CN1306053C - High performance nickel saving gas valve alloy material - Google Patents
High performance nickel saving gas valve alloy material Download PDFInfo
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- CN1306053C CN1306053C CNB2005100513982A CN200510051398A CN1306053C CN 1306053 C CN1306053 C CN 1306053C CN B2005100513982 A CNB2005100513982 A CN B2005100513982A CN 200510051398 A CN200510051398 A CN 200510051398A CN 1306053 C CN1306053 C CN 1306053C
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Abstract
The present invention belongs to the field of manufacturing a nickel saving alloy material particularly a gas valve alloy material prepared and used at high temperature with high performance and load for an internal-combustion engine. The present invention is characterized in that the gas valve alloy material specifically comprises the following chemical ingredients of (by weight percentage) 18 to 25% of Cr, 40 to 50% of Ni, 0.5 to 1.5 % of Nb, 1.8 to 2.8% of Ti, 0.6 to 1.6% of AL, 0.02 to 0.3% of Zr, 0.002 to 0.3% of Re, at most 0.10% of C, at most 1.0% of Si, at most 1.5% of Mn, at most 0.50% of Cu, at most 0.02% of S, at most 0.02% of P and Fe as the rest. Compared with the existing material, the high performance nickel saving gas valve alloy material of the present invention has the characteristics of good performance of combustion gas corrosion resistance and oxidation resistance, high strength and hardness at high temperature, long service life of products, simple production process, economy, etc.
Description
Technical field
The invention belongs to the manufacturing field of joint nickel alloy material.Particularly the oil engine alloy material for gas valve of high-performance high loading is at high temperature used in preparation.
Background technology
In the Application Areas of oil engine, the use of petrol motor and diesel engine is the most extensive at present.For example in various fields such as automobile, tractor, diesel locomotive, ships, tank, generator.And air valve belongs to key part and easy consumable accessories in the oil engine.The common rotating speed of high-speed diesel engine is at 1000-2000 rev/min, the working speed of petrol motor is 2000-6000 rev/min, when the working order of oil engine, the inlet and outlet valve is reciprocating with high frequency, air valve can produce bump (power of taking a seat) to valve seat, causes frictional wear gentle valve disc portion and neck stressed.As the air valve material is by life-time service in the high-temperature fuel gas environment in oil engine, not only need this material will possess excellent oxidation-resistance and anti-exhaust gas corrosion performance, but also require to have characteristics such as very high high temperature tensile strength, creep rupture strength, hot bending fatigue strength and hot hardness.
High loading Diesel Engine's Air Valve in the prior art has two kinds with material, a kind of is nickel-base alloy, as Inconel 751 (HEV3) and Nimonic 80A (is NiCr20TiAl, HEV5) etc., though the use properties of such alloy is better, but prepare the alloy content height in this material, so cost is also high.An other class material is to be matrix with high temperature steel, built-up welding one deck antifriction anticorrosion alloy on the conical surface of valve body, for example 4Cr14Ni14W2Mo (э И 69) is as matrix, conical surface built-up welding material is the Stellite6 cobalt base alloy, the air valve material for preparing such can only be used for the diesel exhaust valve of moderate duty at present, its advantage is that cost is not high, but shortcoming is to satisfy the working strength of high loading parts and components of diesel engine, product is fragile and work-ing life is low, complex manufacturing, there is casting flaw in overlay cladding, and product qualified rate is low.
In addition, Chinese patent CN1118381A (1996) has introduced a kind of high strength heat resistant steel, and the purposes of this steel is to do intake valve of internal combustion engine, vent valve and precombustion chamber nozzle and abaculus.Can see that by contrast material content and the material of the present invention introduced by this patent have very big difference on composition, this patent is Ni 20-28%, Co 0.1-3.0%, and the present invention contains Ni 40-50%, does not contain Co.Very big difference is also arranged on the use range of material, The present invention be directed to use temperature at 750-850 ℃ of high loading vent valve, and this patent is the middle high loading air valve at use temperature≤700 ℃, the present invention aspect hot strength and hot hardness far above this patent high temperature steel.The clear 61-9548 of Japanese Patent (1986) has introduced a kind of air valve alloy, this alloy is with material proposed by the invention bigger difference to be arranged on composition, for example this patent introduction is the air valve alloy that contains B 0.001-0.01%, and material proposed by the invention is not contain the B element, but contain Zr 0.02-0.30% and Re 0.002-0.10%, therefore, the material of contrast patent and our requirement still has bigger difference.
Summary of the invention
The objective of the invention is to propose a kind ofly when high-temperature fuel gas environmental work, have anti-exhaust gas corrosion and antioxidant property is good, hot strength, hot hardness height, and long service life, simple, the economic high performance nickel saving gas valve alloy material of production technique.
Service requirements according to high performance nickel saving gas valve alloy material that the object of the invention proposes, therefore our solution of design is to consider that the working temperature of product spare is in 750 ℃ of-850 ℃ of scopes, to reduce simultaneously under the preceding topic of material cost and simplification technology, improve high performance nickel saving gas valve alloy material good mechanical performance of the present invention by the content of adjusting chromium, nickel and strengthening element.
At the object of the invention content, the high performance nickel saving gas valve alloy material that we proposed, it is characterized in that the concrete chemical component weight % of this alloy material for gas valve is: Cr 18-25%, Ni 40-50%, Nb 0.5-1.5%, Ti 1.8-2.8%, Al 0.6-1.6%, Zr 0.02-0.3%, RE 0.002-0.10%, C 0.043-0.10%, Si 0.29-1.0%, Mn 0.54-1.5%, Cu 0.17-0.50%, S≤0.02%, P≤0.02%, surplus are Fe.
The composition design of high performance nickel saving gas valve alloy material of the present invention, be after the deficiency in considering the prior art material, by elements such as the content of adjusting nickel and the zirconium that adopts trace, rare earths, replace elements such as valuable cobalt or boron, and to an amount of adjustment of other elements in the composition, thereby reach the mechanical behavior under high temperature of improving material of the present invention.Therefore, we add higher chromium element in the composition design, be when guaranteeing that alloy material of the present invention is worked in the high-temperature fuel gas environment, possesses good anti-oxidant and anti-exhaust gas corrosion performance, chromium is formed carbide in alloy, intensity to this alloy has certain contribution, Cr 18-25% in the alloying constituent of the present invention.
Nickel and manganese are austenitic forming elements, and the nickel of part and titanium and aluminium can form Ni
3(promptly therefore γ ' phase when the composition design of alloy of the present invention, mainly is to consider to adopt γ ' to come the reinforced alloys matrix mutually, realizes improving the hot strength and the hot hardness of alloy, therefore Ni 40-50% in this alloying constituent for Al, Ti) intermetallic compound; Because manganese is austenite former, but its corrosion resistance is poor, so should not add Mn in alloying constituent of the present invention≤1.5%.
The adding of aluminium and titanium is in order to form γ ' mutually with nickel, and Al and Ti add-on are influential to the γ ' amount of separating out, and the strengthening effect of Al/Ti comparison γ ' phase is influential, heat processing technique and heat treating regime to the γ ' amount of separating out, separate out size tangible influence all arranged.Add Ti 1.8-2.8% and Al 0.6-1.6% in this alloying constituent, and be to guarantee enough hot strengths and the hot hardness slightly higher than Stellite6 alloy by processing.
Niobium and zirconium are the elements that strong carbide forms in alloying constituent of the present invention, is more stable by their formed carbide when the high temperature, hot strength, hot hardness and wear resistance to this alloy material have tangible contribution, and simultaneously Nb and Zr are strengthened γ ' entering γ ' Xiang Zhongke mutually.Nb and Zr also have crystal grain thinning, improve the characteristics of plasticity and hot workability, so the add-on of niobium and zr element is respectively Nb 0.5-1.5%, Zr 0.02-0.3%.
In alloying constituent of the present invention, add rare earth element, its objective is to improving the deoxy performance of alloy material in smelting process, improve the surface quality of steel ingot and the high-temperature behavior of material, the adding of rare earth can be eliminated harmful elements such as S, P and assembles at crystal boundary in addition, and improve the structure of alloy surface oxide compound, become spherical by stratiform, reach the ability of the anti-oxidant and anti-exhaust gas corrosion that improves material, therefore the rare earth element that is added in alloying constituent of the present invention is meant any one among Ce or the Y, and its add-on is Re0.002-0.010%.
C, Si in high performance nickel saving gas valve alloy material composition of the present invention, Mn, Cu, elements such as S, P are the existence of limiting the quantity of.Though Fe is decided to be surplus in alloy material of the present invention, the content of ferro element is all more than 20%, and the purpose that improves iron level is to adopt cheap iron to substitute expensive nickel, and the nickel valency is ten thousand yuan/ton of 15-16 at present, and the pure iron valency is only at 0.7 ten thousand yuan/ton.So the design that the present invention adopts high ferro to save nickel is to reduce the cost of this alloy material significantly, simultaneously for guaranteeing the corrosion resistance of this alloy material, we also with in the composition when chromium content is set at 20-25%, rare earth Re content is 0.002-0.006%.In alloy material composition of the present invention, C can form carbide with elements such as Cr, Nb, though to some raising of intensity but contribution is little, because of the intensity of this alloy material mainly is the reinforcement that relies on γ ' phase, the raising of C can damage the plasticity of material, so C content is≤0.10% in alloy material of the present invention.Cu belongs to the element of limiting the quantity of in alloy material of the present invention, because of the Cu too high levels can influence the thermoplasticity of alloy and the cogging of alloy pig, reduce the hot workability of material, and therefore limiting the quantity of is≤0.5%.Mn also belongs to the element of limiting the quantity of, and its reason Mn is one of austenizer, though help the effect of austenitizing.But excessive Mn can reduce the resistance to high temperature oxidation and the anti-exhaust gas corrosion effect of steel alloy, P is a harmful element, because a spot of Mn element can combine the back with the S in the steel and form MnS, it is minimum that thereby the deleterious effect that makes S drops to, thus the content of Mn, S, P element be limited in respectively Mn≤1.5%, S, P all≤0.02% scope in.Though the Si element can improve the oxidation-resistance and the anti-exhaust gas corrosion of alloy material, the plastic property of material there is adverse influence, so in alloy material of the present invention, should be controlled at≤1.0%.In addition, boracic not in alloy material of the present invention, because B improves intensity by strengthening crystal boundary in alloy, but boron easy boride that forms bulk in alloy is mingled with and material is become fragile, not only reduce plasticity, but also the hot workability of reduction material, B add the affiliation make the part the B element enter γ ' mutually in and γ ' is softened mutually, influenced the strengthening effect of γ ' phase, therefore the design of our composition is not contain B, but by adjusting the Al/Ti ratio and adding Zr 0.02-0.3% alloy material of the present invention is further strengthened.
The preparation of high performance nickel saving gas valve alloy material of the present invention is similar to the prior art production method, alloy material of the present invention is to adopt to smelt in vacuum induction furnace, through steel-making, casting, forge after again in the 650 work in-process poles that become the setting size with 250 mill millings.Blank after rolling will carry out remollescent thermal treatment.Again through after slightly strong and essence is rectified, equipment such as employing coreless grinding machine carry out mechanical workout, and are prepared into the workpiece product that requires size to the blank after annealing.Product is that its detected result is all qualified by JB/T 6720 " metallographic examination of the oil engine inlet and outlet door " check that standard is carried out.
Adopt high performance nickel saving gas valve alloy material of the present invention and prior art material compared, it is good to have anti-exhaust gas corrosion and an antioxidant property, hot strength, hot hardness height and long product lifecycle, simple, the economic dispatch characteristics of production technique.Steel of the present invention is in addition compared with materials overseas and also had following advantage: 1, comparing with external Inconel 751 alloys (0.08C-15Cr-2.5Ti-1.2Al-1Nb-7Fe-Ni) commonly used and Nimonic 80A (0.08C-20Cr-2.5Ti-1.2Al-1Co-Ni) has higher hot strength and hot hardness, thereby, can reduce the air valve size, weight reduction, reduce the power of taking a seat and the wearing and tearing of air valve, increase the service life.
2, the preparation cost of alloy material of the present invention is more much lower than Inconel 751 and Nimonic 80A alloy.
3, the product of alloy material of the present invention is compared with the air valve product that high temperature steel adds conical surface built-up welding with existing locomotive, ships, not only on the mechanical property of material, has higher hot strength, but also adopted the product preparation structure of not built-up welding, overcome a series of unsafe defective that overlay cladding exists, the security and the work-ing life of product air valve spare have been improved, simplified production technique, made this material that remarkable advantages be arranged on the ratio of performance to price.
Embodiment
Adopt high performance nickel saving gas valve alloy material composition design proposed by the invention, we implement simultaneous test at two kinds of matured product materials of the prior art.The steel-making of embodiment simultaneous test is to have smelted 8 stoves alloy material of the present invention in the 25Kg vacuum induction furnace, make things convenient for us also to smelt a stove Inconel 751 alloys and a stove Nimonic 80A alloy simultaneously in order to contrast, the chemical ingredients of comparative example's alloy material is all listed in table 1.The alloy pig of embodiment all adopts same process to carry out hammer cogging, after waiting to be swaged into coupon and thermal treatment, again sample is carried out the test and the hot hardness test of room temperature and mechanical behavior under high temperature respectively, its detected result is listed in table 2, table 3 and the table 4 respectively, show that by the data in the embodiment performance comparison table over-all properties of alloy alloy material of the present invention is better than Inconel 751 alloys and Nimonic 80A alloy.
In the contrast table of the embodiment of the invention, table 1 is the composition contrast of alloy material of the present invention and prior art material.Table 2 is the room-temperature property contrast of alloy material of the present invention and prior art material.Table 3 is the mechanical behavior under high temperature contrast (750 ℃) of alloy material of the present invention and prior art material.Table 4 is the comparison (800 ℃) of the mechanical behavior under high temperature of alloy material of the present invention and prior art material.In the comparative example, sequence number 1-8 is an alloy material of the present invention.Sequence number is that Inconel 751 and Nimonic 80A alloy all are maturing materials of external air valve alloy.
Table 1 is the composition contrast (weight %) of alloy material of the present invention and prior art material
| Heat (batch) number | C | Si | Mn | Cr | Ni | Fe | Al | Ti | Nb | Zr | Ce | Cu | S | P | Co | |
| The present invention | 1 | 0.057 | 0.75 | 0.59 | 23.7 | 43.5 | Surplus | 0.83 | 2.03 | 0.81 | 0.03 | 0.005 | 0.18 | 0.005 | 0.016 | - |
| 2 | 0.051 | 0.35 | 1.26 | 21.02 | 41.0 | Surplus | 0.97 | 1.91 | 0.95 | 0.02 | 0.005 | 0.17 | 0.005 | 0.016 | - | |
| 3 | 0.056 | 0.33 | 0.55 | 19.07 | 44.5 | Surplus | 1.20 | 2.45 | 1.26 | 0.02 | 0.005 | 0.19 | 0.005 | 0.018 | - | |
| 4 | 0.043 | 0.29 | 0.61 | 19.15 | 45.2 | Surplus | 1.21 | 2.54 | 1.25 | 0.02 | 0.005 | 0.18 | 0.005 | 0.017 | - | |
| 5 | 0.063 | 0.29 | 0.55 | 22.96 | 47.5 | Surplus | 1.45 | 2.63 | 1.38 | 0.02 | 0.004 | 0.19 | 0.005 | 0.018 | - | |
| 6 | 0.051 | 0.31 | 0.54 | 22.10 | 48.6 | Surplus | 1.15 | 2.57 | 1.32 | 0.02 | 0.004 | 0.19 | 0.005 | 0.016 | - | |
| 7 | 0.045 | 0.35 | 0.87 | 20.50 | 41.5 | Surplus | 1.32 | 2.56 | 1.15 | 0.03 | 0.004 | 0.21 | 0.005 | 0.017 | - | |
| 8 | 0.060 | 0.30 | 0.60 | 19.96 | 44.2 | Surplus | 1.20 | 2.32 | 1.01 | 0.02 | 0.005 | 0.25 | 0.005 | 0.016 | - | |
| Inconel751 | 0.055 | 0.14 | 0.77 | 15.32 | Surplus | 6.99 | 1.10 | 2.26 | 0.93 | - | - | ＜0.05 | 0.005 | 0.019 | - | |
| NiCr20TiAl | 0.092 | 0.54 | 0.80 | 19.68 | Surplus | 0.20 | 1.52 | 2.46 | - | - | - | - | 0.005 | 0.018 | 1.07 | |
Table 2 is the room-temperature property contrast of alloy material of the present invention and prior art material
| Heat (batch) number | σ b MPa | σ 0.2 MPa | δ ％ | ψ ％ | HRC | |
| The present invention | 1 | 1260 | 980 | 18 | 49 | 39 |
| 2 | 1270 | 995 | 17 | 45 | 38 | |
| 3 | 1320 | 1140 | 13 | 42 | 42 | |
| 4 | 1335 | 1130 | 13 | 43 | 42 | |
| 5 | 1390 | 1160 | 13 | 37 | 42 | |
| 6 | 1380 | 1160 | 14 | 36 | 41 | |
| 7 | 1380 | 1140 | 13 | 38 | 41 | |
| 8 | 1360 | 1120 | 14 | 38 | 40 | |
| Inconel751 | 1265 | 955 | 18.7 | 31.3 | 37 | |
| NiCr20TiAl | 1130 | 825 | 20.5 | 37.2 | 32 | |
Table 3 is the mechanical behavior under high temperature contrast of alloy material of the present invention and prior art material
| Heat (batch) number | Test temperature ℃ | σ b MPa | σ 0.2 MPa | δ ％ | ψ ％ | HV 1 | |
| The present invention | 1 | 750 | 860 | 790 | 10.9 | 18.8 | 295 |
| 2 | 750 | 850 | 785 | 11.5 | 19.1 | 290 | |
| 3 | 750 | 905 | 825 | 10.5 | 16.0 | 320 | |
| 4 | 750 | 900 | 810 | 11.0 | 16.0 | 315 | |
| 5 | 750 | 925 | 840 | 9.5 | 14.0 | 320 | |
| 6 | 750 | 910 | 825 | 10.0 | 14.5 | 315 | |
| 7 | 750 | 900 | 820 | 10.5 | 15.8 | 315 | |
| 8 | 750 | 880 | 815 | 13.5 | 16.7 | 310 | |
| Inconel751 | 750 | 720 | 615 | 9.5 | 11.0 | 210 | |
| NiCr20TiAl | 750 | 810 | 630 | 12.0 | 16.0 | 240 | |
Table 4 is the mechanical behavior under high temperature contrast of alloy material of the present invention and prior art material
| Heat (batch) number | Test temperature ℃ | σ b MPa | σ 0.2 MPa | δ ％ | ψ ％ | HV 1 | |
| The present invention | 1 | 800 | 585 | 550 | 14.0 | 23.0 | 263 |
| 2 | 800 | 580 | 545 | 17.0 | 29.0 | 260 | |
| 3 | 800 | 595 | 555 | 14.0 | 21.0 | 266 | |
| 4 | 800 | 595 | 550 | 15.5 | 22.0 | 260 | |
| 5 | 800 | 635 | 580 | 13.5 | 16.5 | 275 | |
| 6 | 800 | 625 | 570 | 13.5 | 18.0 | 272 | |
| 7 | 800 | 590 | 555 | 12.0 | 16.0 | 270 | |
| 8 | 800 | 620 | 570 | 15.0 | 18.3 | 268 | |
| Inconel751 | 800 | 570 | 505 | 14.0 | 18.0 | 190 | |
| NiCr20TiAl | 800 | 625 | 570 | 16.0 | 19.5 | 210 | |
Claims (3)
1, a kind of high performance nickel saving gas valve alloy material, it is characterized in that the concrete chemical component weight % of this air valve alloy steel material is: Cr 18-25%, Ni 40-50%, Nb 0.5-1.5%, Ti 1.8-2.8%, Al 0.6-1.6%, Zr 0.02-0.3%, RE 0.002-0.10%, C 0.043-0.10%, Si 0.29-1.0%, Mn 0.54-1.5%, Cu 0.17-0.50%, S≤0.02%, P≤0.02%, surplus are Fe.
2,, it is characterized in that in the composition of this alloy material for gas valve that when chromium content was 20-25%, rare earth RE content was 0.002-0.006% according to the described high performance nickel saving gas valve alloy material of claim 1.
3,, it is characterized in that the rare earth element that is added in this alloy material for gas valve composition is meant any one among Ce or the Y according to the described high performance nickel saving gas valve alloy material of claim 1.
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| CNB2005100513982A CN1306053C (en) | 2005-03-10 | 2005-03-10 | High performance nickel saving gas valve alloy material |
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| CN1306053C true CN1306053C (en) | 2007-03-21 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104018029B (en) * | 2014-05-21 | 2016-03-23 | 西安热工研究院有限公司 | A kind of high ferro ferronickel base two-phase alloys containing rare earth |
| CN105003903A (en) * | 2015-08-05 | 2015-10-28 | 上海锅炉厂有限公司 | Boiler header of ultrahigh steam parameter unit of more than 650 DEG C |
| CN113606010A (en) * | 2021-08-26 | 2021-11-05 | 重庆宗申发动机制造有限公司 | Fuel engine valve |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5951789A (en) * | 1996-10-25 | 1999-09-14 | Daido Tokushuko Kabushiki Kaisha | Heat resisting alloy for exhaust valve and method for producing the exhaust valve |
| CN1453458A (en) * | 2003-06-02 | 2003-11-05 | 北京特冶工贸有限责任公司 | Double-metal exhaust gate for diesel engine of diesel locomotive and its manufacture |
| CN1570184A (en) * | 2004-05-10 | 2005-01-26 | 钢铁研究总院 | Economical air valve steel |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5951789A (en) * | 1996-10-25 | 1999-09-14 | Daido Tokushuko Kabushiki Kaisha | Heat resisting alloy for exhaust valve and method for producing the exhaust valve |
| CN1453458A (en) * | 2003-06-02 | 2003-11-05 | 北京特冶工贸有限责任公司 | Double-metal exhaust gate for diesel engine of diesel locomotive and its manufacture |
| CN1570184A (en) * | 2004-05-10 | 2005-01-26 | 钢铁研究总院 | Economical air valve steel |
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Assignee: Advanced Steel Technology Co., Ltd. Assignor: Central Iron & Steel Research Institute Contract fulfillment period: 2007.12.15 to 2013.12.15 contract change Contract record no.: 2008990000611 Denomination of invention: High performance nickel saving gas valve alloy material Granted publication date: 20070321 License type: Exclusive license Record date: 2008.10.8 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2007.12.15 TO 2013.12.15; CHANGE OF CONTRACT Name of requester: ZHONGLIAN ADVANCED STEEL AND IRON MATERIALS TECHNO Effective date: 20081008 |