CN104162662A - Surface modified amorphous alloy powder, manufacturing method and coating manufactured through surface modified amorphous alloy powder - Google Patents
Surface modified amorphous alloy powder, manufacturing method and coating manufactured through surface modified amorphous alloy powder Download PDFInfo
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Abstract
The invention discloses surface modified amorphous alloy powder. The surface modified amorphous alloy powder is characterized in that the surface of the amorphous alloy powder is covered with an oxidation resisting metal coating based on a surface modification technology. The invention further discloses a manufacturing method of the powder and an amorphous composite coating manufactured through the powder and a manufacturing method of the amorphous composite coating. The amorphous composite coating has the excellent oxidation resisting performance, high binding force and the good wear resisting performance, the problems that interface binding force between previous single-phase amorphous coatings/metal substrates is poor, and the high-temperature oxidation resisting performance is insufficient are solved, and surface oxidation of the amorphous powder in the high-temperature heat spraying process can be effectively reduced. The composite coating has the wide application prospect in aerospace, drilling, thermal power generation and other heat structure materials and the abrasion resisting field.
Description
Technical field
The invention belongs to technical field of surface coating, be specifically related to a kind of amorphous powdered alloy of surface modification, the preparation method of this amorphous powdered alloy and the composite coating that utilizes this amorphous powdered alloy to prepare.
Background technology
Amorphous alloy is called for short non-crystaline amorphous metal, is called again glassy metal, has that long-range is unordered, the metastable structure feature of shortrange order.Compare with traditional crystal alloy, non-crystaline amorphous metal possesses the performance of a lot of excellences, as high strength, high rigidity, wear-resisting and corrosion-resistant etc., thereby causes the great interest of people.The problem that amorphous alloy material exists is that its preparation process is difficult to control, be difficult in practice prepare bulk amorphous material, its application is mainly limited in the low dimensions such as strip, filament, powder in shape, in addition, the intrinsic fragility of non-crystalline material has also limited its application to a certain extent, under most conditions, can not use as structural material.
Amorphous alloy coating refers to one deck amorphous coating obtaining on traditional material surface by surface engineering technology, the application of this coating can improve conventional surface hardness, anti-corrosion and anti-wear performance greatly, in material surface modifying field, there is very huge potential using value, especially the relatively cheap iron base amorphous alloy coatings of cost, there is excellent physics and chemistry performance, as the hardness of superelevation and splendid wear-resisting anti-corrosion property energy, therefore in Surface Engineering field, have broad application prospects.
The preparation of amorphous alloy coating adopts thermal spraying skill method conventionally, and that its coating of preparing has is wear-resistant, corrosion-resistant and high-temperature resistant and the premium properties such as heat insulation, therefore in machine-building, Aero-Space, field of petrochemical industry, has a very wide range of applications.Thermal spraying dusty material used adopts ultrasonic atomizatio method to obtain mostly, and ultrasonic atomizatio method is mainly to utilize high velocity air or current, at full speed impacts liquid metal stream, makes it be atomized into droplet, is frozen into subsequently powder.Gained powder size is more concentrated, and powder pick-up rate is high, and spheroidization degree is good, and the amorphous powdered alloy of used for hot spraying adopts ultrasonic atomizatio method to make mostly at present.
Yet, because metallic inevitably surface oxidation can occur in thermal spray process, formed oxide tissue can greatly reduce adhesion, wearability and other military service performances of coating, and this can have a strong impact on serviceability and the service life of amorphous coating.
Summary of the invention
For problems of the prior art and improvement defect, the coating that the object of the present invention is to provide a kind of non-crystaline amorphous metal composite powder, its preparation method of surface modification and utilize this non-crystaline amorphous metal composite powder to prepare, its method by powder surface modification is at the coated oxidation resistant coat of metal of one deck in amorphous powdered alloy surface, thereby reduce the degree of oxidation of amorphous powdered alloy in thermal spray process, solve the problem that coating performance that current amorphous powdered alloy causes due to the oxidation of pyrolytic coating process reduces.
According to one aspect of the present invention, a kind of non-crystaline amorphous metal composite powder of surface modification is provided, it is characterized in that, it is the composite powder at the coated oxidation resistant coat of metal in amorphous powdered alloy surface by process for modifying surface.
As improvement of the present invention, described powder surface modification technology is that one or more in high-energy ball milling, collosol and gel, vapour deposition, chemical plating, electro-plating method are compound.
As improvement of the present invention, described coat of metal material is that one or more in pure Ni, pure Co, pure Cu, Ni-P, Ni-B, Ni-W, Ni-W-P and Ni-Cu-P are compound.
As improvement of the present invention, the thickness of the described coat of metal is at 1-5 μ m.
As improvement of the present invention, described amorphous powdered alloy adopts the preparation of ultrasonic atomizatio method, and its particle size range is 15-60 μ m, and powder is complete amorphous state.
According to another aspect of the present invention, a kind of non-crystaline amorphous metal composite coating is provided, it is characterized in that, this coating is by utilizing heat spraying method to prepare above-mentioned non-crystaline amorphous metal composite powder.
As improvement of the present invention, the thickness of described amorphous composite coating is at 100-1500 μ m.
As improvement of the present invention, above-mentioned thermal spraying comprises flame-spraying, plasma spraying, detonation flame spraying, electric arc spraying or HVAF.
According to another aspect of the present invention, a kind of preparation method of non-crystaline amorphous metal composite powder of surface modification is provided, it is characterized in that, it at the coated layer of metal coating in described amorphous powdered alloy surface, can form the non-crystaline amorphous metal composite powder of surface modification by process for modifying surface.
According to of the present invention, provide a kind of preparation method of non-crystaline amorphous metal composite coating more on the one hand, it is characterized in that, utilize heat spraying method to spray above-mentioned non-crystaline amorphous metal composite powder, can prepare described non-crystaline amorphous metal composite coating.
In general, the above technical scheme of conceiving by the present invention compared with prior art, has following beneficial effect:
The present invention is directed to the problem that Metal Substrate amorphous powdered alloy is easily oxidized in pyrolytic coating process, adopt easy powder surface modification technology, at amorphous powdered alloy plated surface last layer ORC, the equipment and technology that this technology adopts is simple, easy to operate, can obtain even thickness, the coat of metal that adhesion is strong, can be mass-produced.
The present invention is based on the amorphous composite coating that powder surface modification obtains, there is high-bond, excellent antioxygenic property and wear resistance.This composite coating has huge application prospect in thermal structure material field (as Aero-Space, thermal power generation etc.) and high-abrasive material field (as probing, guarded blade utility knife etc.).
Accompanying drawing explanation
Fig. 1 (a), (b) and (c) be respectively amorphous composite powder SEM (SEM) surface topography map of single-phase iron-based amorphous powder, Ni-P and Ni-W-P modification; And (e) be respectively amorphous composite powder SEM (SEM) the Cross Section Morphology figure of Ni-P and Ni-W-P modification (d).
Fig. 2 (a), (b) and (c) be respectively amorphous composite coating SEM (SEM) the Cross Section Morphology figure of single-phase iron-based amorphous coating, Ni-P and Ni-W-P modification.
Fig. 3 (a) powder and (b) X-ray diffractogram of coating
The bond strength contrast of Fig. 4 amorphous composite coating and single-phase amorphous coating.
The antioxygenic property contrast of Fig. 5 amorphous composite coating and single-phase amorphous coating.
The abrasion resistance properties contrast of Fig. 6 amorphous composite coating and single-phase amorphous coating.
The specific embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Embodiment 1
In the present embodiment, preferred amorphous powdered alloy is Fe based amorphous alloy powder.
First by required composition, by for example method of vacuum induction melting, make foundry alloy, then foundry alloy is put into atomizing furnace, adopt ultrasonic gas atomization technology to prepare Fe based amorphous alloy powder.Its powder particle pattern is as shown in Fig. 1 (a), and powder surface is smooth, be subsphaeroidal.In the present invention, particle size range is preferably 15-60 μ m.
Then, above-mentioned powder is carried out to surface modification treatment, preferably chemical plating modification in the present embodiment, but the present invention is not limited to this, for example, can be one or more compound in high-energy ball milling, collosol and gel, vapour deposition, chemical plating, electro-plating method.
In modification, first carry out pre-treatment, can to above-mentioned amorphous powdered alloy, carry out activation processing by palladium ion and make its surface form avtive spot, then through washing and alcohol, clean last filtration drying.
After above-mentioned pre-treatment, can carry out chemical plating modification to above-mentioned amorphous powder, in the present embodiment, the preferred coat of metal is Ni-P, and its concrete technology is as follows:
A) configure the chemical solution of following composition:
B) amorphous powder after above-mentioned pre-treatment is immersed in above-mentioned chemical solution, by this solution of heating water bath, makes its temperature remain on 80-90 ℃; The pH value of regulator solution is 4-5; In this processing procedure, keep solution ceaselessly to stir, the surface treatment time is preferably 1-2h.
C) afterwards to above-mentioned powder washing, alcohol cleaning and filtering, then dry, the amorphous composite powder of acquisition Ni-P modification.Powder morphology after modification is as Fig. 1 (b) with (d), and be coated a layer thickness is the Ni-P coat of metal of 2 μ m visible amorphous powder surface uniform.
Finally, utilize heat spraying method that described amorphous powder is sprayed on to material surface, can form Fe-based amorphous composite coating at material surface.
According to ASTM C633 standard method, Fe-based amorphous composite coating is carried out to extension test to obtain the bond strength of coating, the bond strength of finding the Fe-based amorphous composite coating that this Ni-P is coated reaches 42MPa, be 1.6 times of bond strength of single-phase iron-based amorphous coating, result as shown in Figure 4.
Fe-based amorphous composite coating is peeled off from matrix, used 320# sand papering, remove coating surface oxide layer, use alcohol ultrasonic cleaning, dry, weigh in the balance heavily, then sample is placed in air and is heated to 800 ℃, insulation 20h, after taking-up, be cooled to room temperature and weigh, calculate its oxidation weight gain, the oxidation weight gain of finding the iron-based amorphous coating that this Ni-P is coated is 3.2%, be only 2/3 of single-phase iron-based amorphous coating, result as shown in Figure 5.
Adopt frictional testing machine to carry out ball disc type friction test to Fe-based amorphous composite coating, experiment condition is: load 10N, rotating speed 0.2m/s, the Al of diameter 6mm
2o
3ceramic Balls is as friction pair, time 1000s.Friction finishes the rear Volume Loss amount of measuring Fe-based amorphous composite coating with white light interferometer, calculates rate of depreciation, and the rate of depreciation of finding the Fe-based amorphous composite coating of this Ni-P modification is 5.8x10
-5mm
3n
-1m
-1, be only 1/2 of single-phase iron-based amorphous coating, result is as shown in Figure 6.
Embodiment 2
The present embodiment and difference from Example 1 be, the coat of metal is preferably Ni-W-P coating, and in chemical plating modification technology, the present embodiment chemical plating process used is in addition:
By above-mentioned processing, the bond strength of Fe-based amorphous composite coating prepared by the present embodiment is 35MPa, is 1.3 times of single-phase iron-based amorphous coating.The oxidation weight gain of Fe-based amorphous composite coating prepared by the present embodiment is 1.3%, is 1/4 of single-phase iron-based amorphous coating.The rate of depreciation of Fe-based amorphous composite coating prepared by the present embodiment is 4.3 * 10
-5mm
3n
-1m
-1, be 1/3 of single-phase iron-based amorphous coating.
Certainly, above-described embodiment is only for technical scheme of the present invention is described better, do not form limitation of the invention, for example, in the present invention, amorphous powder is not limited to above-mentioned Fe base amorphous powder, in addition, coat of metal material for powder surface is not limited to above-mentioned two kinds, can be that one or more in Ni, pure Co, pure Cu, Ni-P, Ni-B, Ni-W, Ni-W-P and Ni-Cu-P are compound.The thickness of the coat of metal can be preferably at 1-5 μ m.In addition, the thickness of coating is also not limited to above-mentioned scope, also can specifically select according to actual needs, and for example thickness is at 100-1500 μ m.
Those skilled in the art will readily understand; the foregoing is only preferred embodiment of the present invention; not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. a non-crystaline amorphous metal composite powder for surface modification, is characterized in that, it is for being coated with the composite powder of the oxidation resistant coat of metal on amorphous powdered alloy surface by process for modifying surface.
2. the non-crystaline amorphous metal composite powder of a kind of surface modification according to claim 1, wherein, described powder surface modification technology can be compound for one or more in high-energy ball milling, collosol and gel, vapour deposition, chemical plating, electro-plating method.
3. the non-crystaline amorphous metal composite powder of a kind of surface modification according to claim 1 and 2, wherein, described coat of metal material is that one or more in pure Ni, pure Co, pure Cu, Ni-P, Ni-B, Ni-W, Ni-W-P and Ni-Cu-P are compound.
4. according to the non-crystaline amorphous metal composite powder of a kind of surface modification described in any one in claim 1-3, wherein, the thickness of the described coat of metal is at 1-5 μ m.
5. according to the non-crystaline amorphous metal composite powder of a kind of surface modification described in any one in claim 1-4, wherein, described amorphous powdered alloy adopts the preparation of ultrasonic atomizatio method, and its particle size range is 15-60 μ m, and powder is complete amorphous state.
6. a non-crystaline amorphous metal composite coating, is characterized in that, this coating is by utilizing heat spraying method to prepare the non-crystaline amorphous metal composite powder described in any one in claim 1-5.
7. a kind of non-crystaline amorphous metal composite coating according to claim 6, wherein, the thickness of described non-crystaline amorphous metal composite coating is 100-1500 μ m.
8. according to a kind of non-crystaline amorphous metal composite coating described in claim 6 or 7, wherein, described thermal spraying comprises flame-spraying, plasma spraying, detonation flame spraying, electric arc spraying or HVAF.
9. a preparation method for the non-crystaline amorphous metal composite powder of surface modification, is characterized in that, it at the coated layer of metal coating in amorphous powdered alloy surface, can form the non-crystaline amorphous metal composite powder of surface modification by process for modifying surface.
10. a preparation method for non-crystaline amorphous metal composite coating, is characterized in that, utilizes heat spraying method to spray above-mentioned non-crystaline amorphous metal composite powder, can prepare described non-crystaline amorphous metal composite coating.
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| CN104841931A (en) * | 2015-05-05 | 2015-08-19 | 湖南理工学院 | Cu70Zr20Ti10/Ni-P amorphous alloy composite powder and preparation process thereof |
| CN104942282A (en) * | 2015-07-14 | 2015-09-30 | 长春工业大学 | Pre-processing method for spark plasma sintering interface of amorphous alloy powder |
| CN107236921A (en) * | 2017-06-19 | 2017-10-10 | 河北工业大学 | A kind of preparation method of nitride ceramics amorphous composite coating |
| CN107779807A (en) * | 2017-11-30 | 2018-03-09 | 大连智讯科技有限公司 | A kind of method of electric arc spraying corrosion-inhibiting coating |
| CN108247042A (en) * | 2018-01-26 | 2018-07-06 | 长安大学 | Ni packets Al cladding Fe base noncrystal alloy composite powders and its preparation method and application |
| CN108620576A (en) * | 2017-03-20 | 2018-10-09 | 中国科学院宁波材料技术与工程研究所 | A kind of highly conductive amorphous soft magnet coating |
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| CN112439899A (en) * | 2020-11-19 | 2021-03-05 | 北京工业大学 | Surface-modified zirconium-based amorphous alloy powder and preparation method and application thereof |
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| CN115141998A (en) * | 2021-09-08 | 2022-10-04 | 武汉苏泊尔炊具有限公司 | Amorphous alloy coating and preparation method thereof |
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| CN104841931A (en) * | 2015-05-05 | 2015-08-19 | 湖南理工学院 | Cu70Zr20Ti10/Ni-P amorphous alloy composite powder and preparation process thereof |
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| CN104942282A (en) * | 2015-07-14 | 2015-09-30 | 长春工业大学 | Pre-processing method for spark plasma sintering interface of amorphous alloy powder |
| CN108697095A (en) * | 2015-12-21 | 2018-10-23 | 艾尔尤斯科技有限公司 | Biocidal metallic particles and its production method |
| CN108620576A (en) * | 2017-03-20 | 2018-10-09 | 中国科学院宁波材料技术与工程研究所 | A kind of highly conductive amorphous soft magnet coating |
| CN107236921A (en) * | 2017-06-19 | 2017-10-10 | 河北工业大学 | A kind of preparation method of nitride ceramics amorphous composite coating |
| CN107236921B (en) * | 2017-06-19 | 2019-03-05 | 河北工业大学 | A kind of preparation method of nitride ceramics-amorphous composite coating |
| CN107779807A (en) * | 2017-11-30 | 2018-03-09 | 大连智讯科技有限公司 | A kind of method of electric arc spraying corrosion-inhibiting coating |
| CN108247042A (en) * | 2018-01-26 | 2018-07-06 | 长安大学 | Ni packets Al cladding Fe base noncrystal alloy composite powders and its preparation method and application |
| CN111360272A (en) * | 2020-04-21 | 2020-07-03 | 华中科技大学 | Oxide interface toughening amorphous-based composite material and preparation method thereof |
| CN111360272B (en) * | 2020-04-21 | 2021-10-15 | 华中科技大学 | Oxide interface toughening amorphous-based composite material and preparation method thereof |
| CN112439899A (en) * | 2020-11-19 | 2021-03-05 | 北京工业大学 | Surface-modified zirconium-based amorphous alloy powder and preparation method and application thereof |
| CN115141998A (en) * | 2021-09-08 | 2022-10-04 | 武汉苏泊尔炊具有限公司 | Amorphous alloy coating and preparation method thereof |
| CN115141998B (en) * | 2021-09-08 | 2023-09-29 | 武汉苏泊尔炊具有限公司 | Amorphous alloy coating and preparation method thereof |
| CN114570367A (en) * | 2022-02-28 | 2022-06-03 | 华中科技大学 | Preparation method, product and application of three-dimensional porous amorphous alloy catalyst |
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