CN103484810B - Plasma cladding in-situ synthesized TiB2-TiC-TiN reinforced high-entropy alloy coating material and preparation method thereof - Google Patents
Plasma cladding in-situ synthesized TiB2-TiC-TiN reinforced high-entropy alloy coating material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a plasma cladding in-situ synthesized TiB2-TiC-TiN reinforced high-entropy alloy coating material and a preparation method thereof. The coating material comprises the following components according to atomic percentage: 17-19 percent of Co, 17-19 percent of Cr, 17-19 percent of Fe, 17-19 percent of Ni, 17-19 percent of Mn, 3-10 percent of Ti, 0.5-2 percent of B4C and 1.5-3 percent of BN. The preparation method comprises the steps as follows: (a), pre-treating a substrate; (b), preparing high-entropy alloy coating raw materials; (c), mixing powder; (d), preparing the high-entropy alloy by adopting plasma cladding equipment. The organization structure of the high-entropy alloy coating comprises an FCC phase, a BCC phase and a TiB2-TiC-TiN ternary ceramic phase, and favorable metallurgy bonding between a coating and the substrate is realized; the average Vickers hardness reaches 1,104 Hv.According to the invention, on the basis of the conventional high-entropy alloy coating,a TiB2-TiC-TiN reinforced phase is synthesized in-situ,the strength, hardness and the toughness of the coating are further improved, the match between the hardness and the toughness is achieved, and the potentiality of the high-entropy alloy coating is brought into play to the greatest extent. Moreover, the preparation method is reasonable in working procedures, simple and convenient to implement, is used for preparing durable antisepsis or abrasion proof coatings, and can remarkably prolong the service life of machinery parts.
Description
Technical field
The present invention relates to a kind of plasma cladding in-situ self-generated TiB
2-TiC-TiN strengthens high-entropy alloy coated material and preparation method thereof, belongs to Materials Processing Engineering speciality surface engineering coatings art.
Background technology
All the time, traditional alloy design method is all using one or both elements as major components, the structure property of alloy is usually improved again, as two component system intermetallic compound and block amorphous alloys etc. such as stainless steel, aluminium alloy, Ni-Al by adding other yuan.But along with the development of modern industry, people propose more and more higher requirement to material in use temperature, intensity, wear resistance etc.Although be developed new material processing technique, as rapid solidification, laser processing etc., improve the use properties of material, but can not meet the demands.Taiwan's scholars Ye Junwei professor in 1995 takes the lead in having jumped out the development framework of conventional alloys, proposes new alloy designs theory, i.e. many pivots high-entropy alloy.Because high-entropy alloy has the excellent specific property that a lot of conventional alloys do not have, design as by suitable alloy formula, the property combination such as high rigidity, high work hardening, high temperature resistant softening, high temperature oxidation resisting, corrosion-resistant, high resistivity can be obtained, therefore there is very large application potential, as: high rigidity and anti-corrosion instrument, the mould of wear-resistant temperature-resistant; The corrosion-proof and high-strength degree material of chemical plant, ships; The heat-stable material etc. of turbine blade, heat exchanger and High Temperature Furnaces Heating Apparatus.And existing coating technology, make the application of high-entropy alloy obtain further developing.
Up to now, high-entropy alloy mainly adopts the method such as vacuum arc furnace melting and founding to prepare.In the preparation of coating: professor Ye Junwei (AlCrNbSiTiV) N that adopted magnetron sputtering to prepare
xand (AlCrTaTiZr) O
xhigh-entropy alloy coating (Scripta Materialia, 2010,62:105-108 and Thin Solid Films, 2010,518:2732-2737), but the film thickness prepared by the method only can reach micro-meter scale, be difficult to the advantage playing high-entropy alloy mechanical property aspect, and base material be there are certain requirements.Professor Liang Xiubing of armored force engineering institute adopts High Speed Electric Arc Spraying method to prepare FeCrNiCoCu and FeCrNiCoCuB two kinds of high-entropy alloy coatings (Chinese Surface Engineering, 2011,24:70-73) at AZ91 magnesium alloy matrix surface.Professor Pan Ye of the Southeast China University FeCoNiCrAl that adopted laser melting and coating technique to prepare
2si high-entropy alloy coating (Acta Metallurgica Sinica, 2011,47:1075-1079).But it is also very few about adopting plasma melting coating technique to prepare the document of high-entropy alloy coating aspect research, applicant's research work in earlier stage once adopted plasma melting coating technique successfully to prepare CoCrCuFeNi high-entropy alloy coating (J.B. Cheng, X.B. Liang, Z.H. Wang, B. S. Xu. Plasma Chemistry and Plasma Process, DOI:10.1007/s11090-013-9469-1), although coating has good corrosion resistance nature, but its average hardness is relatively low, is only 195Hv; And there is intercrystalline segregation in coating structure, this directly affects the quality and performance of coating, limits its industrial application to a certain extent.Along with the development of modern science and technology proposes more and more higher requirement to material, in order to improve the hardness of CoCrCuFeNi high-entropy alloy coating, reduce intercrystalline segregation, develop and there is excellent mechanical performance and the research of the plasma cladding high-entropy alloy base composite coating of homogeneous microstructure is still significant.But up to now, yet there are no and utilize plasma melting coating technique to prepare in-situ self-generated TiB
2-TiC-TiN ternary ceramics strengthens the report of CoCrFeNiMn high-entropy alloy coating aspect.
Summary of the invention
Prepare that the hardness of CoCrCuFeNi high-entropy alloy coating is lower for past plasma cladding and the problem such as tissue distribution is uneven, the object of the present invention is to provide a kind of plasma cladding in-situ self-generated TiB
2-TiC-TiN strengthens high-entropy alloy coated material and preparation method thereof, and its tissue of coating utilizing plasma melting coating technique to prepare is by FCC phase matrix and TiB
2the phase composite of-TiC-TiN ternary ceramics, the average Vickers' hardness of coating is up to 1104Hv.This coating can be applicable to the long-effective corrosion of steel construction and the environment such as wear-resisting, and has the features such as cost is lower.
The technical scheme that the present invention realizes above-mentioned purpose is:
A kind of plasma cladding in-situ self-generated TiB
2-TiC-TiN strengthens high-entropy alloy coated material, it is characterized in that: the composition of this coated material, by atomic percentage, is respectively Co 17 ~ 19 %, Cr17 ~ 19 %, Fe 17 ~ 19 %, Ni 17 ~ 19 %, Mn 17 ~ 19 %, Ti 3 ~ 10 %, B
4c 0.5 ~ 2 % and BN 1.5 ~ 3 %.
One prepares a kind of plasma cladding in-situ self-generated TiB according to claim 1
2-TiC-TiN strengthens high-entropy alloy coated material, it is characterized in that preparation method's step is as follows:
The pre-treatment of (a) base material: select soft steel as base material, the pre-treatment of base material comprises deoxidation compound and surface cleaning; Wherein remove oxide compound and adopt grinder buffing or method for turning, till it exposes metalluster; Surface cleaning is in acetone soln, adopt ultrasonic method to clean; Dry in drying baker with alcohol wipe surface of steel plate after cleaning, for subsequent use;
B () prepares high-entropy alloy coating material: the composition of this coating material presses atomic percentage, is respectively Co 17 ~ 19 %, Cr17 ~ 19 %, Fe 17 ~ 19 %, Ni 17 ~ 19 %, Mn 17 ~ 19 %, Ti 3 ~ 10 %, B
4c 0.5 ~ 2 % and BN 1.5 ~ 3 %.Its raw material chooses metal-powder and the compound powder of respective element, and the purity of each raw material is not less than 99.9%, and the granularity of powder is 20 ~ 150 μm;
C () mixes powder: mixed by the various raw materials in step (b), and put into the mixed powder of three-dimensional motion mixer, the mixing machine speed of mainshaft is set as 15-20 rpm, and the mixed powder time is 3-4h, to ensure that powder mixes;
D () prepares high-entropy alloy coating: powder step (c) mixed loads in powder feeder; plasma melting coating equipment is adopted to prepare coating; concrete processing parameter is: cladding electric current 160-180A; cladding voltage 32-34V, ion-gas flow 1.5-1.8 L/min, shielding gas flow amount 2-2.6 L/min; powder feeding gas flow 1.2-1.5 L/min; cladding speed 40-50 mm/min, welding gun amplitude of oscillation 20-25mm, spread of electrodes workpiece surface distance 15-20 mm.
Described preparation method, is characterized in that ion-gas, protection gas and powder feeding gas are argon gas described in step (d).
Described preparation method, it is characterized in that coating prepared in step (d), and thickness is 1.5 ~ 3mm, the weave construction of coating is FCC phase, BCC phase and TiB
2-TiC-TiN ternary ceramics phase; Average Vickers' hardness is up to 1104Hv; Coating and the matrix of preparation produce metallurgical binding.
Technique scheme makes the present invention have following beneficial effect: the present invention discloses a kind of plasma cladding in-situ self-generated TiB on original high-entropy alloy coating basis
2-TiC-TiN strengthens high-entropy alloy coated material and preparation method thereof, overcome artificial additional ceramic particle and may there is pollution, the shortcoming such as combine with coated substrate not firm, the intensity of high-entropy alloy base composite coating, hardness and toughness are all significantly improved, effectively achieve the coupling of hardness and obdurability, played the potential of coating to greatest extent, its procedure arrangement is reasonable, be easy to implement, having can promotional value.
Accompanying drawing explanation
Fig. 1: embodiment 1 prepares the X ray diffracting spectrum of coating,
Fig. 2: embodiment 2 prepares the surface topography map of coating,
Fig. 3: embodiment 3 prepares the Cross Section Morphology figure of coating.
Embodiment
embodiment 1:a kind of plasma cladding in-situ self-generated TiB
2-TiC-TiN strengthens high-entropy alloy coated material and preparation method thereof:
(1), the composition of high-entropy alloy coated material, be respectively by atomic percentage: Co 17 %, Cr17%, Fe 17 %, Ni 17 %, Mn 17%, Ti 10 %, B
4c 2 % and BN 3 %.
(2), the step of high-entropy alloy coating production is as follows:
A () pretreatment of base material: the sheet material first mild steel plate being cut into 40 × 60 × 8mm, then adopts emery wheel to polish to surface of steel plate, removes zone of oxidation, till it exposes metalluster; The steel plate of milled of then fighting each other carries out cleaning by degreasing, and adopt acetone soln to clean in ultrasonic wave, during cleaning, temperature is 25 ° of C; Dry in drying baker with alcohol wipe surface of steel plate after cleaning, for subsequent use;
B () prepares high-entropy alloy coating material: accurate weighing coating material powder; By atomic percentage, the composition of this coating material powder is Co 17 %, Cr17%, Fe 17 %, Ni 17 %, Mn 17%, Ti 10 %, B
4c 2 % and BN 3 %.Its raw material chooses metal-powder and the compound powder of respective element, and the purity of each raw material is not less than 99.9%, and the granularity of powder is 20 ~ 150 μm;
C () mixes powder: mixed by the various raw materials in step (b), and put into the mixed powder of three-dimensional motion mixer, the mixing machine speed of mainshaft is set as 15 rpm, and the mixed powder time is 3h, to ensure that powder mixes;
D () prepares high-entropy alloy coating: powder step (c) mixed loads in powder feeder; plasma melting coating equipment is adopted to carry out cladding operation; protection gas, ion-gas and powder feeding gas used are argon gas; the processing parameter of preparation is: cladding electric current 160A; cladding voltage 32V; ion-gas flow 1.5 L/min; shielding gas flow amount 2 L/min; powder feeding gas flow 1.2 L/min; cladding speed 40 mm/min; the welding gun amplitude of oscillation 20 mm, spread of electrodes workpiece surface distance 15 mm.
The X ray diffracting spectrum that embodiment 1 prepares coating is shown in Fig. 1.Can find out, after plasma cladding, the structure of coating is primarily of FCC phase, BCC phase, TiB
2, TiC and TiN ceramic phase forms.Utilize HVS-1000 type Vickers hardness tester to carry out micro-hardness testing to coating prepared by embodiment 1, result shows that the average microhardness of coating is 1104 Hv.
embodiment 2: a kind of plasma cladding in-situ self-generated TiB
2-TiC-TiN strengthens high-entropy alloy coated material and preparation method thereof:
(1), the composition of high-entropy alloy coated material, be respectively by atomic percentage: Co 18 %, Cr18%, Fe 18%, Ni 18 %, Mn 18%, Ti 7 %, B
4c 1 % and BN 2 %.
(2), the step of high-entropy alloy coating production is as follows:
A () pretreatment of base material: the sheet material first mild steel plate being cut into 50 × 70 × 8mm, then adopts emery wheel to polish to surface of steel plate, removes zone of oxidation, till it exposes metalluster; The steel plate of milled of then fighting each other carries out cleaning by degreasing, and adopt acetone soln to clean in ultrasonic wave, during cleaning, temperature is 25 ° of C; Dry in drying baker with alcohol wipe surface of steel plate after cleaning, for subsequent use;
B () prepares high-entropy alloy coating material: accurate weighing coating material powder; By atomic percentage, the composition of this coating material powder is Co 18 %, Cr18%, Fe 18%, Ni 18 %, Mn 18%, Ti 7 %, B
4c 1 % and BN 2 %; Its raw material chooses metal-powder and the compound powder of respective element, and the purity of each raw material is not less than 99.9%, and the granularity of powder is 20 ~ 150 μm;
C () mixes powder: mixed by the various raw materials in step (b), and put into the mixed powder of three-dimensional motion mixer, the mixing machine speed of mainshaft is set as 18 rpm, and the mixed powder time is 3.5 h, to ensure that powder mixes;
D () prepares high-entropy alloy coating: powder step (c) mixed loads in powder feeder; plasma melting coating equipment is adopted to carry out cladding operation; protection gas, ion-gas and powder feeding gas used are argon gas; the processing parameter of preparation is: cladding electric current 170A; cladding voltage 33V; ion-gas flow 1.7 L/min; shielding gas flow amount 2.5 L/min; powder feeding gas flow 1.3 L/min; cladding speed 45 mm/min; the welding gun amplitude of oscillation 23 mm, spread of electrodes workpiece surface distance 18 mm.
Fig. 2 is the surface topography that embodiment 2 prepares coating.Can find out: the TiB that there is a large amount of strip in coating
2ceramic phase, TiC and the TiN ceramic phase of tiny bulk; Grey be organized as FCC phase, white eutectic structure be BCC phase.
embodiment 3:a kind of plasma cladding in-situ self-generated TiB
2-TiC-TiN strengthens high-entropy alloy coated material and preparation method thereof:
(1), the composition of high-entropy alloy coated material, be respectively by atomic percentage: Co 19 %, Cr19%, Fe 19 %, Ni 19 %, Mn 19%, Ti 3 %, B
4c 0.5 % and BN 1.5 %.
(2), the step of high-entropy alloy coating production is as follows:
A () pretreatment of base material: the sheet material first mild steel plate being cut into 60 × 80 × 8mm, then adopts emery wheel to polish to surface of steel plate, removes zone of oxidation, till it exposes metalluster; The steel plate of milled of then fighting each other carries out cleaning by degreasing, and adopt acetone soln to clean in ultrasonic wave, during cleaning, temperature is 25 ° of C; Dry in drying baker with alcohol wipe surface of steel plate after cleaning, for subsequent use;
B () prepares high-entropy alloy coating material: accurate weighing coating material powder; By atomic percentage, the composition of this coating material powder is Co 19 %, Cr19%, Fe 19 %, Ni 19 %, Mn 19%, Ti 3 %, B
4c 0.5 % and BN 1.5 %; Its raw material chooses metal-powder and the compound powder of respective element, and the purity of each raw material is not less than 99.9%, and the granularity of powder is 20 ~ 150 μm;
C () mixes powder: mixed by the various raw materials in step (b), and put into the mixed powder of three-dimensional motion mixer, the mixing machine speed of mainshaft is set as 20 rpm, and the mixed powder time is 4 h, to ensure that powder mixes;
D () prepares high-entropy alloy coating: powder step (c) mixed loads in powder feeder; plasma melting coating equipment is adopted to carry out cladding operation; protection gas, ion-gas and powder feeding gas used are argon gas; the processing parameter of preparation is: cladding electric current 180A; cladding voltage 34V; ion-gas flow 1.8 L/min; shielding gas flow amount 2.6 L/min; powder feeding gas flow 1.5 L/min; cladding speed 50 mm/min; the welding gun amplitude of oscillation 25 mm, spread of electrodes workpiece surface distance 20 mm.
Embodiment 3 prepares the Cross Section Morphology of coating not eroded as shown in Figure 3, there is metallurgical binding between coating and matrix, and the structure of coating is changed by plane crystal orientation bag-like crystalline substance; Organize the FCC phase primarily of white, the BCC phase of grey and tiny black ceramic phase composite.
Claims (4)
1. a plasma cladding in-situ self-generated TiB
2-TiC-TiN strengthens high-entropy alloy coated material, it is characterized in that: the composition of this coated material, by atomic percentage, is respectively Co 17 ~ 19%, Cr 17 ~ 19%, Fe 17 ~ 19%, Ni 17 ~ 19%, Mn 17 ~ 19%, Ti 3 ~ 10%, B
4c 0.5 ~ 2% and BN 1.5 ~ 3%.
2. prepare a kind of plasma cladding in-situ self-generated TiB according to claim 1 for one kind
2-TiC-TiN strengthens high-entropy alloy coated material, it is characterized in that preparation method's step is as follows:
The pre-treatment of (a) base material: select soft steel as base material, the pre-treatment of base material comprises deoxidation compound and surface cleaning; Wherein remove oxide compound and adopt grinder buffing or method for turning, till it exposes metalluster; Surface cleaning is in acetone soln, adopt ultrasonic method to clean; Dry in drying baker with alcohol wipe surface of steel plate after cleaning, for subsequent use;
B () prepares high-entropy alloy coating material: the composition of this coating material presses atomic percentage, is respectively Co 17 ~ 19%, Cr 17 ~ 19%, Fe 17 ~ 19%, Ni 17 ~ 19%, Mn 17 ~ 19%, Ti 3 ~ 10%, B
4c 0.5 ~ 2% and BN 1.5 ~ 3%.Its raw material chooses metal-powder and the compound powder of respective element, and the purity of each raw material is not less than 99.9%, and the granularity of powder is 20 ~ 150 μm;
C () mixes powder: mixed by the various raw materials in step (b), and put into the mixed powder of three-dimensional motion mixer, the mixing machine speed of mainshaft is set as 15-20rpm, and the mixed powder time is 3-4h, to ensure that powder mixes;
D () prepares high-entropy alloy coating: powder step (c) mixed loads in powder feeder; plasma melting coating equipment is adopted to prepare coating; concrete processing parameter is: cladding electric current 160-180A; cladding voltage 32-34V, ion-gas flow 1.5-1.8L/min, shielding gas flow amount 2-2.6L/min; powder feeding gas flow 1.2-1.5L/min; cladding speed 40-50mm/min, welding gun amplitude of oscillation 20-25mm, spread of electrodes workpiece surface distance 15-20mm.
3. preparation method according to claim 2, is characterized in that ion-gas, protection gas and powder feeding gas are argon gas described in step (d).
4. described preparation method according to claim 2, it is characterized in that the thickness of coating prepared in step (d) is 1.5 ~ 3mm, the weave construction of coating is FCC phase, BCC phase and TiB
2-TiC-TiN ternary ceramics phase; Average Vickers' hardness is up to 1104Hv; Coating and the matrix of preparation produce metallurgical binding.
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