Multicomponent alloy coating
11624104 · 2023-04-11
Assignee
Inventors
- Wu-Han Liu (Miaoli, TW)
- Wei-Tien Hsiao (Zhudong Township, TW)
- Chang-Chih Hsu (Hsinchu, TW)
- Mao-Shin Liu (Hsinchu, TW)
- Zhong-Ren Wu (Taichung, TW)
- Shih-Hsiang Chou (Zhubei, TW)
- Chin-An Wang (Taipei, TW)
Cpc classification
C22C32/0005
CHEMISTRY; METALLURGY
C22C30/00
CHEMISTRY; METALLURGY
C23C4/067
CHEMISTRY; METALLURGY
C23C4/10
CHEMISTRY; METALLURGY
C22C32/00
CHEMISTRY; METALLURGY
International classification
C22C1/05
CHEMISTRY; METALLURGY
C22C30/00
CHEMISTRY; METALLURGY
Abstract
A multicomponent alloy coating is provided. The multicomponent alloy coating includes a hard layer and a plurality of nickel-based particles dispersed in the hard layer. The composition of the multicomponent alloy coating is represented by the following formula (I):
Al.sub.dCo.sub.eCr.sub.gFe.sub.hNi.sub.iSi.sub.jC.sub.kO.sub.m formula (I), wherein 1<d<2, 0.5<e<0.8, 2<g<3.2, 0.05<h<0.3, 2<i<3, j=1, k≥0, m≥0, and iron is present in the amount of less than 3 wt % of the composition of the multicomponent alloy coating.
Claims
1. A multicomponent alloy coating, comprising: a hard layer; and a plurality of nickel-based particles dispersed in the hard layer, wherein the composition of the nickel-based particles comprises nickel, aluminum, carbon and oxygen, wherein aluminum is present in a trace amount to 0.25 wt % of the composition of the nickel-based particles, nickel is present in the amount of greater than 94 wt % of the composition of the nickel-based particles, and carbon is present in the amount of greater than 5 wt % of the composition of the nickel-based particles; and wherein the composition of the multicomponent alloy coating is represented by the following formula (I):
Al.sub.dCo.sub.eCr.sub.gFe.sub.hNi.sub.iSi.sub.jC.sub.kO.sub.m formula (I) wherein 1<d<2, 0.5<e<0.8, 2<g<3.2, 0.05<h<0.3, 2<i<3, j=1, k≥0, m≥0 in the formula (I), and iron is present in the amount of greater than 2 wt % and less than 3 wt % of the composition of the multicomponent alloy coating.
2. The multicomponent alloy coating according to claim 1, wherein nickel is present in the amount of greater than 30 wt % of the composition of the multicomponent alloy coating.
3. The multicomponent alloy coating according to claim 1, wherein aluminum is present in the amount of greater than 9 wt % of the composition of the multicomponent alloy coating.
4. The multicomponent alloy coating according to claim 1, wherein 2.5<k<4 and 0.05<m<0.5.
5. The multicomponent alloy coating according to claim 1, wherein carbon is present in the amount of greater than 0 wt % and less than 9 wt % of the composition of the multicomponent alloy coating.
6. The multicomponent alloy coating according to claim 1, wherein oxygen is present in the amount of greater than 0 wt % and less than 9 wt % of the composition of the multicomponent alloy coating.
7. The multicomponent alloy coating according to claim 1, wherein the composition of the multicomponent alloy coating comprises amorphous carbide.
8. The multicomponent alloy coating according to claim 1, wherein a weight ratio of the hard layer with respect to the nickel-based particles is 65:35 to 90:10.
9. The multicomponent alloy coating according to claim 1, wherein chromium is present in the amount of greater than 50 wt % of the composition of the hard layer.
10. The multicomponent alloy coating according to claim 1, wherein the nickel-based particles are present in the amount of greater than 9 vol. % of the multicomponent alloy coating.
11. The multicomponent alloy coating according to claim 1, wherein the multicomponent alloy coating has a porosity of 0.1%-2%.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION
(8) In the embodiments of the present disclosure, when the elements in the composition of the multicomponent alloy coating satisfy the atomic ratio represented in formula (I), and iron is present in the amount of less than 3 wt % of the composition of the multicomponent alloy coating, the multicomponent alloy coating can be provided with good wear resistance and good toughness. Details of embodiments of the present disclosure are described hereinafter. Specific structures, compositions, and manufacturing processes disclosed in the embodiments are used as examples and for explaining the disclosure only and are not to be construed as limitations. A person having ordinary skill in the art may modify or change the structures, compositions, and manufacturing processes of the embodiments according to actual applications.
(9) Unless explicitly indicated by the description, as used herein, the singular forms “a,” “an” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. It should be further understood that when such as the term “includes” and/or “including,” is used in this specification, it specifies the presence of described features, steps, operations, elements, and/or components, but does not preclude the presence or addition of one or more other features, steps, operations, elements, components, and/or groups thereof.
(10) Throughout this specification, the term “one embodiment” or “an embodiment” means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment. Thus, the phrases “in one embodiment” or “in an embodiment” in various contexts throughout this specification do not necessarily all refer to the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments. It should be appreciated that the following figures are not drawn to scale; rather, these figures are merely illustrations
(11) According to the embodiments of the present disclosure, a multicomponent alloy coating is provided. According to the embodiments of the present disclosure, the multicomponent alloy coating can be used as the protective coating of wheel rims, such as the protective coating of aluminum wheel rims of vehicles and motorcycles.
(12) According to the embodiments of the present disclosure, the composition of the multicomponent alloy coating is represented by the following formula (I):
Al.sub.dCo.sub.eCr.sub.gFe.sub.hNi.sub.iSi.sub.jC.sub.kO.sub.m formula (I)
(13) wherein 1<d<2, 0.5<e<0.8, 2<g<3.2, 0.05<h<0.3, 2<i<3, j=1, k≥0, m≥0, and iron is present in the amount of less than 3 wt % of the composition of the multicomponent alloy coating.
(14) According to the embodiments of the present disclosure, when the elements in the composition of the multicomponent alloy coating satisfy the constituents and the atomic ratio represented in the above formula (I), and iron satisfies the above weight percentage, the multicomponent alloy coating can be provided with good wear resistance and good toughness.
(15) In some embodiments, iron is present in the amount of such as greater than 2 wt % and less than 2.5 wt % of the composition of the multicomponent alloy coating. According to some embodiments of the present disclosure, the multicomponent alloy coating contains greater than 2 wt % and less than 2.5 wt % of iron, and thus despite the face that the multicomponent alloy coating of the present disclosure is not a typical high-entropy alloy, it is still provided with high hardness and high toughness comparable to that of high-entropy alloy.
(16) In some embodiments, iron is present in the amount of such as less than 3 at % (atomic percent) of the composition of the multicomponent alloy coating. In some embodiments, iron is present in the amount of such as greater than 1 at % and less than 2 at % of the composition of the multicomponent alloy coating.
(17) In some embodiments, nickel is present in the amount of such as greater than 30 wt % of the composition of the multicomponent alloy coating. According to some embodiments of the present disclosure, the multicomponent alloy coating contains greater than 30 wt % of nickel, such that it is advantageous to increasing the toughness of the multicomponent alloy coating.
(18) In some embodiments, nickel is present in the amount of such as less than 35 at % of the composition of the multicomponent alloy coating. In some embodiments, nickel is present in the amount of such as greater than 15 at % and less than 25 at % of the composition of the multicomponent alloy coating.
(19) In some embodiments, aluminum is present in the amount of such as greater than 9 wt % of the composition of the multicomponent alloy coating. According to some embodiments of the present disclosure, the multicomponent alloy coating contains greater than 9 wt % of aluminum, such that it is advantageous to increasing the toughness of the multicomponent alloy coating.
(20) In some embodiments, in formula (I), 2.5<k<4 and 0.05<m<0.5. In other words, in some embodiments, in the composition of the multicomponent alloy coating, the atomic ratio of carbon to silicon is about greater than 2.5 to less than 4, and the atomic ratio of oxygen to silicon is about greater than 0.05 to less than 0.5.
(21) In some embodiments, carbon is present in the amount of such as greater than 0 wt % and less than 9 wt % of the composition of the multicomponent alloy coating. In some embodiments, carbon is present in the amount of such as greater than 8 wt % and less than 9 wt % of the composition of the multicomponent alloy coating.
(22) In some embodiments, oxygen is present in the amount of such as greater than 0 wt % and less than 9 wt % of the composition of the multicomponent alloy coating. In some embodiments, oxygen is present in the amount of such as greater than 0 wt % and less than 2 wt % of the composition of the multicomponent alloy coating.
(23) In some embodiments, the composition of the multicomponent alloy coating may include amorphous carbide. For example, in the manufacturing process of the multicomponent alloy coating of the present disclosure, firstly, multicomponent alloy powders are made from a pre-made alloy mixture by such as a gas atomization process. Then, the multicomponent alloy powders are sprayed onto a substrate by such as a high velocity oxygen fuel (HVOF) process to form the multicomponent alloy coating. According to the embodiments of the present disclosure, it is not limited to utilizing a HVOF process to spray multicomponent alloy powders onto a substrate to form the multicomponent alloy coating. Other spray processes, such as a flame spray process, a plasma spray process, an arc spray process, and etc. may be used to form the multicomponent alloy coating of the present disclosure.
(24) Carbon contained in the composition of the as-formed multicomponent alloy coating may be carbon impurity introduced when performing a HVOF process, and the carbon impurity further forms amorphous carbide. Carbide formed in this way does not have reinforcing phase properties. In other words, in some embodiments, the composition of the multicomponent alloy coating does not include crystalline carbide. For example, the composition of the multicomponent alloy coating does not include silicon carbide with high hardness, for example, crystalline silicon carbide.
(25) In current technique, hard ceramic materials or crystalline carbide having high hardness, e.g. silicon carbide materials, are usually added into alloy materials as reinforcing material to increase the hardness of the alloy materials. In contrast, according to some embodiments of the present disclosure, the elements in the composition of the multicomponent alloy coating satisfy the atomic ratio represented in the above-mentioned formula (I), and iron satisfies the above weight percentage. Therefore, the multicomponent alloy coating can be provided with good wear resistance and good toughness without including reinforcing material such as crystalline carbide or the like.
(26) In some embodiments, the composition of the multicomponent alloy coating may be substantially free from niobium (Nb).
(27) In some embodiments, the composition of the multicomponent alloy coating may be substantially free from copper (Cu).
(28) In some embodiments, the composition of the multicomponent alloy coating may be substantially free from manganese (Mn).
(29) In some embodiments, the composition of the multicomponent alloy coating may be substantially free from manganese (Mn).
(30) In some embodiments, the composition of the multicomponent alloy coating may be substantially free from boron (B).
(31) In some embodiments, the composition of the multicomponent alloy coating may be substantially free from molybdenum (Mo).
(32) In some embodiments, the composition of the multicomponent alloy coating may be substantially free from titanium (Ti).
(33) It is to be noted that a person having ordinary skill in the art should understand that due to the selections of the starting materials of each element, in addition to the predetermined elements and the weight percentages thereof, the composition of the prepared multicomponent alloy coating may further include trace amounts of other impurity elements originally existed in the starting materials. In other words, in some embodiments, the multicomponent alloy coating of the present disclosure may include very trace amounts of the above-mentioned Nb, Cu, Mn, W, B, Mo, and/or Ti from the impurities in the starting materials.
(34) In some embodiments, the multicomponent alloy coating has a porosity of such as 0.1%-2%. In some embodiments, the multicomponent alloy coating has a porosity of such as 0.1%-1%. For example, in some embodiments, the multicomponent alloy coating coated on an aluminum substrate has a porosity of such as 1.04%, the multicomponent alloy coating coated on a 304 stainless steel substrate has a porosity of such as 0.78%, and the multicomponent alloy coating coated on an Inconel 718 nickel-based alloy substrate (No. In718) has a porosity of such as 0.89%.
(35) In some embodiments, the multicomponent alloy coating has a Vickers hardness of about 680 Hv.sub.0.1 to 800 Hv.sub.0.1. For example, in some embodiments, the multicomponent alloy coating coated on an aluminum substrate has a Vickers hardness of about 757.4±159 Hv.sub.0.1, the multicomponent alloy coating coated on a 304 stainless steel substrate has a Vickers hardness of about 745.2±120 Hv.sub.0.1, and the multicomponent alloy coating coated on an Inconel 718 nickel-based alloy substrate has a Vickers hardness of about 653.8±126 Hv.sub.0.1.
(36) In some embodiments, the multicomponent alloy coating has a thickness of about 50 μm to about 500 μm.
(37) According to the embodiments of the present disclosure, the multicomponent alloy coating may be formed on an aluminum-based substrate, a cobalt-based substrate, a nickel-based substrate, and/or a copper-based substrate. For example, the multicomponent alloy coating of the embodiments of the present disclosure may be formed on the aforementioned substrates by a thermal spray process, and the as-formed coating has good coating properties.
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(39) In some embodiments, as shown in
(40) In some embodiments, a weight ratio of the hard layer 110 with respect to the nickel-based particles 120 is such as 65:35 to 90:10.
(41) In some embodiments, the nickel-based particles 120 are present in the amount of such as greater than 9 vol. % of the multicomponent alloy coating 100.
(42) In some embodiments, the composition of the hard layer 110 may be represented by the following formula (II):
Al.sub.d1Co.sub.e1Cr.sub.g1Fe.sub.h1Ni.sub.i1Si.sub.j1C.sub.k1O.sub.m1 formula (II)
(43) wherein 0<d1<2, 0.5<e1<0.8, 2<g1<6, 0.05<h1<0.3, 2<i1<3, j1=1, 2<k1<4, and 0.1<m1<0.7.
(44) According to some embodiments of the present disclosure, the hard layer 110 has the composition represented by the above formula (II) and thus has high hardness and good wear resistance.
(45) In some embodiments, chromium is present in the amount of such as greater than 50 wt % of the composition of the hard layer 110. In some embodiments, chromium is present in the amount of such as greater than 55 wt % of the composition of the hard layer 110.
(46) According to some embodiments of the present disclosure, the hard layer 110 contains greater than 50 wt % of chromium, or greater than 55 wt % of chromium. Therefore, it is advantageous to increasing the hardness and wear resistance of the hard layer 110, thereby the multicomponent alloy coating 100 can be provided with excellent wear resistance.
(47) In some embodiments, the composition of the nickel-based particles 120 may be represented by the following formula (III):
Al.sub.d2Ni.sub.i2C.sub.k2O.sub.m2 formula (III)
(48) wherein 0<d2<0.007, i2=2, 0.3<k2<0.4, and 0.01<m2<0.02.
(49) According to some embodiments of the present disclosure, the nickel-based particles 120 have the composition represented by the above formula (III), such that the nickel-based particles 120 dispersed in the hard layer 110 can increase the toughness of the multicomponent alloy coating 100.
(50) In some embodiments, nickel is present in the amount of such as greater than 85 wt % of the composition of the nickel-based particles 120. In some embodiments, nickel is present in the amount of such as greater than 90 wt % of the composition of the nickel-based particles 120.
(51) According to some embodiments of the present disclosure, the nickel-based particles 120 contain greater than 85 wt % of nickel, or greater than 90 wt % of nickel. The nickel-based particles 120 have relatively high toughness, therefore, the nickel-based particles 120 dispersed in the hard layer 110 can render the multicomponent alloy coating 100 having excellent wear resistance as well as toughness.
(52) In some embodiments, carbon is present in the amount of such as greater than 4 wt % of the composition of the nickel-based particles 120. In some embodiments, carbon is present in the amount of such as greater than 5 wt % of the composition of the nickel-based particles 120.
(53) Further explanation is provided with the following embodiments of the present disclosure. Compositions and properties of multicomponent alloy coatings of embodiments and coatings of comparative embodiments are listed for showing the properties of multicomponent alloy coatings according to the embodiments of the present disclosure. However, the following embodiments are for purposes of describing only, and are not intended to be limiting the scope of the present disclosure.
(54) The composition of the multicomponent alloy coating of embodiment 1 (E1) is listed in table 1. The ratio of each element present in the overall coating is represented by weight percent (wt %) and atomic percent (at %). The atomic ratios between elements are listed as well.
(55) TABLE-US-00001 TABLE 1 Multicomponent alloy coating Hard layer Nickel-based Atomic Atomic particles wt % at % ratios wt % at % ratios wt % at % C 8.46 26.15 3.54 5.11 17.27 2.17 5.15 20.78 O 1.15 2.67 0.36 2.10 5.33 0.67 0.31 0.92 Al 10.08 13.88 1.88 4.76 7.17 0.90 0.25 0.46 Si 5.59 7.39 1.00 5.50 7.95 1.00 0 0 Cr 31.67 22.63 3.06 57.76 45.11 5.67 0 0 Fe 2.09 1.39 0.19 1.62 1.18 0.15 0 0 Co 9.09 5.73 0.78 8.00 5.51 0.69 0 0 Ni 31.87 20.16 2.73 15.15 10.48 1.32 94.29 77.84
(56) The composition of the multicomponent alloy coating of comparative embodiment 1 (C1) is listed in table 2. The ratio of each element present in the overall coating is represented by atomic percent (at %).
(57) TABLE-US-00002 TABLE 2 Al Co Cr Fe Ni Si Mo at % <0.5 greater greater greater 1 0 greater than 0.5 than 0.7 than 0.6 than 0.4 and lower and less and less and less than 1 than 1 than 1 than 0.7
(58) Comparative embodiment 2 (C2) is a metal oxide-containing cobalt-based four-component alloy coating made from CoCrAlY/aluminum oxide (Al.sub.2O.sub.3) powders by a HVOF process. Comparative embodiment 3 (C3) is a carbide-containing alloy coating made from Cr.sub.3C.sub.2—NiCr/SiC—Ni powders by a HVOF process. Comparative embodiment 4 (C4) is bulk aluminum metal. Comparative embodiments 7-I to 7-III (C7-I to C7-III) are six-component (FeNiCoCrAlSi) alloy bulks having atomic ratios different from that of embodiment 1 (E1), and each element is present in the amount of 3-35 wt %. Among these three comparative embodiments, comparative embodiment 7-I has the highest aluminum content, comparative embodiment 7-II has the second highest aluminum content, and comparative embodiment 7-III has the lowest aluminum content.
(59) Falling sand wear tests were performed on embodiment 1 (E1) and comparative embodiments 1 to 4 and 7-I to 7-III (C1 to C4 and C7-I to C7-III). The applied force was 13 Newton (Nt), and the falling sand speed was 300-400 g/min. The thicknesses of the coatings E1, C1 to C3, and C7-I to C7-III coated on a substrate are all 200 μm, and C4 is bulk aluminum metal. Please refer to
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(66) High-temperature stability tests were performed on embodiment 1 (E1) and comparative embodiments 2 and 5 (C2 and C5). The composition of comparative embodiment 2 (C2) is as abovementioned. Comparative embodiment 5 (C5) is SKD61 steel. Bulk aluminum materials were placed on alloy coatings of embodiment 1 (E1) and comparative embodiment 2 (C2) and the bulk material of comparative embodiment 5 (C5), respectively, and then these three samples were heated at 700° C. for 30 minutes. Afterwards, the bulk aluminum materials placed on the three samples were removed, and thermal diffusion performance on surfaces of the two coatings of embodiment 1 (E1) and comparative embodiment 2 (C2) and the bulk material of comparative embodiment 5 (C5) were observed. Please refer to
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(71) Vickers hardness tests were performed on the coating of embodiment 1 (E1), the bulk material of embodiment 2 (E2), and the bulk materials of comparative embodiments 6 to 11 (C6 to C11). The test conditions were 1 kgf load for 25 seconds (represented as Hv.sub.1) and 0.1 kgf load for 25 seconds (represented as Hv.sub.0.1). The sizes of the bulk materials of comparative embodiment 6 (C6) and embodiment 2 (E2) are about 5-6 cm. Comparative embodiment 6 (C6) is a six-component (FeNiCoCrAlSi) alloy bulk material having atomic ratios different from that of embodiment 1 (E1), and each element is present in the amount of 3-35 wt %. Comparative embodiment 7-III (C7-III) is a six-component (FeNiCoCrAlSi) alloy coating having a composition and atomic ratios which are the same as that of comparative embodiment 6 (C6). Embodiments 2 (E2) is a six-component (FeNiCoCrAlSi) alloy bulk material having atomic ratios which are the same as that of embodiment 1 (E1) with iron present in the amount of less than 3 wt %. It can be seen that embodiment 1 (E1) and embodiment 2 (E2) are both fracture free. It indicates that the alloy materials having the elements and the ratios thereof according to the embodiments of the present disclosure can be provided with high hardness and toughness whether made into coatings or bulk materials.
(72) Comparative embodiment 8 (C8) is a five-component (FeNiCoCrAl) alloy bulk material, wherein the atomic ratios of iron, cobalt, chromium, and aluminum are greater than 0.4 and less than 0.5 with respect to 1 atomic ratio of nickel. Comparative embodiment 9 (C9) is also a five-component (FeNiCoCrAl) alloy bulk material, and the atomic ratio of each element is 1. Comparative embodiment 10 (C10) is a six-component (FeNiCoCrAlSi) alloy bulk material, and the atomic ratio of each element is 1. Comparative embodiment 11 (C11) is a seven-component (FeNiCoCrAlSiTi) alloy bulk material, and the atomic ratio of each element is 1. The five-component alloy materials of comparative embodiments 8 (C8) and 9 (C9) have high toughness, but the hardness is insufficient. The six-component and seven-component alloy materials of comparative embodiments 10 (C10) and 11 (C11) lose toughness due to too high hardness. Therefore, from the results of comparative embodiments 8-11 (C8-C11), it proves that the compositions and ratios of elements of embodiments 1 (E1) and embodiment 2 (E2) of the present disclosure have unique alloy properties meanwhile maintaining high hardness and toughness of alloy materials.
(73) TABLE-US-00003 TABLE 3 E1 E2 C6 C7-III C8 C9 C10 C11 L1 ~57.5 ~47 ~44 ~59.6 ~80 ~60 ~46 ~40 (μm).sup.a L2 10.71-50.77 0 11.76-14.77 28.74-90.02 0 0 7.51-17.6 31-44 (μm).sup.b Hv.sub.1.sup.c 615 906 1049 591 291 610 1024 1026 Hv.sub.0.1.sup.c 752 768.8 829 760.9 327.3 422.4 846.3 984.1 K.sub.IC.sup.d 2.25 NA 3.30 1.16 NA NA 3.30 1.81 .sup.aL1: diagonal length of a diamond-shaped indentation (μm); .sup.bL2: length of fracture(μm); .sup.cHv: Vickers hardness; .sup.dK.sub.IC (MPa .Math. m.sup.0.5, calculated from the elastic coefficient of Al.sub.2O.sub.3 E = 200 GPa).
(74) As shown in table 3, the five-component alloy bulk material of comparative embodiment 8 (C8) does not have fracture, however, the hardness is too low to provide good wear resistance. In addition, as shown in table 3, the seven-component alloy coating of comparative embodiment 11 (C11) has high hardness, however, the length of fracture is too long and the fracture toughness is too low to provide too toughness.
(75) As shown in
(76) Besides, table 4 and table 5 further list the results of measurements of other properties of embodiment 1 (E1) and comparative embodiments 8 and 11-12 (C8, C11-12). The compositions of comparative embodiments 8 (C8) and 11 (C11) are as previously mentioned, and comparative embodiment 12 (C12) is a 304SS steel.
(77) TABLE-US-00004 TABLE 4 E1 C8 C11 C12 Water contact angle 97 90.7 94.1 85.9 (degree)
(78) TABLE-US-00005 TABLE 5 E1 C8 C11 C12 Corrosion current 4.26E−08 1.05E−07 4.23E−08 2.38E−07 (A/cm.sup.2) Corrosion potential −0.206 −0.262 −0.282 −0.240 (V)
(79) As shown in table 4, compared with comparative embodiments 8 and 11-12 (C8, C11-12), the multicomponent metal coating of embodiment 1 (E1) of the present disclosure has the highest water contact angle, and thus has a more hydrophobic surface.
(80) As shown in table 5, compared with comparative embodiments 8 and 11-12 (C8, C11-12), embodiment 1 (E1) of the present disclosure has the second lowest corrosion current and the highest corrosion potential (the potential tends to be positive), and thus has a better corrosion resistance ability.
(81)
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(83) In contrast, as shown in
(84) While the disclosure has been described by way of example and in terms of the exemplary embodiments, it should be understood that the disclosure is not limited thereto. On the contrary, it will be apparent to those skilled in the art that various modifications and variations can be made to the disclosed embodiments. It is intended that the specification and examples be considered as exemplary only, with a true scope of the disclosure being indicated by the following claims and their equivalents.