CN103484810A - 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 specialty surface engineering technology coatings art.
Background technology
All the time, traditional alloy design method is all to using one or both elements as major components, usually improve again the structure property of alloy by adding other yuan, as the two component system intermetallic compounds such as stainless steel, aluminium alloy, Ni-Al and block amorphous alloy etc.Yet, along with the development of modern industry, people have proposed more and more higher requirement at aspects such as use temperature, intensity, wear resistancies to material.Although people have 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 professors Ye Junwei in 1995 have taken the lead in jumping out the development framework of conventional alloys, propose 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 does not have, such as the design of the alloy formula by suitable, can obtain the property combination such as high rigidity, high work hardening, high temperature resistant softening, high temperature oxidation resisting, corrosion-resistant, high resistivity, therefore there is very large application potential, as: the instrument that high rigidity and wear-resistant temperature-resistant are anti-corrosion, mould; The corrosion-proof and high-strength degree material of chemical plant, ships; The heat-stable material of turbine blade, heat exchanger and High Temperature Furnaces Heating Apparatus etc.And existing coating technology makes the application of high-entropy alloy obtain further developing.
Up to now, high-entropy alloy mainly adopts the method preparations such as vacuum arc furnace melting and founding.Aspect the preparation of coating: professor Ye Junwei adopts magnetron sputtering to prepare (AlCrNbSiTiV) N
xand (AlCrTaTiZr) O
xhigh-entropy alloy coating (Scripta Materialia, 2010,62:105-108 and Thin Solid Films, 2010,518:2732-2737), but the prepared film thickness of the method only can reach micro-meter scale, is difficult to bring into play the advantage of high-entropy alloy mechanical property aspect, and base material be there are certain requirements.Professor Liang Xiubing of armored force engineering institute adopt the High Speed Electric Arc Spraying method the AZ91 magnesium alloy matrix surface prepared FeCrNiCoCu and two kinds of high-entropy alloy coatings of FeCrNiCoCuB (Chinese Surface Engineering, 2011,24:70-73).Professor Pan Ye of Southeast China University adopts laser melting and coating technique to prepare FeCoNiCrAl
2si high-entropy alloy coating (Acta Metallurgica Sinica, 2011,47:1075-1079).Yet the document that relevant employing plasma melting coating technique prepares the aspect research of high-entropy alloy coating is also very few, applicant's research work in earlier stage once adopted the 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, be only 195Hv; And have intercrystalline segregation in coating structure, this has directly affected the quality and performance of coating, has limited to a certain extent its industrial application.Along with the development of modern science and technology has proposed more and more higher requirement to material, in order to improve the hardness of CoCrCuFeNi high-entropy alloy coating, reduce intercrystalline segregation, the research of developing the plasma cladding high-entropy alloy base composite coating with excellent mechanical property and homogeneous microstructure still is significant.But up to now, yet there are no and utilize the 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 the problems such as the lower and tissue distribution of the hardness of CoCrCuFeNi high-entropy alloy coating is inhomogeneous for the past plasma cladding, 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, utilizes its tissue of coating that the plasma melting coating technique prepares 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 long-effective corrosion and the environment such as wear-resisting of steel construction, and has the characteristics such as cost is lower.
The present invention realizes that the technical scheme of above-mentioned purpose is:
A kind of plasma cladding in-situ self-generated TiB
2-TiC-TiN strengthens the high-entropy alloy coated material, and it is characterized in that: the composition of this coated material, by atomic percent, 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 %.
A kind ofly prepare a kind of plasma cladding in-situ self-generated TiB claimed in claim 1
2-TiC-TiN strengthens the high-entropy alloy coated material, it is characterized in that preparation method's step is as follows:
(a) pre-treatment of 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, until it exposes metalluster; Surface cleaning is in acetone soln, to adopt ultrasonic method to be cleaned; With the alcohol wipe surface of steel plate and dry in drying baker, standby after cleaning;
(b) prepare the high-entropy alloy coating material: the composition of this coating material, by atomic percent, 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 is chosen 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 μ m;
(c) mixed powder: the various raw materials in step (b) are mixed, 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 guarantee powder, mixes;
(d) prepare the high-entropy alloy coating: the powder that step (c) is mixed is packed in powder feeder; adopt the plasma melting coating equipment 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, the spread of electrodes workpiece surface is apart from 15-20 mm.
Described preparation method, is characterized in that being argon gas at ion-gas described in step (d), protection gas and powder feeding gas.
Described preparation method, is characterized in that prepared coating in step (d), and reaching thickness is 1.5 ~ 3mm, and the weave construction of coating is the FCC phase, BCC phase and TiB
2-TiC-TiN ternary ceramics phase; Average Vickers' hardness is up to 1104Hv; The coating of preparation and matrix produce metallurgical binding.
Technique scheme makes the present invention have following beneficial effect: the present invention has disclosed 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 have pollution, the shortcoming such as combine with coated substrate not firm, make intensity, hardness and the toughness of high-entropy alloy base composite coating all significantly improve, effectively realized the coupling of hardness and obdurability, brought into play to greatest extent the potential of coating, its procedure arrangement is reasonable, be easy to implement, but there is promotional value.
The accompanying drawing explanation
The X ray diffracting spectrum of Fig. 1: embodiment 1 preparation coating,
The surface topography map of Fig. 2: embodiment 2 preparation coatings,
The Cross Section Morphology figure of Fig. 3: embodiment 3 preparation coatings.
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, by atomic percent, be respectively: 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: at first mild steel plate is cut into to the sheet material of 40 * 60 * 8mm, then adopt emery wheel to be polished to surface of steel plate, remove zone of oxidation, until it exposes metalluster; The steel plate of the milled of then fighting each other carries out cleaning by degreasing, adopts acetone soln to be cleaned in ultrasonic wave, and during cleaning, temperature is 25 ° of C; With the alcohol wipe surface of steel plate and dry in drying baker, standby after cleaning;
(b) prepare the high-entropy alloy coating material: accurate weighing coating material powder; By atomic percent, the composition of this coating material powder is Co 17 %, Cr17%, and Fe 17 %, Ni 17 %, Mn 17%, Ti 10 %, B
4c 2 % and BN 3 %.Its raw material is chosen 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 μ m;
(c) mixed powder: the various raw materials in step (b) are mixed, 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 guarantee powder, mixes;
(d) prepare the high-entropy alloy coating: the powder that step (c) is mixed is packed in powder feeder; adopt the plasma melting coating equipment to carry out the cladding operation; protection gas, ion-gas and powder feeding gas used are argon gas, and 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 of embodiment 1 preparation coating is shown in Fig. 1.Can find out, after plasma cladding the structure of coating mainly by the FCC phase, BCC phase, TiB
2, TiC and TiN ceramic phase form.Coating to embodiment 1 preparation utilizes HVS-1000 type Vickers hardness tester to carry out micro-hardness testing, and 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, by atomic percent, be respectively: 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: at first mild steel plate is cut into to the sheet material of 50 * 70 * 8mm, then adopt emery wheel to be polished to surface of steel plate, remove zone of oxidation, until it exposes metalluster; The steel plate of the milled of then fighting each other carries out cleaning by degreasing, adopts acetone soln to be cleaned in ultrasonic wave, and during cleaning, temperature is 25 ° of C; With the alcohol wipe surface of steel plate and dry in drying baker, standby after cleaning;
(b) prepare the high-entropy alloy coating material: accurate weighing coating material powder; By atomic percent, the composition of this coating material powder is Co 18 %, Cr18%, and Fe 18%, Ni 18 %, Mn 18%, Ti 7 %, B
4c 1 % and BN 2 %; Its raw material is chosen 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 μ m;
(c) mixed powder: the various raw materials in step (b) are mixed, 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 guarantee powder, mixes;
(d) prepare the high-entropy alloy coating: the powder that step (c) is mixed is packed in powder feeder; adopt the plasma melting coating equipment to carry out the cladding operation; protection gas, ion-gas and powder feeding gas used are argon gas, and 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 of embodiment 2 preparation coatings.Can find out: the TiB that has a large amount of strips in coating
2ceramic phase, the TiC of tiny bulk and TiN ceramic phase; Grey be organized as the FCC phase, the eutectic structure of white is the 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, by atomic percent, be respectively: 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: at first mild steel plate is cut into to the sheet material of 60 * 80 * 8mm, then adopt emery wheel to be polished to surface of steel plate, remove zone of oxidation, until it exposes metalluster; The steel plate of the milled of then fighting each other carries out cleaning by degreasing, adopts acetone soln to be cleaned in ultrasonic wave, and during cleaning, temperature is 25 ° of C; With the alcohol wipe surface of steel plate and dry in drying baker, standby after cleaning;
(b) prepare the high-entropy alloy coating material: accurate weighing coating material powder; By atomic percent, the composition of this coating material powder is Co 19 %, Cr19%, and Fe 19 %, Ni 19 %, Mn 19%, Ti 3 %, B
4c 0.5 % and BN 1.5 %; Its raw material is chosen 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 μ m;
(c) mixed powder: the various raw materials in step (b) are mixed, 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 guarantee powder, mixes;
(d) prepare the high-entropy alloy coating: the powder that step (c) is mixed is packed in powder feeder; adopt the plasma melting coating equipment to carry out the cladding operation; protection gas, ion-gas and powder feeding gas used are argon gas, and 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.
As shown in Figure 3, there is metallurgical binding in the Cross Section Morphology of embodiment 3 preparation coating not eroded between coating and matrix, and the structure of coating is by brilliant transformation of crystal orientation, plane bag shape; Tissue is main by white FCC phase, 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 the high-entropy alloy coated material, and it is characterized in that: the composition of this coated material, by atomic percent, 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 %.
2. one kind prepares a kind of plasma cladding in-situ self-generated TiB claimed in claim 1
2-TiC-TiN strengthens the high-entropy alloy coated material, it is characterized in that preparation method's step is as follows:
(a) pre-treatment of 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, until it exposes metalluster; Surface cleaning is in acetone soln, to adopt ultrasonic method to be cleaned; With the alcohol wipe surface of steel plate and dry in drying baker, standby after cleaning;
(b) prepare the high-entropy alloy coating material: the composition of this coating material, by atomic percent, 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 is chosen 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 μ m;
(c) mixed powder: the various raw materials in step (b) are mixed, 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 guarantee powder, mixes;
(d) prepare the high-entropy alloy coating: the powder that step (c) is mixed is packed in powder feeder; adopt the plasma melting coating equipment 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, the spread of electrodes workpiece surface is apart from 15-20 mm.
3. preparation method according to claim 2, is characterized in that being argon gas at ion-gas described in step (d), protection gas and powder feeding gas.
4. according to the described preparation method of claim 2, it is characterized in that prepared coating in step (d), reaching thickness is 1.5 ~ 3mm, and the weave construction of coating is the FCC phase, BCC phase and TiB
2-TiC-TiN ternary ceramics phase; Average Vickers' hardness is up to 1104Hv; The coating of preparation and matrix produce metallurgical binding.
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| CN114574748A (en) * | 2022-03-08 | 2022-06-03 | 山东农业大学 | High-entropy alloy coating material with high wear resistance |
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