32 Chapter 2 Making of metallic glasses and applications Making metallic glasses 2 2 e Casting into a mold In the mold casting method, ingots of the desired alloy composition are obtained by arc melting a mixture of the pure metal elements in a Ti-gettered argon atmosphere (Fig. 2.2.1) (a) (b) FIGURE 2.2.1 Are melting laboratory set up at Shanghai University: (a) a view of the vacuum chamber containing the ingot and viewing and sensing ports; (b) a view of the copper mold for casting seen through the viewing port; (c) a view of the complete assembly (Li et al., 2012), A getter is a deposit of reactive material which is placed inside a vacuum system to remove un- wanted chemical substances, usually in the form of gas. When gas molecules inside the chamber strike the getter material, they combine with it chemically or by physical absorption. Therefore, the getter is a reactive material that is deliberately placed inside a vacuum system for the purpose of improving the efficiency of that vacuum by scavenging unwanted contaminants, A getter eliminates minute amounts of unwanted gases from the already evacuated space. The Ti-getter is usually applied as a coating to the surface of the chamber. To avoid being contaminated by the atmosphere, the getter must be introduced into the vacuum system in an inactive form during assembly, and activated after evacuation. Argon, which is used in the welding of many alloys, is used as a shield gas because it does not react with whichever gases and/or metals are present in the vicinity of the metals being welded. It displacesCasting intoamold 33 other unwanted reactive gases such as nitrogen and oxygen. Similar to its role in welding, argon is used in the synthesis of metallic glasses because it prevents oxidation and displaces unwanted gases such as carbon monoxide. After melting is completed, the liquid alloy is cast into copper molds by suction, to form plate-like samples with a size typically of 5 x 70 x 30 mm or a rod-like sample of 70 x 30 mm, A picture of the melting furnace and the copper mould is shown in Fig. 2.2.2(a)-(b). Positive pressure casting KA Negative pressure casting (b) () FIGURE 2.2.2 (a) A furnace for melting and injection casting metallic components; (b) copper mold with a sample of metallic glass; (c) schematic illustration of positive pressure casting, and negative (suction) pressure casting. Copper mold suction and centrifugal castings are successful in producing BMG samples of differ- ent compositions. The suction casting process shows some practical advantages due (o its operational conditions of less time per cycle, faster melting time, smaller chamber volume, and smaller amount of consumable materials (ceramic crucibles). These conditions also contribute to less oxygen contamina- tion in the suction casting process. For example, the oxygen content in Cu-based alloys of Cu-Zr-Al alloys has a detrimental effect on the glass forming ability (GFA) and on the solidification behavior, leading to the nucleation of primary phases during solidification at low cooling rates. BMG samples prepared by negative pressure casting (Fig. 2.2.2) have higher strength and larger plasticity compared to those prepared by positive pressure casting. The applied reversed pressure plays a key role not only in the formation of cast defect at macro-scale but also in the distribution of free volume at micro-scale, which is responsible for the variable values of strength and plasticity. In the copper mold casting process, negative pressure is also beneficial for reducing the porosity content and homogeneous distribution of free volume, which in turn leads to the improvement in reliability of the BMGs. Fig. 2.2.3 shows two dies, one made from a copper alloy and the other from heat resistant steel. The different die materials were used to test the influence of heat conduction on glass formation and on the die life. Heat-resistant steel has a low heat-conduction rate of 33 W/mK compared with a Cu alloy having a high heat-conduction rate of 230 W/mK. The steel die may be a more suitable choice because of a lower cooling rate during solidification, better thermal contact, higher tool life, and lower manufacturing cost.34 Chapter 2 Making of metallic glasses and applications cad / ‘stotsteove Moen aly *Psan FIGURE 2.2.3 ‘Two types of die (stainless steel and copper alloy) used to establish suitability for casting BMG alloys (see text for explanation), X-ray diffraction and transmission electron microscopy analyses are carried out after casting to confirm the amorphous nature of the as-cast samples. The thermal properties of the alloy are measured using a differential scanning calorimeter (DSC), typically at a heating rate of 20 K/min. The glass transition temperature Ty and crystallization onset temperature T, are determined from the recordings of heat against temperature The ZrasCuso,14A8s.36AlsBer.s alloy has been developed which can be cast into amorphous rods with 73 mm diameter by copper mold casting (Lou et al., 2011). The strong glass-forming ability of this alloy is closely related to the addition of beryllium (Be), which not only suppresses the phase sep- aration happening in the as-cast Be-free BMG but also sustains low Gibbs free energy difference for crystallization. This finding stimulates more interest in developing BMGs and their industrial applica- tions. In 1960 the initial thickness of ribbons made from Au-Si alloy was less than 10 jum, Research and development lead to new alloys with higher glass-forming ability and larger casting sizes, as shown in Fig. 2.2.4. ‘As many studies have already shown, element purity and melting as well as casting conditions are decisive factors determining the quality of BMG samples in terms of achieving single-phase chemi- cally homogeneous glassy states for Zr52 sCu17 9Nit4.6AlioTis (Vitreloy 105) ingot production. The large difference in the melting temperatures of the elements, varying from 933.5 K (Al) to 2,125 K (Zs), causes difficulties in obtaining homogeneous master alloys in the common procedure for BMG preparation, An appropriate mixture of single constituent elements Zr, Cu, Ni, Al, and Ti with very highSpinning wheel method 35 10 wl PaCuNiP ZT-CuNeBe, @2hiNi-Cu 1 Panera “agen Ura fanPo sb Bo rarer! 3 Pé-CuSi a 0.01 “ Rosi . 1 tes 900 1970 1960 7990 "2000 2010 Year FIGURE 2.2.4 ‘A graph showing improvement in the maximum thickness (dimension) of a casting that has increased with time (years) through alloy development (Tsai et al., 2017). purity (> 99.9%) are used for are melting on a Cu hearth under highly purified Ti-gettered Ar atmo- sphere, To ensure a homogeneous chemical composition, the ingots with 2 mass of 20 g are remelted at least three times. A new procedure has been developed to ameliorate the standard method. In this procedure four bi- nary pre-alloys are prepared separately and used as starting material. The final Zrs,sCut7.9Ni146AhoTis master alloy is remelted in several steps for homogenization. Then, flat BMG specimens (3 mm x 10 mm x 85 mm) are cast using the master alloy ingots by means of suction casting into a copper mold. Spinning wheel method In continuous casting, liquid metal is fed into an apparatus where heat is extracted and from which the resulting solid product is collected. Spin casting is one of several continuous casting methods. Typically, with such methods, heat and fluid flow as well as solid-state deformation are important within the processed material. Heat transfer and deformation are important in the contacting device. In spin casting, the heat sink is a single wheel, and deformation effects can often be neglected. Planar flow casting is a particular variant of spin casting where the heat and fluid flow are only weakly coupled. Spin casting, also called melt spinning, involves an impact of the molten metal under pressure onto the solid spinning wheel, with large velocity and thermal gradients, causing a phase-change (liquid to solid). Interest in rapid solidification has led to developments in the so-called chill-block and planar flow casting. The development can be traced back to the “splat-quench” experiments performed in research laboratories in the early stages of making amorphous metals. The main goal of these experiments was36 Chapter 2 Making of metallic glasses and applications (b) FIGURE 2.2.5 (a) Copper wheel spinning on horizontal axis; (b) complete laboratory spinning wheel apparatus at Shanghai Uni- versity. Quartz cot container Motten alloy S. High frequency power supply ‘strut (a) FIGURE 2.2.6 ‘Schematic drawing of a horizontal wheel spinning on the vertical axis (Nowosielski and Babilas, 2007), to cool the liquid metal sufficiently rapidly to achieve micro-crystalline or glassy micro-structure. In such experiments a single drop of molten metal deforms on impact with a cooled substrate (“splat”) and simultaneously freezes (“quench”) (Figs. 2.2.5 and 2.2.6).High-pressure torsion 37 ‘The molten material is driven from a nozzle in the form of a jet, which on impingement with the rotating disc forms a melt puddle. The shape of the puddle is formed under the counteracting forces of the tangential flow of the material and surface adhesion. Because of a large temperature difference at the melt-substrate interface, the melt beneath the puddle solidifies into a ribbon. A good control over the ribbon dimensions and cooling rate can be achieved with a proper control on the melt pressure, nozzle inclination, and nozzle diameter. The high rotational velocity of the wheel (on the order of 40 m/s) produces a thin (10-100 um) ribbon-like solid material, which is found to have amorphous structure. The ribbon thickness, /i, is given, to a first approximation, by the following expression (Budhani et al., 1982): Ar ne e220 where AT is the temperature difference between the opposite sides of the ribbon (top and bottom), and AH is the heat of solidification per unit volume of the melt. High-pressure torsion High-pressure torsion (HPT) has been shown to be an effective technique to synthesize bulk nano- structured materials with superior mechanical properties, such as high strength and good ductility, super-plasticity at high strain rate and low temperatures, high toughness, and high wear resistance. The transition of the crystalline phase into amorphous state is caused by the direct effect of se- vere deformation resulting from the specific mechanical action (Fig. 2.2.7). The deformation-induced dissolution of crystalline particles is usually associated with the movement and diffusion of atoms Compression stage Compression+Torsion stage => eS => 2 (a) (b) FIGURE 2.2.7 ‘A depiction of the high-pressure high-torsion method (HPT) (Meng ct al., 2013).38 Chapter 2 Making of metallic glasses and applications 16, 15 |ge Mito! — FEM simulation @ Experiments gt c E z at s z Comoresion 2 E12 2 . ee | 7 10. ° 7 9 og FSGS EEE TG Bt SO to" o a0 120 180 240 a0 a0 A SGOT TOT BO OO Rotation Angle, degree Diffraction Angle, 26(Cu-Ka) (a) (b) FIGURE 2.2.8 ‘Changes occurring ina sample subjected to HPT process: (a) decreasing thickness ofthe sample under pressure and torsion; (b) micro-structural changes detected by X-ray diffraction, from N =0to N = $0 rotations. in the stress field of dislocations gliding through the crystalline grains. Individual grains break up into smaller and smaller sub-grains until they disappear into the amorphous matrix. The deformation- induced transition from the crystalline to amorphous state also involves redistribution of one or more alloy components. This is most evident in the cases where the chemical compositions of the initial crystalline phase and the final amorphous phase differ substantially. Itis found that the ability to deformation-induced amorphization by high-pressure torsion at room temperature substantially differs from the ability to amorphization by melt quenching. This is due to the difference in the physical conditions controlling the amorphization by severe plastic deformation compared to melt quenching. During the HPT process the thickness of the metallic sample d sive plastic deformation under the applied pressure, and second by high shear during torsional rotations as shown in Fig. 2.2.8(a). A sample gradually changes its micro-structure from purely crystalline to amorphous, as evidenced by X-ray diffraction shown in Fig. 2.2.8(b). es, first as a result of compres- Ti-Ni alloy An alloy of TiNi, a B2 intermetallic compound, is an important engineering material because of its su- perior shape memory and superelastic properties. The alloy with a composition of 50.6 at.%Ni and 49.4 at, %Ti has been studied by (Huang et al., 2004). Metallurgical analysis of the alloy using transmission electron microscopy (TEM) showed that the initial quenched sample has an austenitic B2 (CsCl-type) structure with a grain size of about 30 jm (Fig. 2.2.9(a)). A small amount of NigTi precipitates (less than 0.5%) was found in the initial material. The B2 TiNi has been amorphized by various techniques, such as electron irradiation, shot pening, cold rolling, and high-pressure extrusion.High-pressure torsion 39 re 2s een Pee Ree FIGURE 2.2.9 Micro-structure of the TiNi samples subjected to HPT: (a) initial micro-structure showing erystalline grains devel- oping amorphous grain boundaries; (b) small amorphous region in poly-crystalline matrix; (c) fully amorphized sample (Huang et al, 2004) () (b) FIGURE 2.2.10 Electron diffraction patterns of the TINi samples subjected to HPT: (a) fully amorphous halo; (b) poly-crystalline pattern with amorphous halo; (c) microcrystalline pattern with texture and amorphous halo (Huang et al., 2004), After HPT, the sample becomes amorphous, as shown by the TEM micro-graph in Fig. (c) and by the corresponding electron diffraction pattern shown in Fig. \(c). It is seen that the amorphous phase has a homogeneous contrast, and the corresponding electron diffraction pattern shows two amor- phous rings, as expected. In addition to the pure amorphous regions, nano-crystalline grains co-existing with the amorphous phase were also observed, as shown in Figs. 2.2.9(b) and 2.2.10(b). All the diffraction rings can be indexed as those of B2 TiNi phase. It should be noted that the (100) diffraction ring appears in almost all the electron diffraction patterns from the nano-crystalline regions,40 Chapter 2 Making of metallic glasses and applications = A-e(Fesi) ¥-FeAD,P) @-FesO Be § ew R boo : ‘ = i 2 z 1 « 2 « nt = | cota 1 ee} HO HO oe Angle 28, deg. (a) (>) FIGURE 2.2.11 (@) Temperature evolution at the center of the metallic glass sample during three experiments with rotational speeds of 60, 120, and 180 seconds per revolution (Hobor et al., 2010); (b) changes of the micro-structure with rotation indicated by X-ray scattering curves, from highly crystalline (bottom curve) to almost amorphous (upper curves broad peaks). ndicating that the nano-grains still exist in the ordered B2 structure, and no chemical disordering has occurred. These different morphologies indicate that the amorphization process during the HPT may not be homogeneous. Fe7sBg sSigP4.5 alloy Numerical calculations based on quasi-three-dimensional heat conduction equations have satisfactorily described the micro-structural features and thermal behavior of amorphous Fe7Bg 5SigP45 alloy pro- cessed by HPT with different shear rates. The calculated temperature curves, shown in Fig. 2.2.1 (a), clearly indicate that the rate of temperature rise, as well as the saturation temperature, strongly depends ‘on the speed of rotation and time. For a relatively fast rotation (60 s per rotation) the temperature quickly rises from room temperature to the glass transition temperature (; =710 K) in about one minute, which corresponds to one rota- tion. At this temperature recrystallisation will occur, thus negating the attempt to produce an amorphous solid, Slowing down the rotation speed by a factor of 2 or 3 reduces temperature rise significantly, and consequently amorphization will take place. The destruction of the crystalline structure occurs rapidly in this alloy, as evidenced by X-ray scattering results shown in Fig. 2.2.11 (b). The Bragg peaks of the crystalline state broaden and loose in intensity, and practically disappear after 4 turns, leaving broad amorphous peaks. ZrTiNiCu alloy Compare the extreme variation of free volume for the ZrTiNiCu alloy (yellow line) with that of TiNiCu alloy (red line) in Fig. 2.2.12. The difference between the two alloys is the presence of zirconium inBall milling 41 1,00 t {ews = -HPT,N=50 —L, g 1 000) KON fe Slim A oe = 9.60 z 7 3 ee Nitin z lw tf i “& ZroNinTindus | E se TistNinsCuss 5 020 oe FenBessiores(n] ce FnBsssiores (2) | | 441 t 0.00 + o 1 2 3 4 5 6 7 360 450. 550 650 750 850 a Temperature, T/K (a) (b) FIGURE 2.2.12 (@) Variation of the volume fraction of the erystalline phase on the number of rotations for 5 alloys. The volume fraction was normalized to 100% of the initial crystalline phase at n = 0 (Sundeev et a., 2014). (b) Dependence of the glass transition temperature T,, measured by DSC, on the aluminium content in the ZrCuA\ alloy, following, HPT treatment (Meng et al., 2013) one, and the absence of it in the other, as well as a difference in composition. It appears that the addition of zirconium makes an enormous difference to retention of free volume during the rotations under pressure. Therefore the ability to deform under torsion is a strong function of the composition of the metallic glassy alloys. Ball milling The synthesis of nano-materials and amorphization by a simple, low cost, and high yield method has been a challenge since the very carly developments. The high-energy ball milling has been widely used for the synthesis of various nano-alloys, and nano-quasi-crystalline materials. Mechanical alloying techniques have been utilized to produce amorphous and nano-crystalline alloys, as well as metal/non- metal nano-composite materials by milling and post-annealing, of elemental or compound powders in an inert atmosphere. Mechanical alloying is a non-equilibrium processing technique in which different elemental pow- ders are milled in an inert atmosphere to create a mixed powder with the same composition as the constituents. In high-energy ball milling, plastic deformation, cold-welding, and fracture are predom- inant effects, in which the deformation leads to a change in particle shape, cold-welding leads to an increase in particle size, and fracture leads to a decrease in particle size, resulting in the formation of fine dispersed alloyed particles in the gr42 Chapter 2 Making of metallic glasses and applications Relative Intensity 1 i 0 o 0 100 26 (deg) FIGURE 2.2.13, X-ray diffraction results from powder samples: (I) initially before ball milling, (ID after 5 hours milling with wax added as lubricant, and (IID) 5 hours milling without wax (Araijo et al., 2000). Mechanical milling can induce defects and activate the frozen state of nano-materials’ configuration and lead to the formation of a stable or meta-stable composition. The experimental parameters often play some roles to change the composition, and consequently may lead to a phase transformation which does not form the equilibrium or stable phase. Therefore, it is necessary to control experiments without, any contamination. ‘An example of the structural changes in the powders being processed by ball milling is shown by the graphs in Fig. 2.2.13. The conversion of the powders into an amorphous mixture is obtained after 5 hours of ball milling without lubricant (wax) Cold rolling An alternate route to producing samples by ball milling, with high levels of both plastic deformation and inter-facial area, is by cold rolling of layered elemental sheets which are folded between each deformation cycle. The uncertainty of the effective temperature during ball milling is removed since the sample is in intimate contact with the massive rolls and deformation can be performed at low strain rate to maintain ambient temperature. A complete amorphous phase formation in binary CugoZr4o, ternary CussTizsZrio, and quaternary Cug7TigsZrioNig systems has been studied by (Dinda et al., 2007) by repeated cold rolling foils of each pure metal at ambient temperature. The folded foil samples were rolled in a 2-high rolling mill (diameter of the rolls 150 mm) at a strain rate of approximately 0.5 s~! to a thickness of about 200 um to obtain the starting material. Thereafter, the sample consisting of layers of foils, was folded andCold rolling 43 FIGURE 2.2.14 Side views of the rolled samples of the CuggZrag alloy (Dinda et al., 2007). FIGURE 2.2.15 Intensity [Counts] 100 X (F&R) ee 80 X( F&R) 6000 fox F&R) a 40 X (F&R) 2000 2X (FER) ° -2000 “3 5x:FaR) 2a 0 0 0 0 1 ® ‘A good example of the changes in X-ray scattering from ZrCu alloy samples subjected to folding and rolling (F&R), ‘The crystalline Bragg peaks gradually broaden and merge into the amorphous peaks (Sagel et a., 1998). then rolled for 10 subsequent times with a continuously decreasing spacing between the rolls until the thickness was decreased to about 200 um. This F&R procedure was repeated until the final material was cold-rolled for up to 70-100 passes. Small pieces of the samples were cut during the rolling and used for analysis. The side-on view of the samples is shown in Fig. 2.2.14. ‘The characteristics of the amorphous phase (Fig. 2.2.15) developed by repeated cold deformation indicate that it is compositionally homogeneous, structurally more relaxed as compared to mechani- cally alloyed (ball milling) amorphous powders of similar composition, and without the typical impu- rity levels obtained by mechanical alloying,