glassy amorphous metal injection
Chen Guanying, Petrescu, 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, is a class of disordered atoms-Structure of scale.
Their unique microstructure usually gives excellent performance (Huang et al. , 2016)
To the manufacturer.
In recent years, scientists and researchers have been studying zirconium-
Bulk material based on its superior glass forming capability (GFA)
And their mechanical properties.
Their properties range from high mechanical strength, high fracture strength, excellent elastic limit to good and precise deformation capacity, good scalability, low expansion coefficient and excellent corrosion/wear resistance (Trachenko, 2008).
The zirconium-based BMGs multivariate alloy has excellent glass forming capability (GFA)
They can be produced by conventional melting and casting techniques into parts with a thickness of more than a few centimeters (Liu et al. , 2002).
In addition to this, the advantage of BMGs is the networkshape as-
Cast form provides reduced process costs and offers the possibility to manufacture several custom tools related to special applications in a large number of industrial fields.
The critical cooling rate is high enough (>103°K/s)
It is necessary to make these glass from a molten alloy, in fact, the rapid solidification technology can maintain the liquid amorphous tissue (Huang et al. , 2016; Petrescu et al. , 2015; 2016;
Jamaluddin and others.
2016, Bush, 2000).
Microstructure is the most important feature of BMGs compared with traditional metals;
Ordinary metal for a long time
Ordered crystal structure;
Periodic grid with repeated patterns.
On the contrary, the microstructure of BMGs does not exist for a long time
However, the short-range amorphous structure of glass materials (
Ceramics, polymers and metals); (Aversa et al. , 2015; 2016a; Petrescu et al. , 2016).
Here we analyze the results of the observed morphology of ions and electron microscopy.
Using DSC 822 material and program differential scanning quantity Heat Meter Mettler tolledo operates at a constant heating rate of 1 K/min, and has been used for preliminary volumetric heat meter analysis of our BMG alloysFig. 1).
The sample studied in this paper is a large piece of metal Glass composed of Zr44Ti11Cu10Ni10Be25 (
LM001B, California liquid metal technology company, USA)
3mm thickness, 13mm size per side2.
The sample is cut from a plate made using the Engel injection molding machine, which is at 1050-1100°C.
The sample was selected because of obvious surface defects during the injection molding process.
All cuts and sample preparation are obtained from the plate by water jet cutting. FEI Scios Dual-
Beam has been used for micro, nano-
Representation of the structure of injection molded metal glass.
In particular, we study the presence of surface defects and crystalline phases through ion beam cross-sections (Mirsayar et al. , 2016, 2017;
Petrescu and calauti, 2016-b; Petrescu et al. , 2016 a-e).
Microscopic Observation of internal surface morphology and cross
The part of the surface defect level is by using the FEI Scios dual beam of the focused laser beam (FIB)for cross-
Slicing and scanning electron microscopy (SEM)
For morphological analysis.
The instrument is equipped with the energy dispersion spectrum of the chemical composition analysis detector (EDS).
Results and Discussion Figure 1 shows the DSC heat map.
1 heating section from 360 °C to 570 °C at 380-
Four discharge peaks of 395 ℃ and Crystal (Fig. 1)
At 418, 428, 482 and 520 °c, respectively (
Aversa, Apicella, 2016;
Levandowski and others. , 2005; Geyer et al. , 1996).
The first shoulder that occurs at 418 °c, this behavior may be caused by the precipitation of the 20-sided body phase as an intermediate crystalline product (
Murty and Hono, 2001)
Due to its high mobility and small size, this can be a very rich stage.
The second Crystal Peak (428°C)
Has been with Cu-Ni rich phase (
Aversa and Apicella, 2016).
The phase composition of the twenty-plane body depends on the mismatch between the size of a large number of Zr atoms, Cu, Ni atoms, far more (Saida et al. , 2000).
Surface SEM analysis shows that surface defects have special groove shapes (jetting)
This is the characteristic of flow instability in injection molding parts (Fig. 3).
When the mold becomes cold and/or the front-end slows down resulting in an increase in the glass transition or excessive viscosity of the polymer, similar surface defects in the injection-molded polymer can be observed.
In the case of glass metal injection molding, the cause of surface defects may be the same reason: in fact, the mold is too cold to produce a high temperature gradient in the molten plastic metal, increase the possibility of unstable flow and formation of grooves and ripples.
Groove defect in figure
3 fill with unknown material.
Figure 4 shows the defect portion of the fragment removed.
EDS chemical composition analysis of the material filled with grain waves shows that the fragments are composed of silicon and silicon
Luminous substances produced by water jet BMG plate cutting.
Once removed, the shape of the defect (Fig. 4)
It is clearly shown that the groove is caused by the instability of the molten flow.
The main purpose of microscopic observation is to check the arrangement of atoms, especially the presence of short atoms
Range sequence clusters and their distribution (
Pilarczyk and Podworny, 2015).
Using ion beams enables us to study the internal morphology near the surface where the glass curing process occurs first. A cross-
Use FIB to create sections with a depth of about 60 m.
Platinum deposits (Fig. 5a)
Is used as the target of the beam, so that when the beam hits the surface of the plate, the material is splashed out.
Figure 7 shows the details of the crystalline region and shows the point at which the atomic composition is analyzed.
6 display crystals-phase grains (
Black spots in the picture7)
Disperse with some linear elements (
White line in the picture7)
In the glass phase matrix.
The chemical composition of the selected region was analyzed with EDS.
The image of the linear defect on the front of the slice shows the presence of two types of crystal inclusions: that is, needle-like (white in Fig. 7)
And six-party crystals (
Upper right details of the picture7).
Since very small atoms like be are not detected, the exact composition cannot be determined by EDS.
EDS analysis was performed on specific areas of the injection molding board.
Crystal inclusions are described in the literature;
Liu and others have already reported it. (2002)
From the center of the plate to the outer surface, the number of crystal inclusions is reduced.
This decline should be due to the cooling rate.
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. 8)(
Morito and Egami, 1984).
EDS analysis was then limited to Zr, Ti, Cu and Ni atoms.
In particular, the non-crystalline phase is analyzed (
Inside near the surface and surface)
And two types of crystal inclusions.
Figure 7 shows that these areas are S41, S42, and S43 (
White needle crystal), A44 and A46 (
Hexagonal Dark Crystal)and A45 (
Amorphous glass metal). Table 1.
Composition EDS analysis of amorphous metal alloy glass and crystal inclusions internal crystal Zr 53,2, 43, 8 ± 2, 5 36, 8 ± 2, 47 on amorphous six-policy atomic surface, 2 ± 5, 6 14, 8 ± 5, 4 Ni 15, 9 ± 5, 0 18,3 ± 6, 8 24, 9 ± 5, 4 19,1 ± 7, 2 Cu 15, 0 ± 5, this internal and external surface of the plate.
Comparative component analysis is reported in Table 1.
The composition of amorphous glass metals is richer in zirconium atoms (51,3%)
Outside surface (
Where to cool the molten alloy at the fastest speed)
When it is reduced in the internal layer (43,8% at 20-60 micron deep)
Instead, the composition of Ni and Cu atoms increased from about 15 to 18%).
The two types of crystal inclusions have significantly different components.
Six-Party crystal by Ni-Cu rich phase (about 25% each)
It contains 37% zirconium and 12% Ti.
Compared with the needle crystal phase, the needle crystal contains a higher content of zirconium (47 Vs. 37%)
There are Cu and Ni at 18% and Ti at 15%.
The differences in these components can be attributed to the thermal and flow behavior of the melt during injection molding.
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 the 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.
At this interface layer (B in Fig. 8)
The two driving forces are to induce the crystal core, and the greater the temperature difference with the thermodynamic melting temperature (
Mezzanine above near Glass transition)
The shorter the distance between crystalline atoms (
In layer B, intense shear stress extrusion and compression of alloy atoms with reduced volume8)
It is conducive to the formation and growth of crystals.
Following the theory of potential energy landscape (
De benetty and Stringer, 2001; Klement et al. , 1960)
, The inherent structure associated with the local minimum of energy is a balanced and stable glass state, divided by the energy barrier between different potential equilibrium configurations.
Under high shear and compression conditions, the inherent structure of this balanced glass may become more tight (layer B in Fig. 8)
Enhanced Atomic redistribution in more ordered clusters that are easy to crystallize (
Then the elastic compression energy is stored in the crystal stage).
According to the thermodynamic method, the energy barrier (DG*)
To overcome the uniform core from amorphous to crystalline phase is (Lee et al. , 2006): DG*=16/3pg3(Vmc/(DGm+Ec+PDVm))(1)
Where T = temperature P = static hydraulic DGm = molar free energy change between non-crystal and Crystal g = interface free energy between non-crystal and crystal state (
Crystal core forming critical size)
DVm = molar volume change of transition between amorphous (Vma)
State, finally Ec = elastic strain energy caused by volume change in the crystal process (with Ec=(Vma-Vmc)/3Vmc;
Elastic modulus E.
According to the previous thermodynamic analysis, the presence of shear stress increases the compaction of atoms that produce molar volumes, resulting in a reduction in the blocking energy DG.
Similarly, the melt close to the above temperature increases the value of the free energy DGm and reduces the energy barrier of the crystal.
Conclusion our research group on new materials and technologies is investigating the material and its properties in depth (Aversa et al. , 2016a; 2016b; 2016c; 2016d; 2016e; 2016f; 2016g, 2016h; 2016i; 2016j; 2016k; Petrescu et al. , 2015; 2016).
Microscopic examination of the internal sections of Zr44Ti11Cu10Ni10Be25 (LM001B)
It is shown that the sample also has the characteristic of amorphous structure and also has short
Crystal clusters of range order and size range between 0.
8 and 10 m can be detected.
The presence, behavior and distribution of BMG crystal phases are basically dependent on oxygen impurities, micro-alloy elements, and manufacturing process parameters.
The critical mass of quarterly and ternary zirconium alloys is 0,4% (
Murty and Hono, 2001).
Depending on the alloy, the size range of the 20-sided bulk phase ranges from 10 to 40 nm.
Self-glass forming capacity (GFA)
It can also be defined as resistance to precipitation of the crystal phase, and oxygen also has a harmful effect on it (Eckert et al. , 1998; Gebert et al. , 1998)
It is determined that the processing performance of BMG is low.
Finally, as evidenced by microscopic observations, manufacturing process parameters, geometry, size and thickness have a significant effect on the formation, quantity and distribution of crystal particles.
In fact, for more complex parts and parameters to control a lower manufacturing process, the cooling rate inside the part changes, resulting in different crystalline behavior.
Where the cooling rate is low, it is easier to find crystal particles, especially in the sandwich between the cured external glass metal and the stationary fluid, but close to its glass transition, high shear strain melting.
The authors acknowledge that California Liquid Metal Technology Corporation provides samples for representation.
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