Thermal Expansion of LX‐17, PBX 9502, and Ultrafine TATB

A large quantity of linear strain and LCTE data from −55 °C to 75 °C on LX‐17, PBX 9502 and ultrafine TATB (ufTATB) is presented. Axial and diametral measurements are blended to give final densities, which agree with the liquid immersion values of Baytos et al. The nominal densities at 21, −55 and 75 °C in g ⋅ cm⁻³ are: LX‐17 1.90, 1.920, 1.874; PBX 9502 1.89, 1.907, 1.867; ufTATB 1.80, 1.822, 1.778. Data taken radially show more thermal expansion than that taken transversely in cut‐up parts; both must be combined to get the density. There is no difference between virgin and recycled TATB. Rachet growth data is presented, both at low pressure and at higher pressure, where the swelling is diminished. A Kel‐F strain curve is presented and the theoretical maximum densities are computed.     

The Effects of TATB Ratchet Growth on PBX 9502

PBX 9502 is a plastic‐bonded explosive that contains 95 wt.‐% TATB, a graphitic‐structured high explosive known to undergo “ratchet growth,” i.e., irreversible volume change that accompanies temperature excursions. Earlier studies have reported changes in TATB‐based composites as a function of thermal cycling and density change, however, a clear distinction between density and ratchet‐growth effects has not been made. In the work reported here, an “as‐pressed density” baseline for the mechanical response of recycled PBX 9502 is established over a density range of interest, then high‐density specimens are thermally cycled between −55 and 80 °C to achieve “ratchet‐grown” parts in the same low‐density region. As‐pressed and ratchet‐grown specimens with identical densities are then analyzed using microX‐ray computed tomography and USANS techniques to obtain information about pore‐size distributions. Data show that after ratchet‐growth, PBX 9502 specimens contain, in general, more numerous and smaller voids than specimens that were pressed with lower compaction pressures to match the same density. The mechanical response of the ratchet‐grown material is consistent with damage, showing lower tensile stress and modulus, lower compressive modulus, and higher tensile and compressive strain, than as‐pressed specimens of the same density.     

The Effect of Shear Strain on Texture in Pressed Plastic Bonded Explosives

The insensitive explosive PBX 9502 contains 95 wt‐% of TATB crystals and a plastic bonding agent (Kel‐F). The TATB crystals have plate‐like morphology, similar to that of graphite or boron nitride. We have used X‐ray diffraction to measure the preferred orientation (texture) of the TATB crystals in parts fabricated by pressing PBX 9502 powder. Independently, we have used finite‐element calculations to derive the direction and magnitude of the shear imposed during the consolidation of this composite material. Based on our results, we propose that the texture develops because the applied shear causes the TATB crystals to rotate such that their (002) basal planes are parallel to shear planes. The texture predicted by this model agrees qualitatively with that measured at various locations within the PBX 9502 compact. Further validation of this model is obtained by the measurement of the thermal expansion coefficient of PBX 9502, which is highly anisotropic.     

Time‐Evolution of TATB‐Based Irreversible Thermal Expansion (Ratchet Growth)

TATB is an insensitive high explosive, attractive for use because of its safety aspects. TATB compactions, with or without binder, undergo irreversible volume expansion (or ratchet growth) upon thermal cycling. In the past, experimental elucidation of this phenomenon has focused on irreversible expansion as a function of the number of thermal excursions over a given temperature range, where growth is asymptotic with increasing cycle number. In this paper, we demonstrate that ratchet growth also occurs as a function of time at constant temperature, and that growth is substantial at elevated temperatures. We have measured strain response in PBX 9502, a TATB‐based composite, by performing thermal‐cycling tests with different durations at high temperature. Irreversible growth arises from the thermal ramps themselves (increasing and decreasing), as well as from the subsequent isotherms. PBX 9502 specimens with previously‐identified TATB texture/orientation were used in order to eliminate and/or evaluate texture as a variable. Measurements were also performed on dry‐pressed TATB (no binder) to confirm that expansion as a function of time (constant temperature) is not caused by the binder. A simple analysis of the time‐response data demonstrates consistency in the results. We propose that the primary driving force for irreversible expansion is the proximity of the current strain value (due to thermal history) to the strain saturation point of the current cycle (i.e. strain at infinite high‐temperature hold times or an infinite number of cycles). Such tests should aid in the understanding and modeling of ratchet growth response in these materials.     

Changes in Pore Size Distribution upon Thermal Cycling of TATB‐based Explosives Measured by Ultra‐Small Angle X‐Ray Scattering

Hot‐spot models of initiation and detonation show that voids or porosity ranging from nanometer to micrometer in size within highly insensitive energetic materials affect initiability and detonation properties. Thus, the knowledge of the void size distribution, and how it changes with the volume expansion seen with temperature cycling, are important to understanding the properties of the insensitive explosive 1,3,5‐triamino‐2,4,6‐trinitrobenzene (TATB). In this paper, void size distributions in the 2 nm to 2 μm regime, obtained from small‐angle X‐ray scattering measurements, are presented for LX‐17‐1, PBX‐9502, and ultra‐fine TATB formulations, both as processed and after thermal cycling. Two peaks were observed in the void size distribution: a narrow peak between 7–10 nm and a broad peak between 20 nm and about 1 mm. The first peak was attributed to porosity intrinsic to the TATB crystallites. The larger pores were believed to be intercrystalline, a result of incomplete consolidation during processing and pressing. After thermal cycling, these specimens showed an increase in both the number and size of these larger pores. These results illuminate the nature of the void distributions in these TATB‐based explosives from 2 nm to 2 μm and provide empirical experimental input for computational models of initiation and detonation.     

Enhancement of Creep Properties of TATB‐Based Polymer‐Bonded Explosive Using Styrene Copolymer

In order to investigate the effects of binder component on the creep properties of polymer‐bonded explosive (PBX), three‐point bending creep behaviors of 1,3,5‐triamino‐2,4,6‐trinitrobenzene (TATB)‐based PBX and its styrene copolymer modified formulation were studied by dynamic mechanical analyzer. The experimental results showed that owing to the addition of reinforcing agent (styrene copolymer) with high glass transition temperature and high mechanical strength, the creep resistance performance of the modified formulation was improved with reduced creep strain and constant creep rate and prolonged creep failure time. A six‐element mechanical model was applied to simulate the creep behaviors of TATB‐based PBX and its modified formulation. The constitutive equation of creep curves under different conditions were obtained by nonlinear fit. The predicted theoretical results coincided quite well with the experimental data.     

Continuous Wave Laser Irradiation of Explosives

Quantitative measurements of the levels of continuous wave (CW) laser light that can be safely applied to bare explosives during contact operations were obtained at 532 nm, 785 nm, and 1550 nm wavelengths. A thermal camera was used to record the temperature of explosive pressed pellets and single crystals while they were irradiated using a measured laser power and laser spot size. A visible light image of the sample surface was obtained before and after the laser irradiation. Laser irradiation thresholds were obtained for the onset of any visible change to the explosive sample and for the onset of any visible chemical reaction. Deflagration to detonation transitions were not observed using any of these CW laser wavelengths on single crystals or pressed pellets in the unconfined geometry tested. Except for the photochemistry of DAAF, TATB and PBX 9502, all reactions appeared to be thermal using a 532 nm wavelength laser. For a 1550 nm wavelength laser, no photochemistry was evident, but the laser power thresholds for thermal damage in some of the materials were significantly lower than for the 532 nm laser wavelength. No reactions were observed in any of the studied explosives using the available 300 mW laser at 785 nm wavelength. Tables of laser irradiance damage and reaction thresholds are presented for pressed pellets of PBX9501, PBX9502, Composition B, HMX, TATB, RDX, DAAF, PETN, and TNT and single crystals of RDX, HMX, and PETN for each of the laser wavelengths.     

Comparative study of maleated polypropylene as a coupling agent for recycled low‐density polyethylene/wood flour composites

The effects of the type of coupling agent and virgin polypropylene (PP) content on the mechanical properties and water absorption behavior of recycled low‐density polyethylene/wood flour (WF) composites were investigated. The fractured surfaces of these recycled wood/plastic composites (rWPCs) were examined to gain insight into the distribution and dispersion of WF within the polymer matrix. The results indicate that the use of 100% recycled polymer led to inferior mechanical properties and to a greater degree of moisture absorption and swelling when compared to recycled polymer–virgin PP wood/plastic composites. This could have been related to the poor melt strength and inferior processability of the recycled polymer. The extent of improvement of the mechanical properties depended not only on the virgin PP content in the matrix but also on the presence of maleic anhydride (MA) modified PP as the coupling agent. Higher concentrations of MA group were beneficial; this improvement was attributed to increased chemical bonding (ester linkages) between hydroxyl moieties in WF and anhydride moieties in the coupling agent. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Complex Microwave Permittivity of Secondary High Explosives

We aim to understand how microwaves interact with high explosives by studying the complex permittivity from 1–18 GHz of HMX, RDX, TNT, TATB, PETN, Octol, Comp B, 95 % RDX/5 % Viton A (PBX‐RDX), PBX 9404, PBXN‐5, PBXN‐7, PBXW‐14, PBX 9501, and PBX 9502. The combination of a resonant cavity perturbation technique for determining the room‐temperature complex dielectric constant at discrete frequencies and a wide band open circuit method (1–18 GHz) provides an accurate, broadband measurement that describes the dielectric properties in the frequency range of interest. While the values of the real and imaginary permittivity components did not vary significantly as a function of frequency, we found the real part of the permittivity to be highly dependent on relatively small changes in the material density. We used dielectric mixing theory, specifically the linear‐law approximation, to compare the predicted values based on the dielectric properties of individual components with those of the resulting formulation measured experimentally for a select number of samples; the prediction agrees well within the observed variability of the experimentally measured values.     

Highly Thermal Stable TATB‐based Aluminized Explosives Realizing Optimized Balance between Thermal Stability and Detonation Performance

In this work, a series of TATB‐based aluminized explosives were formulated from 1, 3, 5‐triamino‐2, 4, 6‐trinitrobenzene (TATB), aluminum powders and polymeric binders. The thermal stability, heat of detonation, detonation velocity and pressure of the TATB based aluminized (TATB/Al) explosives were systematically investigated by cook‐off, constant temperature calorimeter, electrometric method and manganin piezo resistance gauge, respectively. The selected PBX‐3 (70 wt% TATB/25 wt% Al/5 wt% fluorine resin) achieved optimized balance between thermal stability and detonation performance, with the thermal runaway temperature around 583 K. The thermal ignition of TATB‐based aluminized explosive occurred at the edge of the cylinder according to the experimental and numerical simulations. Moreover, the critical thermal runaway temperature for PBX‐3 was calculated based on the Semenov's thermal explosion theory and the thermal decomposition kinetic parameters of the explosive, which was consistent with the experimental value.     

被动围压下PBX的冲击动态力学性能

采用铝套筒和TATB基PBX,应用霍普金森压杆被动围压试验方法,研究了PBX在围压下的动态力学响应,得到了该PBX不同应变率下的屈服强度.结果表明,随着应变率的提高,屈服强度有所提高;围压状态下PBX承受的应力远高于无围压状态,变形从脆性向塑性转变,样品未发生明显的破坏.     

Prediction of mechanical properties of recycled fiberglass reinforced polyamide 66

An experimental study of the mechanical performance of in-plant recycled fiberglass reinforced polyamide 66 is reported. The fiber length distributions were used to investigate and to predict the influence of process induced fiber shortening on the short term performance of recycled samples compared to that of virgin samples. The results indicate that fiber shortening has a strong influence on strength. Applying a modified Kelly-Tyson model to the fiber length distribution gave excellent agreement with measured strength. There was no need to vary interface or matrix properties in the theoretical analysis. The effect of reprocessing on these factors does not appear to influence strength within the bounds of the model. The decrease in strength during a continuous in-plant recycling process is small at a 30 wt% regrind level. Indeed, below 50 wt% regrind, the strength remains within design limits. The impact strength of dry unnotched samples indicated that the resistance is related to the reciprocal fiber length.     

Selected physical characteristics of polystyrene/high density polyethylene composites prepared from virgin and recycled materials

Mixtures of polystyrene and high density polyethylene were injection molded from recycled and virgin polymers to generate cocontinuous structures. The mechanical properties of these blends were evaluated to assess their conformance to rule of mixtures behavior in general and to identify areas of synergy or incompatibility in specific. Flexural and tensile data for recycled blends showed that generally the properties are not additive, except in a cocontinuous region of composition near 35/65 PS/HDPE that has been identified previously for recycled materials. Analysis of crystallinity in the HDPE phase of these blends by differential scanning calorimetry indicates a marked reduction in the level of HDPE crystallinity at the 35/65 PS/HDPE composition. Similar blends of virgin PS/HDPE polymer do not show the differing regions of incompatibility and synergy illustrated by the recycled materials, but rather show approximate conformance to the rule of mixtures. Furthermore, the virgin blends show virtually no crystallinity suppression and a more pronounced T_g shift in the polystyrene compared to recycled materials. Detailed characterization of the recycled materials in terms of polymer and particulate impurities should improve understanding of these differences and perhaps provide direction for obtaining enhanced synergistic behavior in virgin polymer blends. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

The use of recycled low-density polyethylene films from protective prepreg for the development of nanocomposites with bentonite clay

Prepreg is a pre-impregnated composite fiber where a thermoset polymer matrix material is present. Before being used, these materials are kept at low temperatures and have a low-density polyethylene (LDPE) film for your protection. The increase in the use of structural composites based on prepregs causes an increase in the amount of protective LDPE film. This material is usually discarded or incinerated and can cause great damage to the environment. Thus, the present work aimed to study the feasibility of recycling up to 100% of protective LDPE (rLDPE) to develop blends-based nanocomposites with rLDPE/virgin LDPE (60/40, 70/30, 80/20, 90/10 and 100/0) with the addition of 5 wt% of compatibilizer agent (maleic anhydride grafted LDPE, LDPE-g-MA), and 1 wt% of bentonite (BNT) using a co-rotational twin-screw extruder, followed by hot pressing in a hydropneumatic press and die-cutting. Water absorption test, thermal aging resistance, morphological characterization by scanning electron microscopy, mechanical properties by Izod impact strength and tensile tests, and differential scanning calorimetry were performed. By the results, it was possible to verify the viability of 100% of the recycling of rLDPE. The results showed a good distribution of 1 wt% of BNT in the matrix, better mechanical properties when compared with virgin LDPE. Furthermore, the thermal properties, water absorption test, and thermal aging resistance showed no statistical differences between the samples. These results confirm the effectiveness and the environmental gain in the use of the recycled material.     

粘结剂增强对TATB基PBX力学性能的影响

采用熔融共混法制备了氟聚合物/增强剂复合粘结剂体系,考察了增强剂含量对复合粘结剂体系性能的影响。动态力学分析(DMA)结果显示,增强剂的玻璃化转变温度大大高于氟聚合物,复合粘结剂体系的储能模量随增强剂含量的增加而增加。随着增强剂含量增加,复合粘结剂体系的拉伸强度明显增加。采用水悬浮法制备了TATB基高聚物粘结炸药(PBX),探讨了粘结剂增强对其力学性能的影响。实验结果表明,随着增强剂含量增加,TATB基PBX的力学性能显著提高。当复合粘结剂体系中增强剂含量为20%时,PBX的力学性能最佳:20℃和60℃下压缩强度为32.15 MPa和20.00 MPa,60℃下劈裂强度为2.84 MPa。     

Recycled milk pouch and virgin LDPE‐LLDPE‐based jute fiber composites

The present investigation deals with the thermo‐mechanical recycling of post consumer milk pouches (LDPE‐LLDPE blend) and its use as jute fiber composite materials for engineering applications. The mechanical, thermal, morphological, and dynamic‐mechanical properties of recycled milk pouch‐based jute fiber composites with different fiber contents were evaluated and compared with those of the virgin LDPE‐LLDPE/jute fiber composites. Effect of artificial weathering on mechanical properties of different formulated composites was determined. The recycled polymer‐based jute fiber composites showed inferior mechanical properties as well as poor thermal stability compared to those observed for virgin polymer/jute fiber composites. However, the jute‐composites made with (50:50) recycled milk pouch‐virgin LDPE‐LLDPE blend as polymer matrix indicated significantly superior properties in comparison to the recycled milk pouch/jute composites. Overall mechanical performances of the recycled and virgin polymeric composites were correlated by scanning electron microscopy (SEM). The dynamic mechanical analysis showed that storage modulus values were lower for recycled LDPE‐LLDPE/jute composites compared to virgin LDPE‐LLDPE/jute composites throughout the entire temperature range, but an increase in the storage modulus was observed for recycled‐virgin LDPE‐LLDPE/jute composites. POLYM. COMPOS. 28:78–88, 2007. © 2007 Society of Plastics Engineers     

Compounding and characterization of recycled multilayer plastic films

Mechanical recycling of multilayer plastic films from food packages was investigated. The multilayer films were manually separated from municipal solid waste, washed, grinded, and finally compounded at 0–100 wt% concentrations with virgin low-density polyethylene (PE-LD). Polyethylene grafted with maleic anhydride (PE-g-MA) compatibilizer was used in two of the compounds to replace 2 and 5 wt% of the PE-LD to study its effect as well. PE-g-MA is expected to improve the mechanical properties of the compounds by promoting the adhesion between incompatible polymer phases. The composition of the compounds was characterized with Fourier-transform infrared spectroscopy and differential scanning calorimetry and their properties were studied with tensile testing and rotational rheometer measurements. All tested compounds had relatively good mechanical properties and processability. This indicates that recycled multilayer films could replace at least part of the virgin PE-LD in applications where high-thermal stability or good visual appearance is not required. The PE-g-MA compatibilizer did not have a significant effect on the mechanical properties of the compounds.     

Headspace solid‐phase microextraction with gas chromatography/mass spectrometry reveals a correlation between the degradation product pattern and changes in the mechanical properties during the thermooxidation of in‐plant recycled polyamide 6,6

The increased susceptibility of in‐plant recycled polyamide 6,6 toward thermooxidation was shown by headspace solid‐phase microextraction with gas chromatography/mass spectrometry (HS‐SPME/GC‐MS), tensile testing, differential scanning calorimetry (DSC), and Fourier transform infrared spectroscopy (FTIR). A correlation between the deterioration in mechanical properties and the formation of degradation products due to thermooxidation was found, and the most prominent decrease in mechanical properties coincided with the largest increase in the abundance of degradation products. The recycled materials had a shorter induction period toward oxidation, and their mechanical properties deteriorated faster than the mechanical properties of virgin material. The same trend was observed with HS‐SPME/GC‐MS because degradation products were found for recycled materials after oxidation times shorter than those for virgin material. Furthermore, larger amounts of degradation products were formed in the recycled materials. The high sensitivity of HS‐SPME/GC‐MS as an analytical tool was demonstrated because it was able to detect changes caused by oxidation considerably earlier than the other methods. Unlike DSC and FTIR, it could also show differences between samples recycled for different times. Four groups of degradation products—cyclic imides, pyridines, chain fragments, and cyclopentanones—were identified in thermooxidized polyamide 6,6. After 1200 h of thermooxidation, 1‐pentyl‐2,5‐pyrrolidinedione was the most abundant degradation product. Approximately four times more 1‐pentyl‐2,5‐pyrrolidinedione was formed in polyamide recycled three times than in virgin polyamide. Pyridines and chain fragments behaved toward oxidation and repeated processing like cyclic imides; that is, their amounts increased during oxidation, and larger amounts were formed in recycled materials than in virgin material. The cyclopentanone derivatives were present already in unaged material, and their amounts decreased during oxidation. Cyclopentanones were not formed because of the thermooxidation of polyamide 6,6. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3396–3407, 2002     

DMA法评价TATB填充含氟共聚物的耐热性

用DMA研究了TATB填充氟聚物的耐热性，并用常规力学性能分析加以验证，探讨了TATB粒径及复合物制样方式对TATB填充氟聚物动力学性能的影响。结果表明，(1)使用大颗粒TATB的PBX，其耐热温度高于使用小颗粒TATB的PBX耐热温度；(2)等静压制试样的耐热性好于模压制试样的耐热性；(3)在耐热温度处，TATB填充含氟共聚物的力学性能呈现突变，表明DMA技术可用于表征材料的耐热性。     

Flame retardant properties of polyurethane produced by the addition of phosphorous containing polyurethane oligomers (II)

Chemical degradation of used PU was intentionally made by the addition of flame retardants such as tris(2-chloropropyl)phosphate (TCPP), triethyl phosphate (TEP) and trimethyl phosphonate (TMP). Final product obtained after the degradation reaction was named as DEP. The structure of degraded products (DEP) was analyzed by FT-IR and ³¹P NMR and it turned out to be phosphorous containing oligourethanes. Rigid polyurethane foam was produced using the degraded products (DEP) as flame retardants. The flammability and thermal stability of recycled rigid polyurethane was investigated. The mechanical properties such as compressive strength and tensile strength of recycled polyurethane were also studied. The recycled polyurethane shows reduced flammability and higher thermal stability over virgin polyurethane. Mechanical strength of recycled polyurethane also shows as high as that of virgin polyurethane. In order to evaluate flame retardant properties of the recycled polyurethane foams with various amounts of DEP, heat release rate (HRR) of the foam was measured by cone calorimeter. Scanning electron micrograph of recycled PU shows uniform cell morphology as virgin-PU.