CN103046047A - Method for strengthening composite TiN on metal surface layer by laser superposition tungsten electrode gas protection arc induction - Google Patents
Method for strengthening composite TiN on metal surface layer by laser superposition tungsten electrode gas protection arc induction Download PDFInfo
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- CN103046047A CN103046047A CN2012105653471A CN201210565347A CN103046047A CN 103046047 A CN103046047 A CN 103046047A CN 2012105653471 A CN2012105653471 A CN 2012105653471A CN 201210565347 A CN201210565347 A CN 201210565347A CN 103046047 A CN103046047 A CN 103046047A
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- gas
- tio
- metal surface
- laser
- tungsten arc
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 45
- 239000010937 tungsten Substances 0.000 title claims abstract description 45
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 23
- 239000002184 metal Substances 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000002131 composite material Substances 0.000 title claims abstract description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title abstract 3
- 238000005728 strengthening Methods 0.000 title abstract 3
- 239000002344 surface layer Substances 0.000 title abstract 3
- 230000006698 induction Effects 0.000 title 1
- 239000011812 mixed powder Substances 0.000 claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims abstract description 11
- 238000000576 coating method Methods 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims description 23
- 229910000975 Carbon steel Inorganic materials 0.000 claims description 13
- 239000010962 carbon steel Substances 0.000 claims description 13
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 10
- 239000000470 constituent Substances 0.000 claims description 9
- 241000931526 Acer campestre Species 0.000 claims description 8
- 230000003287 optical effect Effects 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 abstract 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 abstract 2
- 235000012501 ammonium carbonate Nutrition 0.000 abstract 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- PRKQVKDSMLBJBJ-UHFFFAOYSA-N ammonium carbonate Chemical compound N.N.OC(O)=O PRKQVKDSMLBJBJ-UHFFFAOYSA-N 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 230000001939 inductive effect Effects 0.000 abstract 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 36
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 9
- 238000004381 surface treatment Methods 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 238000005240 physical vapour deposition Methods 0.000 description 4
- 229910000851 Alloy steel Inorganic materials 0.000 description 3
- 229910000639 Spring steel Inorganic materials 0.000 description 3
- 229910001315 Tool steel Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000000151 deposition Methods 0.000 description 2
- 101001087029 Chironomus tentans 60S ribosomal protein L15 Proteins 0.000 description 1
- 229910000997 High-speed steel Inorganic materials 0.000 description 1
- 101001097774 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) 40S ribosomal protein S21-A Proteins 0.000 description 1
- 101001097805 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) 40S ribosomal protein S21-B Proteins 0.000 description 1
- 101000724270 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) 60S ribosomal protein L15-A Proteins 0.000 description 1
- 101000724281 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) 60S ribosomal protein L15-B Proteins 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 102200133015 rs2234916 Human genes 0.000 description 1
- 102220041874 rs587780791 Human genes 0.000 description 1
- 102200082901 rs713040 Human genes 0.000 description 1
- 102220060547 rs786203080 Human genes 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
Abstract
With TiO2Ammonium carbonate and N2The invention discloses a method for strengthening a composite TiN on a metal surface layer by inducing a laser-superposed tungsten electrode gas-shielded arc with gas as a component, and relates to the technical field of metal surface strengthening treatment. Coating TiO on metal surface2Mixed powder with ammonium carbonate in N2In the gas atmosphere, the laser is superposed with tungsten electrode gas protection arc to coat TiO2The metal surface of the mixed powder with ammonium carbonate was scanned. By the method, TiN can be generated on the metal surface layer in an in-situ compounding manner, so that the metal surface is strengthened and the wear resistance is improved.
Description
Technical field
The present invention relates to metal surface enhanced processing technology field.
Background technology
Titanium nitride (TiN) is a kind of non-metering compound, has simultaneously the characteristics of Metallic Solids and covalent crystal, and fusing point is up to 2955 ℃.As top coat, TiN has the good comprehensive mechanical properties such as high rigidity, wear-resistant, high temperature resistant, anti-thermal shock, frictional coefficient be low, is one of thin-film material of studying at present and being most widely used.TiN successfully is applied to as coating be considered to the revolution on the metal cutting tool technograph on the instruments such as cutter, drill bit.
The technology of preparing of TiN coating mainly is physical vapor deposition (PVD) and chemical vapour deposition (CVD) at present.PVD method formation temperature is lower, coating is thinner, and is low with the bonding strength of matrix, and coating is easy to peel off from substrate, and relatively poor around plating property.CVD method depositing temperature is high, but has surpassed the thermal treatment temp of most Common Use Tools materials, thereby it is very limited to can be used to carry out the cutter material kind of coating; Secondly, CVD needs a cover to provide and prepares the equipment that contains the Ti halide gas take muriate as raw material, complex process, and cost is higher, and is inconsistent with the green industry of present promotion.
No matter be PVD method or CVD method, the TiN coating that obtains is all thinner, and thickness only has several micron (μ m), and coating is mechanical bond with matrix, and bonding surface intensity is low, and the use floating coat easily peels off.
Summary of the invention
Purpose of the present invention aims to provide a kind of with TiO
2, volatile salt and N
2Gas is that the laser stack gas tungsten arc of constituent element is induced metal surface composite Ti N enhancement method, can make structural carbon steel upper layer original position composition generation TiN, thereby the structural carbon steel surface is strengthened and the raising wear resistance.
The present invention is achieved by the following technical solutions:
At metallic surface coating TiO
2With the mixed powder of volatile salt, at N
2In the atmosphere, superpose gas tungsten arc at deposited TiO with laser
2Scan with the metallic surface of the mixed powder of volatile salt.
Can at metal surface original position composition generation TiN, realize reinforcement and raising wear resistance to the metallic surface by above method.
The present invention has the following advantages:
1, TiN is at metal surface original position composition generation, rather than at surface deposition, does not therefore have the bonding force problem of coating and matrix;
2, the original position metal surface thickness that is compounded with TiN can reach 500 to 600 microns, and microhardness can reach more than the HV1700 to HV1800, even therefore in use there is wiping on the surface, still has good hardness and wear resistance;
3, the reaction constituent element is TiO
2, volatile salt and N
2Gas take laser stack gas tungsten arc as energy source, can not cause any pollution to environment, is a kind of metal surface enhanced and wear-resisting method of environmental protection.
In addition, for different metals, TiO of the present invention
2Be technical pure TiO
2, TiO
2Be 7:3 with the mixing quality ratio of volatile salt.
Be coated in the described TiO of metallic surface
2With the mixed powder thickness of volatile salt be 1.5～2 millimeters.
N
2The flow of gas is 8～12L/min.
When described scanning, the laser beam vertical irradiation is on the structural carbon steel surface, and gas tungsten arc becomes 30 ° of angles with laser beam.
Laser stack gas tungsten arc scans with 400～600mm/min speed, and laser power is 100～200W, and optical maser wavelength is 1.06 μ m or 10. 6 μ m, and spot diameter is 2～3 millimeters.
The flow of tungsten electrode gas is 7L/min, and flame current is 20～35A.
Embodiment
One, Q235A, 20 steel, 40 steel, 45 steel, 20G, 20Mn, 40Mn and 60Mn structural carbon steel are carried out respectively surface treatment:
1, applies with technical pure TiO on the structural carbon steel surface
2With volatile salt ((NH
3)
2CO
3) mixed powder, its mass ratio is 7:3, thickness is 1.5 millimeters.
2, move with laser stack gas tungsten arc, pass to nitrogen, nitrogen flow is 8L/min.
3, the laser beam vertical irradiation is on the structural carbon steel surface, and gas tungsten arc becomes 30 ° of angles with laser beam.
4, laser stack gas tungsten arc scans with 400mm/min speed, and laser power is 200W, and optical maser wavelength is 1.06 μ m, and spot diameter is 2 millimeters.
5, gas tungsten arc uses nitrogen as shielding gas, and flow is 7L/min, and flame current is 30A.
6, result after testing, original position composition generation thickness can reach 500 microns TiN layer on the structural carbon steel top layer, and microhardness can reach HV1700.
Two, 20MnV, 40Cr, 35CrMoV and 20CrMnSi structural alloy steel are carried out respectively surface treatment:
1, applies with technical pure TiO on the structural alloy steel surface
2With volatile salt ((NH
3)
2CO
3) mixed powder, its mass ratio is 7:3, thickness is 1.5 millimeters.
2, move with laser stack gas tungsten arc, pass to nitrogen, nitrogen flow is 8L/min.
3, the laser beam vertical irradiation is on the structural carbon steel surface, and gas tungsten arc becomes 30 ° of angles with laser beam.
4, laser stack gas tungsten arc scans with 400mm/min speed, and laser power is 100W, and optical maser wavelength is 1.06 μ m, and spot diameter is 2 millimeters.
5, gas tungsten arc uses nitrogen as shielding gas, and flow is 7L/min, and flame current is 20A.
6, result after testing, original position composition generation thickness can reach 500 microns TiN layer on the structural alloy steel top layer, and microhardness can reach HV1750.
Three, 65Mn, 60Si2Mn and 50CrVA spring steel are carried out respectively surface treatment:
1, applies with technical pure TiO on the spring steel surface
2With volatile salt ((NH
3)
2CO
3) mixed powder, its mass ratio is 7:3, thickness is 2 millimeters.
2, move with laser stack gas tungsten arc, pass to nitrogen, nitrogen flow is 12L/min.
3, the laser beam vertical irradiation is on the structural carbon steel surface, and gas tungsten arc becomes 30 ° of angles with laser beam.
4, laser stack gas tungsten arc scans with 600mm/min speed, and laser power is 100W, and optical maser wavelength is 1.06 μ m, and spot diameter is 3 millimeters.
5, gas tungsten arc uses nitrogen as shielding gas, and flow is 7L/min, and flame current is 30A.
6, result after testing, original position composition generation thickness can reach 500 microns TiN layer on the spring steel top layer, and microhardness can reach HV1800.
Four, T8A, T9A, T10A, T11A, 9SiCr, Cr12MoV and 3Cr2Mo tool steel are carried out respectively surface treatment:
1, applies with technical pure TiO in tool steel surface
2With volatile salt ((NH
3)
2CO
3) mixed powder, its mass ratio is 7:3, thickness is 1.5 millimeters.
2, move with laser stack gas tungsten arc, pass to nitrogen, nitrogen flow is 8L/min.
3, the laser beam vertical irradiation is on the structural carbon steel surface, and gas tungsten arc becomes 30 ° of angles with laser beam.
4, laser stack gas tungsten arc scans with 400mm/min speed, and laser power is 100W, and optical maser wavelength is 10. 6 μ m, and spot diameter is 3 millimeters.
5, gas tungsten arc uses nitrogen as shielding gas, and flow is 7L/min, and flame current is 25A.
6, result after testing, original position composition generation thickness can reach 500 microns TiN layer on the tool steel top layer, and microhardness can reach HV1800.
Five, W18Cr4V, W6Mo5Cr4V2 and W6Mo5Cr4V2Al rapid steel are carried out respectively surface treatment:
1, applies with technical pure TiO at surface of high speed steel
2With volatile salt ((NH
3)
2CO
3) mixed powder, its mass ratio is 7:3, thickness is 1.5 millimeters,
2, move with laser stack gas tungsten arc, pass to nitrogen, nitrogen flow is 12L/min,
3, the laser beam vertical irradiation is on the structural carbon steel surface, and gas tungsten arc becomes 30 ° of angles with laser beam.
4, laser stack gas tungsten arc scans with 500mm/min speed, and laser power is 200W, and optical maser wavelength is 10. 6 μ m, and spot diameter is 2 millimeters.
5, gas tungsten arc uses nitrogen as shielding gas, and flow is 7L/min, and flame current is 30A.
6, result after testing, original position composition generation thickness can reach 600 microns TiN layer on the rapid steel top layer, and microhardness can reach HV1800.
Six, YG3X, YG6X, YK15, YG20, YT15, YS25, YW1, YW2 and YL10 Wimet are carried out respectively surface treatment:
1, applies with technical pure TiO at carbide surface
2With volatile salt ((NH
3)
2CO
3) mixed powder, its mass ratio is 7:3, thickness is 2 millimeters.
2, move with laser stack gas tungsten arc, pass to nitrogen, nitrogen flow is 12L/min.
3, the laser beam vertical irradiation is on the structural carbon steel surface, and gas tungsten arc becomes 30 ° of angles with laser beam.
4, laser stack gas tungsten arc scans with 600mm/min speed, and laser power is 200W, and optical maser wavelength is 10. 6 μ m, and spot diameter is 3 millimeters.
5, gas tungsten arc uses nitrogen as shielding gas, and flow is 7L/min, and flame current is 35A.
6, result after testing, original position composition generation thickness can reach 600 microns TiN layer on the Wimet top layer, and microhardness can reach HV1800.
Claims (7)
1. with TiO
2, volatile salt and N
2Gas is that the laser stack gas tungsten arc of constituent element is induced metal surface composite Ti N enhancement method, it is characterized in that at metallic surface coating TiO
2With the mixed powder of volatile salt, at N
2In the atmosphere, superpose gas tungsten arc at deposited TiO with laser
2Scan with the metallic surface of the mixed powder of volatile salt.
2. described with TiO according to claim 1
2, volatile salt and N
2Gas is that the laser stack gas tungsten arc of constituent element is induced metal surface composite Ti N enhancement method, it is characterized in that described TiO
2Be technical pure TiO
2, TiO
2Be 7:3 with the mixing quality ratio of volatile salt.
3. described with TiO according to claim 1 and 2
2, volatile salt and N
2Gas is that the laser stack gas tungsten arc of constituent element is induced metal surface composite Ti N enhancement method, it is characterized in that being coated in the described TiO of metallic surface
2With the mixed powder thickness of volatile salt be 1.5～2 millimeters.
4. described with TiO according to claim 1
2, volatile salt and N
2Gas is that the laser stack gas tungsten arc of constituent element is induced metal surface composite Ti N enhancement method, it is characterized in that N
2The flow of gas is 8～12L/min.
5. described with TiO according to claim 1
2, volatile salt and N
2Gas is that the laser stack gas tungsten arc of constituent element is induced metal surface composite Ti N enhancement method, it is characterized in that when described scanning the laser beam vertical irradiation is on the structural carbon steel surface, and gas tungsten arc becomes 30 ° of angles with laser beam.
6. described with TiO according to claim 5
2, volatile salt and N
2Gas is that the laser stack gas tungsten arc of constituent element is induced metal surface composite Ti N enhancement method; it is characterized in that laser stack gas tungsten arc scans with 400～600mm/min speed; laser power is 100～200W; optical maser wavelength is 1.06 μ m or 10. 6 μ m, and spot diameter is 2～3 millimeters.
7. described with TiO according to claim 6
2, volatile salt and N
2Gas is that the laser stack gas tungsten arc of constituent element is induced metal surface composite Ti N enhancement method, and the flow that it is characterized in that tungsten electrode gas is 7L/min, and flame current is 20～35A.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210565347.1A CN103046047B (en) | 2012-12-24 | 2012-12-24 | Method for strengthening composite TiN on metal surface layer by laser superposition tungsten electrode gas protection arc induction |
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|---|---|---|---|
| CN201210565347.1A CN103046047B (en) | 2012-12-24 | 2012-12-24 | Method for strengthening composite TiN on metal surface layer by laser superposition tungsten electrode gas protection arc induction |
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|---|---|---|---|
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| JPS60258481A (en) * | 1984-06-06 | 1985-12-20 | Toyota Motor Corp | Manufacture of surface coated member containing dispersed particles |
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| CN101812684A (en) * | 2010-04-19 | 2010-08-25 | 姚建华 | Method for preparing metal surface laser strengthened coat |
| CN202152365U (en) * | 2011-03-07 | 2012-02-29 | 山东万丰煤化工设备制造有限公司 | Device for preparing titanium nitride gradient coating layer by laser |
| CN102820458A (en) * | 2012-06-14 | 2012-12-12 | 合肥国轩高科动力能源有限公司 | Synthetic method of nitrogen-enriched carbon coated lithium titanate composite material prepared by introduction of ionic liquid as carbon source |
-
2012
- 2012-12-24 CN CN201210565347.1A patent/CN103046047B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60258481A (en) * | 1984-06-06 | 1985-12-20 | Toyota Motor Corp | Manufacture of surface coated member containing dispersed particles |
| CN1603238A (en) * | 2004-09-27 | 2005-04-06 | 南京大学 | Preparation method of titanium carbide and titanium nitride one dimension nanometer construction material |
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| Title |
|---|
| JELENA BUHA, ET AL.: "Thermal transformation of metal oxide nanoparticles into nanocrystalline metal nitrides using cyanamide and urea as nitrogen source", 《CHEMISTRY OF MATERIALS》 * |
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Inventor after: Wang Hui Inventor after: Chen Xiaolong Inventor after: Zuo Jianmin Inventor after: Tong Han Inventor after: Xiao Shengliang Inventor after: Zhang Rongrong Inventor before: Wang Hui Inventor before: Zuo Jianmin Inventor before: Xiao Shengliang Inventor before: Zhang Rongrong Inventor before: Tong Han |
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Free format text: CORRECT: INVENTOR; FROM: WANG HUI ZUO JIANMIN XIAO SHENGLIANG ZHANG RONGRONG TONG HAN TO: WANG HUI CHEN XIAOLONG ZUO JIANMIN TONG HAN XIAO SHENGLIANG ZHANG RONGRONG |
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Effective date of registration: 20201118 Address after: 226600 Sijin Industrial Concentration Zone, Baidian Town, Haian City, Nantong City, Jiangsu Province Patentee after: NANTONG OUTPACE BUILDING MATERIAL EQUIPMENT Co.,Ltd. Address before: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Patentee before: CHANGZHOU University |
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Effective date of registration: 20220428 Address after: 226600 group 6, fushe village, Baidian Town, Hai'an City, Nantong City, Jiangsu Province Patentee after: Haian chaoming New Material Co.,Ltd. Address before: 226600 Sijin Industrial Concentration Zone, Baidian Town, Haian City, Nantong City, Jiangsu Province Patentee before: NANTONG OUTPACE BUILDING MATERIAL EQUIPMENT CO.,LTD. |
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