller
adsorbates corrosion?

Corroded fishing boat propeller

absorbates corrosion?

Unknown source

Corrosion products under seawater: aluminum hydroxide [Al(OH)3] This warrants chemical analyses on the white materials below the paint

White materials below the paint

Precipitation vs. adsorption

clean

JIG unknown

water jet

Stagnant water

clean

Smokestack

SEM, BSE, and TEM

K. Jeong

These textures point to precipitation

K. Jeong

JIG

X-ray mapping

Detrital Al-silicate

Gypsum

Quantitative analyses using an electron microprobe

Matches with the molecular formula of basaluminite Al4(SO4)(Cl0.5OH9.5) 5H2O

Micro-Raman and FT-IR

Carbon isotopes
Carbons from diesel fuels of Cheonan

Natural occurrence of basaluminite

Natural basaluminite

Rio Tinto Mine, Brazil

Sulfide oxidation of pyrite (FeS2) Sulfates and sulfuric acid Dissolution of Al from adjacent rocks Precipitation of basaluminite

Inside the smokestack

Propeller

Precipitation conditions of amorphous basaluminite

al un og en

Aluminum hydroxide

basaluminite

Basaluminite cannot be formed under seawater, requiring more acidic environments

gibbsite

pH ranges of seawater Amonette et al, 2003

Ingredients of basaluminite formation

JIG p. 106

Diesel fuel (bacteria food) Water (seeding bacteria) Acids (byproducts of diesel biodegradation) Clay suspensions (Al sources)

JIG p. 61

Biodegradation of diesel fuel

Massive micro-biological populations Corrosion products (e.g. H2S) by sulfate reducing bacteria Deterioration of fuel quality Organic acid accumulation Sludge formation

Dissolution of clay minerals

Evidence of corrosion by diesel biodegradation?

Water within the vessel enriched in dissolved metals

unknown

JIG Enhance corrosion in the dotted areas?

JIG

Conclusions and suggestions

Evidences of underwater explosion such as Al2O3 and nano-diamond/graphite were not found from the torpedo fragments and the ship. The white substance is amorphous basaluminite precipitated under more acidic environments than seawater. Localized acidic environments can be formed by the biodegradation of the diesel fuels within the fuel tanks. The white substance should not be presented as an evidence of underwater torpedo explosion. Redo underwater explosion experiments Oxygen isotope study

Seismology and explosion

Rogers and Kopper

KIGAM seismic and sound wave data

Seismic waves, magnitude = 1.5

Sound waves Two peaks with a 1.1 sec interval First peak = shock wave Second peak = water jet The interval was used to estimate explosive power

Lee, H.

Cheonan signals

Hong, 2011

Kursk signals

Rogers and Kopper

Russian Nuclear submarine sank in August, 2000

Bubble pulse frequency

Hong, 2011

Cheonanham

8.5

17.7

34.6 26

Kursk

9.1

8.3 8.6

1.45

Kursk Spacing: function of yield and depth of detonation Kursk: 1.45 Hz = 5,000 Kg TNT at 90 meter JIG: 0.91 Hz (1.1 sec) from sound wave = 250-300 Kg TNT at 10 meter Hong (2011): fundamental frequency of 8.5 Hz and multiples representing reverberation of water column at 44 meter. No second period of bubble oscillation. Detonation depth and yield are questionable. Rogers and Kopper Cheonan

My speculation on the sinking of Cheonan Collision with objects Human torpedo

Damages similar to a torpedo explosion Consistent with no sonar activities detected before and after the explosion

= Russian investigators conclusions

Illustration from Joongang-Ilbo

Acknowledgements
Congresswomen Jeong-Hee Lee, providing Cheonan samples Reporter Jong-Myun Roh, arranging the investigation and presenting the preliminary results at the National Assembly of Korea Dr. Ravinder Sidhu, Electron microprobe, EDS and SEM Dr. Yassir Abdu, FT-IR and Raman Spectroscopy Dr. S. Chaerun, biodegradation and clay minerals Neil Ball, XRD analyses Misuk Yun, carbon isotope analyses Drs. Seunghun Lee and Jae-Jung Suh, constructive discussions Members of BRIC, critical and valuable discussions over many sleepless nights