UNIVERSITY OF CYPRUS i t n e x PhD Thesis f a i j d SYNTHESIS OF REACTIVE STRUCTURES BY BALL MILLING AND ULTRASaONIC CONSOLIDATION H a i s a Anastasia Hadjiafxenti t s DEPARTMENT OF MECHANICAL AND a MANUFACTURING ENGINEERING n A 2012 i UNIVERSITY OF CYPRUS DEPARTMENT OF MECHANICAL AND MANUFACTURING ENGINEERING i t n e Synthesis of Reactive Structures by Ball Milling and Ultrasonic Consolidation x f a i Anastasia Hadjiafxenti j d a H Research Committee Associate Professor Claus Rebholz (supervisor) Professor Charalabos Doumanidis (committee head) a Assistant Professor Theodora Kyratsi (committee member) Professoir Steven Son (external committee member) s Professor Alexander Rogachev (external committee member) a t s a n A A Dissertation submitted to the Graduate School of the University of Cyprus in partial fulfilment of the requirements for the degree of Doctor in Philosophy 2012 ii i t n e x f a i j d a H Ἡ Ἰθάκη σ᾿ ἔδωσε τ᾿ ὡραῖο ταξίδι. Χωρὶς αὐτὴν δὲν θά ῾βγαινες στὸν δρόμο. Ἄλλα δὲν ἔχει νὰ σὲ δώσει πιά. a Κι ἂν πτωχικὴ τὴν βρεῖς, ἡ Ἰθάκη δὲν σὲ γέλασε. i Ἔτσι σοφὸς ποὺ ἔγινες, μὲ τόση πεῖρα, s ἤδη θὰ τὸ κατάλαβες οἱ Ἰθάκες τὶ σημαίνουν. a Κωνσταντίνος Καβάφης t s ------------------------------------------------------------ a Ithaka gave you a splendid journey. n Without her you would not have set out. She hasn't anything else to give you. A And if you find her poor, Ithaka hasn't deceived you. So wise you have become, of such experience, that already you'll have understood what these Ithakas mean. Constantinos Cavafy iii Preface i t n The research contained in this PhD Thesis is mainly based on experimental work carried out in the Mechanical and Manufacturing Engineering Departmenet at the University of Cyprus during the period from October 2007 to December 2012. This x project was devoted to the synthesis of reactive structures using two processes: Ball f Milling (BM) and Ultrasonic Powder Consolidation (UPC), the major and minor parts a of this thesis, respectively. Part of the work on UPC was carried out in the Mechanical i and Industrial Engineering Department at Northeastern University, Boston/USA, in j d April and May 2011. The work on BM was funded through a Marie Curie Excellence Team Award from the European Commission faor 27 months and through an industrial collaboration with Stuckenbrock Medizintechnik GmbH, Tuttlingen/Germany, for 2 H months, while work on UPC was funded by the Cyprus Research Promotion Foundation for 12 months via its Framework Programme for Research, Technological Development and Innovation, co-funded by athe Republic of Cyprus and the European Regional Development Fund. i s This study was mainly directed towards finding a way of approaching nanoscale a multilayer films/foils (MFs) exothermic behaviour (i.e. starting the self-propagating t exothermic reaction, SPER, by using a low energy spark from a battery) by producing s reactive compacts using BM and UPC, in an approach to decrease costs. MFs are a mainly produced through sputtering, which is a relatively expensive and time n consuming Physical Vapour Deposition (PVD) method for large scale manufacturing. Therefore, their use is limited to specialty applications which warrant their cost. MFs A have been industrially used for many years, especially for the bonding of different materials (e.g. ceramic on metal). Potential applications include soldering, adhesive bonding, polymer memory devices, lab-on-a-chip and hyperthermia for cancer treatment. Previous work on BM has been mostly focused on High-Energy BM (HEBM), where the high impact energies rapidly produce well-mixed powders within minutes, iv and intermetallic phase formation (e.g. in the Al-Ni system) during BM or after by uniform heating (e.g. using a hot plate) of green compacts. However, the high local heating during each impact event due to plastic deformation can cause mass diffusion, producing solid-state solutions at interfaces, thus reducing the overall available i enthalpies, or increase contamination originating from the steel or tungsten carbide balls t used during the process. It is highly desirable to retain most of the reactivity and punrity of the powders so that the ignition threshold is sufficiently low, which would enable e local ignition with a low-energy spark from a battery as opposed to uniform heating. x This is especially important if the materials to be joined cannot be uniformly heated to the required temperatures. Low-Energy BM (LEBM) employed in tfhis study is a viable a approach to circumvent this problem by reducing the energy of individual impact events at the expense of processing time. Experiments were carriied out in the Al–Ni system, j because both powders are relatively inexpensive, and their reactions are highly d exothermic and well characterized. a UPC, a relatively new processing tecHhnique, was mainly used for the synthesis of Al/Fe O and Al/Cu O compacts over a wide range of powder ratios at room 2 3 2 temperature, but also for the fabrication of Al-Ni compacts at various temperatures and a pressures. i s The research objectives included: a  Implement BM and UPC to create compacts that exhibit exothermic reactions, t with desired structures controlled by the processing conditions. s a  Develop well-consolidated compacts that allow for easier ignition and maximum n heat release. A  Optimize BM and USC parameters to enhance the resultant heat-release upon ignition.  Evaluate the structural, chemical and thermal properties of powder compacts.  Study the thermal evolution of ignited powder compacts through Infrared Camera monitoring of the reaction, and evaluate the reaction front propagation using high speed camera analysis. v This work has resulted in the following highlights:  Self-propagating high temperature reactions in compacted pellets of interrupted and continuous low-energy ball milled Al and Ni powders at a composition corresponding to AlNi , and continuous ball milled powders at a composition of 3 i t AlNi. n  Formation of a bi-modal structure with nanoscale lamella of Al and Ni weith increasing milling time for both AlNi and AlNi. 3 x f  Ball milled powders cold-pressed into pellets have similar characteristics to MFs a in terms of phase formation sequence and exothermic peak shifts. i j  LEBM of Al/Ni particles with an overall compdosition of NiAl can produce powders, which upon cold-compaction into pellets can be locally ignited (in the a same way as MFs) using a low energy spark and react in a self-propagating H manner with uniform thermal fronts having velocities up to 0.24 m/s.  Ball milled powders can potentially be incorporated into pure foils or surfaces a using rolling to generate thick reactive foils suitable for large scale bonding and i can be ignited away from the weld interface using a spark. s a  Development of Al-based thermite composites, Al/Fe O and Al/Cu O, over a 2 3 2 wide trange of powder ratios at room temperature by UPC. Short processing s times and non-requirement of special processing conditions make this process avery promising. n The work in this thesis has resulted in six papers to date (four main- and two co- A authored); more are planned: 1) Synthesis of Reactive Al/Ni Structures by Ball Milling A. Hadjiafxenti, I.E. Gunduz, C. Tsotsos, T. Kyratsi, C.C. Doumanidis and C. Rebholz Intermetallics, vol. 18, p. 2219, 2010 vi 2) The Influence of Structure on Thermal Behavior of Reactive Al-Ni Powder Mixtures Formed by Ball Milling A. Hadjiafxenti, I.E. Gunduz, C. Tsotsos, S.M. Aouadi, T. Kyratsi, C.C. Doumanidis and C. Rebholz i Journal of Alloys and Compounds, vol. 505, p. 467, 2010 t n 3) Exothermic Reaction Characteristics of Continuously Ball Milled Al/Ni e Powder Compacts x A. Hadjiafxenti, I.E. Gunduz, T. Kyratsi, C.C. Doumanidis, C. Rebholz Vacuum (under revision) f a 4) Fabrication, Characterization and Applications of Novel Nanoheater i j Structures d Z. Gu, Q. Cui, J. Chen, J. Buckley, T. Ando, D. Erdeniz, P. Wong, A. a Hadjiafxenti, P. Epaminonda, I.E. Gunduz, C. Rebholz and C.C. Doumanidis Surface Coatings and Technology, 20H12 (in press); http://dx.doi.org/10.1016/j.surfcoat.2012.06.095 a 5) Spark Ignitable Green Compacts of Continuously Ball-Milled Al/Ni Powders at NiAl Ciomposition s A. Hadjiafxenti, I.E. Gunduz, C.C. Doumanidis and C. Rebholz a Scripta Materialia (under review) t s 6) Ultrasonic Consolidation and Ignition Characteristics of Thermite aComposites S. K. Pillai, A. Hadjiafxenti, T. Ando, C.C. Doumanidis and C. Rebholz n International Journal of Applied Ceramic Technology, vol. 9, p. 206, 2012 A The author’s contribution to the papers In Papers 1-3, I planned and performed all synthesis, completed all the ignition tests using IR and HS cameras, performed all the characterization using SEM, XRD, and DSC, carried out the evaluation/analysis and wrote the papers. vii In Papers 4-5, I planned and performed the synthesis and the analysis based on the Ball Milled experiments, i.e. I performed all the ignition tests using HS camera, performed all the characterization using SEM, XRD, and DSC, carried out most of the evaluation and finally contributed to writing the papers. i t In Paper 6, I helped planning the experiments, contributed to the ignition tests using HS n cameras and performed the characterization using SEM, XRD and DSC. e x f a i j d a H a i s a t s a n A viii Acknowledgements i During my PhD studies I have received help from many people to whom I feel t n grateful. I believe that without their help I might not had the strength and will to finish these studies successfully. e x Hence, I would like to gratitude people within the community of the University f a - Prof. Claus Rebholz, my supervisor, who introduced me to his research team, while with patience and encouragement, supported imy research efforts. j d - Dr. Emre Gunduz, without whom I believe I would not have been able to fulfill a successfully this PhD. His knowledge and guidance were valuable and he always supported me even from abHroad. - Mr. Kyriakos Roussias and Mr. George Vessiaris for their laboratory help. a - Mrs. Chrysi and Miaria also, for help at the Latsia Lab, since their contribution s helped me to save time and fuel. a I would also like to thank people outside my research, who were by my side night t and day, sgiving me the strength to move on and finally to be able to finish with this large step in my life. Hence, I would like to thank my family – father, mother, sister and a two brothers. I hope in the next years we will rejoice when remembering my stress n during the countless weeks and weekends, in addition to the nights I spent at UCY. Last A but not least, a person who always supported me, and spend with me plenty of time in the lab, especially the last two years, my husband Doros, who never refused an evening walk to the lab. Thank you all, I really appreciate your help! ix Abstract i Nanoscale and microscale heating sources, produced by methods such as sputteringt, n chemical reduction and electrochemical deposition, have received increasing attention in recent years as enabling tools for nanofabrication/-manufacturing. These exeothermic materials consist of heterostructures made of reactive multi-material systems, e.g. x bimetallic aluminum (Al) and nickel (Ni) networks, which upon external ignition f release locally concentrated exothermic heat. a i Sputter deposited nanoscale multilayer films/foils (MFs) employed as nanoheater j sources appear very promising in thermal nanotecdhnology, since they are stable, reliable, can be ignited relatively easily with a low-energy spark from a battery, and a show self-propagating exothermic reactions (SPER). However, the usage of MFs is H restricted due to their high production costs (mainly using Physical Vapour Deposition). This thesis was directed towards finding a way of approaching the exothermic behaviour of MFs by producinga reactive compacts using mainly Ball Milling (BM), and to a lesser extent Ultrasonic Powder Consolidation (UPC). i s Although BM has been used extensively to produce materials Al/Ni compounds a with superior high-temperature mechanical properties, here the use of low-energy t interrupted and continuous BM to synthesize materials that exhibit SPER is reported. s Low–Energy BM (LEBM) was used to mix Al/Ni powders with molar ratios of 1:3 and a 1:1, to refine the composite particle microstructures up to the formation of nickel naluminides, and to determine the critical milling time in order to produce ignitable compacts. Experiments were carried out in the Al–Ni system, because both powders are A relatively inexpensive, and their reactions are highly exothermic and well characterized. The milled powders were cold-compacted into pellets and ignited along their edges using either a small propane flame source or a low energy spark from a 9 V battery. The reactions were investigated using high-speed optical and infrared cameras to measure the thermal front velocity, local ignition and maximum pellet temperatures, overall sample temperatures during ignition and the time required for ignition. The pellets were characterized using Differential Scanning Calorimetry (DSC) to measure the overall x