Improving understanding of energetic materials: Compression behavior and co-crystal synthesis

Przemyslaw DeraUniversity of Hawaii

School of Ocean and Earth Science and TechnologyHawaii Institute of Geophysics & Planetology

ARL Summer MeetingHonolulu, HI, August 20, 2015

Partnership for eXtreme Xtallography:https://sites.google.com/site/partnershipx2/

ThinkTech Hawaii interview about extreme conditions research at HIGP:https://www.youtube.com/watch?v=tM0sErJ6rKg

Our research is supported by:NSF (Geophysics, GeoInformatics, EarthCube and SISI)CDAC/DOE-NNSANASA (ASTID and SERA)

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Structural, electronic and magnetic phase transitions have consequences on physical properties and behavior of technologically-relevant materials and play important role in the energy release from explosives.

These phenomena can significantly affect mechanical/elastic and transport properties, which are often critical for the material’s performance in the field setting. In particular, some phase transitions may lead to catastrophic mechanical failure of armor ceramics or may affect sensitivity of molecular explosives or solid propellants.

Factors that can trigger phase transitions include:• Pressure• Temperature• Stress anisotropy (shear component)• Stress/strain rate

Structural transformations and energetic materials

Polymorphic pressure-induced transformation in Be(OH)2, hydrogen-bonded analog of silicaShelton, Dera et. al. in press

• Effects of temperature and hydrostatic pressure defining stable phase diagrams are fairly routine to measure, and for most fundamental systems have already been established.

• The effects of stress anisotropy and stress/strain rate are even more important/realistic for technological applications, but they are also much more elusive (e.g. path-dependent), harder to quantitatively control and often lead to metastable behavior.

• All of these effects can be measured using novel synchrotron in situ X-ray diffraction techniques developed by our group.

Stress anisotropy and stress/strain rate are capable of:• changing pressure/temperature at which known stable phase

transitions take place (e.g. SiO2 quartz)• inducing new metastable phase transitions (e.g. CuGeO3)• suppressing known phase transitions (e.g. SiO2 cristobalite)• changing deformation mechanism (e.g. SiO2 quartz)

Stress-rate controlled metastability

Polymorphic pressure-induced transformation in SiO2 cristobalite can be suppressed by rapid compression Dera et. al. Phys. Chem. Mineral. (2011)

0.1mm

Ruby sphere

Explosive samples

Polymorphism related to hydrogen bond transformations plays important role in controlling explosive materials stability

• Stable and unstable molecules that have compatible molecular geometries and H-bond formation capabilities can often be combined in co-crystals that inherit a combination of properties of the parent compounds.

• Hydrothermal conditions (high p and T) often promote co-crystal formation

• This route offers possibility for synthesis of hybrid molecular materials with improved properties (e.g. high energy storage and high stability)

Stable molecular analogs of explosives provide convenient test cases to understand hydrogen bond transformations

• s-triazine ring• 6 out of 9 non-H atoms are nitrogen • The molecule in the crystal is not flat because of extensive

intermolecular hydrogen bonding• Stable, fire-retardant properties (used for kitchen laminate

applications)• Molecular geometry compatible with TATB and TNB• Forms co-crystals with some molecular explosives• Synchrotron in situ single crystal X-ray diffraction (below)

provides unparalleled insight into the atomic details of compression behavior

Melamine

0.4

0.5

0.6

0.7

0.8

0.9

1

0 10 20 30 40

Series1Series2Series3Series4Power (Series1)Log. (Series1)

benzene

graphite

melamine

• Two experiments carried out in Ne and He pressure media• No symmetry change or volume discontinuity detected up to 35 GPa• Displacive phase transition at 35 GPa to a triclinic phase• Amorphisation observed above 45 GPa

V/V0

31 32 33 34 35 36

x10^3

5.0

10.0

15.0

20.0

25.0

30.0[ _p _ ]

P=40 GPa P=45 GPa

p [GPa]P=30 GPa

P=1 GPa

de-distance to the nearest atom outside Normalized contact distance dnorm

Synchrotron single-crystal X-ray diffraction and Hirshfeld surface analysis

In situ Raman spectroscopy

Chart1

0000

0.960.611

2.86122

4.731.333

7.722.855

10.468.21010

16.8210.31515

19.8132020

23.5414.82525

253030

37.573535

4040

1

1

1

1

0.9059001477

0.9

0.8929387755

0.9740888383

0.8013417286

0.83

0.8388979592

0.9530182232

0.7326292658

0.72

0.8022857143

0.9353644647

0.6790151321

0.7

0.752244898

0.9068906606

0.6331297264

0.644

0.68

0.8562072893

0.5764365966

0.63

0.6366530612

0.8208997722

0.5619532013

0.62

0.6057142857

0.7935649203

0.5347782344

0.61

0.5820408163

0.7713553531

0.5246928855

0.5628571429

0.7525626424

0.4838305356

0.5465306122

0.736332574

0.5327346939

0.7218109339

Sheet1

Melamine

C1C1b

#p1p2abcbetasasbscsbetaVV/V0# peaksp1p2acsascc/aVV/V0# peaks

010.34837.495027.29499108.464676.53980464571

10.960.969.961017.455227.13241107.0620.00580.00250.0110.059612.8775089240.90590014772660

22.622.869.488937.38876.95258105.5320.00460.0020.00710.043542.13957649180.80134172862.622.862.459466.475270.000670.00282.632801509333.9209526808

34.734.739.157997.330196.82412104.360.00230.00110.00420.022495.65286035970.73262926584.734.73

47.367.728.890467.273656.7111103.4370.00310.00170.00540.037459.38076483390.67901513217.367.72

59.910.468.687697.238716.5531102.4530.00370.0020.00430.031428.33746143740.63312972649.910.46

616.4416.828.384567.14916.40551101.7890.00670.00270.00660.051389.98230243720.576436596616.4416.82

719.5619.88.303737.123096.36673101.8850.00540.00210.00630.053380.18370900220.561953201319.5619.8

822.8923.548.156847.101756.27903101.4460.00240.00110.00350.028361.79876225080.534778234422.8923.54

9258.106237.061286.23778101.471354.97562222140.5246928855025

1037.577.88356.985096.0816100.6010.00240.000830.00210.022327.33061606270.483830535677937.57

11

12

13

14

15

16

17

18

19

20

21

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01

0.60.9

10.838.6666666667

1.30.72

2.80.7

8.20.644

10.30.63

130.62

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water

23.94.212.3Fei

Graphite eos

0.58333333330.6BM33.88.935.12

Benzene eos

1.2661.293V5.58.5245

1.3681.362

benzenegraphite

1.3611.25802451035.121

1.4491.3491218.770.8929387755134.210.9740888383

2205.530.8388979592233.470.9530182232

1.3091.3333196.560.8022857143332.850.9353644647

1.3621.3545184.30.752244898531.850.9068906606

10166.60.681030.070.8562072893

15155.980.63665306121528.830.8208997722

20148.40.60571428572027.870.7935649203

25142.60.58204081632527.090.7713553531

30137.90.56285714293026.430.7525626424

35133.90.54653061223525.860.736332574

7.6637.2720.94897559740130.520.53273469394025.350.7218109339

7.4957.0580.941694463

6.1765.4130.8764572539

6.1235.3180.8685284991nitrobenzene

0592.91

0.49555.40.9367515601

1.35517.80.8733344578

2.08497.60.8392646315

2.99479.10.8080620678

3.984630.7809074043

5.024530.7640411537

6.11446.10.7524034407

Sheet1

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0.00580.0058

0.00460.0046

0.00230.0023

0.00310.0031

0.00370.0037

0.00670.0067

0.00540.0054

0.00240.0024

Sheet2

Sheet3

65

4

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N2 2 0.033455 0.796978 0.115475 11.00000 0.01276N2 2 0.029757 0.799934 0.113758 11.00000 0.01753N2 2 0.018045 0.799036 0.117675 11.00000 0.02098N2 2 0.030143 0.805559 0.113076 11.00000 0.02324

N3 2 0.707571 0.639271 0.058783 11.00000 0.01405N3 2 0.693899 0.647397 0.066185 11.00000 0.02441N3 2 0.699652 0.650523 0.062718 11.00000 0.02817N3 2 0.740326 0.651525 0.054217 11.00000 0.02031

C1 1 0.833214 0.788465 0.064139 11.00000 0.01509C1 1 0.825320 0.795812 0.066598 11.00000 0.01648C1 1 0.828915 0.797313 0.064005 11.00000 0.01323C1 1 0.808847 0.798337 0.072983 11.00000 0.01691

C2 1 0.795297 0.487087 0.132713 11.00000 0.01984C2 1 0.808720 0.490667 0.123755 11.00000 0.01353C2 1 0.799406 0.496328 0.127269 11.00000 0.01622C2 1 0.810320 0.504261 0.122625 11.00000 0.01468

C3 1 0.147620 0.631376 0.163122 11.00000 0.01478C3 1 0.139921 0.635541 0.163381 11.00000 0.01355C3 1 0.122298 0.640362 0.169399 11.00000 0.01657C3 1 0.112577 0.643568 0.170377 11.00000 0.01865

N4 2 0.727265 0.952758 0.020076 11.00000 0.02394N4 2 0.723529 0.957020 0.022047 11.00000 0.02504N4 2 0.724895 0.959673 0.020398 11.00000 0.02220N4 2 0.736925 0.960662 0.016413 11.00000 0.01439

217

N1 2 -0.009735 0.492546 0.188979 11.00000 0.01968N1 2 -0.001734 0.496340 0.181615 11.00000 0.03971N1 2 0.008071 0.473628 0.198305 11.00000 0.00772

N2 2 0.019432 0.806662 0.114229 11.00000 0.02452N2 2 0.022875 0.808356 0.123924 11.00000 0.00788N2 2 0.034763 0.791486 0.117089 11.00000 0.01235

N3 2 0.678334 0.655231 0.075310 11.00000 0.02381N3 2 0.709455 0.666819 0.062674 11.00000 0.00585N3 2 0.705494 0.637070 0.057545 11.00000 0.01249

C1 1 0.827587 0.803060 0.063936 11.00000 0.01946C1 1 0.818940 0.809762 0.070509 11.00000 0.02459C1 1 0.843508 0.788554 0.058878 11.00000 0.01704

C2 1 0.802760 0.503756 0.125009 11.00000 0.01794C2 1 0.822695 0.506484 0.123043 11.00000 0.00027C2 1 0.807157 0.486879 0.125400 11.00000 0.01497

C3 1 0.125019 0.646246 0.162784 11.00000 0.01996C3 1 0.087118 0.641708 0.174496 11.00000 0.04355C3 1 0.139286 0.629702 0.168954 11.00000 0.01552

N4 2 0.732660 0.961679 0.018565 11.00000 0.03245N4 2 0.729616 0.946478 0.010639 11.00000 0.05239N4 2 0.717801 0.954352 0.026667 11.00000 0.015081.5610.6987466428

2.234

0010.50430.18130111

0.96-0.00170.99830.49630.18160.960.99830.98413642671.0016547159

2.86-0.00970.99030.49250.18892.860.99030.97660122941.0419194705

4.730.0061.0060.48750.18454.731.0060.96668649611.0176503034

7.720.0011.0010.48330.19127.721.0010.95835812021.054605626

10.46-0.0050.9950.48170.195110.460.9950.95518540551.0761169333

16.820.0051.0050.47890.196616.821.0050.94963315491.084390513

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23.54

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8.6666666667-9.6666666667-11.6666666667

-1-3

7.66666666675.6666666667

16.333333333314.3333333333

25

PX2 Partnership for eXtreme XtallographyNew Advanced Experimental Facility of HIGP at Argonne National Laboratory

X-ray beam: Bending magnet source, 30 keV fixed energy, 10x15 micrometers focal spot size

Goniometer: Unique six-circle diffractometer high rotation speed (up to 15deg/sec), high precision of rotation ( less than 10 micrometers sphere of confusion)High load capacity (up to 25 lb)

Detectors: Mar165 CCDUltrafast Perkin Elmer XRD1642 flat panel pixel array detector (30 exposures/sec)

Laser optics: Online Raman spectroscopyUnique laser heating system for single crystal experiments including 200 W NIR fiber laser

Mission: Advanced research at conditions of extreme pressure, temperature and strain rates, exploring structure, defects, strain, and transformations of minerals and materials of technological interest

Access: Up to 50% beam time available for high pressure experiments

In house facilities for extreme conditionsresearch at HIGP:

Diamond anvil cellsDynamic compression membrane setup NIR laser heating CO2 laser heating In situ ambient and high temperature Raman

spectroscopy in DACLarge volume presses for sample synthesis

Our facilities

Improving understanding of energetic materials: Compression behavior and co-crystal synthesisSlide Number 2Slide Number 3Polymorphism related to hydrogen bond transformations plays important role in controlling explosive materials stabilityStable molecular analogs of explosives provide convenient test cases to understand hydrogen bond transformationsSlide Number 6Slide Number 7