CN105088108A - Iron-base amorphous alloy, powder material of alloy and wear-resisting anticorrosion coating of alloy - Google Patents
Iron-base amorphous alloy, powder material of alloy and wear-resisting anticorrosion coating of alloy Download PDFInfo
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Abstract
The invention provides an iron-base amorphous alloy. The chemical formula of the iron-base amorphous alloy is FeaCrbNicModPeCfBgSih, wherein a, b, c, d, e, f, g and h are molar contents of corresponding atoms, b is larger than or equal to 5 and smaller than or equal to 15, c is larger than or equal to 2 and smaller than or equal to 15, d is larger than or equal to 2 and smaller than or equal to 8, e is larger than or equal to 6 and smaller than or equal to 12, f is larger than or equal to 2 and smaller than or equal to 6, g is larger than or equal to 3 and smaller than or equal to 6, h is larger than or equal to 1 and smaller than or equal to 5, and the balance is iron. According to the chemical formula, compounding and smelting are carried out to obtain an ingot casting; then, resmelting is carried out, and through vacuum spraying and cooling, a powder material of the iron-base amorphous alloy is obtained. By means of the supersonic speed flame spraying technology, the iron-base amorphous alloy powder is sprayed to the surface of a base body to prepare an iron-base amorphous alloy coating. The coating is high in amorphous content, low in porosity and oxygen content and high in diamond pyramid hardness and has the good wear-resisting anticorrosion performance and has the wide application prospect in fields of energy, chemical engineering, national defense, aerospace, ships and the like.
Description
Technical field
The invention belongs to field of surface engineering technique, the wear-and corrosion-resistant coating being specifically related to a kind of Fe-based amorphous alloy of high amorphous formation ability, its powdered material and utilizing this powdered material obtained.
Background technology
In the fields such as the energy, chemical industry, national defence, aerospace and boats and ships, the long-term fully loaded of equipment component parts runs under the severe environment of high temperature, oxidation, high temperature corrosion and mechanical wear, cause these equipment unit very easily corroded and wear and tear and damage, annual financial loss is up to tens yuan.How to improve the use properties of these equipment, extend its work-ing life and become above-mentioned industry and improve Business Economic Benefit and strengthen core competitiveness matter of utmost importance anxious to be resolved.
Adopting in equipment matrix surface metallize coating is one of solution to the problems described above.
Compared with common metal, non-crystaline amorphous metal does not have crystal particle crystal boundary, the existence of defect, thus shows the physical and chemical performance of many excellences.Wherein, Fe-based amorphous alloy is not only cheap, and wear-resistant superior with corrosion resistance nature, compared with conventional coating, has the characteristics such as high rigidity, high temperature resistant, low wearing and tearing, low-friction coefficient by the coating that Fe-based amorphous alloy is made.
Conventional spraying method comprises hypersonic flame spraying (HighVelocityOxygenFuel is called for short HVOF), plasma spraying, electric arc spraying, detonation flame spraying etc.Wherein, compared to other hot-spraying techniqueies, not only content of amorphous is high, oxygen level is low, porosity is low but also high with substrate combinating strength for the coating utilizing HVOF technology to prepare.
Therefore, the Fe base amorphous/nanocrystalline coating utilizing HVOF technology to prepare wear-and corrosion-resistant in recent years becomes the focus of research.Such as, a large amount of compositions being suitable for preparing iron base amorphous alloy coatings has been prepared under the support of advanced project research office (DARPA) of Department of Defense by Deng20Yu Jia scientific research institution of U.S. LawrenceLivermore National Laboratory.The SAM series trade mark alloys such as Fe-Cr-Mo-C-B-Y, Fe-Cr-Mo-Mn-W-C-B-Si of protecting as applied in patent documentation US8480864B2; its neutron absorption capability is 7 times of stainless steel and Ni based high-temperature alloy (C22), is more than 3 times of boron steel.And its corrosion resistance nature is much better than high temperature Ni base alloy.There is during the coated material of this alloy as a kind of low cost the intensity of superelevation; lower frictional coefficient and thermal expansivity; excellent toughness and wearability; and outstanding high temperature red hardness; also there is good resistance to high temperature oxidation, chlorine-resistant spot corrosion and sulfuration resistant performance simultaneously; be suitable for the anticorrosion antiwear protection within the scope of less than 650 DEG C wide warm areas, therefore have broad application prospects in above-mentioned field as structure coating material.At home, the application of iron base amorphous alloy coatings causes scholars' interest greatly.Such as, the units such as metal institute of the Chinese Academy of Sciences, the Central China University of Science and Technology, Beijing Institute of Technology, Nanchang University of aviation, Tongji University carry out the research work of amorphous coating in succession, utilize HVOF technology to prepare high-quality iron-based amorphous coating.
In the research of iron-based amorphous coating, amorphous formation ability and wear-and corrosion-resistant performance are the performances that coating is paid close attention to.In order to improve amorphous formation ability and the wear-and corrosion-resistant performance of iron-based amorphous coating, usually in non-crystalline material, add rare earth element yttrium (Y) or erbium (Er) etc., strategy elemental tungsten (W), and a large amount of chromium (Cr) and molybdenum (Mo) element.As everyone knows, rare earth element significantly can worsen the toughness of alloy, is unfavorable for the wear resisting property of coating, and expensive; W elements is rare refractory metal, is unfavorable for melting or spraying; The refinement of chromium element can to human body and environmental pollution; Molybdenum element price costly, increases material cost.Therefore, by reducing or replacing above-mentioned element, develop and there is high performance Fe base amorphous alloy coating material have important practical significance.
Summary of the invention
For the above-mentioned state of the art, the present invention aims to provide a kind of Fe-based amorphous alloy, this Fe-based amorphous alloy cost is low, fusing point is low, and has high amorphous formation ability, utilizes the powdered material of this Fe-based amorphous alloy to spray obtained coating and has good wear-and corrosion-resistant performance.
In order to realize above-mentioned technical purpose, the present inventor is found after being explored by great many of experiments, when the chemical molecular formula of Fe-based amorphous alloy is following, this Fe-based amorphous alloy not only has good plasticity, and there is high amorphous formation ability, utilize the powdered material of this Fe-based amorphous alloy to spray obtained coating and there is excellent wear-resisting, corrosion resistance nature:
Fe
aCr
bNi
cMo
dP
eC
fB
gSi
h
In formula, a, b, c, d, e, f, g, h are the molar content of corresponding atom, and meet 5≤b≤15,2≤c≤15,2≤d≤8,6≤e≤12,2≤f≤6,3≤g≤6,1≤h≤5, a+b+c+d+e+f+g+h=100.
As preferably, 6≤b≤12, more preferably 8≤b≤10.
As preferably, 4≤c≤10, more preferably 3≤c≤5.
As preferably, 2.5≤d≤6, more preferably 3≤d≤4.
As preferably, 8≤e≤11, more preferably 9.8≤e≤10.5.
As preferably, 3≤f≤5, more preferably 3.5≤f≤4.5.
As preferably, 4.5≤g≤5.5.
As preferably, 1.5≤h≤4, more preferably 2≤h≤3.5.
Present invention also offers a kind of Fe-based amorphous alloy powdered material, be carry out preparing burden with the chemical molecular formula of above-mentioned Fe-based amorphous alloy and obtain, its preparation method comprises the steps:
(1) preparation of mother alloy
Prepare burden according to the above-mentioned chemical molecular formula of described Fe-based amorphous alloy, obtain raw material, in smelting furnace, carry out melting, after cooling, obtain mother alloy ingot;
As preferably, each element is industrial raw material, and selects the master alloys such as FeC, FeP, FeMo, FeB, to reduce costs, reduces raw-material volatilization simultaneously, obtains the mother alloy of uniform composition.
(2) preparation of amorphous powdered alloy
The mother alloy ingot that step (1) obtains is broken into fritter, refuse, obtains mother alloy melt, utilize vacuum gas atomization device by its spray cooling, obtain Fe-based amorphous alloy powder.
As preferably, described spray process carries out in argon atmosphere.
As preferably, the particle diameter of described amorphous powdered alloy is 20 ~ 50 μm.
Present invention also offers a kind of wear-and corrosion-resistant coating of matrix surface, is utilize hypersonic flame spraying technology, and spray gas is oxygen and propane, is obtained by above-mentioned Fe-based amorphous alloy powder spraying at matrix surface.
As preferably, described spraying coating process condition is: oxygen flow 25L/min, propane flow 35L/min, powder feeding rate 30L/min, pressurized air 0.5MPa, spray distance 300mm, powder size distribution 20-50 μm.
The amorphous phase volume fraction of the wear-and corrosion-resistant coating utilizing aforesaid method to obtain reaches more than 85%, and porosity is lower than 1%, and oxygen level is lower than 0.2%, and Vickers' hardness reaches more than 900.
Compared with prior art, the present invention has following beneficial effect:
(1) by the adjustment of elemental composition and each component content, obtain a kind of Fe-based amorphous alloy, its powdered material prepares coating by spraying technology at matrix surface, with stainless steel conventional at present and the SAM series trade mark alloy phase ratio be widely studied, corrosion-resistant element Cr containing relatively small amount in this powdered material, Mo etc., and containing P element in this powdered material, be conducive to reducing material melting point, improve plasticity and amorphous formation ability, and can oxidation be reduced, be suitable for utilizing hot-spraying techniques to prepare amorphous alloy coating.
(2) coating that Fe-based amorphous alloy powdered material of the present invention is obtained is utilized, when adulterating the elements such as less Cr, Mo, still obtain the corrosion potentials and corrosion electric current density of working as with SAM series trade mark alloy phase, and coating is combined with matrix closely, porosity is low, oxygen level is low, and Vickers' hardness is high.Excellent wear-and corrosion-resistant performance and good manufacturability, make it at the energy, the fields such as chemical industry, national defence, aerospace and boats and ships have broad application prospects.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of amorphous powdered alloy obtained in the embodiment of the present invention 1;
Fig. 2 is amorphous powdered alloy obtained in the embodiment of the present invention 1 and congruent amorphous alloy strips, and the X-ray diffractogram of the amorphous alloy coating utilizing this amorphous powdered alloy to obtain;
Fig. 3 is the scanning electron microscope (SEM) photograph in amorphous alloy coating cross section obtained in the embodiment of the present invention 1;
Fig. 4 is amorphous alloy coating obtained in the embodiment of the present invention 1 and the frictional coefficient figure of 45 steel;
Fig. 5 is amorphous alloy coating obtained in the embodiment of the present invention 1 and the wear volume figure of 45 steel;
Fig. 6 is amorphous alloy coating obtained in the embodiment of the present invention 1, and congruent amorphous alloy strips and the polarization curve of 45 steel in 3.5wt.%NaCl solution.
Embodiment
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail, it is pointed out that the following stated embodiment is intended to be convenient to the understanding of the present invention, and any restriction effect is not play to it.
Embodiment 1:
In the present embodiment, the molecular formula of Fe-based amorphous alloy is Fe
63cr
8mo
3.5ni
5p
10b
4c
4si
2.5.
The preparation method of this Fe-based amorphous alloy powdered material is as follows:
(1) by technical grade starting material Fe, Cr, Ni, Si, FeC, FeP, FeMo, FeB are according to molecular formula Fe
63cr
8mo
3.5ni
5p
10b
4c
4si
2.5in atomic percent preparation raw material, utilize the uniform mother alloy ingot of vacuum induction furnace prepared composition.
(2) the mother alloy ingot emery wheel obtained is ground off surface impurity, be then placed in vacuum gas atomization device and obtain Fe-based amorphous alloy powder.As a comparison, by the mother alloy ingot that obtains by melt spinning, iron-based amorphous alloy ribbon material is obtained.
As shown in Figure 1, wherein (b) figure is the enlarged view of (a) figure to the scanning electron microscope (SEM) photograph of above-mentioned obtained amorphous powdered alloy, and it is subsphaeroidal for showing this powdered alloy, and size distribution, below 50 μm, has good mobility.
The non-crystal structure of above-mentioned obtained amorphous powdered alloy and amorphous alloy strips is as shown in Figure 2, similar to amorphous alloy strips, and the diffraction peak of this amorphous powdered alloy display broadening, illustrates that this powder has complete amorphous structure.
Adopt hypersonic flame spraying technology, above-mentioned obtained amorphous powdered alloy is used to prepare iron base amorphous alloy coatings on matrix 45 steel surface, the processing parameter of preparation is: oxygen flow 25L/min, propane flow 35L/min, powder feeding rate 30L/min, pressurized air 0.5MPa, spray distance 300mm.
Utilize aforesaid method to obtain the non-crystal structure of iron base amorphous alloy coatings as shown in Figure 2, the amorphous alloy coating prepared by this processing parameter does not have obvious crystallization peak, illustrates that this alloying constituent has high amorphous formation ability, is suitable for preparing amorphous alloy coating.
Utilize aforesaid method to obtain the Cross Section Morphology of iron base amorphous alloy coatings as shown in Figure 3, therefrom can find out, the combination of itself and matrix is tight, and coating porosity is lower than 1%.
The frictional coefficient of above-mentioned obtained iron base amorphous alloy coatings and matrix thereof is tested with friction wear testing machine, result as shown in Figure 4, therefrom can find out, at load 20N, speed is under the friction condition of 0.1m/s, the frictional coefficient of this iron base amorphous alloy coatings is between 0.6-0.7, less times greater than 45 steel, but along with the increase of frictional distance, the frictional coefficient of this iron base amorphous alloy coatings is highly stable, and 45 steel fluctuations are comparatively violent, illustrate that the surface of 45 steel constantly comes off under the effect of friction pair.After friction 240m, the wear volume figure of iron base amorphous alloy coatings and matrix thereof as shown in Figure 5, after being presented at friction 240m, the wear rate of this iron base amorphous alloy coatings is less than 1/4 of 45 steel wear rates, illustrates that this iron base amorphous alloy coatings has excellent abrasion resistance properties.
With the corrosion resistance nature of the above-mentioned obtained iron base amorphous alloy coatings of electrochemical workstation test, its polarization curve as shown in Figure 6, and contrasts with above-mentioned obtained amorphous alloy strips and 45 steel.As can be seen from Figure 6, this iron base amorphous alloy coatings has between wide passivation region in 3.5wt.%NaCl solution, and lower corrosion electric current density and higher corrosion potentials, although its corrosion resistance nature is lower than amorphous band, are much better than 45 steel.
Utilize Vickers' hardness to test the hardness of above-mentioned obtained iron base amorphous alloy coatings, load used is 1kg, 15 seconds action time, and random selecting 10 place is measured in region, and its average hardness value can reach more than 900, is 3 times of 45 steel.
Embodiment 2:
In the present embodiment, the molecular formula of Fe-based amorphous alloy is Fe
61cr
10mo
3.5ni
5p
10b
4c
4si
2.5.
The preparation method of this Fe-based amorphous alloy powdered material is substantially identical with the method preparing powdered material in embodiment 1, and difference is according to molecular formula Fe
61cr
10mo
3.5ni
5p
10b
4c
4si
2.5in atomic percent preparation raw material.
Identical with embodiment 1, above-mentioned obtained powdered alloy is subsphaeroidal, and size distribution, below 50 μm, has good mobility; The X-ray diffractogram of this amorphous powdered alloy shows this powder and has complete amorphous structure.
Adopt hypersonic flame spraying technology, above-mentioned obtained amorphous powdered alloy is used to prepare iron base amorphous alloy coatings on matrix 45 steel surface, the processing parameter of preparation is: oxygen flow 30L/min, propane flow 35L/min, powder feeding rate 30L/min, pressurized air 0.5MPa, spray distance 320mm.
Identical with embodiment 1, the X-ray diffractogram of above-mentioned obtained iron base amorphous alloy coatings shows this alloying constituent and has high amorphous formation ability, is suitable for preparing amorphous alloy coating; The combination that the Cross Section Morphology figure of this iron base amorphous alloy coatings shows itself and matrix is tight, and coating porosity is lower than 1%.
The method identical with embodiment 1 tests abrasion resistance properties, the corrosion resistance nature of this iron base amorphous alloy coatings, and hardness, and result shows its wear rate much smaller than 45 steel wear rates, and erosion resistance is much better than 45 steel, and its average hardness value can reach more than 900.
Embodiment 3:
In the present embodiment, the molecular formula of Fe-based amorphous alloy is Fe
59cr
12mo
3.5ni
5p
10b
4c
4si
2.5.
The preparation method of this Fe-based amorphous alloy powdered material is substantially identical with the method preparing powdered material in embodiment 1, and difference is according to molecular formula Fe
59cr
12mo
3.5ni
5p
10b
4c
4si
2.5in atomic percent preparation raw material.
Identical with embodiment 1, above-mentioned obtained powdered alloy is subsphaeroidal, and size distribution, below 50 μm, has good mobility; The X-ray diffractogram of this amorphous powdered alloy shows this powder and has complete amorphous structure.
Adopt hypersonic flame spraying technology, above-mentioned obtained amorphous powdered alloy is used to prepare iron base amorphous alloy coatings on matrix 45 steel surface, the processing parameter of preparation is: oxygen flow 20L/min, propane flow 35L/min, powder feeding rate 30L/min, pressurized air 0.5MPa, spray distance 280mm, powder size distribution 20 ~ 50 μm.
Identical with embodiment 1, the X-ray diffractogram of above-mentioned obtained iron base amorphous alloy coatings shows this alloying constituent and has high amorphous formation ability, is suitable for preparing amorphous alloy coating; The combination that the Cross Section Morphology figure of this iron base amorphous alloy coatings shows itself and matrix is tight, and coating porosity is lower than 0.5%.
The method identical with embodiment 1 tests abrasion resistance properties, the corrosion resistance nature of this iron base amorphous alloy coatings, and hardness, and result shows its wear rate much smaller than 45 steel wear rates, and erosion resistance is much better than 45 steel, and its average hardness value can reach more than 900.
Above-described embodiment is used for explaining and the present invention is described, instead of limits the invention, and in the protection domain of spirit of the present invention and claim, any amendment make the present invention and change, all fall into protection scope of the present invention.
Claims (10)
1. a Fe-based amorphous alloy, is characterized in that: its chemical molecular formula is Fe
acr
bni
cmo
dp
ec
fb
gsi
h, wherein a, b, c, d, e, f, g, h are the molar content of corresponding atom, and meet 5≤b≤15,2≤c≤15,2≤d≤8,6≤e≤12,2≤f≤6,3≤g≤6,1≤h≤5, a+b+c+d+e+f+g+h=100.
2. Fe-based amorphous alloy as claimed in claim 1, is characterized in that: 6≤b≤12, is preferably 8≤b≤10.
3. Fe-based amorphous alloy as claimed in claim 1, is characterized in that: 4≤c≤10, is preferably 3≤c≤5.
4. Fe-based amorphous alloy as claimed in claim 1, is characterized in that: 2.5≤d≤6, is preferably 3≤d≤4.
5. Fe-based amorphous alloy as claimed in claim 1, is characterized in that: 8≤e≤11, is preferably 9.8≤e≤10.5.
6. Fe-based amorphous alloy as claimed in claim 1, is characterized in that: 3≤f≤5; Be preferably 3.5≤f≤4.5; Be preferably 4.5≤g≤5.5.
7. Fe-based amorphous alloy as claimed in claim 1, is characterized in that: 1.5≤h≤4, is preferably 2≤h≤3.5.
8. a Fe-based amorphous alloy powder, is characterized in that: its preparation method comprises the steps:
(1) prepare burden according to the chemical molecular formula of the Fe-based amorphous alloy described in claim arbitrary in claim 1 to 7, obtain raw material, in smelting furnace, carry out melting, after cooling, obtain mother alloy ingot;
(2) mother alloy ingot that step (1) obtains is broken into fritter, refuse, obtains mother alloy melt, utilize vacuum gas atomization device by its spray cooling, obtain Fe-based amorphous alloy powder;
As preferably, described spray process carries out in argon atmosphere;
As preferably, the particle diameter of described amorphous powdered alloy is 20 ~ 50 μm.
9. a wear-and corrosion-resistant coating for matrix surface, is characterized in that: utilize hypersonic flame spraying technology, spray gas is oxygen and propane, and the Fe-based amorphous alloy powder spraying that claim 8 is obtained obtains at matrix surface.
10. the wear-and corrosion-resistant coating of matrix surface as claimed in claim 9, it is characterized in that: described spraying coating process condition is: oxygen flow 20 ~ 35L/min, propane flow 30 ~ 40L/min, powder feeding rate 25 ~ 35L/min, pressurized air 0.2 ~ 0.8MPa, spray distance 200 ~ 350mm;
As preferably, the amorphous phase volume fraction of described coating is more than 85%, and porosity is lower than 1%, and oxygen level is lower than 0.2%, and Vickers' hardness reaches more than 900.
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