FACILITIES AND EQUIPMENT
The energetic materials group has 15,000 sq. ft. of lab, office and conference space in the Richard E. Beaupre Center for Chemical & Forensic Sciences at URI campus. In addition, thirteen miles from campus we own our own explosives range. It is situated on 2200 acres of wildness, and has two outdoor and one indoor magazines, a 2200 ft2 firing chamber, a 200 ft2 cookoff chamber, a chemical and tool storage. The firing range has a 30 lb TNT equivalence rating. We maintain ATF licenses to store and manufacture explosives, and have DOT shipping exemptions (25 g solid and liquid) and DEA schedule 1 and 2 licenses. Our firing site manager is also a member of the Rhode Island state bomb squad.
1. Chromatography/Mass Spectrometry Equipment
4. Surface Chemistry Analysis Equipment
5. Explosive Sensitivity and Stability Testing Equipment
GAS/LIQUID CHROMATOGRAPHY AND MASS SPECTROMETRY
With technology moving forward and the advent of new instrumentation and techniques, mass spectrometry is becoming a "work horse" of modern age detection and identification of all types of molecules. Unlike in the past when most of the separation of small molecules was primarily done using gas chromatograph (GC) coupled to various commonly used detectors, including mass spectrometers, today most of detection and separation is performed using liquid chromatograph (LC) coupled to mass spectrometer, UV, fluorescence and other types of detectors. The advantage of using LC technique is the ability to analyze more polar and thermally labile compounds without additional workup. Most of energetic materials would, as a result, automatically benefit by transitioning from gas to liquid chromatography for their detection and quantification. However, if the headspace is of concern, or lower and more sensitive detection limits are in order, then gas chromatography is still a very relevant technique for these types of applications. Our lab currently employs both chromatography methods to get overall unbiased results for small molecules elucidation, detection and quantification. The power of mass spectrometry adds additional level of certainty by providing the mass of the compounds that we are trying to identify, and provides accurate mass measurements of up to 5 decimal points and lower than 2 ppm mass shifts in the case of Orbitrap™.
Thermo LTQ Orbitrap XL ion Trap-Orbitrap™ Mass Spectrometer. This instrument is capable of performing a wide range of application from large molecules discovery (proteomics, metabolomics, etc.) to small molecules elucidation (forensic applications). Having linear ion trap instrument in tandem with Orbitrap™ provides enhanced flexibility of fragmentation experiments for advanced applications in molecule research. HCD collision cell, provides the capability of acquiring spectra similar to triple-quadrupole mass spectrometry techniques. Orbitrap’s mass accuracy lowers false positive rates, high resolution leads to high confidence results. Parallel acquisition mode streamlines productivity and provides comprehensive structural information. This instrument provides high MS and MS/MS sensitivities, wide dynamic range and fast cycle times."
Thermo Exactive™ Orbitrap Mass Spectrometer. Main objective of this instrument is to screen, identify and quantify compounds in complex samples rapidly and with high confidence. This small scale bench top instrument provides high resolution, accurate mass data and rapid full scan capabilities to increase throughput. With resolving power of up to 100,000 FWHM and better than 1 ppm accuracy, it is an ideal instrument for wide range of forensic, clinical and other type of research applications. Its easy-to-use approach gained it a wide spread use in environmental, food safety, clinical, forensics and academic laboratories. This instrument became one of our main screening tools for wide variety of energetic materials and bio-transformation work.
Sciex QTRAP® 5500 LC-MS/MS System. This is one of the most innovative triple quadrupole mass spectrometers available for research purposes. Added capability of linear acceleratorTM trap technology allows the scientists to perform MS3 experiments. The speed and unparallel sensitivity enables solution-based workflows that help us to solve problems that other mass spectrometers cannot. This instrument adds capability to run multi-reaction monitoring (MRM) experiments for trace level quantification, and at the same time collect full scan data for future data mining. In addition to providing very low limits of detection, QTRAP is used for targeted analyte identification in "omics"-sphere, but also is a valuable tool in independent data analysis for sensitive compound identification and confirmation in a single run. Most of our quantification work is solely devoted to this instrument, with recent transitions to biotransformation identification and screening for targeted analytes.
Agilent 6890 Gas Chromatograph (GC x 4) and 5973 MSD (x2). This instrument is designed with dual split/splitless injector port and suitable for wide variety of applications, including: hydrocarbon processing, food safety, pesticide determination, chemical, biochemical, forensic applications and others. It is known to be robust and delivers unprecedented levels of performance, convenience, and ease of applications. Supported sample introduction techniques are direct headspace and solvent-based injections, but can be retrofitted for solid-phase micro-extraction or on-column injections. The power of mass spectrometry offers reliable spectral library search to identify compounds of interest. Other detectors that are widely used for energetic materials detection are FID and ECD, both are available in our lab.
Thermo Trace Ultra™ GC with ISQ™ 7000 MS is another system in our lab that provides extra versatility in our routine applications. This instrument is equipped with head space autosampler and retrofitted for SPME injection. Low detection limits and a unique ion path for neutrals eliminations, provides us with robust methods for explosives vapor detection. Easy of use software enables routine detection of newly synthesized energetic materials and comparison to tabulated database on regular bases.
Thermo Flash 2000 Elemental Analyzer Coupled with Delta V™ Isotope Ratio Mass Spectrometer. This fully automated elemental analyzer allows us to examine isotope ratios of C, N, S, O and H, which are the most common building blocks of explosive materials, as well as other organic compounds. This instrument provides us with ability to discover the source, and predict mechanistic routes of the final product subjected to specific synthetic pathways. Two modes of operations (Combustion and High Temperature conversion) allows simultaneous separation of both N2 and CO2 or H2 and CO, depending on our needs of application. Embedded TCD permits stand-alone determination of elemental weight percentages, enabling structural confirmation for other analytical techniques.
Teledyne ISCO CombiFlash® Rf 150. Our purification and fractionation system becomes very important and essential during complex synthetic workup. We are heavily relying on this system for purification of our in-house made standards. The chromatographic system operates at up to 150 psi pressure and uses mass spectrometer as a detector in either ESI or APCI modes. Certain compounds will only ionize under ESI conditions and would not produce any signal in APCI mode, and vice versa; having both sources minimizes the chance that we will miss compounds of interest. In cases when compounds do not ionize at all, we have orthogonal UV detector which helps us resolve that problem.
OTHER CHROMATOGRAPHY RELATED EQUIPMENT:
A large part of energetic materials research is the thermal behavior of these compounds. For a long time, this has been the foundation of our lab’s energetic materials research. Differential scanning calorimetry (DSC) is an integral instrument in the laboratory; we can screen on the small scale for adverse interactions between materials, as well as look at the thermal properties (ie. melting, decomposition) for energetics. We can look at very small thermal events (just fractions of a watt!) using a thermal analysis monitor (TAM), or even go to a larger scale and look at combustion (Parr Bomb Calorimetry) or even detonation (Parr Detonation Calorimeter) all right in our laboratory.
TA Instruments DSC Q100 is the “work horse" of our research group. Ease of use and accuracy of measurements make this instrument a good first technique for screening energetic materials whether novel or published. Combined with our in-house developed DSC sealer, which creates hermetically sealed glass capillary tube, it takes advantage of controlled environment and provides us with extra versatility in our routine analysis.
TA Instruments TGA Q5000 – Nicolet 6700 FTIR – MS. The Q5000 TGA provides measurements of mass loss or absorption of materials at temperatures ranging from 5 to 1000 °C. With a mass sensitivity of less than 0.1 µg this instrument can detect very minute changes in the sample’s mass. With the Nicolet FTIR attached, any gasses that are evolved can be analyzed. Additionally, if required, this instrument can be retrofitted with a mass spectrometer to provide mass-to-charge information on samples under investigation. By comparing data from the mass spectrometer to our library, we can identify the gasses present.
TA Instruments SDT Q600 Simultaneous DSC/TGA. This instrument measures what is done separately by a DSC and TGA simultaneously. It is able to measure both the mass and thermal energy change of a sample. Whenever we need to achieve higher temperature than what the DSC can provide us, we turn our attention to the data produced by Q600. The true differential heat flow on the sample can be performed from ambient to 1,500 °C. With heating rates anywhere from 0.1 to 25 °C, sample capacity of up to 200 mg and balance sensitivity of 0.1 µg, we can rely on getting right measurement for even most complex samples.
TA Instruments TAM III Isothermal Calorimeter. Whenever we need to find the binding constants or the heat evolution from our samples we refer to our isothermal calorimeter. With a temperature range from 2 to 150 °C and temperature stability of ±0.0002 °C, this was never easier. Most of the explosive materials and organic compounds have melting points within this region, and it gives us a very reliable data. With baseline stability of 0.02 µW/h and noise level of 2.5 nW, we can observe even smallest of the events without missing any information. Perfusion type of the experiments provide us with the insight of what can happen to our materials, if we mix it with other solvents or analytes. The binding constants can be calculated that way, as well. If sorption experiments are needed to be performed, we can add various gases to the setup. Overall, it is a very versatile instrument, with a capability of performing various types of tests based on our needs – anywhere from nanocalorimeter to macrocalorimeter scale.
Parr Instrument Company 6790 Detonation Calorimeter. This instrument was solely designed to handle high explosive compounds. Whenever we need to assess the heat of detonation of our synthesized energetic materials, we use this piece of equipment. With only few ever produced, we are proud to own one and use to test our materials. This calorimeter is rated up to 25 g of TNT equivalent high explosive charge, with a nominal total energy release of ≈160 kJ. Calorimetric measurements could be made within few hours, with a precision of several tenths of a percent. The spherical bomb is made of 3.2 cm thick stainless steel shell, with an inside diameter of 21.6 cm and internal volume of 5.3 liters.
Parr Instrument Company 6200 Isoperibol Calorimeter and 6510 Water Handler. This is instrument allows us to measure energy release of all tested materials either under oxygen or inert environment for comparison. It lets us to test small scale samples of pyrotechnic mixtures, and capture released gases for future analytical testing. With additional precise pressure gauge probe, we can measure the amount of pressure is released by initiating various mixtures of energetic materials.
Spectroscopic methods were a backbone of analytical chemistry for a long time, mainly due to established and well understood principles. Additionally, what helped these techniques to prosper, was the fact that introduced instrumentation was easy to use and cheap to acquire. These characteristics assured the spread of spectroscopic devices into virtually any laboratory as standalone systems, or eventually as tandem methods coupled to newly emerging and compatible techniques. Because molecular behavior observed on these systems was well documented, spectroscopic instruments became an essential part of many research laboratories. Most of these methods rely on the measurement of radiation intensity as a function of wavelength. We take advantage of our array of spectroscopic devices to probe the molecular structure, dynamics and behavior for all compounds that we investigate. Each type of instrument provides a slightly different answer to our questions and guides us towards achieving better scientific results.
Rigaku MiniFlex 600 Benchtop Powder X-ray Diffractometer (XRD). Powder XRD is used for analyzing the crystallinity of a sample. Crystal planes of the sample act as a grating, which coherently scatters the light providing a unique pattern based on the lattice spacing of the sample. These patterns can be compared to a standard or a library diffraction pattern for identification. Using powder XRD we can differentiate between polymorphs of energetics (whether organic or inorganic), as well as detect non-covalent interactions between materials. With our recent work in the synthesis and application of metal organic frameworks (MOFs), we can use the MiniFlex to ensure that we have a structurally correct sample.
Rigaku Nex QC+ QuantEZ, X-ray Fluorescence (XRF). XRF is a non-destructive technique to measure elements Na through U in solids, liquids, powders and alloys. Using a 50 kV X-ray tube the instrument sends a photon of sufficient energy (> energy binding the electron to the atom) which ejects an electron from an atom. The fluorescent emission is characteristic of particular transitions in elements and can be used for characterization. XRF can give us information about metal impurities in samples as well as elemental composition of post blast residue.
Andor/Ondax Raman Laser System with Spectrophotometer. The innovative new development in the THz-Raman spectroscopy allows us to “fingerprint” our compounds in terahertz/low-frequency regime. This region is full of important structural information about the molecule or its crystal lattice. This instrument enables us to simultaneously analyze both molecular structure and chemical composition. We can monitor the formation of our products real time in vitro and predict the mechanistic pathways that possibly take place. As with many organic compounds polymorphism can be an issue, and terahertz region help to differentiate between these types of compounds. One of the benefits of monitoring reaction real time we can observe co-crystal formation or use it for advanced forensic applications. The explosive detection and analysis, including formulation methodologies are greatly benefit from using this method.
OTHER SPECTROSCOPY RELATED INSTRUMENTS:
SURFACE CHEMISTRY/MATERIALS SCIENCE
Surface chemistry of newly synthesized materials is an extremely important feature to be able to establish. There are many instances when one needs to know the topography, porosity or viscosity of compounds under investigation among myriad of other factors. The absolute measurement techniques are still in use, but getting replaced with modern instrumentation to speed up the process and allow not only physical determination, but also measurements of chemical processes in real time. Our lab is equipped with most modern tools to help us to investigate any properties needed for characterizing energetic materials, molecular organic frameworks, polymers and any compounds in general. We are trying to push innovative technologies forward and establish new methods to solve any arising chemistry problems.
TA Instruments ARES G2 Rheometer. This instrument is used to predict materials failures based on two independently measured variables – stress and strain. We can predict viscosity of semi-fluidic materials based on their accurately measured stress and its strain rates. ARES G2 is the most advanced rotational rheometer currently available for research and material development. It features dedicated actuator for deformation control, torque rebalance transducer and force rebalance transducer for independent and simultaneous shear stress and normal stress measurements. We use this instrument to measure viscosities and shear rates of newly developed metal organic frameworks, and multiple-part foam mixtures. With integrated temperature control we can predict the structural failure of new materials based on their shear and stress rates.
Micromeritics Accelerated Surface Area and Porosimetry System 2020 Plus. We rely on this instrument to measure the porosity and surface areas of materials, including newly synthesized metal organic frameworks. Additionally, we can measure the sorption of various gases to the surface of these materials with newly added feature. This will allow us to predict which iteration of the material suits better for specific environmental and forensic application for capturing particular gases or contaminants.
Horiba LA-950V2 Particle Size Analyzer. This instrument helps us to determine the particle size distribution of metal organic frameworks, and makes it easier to standardize synthesis method to acquire more consistent results. It is capable of analyzing particle sizes in the range from 10 nm to 3 mm, with accuracy of 0.6%. It features fast scan rates and high-speed analysis for off-line particle grow control.
EXPLOSIVES SENSITIVITY EQUIPMENT
TRANSPORTATION SECURITY ADMINISTRATION DEVICES
RANGE FACILITIES, CAPABILITIES AND EQUIPMENT
We offer access to testing facilities and equipment as well as technical and intellectual support to all our collaborators. The range is conveniently located within 30 minute drive from major transportation hubs: Amtrak and T.F. Green International Airport. Because of our extended expertise in the field of energetic materials, we constantly try to improve our detection techniques and use them to drive the technology forward. On-site laboratory lets us extend our research efforts into the field settings, but still have the ability for sample preparation, handling, and disposal. We often host general hands-on experiments and demonstrations for large groups of qualified personnel, to demonstrate novel developments in threat detection, mitigation, and analysis.
On-site Laboratory and equipment:
WORKSHOP CAPABILITIES AND EQUIPMENT
Research at the URI Energeics Laboratory often requires unique parts for workholding, instrument repair, and instrument retrofit. Equipment at the main lab includes equipment found both in traditional machine and fabrication shops as well as modern 3D prototyping maker spaces. In addition to a variety of hand tools, the shop has three fused deposition modeling (FDM) printers capable of printing in ABS, PLA, PET, Nylon, and other plastics, and one selective laser sintering (SLS) printer for printing in 17-4 stainless tool steel. Other machines include a metal lathe, mini mill, CNC plasma table, CNC laser cutter/engraver, drill press, band saw, industrial ovens, and sandblasting and powder coating equipment. Additional equipment for larger scale parts can be found at our range facility, which is also equipped with its own workshop for prototyping.
MakerBot Replicator 3D Printer (3x). These versatile and easy to use 3D-printers help us to prototype our new parts in very quick and efficient way. Multiple types of plastics are suited for printing applications, which expands our abilities to use these parts for various applications. This approach often saves us time and money for introducing new technologies for our experimental setups.
3D Systems ProX DMP 100 Metal Printer. This printer is designed for manufacturing of small, complex fine detail metal parts at high quality for our more rigorous applications. With a build volume of 100x100x100 mm and atmospheric controlled external recycling station we can print 17-4PH stainless steel parts. This instrument features of up to 5 Ra µm surface finish quality and sharpest corner radiuses, with typical accuracy of ± 50 µm.
Fisher Scientific – Isotemp Vacuum Oven Model 282
Fisher Scientific – Isotemp Oven (3x)
Fisher Scietific – Upright Explosives Handling Freezer
Agilent – Ovens for Isothermal Analysis (4x)
Organomation – OA-SYS Multivap System 118
Organomation – OA-HEAT Evaporator
Biotage – TurboVap LV
Eppendorf – 5702 Centrifuge
Resodyne Corporation – LabRam Sonic Mixer
Resodyne Corporation – LabRam Sonic Coating Mixer
Enerpac – Mechanical Press
Vacuum Atmosphere – Glove Box
Parker Balston – Hydrogen Generator
Parker Balston – Nitrogen Generator
Metter Toledo – XS205 Dual Range Analytical Balance (3x)
Metter Toledo – MT5 Microbalance
Metter Toledo – XPE26 Microbalance
Metter Toledo – AL204 Analytical Balance