CN1407127A - Ti alloy reinforcing method - Google Patents
Ti alloy reinforcing method Download PDFInfo
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- CN1407127A CN1407127A CN02106048A CN02106048A CN1407127A CN 1407127 A CN1407127 A CN 1407127A CN 02106048 A CN02106048 A CN 02106048A CN 02106048 A CN02106048 A CN 02106048A CN 1407127 A CN1407127 A CN 1407127A
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- alloy
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- poppetvalve
- hardness
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- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 32
- 230000003014 reinforcing effect Effects 0.000 title abstract 2
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 abstract description 8
- 125000004430 oxygen atom Chemical group O* 0.000 abstract description 8
- 229910003077 Ti−O Inorganic materials 0.000 abstract description 3
- 239000006104 solid solution Substances 0.000 abstract 1
- 239000000956 alloy Substances 0.000 description 13
- 150000001721 carbon Chemical group 0.000 description 13
- 238000009792 diffusion process Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 229910045601 alloy Inorganic materials 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000007669 thermal treatment Methods 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
Images
Classifications
-
- 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/28—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases more than one element being applied in one step
Abstract
The invention provides a Ti alloy reinforcing method. Ti alloy is heated in an atmosphere of CO2 in a heating furnace. O and C atoms are introduced into the Ti alloy to harden it without forming Ti oxide, thereby increasing hardness by Ti-O and Ti-C solid solutions thus formed.
Description
Technical field
The present invention relates to strengthen the Ti alloy to improve the method for its wear resistance.
Background technology
In automotive industry, poppetvalve and other valve operational unit are by having high strength and low-gravity Ti alloy is made.Poppetvalve need have wear resistance and anti-scratch performance with position that different valve operational unit engages.
For strengthening the Ti alloy material, many kinds of methods have been developed to obtain wear resistance and anti-scratch performance.For example, disclose at Ti alloy surface formation oxide compound among the open 62-256956 of Japanese Patent.Disclose at surface formation nitride among the open 61-81505 of Japanese Patent.Japanese Patent 2,909 discloses by cementation process in 361 and makes carbon atom diffuse into the Ti alloy.
The wear resistance of Ti alloy material and anti-scratch performance are improved in the preceding method, but its surface is too hard, so that impacted possibly during different components bonding.
Be numbered 2001-25415 Japanese Patent Application Publication a kind of Ti alloy poppetvalve, Ti-O and Ti-C sosoloid have wherein been formed, and a kind of method of the Ti of manufacturing alloy poppetvalve disclosed, this method may further comprise the steps: be lower than heating Ti alloy poppetvalve under the temperature of β transition point in a plasma body vacuum oven, in described vacuum oven, contain and be lower than the stoichiometric oxygen that forms titanium oxide and form O and C diffusion layer, thereby contain the valve body that Ti-O and Ti-C sosoloid strengthen poppetvalve in the described diffusion layer with diffusion O atom and C atom.
Be diffusion O atom and C atom,, under about 800 ℃ temperature, heat-treat being lower than in the presence of the stoichiometric oxygen that forms titanium oxide.In the presence of a kind of gas that is used for ionization carburizing or plasma carbonizing, carry out glow discharge, and the amount of oxygen of being supplied with is lower than the stoichiometry that forms titanium oxide.Oxygen/the carbon diffusion layer of Xing Chenging has not only improved wear resistance and anti-scratch performance like this, and has weakened it and impacted the character of other parts.
But as previously mentioned, thermal treatment is in a plasma body vacuum oven, carries out in the presence of oxygen, and carries out complicated plasma carbonizing process by glow discharge.In addition, must in the plasma body vacuum oven, use a kind of vacuum electric-discharge device and plasma electrical source, thereby increase cost.The invention summary
Consider the defective of present technology, an object of the present invention is to provide a kind of method of the Ti of enhancing alloy, this method does not form titanium oxide and diffusion oxygen atom and carbon atom.
According to the present invention, a kind of method of the Ti of enhancing alloy is provided, this method is included in the process furnace, at CO
2Heating Ti alloy in the atmosphere, under the temperature of 600-900 ℃ enters in the Ti alloy C atom and O atomic diffusion.
Description of drawings
By the description of carrying out below in conjunction with accompanying drawing, it is more obvious that the features and advantages of the present invention will become, wherein:
Fig. 1 is the Photomicrograph of the Ti alloy of processing in the embodiments of the invention 1;
Fig. 2 shows the Sauerstoffatom of the Ti alloy material among Fig. 1 and the figure of carbon atom concn;
Fig. 3 is the change curve of the hardness of the Ti alloy material among Fig. 1 with the degree of depth;
Fig. 4 is the Photomicrograph of the Ti alloy of processing in the embodiments of the invention 3;
Fig. 5 is the Photomicrograph of the Ti alloy of comparative example 2 processing;
Fig. 6 is the wear test figure as a result of Ti alloy material;
Fig. 7 is the synoptic diagram of abrasion resistance tester.
Summary of the invention
Below thermal treatment of the present invention will be described.
The Ti alloy comprises the α alloy, as Ti-5Al-2.5Sn; Nearly α alloy is as Ti-6Al-2Sn-4Zr-2Mo (this paper is called " Ti6242 ") and Ti-8Al-Mo-V; The alpha-beta alloy is as Ti-6Al-4V, Ti-6Al-6V-2Sn and Ti-6Al-2Sn-4Zr-6Mo; And beta alloy, as Ti-13V-11Cr-3Al and Ti-15Mo-5Zr-3Al.The preferred Ti6242 that uses.
In thermal treatment, the Ti alloy is placed a process furnace, use CO
2Purge the air in the stove.At CO
2In the atmosphere,, heat under preferred 800-850 ℃ the temperature at 600-900 ℃.
The velocity of diffusion of carbon atom is too slow when being lower than 600 ℃, and this is disadvantageous to cost.Form oxide skin when being higher than 900 ℃, thereby and the temperature β transition point that is higher than Ti change its structure, this is worthless.
In thermal treatment, for replenishing because carbon atom and Sauerstoffatom enter the CO of Ti alloy loss
2And keep CO in the stove
2Atmosphere can be constantly with CO
2Add in the process furnace.Air inlet speed can be 0.5-3.0 liter/minute (l/min), preferred 1.0-2.5l/min.
At CO
2In treatment time influence wear resistance or hardness, the treatment time can be preferably 1-3 hour.By thermal treatment, O atom and C atomic diffusion are extremely from the degree of depth place of surperficial 25-50 μ m, and surface hardness is HV550-1000.
When with the poppetvalve in the Ti alloy manufacturing car combustion engine, suitable Vicker hardness is HV700-850.The valve of being handled by the inventive method not only has wear resistance and anti-scratch performance, and its character of impacting other parts is weakened.
Embodiment
, put into a poppetvalve sample of making by Ti6242, and introduce CO not in (muffle) stove horse that a volume is 24l
2Purging air.CO
2The flow velocity of adding in the stove is 1l/min, and sample is heated to 800 ℃, and keeps this temperature 2 hours.Then, under the situation of ingress of air not, poppetvalve is cooled to room temperature.After the cooling, from stove, take out sample, and carry out every test.
Fig. 1 is the Photomicrograph of this sample part.As shown in Photomicrograph, Sauerstoffatom and carbon atom are introduced in certain degree of depth.
Fig. 2 shows by the curve of electric field radiation type Auger (Auger) Electron Energy Disperse Spectroscopy at the mean value of the Sauerstoffatom of each depth survey and carbon atom concn.Axis of abscissa is represented apart from the sample surfaces degree of depth among the figure, the concentration of length axis represention oxygen atom and carbon atom (atom %).Concentration unit " atom % " refers to that Sauerstoffatom and carbon atom account for the ratio of the total atom number of analysis.This curve display Sauerstoffatom and the carbon atom in the diffusion layer of sample.
TiC can be discerned with the X-ray diffraction that X ray microdiffraction instrument carries out, but titanium oxide can not be found.Therefore, Sauerstoffatom does not combine with titanium, and still keeps atomic condition.Carbon atom part combines with titanium and forms TiC, but remaining be to spread with carbon atom form.
The subregion hardness of the sample that the Micro-Vickers hardness tester measurement of being made by Shimazu company so makes.Fig. 3 shows Hardness Distribution.Axis of abscissa is represented the degree of depth (μ m) on distance surface, and length axis is represented the hardness (HV) under the 100gf.This figure shows according to method of the present invention, all is improved until 50 μ m place hardness.
Fig. 2 and Fig. 3 proof increase the Ti hardness of alloy owing to have Sauerstoffatom and carbon atom.
As shown in Figure 3, surface hardness is HV830.
Embodiment 2-9 and comparative example 1-3
Under differing temps and time conditions, Ti6242 is carried out surface treatment, the results are shown in the following table.
Table
| Temperature (℃) | Time (hour) | Surface hardness (HV) | Zone of | |
| Embodiment | ||||
| 2 | ????750 | ????3 | ????570 | Do not have |
| ????3 | ????800 | ????0.5 | ????630 | Do not have |
| ????4 | ????710 | ????50 | ????680 | Do not have |
| ????5 | ????800 | ????1 | ????710 | Do not have |
| ????6 | ????800 | ????1.5 | ????790 | Do not have |
| ????7 | ????800 | ????3 | ????870 | Do not have |
| ????8 | ????850 | ????1 | ????930 | Do not have |
| ????9 | ????850 | ????2 | ????960 | Do not have |
| Comparative example 1 | ????850 | ????55 | ????1030 | Form zone of oxidation |
| ????2 | ????900 | ????1 | ????980 | Form zone of oxidation |
| ????3 | ????1000 | ????0.5 | ????1030 | Form zone of oxidation |
At CO
2In the atmosphere,, so just O atom and C atom are incorporated in the Ti alloy and can form oxide compound at 710-850 ℃ of heating Ti6242 0.5-50 hour.
Fig. 4 is the Photomicrograph of the Ti alloy poppetvalve of processing among the embodiment 3, has formed O and C diffusion layer.
The poppetvalve that is used in the car combustion engine can experience harsh conditions such as high temperature.It is HV 700-850 that a kind of poppetvalve like this needs hardness.In embodiment 1,5 and 6, need the condition of sample experience to be: 800 ℃ following 1-2 hour.
Shown in comparative example 1,850 ℃ temperature is identical with embodiment 8 and 9, but its time-consuming hardness that reached HV1030 in 55 hours.But should the time oversize, thereby have formed zone of oxidation from the teeth outwards.Be out of shape very big, so improper.
In comparative example 2 and 3, when temperature surpassed 900 ℃, surface hardness was enough, but had formed a thick oxide layer and cause big distortion, and this is unsuitable for practical application.
Fig. 5 is the Photomicrograph of the poppetvalve of comparative example 2, has wherein formed zone of oxidation on O atom and C atomic diffusion layer.
Fig. 6 show embodiment 1 and 3 and comparative example 2 in Ti6242, untreated Ti alloy and the wear test result of the high temperature steel handled of tufftridy (tuftriding).
For testing, as shown in Figure 7, with test specimen 2 and valve guide 1 interlock of making by Fe agglomerating material.Load the vertical weight " W " of 6kgf, 1 and 2 between add lubricating oil and on one side test specimen 2 slidably reciprocated 50 hour on one side.
Maximum by the test specimen wearing and tearing that untreated Ti6242 makes, wearing and tearing reduce successively by the order of embodiment 3, embodiment 1, high temperature steel and comparative example 2.Wearing and tearing and the high temperature steel of embodiment 1 are suitable.Because the difference of surface strength, the wearing and tearing of embodiment 3 are greater than embodiment 1.The wearing and tearing minimum of comparative example 2, it seems that this caused by lip-deep zone of oxidation.Comparative example 2 is too hard, thus with the wearing and tearing maximum of the valve guide of its interlock.
Claims (7)
1. method that strengthens the Ti alloy, it may further comprise the steps:
In a process furnace, at CO
2Heating Ti alloy in the atmosphere, under the 600-900 ℃ temperature is so that carbon atom and Sauerstoffatom diffuse into the Ti alloy.
2. the desired method of claim 1, wherein said method was carried out 0.5-50 hour.
3. the desired method of claim 1, wherein said method is carried out under 800-850 ℃ temperature.
4. the desired method of claim 3, wherein said method was carried out 1-3 hour.
5. the desired method of claim 1 is wherein with CO
2Continue to introduce in the process furnace.
6. the desired method of claim 1, wherein said method was carried out under about 800 ℃ temperature 1-2 hour.
7. the desired method of claim 6, wherein said Ti alloy is used for making the poppetvalve of oil engine.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001265462A JP2003073799A (en) | 2001-09-03 | 2001-09-03 | Surface treatment method for titanium-based material |
| JP265462/2001 | 2001-09-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1407127A true CN1407127A (en) | 2003-04-02 |
Family
ID=19091920
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN02106048A Pending CN1407127A (en) | 2001-09-03 | 2002-04-10 | Ti alloy reinforcing method |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20030041922A1 (en) |
| EP (1) | EP1288328A1 (en) |
| JP (1) | JP2003073799A (en) |
| KR (1) | KR20030020228A (en) |
| CN (1) | CN1407127A (en) |
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| JP2982579B2 (en) * | 1993-09-30 | 1999-11-22 | 日本鋼管株式会社 | Surface treatment method for titanium bolts or nuts |
| JP2943626B2 (en) * | 1994-10-04 | 1999-08-30 | 日本鋼管株式会社 | Surface hardening method for titanium material |
| EP1076112B1 (en) * | 1999-08-10 | 2007-05-30 | Fuji Oozx Inc. | Poppet valve made of titanium alloy |
-
2001
- 2001-09-03 JP JP2001265462A patent/JP2003073799A/en active Pending
-
2002
- 2002-03-27 EP EP02290753A patent/EP1288328A1/en not_active Withdrawn
- 2002-03-28 US US10/109,338 patent/US20030041922A1/en not_active Abandoned
- 2002-04-10 CN CN02106048A patent/CN1407127A/en active Pending
- 2002-04-30 KR KR1020020023627A patent/KR20030020228A/en not_active Application Discontinuation
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| CN102703852A (en) * | 2012-06-15 | 2012-10-03 | 西北有色金属研究院 | Method for composite hydrogen-free oxygen-carburizing on surface of two-phase titanium alloy |
| CN102703852B (en) * | 2012-06-15 | 2014-03-12 | 西北有色金属研究院 | Method for composite hydrogen-free oxygen-carburizing on surface of two-phase titanium alloy |
| CN114174550A (en) * | 2019-08-23 | 2022-03-11 | 医乐世医疗技术皮诺公司 | Hardfacing for dental implants |
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| Publication number | Publication date |
|---|---|
| JP2003073799A (en) | 2003-03-12 |
| US20030041922A1 (en) | 2003-03-06 |
| KR20030020228A (en) | 2003-03-08 |
| EP1288328A1 (en) | 2003-03-05 |
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