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Metals and Materials International

, Volume 24, Issue 5, pp 1090–1098 | Cite as

Structure and Stoichiometry of MgxZny in Hot-Dipped Zn–Mg–Al Coating Layer on Interstitial-Free Steel

  • Jae Nam Kim
  • Chong Soo Lee
  • Young Sool Jin
Article
  • 226 Downloads

Abstract

Correlations of stoichiometry and phase structure of MgxZny in hot-dipped Zn–Mg–Al coating layer which were modified by additive element have been established on the bases of diffraction and phase transformation principles. X-ray diffraction (XRD) results showed that MgxZny in the Zn–Mg–Al coating layers consist of Mg2Zn11 and MgZn2. The additive elements had a significant effect on the phase fraction of Mg2Zn11 while the Mg/Al ratio had a negligible effect. Transmission electron microscope (TEM) assisted selected area electron diffraction (SAED) results of small areas MgxZny were indexed dominantly as MgZn2 which have different Mg/Zn stoichiometry between 0.10 and 0.18. It is assumed that the MgxZny have deviated stoichiometry of the phase structure with additive element. The deviated Mg2Zn11 phase structure was interpreted as base-centered orthorhombic by applying two theoretical validity: a structure factor rule explained why the base-centered orthorhombic Mg2Zn11 has less reciprocal lattice reflections in the SAED compared to hexagonal MgZn2, and a phase transformation model elucidated its reasonable lattice point sharing of the corresponding unit cell during hexagonal MgZn2 (a, b = 0.5252 nm, c = 0.8577 nm) transform to intermediate tetragonal and final base-centered orthorhombic Mg2Zn11 (a = 0.8575 nm, b = 0.8874 nm, c = 0.8771 nm) in the equilibrium state.

Keywords

Zn–Mg–Al coating Mg2Zn11 Base-centered orthorhombic TEM-SAED CALPHAD 

1 Introduction

Zn–Mg–Al-coated steel products have superior corrosion resistance, so they are competitively commercialized by large steel makers [1, 2, 3, 4, 5] and widely used in construction and automotive industries. It is reported that the structure and the chemistry of the coating layer has great influence on the corrosion resistance, adhesion, and formability of the steel [6, 7, 8, 9, 10, 11, 12]. Mg has strong affinity for oxygen, as a consequence Mg2Zn11 is more susceptible [13, 14] to cracking and pull out during subsequent processing, but less susceptible [15] to discontinuous yielding during plastic deformation than other MgxZny phases. Therefore, understanding of structure and chemical behavior of the coating layer is important to know the effect on various properties of Zn–Mg–Al coated steel products. It is expected that the rapid solidification of the Zn–Mg–Al coating causes a deviation of chemical composition and microstructure of the phases [16, 17] from the equilibrium values. Nevertheless, little corroborating result is available to understand the MgxZny system.

There are many MgxZny phases based on the binary Mg-Zn phase diagram [18]; intermetallic phases of Mg7Zn3 (or Mg51Zn20), MgZn (or Mg21Zn25), Mg2Zn3 (or Mg4Zn7), MgZn2, Mg2Zn11 [19, 20]. The Mg7Zn3 phase has an orthorhombic structure (space group Immm, a = 1.4083 nm, b = 1.4486 nm, c = 1.4025 nm) [21]. The Mg2Zn3 phase has a triclinic structure (a = 1.724 nm, b = 1.445 nm, c = 0.520 nm, α = 96°, β = 89°, γ = 138°), but this structure has not been confirmed [22]. The diffraction lines of equilibrium MgZn phase have been successfully indexed [23] on the basis of rhombohedral unit cell with a = 2.569 nm, c = 1.8014 nm of lattice parameter in a hexagonal version. However, there is a still considerable debate on the exact stoichiometry in the Mg-Zn phase. Similarly, there is uncertainty in the specific detail of crystal structure of the Mg-Zn phase.

MgxZny phases in the commercial ternary Zn–Mg–Al coating system, equilibrium phase Mg2Zn11 is rare [24, 25, 26], whereas meta-stable MgZn2 is common due to the rapid solidification process. Equilibrium Mg2Zn11 has been known as primitive-cubic [27, 28] (space group Pm3, Pearson symbol ‘cP’ 39.00, a = 8.552 nm) in the international committee of powder diffraction (ICDD) data file, PDF # 006-0664. Likewise, meta-stable MgZn2 has been known as hexagonal (space group P63/mmc, Pearson symbol ‘hP’12.00, a1 = a2 = 5.2225 nm, c = 8.5684 nm) in the PDF # 034-0457.

The present paper reports the structure and stoichiometry of MgxZny phase in the ternary Zn–Mg–Al coating system which were modified by additive element. Compare with the results of previous studies, correlations of Mg/Al ratio, stoichiometry, phase fraction, additive element, detail structure and lattice parameters of MgxZny have been discussed on the bases of diffraction and phase transformation principles.

2 Materials and Methods

2.1 Conditions of Materials and Hot-Dip Coating Experiments

A vertical-type continuous hot-dip galvanizing simulator was used for the coating experiments. Commercial interstitial-free (IF) steel sheets of 105 × 175 × 0.7 mm were ultrasonically degreased and cleaned in acetone. Before hot-dipping, the samples were annealed at 1093 K for about 1 min in an atmosphere composed of 25: 75 H2: N2 (vol.%) with a dew point of 213 K. The annealed samples were cooled to 723 K, dipped in a molten Zn-bath at 713 K for 4 s, and then transferred to a cooling chamber. Average coating weight (~ 100 g/m2) was obtained by N2 gas-wiping. The weight composition ratio of Mg/Al was controlled to about 1.2, which is equivalent to Zn-3%Mg-2.5%Al. And this Zn–Mg–Al bath modified by additive element such as Ti, Sr, etc. (Table 1).
Table 1

The ratio of Mg/Al, coating weight (g/m2), and additive element in the experiments

Sample #

Mg/Al ratio

Coating weight (g/m2)

Additive element

1

1.2

110

Yes

2

1.2

107

Yes

3

1.0

128

No

4

0.9

75

Yes

5

0.9

72

Yes

2.2 Characterization of MgxZny Phase in Zn–Mg–Al Coating Layer

The possible phases in the An–Mg–Al coating layer were estimated by calculation of the phase diagram (CALPHAD) with thermodynamic database [29], which contains information of crystal structure, electronic structure, and thermodynamic signature for many binary and ternary alloys. The actual phases present in the samples were identified and compared by XRD using Cu Kα at 30 kV, 20 mA to avoid saturation of the scintillation counter from the highly-textured strong Zn peaks with scan range 10° ≤ 2θ ≤ 0°, step size of 0.01°. The structure and stoichiometry of MgxZny were precisely characterized by FEI Osiris scanning transmission electron microscope (STEM) at 200 kV with a probe size of 1 nm, and energy dispersive of X-ray spectrometer (EDX). Site-specific TEM foils were prepared by focused ion beam (FIB) using Ga+ source at 30 kV, 15 nA–80 pA in order to control the polishing speed and beam damage of the samples.

3 Results

3.1 CALPHAD Results of Solidification Structure of Zn–Mg–Al Coating Layer

CALPHAD analysis provided two phase diagrams: equilibrium phases (Fig. 1a) and meta-stable phases (Fig. 1b). The meta-stable equilibrium diagram was calculated by rejection of equilibrium Mg2Zn11 phase at the step of defining system in ssol5. The equilibrium phase diagram (Fig. 1a) showed that Zn-3%Mg-2.5%Al coating solidifies in the equilibrium state, L → L + MgZn2 reaction takes places at 675 K and ternary eutectic reaction of Zn + Al1 + Mg2Zn11 occurs at 615 K. On the other hand, ternary eutectic reaction of Zn + Al + MgZn2 takes places at 623 K in the meta-stable state (Fig. 1b).
Fig. 1

CALPHAD results of Zn–Mg–Al system: a equilibrium, b meta-stable phase diagram

3.2 XRD Results of Solidification Structure for Zn–Mg–Al Coating Layer

XRD identified four crystal phases which were Zn phase, Al phase, MgZn2 phase, and Mg2Zn11 phase (Fig. 2). Diffraction lines at 19.67°, 41.31° and 72.35° correspond to (10–10), (20–21) and (22–40) MgZn2 phase, and lines at 17.91°, 34.74° and 42.19° correspond to (111), (311), and (400) Mg2Zn11 phase. Solidification of hot-dipped coating process yielded a highly-textured family of basal plane (0002) and (0004) Zn. The sample #4 showed strong (111) Mg2Zn11 peaks (Fig. 2d). On the other hand, sample #2 (Fig. 2b) and sample #4 (Fig. 2d) showed strong (10–10) MgZn2 peak.
Fig. 2

XRD results using Cu-Kα radiation: a sample #1, b sample #2, c sample #3, d sample #4, e sample #5

Phase fraction analysis by X-ray diffraction is based on the fact that the intensity of diffraction pattern of a particular phase in a mixture of phases depends on the phase fraction of that phase in the mixture. The relation between intensity and fraction is not generally linear, because the diffracted intensity depends distinctly on the absorption coefficient of the mixture. The relation between diffracted intensity and phase fraction is given by [30],
$$I_{J} = K_{J} \frac{{W_{J} }}{{(\bar{\mu } /\rho )}}$$
(1)
where IJ is diffracted intensity of J phase, KJ is constant, WJ is weight fraction of J phase, and \(\bar{\mu } /\rho\) is mass absorption coefficient. The phase fractions of the 5 samples were determined based on the Eq. (1), and summarized in Table 2.
Table 2

XRD phase fractions (wt%) in the coating layer of the samples

Sample #

Zn

Mg2Zn11

MgZn2

Al

1

74.0

9.2

14.6

2.2

2

75.3

9.8

12.9

1.9

3

85.6

12.1

1.3

1.0

4

73.9

22.9

2.6

0.6

5

95.9

1.5

2.2

0.4

3.3 SEM and TEM Microstructure of MgxZny Phase in the Zn–Mg–Al Coating Layer

SEM images of plain view (Fig. 3, left) showed granular η-Zn and binary Zn + MgxZny lamellar on the surface of the coating layer. It can be seen that the size and morphology of η-Zn and Zn + MgxZny varied greatly depending on the samples. SEM images of cross-section view (Fig. 3, right) depicted the total thickness and microstructure of the entire coating layers. It can be seen that the granular η-Zn phases are preferentially present on the top surface region.
Fig. 3

SEM microstructure of plane view (left) and cross-section view (right): a sample #1, b sample #2, c sample #3, d sample #4, e sample #5

STEM images of cross-sectional thin foils were observed (Fig. 4, left) and quantified by STEM-EDX (Fig. 4, right) to determine the stoichiometry of MgxZny phase. Dark-gray phases of STEM images are correspond to η-Zn and light-gray phases correspond to MgxZny. These are distinguished from the white color of Al phase. A very thin Fe–Al inhibition layer (I/L) between coating layer and IF steel substrate can be observed in Fig. 4a, c.
Fig. 4

STEM images of cross-sectioned samples (left) and STEM-EDX point analysis results (right): a sample #1, b sample #2, c sample #3, d sample #4, e sample #5

4 Discussion

4.1 The Formation of Equilibrium Phase of Mg2Zn11

As mentioned in the introduction section, the equilibrium phase Mg2Zn11 is rarely observed in commercial ternary Zn–Mg–Al coating products. It may be assumed that the possible kinetics in the experimental coating conditions overcome the energy barrier, ΔGa and transformed to equilibrium phase partially. CALPHAD can only suggest thermo-dynamics information whether a process or a reaction can occur. Basically, increase in temperature and in the mobility of atoms increases the chance that they will overcome ΔGa. Another way to promote the reaction is to use catalysts to reduce ΔGa, i.e., to decrease the activation energy. A simultaneous existence of equilibrium Mg2Zn11 and metastable MgZn2 has been reported in Zn-1.6%Mg-1.65%Al based alloy system [31], and it concluded that quantitative results confirm a gradual decrease in the quantity of Mg2Zn11 phase as Sn content increases, and that the quantity of MgZn2 is highest at 1 wt% Sn. According to the CALPHAD result from liquid to solid in the equilibrium state (Fig. 1a) of Zn-3%Mg-2.5%Al system can describe as follow,
Step (1)

L → L + MgZn2 at 675 K

Step (2)

L + MgZn2 → L + MgZn2 + Mg2Zn11 at 640 K

Step (3)

L + MgZn2 + Mg2Zn11 → L + Zn + Mg2Zn11 at 625 K

Step (4)

L + Zn + Mg2Zn11 → Zn +Al1 + Mg2Zn11 at 615 K

Step (5)

Zn +Al1 + Mg2Zn11 → Zn +Al + Mg2Zn11 at 550 K

The phase faction of equilibrium Mg2Zn11 varied between 1.5 and 22.9% (Fig. 5a) in accordance with additive element which is presumed change the activation energy, ΔGa to start transformation the equilibrium phase. The sample #4 showed the highest fraction Mg2Zn11 (22.9%). It can be conclude that the additive elements had a significant effect on the Mg2Zn11 fraction because the hypothetical additive element trend line (tAdd.) shows steep slope with respect to Mg2Zn11 phase fraction as shown in Fig. 5b while Mg/Al ratio had a negligible influence on the phase fraction of Mg2Zn11 because the gentle slope of the linear Mg/Al trend line (tMg/Al) with respect to Mg2Zn11 phase fraction.
Fig. 5

Comparison of XRD quantification results, a XRD phase fraction of hot-dip Zn–Mg–Al coating simulated samples, b Mg2Zn11 phase fraction versus additive element and Mg/Al ratio

4.2 Stoichiometry and Phase Structure of the MgxZny

The Mg/Zn stoichiometry of small areas MgxZny were varied between 0.10 and 0.18 (stoichiometry of Mg2Zn11 = 0.18). The correlation of Mg/Zn stoichiometry and MgxZny phase fraction was elucidated in Fig. 6. In spite of the comparison between EDX small area Mg/Zn stoichiometry and large area XRD analysis results, the Mg2Zn11 phase tends to increase (R2 = 0.0259) while the MgZn2 phase obviously decrease (R2 = 0.7736) as the Mg/Zn stoichiometry approaches to 0.18.
Fig. 6

The correlation between MgxZny phase fraction and Mg/Zn stoichiometry

SAED analyses results of MgxZny which have different Mg/Zn ratio between 0.10 and 0.18 were indexed as [001], [1, 2, 3, 4, 5, 6, 7, 8, 9, 10], [3, 4, 5, 6, 7, 8, 9, 10, 11], MgZn2 and [124] Mg2Zn11. Here, in the notation of hexagonal structure, four axes (h, k, i, l) were not used for the transmitted beam and zone axis direction. Stoichiometry of Mg/Zn ratio and indexed SAED results (Fig. 7) of the small areas MgxZny were summarized in Table 3. The SAED patterns of small areas MgxZny which have different Mg/Zn stoichiometry were indexed as dominantly MgZn2 (Table 3).
Fig. 7

TEM-SAED analyses results of MgxZny at SADP points in Fig. 4: a sample #1, b sample #2, c sample #3, d sample #4, e sample #5

Table 3

Stoichiometry, phase structure, and SAED crystallographic data of the MgxZny phases

Sample #

Stoichiometry (Mg/Zn ratio)

Phase structure

Zone axis

hkl

ϕ

1

0.17

MgZn2

[001]

(10–10) (01–10)

60°

MgZn2

[1–10]

(0002) (–1–120)

90°

2

0.15

MgZn2

[1–10]

(0002) (–1–120)

90°

MgZn2

[001]

(10–10) (01–10)

60°

3

0.10

MgZn2

[1–10]

(0002) (–1–120)

90°

MgZn2

[3–10]

(01–11) (–1013)

80°

4

0.18

Mg2Zn11

[124]

(2–10) (0–21)

66.42°

MgZn2

[1–10]

(0002) (–1–120)

90°

5

0.18

MgZn2

[1–10]

(0002) (–1–120)

90°

MgZn2

[3–10]

(01–11) (–1013)

80°

The stoichiometry did not correspond to relevant MgxZny phase structure in the SAED results. It was reviewed by the following categories.
  • The accuracy and reliability of STEM-EDX quantification: the EDX instrument which is used in this study has the highest sensitivity by four large activation windows (4 × 100 mm2) compare with the normal size window (1 × 10–1 × 40 mm2). Quantification by STEM-EDX is more reliable than SEM–EDX because thin foil effect obviously reduce the matrix correction errors.

  • Failed keeping area while finding zone axis: it was carefully manipulated the sample position and height during x and y movement. If the area is slightly changed, its periphery is HCP-Zn or FCC-Al as shown in STEM images (Fig. 4). These phases wouldn’t be interpreted as MgZn2 or Mg2Zn11.

  • Crystal structure of the Mg2Zn11: according to the diffraction principles, the primitive-cubic structure can give a strong reciprocal lattice reflection at any integer combination of (h, k, l) because there is only one atom per unit cell in the primitive-cubic crystal (here and hereafter, it is not considered large unit cell containing many atoms but the smallest unit cell is considered to simplify the summation), therefore structure factor, F = f (f is atomic scattering amplitude) [32]. If there is more than one atoms in the basis of the unit cell, interference between wavelets scattered by the atoms in the basis lead to cancelling and disallowing certain combination of (h, k, l) in the SAED pattern [33]. Consequently, hexagonal structure disallowing reciprocal lattice reflection when (h + 2 k) = 3n with (l) odd, consequent |F|2 = 0, no reflection occur. Thus, hexagonal lattice plane such as (001), (003), (113), (005) are forbidden (here and hereafter, it is not considered notation h + k = − i). From this perspective, the hexagonal MgZn2 allows less reflections possibility than primitive-cubic Mg2Zn11 does. However, the results (Table 3) are not agreed with this diffraction principle because hexagonal MgZn2 have more reflection than primitive-cubic Mg2Zn11. If Mg2Zn11 structure is assumed as base-centered cubic, it would have less reciprocal lattice reflection than hexagonal MgZn2 because base-centered cubic structure disallowing reciprocal lattice reflection when (h) and (k) are mixed, consequent |F|2 = 0. Thus, e.g. base-centered lattice planes of (011), (012), (013) and (101), (102), (103) have no reflections. This means that the base-centered cubic Mg2Zn11 allows less reciprocal lattice reflections possibility than hexagonal MgZn2 phase. And this assumption has a good agreement with the SAED result (Table 3).

However, in a strict sense, the classification of crystal structure must be related to the crystal symmetry [34, 35]. In this regard, cubic crystal structure implies four threefold axes of rotation symmetry along the entire lattices axis. The base-centered cubic does not satisfy the requirement four threefold axes of rotation along the other 2 axes. If the base-centered cubic structure is regarded as base-centered orthorhombic with distorted unit cell having geometry of a ≠ b ≠ c, α = β = γ = 90° then the structure factor rule satisfy the reciprocal lattice reflection result (Table 3) and good agreement to the 14 Bravais lattice with the crystal symmetric nature. In summary of stoichiometry and phase structure relationship, the following estimation can be made. The stoichiometry of Mg2Zn11 does not necessarily consistent with phase structure which modified by additive element in hot-dipped coating process. And the crystal structure of Mg2Zn11 is assumed to be base-centered orthorhombic system.

4.3 Phase Transformation Model of Meta-Stable MgZn2 to Equilibrium Mg2Zn11

A phase transformation model (Fig. 8) has been applied to examine the validity of the base-centered orthorhombic crystal system of Mg2Zn11. The sequences of phase transformation from hexagonal (Fig. 8a) to intermediate tetragonal (Fig. 8b) and final base-centered orthorhombic (Fig. 8c) are well elucidated with its lattice point sharing of the corresponding unit cell as illustrated large green spheres and large blue spheres. One hexagonal unit cell (a = b ≠ c, α = β = 90°, γ = 120°) of metastable MgZn2 shares three tetragonal unit cell (a = b ≠ c, α = β = γ = 90°) which have lattice parameters ac = 0.5223 nm, cc = 0.8568 nm (here, subscript c means cited value from PDF # 034-0457). The rapid solidification slightly changed the lattice parameters of hexagonal MgZn2 (Fig. 8a); am = 0.5252 nm, cm = 0.8577 nm (here, subscript m means measured value by XRD). The hexagonal unit cell transforms to an intermediate tetragonal cell (Fig. 8b) followed by tetragonal unit cell transforms to two adjacent base-centered orthorhombic unit cells (Fig. 8c). It is agreed with CALPHAD result which provided phase transformation in the equilibrium state: Step (2), L + MgZn2 → L + MgZn2 + Mg2Zn11 at 640 K, and Step (5), Zn + Al1 + Mg2Zn11 → Zn + Al + Mg2Zn11 at 550 K.
Fig. 8

Schematic phase transformation model from MgZn2 to Mg2Zn11: a hexagonal unit cell share three tetragonal unit cell and its corresponding [u,v,w] of indexed SAED in Fig. 5, b one tetragonal unit cell transform two base-centered orthorhombic, c stable base-centered orthorhombic unit cell expanded ~ 63.2% on the a axis, ~ 68.9% on the b axis, and ~ 2.26% on the c axis with respect to the experimental value of hexagonal unit cell

The ratio between transformation temperature (Ttrans.) and melting temperature (Tmelt.) of Mg2Zn11 is,
$$\frac{{T_{trans.} }}{{T_{melt.} }} = \frac{{640\;{\text{K}}}}{{680\;{\text{K}}}} = 0.94$$
(2)
The ratio is high enough to suggest the diffusional phase transformation [36] not twinning accommodated diffusion less transformation.
Lattice parameters (a ≠ b ≠ c, α = β = γ = 90°) of base-centered orthorhombic crystal structure can be precisely determined by referring to various documents and literatures [37, 38, 39, 40]. General principles is based on that described by Bradley and Taylor (1937), who made use of the relation:
$$q_{hkl} = \sin^{2} \theta_{hkl} = h^{2} A + k^{2} B + l^{2} C$$
(3)
where A = λ2/4a2, B = λ2/4b2, C = λ2/4c2.

The lattice parameters of base-centered orthorhombic unit cell were determined: a = 0.8575 nm, b = 0.8874 nm, c = 0.8771 nm. The volumetric value of orthorhombic unit cell should not only have similar value to the hexagonal unit cell but also represent a significant positive expansion of the orthorhombic cell [41]. The orthorhombic unit cell Mg2Zn11 has a volume of 0.66743 nm3, and hexagonal unit cell MgZn2 has a volume of 0.70975 nm3. The difference of unit cell volume, ΔV = 5.96%, is completely reasonable comparison to the value which is in the above statement.

5 Conclusions

The structure and stoichiometry of MgxZny which were modified by additive element in hot-dipped Zn–Mg–Al coating on IF steel were evaluated using XRD and TEM. The following conclusions can be drawn.
  1. 1.

    The MgxZny phases of the coating layer were identified as Mg2Zn11 and MgZn2. The phase fraction of Mg2Zn11 varied from 1.5 to 22.9% depending on the sample. The amount of Mg2Zn11 was significantly influenced by additional elements but negligibly influence by Mg/Al ratio.

     
  2. 2.

    The small areas MgxZny which have stoichiometry of Mg/Zn ratio between 0.10 and 0.18 were dominantly indexed as MgZn2 by SAED analyses. It is assumed that the MgxZny have deviated stoichiometry with additive element, and does not necessarily coincide with its phase structure. The deviated Mg2Zn11 phase is thought to be base-centered orthorhombic because a structure factor rule well explained why the base-centered orthorhombic structure has less reciprocal lattice reflections in the SAED compare to the hexagonal structure MgZn2.

     
  3. 3.

    The phase transformation model elucidated perfectly with its lattice point sharing of the corresponding unit cell during hexagonal MgZn2 (a, b = 0.5252 nm, c = 0.8577 nm) transform to intermediate tetragonal and final base-centered orthorhombic Mg2Zn11 (a = 0.8575 nm, b = 0.8874 nm, c = 0.8771 nm) in the equilibrium state.

     
  4. 4.

    The results of phase transformation greatly expand a, b from hexagonal unit cell (a, b = 0.5252 nm) to base-centered orthorhombic unit cell (a ≈ 0.8575 nm, 0.8874 nm), however, the volumetric value of orthorhombic unit cell Mg2Zn11 (0.66743 nm3) have similar value to the hexagonal unit cell MgZn2 (0.70975 nm3). The difference of unit cell volume (ΔV = 5.96%) is completely reasonable comparison to the value which is expected.

     

Notes

Acknowledgement

This work was supported by a Grant from POSCO Korea.

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Copyright information

© The Korean Institute of Metals and Materials, corrected publication 04/2018 2018
corrected publication 04/2018

Authors and Affiliations

  1. 1.Graduate Institute of Ferrous Technology (GIFT)Pohang University of Science and Technology (POSTECH)Nam-Gu PohangKorea

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