10 Search Results

Many structure/property relationships of hydrolyzed poly(ester urethane) (PEU) – a thermoplastic – have been reported. Examples include changes in molecular weight vs. elongation at break and crosslink density vs. mechanical strength. However, the effect of molecular weight (or molar mass) reduction on some physical, thermal, and chemical properties of hydrolyzed PEU have not been reported. Therefore, a large set of hydrolyzed PEU (Estane®5703) samples were obtained from two aging experiments: 1) accelerated aging conducted under various environments (air, nitrogen, moisture) and at 64 °C and below for almost three years, and 2) natural aging conducted under ambient conditions for moremore » than three decades. The hydrolyzed samples were characterized via multi-detection gel permeation chromatography (GPC), thermogravimetric analysis (TGA), modulated differential scanning calorimetry (mDSC), UV–vis spectroscopy, nuclear magnetic resonance (NMR), and Fourier-transform infrared (FTIR) spectroscopy techniques. Hydrolysis of ester linkages in the soft-segments decreases both the molecular weight (M_w) and the melting point (T_m) of Estane (from ~55 °C to 39 °C). Aging above this T_m, increased mobility of polymer chains and water diffusivity in the PEU matrix alter the PEU degradation pathway from those expected at aging temperatures below this T_m and have significant bearing on the critical molecular weight (M_C) at which the physical, chemical, thermal, and mechanical properties of Estane change abruptly. While a M_C value of 20 kDa is found for PEU hydrolysis at mild temperatures (e.g., as low as 39 °C), the value of M_C increases with increasing aging temperatures. To complement the existing structure/property relationships reported in the literature, more correlations are obtained, which include the effect of M_w on polydispersity, intrinsic viscosity (Mark-Houwink equation), UV extinction coefficient, and dn/dc (GPC analysis) values. Furthermore, we seek to bolster previously reported aging models for PEU by developing a practical model with which the extent of degradation and material performance can be predicted based on aging under different temperature ranges both above and below the melting point of Estane.« less

Two historic-period metal artifacts were provided by the New Mexico Historic Sites to Los Alamos National Laboratory for non-destructive analysis. The artifacts were a crossbow quarrel (or bolthead) and a reliquary pendant recovered from Kuaua Pueblo (also known as the Coronado Historic Site) in Bernalillo, NM. The quarrel is a heavily patinated metal that had been flattened due to compressive forces. The pendant consisted of a metal casing that had previously surrounded two center gemstones on the front and rear face of the pendant. The gemstone in the rear setting had fractured and was displaced from the setting, leaving onlymore » a small, loose fragment within the pendant for study. The front gem appeared to be very dark, near-black in color, and the fragment of the rear gem was a bright red color. The artifacts were analyzed to ascertain their composition and glean insight into their provenance using the following X-ray techniques: X-ray computed tomography, confocal micro X-ray fluorescence, and X-ray diffraction. Infrared spectroscopy and electron microscopy were used on selected areas. Ultraviolet Raman spectra were collected on the two gems and the pendant. The metal material of the artifacts was found to be primarily composed of copper. The gems in the pendant were composed of manganese (front gem) and calcium (side gem).« less

In the thermal aging of nitroplasticizer (NP), the produced nitrous acid (HONO) can decompose into reactive nitro-oxide species and nitric acid (HNO₃). These volatile species are prone to cause cascaded deterioration of NP and give rise to various acidic constituents. To gain insight on the early stage of NP degradation, an adequate method for measuring changes in the concentrations of HONO, HNO₃, and related acidic species is imperative. The typical assessment of acidity in nonaqueous solutions (i.e., acid number) cannot differentiate acidic species and thus presents difficulty in the measurement of HONO and HNO₃ at a micromolar concentration level. Usingmore » liquid–liquid extraction and ion chromatography (IC), we developed a fast and unambiguous analytical method to accurately determine the concentration of HONO, HNO₃, acetic/formic acids, and oxalic acid in aged NP samples. Given by the overlay analysis results of liquid chromatography coupled with quadrupole time-of-flight mass spectrometry and IC, the prominent increase of produced HONO after the depletion of antioxidants is the primary cause of HNO₃ formation in the late stage of NP degradation, which results in the acid-catalyzed hydrolysis of NP into 2,2-dinitropropanol and acetic/formic acids. Our study has demonstrated that the aging temperature plays a crucial role in accelerating the formation and decomposition of HONO, which consequently increases the acidity of aged NP samples and hence accelerates the hydrolyzation of NP. Therefore, to prevent NP from undergoing rapid degradation, we suggest that the concentration of HNO₃ should be maintained below 1.35 mM and the temperature under 38 °C.« less

In the eutectic mixture of bis(2,2-dinitropropyl) acetal (BDNPA) and bis(2,2-dinitropropyl) formal (BDNPF), also known as nitroplasticizer (NP), n-phenyl-β-naphthylamine (PBNA), an antioxidant, is used to improve the long-term storage of NP. PBNA scavenges nitrogen oxides (e.g., NO_x radicals) that are evolved from NP decomposition, hence slowing down the degradation of NP. Yet, little is known about the associated chemical reaction between NP and PBNA. Herein, using liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QTOF), we thoroughly characterize nitrated PBNA derivatives with up to five NO₂ moieties in terms of retention time, mass verification, fragmentation pattern, and correlation with NP degradation. The propagationmore » of PBNA nitration is found to depend on the temperature and acidity of the NP system and can be utilized as an indirect, yet reliable, means of determining the extent of NP degradation. At low temperatures (<55 °C), we find that the scavenging efficiency of PBNA is nullified when three NO₂ moieties are added to PBNA. Hence, the dinitro derivative can be used as a reliable indicator for the onset of hydrolytic NP degradation. At elevated temperatures (≥55 °C) and especially in the dry environment, the trace amount of water in the condensed NP (<700 ppm) is essentially removed, which accelerates the production of reactive species (e.g., HONO, HNO₃ and NO_x). In return, the increased acidity due to HNO₃ formation catalyzes the hydrolysis of NP and PBNA nitro derivatives into 2,2-dinitropropanol (DNPOH) and nitrophenol/dinitrophenol, respectively.« less

As an antioxidant, N-phenyl-β-naphthylamine (PBNA) inhibits the activity of oxidants, such as NO_x, to prevent the degradation of energetic materials. In the presence of NO_x, nitrated products can be generated in the process potentially. To characterize nitrated PBNA in a nontargeted analysis of complex samples as such, liquid chromatography tandem quadrupole time-of-flight (LC-QTOF), as an excellent analytic technique, is used due to its high resolution and sensitivity. However, a systematic approach of instrumentation optimization, data interpretation, and quantitative determination of products is needed. Through a step-by-step evaluation of the instrumental parameters used in the Q0, Q1, and Q2 compartments ofmore » LC-QTOF, optimal ion yields of precursor ions and high-resolution MS² fragmentation spectra at low mass defects were obtained in both negative and positive electrospray ionization modes. Through rationalization of the fragmentation pathways and verification using theoretical masses, the mononitro derivative of PBNA was accurately identified as N-(4-nitrophenyl)-naphthalen-2-amine and further confirmed using a reference standard. Using strict criteria provided by the analytical guidelines (e.g., SANTE), limit of quantitation, limit of detection, and calibration were established for the quantitation of PBNA and nitrated PBNA. From optimization to characterization and subsequent quantification of the mononitro-PBNA derivative, for the first time, the applicability of this strategy is demonstrated in the aged energetic binders.« less

Air impermeability has been observed in low-density aerogel and cryogel materials, which has led to a series of experiments to investigate the feasibility of an air buoyant vacuum vessel, as well as the fabrication and testing of sub-buoyant prototypes. Here, bulk samples of silica aerogel were shown to isolate vacuum from ambient air for several hours with optimal vacuum isolation occurring at a density of approximately 85 mg cm^–3. It was demonstrated using polyimide aerogel and cryogel materials that the ability of these foam materials to provide an air impermeable layer between vacuum and atmosphere, in spite of being comprisedmore » of mostly void space, is related to material stiffness. It is hypothesized that this behavior is due to local deformation of the random nanostructure of the material. Spherical shell vacuum vessels were produced using the polyimide cryogel, and less than 133 Pa vacuum containment was demonstrated under active pumping. In order to approach the non-buoyant to buoyant transition for these vacuum vessels, a polyimide composite was produced using helical fibers for which preliminary mechanical testing was performed.« less

Eutectic bis(2,2-dinitropropyl) acetal - bis(2,2-dinitropropyl) formal mixture, nitroplasticizer (herein called NP) has historically been produced by either the ter Meer or oxidative nitration synthesis process, wherein 2,2-dinitropropanol (DNPOH) is produced as an intermediate step in both processes. Therefore that DNPOH, could be present in NP either as a production or hydrolysis degradation product is worth investigation. Here, we synthesized DNPOH, validated the synthesis using NMR, and identified DNPOH in aged NP using liquid chromatography tandem time of flight – quadrupole mass spectrometry (LC-QTOF). Using these results, for the first time we positively identify that DNPOH is absent from NP aftermore » its production, but is present as a degradation product through hydrolysis from a thermo-chemical aging profile of NP. To hydrolyze NP, prerequisite is the presence of both water and acid. Despite the presence of water in NP, DNPOH is only generated in the late stage of the aging process, when acid concentration is sufficiently high. It has been previously shown both theoretically and experimentally that a primary step of NP degradation is HONO elimination followed by decomposition, wherein nitric acid, nitrous acid, and water are produced (NP→NP’+2HONO and 2HONO→NO+NO₂+H₂O). It is shown from this reaction series that water slows HONO decomposition and therefore in small quantities, 100 s of ppm, water actually stabilizes NP against hydrolysis by equilibrium and reducing acidity.« less

The effect of water concentration on the aging behavior of blend components in plastic bonded explosive (PBX) 9501 is investigated when samples were aged up to 24 months under various conditions. Additionally, the blend components studied here are: poly(urethane ester) (Estane®5703) (Estane), nitroplasticizer (NP), and antioxidant Irganox 1010 (Irg1010). The experimental results reveal that NP is prone to thermally degrading and producing H₂O, NO_x, and HNO_x species, which are the predominant species to consume Irg1010 during PBX 9501 aging under inert environment. As Irg1010 is completely consumed, Estane degrades through oxidation and NP addition, in addition to well anticipated hydrolysis.more » The competition among hydrolysis, oxidation, and NP addition results in non-monotonical changes in the molecular weight of Estane over the aging process.« less

Abstract This study is the first attempt to document methodology development undergone using liquid chromatography tandem quadrupole time of flight mass spectrometry (LC‐QTOF) to investigate degradation products of eutectic bis(2,2‐dinitropropyl) acetal/formal nitroplasticizer (called NP here). Method properties investigated are: desolvation temperature (°C) and spray voltage (V) of the electrospray ionization source, and the development of an acetone system rinse to prevent any residual contamination between sample injections. Details are given on why it is essential to investigate method optimization with changes shown in MS/MS analysis in addition to MS results. Trends in MS/MS analytic results reveal important relationships between baselinemore » and aged materials. In addition to verification of previously proposed fragments, insights offered by this newly developed methodology will also identify new degradation products and shed light on the complexity of NP degradation chemistry.« less

Here, the aging behavior of a eutectic mixture of bis(2,2-dinitropropyl) acetal and formal [called NP here] has been studied in various atmospheres [dry (air or nitrogen) versus wet] at temperatures 70 °C and below. The properties of aged samples were analyzed using Fourier transform infrared (FTIR) spectroscopy, Karl Fischer (KF) titration, liquid chromatography/mass spectrometry (LC/MS), and thermogravimetric analysis (TGA) over a period of three years. The results indicate that at aging temperatures up to 55 °C, the initial rates of water production from nitrous acid (HONO) formation and decomposition into the water, NO, and NO₂ follows a 1st order ratemore » law and the rate constants follow an Arrhenius law as a function of temperature. The activation energies and pre-factors for water and volatiles production yield a single linear kinetic compensation plot, suggesting a common degradation pathway between NP and the various combinations of its constituents. Within a narrow temperature range, around 55 °C, a trace amount of water in NP stabilizes its properties by preventing HONO elimination. When the aging temperature is substantially higher than 55 °C, the nature of the degradation mechanism changes. It is suspected that the degradation products of NO_x, water, and HNO₃ serve as catalysts to auto-catalyze (kinetics beyond the 1st order) and further degrade NP. The effect of headspace volume on this auto-catalytic process will be discussed.« less