Compression behavior and co- crystal synthesis · 2017-08-31 · Improving understanding of...
Transcript of Compression behavior and co- crystal synthesis · 2017-08-31 · Improving understanding of...
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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)
http://www.google.com/url?sa=i&rct=j&q=&esrc=s&frm=1&source=images&cd=&cad=rja&docid=CMrSHp--QuUGjM&tbnid=Ny-F8893IF9c9M:&ved=0CAUQjRw&url=http%3A%2F%2Fmanoa.hawaii.edu%2Freis%2Fpartners%2F&ei=1RqlUcv9B9DsqQG_7oDABw&bvm=bv.47008514,d.aWc&psig=AFQjCNFonMRLmh_RSXo6sZ93KgUE-QRpTg&ust=1369861196943743http://www.google.com/url?sa=i&rct=j&q=&esrc=s&frm=1&source=images&cd=&cad=rja&docid=CMrSHp--QuUGjM&tbnid=Ny-F8893IF9c9M:&ved=0CAUQjRw&url=http%3A%2F%2Fmanoa.hawaii.edu%2Freis%2Fpartners%2F&ei=1RqlUcv9B9DsqQG_7oDABw&bvm=bv.47008514,d.aWc&psig=AFQjCNFonMRLmh_RSXo6sZ93KgUE-QRpTg&ust=1369861196943743https://sites.google.com/site/partnershipx2/https://www.youtube.com/watch?v=tM0sErJ6rKg
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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
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• 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
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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)
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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
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0.4
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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
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C1C1b
#p1p2abcbetasasbscsbetaVV/V0# peaksp1p2acsascc/aVV/V0# peaks
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10.697.537.36111.9549.6950595483
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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
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10166.60.681030.070.8562072893
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20148.40.60571428572027.870.7935649203
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6.1235.3180.8685284991nitrobenzene
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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