Species stratification and local plasma composition can affect microsecond-timescale oxidation reaction rates of metals such as Al in an oxidizing atmosphere. Here, we utilize fast, gated emission spectroscopy and a high-speed framing camera to determine the intensity and spatiotemporal evolution of various Al ablation products within a laser-induced plasma. Using a high-purity Al plate, micron- and nano-sized Al powders, and inert micron Al2O3 powder, we studied the effect of Al morphology and reactivity on the oxidation characteristics and plasma hydrodynamics in air at 1 atm over two temporal regimes (2–10 μs and 20–100 μs). We observed an increase in the spatial distribution and intensity of emission from vaporized Al within the plasma for powder-based samples compared to plate Al due to enhanced material dispersion. In nano-Al, AlO emission forms at, and propagates along, the surface of the powder bed from 2–10 μs, whereas for micron powder, there is a delay in AlO formation within the bulk of the plasma until tens of microseconds. We measured electron densities from a variety of spectral lines, which can range from ~ 2 × 1015 to 2 × 1018 cm−3, and which scale inversely with the rate of plasma expansion across morphologies. The Al I and Al II species temperatures from 2 to 10 μs calculated via Boltzmann plots are similar (from ~ 10,000 to 14,000 K), and we performed a suite of local thermodynamic equilibrium (LTE) validity calculations to establish that these two species are in LTE, while H is not. Using image co-registration, we calculated the thickness of the AlO layer surrounding the expanding Al cloud at times > 20 μs, which can range from ~ 50 to 300 μm. These results allow us to begin to understand the complexities of laser ablated metal powder reactions at microsecond timescales.
This is a preview of subscription content, log in to check access.
Buy single article
Instant access to the full article PDF.
Price includes VAT for USA
Subscribe to journal
Immediate online access to all issues from 2019. Subscription will auto renew annually.
This is the net price. Taxes to be calculated in checkout.
D.A. Cremers, L.J. Radziemski, Handbook of Laser-Induced Breakdown Spectroscopy, 2nd edn. (Wiley, Singapore, 2013)
Y.-F. Lu, Z.-B. Tao, M.-H. Hong, Characteristics of excimer laser induced plasma from an aluminum target by spectroscopic study. Jpn. J. Appl. Phys. 38, 2958–2963 (1999)
B. Le Drogoff, F. Vidal, S. Laville, M. Chaker, T. Johnston, O. Barthélemy, J. Margot, M. Sabsabi, Laser-ablated volume and depth as a function of pulse duration in aluminum targets. Appl. Opt. 44(2), 278–281 (2005)
T.N. Piehler, F.C. De Lucia, C.A. Munson, B.E. Homan, A.W. Miziolek, K.L. McNesby, Temporal evolution of the laser-induced breakdown spectroscopy spectrum of aluminum metal in different bath gases. Appl. Opt. 44(18), 3654–3660 (2005)
C.G. Parigger, J.O. Hornkohl, L. Nemes, Measurements of aluminum and hydrogen microplasma. Appl. Opt. 46(19), 4026–4031 (2007)
N.M. Shaikh, S. Hafeez, B. Rashid, M.A. Baig, Spectroscopic studies of laser induced aluminum plasma using fundamental, second and third harmonics of a Nd:YAG laser. Eur. Phys. J. D 44(2), 371–379 (2007)
G. Cristoforetti, S. Legnaioli, V. Palleschi, E. Tognoni, P.A. Benedetti, Observation of different mass removal regimes during the laser ablation of an aluminium target in air. J. Anal. At. Spectrom. 23, 1518–1528 (2008)
G. Cristoforetti, Orthogonal double-pulse versus single-pulse laser ablation at different air pressures: a comparison of the mass removal mechanisms. Spectrochim. Acta Part B 64(1), 26–34 (2009)
G. Cristoforetti, G. Lorenzetti, P.A. Benedetti, E. Tognoni, S. Legnaioli, V. Palleschi, Effect of laser parameters on plasma shielding in single and double pulse configurations during the ablation of an aluminium target. J. Phys. D 42(22), 225207 (2009)
E.H. Piepmeier, H. Malmstadt, Q-switched laser energy absorption in plume of an aluminum alloy. Anal. Chem. 41(6), 700 (1969)
B. Le Drogoff, J. Margot, M. Chaker, M. Sabsabi, O. Barthelemy, T.W. Johnston, S. Laville, F. Vidal, Y. von Kaenel, Temporal characterization of femtosecond laser pulses induced plasma for spectrochemical analysis of aluminum alloys. Spectrochim. Acta Part B 56(6), 987–1002 (2001)
O. Barthélemy, J. Margot, S. Laville, F. Vidal, M. Chaker, B. Le Drogoff, T.W. Johnston, M. Sabsabi, Investigation of the state of local thermodynamic equilibrium of a laser-produced aluminum plasma. Appl. Spectrosc. 59(4), 529–536 (2005)
O. Barthelemy, J. Margot, M. Chaker, M. Sabsabi, F. Vidal, T.W. Johnston, S. Laville, B. Le Drogoff, Influence of the laser parameters on the space and time characteristics of an aluminum laser-induced plasma. Spectrochim. Acta Part B 60(7–8), 905 (2005)
W.T.Y. Mohamed, Fast LIBS identification of aluminum alloys. Prog. Phys. 2, 87 (2007)
A.H. Galmed, M.A. Harith, Temporal follow up of the LTE conditions in aluminum laser induced plasma at different laser energies. Appl. Phys. B 91(3–4), 651–660 (2008)
Q.L. Ma, V. Motto-Ros, W.Q. Lei, M. Boueri, X.S. Bai, L.J. Zheng, H.P. Zeng, J. Yu, Temporal and spatial dynamics of laser-induced aluminum plasma in argon background at atmospheric pressure: interplay with the ambient gas. Spectrochim. Acta, Part B 65(11), 896–907 (2010)
I. Mehboob, J. Iqbal, M. Rafique, M.A. Baig, R. Ahmed, Optical spectroscopic study of laser-produced aluminum plasma. IEEE Trans. Plasma Sci. 46(8), 2920–2929 (2018)
M.A. Ismail, H. Imam, A. Elhassan, W.T. Youniss, M.A. Harith, LIBS limit of detection and plasma parameters of some elements in two different metallic matrices. J. Anal. At. Spectrom. 19(4), 489–494 (2004)
A. Freedman, F.J. Iannarilli Jr., J.C. Wormhoudt, Aluminum alloy analysis using microchip-laser induced breakdown spectroscopy. Spectrochim. Acta Part B 60(7–8), 1076 (2005)
M. Sabsabi, P. Cielo, Quantitative-analysis of aluminum-alloys by laser-induced breakdown spectroscopy and plasma characterization. Appl. Spectrosc. 49(4), 499–507 (1995)
P. Inakollu, T. Philip, A.K. Rai, F.-Y. Yueh, J.P. Singh, A comparative study of laser induced breakdown spectroscopy analysis for element concentrations in aluminum alloy using artificial neural networks and calibration methods. Spectrochim. Acta Part B 64(1), 99–104 (2009)
J.M. Lightstone, J.R. Carney, C.J. Boswell, J. Wilkinson, J. Wilkinson, J.M. Lightstone, C.J. Boswell, J.R. Carney, Time-resolved spectroscopic measurements of aluminum oxidation in a laser ablation event. AIP Conf. Proc. 955(1), 1255–1258 (2007)
J.L. Gottfried, Laser-induced plasma chemistry of the explosive RDX with various metallic nanoparticles. Appl. Opt. 51(7), B13–B21 (2012)
X. Bai, V. Motto-Ros, W. Lei, L. Zheng, J. Yu, Experimental determination of the temperature range of AlO molecular emission in laser-induced aluminum plasma in air. Spectrochim. Acta Part B 99, 193–200 (2014)
S.S. Harilal, B.E. Brumfield, B.D. Cannon, M.C. Phillips, Shock wave mediated plume chemistry for molecular formation in laser ablation plasmas. Anal. Chem. 88(4), 2296–2302 (2016)
C. Kimblin, R. Trainham, G.A. Capelle, X. Mao, R.E. Russo, Characterization of laser-induced plasmas as a complement to high-explosive large-scale detonations. AIP Adv. 7, 095208 (2017)
J.L. Gottfried, S.W. Dean, C.-C. Wu, J. Frank, C. De Lucia, Optimizing the performance of aluminized explosives: laser-based measurements of energy release and spectroscopic diagnostics, IEEE RAPID, Miramar Beach, FL, paper #WB3–3 (2019)
J.L. Gottfried, S.W. Dean, C.-C. Wu, J. Frank, C. De Lucia, Measuring fast and slow energy release from aluminum powders, APS SCCM (Shock19), Portland, OR, in press (2019).
J.L. Gottfried, Influence of exothermic chemical reactions on laser-induced shock waves. Phys. Chem. Chem. Phys. 16, 21452–21466 (2014)
J.L. Gottfried, E.J. Bukowski, Laser-shocked energetic materials with metal additives: evaluation of chemistry and detonation performance. Appl. Opt. 56(3), B47–B57 (2017)
R. Viskup, B. Praher, T. Stehrer, J. Jasik, H. Wolfmeir, E. Arenholz, J.D. Pedarnig, J. Heitz, Plasma plume photography and spectroscopy of Fe–oxide materials. Appl. Surf. Sci. 255(10), 5215–5219 (2009)
E.J. Judge, J.E. Barefield, J.M. Berg, S.M. Clegg, G.J. Havrilla, V.M. Montoya, L.A. Le, L.N. Lopez, Laser-induced breakdown spectroscopy measurements of uranium and thorium powders and uranium ore. Spectrochim. Acta Part B 83–84, 28–36 (2013)
J.L. Gottfried, D.K. Smith, C.-C. Wu, M.L. Pantoya, Improving the explosive performance of aluminum nanoparticles with aluminum iodate hexahydrate (AIH). Sci. Rep. 8, 8036 (2018)
S.A. Davari, J.L. Gottfried, C. Liu, E.L. Ribeiro, G. Duscher, D. Mukherjee, Graphitic-coated Al nanoparticles manufactured as superior energetic materials via laser ablation synthesis in organic solvents. Appl. Surf. Sci. 473, 156–163 (2019)
E.R. Wainwright, S.W. Dean, S.V. Lakshman, T.P. Weihs, J.L. Gottfried, Evaluating compositional effects on the laser-induced combustion and shock velocities of Al/Zr-based composite fuels. Combust. Flame 213, 357–386 (2020)
J.L. Gottfried, Laboratory-scale method for estimating explosive performance from laser-induced shock waves. Propellants Explos. Pyrotech. 40(5), 674–681 (2015)
J.L. Gottfried, T.M. Klapötke, T.G. Witkowski, Estimated detonation velocities for TKX-50, MAD-X1, BDNAPM, BTNPM, TKX-55 and DAAF using the laser-induced air shock from energetic materials technique. Propellants Explos. Pyrotech. 42, 353–359 (2017)
C.-D. Park, M. Mileham, L.J. van de Burgt, E.A. Muller, A.E. Stiegman, The effects of stoichiometry and sample density on combustion dynamics and initiation energy of Al/Fe2O3 metastable interstitial composites. J. Phys. Chem. C 114(6), 2814–2820 (2010)
R.W. Conner, D.D. Dlott, Ultrafast emission spectroscopy of exploding nanoaluminum in Teflon: observations of aluminum fluoride. Chem. Phys. Lett. 512(4–6), 211–216 (2011)
S. Roy, N. Jiang, H.U. Stauffer, J.B. Schmidt, W.D. Kulatilaka, T.R. Meyer, C.E. Bunker, J.R. Gord, Spatially and temporally resolved temperature and shock-speed measurements behind a laser-induced blast wave of energetic nanoparticles. J. Appl. Phys. 113(18), 184310 (2013)
J.L. Gottfried, S.W. Dean, E.S. Collins, C.-C. Wu, Estimating the relative energy content of reactive materials using nanosecond-pulsed laser ablation. MRS Adv. 3(17), 875–886 (2018)
M. O’Neil, A. Demko, E.L. Petersen, W.D. Kulatilaka, Ultrashort-pulse laser-induced breakdown spectroscopy for detecting airborne metals during energetic reactions. Appl. Opt. 58(10), C79–C83 (2019)
E.R. Wainwright, T.A. Schmauss, S. Vummidi-Lakshman, K.R. Overdeep, T.P. Weihs, Observations during Al: Zr composite particle combustion in varied gas environments. Combust. Flame 196, 487–499 (2018)
S. Vummidi Lakshman, J.D. Gibbins, E.R. Wainwright, T.P. Weihs, The effect of chemical composition and milling conditions on composite microstructure and ignition thresholds of AlZr ball milled powders. Powder Technol. 343, 87–94 (2019)
E.R. Wainwright, S.V. Lakshman, A.F.T. Leong, A.H. Kinsey, J.D. Gibbins, S.Q. Arlington, T. Sun, K. Fezzaa, T.C. Hufnagel, T.P. Weihs, Viewing internal bubbling and microexplosions in combusting metal particles via X-ray phase contrast imaging. Combust. Flame 199, 194–203 (2019)
D.G. Weisz, J.C. Crowhurst, M.S. Finko, T.P. Rose, B. Koroglu, R. Trappitsch, H.B. Radousky, W.J. Siekhaus, M.R. Armstrong, B.H. Isselhardt, M. Azer, D. Curreli, Effects of plume hydrodynamics and oxidation on the composition of a condensing laser-induced plasma. J. Phys. Chem. A 122(6), 1584–1591 (2018)
J.L. Gottfried, Laser-induced air shock from energetic materials (LASEM) method for estimating detonation performance: challenges, successes and limitations. AIP Conf. Proc. 1979(1), 100014 (2018)
L.M. Cabalín, J.J. Laserna, Experimental determination of laser induced breakdown thresholds of metals under nanosecond Q-switched laser operation. Spectrochim. Acta Part B 53(5), 723–730 (1998)
S.-B. Wen, X. Mao, R. Greif, R.E. Russo, Laser ablation induced vapor plume expansion into a background gas: II. Experimental analysis. J. Appl. Phys. 101(2), 023115 (2007)
E.L. Dreizin, Metal-based reactive nanomaterials. Prog. Energy Combust. Sci. 35(2), 141–167 (2009)
D. Sundaram, V. Yang, R.A. Yetter, Metal-based nanoenergetic materials: synthesis, properties, and applications. Prog. Energy Combust. Sci. 61, 293–365 (2017)
R. Thiruvengadathan, Aluminum-based nano-energetic materials: state of the art and future perspectives, in Nano-Energetic Materials, ed. by S. Bhattacharya, A.K. Agarwal, T. Rajagopalan, et al. (Springer Singapore, Singapore, 2019), pp. 9–35
C. Colón, G. Hatem, E. Verdugo, P. Ruiz, J. Campos, Measurement of the stark broadening and shift parameters for several ultraviolet lines of singly ionized aluminum. J. Appl. Phys. 73(10), 4752–4758 (1993)
D.M. Surmick, C.G. Parigger, Aluminum monoxide emission measurements in a laser-induced plasma. Appl. Spectrosc. 68(9), 992–996 (2014)
R.A. Yetter, G.A. Risha, S.F. Son, Metal particle combustion and nanotechnology. Proc. Combust. Inst. 32(2), 1819–1838 (2009)
J. Ashkenazy, R. Kipper, M. Caner, Spectroscopic measurements of electron density of capillary plasma based on Stark broadening of hydrogen lines. Phys. Rev. A 43(10), 5568–5574 (1991)
H.R. Griem, Spectral Line Broadening by Plasmas (Academic, New York, 1974)
A.M. El Sherbini, T.M. El Sherbini, H. Hegazy, G. Cristoforetti, S. Legnaioli, V. Palleschi, L. Pardini, A. Salvetti, E. Tognoni, Evaluation of self-absorption coefficients of aluminum emission lines in laser-induced breakdown spectroscopy measurements. Spectrochim. Acta Part B 60(12), 1573–1579 (2005)
M.C. Quintero, A. Rodero, M.C. García, A. Sola, Determination of the excitation temperature in a nonthermodynamic-equilibrium high-pressure helium microwave plasma torch. Appl. Spectrosc. 51(6), 778–784 (1997)
M.L. Najarian, R.C. Chinni, Temperature and electron density determination on laser-induced breakdown spectroscopy (LIBS) plasmas: a physical chemistry experiment. J. Chem. Educ. 90(2), 244–247 (2013)
N.M. Shaikh, S. Hafeez, B. Rashid, S. Mahmood, M.A. Baig, Optical emission studies of the mercury plasma generated by the fundamental, second and third harmonics of a Nd:YAG laser. J. Phys. D 39(20), 4377–4385 (2006)
A.E. Kramida, Y. Ralchenko, J. Reader, N.A. Team, NIST Atomic Spectra Database (version 5.1). (National Institute of Standards and Technology, Gaithersburg, MD), https://physics.nist.gov/asd. Accessed Sept 2019.
G. Cristoforetti, A. De Giacomo, M. Dell'Aglio, S. Legnaioli, E. Tognoni, V. Palleschi, N. Omenetto, Local thermodynamic equilibrium in laser-induced breakdown spectroscopy: beyond the McWhirter criterion. Spectrochim. Acta Part B 65(1), 86–95 (2010)
W.L. Wiese, M.W. Smith, B.M. Miles, Atomic transition probabilities. Vol. 2: sodium through calcium. A critical data compilation, U.S. Department of Commerce, National Bureau of Standards (Washington, DC), Report No. NSRDS-NBS (1969)
R.C. Hilborn, Einstein coefficients, cross sections, f values, dipole moments, and all that. Am. J. Phys. 50(11), 982–986 (1982)
N.H. Yen, L.Y. Wang, Reactive metals in explosives. Propellants Explos. Pyrotech. 37(2), 143–155 (2012)
I. Glassman, R.A. Yetter, Combustion, 4th edn. (Academic Press, New York, 2008)
E.T. Turkdogan, P. Grieveson, L.S. Darken, Enhancement of diffusion-limited rates of vaporization of metals. J. Phys. Chem. 67(8), 1647–1654 (1963)
This work was funded by the Defense Threat Reduction Agency under HDTRA-15-1-0006.
Conflict of interest
The authors declare that they have no conflict of interest.
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Electronic supplementary material
Below is the link to the electronic supplementary material.
About this article
Cite this article
Wainwright, E.R., Dean, S.W., De Lucia, F.C. et al. Effect of sample morphology on the spectral and spatiotemporal characteristics of laser-induced plasmas from aluminum. Appl. Phys. A 126, 83 (2020). https://doi.org/10.1007/s00339-019-3201-9