CN115976430A - Iron-based metallic glass alloy powder and use thereof for coatings - Google Patents
Iron-based metallic glass alloy powder and use thereof for coatings Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 196
- 239000000843 powder Substances 0.000 title claims abstract description 101
- 239000000956 alloy Substances 0.000 title claims abstract description 99
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 98
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 90
- 239000005300 metallic glass Substances 0.000 title claims abstract description 72
- 238000000576 coating method Methods 0.000 title claims abstract description 54
- 239000011248 coating agent Substances 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 39
- 239000002184 metal Substances 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 19
- 239000011521 glass Substances 0.000 claims description 15
- 239000007921 spray Substances 0.000 claims description 10
- 238000009692 water atomization Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 6
- 238000005260 corrosion Methods 0.000 abstract description 38
- 230000007797 corrosion Effects 0.000 abstract description 38
- 229910052759 nickel Inorganic materials 0.000 abstract description 5
- 238000004781 supercooling Methods 0.000 abstract description 5
- 229910052804 chromium Inorganic materials 0.000 abstract description 4
- 229910052752 metalloid Inorganic materials 0.000 abstract description 4
- 229910052710 silicon Inorganic materials 0.000 abstract description 4
- 229910000619 316 stainless steel Inorganic materials 0.000 description 24
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 18
- 238000009689 gas atomisation Methods 0.000 description 18
- 238000007496 glass forming Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
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- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000011247 coating layer Substances 0.000 description 6
- 230000010287 polarization Effects 0.000 description 6
- 229910000746 Structural steel Inorganic materials 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 229910052758 niobium Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000007751 thermal spraying Methods 0.000 description 4
- 238000004017 vitrification Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000005280 amorphization Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000000889 atomisation Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- 238000005258 corrosion kinetic Methods 0.000 description 2
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- 230000008025 crystallization Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
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- 150000002739 metals Chemical class 0.000 description 2
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- 239000011780 sodium chloride Substances 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 238000012387 aerosolization Methods 0.000 description 1
- 238000010420 art technique Methods 0.000 description 1
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
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- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
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- 239000007791 liquid phase Substances 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
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- 239000013535 sea water Substances 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/02—Amorphous alloys with iron as the major constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/065—Spherical particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/08—Metallic powder characterised by particles having an amorphous microstructure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/145—Chemical treatment, e.g. passivation or decarburisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
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- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/002—Making metallic powder or suspensions thereof amorphous or microcrystalline
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
- B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/02—Making ferrous alloys by powder metallurgy
- C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
- C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
- C22C33/0285—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5% with Cr, Co, or Ni having a minimum content higher than 5%
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
- B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
- B22F2009/0824—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid with a specific atomising fluid
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
- B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
- B22F2009/0824—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid with a specific atomising fluid
- B22F2009/0828—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid with a specific atomising fluid with water
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- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/35—Iron
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- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2304/00—Physical aspects of the powder
- B22F2304/10—Micron size particles, i.e. above 1 micrometer up to 500 micrometer
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- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
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Abstract
The present invention provides an iron-based metallic glass alloy powder and its use for coatings, the iron-based metallic glass alloy powder comprising: fe is used as a main component; metalloid element groups of Si, B and C; a small amount of supercooling improving element-Mo; and corrosion resistance-modifying components-Cr and Ni, wherein the total amount of the metalloid element group, the amount of the supercooling-improving element, and the total amount of the corrosion resistance-modifying component are set to predetermined ranges.
Description
Technical Field
The present invention relates to an iron-based metallic glass alloy powder (iron-based metallic glass alloy powder) and its application for coating, and in particular, to an iron-based metallic glass alloy powder having high hardness, high corrosion resistance and low manufacturing cost, and its application for coating.
For the background of the related art of the present invention, please refer to the following technical documents:
[1] U.S. patent publication No. 2005/0034792A1.
[2]Shujie Pang,Tao Zhang,Katsuhiko Asami,and Akihisa Inoue,New Fe-Cr-Mo-(Nb,Ta)-C-B Glassy Alloys High Glass-Forming Ability and Good Corrosion Resistance,Materials Transactions,Vol.42,No.2(2001),pp.376-379.
[3]Jun Shen,Qingjun Chen,Jianfei Sun,Hongbo Fan,and Gang Wang,Exceptionally high glass-forming ability of an FeCoCrMoCBY alloy,Applied Physics Letters,86(2005),151907.
[4]S.P.Pang,T.Zhang,K.Asami,A.Inoue,Synthesis of Fe-Cr-Mo-C-B-P bulk metallic glasses with high corrosion resistance,Acta Materialia,50(2002),pp.489-497.
[5] U.S. patent publication No. 2016/0298216 A1.
[6] U.S. patent publication No. 2019/0119797 A1.
Background
Amorphous alloys (amorphous alloys) are novel amorphous materials having mechanical, physical and chemical properties superior to those of general metals, or are manufactured by modern rapid solidification metallurgy. Amorphous alloys, also called metallic glass or liquid metal, have irregular internal atomic arrangement, longer range order of atomic arrangement and formation of grain boundaries compared to general metals, and have more uniform distribution of constituent elements than general metal alloys due to irregular atomic arrangement and lack of grain boundaries or precipitates.
Amorphous alloys have documented certain excellent physical, mechanical and chemical properties, for example, strength, toughness, hardness, modulus, etc. of amorphous alloys have been a breakthrough in the record of metallic materials. Amorphous alloys of some compositions are excellent soft magnetic, catalytic, wear resistant, corrosion resistant materials.
With respect to the prior art of amorphous alloys, many studies have confirmed that bulk amorphous alloy materials can be obtained by precisely controlling the concentration and composition of elements. The prior art discloses that a bulk amorphous alloy "1" having a high glass-forming ability can be obtained by increasing a large difference in the atomic sizes of constituent elements. The prior art discloses a typical Fe-based bulk amorphous alloy with high glass forming ability, which contains Fe 45 Cr 16 Mo 16 C 18 B 5 And performance improvement of the iron-based bulk amorphous alloy is performed by adding Nb and Ta "2".
Another prior art is disclosed in Fe 48-x Co x Cr 15 Mo 14 C 15 B 6 Y 2 The addition of Co to (x =0,3,5,7,9) can further improve the glass forming ability of the amorphous alloy by "3". However, as is well known, the addition of Mo, co, Y, nb, and Ta to an amorphous alloy significantly increases the cost for producing the amorphous alloy.
Further, austenitic stainless steels, such as AISI 304 or AISI 316 stainless steels, are composed of 16-18Cr (weight percent) and 8-10Ni (weight percent). The Cr and Ni oxide films formed on the surfaces may protect AISI 304 and AISI 316 stainless steels from rusting or reduce the corrosion rate in certain environments. Conventional stainless steel powder has been used as a coating material to improve the corrosion resistance of the surface of structural steel or components. However, the hardness of the stainless steel coating is low, with a Vickers hardness (Vickers hardness) value of about Hv 200. The wear resistance of the stainless steel coating is also low. The iron-based amorphous alloy coating can provide excellent properties including high wear resistance, corrosion resistance, etc., as compared to the crystalline structure of general metal coatings. The prior art discloses a composition of Fe 43 Cr 16 Mo 16 C 15 B 10 The bulk iron-based amorphous alloy of (1), which can be cast into a rod "4" having a diameter of 2.5 cm by pouring a molten alloy into a copper mold under high-speed cooling. This prior art technique uses high Mo content to achieve high glass forming capability, but also makes this alloy very expensive. Such high prices limit their use in the market.
The particle size of the produced amorphous alloy powder is usually less than 300 μm. For typical thermal spray applications, the alloy powder size used is typically less than 50 μm, and the coating thickness is typically less than 100 μm for a single pass. In order to meet practical requirements without over-design, the constituent elements of the amorphous alloy powder may be adjusted, and the glass forming ability of the amorphous alloy powder may be low relative to that of the bulk amorphous alloy. The present invention has confirmed that the Mo content in the iron-based metallic glass alloy can be greatly reduced, but amorphous alloy powder can still be produced by gas atomization.
However, many iron-based metallic glass alloys have poor corrosion resistance compared to AISI 316 stainless steels, which contain abundant elements that promote the formation of stable passive films on the surface in corrosive environments. The Cr in the traditional stainless steel has obvious positive influence on the corrosion resistance, and a stable passive film is formed. In order to further improve the corrosion resistance at high temperatures, it is advisable to increase the Cr content of the iron-based metallic glass alloy powder. In addition, the corrosion resistance of the Fe-based metal glass alloy powder can be improved by increasing the Cr content and additionally adding Ni. The hardness of the thermal spray coating using the iron-based metallic glass alloy powder can be higher than Hv 800 or more, and is much harder than austenitic stainless steel (Hv 200). The high hardness and high corrosion resistance of iron-based metallic amorphous coatings are very useful in many applications. In addition, an iron-based metallic glass alloy powder can be used as fine particles for bead blasting.
As for the prior art of iron-based metallic glass alloy powders, there is a prior art disclosing an iron-based metallic glass alloy powder having a composition of (Fe) 1-s-t Co s Ni t ) 100-x-y {(Si a B b ) m (P c C d ) n } x M y ) The proportion of each component is as follows: 19 ≦ x ≦ 30;0<y ≦ 8.0; s is 0 to 0.35;0 ≦ t ≦ 0.35; s + t ≦ 0.35"5". The iron-based metallic amorphous powder composition disclosed in the prior art includes mainly Fe and a group of metalloid elements consisting of Si, B, P and C, and a small amount of Nb and Mo to increase supercooling (degree of super-cooling). In the iron-based metallic glass alloy powder disclosed by the prior art, the component proportion of M (M: one or both of Nb and Mo) is between 0.05 and 2.4 to improve the supercooling degree, the component proportion of Co is less than 25.2 (atomic percentage), the component proportion of Ni is less than 25.2 (atomic percentage), and the atomic percentage of Co + Ni is less than or equal to 25.2. This prior art discloses that an iron-based metal glass alloy powder for electronic parts having low eddy current loss is produced by a water atomization method (water atomization) and has a particle size of 0.5 to 50 μm.
Also disclosed in the prior art is an iron-based metallic glass alloy powder having the composition (Fe) 1-s-t Co s Ni t ) 100-x-y {(Si a B b ) m (P c C d ) n } x M y ) The proportion of each component is as follows: x is more than or equal to 19 and less than or equal to 22; y is more than or equal to 0 and less than or equal to 6; s is more than or equal to 0 and less than or equal to 0.35; t is more than or equal to 0 and less than or equal to 0.35; s + t is not less than 0 and not more than 0.35[ 2 ]]. The prior art discloses iron-based metallic glass alloy powder compositions wherein M may be Nb and/or Mo. The composition ratio of Nb and Mo is preferably as low as possible within a range in which necessary magnetic characteristics can be obtained. When s + t>At 0.35, not only does the increase in the Co or Ni content increase the cost of the raw material, but also the supercooling degree decreases to an immeasurable degree. The iron-based metallic glass alloy powder disclosed in the prior art is produced by a water atomization method, and the particle size of the powder is 30 μm or less. The iron-based metal glass alloy powder disclosed in this prior art is used as a powder compact material for various electronic components or as a coating material for forming a magnetic thin film on an electronic circuit board. The electronic component uses fine particles in order to reduce eddy current loss. It is emphasized that the cooling rate of the water atomization process is higher than that of the gas atomization process.
From a review of the prior art of metallic glass alloys, it is clear that there is still room for improvement in the design of compositions for iron-based metallic glass alloy powders that have high hardness, high corrosion resistance, and are inexpensive to manufacture.
Disclosure of Invention
Therefore, an object of the present invention is to provide an iron-based metallic glass alloy powder having advantages of high amorphization forming ability, low manufacturing cost, etc., and its use for a coating, and when the iron-based metallic glass alloy powder according to the present invention is used to form a coating on the surface of structural steel or a component, the coating has advantages of high hardness, high corrosion resistance, etc.
According to a preferred embodiment of the present invention, the iron-based metallic glass alloy powder has a chemical formula of: fe (100-a-b-c-d) Cr a Ni b Mo c (B e C f Si g ) d Wherein a is more than or equal to 18 and less than or equal to 24; b is more than or equal to 10 and less than or equal to 14; c is more than or equal to 6 and less than or equal to 8; d is more than or equal to 20 and less than or equal to 28; e is more than or equal to 10 and less than or equal to 12; f is more than or equal to 6 and less than or equal to 10; g is more than or equal to 4 and less than or equal to 6.
In one embodiment, the iron-based metallic glass alloy powder according to a preferred embodiment of the present invention may be produced by an air atomization method or a water atomization method.
In one embodiment, the particle size of the iron-based metallic glass alloy powder according to the present invention ranges from 5 μm to 300. Mu.m.
A coating according to a preferred embodiment of the invention is formed from an iron-based metallic glass alloy powder according to the invention.
In one embodiment, the coating according to the preferred embodiment of the present invention is formed by a high velocity flame thermal spray process.
Different from the prior art, the iron-based metal amorphous alloy powder has the advantages of high vitrification forming capability, low manufacturing cost and the like, and can be successfully prepared by an air atomization method. Also, when the iron-based metallic amorphous alloy powder according to the present invention is used to form a coating layer on the surface of structural steel or a component, the coating layer has advantages of high hardness, high corrosion resistance, and the like.
The advantages and spirit of the present invention will be further understood by the following embodiments and the accompanying drawings.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) micrograph of a powder made by a gas atomization process and a composition of an iron-based metal glass alloy powder according to the present invention;
FIG. 2 is a diagram showing the results of X-ray diffraction (XRD) spectrum analysis of the iron-based metallic glass alloy powder produced by the gas atomization method according to the present invention;
FIG. 3 is an SEM micrograph of iron-based metallic glass alloy powder produced by the gas atomization method of the present invention after hardness testing;
FIG. 4 is a graph of the iron-based metallic glass alloy powder according to the present invention as measured by Differential Scanning Calorimetry (DSC) testing;
FIG. 5 is an SEM micrograph of the top surface morphology of a coating formed on an AISI 316 stainless steel substrate by a thermal spray process using an iron-based metallic glass alloy powder according to the present invention;
FIG. 6 is an SEM micrograph of a cross-section of an amorphous coating formed on an AISI 316 stainless steel substrate by a thermal spray process using an iron-based metallic glass alloy powder according to the present invention;
FIG. 7 is a graph of the cyclic polarization of AISI 316 stainless steel with coupons of amorphous coating according to the invention in 3.5wt% aqueous sodium chloride;
FIG. 8 is a graph of the cyclic polarization of AISI 316 stainless steel and coupons of amorphous coatings according to the present invention in 0.5M HCl aqueous solution;
FIG. 9 is a photograph of the surface morphology of AISI 316 stainless steel coupon after 4 hours of aeration in gaseous HCl at 400 ℃;
fig. 10 is a surface morphology photograph after a coupon using the iron-based metallic glass alloy powder according to the present invention and forming an amorphous coating layer on an AISI 316 stainless steel substrate through a thermal spraying process was aerated in gaseous HCl at 400 ℃ for 4 hours.
Detailed Description
The invention relates to a composition design of an iron-based metallic glass alloy powder, in particular comprising: fe is used as a main component; metalloid element groups of Si, B and C; a small amount of vitrification (amorphization) to form the element-Mo; and corrosion resistance improving components-Cr and Ni. B. The atomic size of C and Si is smaller than that of Fe; the atomic sizes of Cr and Ni are similar to the atomic size of Fe; the atomic size of Mo is larger than that of Fe. The invention has the advantages of high vitrification forming ability, low manufacturing cost, high hardness, high corrosion resistance and the like in the aspect of component design of the iron-based metal glass alloy powder.
The iron-based metallic glass alloy powder according to a preferred embodiment of the present invention is represented by the following compositional formula:
Fe (100-a-b-c-d) Cr a Ni b Mo c (B e C f Si g ) d wherein a is more than or equal to 18 and less than or equal to 24; b is more than or equal to 10 and less than or equal to 14; c is more than or equal to 6 and less than or equal to 8; d is more than or equal to 20 and less than or equal to 28; e is more than or equal to 10 and less than or equal to 12; f is more than or equal to 6 and less than or equal to 10; g is more than or equal to 4 and less than or equal to 6.
In one example, the iron-based metallic glass alloy powder according to the present invention is represented by the following compositional formula: fe 26 Cr 24 Ni 14 Mo 8 B 12 C 10 Si 6 。
In another example, the iron-based metallic glass alloy powder according to the present invention is represented by the following compositional formula: fe 46 Cr 18 Ni 10 Mo 6 B 10 C 6 Si 4 。
In one embodiment, the iron-based metallic glass alloy powder according to the present invention may be prepared by an air-atomization method or a water-atomization method. It is emphasized that the cooling rate of the gas atomization process is lower than that of the water atomization process.
Referring to fig. 1, fig. 1 is an SEM micrograph of a powder of the composition of an iron-based metallic glass alloy powder according to the present invention and made by an aerosolization process. As shown in FIG. 1, the iron-based metallic glass alloy powder produced by the gas atomization method of the present invention has a spherical shape.
Referring to FIG. 2, FIG. 2 is a graph showing the result of X-ray diffraction (XRD) spectrum analysis of the iron-based metal glass alloy powder according to the present invention produced by the gas atomization method. As shown in fig. 2, the iron-based metallic glass alloy powder according to the present invention prepared by the gas atomization method exhibited a broad diffraction peak only in a low angle region (40 to 50 °) in the XRD pattern, and then disappeared as the angle increased, confirming that the composition of the iron-based metallic glass alloy powder according to the present invention had a high glass forming ability.
Referring to fig. 3, fig. 3 is an SEM micrograph of the iron-based metallic glass alloy powder according to the present invention prepared by the gas atomization method after hardness test. Fig. 3 shows hardness indentation of the iron-based metallic glass alloy powder after hardness testing. According to the invention, the iron-based metal glass alloy powder prepared by the gas atomization method is embedded into a test piece through hardness test, then the iron-based metal glass alloy powder is ground to provide a flat surface, and the flat surface of the iron-based metal glass alloy powder is pressed under a load of 100g by a micro Vickers hardness tester to measure. The hardness of the iron-based metal glass alloy powder prepared by the gas atomization method is about Hv 1200 through the test of a micro Vickers hardness tester. It was confirmed that the hardness of the iron-based metallic glass alloy powder produced by the gas atomization method of the present invention was equal to or greater than Hv 1200. The iron-based metal glass alloy powder produced by the gas atomization method of the present invention has high hardness, which means that the iron-based metal glass alloy powder produced by the gas atomization method of the present invention has high wear resistance.
Referring to fig. 4, fig. 4 is a graph of the iron-based metallic glass alloy powder according to the present invention measured by Differential Scanning Calorimetry (DSC) testing. Differential scanning calorimetry testing was performed at a heating rate of 20 deg.C/min. In fig. 4, the characteristic temperatures measured by the continuous temperature-increasing DSC curve are indicated together. These characteristic temperatures include the glass transition temperature (T) g ) Crystallization temperature (T) x ) Crystallization peak temperature (T) p ) Solid phase temperature (T) s ) And temperature of liquid phase (T) l ). There is a prior art document which proposes to simplify the glass transition temperature (= T) g /T l ) Is an important index of vitrification forming ability. The higher the simplified glass transition temperature, the greater the glass forming ability of the alloy. Another document proposes Δ T x (＝T x -T g ) And is one of the indexes for determining the glass forming ability. When Δ T x The larger the value, the smaller the critical cooling rate required for amorphization, and the more easily amorphous powder is formed. As shown in FIG. 4, the simplified glass transition of the iron-based metallic glass alloy powder according to the present invention is 0.475, Δ T x =46 ℃. Simplified glass transition temperature and delta T of iron-based metallic glass alloy powder according to the invention in the field of iron-based metallic glass alloy powder x Are relatively high, which confirms that the iron-based metallic glass alloy powder according to the invention has a high glass forming ability. The iron-based metallic glass alloy powder according to the present invention can successfully produce amorphous powder by gas atomization method with a slow cooling rate, which also reflects the high glass forming ability of the iron-based metallic glass alloy powder according to the present invention. In addition, it should be noted that the iron-based metallic glass alloy powder according to the present invention can be easily manufactured into a large-sized amorphous powder by a water atomization method in which the cooling rate is fast, and the manufacturing cost by the water atomization method is low.
In one embodiment, the particle size of the iron-based metallic glass alloy powder according to the present invention ranges from 5 μm to 300. Mu.m.
In practical application, the iron-based metal glass alloy powder has high hardness and high corrosion resistance, and can be applied to raw materials of thermal spraying and powder metallurgy. In addition, the spherical amorphous alloy powder produced by gas atomization of the present invention can be used as a ball striking ball required for a ball striking process.
A coating according to a preferred embodiment of the present invention is formed from the iron-based metallic glass alloy powder according to the present invention, the coating being an amorphous coating. When the iron-based metallic glass alloy powder according to the present invention is used to form a coating on the surface of structural steel or a component, the coating has advantages of high hardness, high corrosion resistance, and the like.
In one embodiment, the coating according to the present invention is formed by a high velocity flame thermal spray process, but the invention is not limited thereto.
Referring to fig. 5, fig. 5 is an SEM micrograph of the top surface morphology of an amorphous coating formed on an AISI 316 stainless steel substrate by a thermal spray process using the iron-based metallic glass alloy powder according to the present invention. As shown in fig. 5, the amorphous coating layer formed using the iron-based metallic glass alloy powder according to the present invention is a dense coating layer, and can effectively protect a substrate.
Referring to fig. 6, fig. 6 is an SEM micrograph of a cross-section of an amorphous coating formed on an AISI 316 stainless steel substrate by a thermal spray process using an iron-based metallic glass alloy powder according to the present invention. Fig. 6 shows hardness indentation of the amorphous coating after the hardness test by a micro vickers hardness tester under a load of 50g and indicates the hardness value. As shown in fig. 6, the hardness value of the coating reaches above Hv 1100 close to the original powder hardness, while the AISI 316 stainless steel substrate has a hardness value of Hv 184. The above hardness values confirm that the hardness of the amorphous coating formed using the iron-based metallic glass alloy powder according to the present invention is equal to or greater than Hv 1100.
In order to simulate the corrosive environment of seawater, the present invention uses 3.5wt% sodium chloride aqueous solution as a test solution, and performs cyclic polarization curve corrosion resistance evaluation on AISI 316 stainless steel coupons and coupons using the iron-based metallic glass alloy powder according to the present invention and forming an amorphous coating on AISI 316 stainless steel substrates by a thermal spraying process, and the results thereof are shown in fig. 7. Important corrosion kinetic parameters such as corrosion potential (E) are determined by the circular polarization curve of FIG. 7 corr ) And corrosion current density (I) corr ) Are collated in Table 1.
TABLE 1
| Test piece | E corr (V) | I corr (μA/cm 2 ) |
| AISI 316 stainless steel | -0.56 | 3.96 |
| Amorphous coating | -0.56 | 4.7 |
From the results listed in table 1 it can be found that the corrosion potential of the amorphous coating is about the same as the corrosion potential of AISI 316 stainless steel, but the corrosion current density of the amorphous coating is slightly higher than the corrosion current density of AISI 316 stainless steel. As shown in fig. six, even if there are micro-sized spray defects in the coating, such as micro-holes and the interface between the stacked layers. However, the amorphous coating according to the present invention still has high corrosion resistance. It is believed that the reduction of micro-defects in the amorphous coating according to the present invention may further enhance the corrosion resistance of the amorphous coating according to the present invention.
The present invention also uses 0.5M HCl aqueous solution as a test solution to evaluate the cyclic polarization curve corrosion resistance of AISI 316 stainless steel coupons and coupons using the iron-based metallic glass alloy powder according to the present invention and forming amorphous coatings on AISI 316 stainless steel substrates by thermal spray process, and the results are shown in fig. 8. Important corrosion kinetic parameters such as corrosion potential (E) are determined by the circular polarization curve of FIG. 8 corr ) And corrosion current density (I) corr ) Are collated in Table 2.
TABLE 2
| Test piece | E corr (V) | I corr (μA/cm 2 ) |
| AISI 316 stainless steel | -0.34 | 58.2 |
| Amorphous coating | -0.29 | 39.2 |
From the results listed in table 2, it can be seen that the corrosion potential of the amorphous coating is slightly negative than that of AISI 316 stainless steel, but the corrosion current density of the amorphous coating is much lower than that of AISI 316 stainless steel.
The results of fig. 7, fig. 8, table 1 and table 2 confirm that the amorphous coating formed using the iron-based metallic glass alloy powder according to the present invention has good corrosion resistance.
Referring to fig. 9 and 10, fig. 9 is a photograph showing the surface morphology of AISI 316 stainless steel coupons after being aerated in gaseous HCl at 400 ℃ for 4 hours. Fig. 10 is a surface topography photograph of a coupon using the iron-based metal glass alloy powder according to the present invention and forming an amorphous coating layer on AISI 316 stainless steel substrate through a thermal spraying process after being aerated in gaseous HCl at 400 ℃ for 4 hours. As shown in FIGS. 9 and 10, the extensive formation of brittle CrCl was observed in the AISI 316 stainless steel test piece 3 ·6H 2 O spalls, indicating that AISI 316 stainless steel is less resistant to chloride attack.
In contrast, the test pieces forming the amorphous coating still showed no material cracking and peeling. This means that the AISI 316 stainless steel coupons are much less resistant to chloride attack at high temperatures than the amorphous coating according to the invention. The amorphous coating according to the invention shows good resistance to gaseous chloride attack at 400 ℃.
From the above detailed description of the preferred embodiments, it is believed that the iron-based metallic glass alloy powder according to the present invention has the advantages of high glass forming ability, low manufacturing cost, etc., and can be successfully manufactured by the gas atomization method. For example, the amorphous alloy powder with larger size can be obtained by the water mist method, and the cost is lower. Also, when the iron-based metallic glass alloy powder according to the present invention is used to form a coating on the surface of structural steel or a component, the coating has advantages of high hardness, high corrosion resistance, etc., and even has the ability to resist gaseous chloride corrosion at high temperatures.
The foregoing detailed description of the preferred embodiments is intended to more clearly illustrate the features and spirit of the present invention, and is not intended to limit the scope of the invention to the particular embodiments disclosed. On the contrary, it is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention. The scope of the invention should, therefore, be determined with reference to the above description, and all changes that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (9)
1. An iron-based metallic glass alloy powder represented by the following compositional formula:
Fe (100-a-b-c-d) Cr a Ni b Mo c (B e C f Si g ) d ，
wherein a is more than or equal to 18 and less than or equal to 24; b is more than or equal to 10 and less than or equal to 14; c is more than or equal to 6 and less than or equal to 8; d is more than or equal to 20 and less than or equal to 28; e is more than or equal to 10 and less than or equal to 12; f is more than or equal to 6 and less than or equal to 10; g is more than or equal to 4 and less than or equal to 6.
2. The iron-based metal glass alloy powder of claim 1, produced by an air-or water-atomization process.
3. The iron-based metallic glass alloy powder according to claim 2, having a particle size in the range of 5-300 μm.
4. The iron-based metallic glass alloy powder of claim 2, represented by the following compositional formula:
Fe 26 Cr 24 Ni 14 Mo 8 B 12 C 10 Si 6 。
5. the iron-based metallic glass alloy powder according to claim 2, represented by the following compositional formula:
Fe 46 Cr 18 Ni 10 Mo 6 B 10 C 6 Si 4 。
6. the iron-based metallic glass alloy powder of claim 2, having a hardness equal to or greater than HV 1200.
7. A coating formed from an iron-based metallic glass alloy powder represented by the following compositional formula:
Fe (100-a-b-c-d) Cr a Ni b Mo c (B e C f Si g ) d ，
wherein a is more than or equal to 18 and less than or equal to 24; b is more than or equal to 10 and less than or equal to 14; c is more than or equal to 6 and less than or equal to 8; d is more than or equal to 20 and less than or equal to 28; e is more than or equal to 10 and less than or equal to 12; f is more than or equal to 6 and less than or equal to 10; g is more than or equal to 4 and less than or equal to 6.
8. The coating of claim 7 formed by a high velocity flame thermal spray process.
9. The coating of claim 8, having a hardness equal to or greater than Hv 1100.
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