CN103334045A - Laser combustion synthesized TiN-enhanced titanium-based composite material and method thereof - Google Patents
Laser combustion synthesized TiN-enhanced titanium-based composite material and method thereof Download PDFInfo
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- CN103334045A CN103334045A CN2013102251955A CN201310225195A CN103334045A CN 103334045 A CN103334045 A CN 103334045A CN 2013102251955 A CN2013102251955 A CN 2013102251955A CN 201310225195 A CN201310225195 A CN 201310225195A CN 103334045 A CN103334045 A CN 103334045A
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- 239000010936 titanium Substances 0.000 title claims abstract description 69
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 64
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title abstract description 15
- 239000011159 matrix material Substances 0.000 claims abstract description 56
- 229910052718 tin Inorganic materials 0.000 claims abstract description 53
- 238000002360 preparation method Methods 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 11
- 230000001360 synchronised effect Effects 0.000 claims abstract description 11
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 8
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 8
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 7
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 6
- 238000005275 alloying Methods 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 238000010309 melting process Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 239000004065 semiconductor Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 12
- 238000005049 combustion synthesis Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 5
- 229910045601 alloy Inorganic materials 0.000 abstract description 4
- 239000000956 alloy Substances 0.000 abstract description 4
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 239000004480 active ingredient Substances 0.000 abstract 2
- 239000003623 enhancer Substances 0.000 abstract 1
- 239000000919 ceramic Substances 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 238000006356 dehydrogenation reaction Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- 229920002994 synthetic fiber Polymers 0.000 description 4
- 238000005266 casting Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 230000002929 anti-fatigue Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000012254 powdered material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
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Abstract
The invention relates to a laser combustion synthesized TiN-enhanced titanium-based composite material and a method thereof, belonging to the field of material preparation and processing technology. The prepared TiN-enhanced titanium-based composite material comprises the active ingredients in mole percentage: 5-50% of TiN, 5-50% of TiR, and 0-20% of alloy element, wherein R is one or more of Al, Si and B, and the alloy element is a mixture of any ratio of one or more of Nb, Ta, Zr, Hf, V, Ni and Mo. The method comprises the steps of: preparing the Ti, R and the alloy elements according to the active ingredients of the TiN-enhanced titanium-based composite material, then conducting laser combustion synthesis reaction to the prepared mixture through a preset or synchronous powder feeding mode, thus finally obtaining the TiN-enhanced titanium-based composite material. The TiN enhancer in the composite material has high hardness and good wear resistance, and the TimRn matrix phase also has excellent high-temperature oxidation resistance property. In addition, a great deal of heat released in the laser combustion synthesis reaction can enable the temperature field of a laser molten pool to be more uniformly distributed, and the tissues of the accordingly obtained composite material is also compact and uniform.
Description
Technical field
The present invention relates to the synthetic TiN of a kind of laser combustion and strengthen titanium matrix composite and method thereof, belong to material preparation and processing technique field.
Background technology
Titanium matrix composite is because having higher room temperature specific tenacity and comparing Young's modulus, good anti-fatigue performance and high temperature creep-resisting performance and excellent corrosion resisting property have good future in engineering applications at members such as aerospace turbine engine blade, undercarriage, electrical instrumentation and automotive industrys.The common method for preparing titanium matrix composite mainly contains ceramic enhancement phase method and the original position generation ceramic phase method of adding, with add the ceramic enhancement phase method and compare, the ceramic enhancement phase that original position generates in the ceramic phase method is to generate by thermopositive reaction " original position " in metal melt in preparation process, in air, do not expose, problems such as surface contamination and oxidation have been avoided, improve itself and the combination of matrix phase, thereby improved the over-all properties of titanium matrix composite.
Through to the retrieval of prior art document, experts and scholars benefit our pursuits having carried out some aspect the synthetic titanium matrix composite of burning both at home and abroad.People such as SASTRY SHANKAR M have applied for being entitled as the patent (patent No. US 55759783A) of " Advanced titanium composite " in nineteen eighty-three, this titanium matrix composite matrix is titanium or titanium alloy mutually, and wild phase is defined as a kind of or some kinds of compounds that form with Ti among B, C, N and the Si.The clean people of grade of the Lv Wei of Shanghai Communications University was in 2005 and successively disclosed the burning synthesis method (publication number CN 1609048A) of polyelement reinforced titanium base composite material in 2006 and the synthetic Re that burns
2O
3Mix the patent of the method (publication number CN 1737178A) that strengthens titanium matrix composite with TiB.The burning of these several titanium matrix composites is synthetic, and what adopt all is fusion castings, and must carry out at least twice melting and just can reach required tissue and performance.In addition, fusion casting only is applicable to the preparation of block matrix material, can not be used for the preparation of material surface modifying coating.The matrix material wild phase size of fusion casting preparation is thick relatively in addition, the homogeneity relative deficiency.
Summary of the invention
For overcoming deficiency and the defective that prior art exists, the invention provides the synthetic TiN of a kind of laser combustion and strengthen titanium matrix composite and method thereof, TiN enhancing body has high rigidity and good wear resistance, Ti in the matrix material that makes
m R
n Matrix has excellent high-temperature oxidation resistance mutually again.
For achieving the above object, technical scheme of the present invention is: composition and molar percentage that the TiN for preparing strengthens titanium matrix composite are: TiN 5～50%, TiR 5～50%, alloying element 0～20%, wherein R is any one among Al, Si and the B, and alloying element is one or more the arbitrary proportion mixture among Nb, Ta, Zr, Hf, V, Ni and the Mo.The preparation method comprises following: the composition that strengthens titanium matrix composite according to TiN is prepared burden Ti, R and alloying element, then with the compound of preparation by presetting or the synchronous powder feeding system mode is carried out the laser combustion building-up reactions, finally make TiN and strengthen titanium matrix composite.
The compound of described preparation by preset or the synchronous powder feeding system mode to carry out the thickness that the laser combustion building-up reactions need distribute be 1～2mm.
Described laser combustion building-up reactions adopts CO
2Continuous laser, Nd:YAG pulse laser or semiconductor laser melting and coating process, laser energy density are 12～20 KNscm
-2
Described laser combustion building-up reactions need feed shielding gas or carry out under vacuum condition, and shielding gas is one or more arbitrary proportion mixtures in nitrogen, argon gas or the helium.
The present invention is foundation with the high-temp combustion chemical reaction between the nitride of Ti and B, Al and Si, utilizes the mutual heat effect of high energy laser beam and material, makes original powdered material generation combustion chemistry reaction, thereby prepares TiN/Ti
m R
n Matrix material.The combustion chemistry reaction formula is
The invention has the beneficial effects as follows: TiN of the present invention strengthens surface modification, the welding that titanium matrix composite and preparation method thereof can apply to material, compare with existing titanium matrix composite, TiN in the matrix material of the present invention strengthens body and generates in the chemical reaction process in position, so it and Ti
m R
n The matrix phase interface is in conjunction with good, and TiN enhancing body has high rigidity and good wear resistance, Ti in the matrix material
m R
n Matrix has excellent high-temperature oxidation resistance mutually again.Simultaneously, it is more even that the big calorimetric that the laser combustion building-up reactions is emitted distributes the laser molten pool temperature field, and the corresponding microstructure of composite that obtains is also fine and close and even.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment one: composition and molar percentage that the TiN of the present invention's preparation strengthens titanium matrix composite are: TiN 35%, TiR50%, alloying element 15%, and wherein R is Al, alloying element is Nb, Ta, Zr, Hf, V, Ni and Mo arbitrary proportion mixture.Concrete preparation method and step are: the composition that strengthens titanium matrix composite according to TiN is prepared burden Ti, Al and alloying element, and (it is 1mm that the compound of preparation carries out the thickness that the laser combustion building-up reactions need distribute by preset mode then the compound of preparation to be carried out the laser combustion building-up reactions by preset mode; The laser combustion building-up reactions adopts CO
2Continuous laser melting and coating process, laser energy density are 18 KNscm
-2The laser combustion building-up reactions need feed shielding gas carries out, and shielding gas is nitrogen), finally make TiN and strengthen titanium matrix composite.
Embodiment two: composition and molar percentage that the TiN of the present invention preparation strengthens titanium matrix composite are: TiN 50%, TiR 45%, alloying element 5%, wherein R is Si, alloying element be Nb.Concrete preparation method and step are: the composition that strengthens titanium matrix composite according to TiN is prepared burden Ti, Si and alloying element, and (it is 2mm that the compound of preparation carries out the thickness that the laser combustion building-up reactions need distribute by the synchronous powder feeding system mode then the compound of preparation to be carried out the laser combustion building-up reactions by the synchronous powder feeding system mode; The laser combustion building-up reactions adopts Nd:YAG pulse laser melting and coating process, and laser energy density is 20 KNscm
-2The laser combustion building-up reactions need feed under the shielding gas carries out, and shielding gas is argon gas), finally make TiN and strengthen titanium matrix composite.
Embodiment three: composition and molar percentage that the TiN of the present invention's preparation strengthens titanium matrix composite are: TiN 5%, TiR 48%, alloying element 20%, all the other are impurity, wherein R is B, and alloying element is the arbitrary proportion mixture among Ta, Zr, Hf, V, Ni and the Mo.Concrete preparation method and step are: the composition that strengthens titanium matrix composite according to TiN is prepared burden Ti, B and alloying element, and (it is 1.8mm that the compound of preparation carries out the thickness that the laser combustion building-up reactions need distribute by preset mode then the compound of preparation to be carried out the laser combustion building-up reactions by preset mode; The laser combustion building-up reactions adopts the semiconductor laser melting and coating process, and laser energy density is 12 KNscm
-2The laser combustion building-up reactions need feed shielding gas carries out, and shielding gas is several arbitrary proportion mixtures in nitrogen, argon gas and the helium), finally make TiN and strengthen titanium matrix composite.
Embodiment four: composition and molar percentage that the TiN of the present invention preparation strengthens titanium matrix composite are: TiN 49%, TiR 5%, all the other are impurity, and wherein R is B, and alloying element is the arbitrary proportion mixture among Zr, Hf, V, Ni and the Mo.Concrete preparation method and step are: the composition that strengthens titanium matrix composite according to TiN is prepared burden Ti and B, and (it is 2mm that the compound of preparation carries out the thickness that the laser combustion building-up reactions need distribute by the synchronous powder feeding system mode then the compound of preparation to be carried out the laser combustion building-up reactions by the synchronous powder feeding system mode; The laser combustion building-up reactions adopts Nd:YAG pulse laser melting and coating process, and laser energy density is 16 KNscm
-2The laser combustion building-up reactions need be carried out under vacuum condition), finally make TiN and strengthen titanium matrix composite.
Embodiment five: composition and molar percentage that the TiN of the present invention preparation strengthens titanium matrix composite are: TiN 49%, TiR 5%, all the other are impurity, and wherein R is B.Concrete preparation method and step are: the composition that strengthens titanium matrix composite according to TiN is prepared burden Ti and B, and (it is 2mm that the compound of preparation carries out the thickness that the laser combustion building-up reactions need distribute by the synchronous powder feeding system mode then the compound of preparation to be carried out the laser combustion building-up reactions by the synchronous powder feeding system mode; The laser combustion building-up reactions adopts Nd:YAG pulse laser melting and coating process, and laser energy density is 16 KNscm
-2The laser combustion building-up reactions need be carried out under vacuum condition), finally make TiN and strengthen titanium matrix composite.
Embodiment five: as shown in Figure 1, the TiN of present embodiment strengthens the surface modifying method that titanium matrix composite is applied to the titanium material: the pure titanium material surface that will treat modification carry out surface preparation (polish, remove contamination, oil removing, deoxidation film, pickling and dehydrogenation technology, wherein pickling and dehydrogenation are to be that 70wt% nitric acid and concentration are to clean 15min in the mixing solutions of hydrofluoric acid according to volume ratio 10:1 of 60wt% in concentration), apply synthetic materials in advance at pure titanium material surface then, adopt laser melting coating that the laser combustion building-up reactions is carried out on titanium material surface; (; The thickness that pure titanium material surface applies the burning synthetic materials in advance is 2mm; Laser combustion is synthetic to be the CO that adopts
2The combustion synthesis reaction that continuous laser technology is carried out, laser energy density are 12KNscm
-2The laser combustion building-up reactions need feed shielding gas, and shielding gas is nitrogen), finally obtain the surface and be the pure titanium material through surface modification.The titanium matrix composite for the TiN enhancing of the pure titanium material surface cladding of surface modification, wherein Ti, RN and alloy element component and molar percentage are 10%:10%:15%, wherein RN is AlN, and alloying element is the arbitrary proportion mixture of Nb, Ta, Zr, Hf, V, Sn, Ni and Mo.
Embodiment six: as shown in Figure 2, the TiN of present embodiment strengthens the method that titanium matrix composite is applied to weld: (be the matrix material of 5wt% for wild phase content with titanium matrix composite to be welded, wild phase is TiN) the weld carry out surface preparation and (comprise polishing, remove contamination, oil removing, the deoxidation film, pickling and dehydrogenation technology, wherein pickling and dehydrogenation are to be that 70wt% nitric acid and concentration are to clean 18min in the mixing solutions of hydrofluoric acid according to volume ratio 10:1 of 60wt% in concentration), again the weld is docked, applying the thickness that burning synthetic materials when welding joint applies the burning synthetic materials in advance in advance at joint is 1mm), adopt the laser melting coating combustion synthesis reaction (CO of employing then
2The combustion synthesis reaction that continuous laser carries out, laser energy density are 12KNscm
-2Feed shielding gas in the reaction process, shielding gas is nitrogen) weld is welded, finally obtain the titanium matrix composite that welds.The TiN that is of commissure cladding strengthens titanium matrix composite during welding, and wherein Ti, RN and alloying element are according to mol ratio 5%:10%:12%, and wherein RN is AlN, and alloying element is Nb, Ta, Zr, Hf, V, Sn, Ni and Mo.
Below by reference to the accompanying drawings the specific embodiment of the present invention has been done detailed description, but the present invention is not limited to above-mentioned embodiment, in the ken that those of ordinary skills possess, can also under the prerequisite that does not break away from aim of the present invention, make various variations.
Claims (5)
1. the synthetic TiN of laser combustion strengthens titanium matrix composite, it is characterized in that concrete composition and molar percentage are: TiN 5～50%, TiR 5～50%, alloying element 0～20%, wherein R is any one among Al, Si and the B, and alloying element is one or more the arbitrary proportion mixture among Nb, Ta, Zr, Hf, V, Ni and the Mo.
2. a laser combustion as claimed in claim 1 is synthesized the preparation method that TiN strengthens titanium matrix composite, it is as follows to it is characterized in that concrete grammar comprises: the composition that strengthens titanium matrix composite according to TiN is prepared burden Ti, R and alloying element, then with the compound of preparation by presetting or the synchronous powder feeding system mode is carried out the laser combustion building-up reactions, finally make TiN and strengthen titanium matrix composite.
3. the synthetic TiN of laser combustion according to claim 2 strengthens the preparation method of titanium matrix composite, it is characterized in that: the compound of described preparation by preset or the synchronous powder feeding system mode to carry out the thickness that the laser combustion building-up reactions need distribute be 1～2mm.
4. the synthetic TiN of laser combustion according to claim 2 strengthens the preparation method of titanium matrix composite, and it is characterized in that: described laser combustion building-up reactions adopts CO
2Continuous laser, Nd:YAG pulse laser or semiconductor laser melting and coating process, laser energy density are 12～20 KNscm
-2
5. the synthetic TiN of laser combustion according to claim 2 strengthens the preparation method of titanium matrix composite; it is characterized in that: described laser combustion building-up reactions need feed shielding gas or carry out under vacuum condition, and shielding gas is one or more arbitrary proportion mixtures in nitrogen, argon gas or the helium.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108723363A (en) * | 2017-04-14 | 2018-11-02 | 中南大学 | It is a kind of ceramics and/or refractory metal between compound increase material manufacturing method |
| CN111906309A (en) * | 2020-08-19 | 2020-11-10 | 昆明理工大学 | Method for manufacturing homogeneous composite material by laser near-net-shape additive manufacturing |
| CN112962095A (en) * | 2020-10-09 | 2021-06-15 | 山东大学 | Method for preparing ceramic-reinforced laser-cladding refractory high-entropy alloy coating on surface of titanium alloy and application |
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2013
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108723363A (en) * | 2017-04-14 | 2018-11-02 | 中南大学 | It is a kind of ceramics and/or refractory metal between compound increase material manufacturing method |
| CN111906309A (en) * | 2020-08-19 | 2020-11-10 | 昆明理工大学 | Method for manufacturing homogeneous composite material by laser near-net-shape additive manufacturing |
| CN112962095A (en) * | 2020-10-09 | 2021-06-15 | 山东大学 | Method for preparing ceramic-reinforced laser-cladding refractory high-entropy alloy coating on surface of titanium alloy and application |
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