CN103255415A - TiC-enhanced high-entropy alloy coating and preparation method thereof - Google Patents
TiC-enhanced high-entropy alloy coating and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a TiC-enhanced high-entropy alloy coating and a preparation method thereof and belongs to the technical field of coatings. The TiC-enhanced high-entropy alloy coating consists of 0.1-35% by mole of NbC and 65-99.9% by mole of high-entropy alloy matrix; and the high-entropy alloy matrix is CrCoCuFeMnNi and comprises the following ingredients in percentage by atom: 5-35% of Cr, 5-35% of Co, 5-35% of Fe, 5-35% of Mn, 5-35% of Ni and 5-35% of Cu. The TiC-enhanced high-entropy alloy coating is prepared by adopting a situ synthesis method or non-situ synthesis method. According to the TiC-enhanced high-entropy alloy coating and the preparation method of the TiC-enhanced high-entropy alloy coating, the strength and hardness of the coating are enhanced effectively.
Description
Technical field
The invention belongs to the coating technology field, relate to the high-entropy alloy coating that a kind of TiC strengthens, the invention still further relates to a kind of method that adopts plasma cladding to prepare this coating.
Background technology
High-entropy alloy is a kind of brand-new alloy designs theory, and its constituent element number is defined between the 5-13, and the atomic percentage conc of every kind of constituent element is between 5%-35%.Because the metallic element kind is many in the alloy, the randomness that atom is arranged is big, and high entropy effect has promoted the mixing between element, makes alloy phase form and is tending towards simple body-centered cubic or face-centred cubic structure, the formation of the intermetallic compound of the perhaps mixed structure of the two, and inhibition fragility.High-entropy alloy has very excellent mechanical property, for example has that high rigidity, high temperature resistance are softening, characteristics such as high temperature oxidation resisting, corrosion-resistant and high resistivity, has to be widely used the advantage of application potential diversification.
Present research about high-entropy alloy mainly is confined to the combination between the alloy heterogeneity, and the preparation method also mainly adopts the vacuum arc fumace fusion casting.High-entropy alloy has very excellent mechanical property, and high-entropy alloy is introduced the material surface field, is used for material surface modifying, is of great practical significance.In the high-entropy alloy coating, add TiC as wild phase, can effectively improve the mechanical properties such as hardness of high-entropy alloy coating, the application potential of performance high-entropy alloy.Believe that the high-entropy alloy coating that this TiC strengthens has very wide application prospect.The coating of preparation and the bonding strength height of base material, the surface quality excellence, comprehensive mechanical property is stable, durable.
Summary of the invention
The purpose of this invention is to provide the high-entropy alloy coating that a kind of TiC strengthens, obtain the coating that mechanical property is better than the high-entropy alloy matrix.
For achieving the above object, the present invention adopts following technical scheme.
The high-entropy alloy coating that a kind of TiC strengthens is characterized in that, by mole per-cent by the preferred 1%-20% of the TiC(of 0.1%-35%) and the high-entropy alloy matrix of 65%-99.9% form; The high-entropy alloy matrix is CrCoCuFeMnNi, and its composition is: Cr:5-35at.%; Co:5-35at.%; Fe:5-35at.%; Mn:5-35at.%; Ni:5-35at.%; Cu:5-35at.%.
The above-mentioned high-entropy alloy coating that contains the TiC enhancing adopts in-situ synthetic method or the preparation of ex situ synthetic method.
Adopt the method for plasma cladding to prepare the high-entropy alloy coating that carbide-containing strengthens, it is characterized in that, carry out according to the following steps:
A) pretreatment of base material, base material are preferably used soft steel, and pretreatment of base material comprises removes oxide compound and surface cleaning; Wherein, remove oxide compound and adopt mechanical means such as turning, polishing, until exposing metalluster; Surface cleaning can be cleaned with heat alkali liquids such as metal cleaner, sodium hydroxid and gasoline, acetone and other organic solvent.
B) prepare starting material, take by weighing required each the pantogen material of TiC and high-entropy alloy matrix, add an amount of slag former then in powdered alloy, the slag former add-on is the 5-15wt.% of powdered alloy; Consisting of of slag former: rutile: 50-100wt.%; Fluorite: 0-25wt.%; Mica: 0-25wt.%.
C) mix powder, the raw material in the step b) is put into mixed powder machine mix.
D) preparation high-entropy alloy coating, the processing parameter that adopts plasma spraying welding equipment to prepare coating is: untransferable arc voltage: 18-21V; Untransferable arc electric current: 58-63A; Transferred arc voltage: 29-32V; Transferred arc electric current: 100-130A; Powder feeding voltage: 4.0-5.5V; Ion gas: 200-350L/h; Powder feeding gas: 300-600L/h; Protection gas: 360-450L/h; Surfacing speed: 25-30mm/min; The welding gun amplitude of oscillation: 15-25mm; Spray distance: 10-15mm.
The present invention is preferred, and the composition of slag former comprises rutile, fluorite and three kinds of materials of mica in the step b).Because the surface tension of liquid high-entropy alloy is excessive, and is very big with the wetting angle angle of base material, can't be well at substrate surface generation epitaxial solidification, moulding is not good.Slag former can reduce the surface tension of liquid molten drop, and can form skull on the cladding layer surface after the cladding end, and is not residual in cladding layer.Slag former has namely improved moulding, does not influence coated component again.
The present invention is preferred, when adopting original position to synthesize wild phase, carbon ferrochrome (comprising high carbon ferro-chrome, medium carbon ferrochrome, low carbon ferrochromium) is adopted in the transition of carbon in the step b), and does not adopt graphite, titanium elements then directly adopts metal titanium, takes by weighing other required element materials of high-entropy alloy matrix.Raw materials used purity requirement is more than 99%, and granularity is between 80 orders-300 order.
The present invention is preferred, and in the described step d), described ion gas, protection gas, powder feeding gas are argon gas.In order to reduce base material to the influence of high-entropy alloy coating, adopt identical processing parameter, repeat cladding process, cladding layer is reached more than 4 layers, coat-thickness reaches 8-10mm, to avoid base material to the influence of coating.
The adding of TiC has changed the microstructure of matrix significantly, TiC is evenly distributed on the matrix can hinder dislocation motion effectively, thereby cause piling up of dislocations and dislocation tangling, play the effect that particle strengthens, make that the intensity of coating, hardness are effectively improved.
Principal feature of the present invention is: be matrix with the high-entropy alloy, as wild phase, the high-entropy alloy-base composite material comprehensive mechanical property of preparation has obtained reinforcement with TiC.Wild phase generates in position, high-entropy alloy matrix Central Plains or outside the adding.The present invention has further improved the mechanical property of material on the basis of original high-entropy alloy, the hardness ratio high-entropy alloy matrix of the high-entropy alloy coating that carbide strengthens has had and has significantly improved, the potentiality of high-entropy alloy have been brought into play greatly, and make this emerging material of high-entropy alloy be applied to the surface modification field and may become, can be used for preparing the high-entropy alloy coating of the carbide enhancing of satisfying different operating modes.
Description of drawings
Fig. 1 is the process figure that preparation TiC strengthens the high-entropy alloy coating process in the embodiment of the invention.
Embodiment
The present invention is explained in detail in conjunction with the embodiments, so that advantages and features of the invention can be easy to be it will be appreciated by those skilled in the art that but the present invention is not limited to following examples.
Embodiment 1
The high-entropy alloy coating that a kind of TiC strengthens, its composition is CrCoCuFeMnNi-(TiC)
0.2, the method that TiC adds matrix is that original position is synthetic.Adopt the method preparation of plasma cladding to contain the high-entropy alloy coating that TiC strengthens, carry out according to the following steps:
A) pretreatment of base material, at first, it is 10mm that mild steel plate is cut into thickness, and width is 100mm, and length is the sheet material of 2000mm; Then, with milling machine the carbon steel sheet surface is cut, remove zone of oxidation, until exposing metalluster; Then, carbon steel sheet is carried out cleaning by degreasing, the grease-removing agent main component is potassium hydroxide, and uses organic complexing agent as cleaning additive, and temperature control is cleaned the back flushing with clean water that finishes during cleaning about 25 ℃; With alcohol wipe surface of steel plate and oven dry, standby at last.
B) prepare raw material, according to CrCoCuFeMnNi-(TiC)
0.2Component proportions choose the metal-powder of respective element, high carbon ferro-chrome (containing 7% C, 30% Fe, 63% Cr) is adopted in the transition of carbon.And in powdered alloy, adding the slag former of 10wt.%, the slag former composition is: rutile: 60wt.%; Fluorite: 20wt.%; Mica: 20wt.%.The accurate needed powder of weighing, the purity of powder is more than 99%, and granularity is between 80 orders-300 order.The powdered alloy composition is as shown in table 1 below:
Table 1 alloy raw material composition quality
C) mix powder, with the various powder of accurately weighing, pack into successively to mix and mix powder in the powder machine to guarantee that powder mixes is even.
D) preparation high-entropy alloy coating.The powdered alloy that mixes is packed in the powder feeder, adopt plasma spraying welding equipment to carry out the cladding operation.Used protection gas, ion gas and powder feeding gas are argon gas, and concrete processing parameter is: untransferable arc voltage: 18V; Untransferable arc electric current: 60A; Transferred arc voltage: 29V; Transferred arc electric current: 110A; Powder feeding voltage: 5.5V; Ion gas: 350L/h; Powder feeding gas: 540L/h; Protection gas: 400L/h; Surfacing speed: 30mm/min; The welding gun amplitude of oscillation: 15mm; Spray distance: 10mm.Adopt identical processing parameter, repeat cladding process, cladding layer is reached more than 4 layers, coat-thickness reaches 8-10mm, to avoid base material to the influence of coating.
Embodiment 2
The high-entropy alloy coating that a kind of TiC strengthens, its composition is CrCoCuFeMnNi-(TiC)
0.3, the method that TiC adds matrix is that original position is synthetic.Adopt the method preparation of plasma cladding to contain the high-entropy alloy coating that TiC strengthens, carry out according to the following steps:
A) pretreatment of base material, at first, it is 10mm that mild steel plate is cut into thickness, and width is 100mm, and length is the sheet material of 2000mm; Then, with milling machine the carbon steel sheet surface is cut, remove zone of oxidation, until exposing metalluster; Then, carbon steel sheet is carried out cleaning by degreasing, the grease-removing agent main component is potassium hydroxide, and uses organic complexing agent as cleaning additive, and temperature control is cleaned the back flushing with clean water that finishes during cleaning about 25 ℃; With alcohol wipe surface of steel plate and oven dry, standby at last.
B) prepare raw material, according to CrCoCuFeMnNi-(TiC)
0.3Component proportions choose the metal-powder of respective element, high carbon ferro-chrome (containing 7% C, 30% Fe, 63% Cr) is adopted in the transition of carbon.And in powdered alloy, adding the slag former of 10wt.%, the slag former composition is: rutile: 70wt.%; Fluorite: 15wt.%; Mica: 15wt.%.The accurate needed powder of weighing, the purity of powder is more than 99%, and granularity is between 80 orders-300 order.The powdered alloy composition is as shown in table 2 below:
Table 2 alloy raw material composition quality
C) mix powder, with the various powder of accurately weighing, pack into successively to mix and mix powder in the powder machine to guarantee that powder mixes is even.
D) preparation high-entropy alloy coating.The powdered alloy that mixes is packed in the powder feeder, adopt plasma spraying welding equipment to carry out the cladding operation.Used protection gas, ion gas and powder feeding gas are argon gas, and concrete processing parameter is: untransferable arc voltage: 18V; Untransferable arc electric current: 60A; Transferred arc voltage: 29V; Transferred arc electric current: 120A; Powder feeding voltage: 5.5V; Ion gas: 330L/h; Powder feeding gas: 550L/h; Protection gas: 360L/h; Surfacing speed: 30mm/min; The welding gun amplitude of oscillation: 15mm; Spray distance: 11mm.Adopt identical processing parameter, repeat cladding process, cladding layer is reached more than 4 layers, coat-thickness reaches 8-10mm, to avoid base material to the influence of coating.
Embodiment 3
The high-entropy alloy coating that a kind of TiC strengthens, its composition is CrCoCuFeMnNi-(TiC)
0.4, the method that TiC adds matrix is that original position is synthetic.Adopt the method preparation of plasma cladding to contain the high-entropy alloy coating that TiC strengthens, carry out according to the following steps:
A) pretreatment of base material, at first, it is 10mm that mild steel plate is cut into thickness, and width is 100mm, and length is the sheet material of 2000mm; Then, with milling machine the carbon steel sheet surface is cut, remove zone of oxidation, until exposing metalluster; Then, carbon steel sheet is carried out cleaning by degreasing, the grease-removing agent main component is potassium hydroxide, and uses organic complexing agent as cleaning additive, and temperature control is cleaned the back flushing with clean water that finishes during cleaning about 25 ℃; With alcohol wipe surface of steel plate and oven dry, standby at last.
B) prepare raw material, according to CrCoCuFeMnNi-(TiC)
0.4Component proportions choose the metal-powder of respective element, high carbon ferro-chrome (containing 7% C, 30% Fe, 63% Cr) is adopted in the transition of carbon.And in powdered alloy, adding the slag former of 15wt.%, the slag former composition is: rutile: 70wt.%; Fluorite: 15wt.%; Mica: 15wt.%.The accurate needed powder of weighing, the purity of powder is more than 99%, and granularity is between 80 orders-300 order.The powdered alloy composition is as shown in table 3 below:
Table 3 alloy raw material composition quality
C) mix powder, with the various powder of accurately weighing, pack into successively to mix and mix powder in the powder machine to guarantee that powder mixes is even.
D) preparation high-entropy alloy coating.The powdered alloy that mixes is packed in the powder feeder, adopt plasma spraying welding equipment to carry out the cladding operation.Used protection gas, ion gas and powder feeding gas are argon gas, and concrete processing parameter is: untransferable arc voltage: 18V; Untransferable arc electric current: 60A; Transferred arc voltage: 29V; Transferred arc electric current: 115A; Powder feeding voltage: 5.5V; Ion gas: 330L/h; Powder feeding gas: 580L/h; Protection gas: 400L/h; Surfacing speed: 30mm/min; The welding gun amplitude of oscillation: 15mm; Spray distance: 13mm.Adopt identical processing parameter, repeat cladding process, cladding layer is reached more than 4 layers, coat-thickness reaches 8-10mm, to avoid base material to the influence of coating.
Embodiment 4
The high-entropy alloy coating that a kind of TiC strengthens, its composition is CrCoCu
1.2FeMn
0.8Ni-(TiC)
0.3, the method that TiC adds matrix is directly to add.Adopt the method preparation of plasma cladding to contain the high-entropy alloy coating that TiC strengthens, carry out according to the following steps:
A) pretreatment of base material, at first, it is 10mm that mild steel plate is cut into thickness, and width is 100mm, and length is the sheet material of 2000mm; Then, with milling machine the carbon steel sheet surface is cut, remove zone of oxidation, until exposing metalluster; Then, carbon steel sheet is carried out cleaning by degreasing, the grease-removing agent main component is potassium hydroxide, and uses organic complexing agent as cleaning additive, and temperature control is cleaned the back flushing with clean water that finishes during cleaning about 25 ℃; With alcohol wipe surface of steel plate and oven dry, standby at last.
B) prepare raw material, according to CrCoCu
1.2FeMn
0.8Ni-(TiC)
0.3Component proportions choose the metal-powder of respective element, the adding mode of titanium carbide is directly to add titanium carbide granule in mixed powder.And in powdered alloy, adding the slag former of 10wt.%, the slag former composition is: rutile: 80wt.%; Fluorite: 10wt.%; Mica: 10wt.%.The accurate needed powder of weighing, the purity of powder is more than 99%, and granularity is between 80 orders-300 order.The powdered alloy composition is as shown in table 4 below:
Table 4 alloy raw material composition quality
C) mix powder, with the various powder of accurately weighing, pack into successively to mix and mix powder in the powder machine to guarantee that powder mixes is even.
D) preparation high-entropy alloy coating.The powdered alloy that mixes is packed in the powder feeder, adopt plasma spraying welding equipment to carry out the cladding operation.Used protection gas, ion gas and powder feeding gas are argon gas, and concrete processing parameter is: untransferable arc voltage: 18V; Untransferable arc electric current: 60A; Transferred arc voltage: 29V; Transferred arc electric current: 110A; Powder feeding voltage: 5.5V; Ion gas: 300L/h; Powder feeding gas: 600L/h; Protection gas: 420L/h; Surfacing speed: 30mm/min; The welding gun amplitude of oscillation: 15mm; Spray distance: 12mm.Adopt identical processing parameter, repeat cladding process, cladding layer is reached more than 4 layers, coat-thickness reaches 8-10mm, to avoid base material to the influence of coating.
Embodiment 5
The high-entropy alloy coating that a kind of TiC strengthens, its composition is CrCoCuFe
1.4MnNi-(TiC)
0.5, the method that TiC adds matrix is directly to add.Adopt the method preparation of plasma cladding to contain the high-entropy alloy coating that TiC strengthens, carry out according to the following steps:
A) pretreatment of base material, at first, it is 10mm that mild steel plate is cut into thickness, and width is 100mm, and length is the sheet material of 2000mm; Then, with milling machine the carbon steel sheet surface is cut, remove zone of oxidation, until exposing metalluster; Then, carbon steel sheet is carried out cleaning by degreasing, the grease-removing agent main component is potassium hydroxide, and uses organic complexing agent as cleaning additive, and temperature control is cleaned the back flushing with clean water that finishes during cleaning about 25 ℃; With alcohol wipe surface of steel plate and oven dry, standby at last.
B) prepare raw material, according to CrCoCuFe
1.4MnNi-(TiC)
0.5Component proportions choose the metal-powder of respective element, the adding mode of titanium carbide is directly to add titanium carbide granule in mixed powder.And in powdered alloy, adding the slag former of 12wt.%, the slag former composition is: rutile: 70wt.%; Fluorite: 15wt.%; Mica: 15wt.%.The accurate needed powder of weighing, the purity of powder is more than 99%, and granularity is between 80 orders-300 order.The powdered alloy composition is as shown in table 5 below:
Table 5 alloy raw material composition quality
C) mix powder, with the various powder of accurately weighing, pack into successively to mix and mix powder in the powder machine to guarantee that powder mixes is even.
D) preparation high-entropy alloy coating.The powdered alloy that mixes is packed in the powder feeder, adopt plasma spraying welding equipment to carry out the cladding operation.Used protection gas, ion gas and powder feeding gas are argon gas, and concrete processing parameter is: untransferable arc voltage: 18V; Untransferable arc electric current: 60A; Transferred arc voltage: 29V; Transferred arc electric current: 115A; Powder feeding voltage: 5.5V; Ion gas: 350L/h; Powder feeding gas: 550L/h; Protection gas: 400L/h; Surfacing speed: 30mm/min; The welding gun amplitude of oscillation: 15mm; Spray distance: 12mm.Adopt identical processing parameter, repeat cladding process, cladding layer is reached more than 4 layers, coat-thickness reaches 8-10mm, to avoid base material to the influence of coating.
It is attractive in appearance that the high-entropy alloy that prepared TiC strengthens among the embodiment 1 is coated with formable layer, the following narration of its Performance Detection:
Adopt HXD-1000 digital micro-analysis sclerometer that coating is carried out the Vickers' hardness test, experiment is 300gf with load, and the load dwell time is 10S, and end-result is got average value measured 5 times, with the accuracy that guarantees to measure.Preparation method of sample is as follows: adopt the line cutting along the cross section intercepting 15mm * 15mm * 10mm sample of cladding layer, then with the surface of sample successively through 200#, 400#, 600#, 800#, 1000# water-proof abrasive paper grind, and carry out polished finish to guarantee the accuracy of numerical value.
Table 6 embodiment 1 floating coat microhardness (HV)
Wherein, CrCoCuFeMnNi plasma cladding coating nominal composition is as shown in table 7:
Table 7 alloying constituent quality
Claims (5)
1. the high-entropy alloy coating that TiC strengthens is characterized in that, is made up of the TiC of 0.1%-35% and the high-entropy alloy matrix of 65%-99.9% by mole per-cent; The high-entropy alloy matrix is CrCoCuFeMnNi, and its composition is: Cr:5-35at.%; Co:5-35at.%; Fe:5-35at.%; Mn:5-35at.%; Ni:5-35at.%; Cu:5-35at.%.
2. the high-entropy alloy coating that strengthens according to a kind of TiC of claim 1 is characterized in that the content of TiC is 1%-20%.
3. the method for the high-entropy alloy coating of the described a kind of TiC enhancing of preparation claim 1 is characterized in that, carries out according to the following steps:
A) pretreatment of base material, base material are preferably used soft steel, and pretreatment of base material comprises removes oxide compound and surface cleaning;
B) prepare starting material, take by weighing required each the pantogen material of TiC material and high-entropy alloy matrix, add an amount of slag former then in powdered alloy, the slag former add-on is the 5-15wt.% of powdered alloy; Consisting of of slag former: rutile: 50-100wt.%; Fluorite: 0-25wt.%; Mica: 0-25wt.%;
C) mix powder, the raw material in the step b) is put into mixed powder machine mix;
D) preparation high-entropy alloy coating, the processing parameter that adopts plasma spraying welding equipment to prepare coating is: untransferable arc voltage: 18-21V; Untransferable arc electric current: 58-63A; Transferred arc voltage: 29-32V; Transferred arc electric current: 100-130A; Powder feeding voltage: 4.0-5.5V; Ion gas: 200-350L/h; Powder feeding gas: 300-600L/h; Protection gas: 360-450L/h; Surfacing speed: 25-30mm/min; The welding gun amplitude of oscillation: 15-25mm; Spray distance: 10-15mm.
4. according to the method for claim 3, it is characterized in that raw materials used purity requirement is more than 99%, granularity is between 80 orders-300 order.
5. according to the method for claim 3 or 4, it is characterized in that when adopting original position to synthesize wild phase, carbon ferrochrome is adopted in the transition of carbon in the step b), titanium elements then directly adopts metal titanium, and takes by weighing other required element materials of high-entropy alloy matrix.
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