bulk metallic glasses processability
Petrescu, Phillip Beto, Chan Guanying, Florian Ion T.
Petrescu, Francisco tamborino and Antonio appicola.
This is an open access article distributed under the terms of the creation Commons attribution license, which allows unrestricted use, distribution and reproduction on any media, provided that the original author and source are credited
Bulk metal glass (BMGs)
Even known as bulk amorphous alloys, it is a new type of advanced material with disordered atoms. Structure of scale.
Their unique microstructure gives excellent physical and chemical properties (Huang et al. , 2016)
To the manufacturer (Schroeder in 2020b; Schroers et al. , 1999; Mirsayar et al. , 2016, 2017).
The range atomic order results in the unique physical, chemical and mechanical properties of bulk metallic glass, which have pilot applications in a wide range of fields from sporting goods to precision mechanical components, electronic and biomedical (Wang et al. , 2004;
Schroeder in 20 yearsKumar et al. , 2009;
Bamboo inside the well, 2011). Zr-
BMGs-based technologies attract people because they can be processed into larger parts due to their wide range of super parts
Cooling liquid areas and high glass-Ability to form. Among the Zr-
Recently developed Cu, Al, Ti, Ni (Wang, 2007; Shen et al. , 2005; Jiang et al. , 2008; Liu et al. , 2007; Mattern et al. , 2002)
, We studied a commercial BMG containing the same atom but adding Be.
In the past few years
The bulk material based on its superior glass forming capability has been thoroughly explored (GFA).
These performance advantages include high mechanical strength, high fracture strength, excellent elastic limit and good and precise deformation capacity, good scalability, low expansion coefficient and excellent corrosion/wear resistance (Aversa et al. , 2016a; 2016b; 2016c; 2016d; 2016e; 2016f; 2016g; 2016h; 2016i; 2016j; 2016k; 2016l).
The zirconium-based BMGs multivariate alloys have excellent GFA, which can be produced into parts with a thickness greater than a few centimeters through traditional melting and casting techniques (Liu et al. , 2002).
In addition to other advantages, the utilization of BMGs reduces process costs and provides the possibility to manufacture a variety of industrial products (
Morito and Egami, 1984; Aversa et al. , 2016 a-o, 2017 a-e).
Compared with other conventional metals, the microstructure of BMGs has the advantage of not presenting for a long time
Series of ordered crystal structures.
On the contrary, their microstructure has a short
A range of organized amorphous arrangements, which are characteristic of all glass materials, such as glass materials in ceramics and polymers (Busch, 2000; Petrescu et al. , 2016 a-e).
Therefore, an important problem in the processing of glass forming materials is the flow of molten materials during cooling.
This problem is particularly critical for the thermodynamics of popular Crystal forming materials.
For these materials, such as metals, a sufficiently high cooling rate is required to avoid molten crystals and maintain a liquid amorphous structure (Huang et al. , 2016)
In Cured Glass (
De benetty and Stringer, 2001; Eckert et al. , 1998).
The heat of the melting that describes the interaction between the basic molecules and atoms occurring in the liquid phase has been studied in depth, and different imaging and theoretical models have been proposed in the literature (Eyring, 1936;
Glasstone, etc. , 1941).
Eyring has developed many different models to predict the viscosity of liquid (1936).
Considering one of the modifications of the atomic structure to better adapt to metal melting, the derivation is as follows :(1)
Among them, di is the diameter of the space occupied by atomic species.
These methods have been verified for single metal or simple biMetal alloy.
There are usually three or more metal atoms of different sizes and physical properties that form a glass-like metal structure, so a more complex model should be applied.
This atomic/molecular dynamics method, which is contrary to fluid dynamics, does not utilize a state equation or a direct continuum-
A class equation, but it is directly based on the Law of interaction between atoms (
Cubic and Mason, 2012)
The influence of inertia controlling the molten flow on the viscous force is derived.
In a moving fluid, flow instability can be generated at different sizes (Fig. 1).
The dynamics can describe Kelvin-Helmholtz (Fig. 1d)
Patterns like streets (Fig. 1d).
The molecular dynamics of the alloy atomic interaction and the derived flow properties can be used to quantitatively evaluate the evolution of the molten BMG fluid dynamics of the micro-fluid turbulence in complex component alloys.
The future development of computing resource capability includes that any increase in the complexity of simulation computing does not necessarily accompany the reduction of the scale of the system to be modeled.
A computing tool that no longer takes into account the size and size will result in a potential increase in processing complexity, which will greatly improve the fidelity of the simulation.
Future machines can enable complete tissue engineering modeling of human cells or a set of cells to overcome technical barriers, as this has already happened in the pioneering work of our research team (
Annunziata, etc. , 2006; Apicella et al. , 2010; 2015;
Apicella and Aversa, 2016; Aversa et al. , 2009; 2016b; 2016c; 2016d; 2016e; 2016f; 2016g; 2016h; 2016i; 2016j; 2016k; 2016l;
Sorentino, etc. , 2007)
Here, we evaluate the connections on the atomic, molecular and cellular scales of physics, chemistry, and biology. High-
The performance molecular dynamics code (Alchorn, 2008)
Study on the formation and evolution of Kelvin-
Flow instability of Helmholtz microfluids using molecular dynamics techniques (Fig. 1a-c).
By (Gostin et al. , 2010; Aversa et al. , 2016e)
The difference in atomic radius and the free energy of mixing between components are conducive to the generation of structures with short, medium non-uniform chemistry and morphology rather than uniform
A range order that causes partial component separation or phase separation (Aversa et al. , 2016e).
Except for these chemicals.
The physical properties, the effects of treatment on local flow and the derived micro-fluid flow instability may further facilitate phase separation, which has been studied and discussed in this study (Trachenko, 2008).
Specifically, we analyze here the results of morphological microscopic observations performed by optical, ion, and electron microscopy on injection molded glass metal plates.
Commercial bulk metal glass made of materials and procedural atoms Zr44Ti11Cu10Ni10Be25 (
LM001B, California liquid metal technology company, USA)
In the form of an injection mold board of 3 and 2mm thick (
Engel injection molding machine, 1050-1100°C)
The size of 13mm per side is used (Fig.
2. left hand side).
The water jet cuts the sample observed by the microscope from the plate.
Three areas of the sample were investigated.
Transverse and surface cutting samples (
Figure and see the third surface area of the obvious molding defect. FEI Scios Dual-
Beam ion and electron microscopy and Leitz optical microscopy were used.
Surface etching of the sample using methanol (33. 3%)
Hydrochloric acid (33. 3%), Nitric acid (33. 3%)
, Hf 0. 1% (
Petrescu and calauti, 2016-b).
In particular, we check the surface defects (Fig.
2. bottom right hand side)
The presence of an unstable mode of microfluid flow.
Internal surface morphology and cross
The part of the surface defect is by using the FEI Scios dual beam of FIB (
For cross-section and scanning electron microscopy (SEM)
For morphological analysis and chemical composition analysis (
Energy dispersion spectrum (EDS).
Results and discussion surface scanning electron microscopy reveals the presence of surface groove-like defects that are characteristic of the flow instability observed in polymer injection molding parts (Fig. 3).
These melt flow instability is usually related to filling the mold forward. Kelvin-Helmholtz (KH)
When the adjacent fluid layer experiences a high shear force, the flow instability is described as the occurrence, which proves the transition from smooth to turbulent, similar to the large red dots and other fluid swirls that can be seen in Jupiter\'s atmosphereFig. 4a).
However, in our case, the instability of the flow occurs in the micro-scale level (Fig.
Left hand side).
Focused Ion Beam (FIB)cross-
The part of the groove defect is shown in the figure. 5.
Shape of the cross-
The segmented grooves show maturity and overlap (Fig. 5 right)
Molten flow of metal.
When the mold is too cold and/or slow forward front leads to early polymer glass transition or high viscosity accumulation, similar surface defects are observed in polymer injection molding partsup.
Surface defects of glass metal injection molded parts may be due to the same reason.
In fact, a supercooled mold can produce a high temperature gradient through a molten metal (Fig. 9)
Lead to changes in high viscosity, increase instability and micro-fluid flow
Groove and corrugated formation (
In the picture. 9)
See figure, for example. 3 (right top)and 5.
In fact, the cooling rate is lower in the center than in the external area of the sample, which adds a short-
Therefore, the range order of the crystalphase grains.
In addition, in the injection-molded part, in the area near the solidified glass, the flow of the molten alloy may cause high shear stress, there is a static fluid, but it has a high viscous layer (Fig. 9).
Therefore, groove surface defects can be attributed to the flow of molten BMG microfluids in the mold, which are frozen by a glass transition process at the interface of the cold mold surface.
However, there are still some questions about the composition inside the unstable flow alignment. Figure 2 (Top right), Fig.
4b and 6b show an optical microscope image of the acid etching surface of the injection partmolded sample.
The morphological development of the interface between two different velocity flows has experienced a transient state (Fig. 2a-c)
, Where the interface size growth of the dominant structure with the same diffusion control dynamics (Fig. 2c).
The theoretical shapes of the main KH structures evaluated using molecular dynamics methods are compared in figure 1
6 flow pattern shown with acid erosion on the surface of the plate section (Fig. 6 right).
The promotion of the momentum thickness formula is (Alchorn, 2008)
In very early stages, the interface grows at the square root of time (hundred of ps)
Regime related to momentum diffusion.
Various fluctuations induced at the atomic level lead to momentum diffusion and Vortex states (Fig. 2a)
Even in a higher range of dimensions, this is a feature of the behavior of continuous fluid dynamics (Fig. 4a and 4b).
Because it happens at a scale of 106 m in the wood Nebula pattern (Fig. 2a and 4a)
, Or in the flow of a river of 1 m (Fig. 2d).
When fluids with different densities and viscosity move each other, they cause unstable shear flow along the interface between these two fluid layers.
Similarly, atomic fluctuations caused similar instability patterns last month-3 meter scale (Fig. 5a-c).
It can be recognized in the figure. 7 (right)
Classic caman Whirlpool Street (Fig. 7 left)
, Which is formed by repeating the vortex generated by the unstable separation of fluid flow around the obstacle.
The formation of the vortex street occurs at a specific narrow ratio between the inertia force and the viscosity force, using the infinite Reynolds number (Re)
And achieve a typical value of about 90.
The Reynolds number connects the free flow speed of the undisturbed flow with the flow speed of the local fluid near the disturbance, that is :(2)
Where U is the speed of free flow without interference (Fig. 9)
L is the characteristic length of the interruption (
Or a solid interacting as it may be the thickness of the inner space of the mold as reported in figure 19)
And motion viscosity m0 (
Ratio of fluid density to its dynamic viscosity).
For common fluids under constant temperature conditions, the number of Re basically depends on the dynamic viscosity of the fluid, while for multi-component fluids, such as BMG molten alloys, fluid with different densities can be formed, this also depends on the fluid density.
In fact, in these liquids, a locally beneficial separation of thermodynamics may occur in the molten flow of compression and high shear (
Apicella and Aversa, 2016; Aversa et al. , 2016f)
Results in the formation of fluid at different densities.
Partial aggregation of atoms with different potential resistance and potential resistance
Then, the negative will cause the flow mixing change of the inertia force (
Depends on local density)
Adhesive force (
This depends on the local interatomic interaction in the molten alloy).
Local fluid instability is then generated.
Flow instability, in the form of a kárm á nvortex street pattern, exists in the Optical micrograph of the surface of the sample reported in figure 1
4b, 6b, 7a and 8.
This instability can be described in Kelvin.
The Helmholtz shear flow is generated by the different flow behavior of two fluid layers with different density and viscosity.
Layers of different densities and viscosity moving at different speeds produce what is called \"speed shear\" on the interface between the two fluids \". Aversa et al. (2016a)
The metal atomic segregation of BMG alloys when subjected to high shear adjacent flow (Fig. 9).
High Shear reduces the free energy of thermodynamic mixing, which is conducive to the generation of a more ordered structure with different components in large alloys.
The resulting density and viscosity differences can lead to local Kelvin-
Helmholtz mhoz instability, as observed in an optical microscope in the figure4, 6 and 7.
According to this atomic level method contrary to fluid dynamics, molecular dynamics does not use a state equation or a direct continuum-
Equation of magnitude, but it is based directly on the law of force between atoms.
New methods proposed by Alchorn (2008)
For microfluid flow dynamics, only the physical properties of the interaction are considered
The flow dynamic relationship is no longer considered as a numerical artifact related to temperature, pressure and other transmission properties (
Diffusion, viscosity and surface tension)
But they are derived directly from basic inter-atomic forces.
Instead, additional degrees of freedom are added to the fluid dynamics simulation to obtain the results of convergence, and the molecular dynamics method overcomes the limitations brought about by the use of high computational resources (Alchorn, 2008).
The surface etching of the sample surface and cross section clearly has a preferred corrosion path (
The dark area in the figure. 2, 4, 6 and 8).
Flow instability patterns can be identified in observed corrosion pits.
In particular, it can be assumed that flow instability is conducive to further separation of Cu-rich phases that are more susceptible to corrosion and corrosion.
Figure 8 compares the patterns found in the classic kármann Whirlpool Street and in different areas where the plate sections are corroded.
It can be inferred from the similarity of the geometric paths of corrosion to different interests on the surface of the sample.
EDS chemical composition analysis in different regions of the sample surface shows that differences in composition can be observed.
Partial segregation of components or phase separation in BMG samples confirm local corrosion by hole erosion instead of generalized corrosion after acid corrosion.
The flow instability of the interface between micro-fluid simulations of mixed fluids of different viscosity indicates that the mutual diffusion of atomic levels initially leads to the widening of the interface between the two fluids, thus activating the development of wave structures (Fig. 1a)
Vertical amplitude growth (Fig. 1b)
Badge forming Micron
Scale the vortex in the direction of flow (Fig.
Figure 1c and left. 6).
Once BMG is immersed in an acid solution, a couple can be formed in these different constituent areas, resulting in a classic point corrosion pattern as shown in the electron microscope as shown10.
EDS analysis is limited to zirconium, titanium, copper and nickel atoms.
Amorphous glass metal with zirconium-rich atoms (51,3%)
The area was found on the outer surface, while at 20-
Internal layer depth 60 microns (43,8%)
In contrast, the concentration of Ni and Cu atoms increased from 15 to 18%.
In addition, regions with significantly different components were observed.
Especially crystals rich in Cu and Ni (
25% instead of 15%)
The difference is in Zr (37%)
And other rich in zirconium (47%)
18% Cu and Ni were found.
In general, the zirconium element can promote the strong passivation of BMG to form zirconium-
Oxide with high protection for corrosion (Cai et al. , 2012).
Then, the zirconium-rich region may show higher corrosion resistance than the Cu-rich phase, and the Cu-rich phase is more prone to corrosion in the presence of cl (Tam et al. , 2007).
The difference in composition observed in our samples can be attributed to the heat and flow behavior of the melt during injection molding.
The viscosity of the BMG varies by many orders of magnitude from equilibrium liquid cooling to pre-glass pre-forming substeady under-cooling liquid.
In particular, the high temperature melt viscosity can be from about 10-Mono 3 Pa s
For dense polyatomic or simple binary liquids, _ 102 Pa s.
Assembly systems like our glass forming alloy (
1998. Ida and Gersley; Way et al. , 2007).
These shear stresses, when local crystals occur in shear bands formed in highly deformed BMG (Kanugo et al. , 2004)
Greatly reduce the nuclear energy barrier conducive to atomic aggregation and early formation of Nano and Micron
In our sample
Crystal particles of micron size are observed from layers between 20 and 40 microns on the outer surface (Aversa et al. , 2016b).
At this interface layer (Fig. 8)
The two driving forces act to induce aggregation, that is, a higher distance from the thermodynamic melting temperature, and a higher distance from atoms squeezed and compacted by strong high-speed shear stress (Report in the picture9).
According to the thermodynamic method proposed by Lee et al. (2006)
Energy Barrier (DG*)
The uniform core from the amorphous liquid is :(3)
With the change of the DGm = molar free energy in the transition amorphous/crystal phase, T is the temperature, P is the static hydraulic, g is the interface free energy to form the critical size crystal core)
DVm is the molar volume change of the transition between amorphous and crystal posture.
Indicates the elastic strain energy caused by the volume change, and E indicates the elastic modulus and.
According to Equation 3, in the area reported in figure 3, the presence of high-speed shear stress increases
9, the reduction in compaction of atoms producing molar volumes, the decrease in blocking energy DG *, accompanied by aggregation and phase separation, increases the possibility of generating flow instability.
Conclusion The microfluid shear flow instability, including the presence of fluids with different viscosity, has been observed in our injection molded bulk metallic glass. Our Zr44-Ti11-Cu10-Ni10-
Be25BMG formed by different space-bit barrier metal atoms experiences significant temperature gradients and shear flow stresses when injecting the mold.
This state of stress
Dynamically facilitates the aggregation of similar size atoms, resulting in micro-segregation
Fluid phase with different density and viscosity.
A wide variety of viscous flow instability such as folding and rotation can then be produced.
It has been discussed how in the process of injection into the mold, different space-bit barrier atoms are biased in BMG, resulting in melt with different viscosity and forming a flow.
These circulation forms a complex hierarchical flow pattern to rearrange itself, depending on the mold geometry and processing conditions that can be described by the infinite Reynolds number special value interval.
Finally, it is proved by microscopic observation that manufacturing process parameters, geometry, size and thickness may have a significant impact on the formation of microfluid defects.
The shape, type and distribution of these defects will be strongly dependent on the processing conditions.
In fact, for more complex parts and manufacturing processes with lower control of convection parameters, changes in the cooling rate inside the parts may result in-
Excessive thermal gradients and severe flow instability occur, especially in the interlayers between the cured external glass metal and the stationary fluid, but close to the melting of its glass transition, high shear strain.
Acknowledging the author\'s recognition of liquid metal technology, Ca usa providing samples for representation, Dr. Francesco Tatti (
FEI Company application expert SEM-SDB)
Preparation for SEM analysis.
The author\'s contribution all authors make the same contribution to the experimental part and the preparation of the paper.
This article is original.
The author states that this is not an ethical issue that may arise after the publication of the manuscript.
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