CN107761093A - A kind of preparation method of titanium alloy grading powder laser cladding layer and the titanium alloy with the cladding layer - Google Patents
A kind of preparation method of titanium alloy grading powder laser cladding layer and the titanium alloy with the cladding layer Download PDFInfo
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- CN107761093A CN107761093A CN201710862404.5A CN201710862404A CN107761093A CN 107761093 A CN107761093 A CN 107761093A CN 201710862404 A CN201710862404 A CN 201710862404A CN 107761093 A CN107761093 A CN 107761093A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
- C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
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Abstract
The invention discloses a kind of preparation method of titanium alloy grading powder laser cladding layer, including step：1) titanium alloy base material is pre-processed, removes oxide skin, greasy dirt and the rusty stain on surface；2) it is as needed, 5~140 μm of 70Ni bags B by particle diameter4C powder carries out sieve classification；3) powder of the different grain size size class after classification is subjected to mixing match, obtains 70Ni bags B4C grading powder；4) in proportion by the 70Ni bags B4C gradings powder and TC4 powder are well mixed, and coating mixed coating grading powder is made；5) in the preset coating mixed coating grading powder of titanium alloy substrate surface; using the wide hot spot of 3mm × 12mm, 3mm × 24mm, 6mm × 12mm or 6mm × 24mm rectangle; in the case where power is 2~8kw; with 5~20mm/s sweep speed; under argon gas protection environment; laser melting coating is carried out to the test block for preseting coating mixed coating grading powder, obtains titanium alloy grading powder laser cladding layer.Cladding layer hardness height, wearability and self-lubricating property prepared by the method is good.
Description
Technical field
The present invention relates to field of laser cladding, a kind of method for preparing laser cladding layer more particularly to titanium alloy grading powder
And the titanium alloy with the cladding layer.
Background technology
The advantages that titanium alloy has that specific strength is high, anticorrosive excellent heat resistance, and bio-compatibility is good, in space flight and aviation, stone
Oiling work, biomedical engineering etc. are all widely used.But its hardness, coefficient of friction are relatively low, it is difficult to self-lubricating, institute
It is unsatisfactory with its anti-wear performance.With the development of modern science and technology, requiring the parts of some relative motions can work long hours
Worked under the special operation conditions such as high temperature, high vacuum, deep-etching and intense radiation.Under such exacting terms, conventional additional lubrication
Oil and lubricating grease can not meet its requirement.This requires parts inherently to have preferable wearability and excellent self lubricity
Can, therefore these shortcomings of titanium alloy limit its application to a certain extent.
Laser melting and coating technique has obtained great development in recent years as a material surface modification.It is logical
Cross and add cladding material in material surface, using the laser beam of high-energy-density, be allowed to the side of the consolidation together with substrate surface thin layer
Method, substrate surface formed with its be metallurgical binding increasing material cladding layer, so as to significantly improve material surface it is wear-resisting, anti-corrosion,
A kind of surface reinforcing method of heat-resisting, anti-oxidant and electrical characteristic etc..But there is presently no by this New technical use in titanium
The report of alloy.
The content of the invention
For technical problem present in prior art, it is an object of the present invention to provide one kind can significantly improve titanium
The preparation method of the titanium alloy grading powder laser cladding layer of alloy surface performance.
It is a further object of the present invention to provide a kind of titanium alloy with above-mentioned titanium alloy grading powder laser cladding layer.
Therefore, technical scheme is as follows：
A kind of preparation method of titanium alloy grading powder laser cladding layer, comprises the following steps：
1) titanium alloy base material is pre-processed, removes oxide skin, greasy dirt and the rusty stain on surface；
2) it is as needed, 5~140 μm of 70Ni bags B by particle diameter4C powder carries out sieve classification；
3) powder of the different grain size size class after classification is subjected to mixing match, obtains 70Ni bags B4C grading powder；
4) in proportion by the 70Ni bags B4C gradings powder and TC4 powder are well mixed, and coating mixed coating grading is made
Powder；
5) in the preset coating mixed coating grading powder of titanium alloy substrate surface, using 3mm × 12mm, 3mm × 24mm,
6mm × 12mm or 6mm × 24mm wide the hot spot of rectangle, in the case where power is 2~8kw, with 5~20mm/s scanning speed
Degree, under argon gas protection environment, laser melting coating is carried out to the test block for preseting coating mixed coating grading powder, obtains titanium alloy level
With powder laser cladding layer.
Wherein：
70Ni bags B described in step 2)4C powder diameters d grading range is respectively：d≤23μm；23μm<d≤45μm；
45μm<d≤75μm；75μm<d≤96μm；d>96 μm of five ranks.
When mixing match is carried out in step 3), selected powder is any one in five ranks, either
Wherein any several mixtures with any ratio.
When being mixed in step 4), 70Ni bags B4The mass fraction of C grading powder is 5%~30%, and surplus is TC4 powder
End.
In step 5), it is in the method for the preset coating mixed coating grading powder of titanium alloy substrate surface：Using organic
Coating mixed coating grading powder is preset on titanium alloy substrate surface by binding agent, and pre-set thickness is 1~3mm, is then placed in dry
In dry case, dried 2~4 hours at 120~160 DEG C.
A kind of titanium alloy, it has above-mentioned titanium alloy grading powder laser cladding layer.
The invention has the advantages that：
This method uses laser melting and coating technique, using the laser beam of high-energy-density, makes preset TC4+Ni bags B4C grading powder
Mixed powder coat consolidation together with TC4 substrate surface thin layers, form a kind of controllable the having of performance and be different from substrate surface
The surface fused coating of matter.This method can also expand the scheme applied to other variety classes grading powder and different ratio.Utilize this
Method can obtain and be substantially distinguished from base material, have high rigidity, high abrasion, the cladding layer of self-lubricating property, meet to close titanium
The property requirement of golden structural member, parts, so as to expand the use range of titanium alloy.Embody in the following areas：
In step 2), using the boron carbide (B of nickel packet form4C), in the case of nickel bag, B can be suppressed4C reaction, protect
Stay B in cladding layer4The residual of C phases.B4C has low hardness height, density, high temperature resistant, corrosion-resistant, chemical property is stable, and boron,
Carbon is strong effective solution strengthening element, and boron carbide can significantly optimize the microstructure and property of titanium-base alloy coating.
In step 2), the boron element in nickel bag boron carbide has strong deoxidation slag making function in cladding process, preferentially
With melted together with oxygen and the oxide of workpiece surface in alloy powder generation low melting point borate and cladding in weld pool surface,
Liquid metal over oxidation can be prevented, so as to improve wettability of the melt to parent metal, reduces being mingled with cladding layer
And oxygen content, improve cladding layer capability.
In step 2), step 3) and step 4), by preparing grading powder, to the nickel bag B of different grain size rank4C ratio enters
The accurate control of row, it is determined that technological parameter under carry out laser melting coating, because granularity level is different, metallurgical reaction can be significantly affected
During chemical reaction and mass transport degree so that B4C obtains different degrees of reservation in cladding layer, while former
The new thing phase of position generation heterogeneity and different proportion, the ratio for making the generation of cladding layer situ mutually and retaining phase realize that direction can
Control, so as to realize the accurate control of laser cladding layer performance within the specific limits.
Brief description of the drawings
Fig. 1 is the SEM microstructure images of cladding layer made from the preparation method of example one；
Fig. 2 is the SEM microstructure images of cladding layer made from the preparation method of example two；
Fig. 3 is the SEM microstructure images of cladding layer made from the preparation method of example three；
Fig. 4 is the XRD diffraction patterns of cladding layer made from example one, two, three；
Fig. 5 is the microhardness curve map of cladding layer made from example one, two, three；
Fig. 6 is the friction coefficient curve figure of cladding layer made from comparative example and example one, two, three.
Embodiment
The preparation method of the present invention is described in detail with reference to embodiment.
The concept explanation referred in the present invention is as follows：
Grading powder (Graded Powder)：The alloy powder of finger different grain size scope is used for after mixing according to a certain percentage
Basis or the mixed-powders of other purposes are done, it matches and difference different according to specific design of material.
Primary powder (Raw Powder)：Refer to size distribution not by outside direct intervention, preparation is directly produced with alloy material
Alloy powder.
Comparative example
A kind of preparation method of titanium alloy laser cladding layer, comprises the following steps：
1) test block that size is 30mm × 60mm × 7mm is cut into, is made as matrix material from TC4 titanium alloys
Surface scale, then greasy dirt and rusty stain with washes of absolute alcohol surface are dispelled with the sand paper of 600 mesh；
2) organic binder bond is used to be preset at mass fraction in treated test block for 100% TC4 alloy powders, in advance
It is about 1.0mm to put thickness.With 101-3AB type electric drying oven with forced convections, in 140 DEG C of dry 3 hours；
3) high power semiconductor lasers cladding is used, from 3mm × 12mm rectangular laser hot spot, laser power 4kw,
Sweep speed is 10mm/s, argon gas protection, carries out laser melting coating to the test block for preseting coating, obtains thickness about 1mm laser
Cladding layer；
4) it is using the progress hardness measurement of HV-1000 type micro-hardness measurements instrument, loaded load 300g, dwell time
10s, it is 305HV to measure cladding layer average hardness, maximum hardness 351；
5) friction and wear behavior test is carried out to cladding layer using M-2000 type vacuum abrasion testers, emery wheel material is warp
Cross the GCr15 steel of Quenching Treatment, last wheel diameter D=40mm.Specimen size is 15mm × 7mm × 6.5mm, and emery wheel rotating speed is
200rad/min, 100N, wearing- in period 15min are loaded, it is 0.015g to measure wear extent.
The friction coefficient curve figure of obtained laser cladding layer is shown in Fig. 6.
Example one
1) from TC4 titanium alloys as matrix material, it is 30mm × 60mm × 7mm to cut into size with wire cutting machine
Test block, dispel surface scale, then greasy dirt and rusty stain with washes of absolute alcohol surface using the sand paper of 600 mesh；
2) it is respectively 23 μm by granularity level<d≤45μm、45μm<The nickel bag boron carbide powder of d≤75 two size class
Each 50wt% mixing, is obtained grading powder, is mixed with 20% mass percent with TC4 alloy powders, by mechanically mixing
It is until well mixed.Cladding material is preset in treated test block using organic binder bond, pre-set thickness is about 1.0mm.
With 101-3AB type electric drying oven with forced convections, in 140 DEG C of dry 3 hours；
3) high power semiconductor lasers cladding is used, from 3 × 12 rectangular laser hot spot, laser power 4kw, scanning
Speed is respectively 10mm/s, argon gas protection, carries out laser melting coating to the test block for preseting coating, obtains thickness about 1mm laser
Cladding layer；
4) using HV-1000 type micro-hardness measurements instrument carry out hardness measurement, loaded load 300g, dwell time 10s,
It is 823.5HV, highest hardness value 1007.4HV to measure cladding layer average hardness, is appeared in close to the region on cladding layer top；
5) friction and wear behavior test is carried out to cladding layer using M-2000 type vacuum abrasion testers, emery wheel material is warp
Cross the GCr15 steel of Quenching Treatment, last wheel diameter D=40mm.Specimen size is 15mm × 7mm × 6.5mm, and emery wheel rotating speed is
200rad/min, load 100N, wearing- in period 15min.It is 0.0025g to measure wear extent.
The SEM microstructure images of obtained laser cladding layer, XRD diffraction patterns, microhardness curve map, coefficient of friction
Curve map is shown in Fig. 1, Fig. 4-Fig. 6.
Example two
1) from TC4 titanium alloys as matrix material, it is 30mm × 60mm × 7mm to cut into size with wire cutting machine
Test block, dispel surface scale using the sand paper of 600 mesh, then with absolute ethyl alcohol clean the greasy dirt and rusty stain on surface；
2) filter out molecular sieve 45 μm<D≤75 μm and 75 μm<The nickel bag boron carbide of the size class of d≤96 μm two
Each 50wt% of powder is mixed, and obtains grading powder, is mixed with 20% mass percent with TC4 alloy powders, is passed through machine
The mixing of tool formula is until well mixed.Cladding material is preset in treated test block using organic binder bond, pre-set thickness is about
For 1.0mm.With 101-3AB type electric drying oven with forced convections, in 140 DEG C of dry 3 hours；
3) high power semiconductor lasers cladding is used, from 3mm × 12mm rectangular laser hot spot, laser power 4kw,
Sweep speed is respectively 10mm/s, and argon gas is protected.Laser melting coating is carried out to the test block for preseting coating, obtains thickness about 1mm's
Laser cladding layer.
4) using HV-1000 type micro-hardness measurements instrument carry out hardness measurement, loaded load 300g, dwell time 10s,
It is 910.7HV to measure cladding layer average hardness, highest hardness value 1405.7HV, appears in the B remained in cladding layer4C
On grain.
5) friction and wear behavior test is carried out to cladding layer using M-2000 type vacuum abrasion testers, emery wheel material is warp
Cross the GCr15 steel of Quenching Treatment, last wheel diameter D=40mm.Specimen size 15mm × 7mm × 6.5mm, emery wheel rotating speed are
200rad/min, load 100N, wearing- in period 15min.It is 0.0035g to measure wear extent.
The SEM microstructure images of obtained laser cladding layer, XRD diffraction patterns, microhardness curve map, coefficient of friction
Curve map is shown in Fig. 2, Fig. 4-Fig. 6.
Example three
1) from TC4 titanium alloys as matrix material, it is 30mm × 60mm × 7mm to cut into size with wire cutting machine
Test block, dispel surface scale using the sand paper of 600 mesh, then with absolute ethyl alcohol clean the greasy dirt and rusty stain on surface.
2) filter out molecular sieve 75 μm<D≤96 μm and d>The nickel bag boron carbide powder of 96 μm of two size class is each
50wt% carries out being mixed to get grading powder, is mixed with 20% mass percent with TC4 alloy powders, by mechanically mixing
It is until well mixed.Cladding material is preset in treated test block using organic binder bond, pre-set thickness is about 1.0mm.
With 101-3AB type electric drying oven with forced convections, in 140 DEG C of dry 3 hours.
3) high power semiconductor lasers cladding is used, from 3mm × 12mm rectangular laser hot spot, laser power 4kw,
Sweep speed is respectively 10mm/s, and argon gas is protected.Laser melting coating is carried out to the test block for preseting coating, obtains thickness about 1mm's
Laser cladding layer.
4) using HV-1000 type micro-hardness measurements instrument carry out hardness measurement, loaded load 300g, dwell time 10s,
It is 788.4HV, highest hardness value 1419.1HV to measure cladding layer average hardness, appears in what is remained in cladding layer
B4On C particles.
5) friction and wear behavior test is carried out to cladding layer using M-2000 type vacuum abrasion testers, emery wheel material is warp
Cross the GCr15 steel of Quenching Treatment, last wheel diameter D=40mm.Specimen size 15mm × 7mm × 6.5mm, emery wheel rotating speed are
200rad/min, 100N, wearing- in period 15min are loaded, it is 0.0056g to measure wear extent.
The SEM microstructure images of obtained laser cladding layer, XRD diffraction patterns, microhardness curve map, coefficient of friction
Curve map is shown in Fig. 3-Fig. 6.
The performance parameter test of above-mentioned comparative example and 3 embodiments the results are shown in Table 1：
Table 1
As can be seen from Table 1, the average hardness of the floating coat of example two is maximum.Because absorbing same laser energy
Under conditions of, Ni bags B in example one4C almost all is decomposed, and Ni, B and the C decomposited is simultaneously in situ raw with the Ti in matrix respectively
Into Ti2Ni、TiB、TiB2, the hardening constituent such as TiC, compared with comparative example, generated in-situ hardening constituent greatly improves the hard of coating
Degree；And embodiment two generates Ti in the original location2Ni、TiB、TiB2, the hardening constituent such as TiC while, also remain with part not molten B4C,
The B not melted in coating4C presence improves the average hardness of coating；But in embodiment three, substantial amounts of B4C is not divided
Solution, for the reinforcing phase amount of coating situ generation much smaller than embodiment one and embodiment two, this also results in the cladding of embodiment three
Layer average hardness reduces, but maximum hardness and embodiment two are close, when the pressure head of microhardness testers measures not molten B4On C
When, the maximum hardness of coating has reached B4C rank, far above coating other positions.
In addition, can also be illustrated by table 1, with matching somebody with somebody powder Ni bags B in embodiment one, two, three4The increase of C granularity level, in phase
Under the conditions of same frictional wear experiment, the wear extent of coating gradually increases, because Ni bags B in fore-put powder4C granularity level
Increase cause under conditions of identical laser energy is absorbed, the B retained in coating4C quantity is also more.In fretting wear
During, generated in-situ Ti2Ni、TiB、TiB2, the hardening constituent such as TiC and the B retained4C is more wear-resisting compared with Ti matrixes, improves
The wearability of coating, reduces wear extent；At the same time the B retained4Easily projection is on friction surface in wear process by C, most
It will be come off when shearing force is more than its adhesion with matrix in whole wear process, exacerbate coating abrasion effect.
It can be seen that powder size distribution influences significantly, to pass through the level for selecting suitably to match on titanium alloy surface cladding layer capability
With powder, the controllable special cladding layer of energy processability, so as to obtain that there is the titanium alloy of grading powder laser cladding layer, meet to titanium
The property requirement of alloy structure part, parts, expand the use range of titanium alloy.
Although the present invention only lists 3 specific embodiments, those skilled in the art can be in the base of the present invention
Limited experiment is combined on plinth, its titanium alloy grading powder being actually needed is met by changing component proportion and processing conditions
Laser cladding layer and the titanium alloy with the cladding layer.
Claims (6)
1. a kind of preparation method of titanium alloy grading powder laser cladding layer, it is characterised in that comprise the following steps：
1) titanium alloy base material is pre-processed, removes oxide skin, greasy dirt and the rusty stain on surface；
2) it is as needed, 5~140 μm of 70Ni bags B by particle diameter4C powder carries out sieve classification；
3) powder of the different grain size size class after classification is subjected to mixing match, obtains 70Ni bags B4C grading powder；
4) in proportion by the 70Ni bags B4C gradings powder and TC4 powder are well mixed, and coating mixed coating grading powder is made；
5) in the preset coating mixed coating grading powder of titanium alloy substrate surface, using 3mm × 12mm, 3mm × 24mm, 6mm
× the 12mm or 6mm × 24mm wide hot spot of rectangle, in the case where power is 2~8kw, with 5~20mm/s sweep speed,
Under argon gas protection environment, laser melting coating is carried out to the test block for preseting coating mixed coating grading powder, obtains titanium alloy grading powder
Laser cladding layer.
2. preparation method as claimed in claim 1, it is characterised in that：70Ni bags B described in step 2)4C powder diameters d point
Level scope be respectively：d≤23μm；23μm<d≤45μm；45μm<d≤75μm；75μm<d≤96μm；d>96 μm of five ranks.
3. preparation method as claimed in claim 2, it is characterised in that：When mixing match is carried out in step 3), selected powder
End is any one in five ranks, or wherein any several mixtures with any ratio.
4. preparation method as claimed in claim 3, it is characterised in that：When being mixed in step 4), 70Ni bags B4C grading powder
Mass fraction be 5%~30%, surplus is TC4 powder.
5. preparation method according to claim 4, it is characterised in that：In step 5), in the preset institute of titanium alloy substrate surface
The method for stating coating mixed coating grading powder is：Coating mixed coating grading powder is preset at using organic binder bond titanium alloy-based
On material surface, pre-set thickness is 1~3mm, is then placed in drying box, is dried 2~4 hours at 120~160 DEG C.
6. a kind of titanium alloy, it has titanium alloy grading powder laser cladding layer according to any one of claims 1 to 5.
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