TWI710648B - Fe-BASED METALLIC GLASS ALLOY - Google Patents

Abstract

A Fe-based metallic glass alloy is disclosed, which is formed of an alloy having a formula (Fe ₄₁Cr ₁₅Mo ₁₄C ₁₂B ₉Co ₇Y ₂) _100-(x+z)Ta _xAl _zor a formula Fe _41+wCr ₁₅Mo ₁₄C _4mB _3mCo ₇Y _2-wTa _pAl _q, wherein x is 0 or 2 to 5, z is 0 or 3 to 6, and one of x and z is 0; and w is 0 to 2, m is 2 to 3, p is 0 or 3.5, q is 0 or 3.5n, wherein n is 1 to 2, and one of p and q is 0.

Description

Iron-based metallic glass alloy

The invention provides an iron-based metallic glass alloy, especially an iron-based metallic glass alloy containing tantalum or aluminum.

Metallic glass is a metal material with disordered interatomic structure, and because it does not have a long-range ordered structure, many characteristics of metallic glass are different from general metals. For example, metallic glass has higher tensile strength and lower Elastic modulus, etc. Among them, the iron-based metallic glass alloy has the advantages of good magnetic properties, high strength, high corrosion resistance, and relatively low price, and has high commercial application value.

However, although iron-based metallic glass has high strength, it still has the disadvantage of not having plastic strain and being very brittle at room temperature, which greatly limits its application range.

Therefore, there is an urgent need to develop a new iron-based metallic glass alloy that can improve the shortcomings of poor toughness and improve its utilization.

In view of this, the present invention provides an iron-based metallic glass alloy by introducing composite material tantalum or aluminum to improve the toughness of the iron-based metallic glass alloy.

To achieve the above objective, the present invention provides an iron-based metallic glass alloy formed by an alloy of the formula (Fe ₄₁ Cr ₁₅ Mo ₁₄ C ₁₂ B ₉ Co ₇ Y ₂ ) _100-(x+z) Ta _x Al _z , wherein , X is 0 or 2 to 5, z is 0 or 3 to 6, and one of x and z is 0.

In an embodiment of the present invention, x is 2 to 5, and z is 0.

In an embodiment of the present invention, x is 0 and z is 3-6.

In the embodiment of the present invention, the iron-based metallic glass alloy is selected from (Fe ₄₁ Cr ₁₅ Mo ₁₄ C ₁₂ B ₉ Co ₇ Y ₂ ) ₉₈ Ta ₂ , (Fe ₄₁ Cr ₁₅ Mo ₁₄ C ₁₂ B ₉ Co ₇ Y ₂ ) ₉₇ Ta ₃ , (Fe ₄₁ Cr ₁₅ Mo ₁₄ C ₁₂ B ₉ Co ₇ Y ₂ ) ₉₆ Ta ₄ , (Fe ₄₁ Cr ₁₅ Mo ₁₄ C ₁₂ B ₉ Co ₇ Y ₂ ) ₉₅ Ta ₅ , (Fe ₄₁ Cr ₁₅ Mo ₁₄ C ₁₂ B ₉ Co ₇ Y ₂ ) ₉₇ Al ₃ , (Fe ₄₁ Cr ₁₅ Mo ₁₄ C ₁₂ B ₉ Co ₇ Y ₂ ) ₉₆ Al ₄ , (Fe ₄₁ Cr ₁₅ Mo ₁₄ C ₁₂ B ₉ Co ₇ Y ₂ ) A group consisting of ₉₅ Al ₅ and (Fe ₄₁ Cr ₁₅ Mo ₁₄ C ₁₂ B ₉ Co ₇ Y ₂ ) ₉₄ Al ₆ . Preferably, the iron-based metallic glass alloy is selected from (Fe ₄₁ Cr ₁₅ Mo ₁₄ C ₁₂ B ₉ Co ₇ Y ₂ ) ₉₈ Ta ₂ , (Fe ₄₁ Cr ₁₅ Mo ₁₄ C ₁₂ B ₉ Co ₇ Y ₂ ) ₉₇ Ta ₃ , (Fe ₄₁ Cr ₁₅ Mo ₁₄ C ₁₂ B ₉ Co ₇ Y ₂ ) ₉₅ Ta ₅ , (Fe ₄₁ Cr ₁₅ Mo ₁₄ C ₁₂ B ₉ Co ₇ Y ₂ ) ₉₅ Al ₅ , and (Fe ₄₁ Cr ₁₅ Mo ₁₄ C ₁₂ B ₉ Co ₇ Y ₂ ) ₉₄ Al ₆ .

The present invention also provides an iron-based metallic glass alloy formed by an alloy of the formula Fe _41+w Cr ₁₅ Mo ₁₄ C _4m B _3m Co ₇ Y _2-w Ta _p Al _q , wherein w is 0 to 2, m is 2 to 3, p is 0 or 3.5, q is 0 or 3.5n, where n is 1 to 2, and one of p and q is 0.

In an embodiment of the present invention, w is 2, m is 2 to 3, p is 0, and q is 0 or 3.5n, where n is 1 to 2.

In an embodiment of the present invention, w is 1 to 2, m is 2 to 3, p is 0, and q is 3.5n, where n is 1. Preferably, w is 2.

In an embodiment of the present invention, w is 0, m is 2 to 3, p is 0 or 3.5, q is 0 or 3.5n, where n is 1 to 2, and one of p and q is 0.

In the embodiment of the present invention, the iron-based metallic glass alloy is selected from Fe ₄₁ Cr ₁₅ Mo ₁₄ C ₁₀ B _7.5 Co ₇ Y ₂ Ta _3.5 , Fe ₄₁ Cr ₁₅ Mo ₁₄ C ₁₀ B _7.5 Co ₇ Y ₂ Al _3.5 , Fe ₄₁ Cr ₁₅ Mo ₁₄ C ₈ B ₆ Co ₇ Y ₂ Al ₇ , Fe ₄₂ Cr ₁₅ Mo ₁₄ C ₁₀ B _7.5 Co ₇ Y ₁ Al _3.5 , Fe _42.5 Cr ₁₅ Mo ₁₄ C ₁₀ B _7.5 Co ₇ Y _0.5 Al _3.5 , Fe ₄₃ Cr ₁₅ Mo ₁₄ C ₁₀ B _7.5 Co ₇ Al _3.5 , and Fe ₄₃ Cr ₁₅ Mo ₁₄ C ₈ B ₆ Co ₇ Al ₇ . Preferably, the iron-based metallic glass alloy is selected from Fe ₄₁ Cr ₁₅ Mo ₁₄ C ₁₀ B _7.5 Co ₇ Y ₂ Ta _3.5 , Fe ₄₁ Cr ₁₅ Mo ₁₄ C ₁₀ B _7.5 Co ₇ Y ₂ Al _3.5 , Fe ₄₃ Cr ₁₅ Mo ₁₄ C ₁₀ B _7.5 Co ₇ Al _3.5 and Fe ₄₃ Cr ₁₅ Mo ₁₄ C ₈ B ₆ Co ₇ Al ₇ .

In the embodiment of the present invention, the iron-based metallic glass alloy is an amorphous alloy.

In an embodiment of the present invention, the hardness of the iron-based metallic glass alloy may be greater than 800Hv. In another embodiment of the present invention, the hardness of the iron-based metallic glass alloy may be greater than 1000 Hv.

In the embodiment of the present invention, the fracture toughness of the iron-based metallic glass alloy may be greater than 3 MPa·m ^1/2 . Preferably, the fracture toughness of the iron-based metallic glass alloy may be greater than 5 MPa·m ^1/2 . More preferably, the fracture toughness of the iron-based metallic glass alloy may be greater than 7 MPa·m ^1/2 or greater than 10 MPa·m ^1/2 .

Therefore, the present disclosure improves the toughness of the iron-based metallic glass alloy by introducing the composite material tantalum or aluminum into the iron-based metallic glass alloy.

The following is a specific embodiment to illustrate the implementation of the present disclosure. Those familiar with the art can easily understand the other advantages and effects of the present disclosure from the content disclosed in this specification. The present disclosure can also be implemented or applied by other different specific embodiments, and various details in this specification can also be modified and changed according to different viewpoints and applications without departing from the spirit of the creation.

All technical and scientific terms described in the specification of the present invention and the scope of the patent application, unless otherwise defined, are definitions that can be known to those with ordinary knowledge in the technical field of the present invention. The singular terms "one", "one", "the", or similar terms, unless otherwise specified, can refer to more than one object. The "or", "and", and "and" used in this manual refer to "or/and" unless otherwise specified. In addition, the terms "include" and "include" are not restrictive open-ended conjunctions. The foregoing definitions only illustrate the meaning of the term definition and should not be interpreted as a restriction on the subject of the invention. Unless otherwise specified, the materials used in the present invention are commercially available and readily available.

In order to test the iron-based metallic glass alloy with a specific composition, the formula (Fe ₄₁ Cr ₁₅ Mo ₁₄ C ₁₂ B ₉ Co ₇ Y ₂ ) _100-(x+z) Ta _x Al _z or the formula Fe _41+w Cr ₁₅ Mo ₁₄ C _4m B _3m Co ₇ Y _2-w Ta _p Al _q alloy is tested, where x is 0 or 2 to 5, z is 0 or 3 to 6, and one of x and z is 0; And w is 0 to 2, m is 2 to 3, p is 0 or 3.5, q is 0 or 3.5n, where n is 1 to 2, and one of p and q is 0. Here, the coefficients m, n, p, q, w, x, and z are the atomic percentages (at%) of each specific metal per unit alloy. The aforementioned alloy is put into a vacuum arc melting furnace, evacuated and backfilled with argon gas, and an arc melting step is performed to form an ingot. Then, the ingot is melted by a vacuum suction casting method to form a metallic glass alloy rod with a diameter of 2-4 mm.

(I) Use Vickers hardness machine and formula (I) to calculate the Vickers hardness of iron-based metallic glass alloys. Among them, P is the load (kg-f); A is the surface area of the indentation (mm ² ); d is the average diagonal length of the indentation (mm).

(I)

The fracture toughness of iron-based metallic glass alloys was calculated using the indentation calculation fracture toughness theory formula (II) proposed by Granstis et al. Among them, Kc is the fracture toughness (MPa∙m1/2); E is the Young's modulus (GPa) of the material; H is the material hardness value (GPa); P is the indentation load (N); C is the indentation center to the four-side cracks End length (m). K _c = 0.016(P/A ^1.5 )(E/H) ^1/2 (II)

Example

The experimental results of the iron-based metallic glass alloy with the above specific composition are recorded in Table 1.

Table 1 Example composition Load(kg) Hardness (kgf/mm ² ) Fracture toughness (MPa·m ^1/2 ) 1 (Fe ₄₁ Cr ₁₅ Mo ₁₄ C ₁₂ B ₉ Co ₇ Y ₂ ) ₉₈ Ta ₂ 2 1176±30 5.45±0.8 2 (Fe ₄₁ Cr ₁₅ Mo ₁₄ C ₁₂ B ₉ Co ₇ Y ₂ ) ₉₇ Ta ₃ 2 1125±12 6.56±1 3 (Fe ₄₁ Cr ₁₅ Mo ₁₄ C ₁₂ B ₉ Co ₇ Y ₂ ) ₉₆ Ta ₄ 2 1188±28 3.74±0.2 4 (Fe ₄₁ Cr ₁₅ Mo ₁₄ C ₁₂ B ₉ Co ₇ Y ₂ ) ₉₅ Ta ₅ 2 1235±24 5.4±0.9 5 Fe ₄₁ Cr ₁₅ Mo ₁₄ C ₁₀ B _7.5 Co ₇ Y ₂ Ta _3.5 2-5 1224±32 10.2±0.9 6 (Fe ₄₁ Cr ₁₅ Mo ₁₄ C ₁₂ B ₉ Co ₇ Y ₂ ) ₉₇ Al ₃ 5 1086±45 4.49±1.1 7 (Fe ₄₁ Cr ₁₅ Mo ₁₄ C ₁₂ B ₉ Co ₇ Y ₂ ) ₉₆ Al ₄ 5 1130±34 3.39±0.5 8 (Fe ₄₁ Cr ₁₅ Mo ₁₄ C ₁₂ B ₉ Co ₇ Y ₂ ) ₉₅ Al ₅ 10 1084±61 8.109±1.1 9 (Fe ₄₁ Cr ₁₅ Mo ₁₄ C ₁₂ B ₉ Co ₇ Y ₂ ) ₉₄ Al ₆ 5 1105±47 6.326±1.4 10 Fe ₄₁ Cr ₁₅ Mo ₁₄ C ₁₀ B _7.5 Co ₇ Y ₂ Al _3.5 10 1038±52 7.61±0.8 11 Fe ₄₁ Cr ₁₅ Mo ₁₄ C ₈ B ₆ Co ₇ Y ₂ Al ₇ 5 1134±56 4.15±1.1 12 Fe ₄₂ Cr ₁₅ Mo ₁₄ C ₁₀ B _7.5 Co ₇ Y ₁ Al _3.5 3 1216±57 2.45±0.2 13 Fe _42.5 Cr ₁₅ Mo ₁₄ C ₁₀ B _7.5 Co ₇ Y _0.5 Al _3.5 3 1140±39 4.14±0.6 14 Fe ₄₃ Cr ₁₅ Mo ₁₄ C ₁₀ B _7.5 Co ₇ Al _3.5 20 926.6±22.4 12.29±0.9 15 Fe ₄₃ Cr ₁₅ Mo ₁₄ C ₈ B ₆ Co ₇ Al ₇ 50 854±6.2 16.61±2.2

From the experimental results in Table 1, it can be found that after tantalum or aluminum is introduced, the iron-based metallic glass alloy still has high hardness performance, and the fracture toughness of some embodiments can even be greater than 10 MPa · m ^1/2 , such as Fe ₄₁ in embodiment 5 Cr ₁₅ Mo ₁₄ C ₁₀ B _7.5 Co ₇ Y ₂ Ta _3.5 , Fe ₄₃ Cr ₁₅ Mo ₁₄ C ₁₀ B _7.5 Co ₇ Al _3.5 of Example 14, and Fe ₄₃ Cr ₁₅ Mo ₁₄ C ₈ B ₆ Co of Example 15 ₇ Al ₇ .

In addition, the corrosion resistance of iron-based metallic glass alloy and 316 stainless steel was compared by the open circuit potential method and the dynamic polarization method. The dynamic polarization test was carried out in a 3.5 wt% sodium chloride aqueous solution. The results are shown in Figure 1. The corrosion potential (E _corr ), corrosion current density (I _corr ), and corrosion current density (I _corr ) were obtained by the Tafel extrapolation method. The initial potential (E _pp ) and pitting potential (E _pit ) of the passivation layer are shown in Table 2. Among them, the scanning range is -500 to 1600 mV; the scanning rate is 1 mV/s; the reference electrode is a saturated calomel electrode (SCE); the counter electrode is a platinum electrode; and the electrolyte is a 3.5 wt% sodium chloride solution.

Table 2 E _corr (V) I _corr (A/mm ² ) E _pp (V) E _pit (V) E _pit -E _pp (V) Fe ₄₁ Cr ₁₅ Mo ₁₄ C ₁₀ B _7.5 Co ₇ Y ₂ Ta _3.5 -0.24 4 x 10 ^-9 -0.054 0.979 1.033 316 stainless steel -0.231 4 x 10 ^-9 -0.061 -0.008 0.053

It can be seen from the results in Table 2 that the corrosion potential of the iron-based metallic glass alloy is slightly lower than that of 316 stainless steel, indicating that it is less likely to lose electrons to form cations and has a stronger corrosion resistance. In addition, from the Taffer curve, the initial potential of the passivation layer E _pp and the pitting potential E _pit can also be known. The difference between the two shows that the iron-based metallic glass alloy has an excellent passivation layer interval (1.033V), and The passivation layer interval of 316 stainless steel is only 0.053V, which means that the passivation layer interval of 316 stainless steel is less stable than iron-based metallic glass alloy.

Furthermore, the surface of the test piece after the dynamic polarization experiment was observed with an optical microscope. As shown in Figure 2, it can be clearly observed that the surface of the iron-based metallic glass alloy is still smooth, and only slight pitting occurs. Phenomenon, the hole diameter is less than 50µm. In contrast to 316 stainless steel, many holes can be observed by naked eyes, and the hole diameter is 50-300µm. Therefore, it is again verified that the iron-based metallic glass alloy has better corrosion resistance than 316 stainless steel.

Because the iron-based metallic glass alloy described in this case has the advantages of high hardness, improved toughness, wear resistance, or corrosion resistance. Therefore, the iron-based metallic glass alloy described in this case is produced by a powder spraying manufacturing method to produce a powder suitable for laminated manufacturing. Wherein, the powder spray manufacturing method includes: putting the ingot alloy into a crucible and heating it with high frequency until the ingot alloy becomes a liquid phase; then pour the liquid phase alloy into a heat preservation crucible, and add to the heat preservation crucible The liquid phase alloy in the heat preservation crucible flows into the atomizing nozzle area; the liquid phase alloy flowing out from the atomizing nozzle area is atomized by argon gas to obtain alloy powder. The powder can be applied to build-up manufacturing later.

In addition, in multilayer manufacturing, the nature of the metal powder will directly affect the material properties of the final molding. Since the iron-based metallic glass alloy of this case has advantages that common crystalline materials do not have, such as low enthalpy, no volume change between solid and liquid phases, etc., it also improves the shortcomings of common amorphous metal materials, such as toughness. Therefore, the process stability and the quality of molding construction can be improved.

Figure 1 shows the dynamic polarization test results of iron-based metallic glass alloy and 316 stainless steel. Figure 2 shows the surface of the iron-based metallic glass alloy and 316 stainless steel specimen after the dynamic polarization test.

Claims (12)

An iron-based metallic glass alloy formed by an alloy of the formula (Fe ₄₁ Cr ₁₅ Mo ₁₄ C ₁₂ B ₉ Co ₇ Y ₂ ) _100-(x+z) Ta _x Al _z , where x is 0 and z is 3. To 6. The iron-based metallic glass alloy described in item 1 of the scope of patent application, wherein the iron-based metallic glass alloy is selected from (Fe ₄₁ Cr ₁₅ Mo ₁₄ C ₁₂ B ₉ Co ₇ Y ₂ ) ₉₇ Al ₃ , (Fe ₄₁ Cr ₁₅ Mo ₁₄ C ₁₂ B ₉ Co ₇ Y ₂ ) ₉₆ Al ₄ , (Fe ₄₁ Cr ₁₅ Mo ₁₄ C ₁₂ B ₉ Co ₇ Y ₂ ) ₉₅ Al ₅ , and (Fe ₄₁ Cr ₁₅ Mo ₁₄ C ₁₂ B ₉ Co ₇ Y ₂ ) A group consisting of ₉₄ Al ₆ . The iron-based metallic glass alloy described in item 1 of the scope of patent application, wherein the iron-based metallic glass alloy is an amorphous alloy. The iron-based metallic glass alloy described in item 1 of the scope of patent application, wherein the hardness of the iron-based metallic glass alloy is greater than 1000Hv. The iron-based metallic glass alloy described in item 1 of the scope of patent application, wherein the iron-based metallic glass alloy is used for laminated manufacturing. An iron-based metallic glass alloy formed by an alloy of the formula Fe _41+w Cr ₁₅ Mo ₁₄ C _4m B _3m Co ₇ Y _2-w Ta _p Al _q , where w is 0 to 2, m is 2 to 3, p is 0 or 3.5, q is 0 or 3.5n, where n is 1 to 2, and one of p and q is 0. The iron-based metallic glass alloy described in item 6 of the scope of patent application, wherein w is 0. The iron-based metallic glass alloy described in item 6 of the scope of patent application, wherein w is 1 to 2, and p is 0. The iron-based metallic glass alloy described in item 6 of the scope of patent application, wherein the iron-based metallic glass alloy is selected from Fe ₄₁ Cr ₁₅ Mo ₁₄ C ₁₀ B _7.5 Co ₇ Y ₂ Ta _3.5 , Fe ₄₁ Cr ₁₅ Mo ₁₄ C ₁₀ B _7.5 Co ₇ Y ₂ Al _3.5 , Fe ₄₁ Cr ₁₅ Mo ₁₄ C ₈ B ₆ Co ₇ Y ₂ Al ₇ , Fe ₄₂ Cr ₁₅ Mo ₁₄ C ₁₀ B _7.5 Co ₇ Y ₁ Al _3.5 , Fe _42.5 Cr ₁₅ Mo ₁₄ C ₁₀ B _7.5 Co ₇ Y _0.5 Al _3.5 , Fe ₄₃ Cr ₁₅ Mo ₁₄ C ₁₀ B _7.5 Co ₇ Al _3.5 , and Fe ₄₃ Cr ₁₅ Mo ₁₄ C ₈ B ₆ Co ₇ Al ₇ . The iron-based metallic glass alloy described in item 6 of the scope of patent application, wherein the iron-based metallic glass alloy is an amorphous alloy. The iron-based metallic glass alloy described in item 6 of the scope of patent application, wherein the hardness of the iron-based metallic glass alloy is greater than 800Hv. The iron-based metallic glass alloy described in item 6 of the scope of patent application, wherein the iron-based metallic glass alloy is used for laminated manufacturing.

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