Experimental evidence of triboluminescence induced by hypervelocity impact

The emission of light due to crystal fracture, or triboluminescence (TL), is a phenomenon that has been known for centuries. One of the most common examples of TL is the flash created from chewing wintergreen Lifesavers^®. For the last couple of years, the authors have been measuring fluorescence properties of phosphors like zinc sulfide doped with manganese (ZnS:Mn). Preliminary results indicate that impact energies greater than 16 mJ produced measurable TL from ZnS:Mn. Light was generated from the interaction of a dropped mass and a small number of luminescence centers in the ZnS:Mn powder. To extend this research, a two-stage hypervelocity light gas gun located at NASA's Marshall Space Flight Center (MSFC) was used to evaluate equipment and settings that show promise for hypervelocity TL detection. In these experiments, a projectile was accelerated to approximately 5–6 km/s before striking a ZnS:Mn phosphor-coated aluminum plate. This paper will provide an overview into the first experimental evidence of TL emission from ZnS:Mn due to hypervelocity impact. It is hoped that these results will generate interest in future hypervelocity research.     

Crater distribution on the rear wall of AL-Whipple shield by hypervelocity impacts of AL-spheres

All spacecraft in low orbit are subject to hypervelocity impact by meteoroids and space debris, which can in turn lead to significant damage and catastrophic failure. In order to simulate and study the hypervelocity impact of space debris on spacecraft through hypervelocity impact on AL-Whipple shield, a two-stage light gas gun was used to launch 2017-T4 aluminum alloy sphere projectiles. The projectile diameters ranged from 2.51 mm to 5.97 mm and impact velocities ranged from 0.69 km/s to 6.98 km/s. The modes of crater distribution on the rear wall of AL-Whipple shield by hypervelocity impact of AL-spheres in different impact velocity ranges were obtained. The characteristics of the crater distribution on the rear wall were analyzed. The forecast equations for crater distribution on the rear wall of AL-Whipple shield by normal hypervelocity impact were derived. The results show that the crater distribution on the rear wall is a circular area. As projectile diameter, impact velocity and shielding spacing increased, the area of crater distribution increased. The critical fragmentation velocity of impact projectile is an important factor affecting the characteristics of the crater distributions on the rear wall.     

Investigation and comparison between new satellite impact test results and NASA standard breakup model

This paper summarizes two new satellite impact tests conducted in order to investigate on the outcome of low- and hypervelocity impacts on two identical target satellites. The first experiment was performed at a low velocity of 1.5 km/s using a 40-g aluminum alloy sphere, whereas the second experiment was performed at a hypervelocity of 4.4 km/s using a 4-g aluminum alloy sphere, by a two-stage light gas gun. To date, approximately 1500 fragments from each impact test have been collected for detailed analysis. Each piece was analyzed based on the method used in the NASA standard breakup model 2000 revision. The detailed analysis will conclude (1) the similarity in mass distribution of fragments between low- and hypervelocity impacts encourages the development of a general-purpose mass-based distribution model applicable for a wide impact velocity range, and (2) the difference in area-to-mass ratio distribution between the impact experiments and the NASA standard breakup model suggests to describe the area-to-mass ratio by a bi-normal distribution.     

Generation of transient vibrations on aluminum honeycomb sandwich panels subjected to hypervelocity impacts

This paper presents the results of a set of experiments aimed at discovering the main features of impact-induced vibrations on all-aluminum honeycomb sandwich panels, representative of the GOCE satellite's top floor, which is exposed to the orbital debris environment. The activity focused on the characterization of the vibrations induced in the vicinity of internal payloads by hypervelocity impacts occurring on the vehicle's external shell. More than 30 tests were realized by launching 0.8–2.3 mm aluminum projectiles in the velocity range 4–5.5 km/s on targets with tri-axial accelerometer assemblies mounted on both the front and rear face of the panel, at a nominal distance of 150 mm from the impact point. It was found that a hypervelocity impact produces in both the front and rear side of the sandwich panel a vibration environment which can be described through the shock response spectrum (SRS) of three different types of waves that can be distinguished on the basis of the acceleration direction: out-of-plane, in-plane longitudinal and in-plane shear. The influence of projectile mass and velocity on SRS appeared to vary with frequency, with the most significant difference in the range between ∼10³ and ∼10⁴ Hz. The results of whole experimental set were used to derive an interpolation law through standard techniques of nonlinear fit. The empirical equation obtained makes it possible to predict the near-field vibration environment produced by hypervelocity impacts with debris having given size and velocity, reproducing all the test data with an average uncertainty of ±6 dB.     

Optical properties of Mn-doped ZnS semiconductor nanoclusters synthesized by a hydrothermal process

Undoped and Mn-doped ZnS nanoclusters have been synthesized by a hydrothermal approach. Various samples of the ZnS:Mn with 0.5, 1, 3, 10 and 20 at.% Mn dopant have been prepared and characterized using X-ray diffraction, energy-dispersive analysis of X-ray, high resolution electron microscopy, UV-vis diffusion reflection, photoluminescence (PL) and photoluminescence excitation (PLE) measurements. All the prepared ZnS nanoclusters possess cubic sphalerite crystal structure with lattice constant a = 5.408 ± 0.011 ?. The PL spectra of Mn-doped ZnS nanoclusters at room temperature exhibit both the 495 nm blue defect-related emission and the 587 nm orange Mn²⁺ emission. Furthermore, the blue emission is dominant at low temperatures; meanwhile the orange emission is dominant at room temperature. The Mn²⁺ ion-related PL can be excited both at energies near the band-edge of ZnS host (the UV region) and at energies corresponding to the Mn²⁺ ion own excited states (the visible region). An energy schema for the Mn-doped ZnS nanoclusters is proposed to interpret the photoluminescence behaviour.     

Initial evidence of a triboluminescent wavelength shift for ZnS:Mn caused by ballistic impacts

The triboluminescent properties of zinc sulfide doped with manganese (ZnS:Mn) were studied using ballistic impacts of specially prepared rounds manufactured in two different calibers. The triboluminescent emission spectrum was then rerecorded as the rounds impacted the target. Results show a ~ 1 nm shift in the emission spectrum with increased impact energy.     

Time resolved spectroscopic studies on some nanophosphors

Time resolved spectroscopy is an important tool for studying photophysical processes in phosphors. Present work investigates the steady state and time resolved photoluminescence (PL) spectroscopic characteristics of ZnS, ZnO and (Zn, Mg)O nanophosphors both in powder as well as thin film form. Photoluminescence (PL) of ZnS nanophosphors typically exhibit a purple/blue emission peak termed as self activated (SA) luminescence and emission at different wavelengths arising due to dopant impurities e.g. green emission for ZnS: Cu, orange emission for ZnS: Mn and red emission for ZnS: Eu. The lifetimes obtained from decay curves range from ns to ms level and suggest the radiative recombination path involving donor-acceptor pair recombination or internal electronic transitions of the impurity atom. A series of ZnMgO nanophosphor thin films with varied Zn: Mg ratios were prepared by chemical bath deposition. Photoluminescence (PL) excitation and emission spectra exhibit variations with changing Mg ratio. Luminescence lifetime as short as 10⁻¹⁰ s was observed for ZnO and ZnMgO (100: 10) nanophosphors. With increasing Mg ratio, PL decay shifts into microsecond range. ZnO and ZnMgO alloys up to 50% Mg were prepared as powder by solid state mixing and sintering at high temperature in reducing atmosphere. Time resolved decay of PL indicated lifetime in the microsecond time scale. The novelty of the work lies in clear experimental evidence of dopants (Cu, Mn, Eu and Mg) in the decay process and luminescence life times in II–VI semiconductor nanocrystals of ZnS and ZnO. For ZnS, blue self activated luminescence decays faster than Cu and Mn related emission. For undoped ZnO nanocrystals, PL decay is in the nanosecond range whereas with Mg doping the decay becomes much slower in the microsecond range.     

A thermoluminescence study on the state of Cl in ZnS:Ag by electron beam

The degradation behavior of ZnS:Ag, Cl as a phosphor for CL by EB irradiation at 7 kV was examined by TL measurement. After EB irradiation, TL intensity decreased and the TL peak shifted to the lower temperature side. By comparing TL thermograms of mechanically damaged ZnS:Ag, Cl, ZnS:Cl with varying Cl concentration as well as ZnS:Ag, Al after EB irradiation, we conclude that the decrease in the effective concentration of Cl⁻, serving as active luminescence center, is responsible for the CL degradation of ZnS:Ag, Cl by EB irradiation.     

Characterization of prompt flash signatures using high-speed broadband diode detectors

Impact flash is a brief, intense flash of light released when a target is impacted by a hypervelocity particle. It is caused by emissions from a jet of shocked material which is thrown from the impact site. Impact flash phenomenology has been known for decades, and is now being considered for applications where remote diagnostics are required to observe and diagnose impacts on satellites and space craft where micrometeoroid and orbital debris impacts are common. Additionally, this phenomena and remote diagnostics are under consideration for missile defense applications. Currently, optical signatures created from hypervelocity impact can be utilized as the basis for detectors (spectrometers, pyrometers), which characterize the material composition and temperature. More recent interest has focused on study of hypervelocity impact generated debris and the physics of the associated rapidly expanding and cooling multiphase debris cloud. To establish this capability technically in the laboratory, we have conducted a series of experiments on a two-stage light gas gun at impact velocities ranging from 6 to 19 km/s, which is representative for light emissions resulting from hypervelocity impacts in space. At these high impact velocities jetting is no longer the dominant mechanism for observed impact flash signatures. The focus of this work is to develop fast, inexpensive photo-diodes for use as a reliable prompt flash, and late time radiating debris cloud diagnostic to: (a) characterize material behavior in the shocked and expanding state when feasible; (b) ascertain scaling of luminosity with impact velocity; (c) determine the temperature of the impact flash resulting from radiating emissions when multiple silicon diodes are used in conjunction with narrow band pass filtering at specific wavelengths as a pyrometer. The results of these experiments are discussed in detail using both a metallic target, such as aluminum, and an organic material such as Composition-B explosive.     

HVI tests on CFRP laminates at low temperature

The paper reports a result of low temperature hypervelocity impact (HVI) tests of aluminum sphere against a 16-ply quasi-isotropic Carbon Fiber Reinforced Plastic (CFRP) laminate plate at speed ranging from 1.4 to 5.4 km/s in air at 10 Pa. The result was compared with room temperature impacts. At low speed impact on CFRP plates, fracture patterns of specimens varied depending on their temperatures, whereas at high-speed impact, any significant differences in the fracture patterns around penetration holes and independent of the temperatures.     

Effect of activator distribution on photo- and X-ray excited luminescence properties of ZnS:Cu,Cl phosphors

ZnS:Cu,Cl phosphors were prepared by conventional solid state reaction with the aid of NaCl-MgCl₂ flux. The copper activator was introduced into the phosphor precursors by three different methods: co-precipitated with ZnS (CP), wet-coated onto ZnS powders (WC), and simply mixed with ZnS in a mortar (SM). The samples were characterized by X-ray powder diffraction, photoluminescence spectra and X-ray excited luminescence spectra. The results show that both photo- and X-ray excited luminescence intensities of the as-prepared ZnS:Cu,Cl phosphors are in the decreasing order of CP > WC > SM. The different copper activator distribution in the phosphors resulting from the different methods was the main reason responsible for the different luminescence intensity, and uniform distribution is beneficial to the luminescence of the phosphors.     

Vulnerability of spacecraft harnesses to hypervelocity impacts

During a study performed in framework of a European Space Agency contract, the vulnerability of spacecraft harnesses has been assessed. The harnesses consisted of three different space-grade cable types: power cables, screened twisted pair data cables and radio frequency (RF) cables. They were alternately shielded by two different types of representative spacecraft structure walls. Ten hypervelocity impact (HVI) tests at 0° incidence have been performed with impact velocities ranging from 6.4 km/s to 7.7 km/s. Projectiles have been aluminium spheres with diameters ranging from 1.5 mm to 4.0 mm. During the tests, all cables were operated at their representative conditions and the disturbances, induced by the impacts, were measured. The malfunction observed could be related to two physical failure mechanisms: (1) short circuits caused by a conducting cloud of molten and evaporated aluminium and, for the data cables, (2) strands being bent by impacting fragments creating a short circuit between screen and signal cable. The influence of a more complex structure wall to the failure mechanism in (1) is shown. Malfunction was dependent on mechanical damage, but no clear correlation between severity of malfunction and mechanical damage could be established. The data cables were the most vulnerable cable, while the RF cables were the most robust. The disturbances recorded could pose a significant threat to connected electronic equipment. Examples of electrical performance are given.     

SPH evaluation of out-of-plane peak force transmitted during a hypervelocity impact

Smooth particle hydrodynamics (SPH) technique is applied to simulate a hypervelocity impact of an aluminum sphere on a simple aluminum target and on a honeycomb structure sandwich panel in order to provide a useful input to Finite Element Model or Statistical Energy Model on evaluating the vibration environment induced by the projectile on the target. The impact velocity range lays between 4 and 5 km/s. Different approaches have been analyzed. At first, the application of SPH technique for direct calculation of the vibration environment is described. Then the calculation of equivalent force impulse is evaluated. Two strategies have been applied: shear stress analysis and momentum calculation using drift velocity measurement. Momentum approach revealed to be the most convenient and reliable method. Results for an aluminum plate and a honeycomb sandwich panel are reported and compared to results of experiments and Finite Element Analysis.     

Radiative interface state study in CdSe/ZnS quantum dots covered by polymer

The paper presents the transformation of photoluminescence (PL) spectra of nonconjugated and bioconjugated core/shell CdSe/ZnS QDs covered by PEG polymer at the aging in ambient air. Studied QDs are characterized by the sizes: (i) 3.6-4.0 nm and color emission with the maxima at 560-565 nm (2.19-2.25 eV) and (ii) 5.2-5.3 nm and with emission at 605-610 nm (2.02-2.08 eV). The part of 565 nm CdSe/ZnS QDs has been bioconjugated to the mouse anti PSA (Prostate-Specific Antigen) antibodies and the part of 605 nm QDs has been bioconjugated to the antihuman IL10 (Interleukin 10) antibodies using the commercially available 565 nm and 605 nm QD conjugation kits. It is revealed that the aging process in ambient air has the very strong impact on PL spectra of nonconjugated core/shell CdSe/ZnS QDs covered with PEG polymer. The aging process relates to the polymer modification in ambient air that is accompanied by the three effects: (i) polymer transparency increasing for the emission of CdSe cores (2.03 or 2.20 eV), (ii) the intensity stimulation of high energy PL bands (2.37, 2.73 and 3.06 eV) related to the interface states at the ZnS/PEG polymer interface and (iii) the elastic strain modification in QD systems. The concentration of interface states at the ZnS/polymer interface increases at the aging of PEG polymer in ambient air.     

Response of composite materials to hypervelocity impact

Investigation of composite materials response to hypervelocity impact by space debris has been carried out. In order to simulate hypervelocity impact, a unique laser driven flyer plate (LDFP) system was used, generating hypervelocity debris with velocities of up to 3 km/s. The materials studied in this research were Kevlar 29/epoxy and Spectra1000/epoxy thin film micro-composites (thickness of about 100 μm). Both Spectra and Kevlar fibers are used in long-duration spacecraft outer wall shielding to reduce the perforation threat. The micro-mechanical response of different composites was studied and correlated to the fiber, the matrix and the fiber/matrix interface properties. Visual and microscopic examinations of the damaged area identified fiber debonding as the prevailing failure mechanism. On the basis of a simple energy balance model it can be stated that for Spectra/epoxy composite the dominant mechanism is new surface creation, whereas for Spectra surface-treated fibers/epoxy the fiber pull out is the dominant mechanism. For Kevlar/epoxy fiber, pull out mechanism plays an important role.     

Synthesis and photoluminescence properties of Cl-doped ZnS nanoparticles prepared by a solid-state reaction

ZnS:Cl⁻ nanoparticles with strong blue emission have been synthesized successfully by a solid-state reaction at low temperature. The dependence of photoluminescence (PL) properties of ZnS:Cl⁻ nanoparticles on the Cl⁻ contents was researched, and the influences of the annealing ambience and using polyvinyl alcohol (PVA) during the synthesis on the PL of ZnS:Cl⁻ (Cl/Zn = 0.35) nanoparticles were discussed. X-ray power diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and ultraviolet-visible spectroscopy were used to characterize their structure, chemical state, diameter, surface states, and PL properties. The results showed that ZnS:Cl⁻ nanoparticles had a cubic blende crystal structure and an average crystallite size of 17.40–19.16 nm. The most intensity blue emission peaking at about 425 nm was obtained when Cl/Zn = 0.35 under 330 nm excitation at room temperature. The emission intensity of ZnS:Cl⁻ (Cl/Zn = 0.35) was increased 3-fold than that of ZnS. The results showed that the PL of ZnS:Cl⁻ (Cl/Zn = 0.35) nanoparticles was enhanced after annealing or using PVA during the synthesis, and annealing in vacuum had a stronger effect in improving the luminescence properties of ZnS nanoparticles than in air. This work suggests that it is an effective method to improve the PL intensity of ZnS nanocrystals by doping with Cl⁻ in ZnS.     

Effect of direct quenching on the microstructure and mechanical properties of the lean-chemistry HSLA-100 steel plates

The influence of direct quenching on structure-property behavior of lean chemistry HSLA-100 steels was studied. Two laboratory heats, one containing Cu and Nb (C:0.052, Mn:0.99, Cu:1.08, Nb:0.043, Cr:0.57, Ni:1.76, Mo:0.55 pct) and the other containing Cu, Nb and B (C:0.04, Mn:1.02, Cu:1.06, Nb:0.036, Cr:0.87, Ni:1.32, Mo:0.41, B:0.002 percent) were hot-rolled into 25 and 12.5 mm thick plates by varying finish-rolling temperatures. The plates were heat-treated by conventional reheat quenching and tempering (RQT), as well as by direct quenching and tempering (DQT) techniques. In general, direct-quench and tempered plates of Nb-Cu heat exhibited good strength (yield strength ∼ 900 MPa) and low-temperature impact toughness (average: 74 J at −85 °C); the Charpy V-notch impact energies were marginally lower than conventional HSLA-100 steel. In Nb-Cu-B heat, impact toughness at low-temperature was inferior owing to boron segregation at grain boundaries. Transmission electron microscopy (TEM) and scanning auger microprobe (SAM) analysis confirmed existence of borocarbides at grain boundaries in this steel. In general, for both the steels, the mechanical properties of the direct-quench and tempered plates were found to be superior to reheat quench and tempered plates. A detailed transmission electron microscopy study revealed presence of fine Cu and Nb (C, N) precipitates in these steels. It was also observed that smaller martensite inter-lath spacing, finer grains and precipitates in direct-quench and tempered plates compared to the reheat quench and tempered plates resulted in their superior strength and good impact toughness.     

A new fluorescent film sensor for Pb(II) ions developed by simulating bio-mineralization process synthesizing of ZnS/CS nanocomposite

Chitosan/zinc sulfide (CS/ZnS) nano-composite films have been prepared by simulating bio-mineralization process. Factors affecting the hydrothermal stability and fluorescence properties of the films have been studied. Furthermore, the sensing properties of nano-composite films to lead ions have been systematically investigated. SEM and TEM observations showed that the size of ZnS particles is 70 nm, and the particles are evenly distributed within the CS films. The fluorescence emission of the nano-composite films indicates that the sizes of real fluorescing ZnS particles are less than 20 nm. This suggests that ZnS particles observed via SEM and TEM may be aggregates of smaller ZnS particles, and the smaller particles may be separated by the organics. The fluorescence emission (363 nm) of the nano-composite films is very sensitive to the presence of Pb ions. C_(Pb²⁺₎ increased from 0 to 664.2 mg L⁻¹ increases the emission dramatically. The emission is hardly affected by common ions in water, except for the iron ions. The films may be developed as excellent sensing films for Pb ions in water.     

Multicolor luminescence from transition metal ion (Mn2+ and Cu2+) doped ZnS nanoparticles

Mn and Cu doped ZnS nanoparticles in powder form were prepared by a simple solvothermal route. Particle size and crystal structure of the products were investigated through X-ray diffraction study revealing the formation of cubic ZnS nanoparticles of average diameter 2.5 nm. Particle size was also verified by the high resolution transmission electron microscopic images. Blue emission at approximately 445 nm was observed from the undoped sample, which was attributed to the presence of large surface defects. With increasing doping concentration the defect related emission gradually quenches and subsequently the impurity related emissions appeared. Mn doped samples exhibited orange emission at approximately 580 nm which may be attributed to the transition between (4)T1 and (6)A1 energy levels of the Mn2+ 3d states. Whereas, the Cu doped ZnS nanoparticles exhibited a red shifted strong blue emission at approximately 466 nm which is attributed to the transition of the electrons from the surface states to the 't2' levels of Cu impurities.     

Plasmon assisted intense blue-green emission from ZnO/ZnS nanocrystallites

Excellent luminescence properties of ZnO/ZnS nanocrystallites prepared using simple wet chemical approach at room temperature have been reported. ZnS coating on the surface of ZnO nanocrystallites enhanced the green emission (around 500 nm) by a factor of 2. The intensity of the blue emission around 450 nm of ZnO/ZnS nanocrystallites is observed to be as high as three times the emission intensity of pure ZnO nanocrystallites. A further overall increase by a factor of ∼2.5 has also been observed in the intensity of wide blue-green emission when the sample was prepared onto grating compared to that of the samples prepared onto uncoated as well as gold coated quartz. The enhanced emission is thought to be due to plasmon assisted electromagnetic field enhancement near nanocrystallites-metal interface. This is supported by power dependent photoluminescence measurements. The strong enhanced blue-green emission covering a wide spectral range of ∼375-650 nm signifies potential optoelectronic applications in near UV and VIS wavelength regimes.