nanoengineered reactive materials and their combustion and synthesis revised

Nanoengineered ReactiveMaterialsd th i C b ti d S th iandtheirCombustionandSynthesis

Richard A YetterRichardA.YetterPennStateUniversity

2012PrincetonCEFRCSummerSchoolOnCombustionC L th 3 hCourseLength:3hrsJune25 29,2012

AbstractIn the nanotechnology community, there has been

tremendous progress in the molecular sciences toward thetotal command of chemistry at all length scales. This progressy g p ghas been inspired by advances in the structural determinationof biological systems. Similar advancements in assembly ofmolecular and nanoscale elements have been made in thepharmaceutical and microelectronics fields as well. Thesedevelopments make it clear that in the foreseeable future itwill be possible to synthesize any desired macroscopict t ith i l ti f t Thistructure with precise location of every atom. This courseexamines how nanotechnology methodologies are currentlybeing applied to develop multifunctional smart reactivematerials for combustion applications and the combustionmaterials for combustion applications and the combustionmethods for materials synthesis.

Outline

IntroductionIntroduction BasicsS h i d bl SynthesisandAssembly

Combustion Applications

Howsmallissmall?

Micrometerandnanometer Bothareinvisiblysmall

Micrometer Sizeofredbloodcell

NanometerNanometer SizeofsmallmoleculeFive times the size of the hydrogen atom Fivetimesthesizeofthehydrogenatom

S.F.SonandR.A.Yetter,Nanoenergetics,2012

ReasonsforNanotechnologyNoSmallMatter,byFrankelandWhitesides

InformationTechnology Smallestpartsoftransistorsarenanoscale Connecting wires are < 40 nm (less than 100 gold atoms laid end to end!)Connectingwiresare

ReasonsforNanotechnology continued Materials

Nanoscale phenomenacontrolgrainboundaries,behaviorofcracktips,voids,andotherinterfaces

Wecanalsomakenewmaterialswithnewproperties Selfassembledmonolayers,rodsorothershapes,tubes,etc. THISISBECOMINGMOREIMPORTANTINNANOENERGETICSANDNANOREACTIVEMATERIALS

Q t Ph QuantumPhenomena Nano isatthescalewherequantumeffectsbegintoemerge

Medicine Nanostructuresandnanoscience shouldbeusefulinselectingspecific

cellstodestroyorprotect,inprecisedeliveryofdrugstotissues,etc. EnergyandtheEnvironment

Nanoscale catalystsareusedtoconvertcrudeoiltousablefuels Nanoscale particlesnaturallyformedareimportantincloudformation NANOENERGETICSCANAPPLYTOENERGYAPPLICATIONS

e.g.,ultrahighsurfaceareametalfoamsmadeviacombustionsynthesisforcatalystsorhydrogenstorage

Risks?Certainly.Safetyisacurrentareaofresearch.FrankelandWhitesides,NoSmallMatter,Belknap/Harvard,2009 S.F.SonandR.A.Yetter,Nanoenergetics,2012

WhatNanotechnologyIsNOT Itisnotapanacea

ItdoesNOTsolveallmaterialsproblemsF ti d ti t i l it t ti ll b Forenergeticandreactivematerials,itcanpotentiallybeagamechangerwithrespecttokinetics(ignitionandreactiontimes)

It ll ill t h th t t b t ld ll Itgenerallywillnotchangetheenergycontent,butcouldallowsomereactives thatcouldnotbeconsideredotherwise(nSi isanexample)

Nano is sexy but micro still pays many of the bills Nano issexy,butmicrostillpaysmanyofthebills. FrankelandWhitesides

Nanotechnologyisnew,right? Romancup,Mayanpaint,cartires,stoplights,etc.,alluse(d)nanomaterials

SEMs, TEMs, AFM, etc. make difference today! WeveSEMs,TEMs,AFM,etc.makedifferencetoday!We veonlybeenabletoimagenanomaterials forafewdecades


TheLycurgusCup ARomanNanotechnology

Whenilluminatedfromoutside,itappearsgreen

However,whenilluminatedfromwithinthecup,itglowsred

Colloidsofgoldandsilveralloyg ynanoparticles (~50100nm)withaAg/Auratioof7:3scatter/absorb lightyieldingthedichroic effects.

Thetransmittedredcolorisduetotinygoldparticlesembeddedintheglass,whichhaveanabsorptionpeakataround520nm.Thereflectedgreenishcolorresultsfromthesilverparticles.

TEMofsilvergoldalloyparticle within glass

TEMofsodiumchlorideparticles within glass

Freestone,I.,Meeks,N.,Sax,M.,Higgitt,C.,GoldBulletin,40,4,270,2007

particlewithinglass particleswithinglass


Why Combustion andWhyCombustionandNanotechnology?

CombustionandNanotechnology

140 160

Wherearetheybeingstudied?Numberofpublicationsdevotedtofuelsandenergeticmaterials

100

120

140

120

140

160

60

80

100

60

80

100

20

40

0

20

40

01995 2000 2005 2010

Year

0

Country

Numberofpublicationsbyyearandcountryforthesearchtermsnano AND(fuelORpropellant ORenergeticmaterial ORexplosive)from19962010.

SurfacetoBulkAtomRatioforSphericalIronCrystalsCrystals

100

60

80 bulk atoms

40

60

0

20 surface atoms

00 5 10 15 20 25 30

particle size (nm)

K.J.Klabunde,J.Stark,O.Koper,C.Mohs,D.G.Park,S.Decker,Y.Jiang,I.LagadicandD.J.Zhang,J.Phys.Chem.100,(1996)1214212153.

MeltingPointandNormalizedHeatofFusion for Tin NanoparticlesFusionforTinNanoparticles

480

500

4050

60

440

460

2030

40

4200 20 40 60 80 100

particle diameter (nm)

100 20 40 60 80 100

particle diameter (nm)

S.L.Lai,J.Y.Guo,V.Petrova,G.Ramanath,andL.H.Allen,Phys.Rev.Lett.77(1996)99102.

Foraluminumparticles:Al i S d Th D L JPC A 110 1518 2006Alavi,S.andThompson,D.L.,JPCA 110,1518,2006.Puri,P.andYang,V.,JPCC110,11776,2007.AlsoAIAA2008938andAIAA20071429.

OtherFeaturesofNanoparticles

Increased specific surface area Increasedspecificsurfacearea Increasedreactivity Increased catalytic activity Increasedcatalyticactivity Lowermeltingtemperatures Lower sintering temperatures Lowersinteringtemperatures Superparamagneticbehavior Superplasticity Superplasticity

StructureoftheAbaloneShell

Structureofthenacre:95 wt.% inorganic material95wt.%inorganicmaterial5wt.%organicmaterial

inorganiclayers:CaCO3 aragonite

organiclayers:

A.LinandA.Meyers,Mat.Sci.Eng.A390,2741,2005.

Nanoparticle SelfAssembly

Sanders,J.V.,Murray,M.J.,Naturev275,1978.

Shevchenko,E.V.,Talapin,D.V.,Kotov,N.A.,OBrien,S.,Murray,C.B.,Naturev439,2006

Kalsin,A.M.,Fialkowski,M.,Paszewski,M.,Smoukov,S.K.,Bishop,K.J.,Grzybowski,B.A.,Science v312,2006

Multiscale StructuresGeckofoothairmicro/nanostructures Climbrapidlyupsmoothverticalsurfaces Footstickingandreleasingmechanismcritical Compliantmicro andnanoscale highaspectratiobetakeratinstructuresattheirfeettoadheretoanysurfacewithapressurecontrolledcontactarea

Adhesionisduemainlytomolecularforces(vander Waalsforces)

Setae

Rowsofsetaefromatoe

Geckofoot Singleseta Finestterminalbranchofsetacalledspatulae Foothairsstartfromthemicrometerscale(stalksorseta)andgodownto100200nmdiameter

Autumn,K.,etal.,Nature,405,681684,2000

( ) g(spatular stalks)bybranching.

Eachfoothas~500ksetae,each30130mlongwith100sofspatular stalks. Attheendsofthespatular stalksareorientedcaps(spatulae)withdiametersof300500nm.

OrganizationandAssemblyattheNanoscale:Example of an Energetic MaterialExampleofanEnergeticMaterial

ProbingQuestions

Limited fundamental understanding of which type ofsupramolecular structures provide desirable performance incombustion mechanical and hazard characteristicscombustion, mechanical, and hazard characteristics.

How do we systematically prepare fuel nanostructures withcontrolled shapes and sizes?

What are the desirable shapes and sizes of thesenanostructures?

What kind of synthetic passivation layers are needed toWhat kind of synthetic passivation layers are needed toproduce rugged systems resisting oxidation during storage,while decreasing sensitivity?

What sorts of oxidizer nanostructures can be synthesized? What sorts of oxidizer nanostructures can be synthesized? Given fuel nanostructure, what are the best forms for theoxidizer: fuel coatings, oxidizer nanostructures, or polymermatrix oxidizer?

ProbingQuestions contd At what length scales do chemical reaction dynamics becomesignificant/dominant?

What structures allow us to control the rate of energy releaseWhat structures allow us to control the rate of energy releaseover a wide range of conditions: passivation layers, 3Darchitectures, or concentration gradients?

What structures lead to focused or directional energy release? What structures lead to focused or directional energy release? What structures lead to reduced sensitivity? What are the fundamental mechanisms of initiation? How dothermal and shock initiation differ?

What structures lead to detonation? Can the structures be made smart? Can the structures be made smart? How best to couple the output of nanoenergetics to usablefunctions (e.g., power, mechanical force, desired chemicals)

EnergyContentasaFunctionofParticleDiameterDiameter

1

0.8

0.6 2 nm

3

0 2

0.4 3 nm

0

0.2

9 8 7 610-9 10-8 10-7 10-6

particle diameter (m)

SomeBasics

HeatsofOxidationofSeveralMaterials

120

140Gravimetric (kJ/gm

fuel)

80

100

120 fuelVolumetric (kJ/cm3

fuel)

i

d

a

t

i

o

n

40

60

H

e

a

t

o

f

O

x

0

20

A

l

)

B

)

e

)

C

)

e

)

L

i

)

g

)

S

i

)

T

i

)

W

)

Z

r

)

l

u

m

i

n

u

m

(

A

B

o

r

o

n

(

B

B

e

r

y

l

i

u

m

(

B

e

C

a

r

b

o

n

(

C

I

r

o

n

(

F

L

i

t

h

i

u

m

(

L

g

n

e

s

i

u

m

(

M

g

S

i

l

i

c

o

n

(

S

T

i

t

a

n

i

u

m

(

T

T

u

n

g

s

t

e

n

(

W

i

r

c

o

n

i

u

m

(

Z

A

B

M

a

g

T

Z

i

ThermodynamicConsiderations

Foroxygencontainingenvironments,earlystudies (Glassman Von Grosse and Conway)studies(Glassman,VonGrosseandConway)recognized

The importance of the volatility of the metal vs Theimportanceofthevolatilityofthemetalvsthemetaloxide

The relationship between the energy required to Therelationshipbetweentheenergyrequiredtogasifythemetalormetaloxideandtheoverallenergyavailablefromtheoxidationreaction agylimitingflametemperature

H > Q (Ho Ho ) HHvapdissoc >QR (HoT,vol Ho298)=HavailGlassman,Combustion,AcademicPress,3rd Edition,1996

ThermodynamicConsiderations Contd

Metal Tbp(K)

Oxide Tvol(K)

Hf,298(kJ/mol)

Hvol(kJ/mol)

HTvol-H298 + Hvol(kJ/mol)(kJ/mol)

Al 2791 Al2O3 4000 -1676 1860 2550B 4139 B2O3 2340 -1272 360 640Be 2741 BeO 4200 -608 740 1060Cr 2952 Cr2O3 3280 -1135 1160 1700Fe 3133 FeO 3400 -272 610 830Hf 4876 HfO2 5050 -1088 1014 1420Li 1620 Li2O 2710 -599 400 680

Mg 1366 MgO 3430 -601 670 920Si 3173 SiO2 2860 -904 606 838Ti 3631 Ti3O5 4000 -2459 1890 2970Zr 4703 ZrO2 4280 -1097 920 1320

Glassman,Combustion,AcademicPress,3rd Edition,1996

ClassificationofMetalCombustion

I VolatileProduct NonvolatileproductII Volatile metal Nonvolatile metal Volatile Metal Nonvolatile MetalII Volatilemetal

Gasphasecombustion

NonvolatilemetalSurfacecombustion

VolatileMetalGasphasecombustion

NonvolatileMetalSurfaceorcondensedphasecombustion

III Soluble Nonsoluble Soluble Nonsoluble Soluble Nonsoluble Soluble Nonsoluble

Productmaydilutemetalduring

Nofluxofproducttometal

Productmaybuildupinmetalduring

Noproductpenetrationintometal

Ifproductreturnstometalitmay

Disruptionstronglyfavoredifproduct

Metalmaydiffusethrough

Productcoatingmakesignitiondifficult

burningandcausedisruptionifitsboilingpoint

d th t

burning diluteitandcausedisruption

returnstometal growingproductlayer,purelycondensedphase

b tiexceedsthatofmetal

combustionpossible

F.A.Williams,"SomeAspectsofMetalParticleCombustion,"PhysicalandChemicalAspectsofCombustion:ATributetoIrvGlassman,F.L.DryerandR.F.Sawyer,eds.,GordonandBreach,TheNetherlands,1997,pp.267289.

ThermodynamicConsiderations EffectofPressure and OxidizerPressureandOxidizer

6000

2Al+1.5O2

(

K

)

5000

2Al 1.5O2

2Al+1.5(O2+3.76N2)

p

e

r

a

t

u

r

e

4000

2Al+3CO2,Reactants at 298K

T

e

m

p

30002Al+3H2O(g),

0 1 1 10 1002000

Al vaporization2Al+3H2O(l),Reactants at 298K

2 (g),Reactants at 398K

Pressure (atm)0.1 1 10 100

GlassmanandYetter,Combustion,AcademicPress,4th Edition,2008

MicronAluminumParticleCombustionOxidizerEffects PressureEffects

Air

60 t2 t 60 atm2 atm1 atm

R.A.YetterandF.L.Dryer,inFireinFreeFall:MicrogravityCombustion,H.Ross,Ed.,AcademicPress,Chapter6,2001.

EquilibriumProductCompositionandTemperature vs Input EnthalpyTemperaturevs.InputEnthalpy

1 4500

Stoichiometric MixtureofAlandO2 at298Kand1atm

0.8

1

4000

4500

T

TAl2O

3(l)

0.63500

4000

F

r

a

c

t

i

o

n

Tempera

O

0 2

0.4

3000

M

o

l

e

F

ture (K)

Al

AlO

O

0

0.2

2500-15 -10 -5 0 5 10 15

O2

Al2O

-15 -10 -5 0 5 10 15

Assigned Enthalpy (kJ/g)Glassman,Combustion,AcademicPress,3rd Edition,1996

FlameStructureofMicronAluminumParticle Burning in AirParticleBurninginAir

c

t

i

o

n

s

1 0 ]

NaturalLuminosity

M

o

l

e

F

r

a

c

0.60.81.0

e

r

a

t

u

r

e

[

K

]

3500

4000

T AlO

Simulated

AlO PLIF

Al2O3 EPMA

r

m

a

l

i

z

e

d

M

0 00.20.4

T

e

m

p

e

2000

2500

3000

Al2O3

T PLIF

AlO PLIF

r / rp

1 2 3 4 5 6 7 8 9 10No

r 0.0 2000AlOPLIF

Burninterruptedparticleon silicon waferr / rp onsiliconwafer

Bucher,P.,etal.Proc.Combust.Inst.,27,2421,1998.

EPMA

ThermodynamicsofCombustionSynthesisHeatsofFormationofChlorides

Chloride Hfo,298K(kJ/mol)

PerClatom

HeatsofFormationofNitrides

Nitride Hfo,298K(kJ/mol)

PerNatom

CsCl 443 443

KCl 437 437

BaCl2 859 430

HfN 369 369

ZrN 365 365

TiN 338 3382RbCl 430 430

SrCl2 829 415

NaCl 411 411

AlN 318 318

BN 251 251

Mg3N2 461 231

LiCl 408 408

CaCl2 796 398

CeCl3 1088 362

g3 2Si3N4 745 186

Li3N 165 165

N2 0 0CeCl3 1088 362

AlCl3 706 235

TiCl4 815 204

SiCl4 663 166

N2 0 0

NaN3 22 7

MClx +xNa +(y/2)N2 xNaCl +MNySiCl4 663 166 MClx +nMCly +(x+ny)Na

(x+ny)NaCl +MMnMClx +xNaxNaCl +M

Glassman,Combustion,AcademicPress,3rd Edition,1996

ExamplesofEnergyContentofThermite andIntermetallic ReactionsIntermetallic Reactions

Reactants HeatofReaction Reactants HeatofReaction

cal/g cal/cm3 cal/g cal/cm3

TNT 649 1073 TNT 649 1073

l l2Al+3CuO 974 4976 Al+Ni 330 1706

2Al+MoO3 1124 4279 Al+Pd 327 2890

2Al + 3NiO 822 4288 2B + Hf 401 33032Al+3NiO 822 4288 2B+Hf 401 3303

Si+2CuO 762 4354 B+Ti 670 2558

3Si +2MoO3 720 3000 3Si+5Ti 428 1590

Si+2NiO 569 3420 C+Ti 736 2760

C +2CuO 11 66 C+Zr 455 2400

Fischer,S.H.andGrubelich,M.C.,32nd AIAA/ASME/SAE/ASEEJointPropulsionConference,LakeBuenaVista,Fl,July13,1996.

ModesofParticleCombustion

11

DiffusionControlledwithEnvelopeFlame

DiffusionControlledwithoutEnvelopeFlame

KineticallyControlled

T/T

T/T

fuel

1T/T

fuel

products

1 T/T1

oxidizerproducts

s0oxidizer

products

s0oxidizer

fuelproducts

s0ss

Diffusionvs KineticControl

B)1(D8d

t20p

b,diff = l )iY1(D8d

t20p

b,diff = l

Diffusioncontrolledcombustionwithvaporizationorsurfacereaction

B)1(D8b,diff +ln )iY1(D8 O,b,diff +ln

dKineticcontrolledsurfacereaction

=

O,p

0pb,kin kPXMW2

dt

As particle size is decreased two conditions defined by Da =1 and Kn =1 arise

XkPdMWtDa O,0pb,diff ==

Asparticlesizeisdecreased,twoconditionsdefinedbyDa=1andKn=1arise

)iY1(D4tDa

O,b,kin +ln

d2Kn = 1 2= 21

2 /

=pd N2

2 21

RTMW8P

/

ShrinkingCoreModelforSphericalParticlesofUnchanging Size

Product Unreactedcore

Low HighUnreacted

core

UnchangingSizeDiffusionthroughProductLayerControls

t

i

o

n

o

f

r

e

a

c

t

a

n

t Typicalpositionindiffusionregion

Lowconversion conversion

Time Time

Product

Reactionzone

R Rrc rc0

C

o

n

c

e

n

t

r

a

t

g

a

s

p

h

a

s

e

r

CAg

CA

0 r

region

n

t

r

a

t

i

o

n

o

f

r

e

a

c

t

a

n

t

Product Unreactedcore

Radialposition

R R R R R R00 0

C

o

n

c

e

n

s

o

l

i

d

ChemicalReactionControls

e

n

t

r

a

t

i

o

n

o

f

a

s

e

r

e

a

c

t

a

n

t

CAg

Radialposition

R R R R R R00 0

RadialpositionR Rrc rc0

C

o

n

c

e

g

a

s

p

h

a

Seeforexample,Levenspiel,O.,ChemicalReactionEngineering,ThirdEdition,J.WileyandSons,1999

ShrinkingCoreModelforSphericalParticlesofUnchanging Size

2pR = pR =

DiffusionthroughProductLayerControls ChemicalReactionControls

UnchangingSize

Ag2 3

2 / 3

6bDCt r r1 3 2

R Rt

= +

Ag

1/ 3

bkCt r1

Rt 1 (1 X)

= =

1 1 0

2 / 3t 1 3(1 X) 2(1 X)= + 1 (1 X)=

Radiusvs.Time Conversionvs.TimeRateofChangeof

Conversionvs.Conversion

0.6

0.8

R

0.6

0.8

X

-0.4

-0.2

/

d

(

t

/

)

Diff i

Diffusioncontrolled

Kineticcontrolled

Kineticcontrolled

0.2

0.4

r

/

R

0.2

0.4

1

-

X

-0.8

-0.6

d

(

1

-

X

)

/Diffusioncontrolled

Diffusioncontrolled

Kineticcontrolled

00 0.2 0.4 0.6 0.8 1

t/0

0 0.2 0.4 0.6 0.8 1t/

-10 0.2 0.4 0.6 0.8 1

X

Seeforexample,Levenspiel,O.,Chemical ReactionEngineering,ThirdEdition,J.WileyandSons,1999

EffectofParticleDiameteronAlBurningTimeTime

100000Wilson and Williams [7]Wong and Turns [2]P ti [4]

Davis [8]Parr et al. [9] (T=1500 K)P t l [9] (T 2000 K)

1000

10000Prentice [4]Olsen and Beckstead [1]Hartman [3]Friedman and Macek [5,6]

Parr et al. [9] (T=2000 K)Park et al. [10] (T=1173 K)Eisenreich et al. [11] (T=900 K)

e

[

m

s

]

100

1000

r

n

i

n

g

T

i

m

e

1

10

B

u d1.8T=1500K

0.10.01 0.1 1 10 100 1000

Diameter [m]

T=2000K

[ ]T.Bazyn,H.Krier,andN.Glumac,ProcCombust.Inst.31(2007)2021&Combust.Flame 145(2006)703.Y.L.Shoshin andE.L.Dreizin,Combust.Flame145(2006)714.

EffectofParticleDiameteronAlIgnitionTemperatureTemperature

3500Parr et al. [20]

3500Derevyaga et al. [34]

e

,

K

3000

[ ]Bulian et al. [38]Assovskiy et al. [40]Yusasa e tal. [37,39]Brossard et al. [36]Ermakove tal. [35]

e

,

K

3000

y g [ ]Merzhanov et al. [33]Friedman et al. [31,32]Trunov et al. [26]CurveFit

T

e

m

p

e

r

a

t

u

r

e

2000

2500

T

e

m

p

e

r

a

t

u

r

e

2000

2500

I

g

n

i

t

i

o

n

T

1000

1500

I

g

n

i

t

i

o

n

T

1000

1500

i l i10-2 10-1 100 101 102 103 104

500

1000

i l i10-2 10-1 100 101 102 103 104

500

1000

Particle Diameter, mParticle Diameter, m

ThermalGravimetricAnalysisofNanoaluminum with CONanoaluminum withCO2

1 6

1.8 7

38nm

1.2

1.4

1.6

5

6

M

a

s

s

(

T

G

)

10m3m

108nm

45nm(2.5nm)45nm(3.6nm)

1.0

3

4

45nm(2.5nmoxide)38nm

10m

1

2

n

e

r

g

y

(

D

S

C

)

3m108nm

45nm(3.6nmoxide)

( )

250 450 650 850 1050 12500

1

E

n10m

Temperature(oC)

K.Brandstadt,D.L.Frost,andJ.A.Kozinski,inAdvancementsinEnergeticMaterialsandChemicalPropulsion,ed.K.K.KuoandJ.deDiosRivera,BegallHouse,2007.IlinAP,GromovAA,andYablunovskiiGV(2001)Combustion,explosion,andshockwaves,37n.4:418422.

PolymorphicPhaseTransformationsinAl2O3 LayerAl2O3 Layer

M.A.Trunov,M.SchoenitzandE.L.Dreizin,CombustionTheoryandModelling,10,2006,603623

AluminumNanoparticle OxidationwithSingleParticle Mass Spectrometry

2

ParticleMassSpectrometryIncreasedrateconstantwith

decreasingparticlesize Shrinkingcoremodel

0.5

0.6

0.7

r

s

i

o

n

,

s

T = 700oC0

2

s

e

c

)

< 50 nmE ~ 32kJ/ l

0 2

0.3

0.4

f

o

r

h

a

l

f

c

o

n

v

e

r

t ~ r1.58-4

-2

(

K

c

o

n

v

)

,

L

n

(

1

/

s

50 - 100 nm

Ea~32kJ/mol

0

0.1

0.2

0 5 10 15 20 25 30 35

T

i

m

e

f

time(s) = 0.0025r(nm)1.582

-8

-6

L

n

(

Ln(Kconv

) = 17.8 - 21000(1/T)

Ln(Kconv

) = 5.2 - 6847(1/T)

Ln(Kconv

) = 3.2 - 3824(1/T)100 -150 nm

Ea~95kJ/mol

radius, nm-80.0008 0.0009 0.001 0.0011 0.0012

1/T (1/K)

Effectivediffusioncoefficient(De)ofoxygeninashlayer=109 ~108 cm2/sfor

OxidationofanAlNanoparticle byMultimillion Atom MD SimulationsMultimillionAtomMDSimulations

35

(

)

15

25T

h

i

c

k

n

e

s

s

95

105

115

Inner Radius

s

(

)

5

15

0 100 200

O

x

i

d

e

T

75

85

95 Outer Radius

R

a

d

i

u

s

1-1 0Pressure (GPa)

0 100 200Time (ps)

P.Vashishta,R.K.Kalia,andA.Nakano,J.Phys.Chem.B2006,110,37273733

S h i d A bl ?SynthesisandAssembly?

HowareNanoenergetics Made? Thecreationofnanoenergeticsisstilla

Nitrated Carbon

currentresearcharea Manyapproachestaken

l l d

100 nm

Nano-CrystallineExplosives Nitrated Carbon

Tube Structures Forexample,NanoAlmadevia:

exploding wires

Explosives Encapsulated

explodingwires condensationtechnique plasmamethods wetchemistryapproaches


SynthesisMethodsS h i G I G h d i b d h i f d i SynthesisGroupI:Gasphasecondensationbasedtechniquesforproductionofnanosized metalparticles,e.g.,wireexplosion,PVD(PhysicalVaporDeposition;e.g.,usingvacuum),CVC(ChemicalVaporDeposition),supercriticalprocessingp p g

SunX.K,Xu J.,.ChenW.D,WeiW.D.,Nanostruct.material ,4,337(1994) Tohno S.,Itoh M.,andTakanoH.,J.AerosolSci.25,839(1994) MagnussonM.H.,Deppert K.,Malm J.O.,Svensson S.,SamuelsonL.,JAerosolSci 28(Suppl1),S471,(1997) MurataT.,Itatani K.,HowellFS,Kishioka A.,andKinosita M.,JAmCeramSoc 76,2909(1993) Danen,W.C.,Martin,J.A.,USPatent5266132(1993);USPatent5606146(1997) B.H.Kear andG.Skandan,Nanostruct.Mater.8,765(1997) HahnH.,Nanostruct.Mater.9,3(1997). Ivanov G.V.,andTepper,F.,.InKuo,K.K.,etal.,Eds.,ChallengesinPropellantsandCombustion100YearsafterAfter Nobel,

Begell House,NewYork,(1997),p.636. Jiang,W.,Yatsui,K.,IEEETransactionsonPlasmaScience,26(5):14981501(1998)

SynthesisGroupII:Plasma,arc,andflamesynthesis FineParticles:synthesis,characterization,andmechanismofgrowth,SugimotoT.,Ed.NewYork,MarcelDekker,Inc.,pp.114,

404(2000) Tomita,S.,Hikita,M.,Fujii,M.,Hayashi,S.,andYamamoto,K., ChemicalPhysicsLetters316:361364(2000) ChopraN.G.,Luicken R.J.,Cherrey K.,Crespi V.H.,CohenM.L.,LouieS.G.,andZettl A.,Science 266,966(1995) Loiseau A.,Willaime F.,Demoncy N.,Hug,G.,andPascard H.,Phys.Rev.Lett.76,4737(1996) Ruoff R.S.,Lorents D.S.,ChanB.,Malhotra R.,andSubramoney S.,Science 259,346(1993) Hwang,J.H.,Dravid,V.P.,Teng,M.H.,Host,J.J.,Elliott,B.R.,Johnson,andD.L.,MasonT.O.,J.Mater.Res.12,1076(1997). SunX.,GutierrezA.,Yacaman M.J.,DongX.,andJinS.,MaterialsScienceandEngineering A286,157(2000). Pratsinis S E Progress in Energy and Combustion Science 24 197 (1998) Pratsinis S.E.ProgressinEnergyandCombustionScience,24,197(1998) Balabanova E.,Vacuum 69,207212(2002) Keil,D.G.,Calcote,H.F.andGill,R.J.,MaterialsResearchSocietySymposiumProceedings 410,167(1996). Axelbaum R.L.,Lottes C.R.,Huertas J.I.,andRosenL.J.,TwentySixthSymposium(International)onCombustion,TheCombustion

Institute,Pittsburgh,(1996),p.1891.S.F.SonandR.A.Yetter,Nanoenergetics,2012

SynthesisMethodscontinued SynthesisGroupIII:Wetchemistry,SolGel,etc.

HyeonLee,J.,Beaucage,G.,Pratsinis,S.E.,ChemMatter,9:24002403(1997) Tillotson,T.M.,Hrubesh,L.W.,Simpson,R.L.,Lee,R.S.,Swansiger,R.W.,Simpson,L.R.,JournalofNon

CrystallineSolids 225:358363(1998)Till t TM G h A E Si R L H b h LW S t h J H J P J F J l f N C t lli Tillotson,T.M.,Gash,A.E.,Simpson,R.L.,Hrubesh,L.W.,Satcher,J.H.,Jr.,Poco,J.F.,JournalofNonCrystallineSolids 285:338345(2001)

SynthesisGroupIV:Mechanicalalloying/activation Suryanarayana C Progress in Materials Science 46 (1 2): 1 184 (2001) Suryanarayana C.,ProgressinMaterialsScience,46(12):1184(2001) Wen,C.E.,Kobayashi,K.,Sugiyama,A.,Nishio,T.,andMatsumoto,A.,JournalofMaterialsScience 35:2099

2105(2000)

Shoshin,Y.L.,Mudryy,R.,S.,andDreizin,E.L.,CombustionandFlame 128:259269(2002) Lu,L.,Lai,M.O.,MechanicalAlloying.Kluwer AcademicPubl.,Boston,1998 ElEskandarany,M.S.,MechanicalAlloying.NoyesPublications.,Norwich,NY,2001

SynthesisGroupV: SoftLithographicPatterning,DecalTransferLithography, PhotolithographyLithography,Photolithography


Nanosized ReactiveMaterials Nanoscale powders

Availableinlargequantitiesnow Potentialingredientinpropellants,pyrotechnics,and

explosives

Smallersizemeanslargersurfacearea Greaterreactivity Fasterburning

Good for combustion efficiency

ThecolorofAlisstronglyrelatedtoparticlesize.Typically200nmpowderisgray(left)and40nmpowderisblack(right),fromPesiri etal.,JournalofPyrotechnics,19,192004 Goodforcombustionefficiency

OriginalnAl wasALEX(EXploded ALuminum) Explodingwires Still sold good value

50 nm; 44 m2/g

Stillsold,goodvalue Consistencynotgoodandsizedistributionbroadandincludes

largeparticles(extremelysphericalparticles,sizerangesfrom50to250nm,oxidelayerthickness~3.1nm)

However some original claims of excess surface energy

40nm

However,someoriginalclaimsofexcesssurfaceenergy Itistruethatatverysmalldiametersthereisasurfaceenergy Notsignificantinparticles>10nm KuoandothersshowedtherewasnoexcessenergyinALEX

aluminumusingcalorimetry

10 m, 0.22 m2/g

10m


AgeingandCoatingofParticles

Ageing test with Alex (air saturated 60 C)

AcceleratedAgeing,RoomTemperature,SaturatedHumidity AgeingtestwithAlex (air,saturated,60 C)y

1

1.2H-15 (Al, 38m)

0.6

0.8

t=0hr t=5hrs t=24hrs0.2

0.4

ALEX (nAl)0

0 5 10 15 20 25Time (days)

C.Dubois,P.G.Lafleur,C.Roy,P.BrousseauandR.A.Stowe,JPPVol.23,No.4,JulyAugust2007

SurfacePassivation ofBareAlNanoparticles UsingPerfluoroalkyl CarboxylicAcids(C13F27COOH)y y ( 13 27 )

FTIRSpectrum

C=O

OH

100nmSEM(225000magnification)ofAlC13F27COOH

R.J.Jouet,A.D.Warren,D.M.Rosenberg,V.J.Bellitto,K.Park,andM.R.Zachariah,Chem.Mater.17(2005)29872996.R.J.Jouet,J.R.Carney,R.H.Granholm,Sandusky,H.W.andA.D.Warren,Mater.Sci.Technol.22(2006)422429.

LowTemperatureStabilityandHighTemperatureReactivityofIronBasedCoreShellNanoparticlesy p

Ironnanoparticles madefromsonochemical methodSelfassembledmonolayerofdioctyl sulfosuccinate sodiumsalt(AOT)oroleicacidHexanesolutionofnanoparticles (withandwithoutSAM),airsaturated,andwithpyrene

Fluorescene lifetimeofpyrene usedasanindicationofpresenceofoxygen~450 ns => no oxygen450ns=>nooxygen~20ns=>oxygen(bimolecularquenchingreaction)

TEMofFe0AOT

C.E.BunkerandJ.J.Karnes,JACS126,10852,2004

SelfAssembledNanoscale Thermite Microspheres

60nm 100nm

nAl(38nm) nCuO(33nm)Kalsinetal.,Science, v312,2006

CreateSelfAssembledMonolayer(SAM)onsurfaceofindividualparticles

Monolayers contain a functionalized group atMonolayerscontainafunctionalizedgroupattailend(either+or charged)

Whenmixedinadilutedandslightlyelevatedtemperaturetheyformmacroscalestructureswithnanoscaleconstituents

~4mnAlTMA(trimethyl(11mercaptoundecyl)

nCuOMUA(11 t d i id )(trimethyl(11 mercaptoundecyl)

ammoniumchloride(11mercaptoundecanoicacid)

Malchi,J.,Foley,T.,Yetter,R.A.,ACSAPPLIEDMATERIALS&INTERFACES,1,11,2420,2009

Nanoenergetic CompositesofCuO Nanorods,Nanowires,andAlNanoparticlesp

R.Shendeetal.,Propellants,Explosives,Pyrotechnics33,No.2(2008)

FabricationofReactiveMultilayerFoils Ni/Al,Monel/Al,andNb/Si MagnetronSputterDeposited FreestandingFoils(10150mThick)

&

Stepper

Motor

Bilayer Thicknesses 25to600nm DepositionTemperature~75C

18"SubstrateCarousel

Water&Power

Ni/Al Foil as depositedSputterGuns

34"(5"x12")

Ni/AlFoilasdeposited

Ni/AlRapidReacted

AsDepositedCuOx/AlMultilayerFoilElementalDistributions

FromTimWeihs,TheJohnsHopkinsUniversityCu Al O Cu+O

NanoPatterning ofNanosized Thermites onaChip

PVDbasedprocesstogrownanoscale thermites (Al/CuO andAl/NiO)onaSi/glasschip

EvaporatedCu

C O/Al450C,5hair

Zhang,Rossietal,Applied Physics Letters,2007,2008Petrantoni etal.,J.Phys Chem.OfSolids,2010

Diam.:40 80nm Al/CuO ~150250nm

Al/CuO onsetT=500oCH 2 9 kJ/ 693 l/

CuO/Al

H=2.9kJ/g=693cal/g

Evaporated

xsec tiltedview

h i l l d h

Al/NiO onsetT=400oCH=2.2kJ/g=526cal/g

450C,2h, underaN2/O2 gasflow

NiO/AlNi

30oC,5x106 mbar

Zhang,Rossietal,Applied Physics A94,2009/g /g

Benefits:(1)Enhancedinterfacialcontactandreactivity,(2)impuritiesandAloxidationduringfabricationsmall,(3)sincedimensionsofCuO nanowires canbetailored,theoxidizerfueldimensionscanbecontrolledatthenanoscale,(4)processusesstandardmicrofabrication techniquesformassproductionandintegrationintofunctionaldevices.

TheSolgelMethodology

Condense Super-criticalextraction

Non-supercriticalextraction of

Sola colloid

Gela 3D structure

AerogelLow density / high porosity

extraction ofliquid phase

Inexpensive homogeneity on nanoscale type and amount of

Xerogel

type and amount of components easily varied

Cast complex shapes Low temp. processing g

Low porosity / high densityLow temp. processing

FromGash,LLNLS.F.SonandR.A.Yetter,Nanoenergetics,2012

LLNLDevelopedFourClassesofMaterialsandProcesses

Crystallites grownin pores may beenergetic

Solid skeleton may be energetic

Energetic powdersare added by a gelmending method

1. Solution crystallization 3. Skeletal Synthesis2. Powder addition

This may be a fuel or oxidizer

This may containan oxidizer or fuel

Can be straight-forward to dope with materials

4. Nano-compositesFromGash,LLNL


ArrestedReactiveMillingNanocomposites Top down approach to composite designStarting Materials Topdown approachtocompositedesign

vs.bottomupapproachofsolgelmethodsoruseofnanoparticles

Micronsized,nanocompositepowdersprepared

Starting Materials

byArrestedReactiveMilling:ahighenergyballmillingprocess

Eachindividualparticle is subjected to pressures as high as 5 GPaARM issubjectedtopressuresashighas5GPa

duringcollisions hasthesamecompositionasbulk hasneartheoreticalmaximumdensity

Milling is arrested before the self-Milling is arrested before the selfsustaining reaction is triggered Cross-sectioned starting

mixture: 2Al + MoO3 ARM nanocomposite

Nanocomposite A range of highly reactive materials produced; B/Ti, B/Mg, B/Zr,

Al/Fe2O3, Al/MoO3, Al/CuO, Al/Bi2O3, MgH2/CuO, Al/SrO2, Al/NaNO3, Mg/MoO3, Si/CuO, Zr/Bi2O3, MgH2/MoO3, Mg/CuO

Backscattered electron SEM ImagesFalse color maps: Al: green; MoO3: red

FromDreizen,NJIT

Liquid surfactant (hexane, kerosene) and type of grinding media are selected to adjust the powder size and the degree of refinement at which the reaction is triggered

Batch sizes: 2 g 400 g; batch synthesis time: 20 200 min

HighVelocityParticleConsolidation(Cold Spray)(ColdSpray)

Particlesareinjectedintoaninertgasstream(N2 orHe),thenacceleratedthroughadeLavalnozzletohighspeed.

Void

Particlesimpactsubstrateorpreviouslydepositedmaterialandmechanicallybondwithit.

Nearfullydense(

SiliconReactives CanAlsoBeUsedWh ili f l ?Whysiliconfuels? Theoxidelayerisonly12nmnaturally Aging(oxidation)likelybetterthanAl Generally less sensitive than Al GenerallylesssensitivethanAl Reactives couldbeintimatelyincorporatedinsiliconbasedmicroscale devices

Tuning and switching possibilities (doping/eTuningandswitchingpossibilities(doping/efield/electrowetting)

Somesystemsproducehighertemperatures Nanoporous Si(PSi)vs.NanoSiliconpowder(nSi)p ( ) p ( ) Surfacepropertiescanbemanipulated

Selfassembledmonolayers areappliedtothesurfaceofsilicon,oneithernanoporous substratesorsilicon

i lExamplesofsurfacesproducedth h hit li ht t dparticles

OxidelayerisstrippedoffwithHFleavingahydrogenterminatedsurface.

Fluorocarbonligands arethenattachedtothesurfaceby

throughwhitelightpromotedhydrosilylation reaction.M.StewartandJ.Buriak (2001).

g yThermallyInducedHydrosilylation producingareactivecompositedevoidofunreactive oxide.

Nanoporous SiliconFabrication

ElectrochemicalEtching Typicaletchdepthsof100200mwithreporteddepthsofover500m(thicknessofwafer)

Dopant TypeandConcentration

PoreMorphology(CrossSection)

PlanView TypicalPoreDimensions

nSi 101000nm

wafer). Porediametersand%porositycanverydramaticallydependingontheHFconcentrationandcurrent.

p,p+,n+ Si 101000nm

310nmp Si

HF BathOxidizerLoadingTechniques

Schematicdiagramillustratingthecharacteristicporemorphologiesandtypicaldimensionsasafunctionofdopant typeandconcentration.Searson andMacaulay(1992)

g q Dropcastmethod fillPSi byplacingthePSi inanoxidizersolventsolutionandallowthesolventtoevaporate(canbedoneunderlowpressuretominimize voids and with surfactant additives)

Cross-section SEM image of PSi etched 60mA/cm2 at x35k magnification.

minimizevoidsandwithsurfactantadditives) Meltcasting(e.g.,sulfur) Supercriticalfluidfilling

FunctionalizedGraphene SheetsasCatalystsSupports

SA~850m2/gbyBET&>1800m2/gbymethylene blueadsorptioninsolventsp

TheC/Oratioisadjustablefrom2to500,i.e.,FGS2 toFGS500. GObyStaudenmaier Method(1898) 4foldvolumeexpansion

H.C.Schniepp,etal.,J.Phys.Chem.B (2006)

Theedgescanbecarboxylated.

Additionalfunctionalgroups can be attached

Withfunctionalgroups,thicknessofgraphene sheet~0.78nm

pThermalexpansion(>500fold)at1050C Bhm(1962)

groupscanbeattached.Latticedefectscanfunctionasradicalsites.

FGSisanideal2Dmacromolecularcarrierfornanoparticles.

Exothermicsurfacereactions

a: epoxide ongraphene,b: hydroxideongraphenec,d: inplaneandoverheadviewofaFGS

reactionsTheparticlesizeisbelow1m.

Aksay, I., Princeton 2010.

MetalDecoratedGraphene Sheets

Graphene asatemplatefornanoparticlel i

DFTcalculationsshowthestabilizationofPtnanoparticles attheITOgraphene junctions.

nucleation.

Indiumtinoxide (ITO)nanoparticles arestabilizedonFGSatlatticedefectsites.

Pt ti l t bili d t th ITO Ptnanoparticles arestabilizedattheITOgraphene junctions.

Coarsening/sinteringofPtnanoparticlesis arrested due to their pinning at the ITOisarrestedduetotheirpinningattheITOgraphene junctions.

Theapproachissuitableforotheroxide/metaljunctionsongraphene/ j g ptemplates.

Aksay, I., Princeton and PNNL 2010.

PolymericNitrogenChainsinaGraphene MatrixandConfinedinsideaCarbonNanotube

LargeenergydifferencebetweensingleNNordoubleN=NandtripleNNbonds.Nitrogenbondenthalpies

NN 159kJ/molN=N 419kJ/molNN 946kJ/mol

(N=N)i159+419

|NN|946

368

ab initioelectronicstructureandmoleculardynamicscalculationsdemonstratestabilityofthei h bi d h i l d i l ilnitrogenphaseatambienttemperatureandpressurewhenintercalatedinamultilayer

graphene matrixorusingcarbonnanotube confinement. Thechargetransferfromthegraphene matrixtothenitrogenchainstabilizestheentirethree

dimensionalstructure.The hybridizationbetweenthenanotube andtheNchainconductionybandsleadstothestabilityofthepolymericnitrogen.

Timoshevskii et al., Phys Review B 80, 115409, 2009; Abou-Rachid, H., et al., Phys. Review Letters, 100, 196401, 2008. Christe, K.O., PEP 32, 3, 2007, 194.

UltraHighPressureSupercriticalFluidProcessing of Reactive MaterialsProcessingofReactiveMaterials

RapidExpansionofaSupercriticalSolution(RESS) RapidExpansionofaSupercriticalSolutionintoanAqueousSolution(RESSAS)

S t ti V l Expansion Nozzle C ll ti S tSupercriticalSolution

Controlledat

RapidExpansionforParticleFormationbyHomogeneous

NanosizedParticleRecovery

SaturationVessel ExpansionNozzle CollectionSystem

SelectedTandPHomogeneousNucleation

Recovery

SCF Solute

FESEMimagesof(a)RESSproducedRDXparticlesand(b)militarygradeRDX

ParticleDistributionofRESSRDXParticles FESEMimagesofRDX

coatedALEXnAl particlesfromtheRESSNprocess

Essel,J.,andKuo,K.,PennState,2012

Aluminum clusters have been studied and consist of metallic Al cores surrounded by a monolayer of a

ClusterAssembledReactiveMaterials

AlI + LiN(SiMe ) Al [N(SiMe ) ] 2-

AluminumclustershavebeenstudiedandconsistofmetallicAlcoressurroundedbyamonolayerofaprotectiveshell.

Particles/clustershavebetween10and100aluminumatomsanddiametersbetween0.5and1.3nm.

AlI + LiN(SiMe3)2 Al77[N(SiMe3)2]202

ThreedimensionalperiodicTableofcluster elements. Castleman, A. W., Jr.;

Al cluster (far right) consists of nested shells containing (from left

clusterelements.Castleman,A.W.,Jr.;Khanna,S.N.J.Phys.Chem.C2009,113,26642675.

Alcluster(farright)consistsofnestedshellscontaining(fromlefttoright)13,44,and20Alatoms,A. Ecker,E. Weckert,and H. Schnckel Nature 1997,387,379.

Metalhalidecocondensationreactor(MHCR)andmetalhalidechemistryenablescreationofotherlowvalent metalclusters(e.g.i f Si) ( i hh i i f l d 20 )Ti,Hf,Si) (B.Eichhorn,UniversityofMaryland,2011).

Reactionsofmetalclusterswithsmallmoleculesoftendependonclustersize andvarydiscontinuously withthenumberofatomsandcomposition,ratherthanscalelinearlywithsize,i.e.,oneatommakesadifference.

Clusterscanactasbuildingblocksfornewmaterials.Selfassembledmonolayers (SAMs)forclusterpassivation andsizecontrol.Liganddirectedassociationforaggregateformation.

Some Examples of NanoenergeticsSomeExamplesofNanoenergeticsCombustion

Nanoscale Thermite Combustion

Nanoscale thermites arepreparedviasonication inasolvent(hexanes)( )

Combustionpropagationtestedininstrumentedburntube

AlCuO


Nanothermite CombustionEff t f E i l R ti Eff t f Ch l Si

1000

104

FuelRichPropagationLimit600

700

nAl/nMoO3

EffectofEquivalenceRatio EffectofChannelSize

10

100

000

e

r

a

t

i

n

g

F

r

o

n

t

300

400

500

nAl/nMoO3

0.1

1

FuelLeanPropagationLimit

A

c

c

e

l

e

100

200

300/ 3

0.010 20 40 60 80 100

Mass Weight Percent nAl

p g

00 100 200 300 400 500 600 700 800

Channel Hydraulic Diameter ( m)

Dutro,G.M.,Son,S.F.,Risha,G.,R.A.Yetter,ProceedingsoftheCombustionSymposium,2009

Nanothermites

42 5

3Al/M O

EffectofPackingDensity EffectofParticleDiameteronIgnitionDelay

2 5

3

3.5

11.5

22.5 nanoAl/MoO3

micronAl/MoO3Al/MoO3

1 5

2

2.5

0 50

0.51

1

1.5

1 1.5 2 2.5 3 3.5 4 4.5log (d) [nm]

-1-0.5

0 0.5 1 1.5 2 2.5 3density [g/cm3] g ( ) [ ]y [g ]

J.J.GranierandM.L.Pantoya,Combust.Flame138(2004)373383.M.L.PantoyaandJ.J.Granier,PropellantsExplosivesPyrotechnics30(2005)5362.V.E.Sanders,B.W.Asay,T.J.Foley,B.C.Tappan,A.N.Pacheco,andS.F.Son,J.Propul.Power23(2007)707714.

PropagationMechanismsofNanothermite Reactions

P Pressure Gradient drives gases forwardP Pressure Gradient drives gases forwardConvectionwave

Whenignitedinaburntube,fastnanothermites( l/ l/ l/ )

Pressuregradientdrivesreactionforward

(Al/CuO,Al/MoO3,Al/Bi2O3)reactthroughaconvectivemechanism

Convective burning is driven

Heat Conduction

Convectiveburningisdrivenbythecreationofalargepressuregradientintheporousmixture,andnotbya temperature gradient

Hot gases penetrate the granular mixtureFlame Zone

Temp= Tf

Porous Reactants

atemperaturegradient

PressureTransducers

FiberOpticCables

Conduction waveTemperature gradient drives reaction forward

ConductionwaveTemperaturegradientdrivesreactionforward

ThT0

PowderFilledTube

EffectofPressureonthePropagationRateinaAl/CuONanothermite

/

s

)

V

e

l

o

c

i

t

y

t

i

n

g

i

n

g

V

e

l

o

c

i

t

y

m

/

s

/

s

/

s

NanoaluminumfromNovacentrix (avg.dp=38nm) Nano CuO fromSigmaAldrich(avg.dp=33nm) Studiesconductedinanopticalstrandburner(V=23liters)

V

f

(

m

/

Aspressureisincreased,severaldifferentmodesofpropagationareobservedP t hi h ti d h d d

F

a

s

t

C

o

n

s

t

a

n

t

V

A

c

c

e

l

e

r

a

t

O

s

c

i

l

l

a

t

S

l

o

w

C

o

n

s

t

a

n

t

1

0

0

s

m

~

1

k

m

~

1

m

/ Pressurizedwith3differentgases(Ar,He,orN2)

Pressure(MPa)

Pressureatwhichpropagationmodechangesdependsonpressurizinggas;Hehasahighthermalconductivity

1000 10002 32 3 3+ +Al CuO Al O Cu

100

1000

]

100

1000

]

Ar He

10

100

o

o

t

[

M

P

a

]

10

V

f

[

m

/

s

]

a

t

i

n

g

e

r

a

t

i

n

g 10

V

f

[

m

/

s

]

l

l

a

t

i

n

g

1

s

s

u

r

e

O

v

e

r

s

h

o

s

c

i

l

l

a

t

i

n

g

10 5 10 15

Pa

[MPa]

O

s

c

i

l

l

A

c

c

e

l

e

10 5 10 15

Pa[MPa]

O

s

c

i

l

0.10 5 10 15P

r

e

s

Pa[MPa]

O

s

TemperatureMeasurementsSuggestthattheFinalProductsarenotGasified

2500

3000

3500

[

K

]

e

r

a

t

u

r

e

r

e t

o

i

n

t

t

2 32 3 3+ +Al CuO Al O CuBurnTubePropagationRate~1km/s

u

m

P

r

e

(

K

)

Al/CuO

0

500

1000

1500

2000

Al/CuO

T

e

m

p

e

r

a

t

u

r

e

E

q

u

i

l

i

b

r

u

m

T

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m

p

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e

a

s

u

r

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d

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p

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t

u

r

C

u

b

o

i

l

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n

g

P

o

i

n

A

l

2

O

3

b

o

i

l

i

n

g

p

A

l

b

o

i

l

i

n

g

p

o

i

n

t

p g /CombustionTemperature~2350150K

E

q

u

i

l

i

b

r

i

u

M

e

a

s

u

r

e

d

C

u

B

P

A

l

2

O

3

B

P

A

l

B

P

T

e

m

p

e

r

a

t

u

r

2500

3000

3500

4000

4500

5000

e

r

a

t

u

r

e

[

K

]

m

u

r

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o

i

l

i

n

g

P

o

i

n

t

i

n

t

n

t

3 2 32 + +Al MoO Al O MoAl/CuO

BurnTubePropagationRate~1km/sCombustionTemperature~2150150K

u

m

B

P

P

r

a

t

u

r

e

(

K

)

Al/MoO3

0

500

1000

1500

2000

Al/MoO3

T

e

m

p

e

E

q

u

i

l

i

b

r

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l

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o

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n

35002 3 2 32 2+ +Al Fe O Al O Fe

p

E

q

u

i

l

i

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r

i

u

M

e

a

s

.

M

o

A

l

2

O

3

B

A

l

B

P

T

e

m

p

e

Al/F O

1500

2000

2500

3000

3500

p

e

r

a

t

u

r

e

[

K

]

r

u

m

a

t

u

r

e

l

i

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P

o

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b

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i

l

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o

i

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t

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p

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t

2 3 2 32 2+ +Al Fe O Al O FeBurnTubePropagationRate~0.1m/sCombustionTemperature~1700150K

u

m

B

P

O

3

B

P

B

P

e

r

a

t

u

r

e

(

K

)

Al/Fe2O3

0

500

1000

1500

Al/Fe2O3

T

e

m

p

E

q

u

i

l

i

b

r

T

e

m

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a

M

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F

e

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B

T

e

m

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MetalOxidesVaporizeorDecomposeatLowTemperatures

2 212 +CuO Cu O O

Compound Tmp(K)

Tbp(K)

Tvol(K)

Al 1687 3013 n/a 2 22 2 +CuO Cu O O

2 3 3 4 213 22

+Fe O Fe O O

Al 1687 3013 n/a

Al2O3 2345 3253 n/a

CuO 1500 decomposes 1400

14 8000 14 1 104

2Fe2O3 1855 decomposes 1750

MoO3 1075 1428 n/a

8

10

12

5000

6000

7000

n

[

m

o

l

/

k

g

]

V

Volume

Cu

O

Cu2O (l)

8

10

12

6000

8000

n

[

m

o

l

/

k

g

]

V [Fe2O

3 (s)

FeO (l)

4

6

8

2000

3000

4000

C

o

n

c

e

n

t

r

a

t

i

o

n

[cm3/g]

OCu2O (s)

O2 4

6

8

2000

4000

C

o

n

c

e

n

t

r

a

t

i

o

n

[cm3/g]

2 3

O

Fe3O

4 (s) O

2

Volume

0

2

0

1000

0 1000 2000 3000 4000 5000

C

Temperature [K]

Cu2 CuO

0

2

00 1000 2000 3000

C

Temperature [K]

O2

EffectsofOxidizervs FuelParticleSizeAl min m nanoparticles (38nm) from Technanog micron particles (2 m) from Valimet

Linear Burning Mass Burning Energetic Mass Burning Rate Avg. mass per

Aluminum:nanoparticles (38nm)fromTechnanogy,micronparticles(2m)fromValimetCopperOxide:nanoparticles (33nm)andmicronparticles(3m)fromSigmaAldrich

Rate [m/s] Rate [kg/s] [kg/s] run [g] % mass Al2O3Nano Al/ Nano CuO 977 3.79 3.14 0.31 17.1Micron Al/Nano CuO 658 4.77 4.72 0.58 1.0Nano Al/Micron CuO 197 1.31 1.08 0.53 17.1

Micron Al/Micron CuO 182 2.02 2.00 0.89 1.0

Linear propagation micron Al - micron CuO20

30

e

[

M

P

a

]

1 82 [MPa/s]

microAl/nanoCuO

Linearpropagationratewasmore

dependantontheCuO particlessize

micron Al micron CuO

nm Al - micron CuO

micron Al - nm CuO

nm Al nm CuO

micronAl/micronCuO

nmAl/micronCuO

micron Al / nm CuO

0

10

0 0.0005 0.001

P

r

e

s

s

u

r

e

Time [s]

1.82[MPa/s]

nm Al-nm CuOmicronAl/nmCuO

nmAl/nmCuO20

30

u

r

e

[

M

P

a

]

Time [s]

0.50[MPa/s]

nanoAl/microCuO

22 212 OOCuCuO +

0 200 400 600 800 1000Linear Burn Rate [m/s]LinearBurningrate[m/s]

0

10

0 0.0005 0.001

P

r

e

s

s

u

Time [s]

Evidencethattheoxidedecompositiondrivesconvectiveburning

SiliconReactives Backgroundk Previouswork:

Siliconpowdershavebeenusedinpyrotechnicformulationssincethe19thcentury,howeveritscombustionhasbeenrelatively unstudiedrelativelyunstudied

Thefastreactionofnanoporous siliconfirstreportedin1992byMcCordetal

In 2002 Mikulec et al reported the first solidstate explosive In2002Mikulec etalreportedthefirstsolidstateexplosiveusingporoussiliconandaGd(NO3)3x6H2O

Clment andcoworkersdevelopedanairbagigniterusingoxidizerfillednanoporous siliconwafersp

Examplesofporefillers:NaClO4 x1H2O,Ca(ClO4)2 x4H2O,MagnesiumPerchlorate,Sulfur,PFPE

Thecombustionofsiliconbasedcompositeshasnotbeenpadequatelystudied

PrototypeofPorousSibasedAirbagyp gIgniter(Clment etal.,2007)


PsiNaClO4 BurningRates>3000m/s Poroussiliconfilms6590mthickwerefabricatedusinggalvanicetchingapproachthatdoesnotrequireanexternalpowersupplyaswell as electrochemical etch

PsiNaClO4 reactionusedtodriveflyerplate:

Plateforce~67mN,wellaselectrochemicaletch. 3.2MsolutionofNaClO4inmethanoldropcastonthechip

HR =9.9kJ/ginN2 and27.3kJ/gO2.

,Equivalentpressureonplatearea~3.4kPa

BeckerC.R.,Apperson,S.,Morris,C.J.,Gangopadhyay,S.,Currano,L.J.,Churaman,W.A.,andStoldt,C.R.,NanoLetters,2011

EnergyoutputandinitiationaredependentonthehydrogenterminationofthePsi.

Currano andChuraman,J.MEMs,18,2009.

Propertiesandflamepropagationvelocities

Electrolyte Thickness Poresize Porosity Surface Velocity Velocityy(HF;EtOH) (m) (nm)

y(%) area

(m2/g)

yfromvideo

(m/s)

yfromwires

(m/s)

20:1 6595 2 42 5 6567 830850 3050 310020:1 6595 2.42.5 6567 830850 3050 3100

3:1 6595 2.82.9 7983 890910 2170 2150

ReactionTuningusingOrderedMultiscaleStructureswithnPS:TheReferenceCase

Degeneratelydoped(1 5mcm)substrateswereusedforreferenceSi Substrateswithlowerdopant concentrationsyieldfragileporouslayers Equivalenceratioofthecompositecannotbeaccuratelydetermined

Experimentalprocedure:p p Porouslayerswereetchedon4wafersusingelectrochemicalprocess Theprocesswastunedtoyieldmechanicallystablethickporouslayerswhosesurfacescanbecleanedevenafterimpregnationwiththeoxidizer

Porosity determined gravimetrically by dissolving porous layers in aqueous NaOHPorositydeterminedgravimetricallybydissolvingporouslayersinaqueousNaOH 5mmwidesampleswerescribedsoakedinMg(ClO4)2 methanolsolutions Variedcompositionswerepreparedusingsolutionsofdifferentconcentrations. Equivalenceratiowasdeterminedgravimetricallyaftercleaningthesurfaces

TopviewSideview

5020nm

FESEMimagesofporouslayersetchedondegeneratelydopedsubstrates.BETmeasurementsindicateasurfacearea~350m2/g

50m 300nm

V.K.Parimi,S.A.Tadigadapa,andR.A.Yetter

PropagationRatesandTemperaturesforDegeneratelyDopedSubstrates

Samplesignitedwith10mspulsefrom200WCO2 laser. Propagationrateobtainedfromxtplotsusinghighspeedvideo Reactiontemperatureestimatedusingmultiwavelengthpyrometry witha

t t d l th b t 475 615

No. th measured Speed (m/s)

Temperature (K) = const ~ 1/ ~ 1/2

spectrometerandwavelengthsbetween475615nm.

1 3.8* 1.2-1.24 5-7.7 2044 1897 17692 4.6* 1.2-3.8 2.6-7.7 1869-2184 1747-2018 1639-18763 5 6 3 3-4 6 4 1-4 53 5.6 3.3 4.6 4.1 4.54 6.7 2.4-3.4 2.5-3.3 1844-1930 1723-1798 1617-16835 8.3 4.7-5.1 3.9-4.9 1706-2043 1824-1897 1647-17716 13.5 3.9-5.2 2.4-2.8 1792-1870 1677-1746 1577-16377 16.5 10.3-19.5 3.2-4 2002 1862 17408 33.1 20.4-20.8 2.6 -3 1886-1993 1760-1853 1650-1732

Fuelrichflameextinctionlimit: Samples soaked in 0 1 M solution ( = 80) did not ignite Samplessoakedin0.1Msolution(th =80)didnotignite Samplessoakedin0.15Msolution(th =56,measured =39)ignitedbutdidnotpropagate


ElectrochemicalEtchofSiliconWaferswithDifferentDopingProducesDifferentStructures

Higherspeedsreportedwithmoderatelydopedptypesubstrates(1 20cm) Moderately doped (25 cm boron) substrates were tested to verify higher ratesModeratelydoped(2 5 cmboron)substratesweretestedtoverifyhigherrates Reactionfrontpropagationsbetween3001,000m/swereobservedforthesesubstrates Micrometerscalecrackswereobservedintheporouslayer Porosityandequivalenceratioestimatesarebelievedtobeincorrect(P0.54,th 9.6)

b d d ll d h h h Porositycannotbedeterminedgravimetricallyduetothehighsensitivity

25cmnPS (topview) 120cmnPS25cmnPS (sideview)

(fromPhysicalOpticsCorporation)V.K.Parimi,S.A.Tadigadapa,andR.A.Yetter

OrderedStructuresFabricatedonDegeneratelyDopedSubstrates

Siwafers(highlydoped0.0010.005cm)werephotolithographically patternedusingthicklayersofphotoresist(KMPRorSPR2207)

AnRFRIEprocesswasusedtoetchpillaredstructuresH i h f h i li i d 35 b id ll fil d h i i Heightofthestructuresislimitedto~35mbysidewallprofileandphotoresistproperties

Usingthickerphotoresistlayersaffectsfeaturesizes Thephotoresistwasstrippedandnanopores wereetchedusingtheelectrochemicalprocess

Topview Sideview SurfaceofPillars

p Thickporouslayersareetchedbelowthesurfaces

Thepillarsare~35mtallandhave8msquarebasesseparatedby~8m.Theporediametersonthepillarsandthesubstrateare~20nm.


ReactionPropagationthroughPatternednPS/Mg(ClO4)2 Composite

PatternednPS

r

o

p

a

g

a

t

i

o

n

.................................................................................................................................................................................................................................................................................................................................................................................................................................................................................

D

i

r

e

c

t

i

o

n

o

f

P

r

4

0

m

m

........................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................

D

=

4

1

8

5

sTopView SideView

=

8

9

2

4

s

=

5

9

0

0

s

=

9

8

6

9

s

=

9

8

8

2

s

=

9

8

9

6

s

Thepillarsare~35mtallandhave8msquarebasesseparatedby~8m.Theporediametersonthepillarsandthesubstrateare~20nm.


EffectofDopingSiliconReactives? Why could doping make a difference? Whycoulddopingmakeadifference?

Oxidation-reduction reaction needs the transfer of electrons,likenp semiconductor

Reducing agent is the electron donor oxidizer is the electron acceptorReducingagentistheelectrondonor,oxidizeristheelectronacceptor Therefore,ann-type reducing agent andp-type oxidizer shouldbe

morereactive(McClain(1982)) Schwab & Gerlach (1967) demonstrated this with the thermiteSchwab&Gerlach (1967)demonstrated this with the thermite

reaction,

3 2 22 2Ge MoO GeO MoO+ + ntypeGe acceleratedreaction,ptypeGe slowedreaction EffectonoxidizerdopingalsoshownbyMcClain&Schwabtoimprove

oxidizerreactivity

ExtraElectron

G.M.Schwab,J.Gerlach.TheReactionofGermaniumwithMolybdenum(VI)OxideintheSolidState,Z.PhysikChem.,56:121,1967.

Phos.

DopedSiPowders ProductionandCharacterizationD d d d d b illi ili

D d Si W f D d Si P d

Dopedpowderswereproducedbymillingsiliconwafersinaplanetaryballmillfor3hours

PowderDesignation

Dopant SSA(m2/g)

www.retsch.com

DopedSiWafer DopedSiPowder intrinsic N/A 10.1

lowpdoped boron 10.6

ndoped arsenic 8.9

highpdoped boron 10.2

Powder Type Dopant Resistivity (-cm)

Conductivity (S/m)

wt% dopant

intrinsic N/A 80 1.25 N/Alow p-doped boron 0.015 6.67103 7.910-5 2.1310-4

BETanalysisshowsSSAshouldnotaffectburningrates

SEM images show that all

ParticlesizingcarriedoutbylaserdiffractionuniformparticlesizesweremeasuredbyMalvern

o p doped bo o 0 0 5 6 6 0 9 0 3 0n-doped arsenic 510-3 2.0104 6.5410-2high p-doped boron 3.510-3 2.86104 1.5510-2 4.3510-2

SEMimagesshowthatallpowdershavesimilarmorphologies

Agreewellwithparticlesizinglmastersizer 2000

XRDanalysisperformedwithBruker D8xraydiffractometer Nocrystallineimpuritiesdetected

results Fracturesurfacesonallparticles

S.F.Son,Purdue,2011

DopedPowders ReactionCharacterization BurningratesofpressedpelletsofdopedSi/PTFEat200psiwereanalyzed DopinghasalargeapparenteffectThe effect contradicts the theory Theeffectcontradictsthetheory

Differentialthermalanalysissupportsburningratedata Apparentactivationenergymeasuredbythe dopedSi/PTFEburningratespp gy yKissingermethod

Higherburningratesamplescorrelatewithloweractivationenergysamples

The effect may be kinetic but not according toTheeffectmaybekinetic,butnotaccordingtotheoriginalhypothesis!

ThermalpropertiesverifiedbyTPSmethodtobenearlyidentical

C ld th ll t f d t h

dopedSi/PTFEapparentactivationenergies

Couldtheverysmallamountofdopant havethesameeffectasdopingoftheSicrystals? Thermodynamicallytheamountofdopant hasanegligibleeffectonenergyortemperature

Couldtherebeacatalyticeffect?

S.F.Son,Purdue,2011

DopedPowders Summary

S ll t f b d dd d t SmallamountofboronpowderaddedtointrinsicSi/PTFEduringprocessing

Nanoborondidnotaffectburningrates Howcanobservedresultsbeexplained?Newhypotheses latticedefectsorelectronmobilityaffectskinetics:

Si/PTFE/Bburningrates

Electronmobility Proportionaltodopantconcentration Substitutional impurity

h l [ ] Latticedefectandstrainenergyduetosubstitutionalimpurities

Proportionaltodopant

enthalpy[20]

concentration

GedopedSineededtoeliminateoneoftheabove

20T.Yoshikawa,K.Morita,S.Kawanishi,andT.Tanaka,ThermodynamicsofImpurityElementsinSolidSilicon,JournalofAlloysandCompounds,Vol.490,2010,pp.3141.S.F.Son,Purdue,2011

LikeCarbonNanotubes andNanothermites,Nanosilicon canbeLightActivatedforIgnitiong g

N.Wang,*B.D.Yao,Y.F.Chan,andX.Y.Zhang,NanoLetters,2003,3,475n

CoalDirectChemicalLoopingProcess:ReactionMechanismsofSolidFuelswithMetalOxides

ReductionIndirectreductionwithaidofgaseousintermediates

CO+MO CO2 +MCO2 +C 2CO

Withcoal,volatilesmayinitiatethereactionC l l l til (CO H t ) CO H O

SpentAirforPower GenerationCoal coalvolatiles(CO,H2,etc)

ChemicalloopingoxygenuncouplingprocessMO M+O2C + O CO Reducer/Fuel Oxidizer/

MOCO2,H2O

Coal

PowerGeneration

C+O2 CO2Directsolidsolidreactions

C+2MO CO2 +2MFuel

ReactorAirReactor

M

Ai

OxidationHeterogeneousversusvaporphasecombustion

M + O2 MO

EnhancerGas Air

M O2 MOM+H2O MO+H2

IgnitionandFlamePropagationofCarbonCopperOxideMixtures

8

FingeringRegime

ContinuousRegimeTemperatureControlled

TubeFurnace0.8cmIDquartztube Embeddedfine

5

6

7 nCuOCuO

e

e

d

[

m

m

/

s

]

DirectSolid

~

5

4

0

o

C

CWCO2 Laser(10.6m)70W

for 0.5 s

wireTC

PC/DAQ

2

3

4

p

a

g

a

t

i

o

n

S

p

e

SolidReactionUncoupledReaction

A

u

t

o

i

g

n

i

t

i

o

n

~

for0.5s

C/CuOpowder

Quartzwool(usedforfilling)

HighSpeed

0

1

0 100 200 300 400 500 600

P

r

o

Preheat Temperature [oC]

CuO mixturedidnotselfpropagateat400oC

Camera

800

900

C

)

ContinuousRegime700

800

C

)

FingeringRegime p [ ]

400

500

600

700

e

m

p

e

r

a

t

u

r

e

(

o

C

150C,video1/10th speed 300C,video1/10th speed

300400500600

e

m

p

e

r

a

t

u

r

e

(

o

C

u = 2 0 mm/s

300

400

0 1 2 3 4 5 6

T

e

Time (s)

u = 5.9 mm/s

WeismillerandYetter,PSU

100200

0 1 2 3 4 5 6

T

e

Time (s)

u100

= 2.0 mm/s

u150

= 2.3 mm/s

How are nano reactive systems beingHowarenano reactivesystemsbeingapplied?

SomeExamplesofNanoenergeticsApplicationsApplications

Ingredientsinpropellantsandexplosives Insitu soldering and weldingIn situsolderingandwelding Gunprimers,detonators,electricmatches Airbags MicroactuatorsMicro actuators Micropumps Microthrusters Micro switches Microswitches Microvalves Dispersedcatalysts Drug injection Druginjection Visiblelightemission Activedenial Chemical looping particles Chemicalloopingparticles and,manyothers

N Al i ( Al) h b

ApplicationsofNano Aluminum(nAl)

2

Nano Aluminum(nAl)hasbeenusedinpropellants,explosives,andpyrotechnics

Propellants

1

1.5 rb = 2.538P0.618

Propellants Alcouldignitenear/onthesurface Wouldimproveheatfeedback

fasterburningE l i

0.5

1

0 390

Explosives Reactinthereactionzoneand

affectdetonation Mixedresults

00 0.5 1 1.5 2

log (P) [MPa]

rb = 2.092P0.390

PropellantInitialtemperature=25oC Pyrotechnics

Canpossiblyextendapplicationsofcomposites,suchasthermites(metal/metaloxidereaction,redoxlog (P) [MPa]

Compositepropellantwith18%Al Compositepropellantwith9%nAl (ALEX)/9%Al

( / ,reactions)orintermetalic (suchasAl+NiAlNi)

Reactivestructures

Mench,M.M.,Yeh,C.L.,andKuo,K.K.,PropellantBurningRateEnhancementandThermalBehaviorofUltrafineAluminumPowders(ALEX),inProc.ofthe29thAnnualConferenceofICT,1998,pp.301 3015.G.V.Ivanov,andF.Tepper,ChallengesinPropellantsandCombustion100YearsafterNobel,pp.636645,(Ed.K.K.Kuoetal.,Begell House,1997).

NanoAluminum/IcePropellantsforReplacementofCryogenicHydrogen

Motivation Cyro-propellant performance without cryo shortcomings Nanotechnology for designing and assembling future propellants Multi-functionality for both propulsion and power applications

y g y g1.5dia.x1.5longcenterperforated80nAlicegrain

2Al+3H2OAl2O3 +3H2

Research nAlH2OcompositesarestudiedasameanstogeneratehydrogenathightemperaturesandatfastratesC it h hi h d it d l iti it Compositeshavehighenergydensityandlowsensitivity

Combustionoccurswithoutheatreleasinggasphasereactions&thusmanyflamespreadingandinstabilityproblemsofconventionalpropellantsareeliminated.

10 rb [cm/s] = 4.5*(P[MPa])0.47

Burningratesof38nAl&liq.H2O

nAlicegraininphenolic tube

80

100

EfficiencyofH2production

1

n

i

n

g

R

a

t

e

[

c

m

/

s

]

ADN* CL-20*

HNF*

20

40

60

80

Dp = 38 nm

0.1

0.1 1 10

B

u

r

n

Pressure [MPa]

JA2# HMX* * Altwood, 1999# Kopicz, 1997

0

20

0 20 40 60 80 100 120 140Pressure [atm]

p

= 1.0Risha,G.A.,Son,S.F.,Yang,V.,&Yetter,R.A.,2008

FGSColloidsforEnhancedCombustionLiquid Strand Burner: NM gas-phase chemistry well understood; liquid-phase chemistry not important at low pressures

ab-initio molecular dynamics simulations show that only vacancies functionalized with groups, such as hydroxyls, ethers, and carbonyls greatly accelerate thermal greatly accelerate thermal decomposition of nitromethanethrough reaction pathways in which protons or oxygens are exchanged between the functional groups and nitromethane or its products

CatalysisatVacancies

DecreasingOcontent

Solids loading ~ 0.05 wt% More reduced FGS is a better accelerant than carbon black or FGS of low C/O (mol/mol). Lower deflagration pressure-limit with carbon additives. Reduced performance of carbon black and FGS19 at ~0.2wt% may be due to particle aggregation at liquid/vapor interface, preventing passage of particles into vapor phase. p p p At low FGS concentrations, the loss of surface defects/surface area lowers the burning rate.

(a)and(b)initialconfiguration;(c)and(d)after10 ps;(e)and(f)finalconfiguration

LM.Liu,R.Car,A.Selloni,D.M.Dabbs,I.A.Aksay,andR.A.Yetter,2012.

J.Sabourin,R.A.Yetter,D.M.Dabbs,I.A.Aksay,andF.L.Dryer,2010.

FGSColloidsforEnhancedFuelDecompositionLiquid Sub/Supercritical Reactor

R t T t 820 K (T 1 4)

Liquid Fuel/Particles Mixtures: 0.005wt% FGS in methylcyclohexane (MCH)

Reactor Temperature 820 K (Tr = 1.4)

Reactor Pressure 4.7 Mpa (Pr = 1.3)

Reactor Coil Length 6.4 m

Pump flow rate 0.5 mL/min

Reynolds Number 844

Residence time 14.9 sec

MCH was ~20 % more decomposed with 0.005wt% FGS than without FGS at above conditions. Gaseous products increased by ~ 20%.

4

5

p y Identified components in gaseous products and condensed phase: similar to those without FGS; however, methane (32% increase), ethane (39% increase), ethylene (18% increase), propane (38% 1

2

3

without FGSwith FGS

), y ( ), p p (increase), propylene (25% increase) all increased.

16 8 10 12 14 16

time (s)

Disperable NanocatalystsBoehmite Particle Carboxylatoalumane Particle

+ +

y

M1/Al2O3 CatalystM1nanocatalystFlowreactor

5000ppmi t l

100ppm ind d

SurrogateJP5 =35ms

O2=20%inN2Fuel=0.24vol.%

experiments

intoluene 1000ppm inndodecane

ndodecane

[

C

O

2

]

(

%

)

50ppm 5ppm

0 5 ppmMetalexchangereactiontoreplace aluminum cations (in 0.5ppm

NoCatalyst

~300oC

replacealuminumcations (intheboehmite particle)withmetalcations ofacetylacetonates,e.g.,Pd,Pt,lanthanum cerium etc

Wickman, D.T. et al., J. Russ. Laser Res., 27, 6, 2006T(oC)

ylanthanum,cerium,etc.

ReactiveFoilsforSolderingandBrazingNanoFoil(IndiumCorporation formerlyReactiveNanocomposites)isanewclassofnanoengineeredmaterial.Itisfabricatedbyvapordepositingthousandsofalternatingnanoscale layersofAluminum(Al)andNickel(Ni).Whenactivatedbyasmallpulseoflocalenergyfromelectrical,opticalorthermalsources,thefoilreactstodeliverlocalizedheatuptotemperaturesof1500Cinfractions(thousandths)ofasecond.Today,thislocalized heat is used in many bonding applications ranging from the bonding of sputter targets to backinglocalizedheatisusedinmanybondingapplicationsrangingfromthebondingofsputtertargetstobackingplates,totheattachingofacomponentsuchasanLEDtoacircuitboard.http://www.indium.com/nanofoil/#ixzz1xQC55sjcNanoFoilProperties

Size thickness40150minfreestandingfforms

CompositionBeforeReaction AlternatinglayersofNiandAlCompositionAfterReaction Ni50Al50FoilDensity 5.66.0g/cm3

HeatofReaction 10501250J/gReaction Velocity 6 58 meters/secondReactionVelocity 6.5 8meters/secondMaximumReactionTemperature

13501500C(24602730F)

ThermalConductivity 3550W/mKRoHS Compliant Pbfree

ThermalBatteries Advantages:Higherheatofreactionthanpyrotechnicheatpellets,Flamefrontvelocityof9m/sisconsiderably

Schematic of NanoFoil heated

fasterthanheatpaper;TheNiAlfoilsareelectricallyconductivebothbeforeandafterinitiation;NanoFoil generatesasignificantlysteepertemperaturerisethanpyrotechnicpellets.

Issues:Uponinitiation,thefoilstendtoflowunderpressure;Appliedloaddropsuponinitiation,whichleadstoanincreaseinthebatteryinternalresistance.

Compression

SchematicofNanoFoilheated2cellthermalbattery

Name Composition

Electrolyte LiBrLiClLiF eutectic(435oC)

Electrolytepellet

MgO/E:47/53

Cathode FeS2Cathode pellet C/Fe/E:78/2/20

C th d

MicrothermHeatpaper

Fusestrip

Cathodepellet C/Fe/E:78/2/20

Anode Li/Al:20/80

Anodepellet A/E:90/10

Heatpaper Zr/BaCrO4fibermix

CathodeElectrodeAnode

NanoFoilBuffer

PhotoofNanoFoilheated2cellthermalbattery

TC

Dischargecablescables

Poret,J.C.,Ding,M.,Krieger,F.,Swank,J.,Chen,G.,McMullan,C.,NANOFOILHEATINGELEMENTSFORTHERMALBATTERIES,ProceedingsoftheArmyScienceConference(26th),Orlando,Floridaon14,December2008

DigitalMicrothruster

15-Thruster Unit(Flown on Shuttle)

Three-layer sandwich of silicon and glass

1024-Thruster Component(Silicon Array Nozzle)(Silicon Array Nozzle)

Silicon nitride rupture diaphragms

Divergingnozzles Lead Styphnate

C6H3N3O8PbC6H3N3O8Pb

0.1 mNs of impulse bit 5-100 mN of p100W of power thrust

Lewisetal.,SensorsandActuators80,143154,2000

MEMSbasedPyrotechnicalMicrothrusters

100 addressable microthrusters with 3 main micromachined layers

Combustion chamber 1.5 x 1.5 x 1 mm

3 3 Th t fil ith th t

glycidyle azide polymer (GAP) mixed with AP and Zr particles propellant

zirconium perchlorate potassium primer

3.3

2.8

2.3

Thrustprofilewithathroatdia.of500m

(

m

N

)

1.6

1.3

0.8

T

h

r

u

s

t

(

Polysilicon resistor igniter at nozzle Insulating groves to eliminate cross-talk

M i i i t d d0.3

0.2300 500 700 900

Time (ms) /

Main grain was screen printed under vacuum

100% ignition success with 250 mW Thrusts ~0.3-2.3 mN

Time(ms)ZPPIgniterpeaks Flamepassesthrough

intermediarychamber

GAP/APcombustioninchamber

Rossietal.,SensorsandActuatorsA,121,508514,2005,SensorsandActuatorsA,126,241252,2006.JournalofMEMs,15,6,18051815,2006.

MEMSDevice Integrating Nanothermite Al/CuO

Microinitiator/Micodetonator CuO/Alnanothermite onigniterchip(1mm)Ignitionofapropellant hasbeendemonstrated

Au/Pt/Crthinfilmheater

PatternedSiO2&Cufilms

CuO nano wiresAl/CuO nEM

Zhang,etal,Nanotechnology 18(2007)Zhang,etal,J.ofMicroElectroMechanical Systems,2008

~1W i iti~1Wignitionpower,0.1msignitiondelay,0.12mJ ignitionenergy60mJ outputenergy

1cm3 MEMSSafe ArmFireMEMSintegratesensors,circuitry,actuator,electricalprotections(pyrotechnicalswitches),highlyenergeticmaterial([Co(NH3)6]2[Mn(NO3)4]3 , Al/CuO nanothermite), moving barrier.([Co(NH3)6]2[Mn(NO3)4]3,Al/CuO nanothermite),movingbarrier.

Pezous etalJ.Phys &Chem.Solids 71,(2010)Pezouset al,Sensors andActuatorsA159 2010

Gas generator EMthin layerChipsize1cm

IntegratedNanothermite

A159,2010

JumpingSensorbasedonMEMsFabricationandNanonergetic PorousSilicon

Ignitionofnanoporousenergeticsiliconviaspark

nanoporoussiliconenergetic

resistor

siliconchipIntegratednanoenergeticsiliconandMEMssensor

Churamanetal.,J.MEMs,21,1,198,2012.

CombustionbasedActuatorsA bi i b t it il (AIBN) Azobisiobutyronitrile (AIBN)decompositionasthesolidchemicalpropellant

Successfullypumpeddeionizedwaterthrougha70mmlongchannelwithacrosssectionof100m*50mataflowrateof17ml/minwhileconsumingonly189mJofelectricpowerdecomposed

(Hongetal.,2003)

DrugInjection

Microenergetic Valve

AppliedonARIAN5LaunchVehicle. Designedtoisolate,priorto

actuation, the gaseous fluid presentactuation,thegaseousfluidpresentintheupstreamhighpressuretank(400bar)orpassivation ofthedownstream pressure tankdownstreampressuretank.

Reacttime

What are new directions forWhatarenewdirectionsfornanotechnologyandcombustion?

d ll d f l d

DirectionsForward Towards atomicallypreciseandfunctionalizednanoenergetic material.

D l t ti t i l t f Developsmartnanoenergetic materialstoperformadesiredfunctioninsteadofsimplyreactinginanuncontrolled fashionuncontrolledfashion. ActivatedbyT,P,thepresenceofaparticularchemicalcompound,orexternalstimuli,suchasanelectricalfieldorlight,e.g.,initiateareactionataparticularT,releaseaparticularcompoundataparticularT,transitionfromadeflagration to a detonation at a particular instant in time,deflagrationtoadetonationataparticularinstantintime,turnonorturnoffareaction,oraccelerateorslowareactionwithtimeorlocation.

Developmultifunctionalnanoenergetic systems.

Nanoengineered EnergeticMaterials Atthemicroscale:engineerthenanoenergetic directlyona

MEMSchip

Heat (200 3000C) pressure (kPa Gpa) specific gases Heat(200 3000 C),pressure(kPaGpa),specificgases(neutralgas,ionizedgas)ondemand=>propulsion,power,actuation,instrumentcalibration,pumping,switches,initiators

MEMsfabricationmethodology:softlithography,screenandinkjet printing PVD etc 102inkjetprinting,PVD,etc.

Newfuelsandoxidizers:poroussilicon,nanothermites, 100

101

10

s

i

t

y

(

M

J

/

k

g

)

F

u

e

l

C

e

l

l

NanoEnergetics

andintermetallics

Scaleuptothemacroscale3

102

101E

n

e

r

g

y

D

e

n

s

F

Ultracapacitor

Capacitor

103

102 103 104 106 107105PowerDensity (W/kg)

ChallengesandIssuesf d Scientificoriented

Thermalquenching NewEMformulation Structuralmaterialdevelopment

Engineeringoriented Selection of EM and structural material SelectionofEMandstructuralmaterial Fabricationandintegrationofthedevice IgnitionP l Pressurecontrol

Filling Sealing(Supergluesofar!)

Publicperception,safety,andregulationsaffectthingsalso

Summary Nanoenergetics havenumerouscharacteristicsthatmakethemattractiveforuseinfuelsandenergeticmaterials.F i iti d b ti ti h t Fromanignitionandcombustionperspective,heterogeneousandcondensedphaseprocessesbecomesignificantlymoreimportant.

Fabricationandassemblyofenergeticcompositematerials(byvarioustechniques,selfassembly,coldspraying,ballmilling,solgel gasphase processes etc) are research directionsgel,gas phaseprocesses,etc)areresearchdirections.

CurrentresearchisemphasizingmanipulationofindividualatomsandmoleculestoproduceorganizedMEMsembedded

ltif ti l ti t i l f ti fmultifunctionalnano energeticmaterialsforgenerationofgaspressure(kPaGpa),heat(200 3000C),andchemicalspecies(Neutralgas,Ionizedgas)withhighlycontrollableperformances(rateofheatrelease,)andproperties(sensitivity,stability).

Thank youThankyouQuestions?

nanoengineered reactive materials and their combustion and synthesis revised

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