CN1218057C - High-temp Ni-Al self-lubricating material and preparation thereof - Google Patents
High-temp Ni-Al self-lubricating material and preparation thereof Download PDFInfo
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- CN1218057C CN1218057C CN 03125236 CN03125236A CN1218057C CN 1218057 C CN1218057 C CN 1218057C CN 03125236 CN03125236 CN 03125236 CN 03125236 A CN03125236 A CN 03125236A CN 1218057 C CN1218057 C CN 1218057C
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Abstract
The present invention provides a set of high-temperature self-lubricating Ni-Al alloy materials. The present invention is characterized in that a component graphite with lubrication action is added in the series of high-temperature self-lubricating Ni-Al alloy materials, and the series of high-temperature self-lubricating Ni-Al alloy materials are prepared by a smelting process. Each high-temperature self-lubricating Ni-Al alloy material is prepared from 4.33 wt% to 12.73 wt% of Ni, 3.5 wt% of Al and C as the rest; compared with an alloy material prepared by powder metallurgy sintering, the Ni-Al-graphite alloy material prepared from the Ni-Al-graphite alloy according to the proportion by the smelting process has the advantages of compact tissue, no cavity, no microcrack, close combination of graphite and the base, uniform distribution, etc., and therefore, the Ni-Al-graphite alloy material has good dynamic ductility, high strength, small friction coefficient and less capability of graphite desquamation in the wear process because of uniform and fine crystallized graphite distribution; the Ni-Al-graphite series alloys has high temperature strength and resistance to high temperature oxidation, which are the best of the properties of nickel-base alloys, and are ideal high-temperature self-lubricating materials; the smelting process has the advantages of simple production method, large once production quantity, low cost, capability of conveniently casting component parts of various shapes, etc.
Description
Technical field: the present invention relates to a kind of high temperature Ni-Al self-lubrication alloy and preparation method thereof, be applicable to self-lubricating bearing material, sliding material, pyrometallurgy machinery self-lubricating material, high temperature chemical machinery self-lubricating material and the high-temperature engine material of in high temperature oxidation and strong corrosive environment, working.
Technical background: Ni base alloy is the material of using as in the high temperature corrosive environments such as gas turbine blade, high-temperature engine, pyrometallurgy, high temperature chemical industry, high-temperature boiler always.Add component A l in Ni base alloy after, its resistance to high temperature oxidation and corrosion resistance nature further improve.Since late 1970s, with intermetallic compound Ni
3Al is the extremely World Focusing of new type high temperature material of representative, hot strength that it is superior and high temperature oxidation corrosion resistance performance are considered to have vital role in fields such as engine of new generation and high temperature chemical industry and metallurgy, and the maximum operation (service) temperature of this material can reach 1200 ℃.
In graphitiferous solid self-lubricant material, kinds such as pure graphite mould and metal/graphite be compound are arranged.Is not having under the dry friction and wear condition of oil lubrication, during the friction of pure graphite and most of metal parts, having low frictional coefficient, but that its shortcoming is a matter is crisp, intensity is low, shock resistance is poor that the wear loss of pure graphite bearing in the unit time is also big.After metallic substance and graphite are compound, can effectively overcome above-mentioned shortcoming.That has researched and developed at present has Cu-graphite, bronze-graphite, Ag-graphite, Al-graphite, Ni alloy-graphite, Fe-graphite, solid self-lubricant materials such as Zn-graphite, but above-mentioned materials mainly adopts powder metallurgy sintered method preparation, exist and engage not closely between graphite and the metallic matrix, Graphite Distribution is difficult for evenly, and graphite easily comes off in process of friction and wear, cause porous in the material, stopping property is poor, and impelling strength is lower, the preparation cost height of metal powder, preparation section is various, easily brings shortcomings such as oxide compound and impurity into.For density and the intensity that improves sintered metal product, some product also will be through repeatedly pressing sintering again.
Wherein Ni base-graphite solid self-lubricant material has resistance to high temperature oxidation preferably, advantage that erosion resistance is strong, and Ni alloy-graphite self-lubricating material of having reported at present all adopts powder metallurgy sintered method preparation.Niu Shuqin, the Pei of Zhu family, Ou Yangjinlin. the development of several high temperature self-lubricating composite materials and performance study. the tribology journal, 1995,15 (4): 324-332, Ni-Cr-graphite openly reported in one literary composition, Ni-Cr-Ag-graphite, Ni-Cr-PbO-Sb-graphite, preparation method and the composition and the performance of multiple solid self-lubricant materials such as Ni-Cr-SiC-graphite, the preparation method is with Ni, Cr, Ag, PbO, Sb, SiC, after powder such as graphite mix by a certain percentage, coldmoulding in mould, installing is then having the coil central authorities of vacuum Frequency Induction Heating, carries out Thermocompressed sintering and forming under the pressure condition of 1100 ℃-1250 ℃ and 10-25MPa.Wherein Ni-Cr-graphite series material at room temperature with the Mo-0.5Ti-0.08Zr alloy to the mill, coefficientoffriction is 0.37-0.46; Ni-Cr-Ag-graphite series material coefficientoffriction at room temperature is 0.32-0.43; Ni-Cr-PbO-Sb-graphite series material coefficientoffriction at room temperature is 0.35-0.43; Ni-Cr-SiC-graphite series material coefficientoffriction at room temperature is 0.30-0.32.The notched bar impact strength of above-mentioned all material is all at 1.02-3.76J/cm
2In the scope.Table 1 is the partial properties of Ni-Cr-Ag-graphite series alloy.Its result of study shows that along with the increase of content of graphite in the material, the density of material, hardness, impelling strength, ultimate compression strength all reduce, and frictional coefficient increases.The minimum value of frictional coefficient is 0.32, and its maximum impact toughness is less, and 2.88J/m is only arranged
2(* 10
4).This is the inevitable outcome that graphitiferous type mmaterial porous and tiny crack exist.
The object of the present invention is to provide and a kind of graphite is joined in the Ni-Al based high-temperature alloy by smelting process, it is even that acquisition has Graphite Distribution, and tight with matrix bond, frictional coefficient is little, the impelling strength height, the solid self-lubricant material of the novel anti high temperature corrosion-resisting that heat resisting temperature is high.And providing that a kind of to have production method simple. turnout is big. and cost is low. the preparation technology of convenient casting.Become the high-temp solid self-lubricating material not see any report with graphite by smelting method for preparing the Ni-Al alloy at present.
Summary of the invention: to achieve these goals, the invention provides one group of high-temperature self-lubrication Ni-Al alloy material, it is characterized in that having added in this series alloy the constituent element graphite with lubrication, the mass percent of alloy material set of dispense ratio is Ni-4.33～12.73%Al-3.5%C.
To achieve these goals, the preparation method's of above-described high-temperature self-lubrication Ni-Al alloy material step is as follows: (1). the pure plumbago crucible of heating melting crucibles, raw material employing purity is 99.8% electrolytic nickel, and purity is 98% commercial-purity aluminium, and purity is 99% Graphite Powder 99.(2). the configuration alloy compositions claims above-mentioned Ni, Al, graphite to join by ratio requirement.(3). with claiming the Graphite Powder 99 for preparing to be positioned over the bottom of vacuum medium frequency induction melting furnace smelting pot, the Ni piece for preparing is placed on it earlier, with claiming the aluminium block for preparing to be contained in the loading hopper, to be added.(4). before melting earlier with mechanical pump to extracting rough vacuum to 1.25 * 10 in the stove
-1Pa charges into argon gas to 1.01 * 10 then
5The Pa normal atmosphere is protected.(5). the melting Heating temperature was higher than 1650 ℃, to temperature back insulation 5-8 minute.(6). treat after the Ni-C liquid alloy reaction evenly again that with aluminium block by pouring in the loading hopper in the liquid alloy, after insulation 2-4 minute, powered-down pours into liquid alloy in the casting mold.
Adopt the Ni-Al-graphite alloy material of above-mentioned Ni-Al-graphite alloy and proportioning and smelting method for preparing to get everything ready fine and close in a organized way with respect to powder metallurgy sintered legal system, there is not the cavity, the non-microcracked tissue defects that waits, graphite and matrix bond are tight, advantage (seeing the metallographic structure photo of the Ni-Al-graphite alloy that Fig. 1～Fig. 3 provides) such as be evenly distributed, thereby the impelling strength of material, intensity is higher, because the crystalline Graphite Distribution is evenly tiny, graphite is difficult drop-off in wear process, coefficient of friction is little, Ni-Al-graphite is that the hot strength and the high temperature oxidation resistance of alloy is best in the nickel-base alloy, is a kind of comparatively ideal high temperature self-lubricating composite.It is simple that smelting process has production method, and a batch is big, and cost is low, can conveniently water advantages such as casting out the different shape part.
Description of drawings
Fig. 1. be that the Ni-12.73%Al-3.5%C alloy is atomic percent Ni
3The tissue topography of graphite in the Al-graphite alloy.
Fig. 2. be that the Ni-8.13%Al-3.5%C alloy is atomic percent Ni
5The tissue topography of graphite in the Al-graphite alloy.
Fig. 3 .Ni-4.33%Al-3.5%C alloy organizing pattern, i.e. atomic percent Ni
10Al-graphite alloy Ni
10The tissue topography of Al-graphite alloy.
Fig. 4. be the influence curve of aluminium content to Ni-Al-graphite alloy impelling strength.
Fig. 5. be Ni-Al-graphite alloy and 45# annealed steel dry friction and wear trial curve.
Fig. 6. be Ni-Al-graphite alloy and GCr15 bearing steel dry friction and wear trial curve.
Embodiment: the invention will be further described by embodiment and comparative example below in conjunction with accompanying drawing.
Embodiment 1. gets following proportioning components and the above-mentioned processing step of root a tree name prepares high temperature self-lubricating composite: (the atomic ratio concise representation is Ni to Ni-4.33%Al-3.5%C
3The Al-graphite alloy).
Embodiment 2. gets following proportioning components and the above-mentioned processing step of root a tree name prepares high temperature self-lubricating composite: (the atomic ratio concise representation is Ni to Ni-8.13%Al-3.5%C
5The Al-graphite alloy).
Embodiment 3. gets following proportioning components and the above-mentioned processing step of root a tree name prepares high temperature self-lubricating composite: (the atomic ratio concise representation is Ni to Ni-12.73%Al-3.5%C
3The Al-graphite alloy).
Comparative example
1.Ni-Al-the research of graphite alloy does not still have any report at present, in the various materials that document [1] is reported, the Ni-Cr-Ag-graphite material is more close with material of the present invention, and performance and the material of the present invention of therefore getting this material compare.Table 1 is the performance data of the Ni-Cr-Ag-graphite solid self-lubricating material reported of document [1].In order to investigate the friction and wear behavior between material of the present invention and the differentiated friction auxiliary material, adopt respectively the low 45# annealed steel (HRC=28) of high GCr15 bearing steel (HRC=58) of hardness and hardness as the dry friction and wear performance to mill material (in the document [1] report to mill material Mo-0.5Ti-0.08Zr hardness of alloy between the hardness of GCr15 bearing steel (HRC=58) and 45# annealed steel (HRC=28)).Obtain frictional coefficient and be respectively 0.13～0.40 and 0.15～0.40.This performance is lower in the Ni base-graphite alloy of having reported at present.Representative instance is as follows:
(1). (the atomic ratio concise representation is Ni to adopt Ni-4.33%Al-3.5%C
10The Al-graphite alloy) solid self-lubricant material of proportioning and GCr15 bearing steel are to mill, frictional coefficient is 0.15, with the 45# annealed steel to the mill, frictional coefficient is 0.13 (seeing Table 2), far below Niu Shuqin, the Pei of Zhu family, the friction co-efficient value (seeing Table 1) of Ni (Cr) alloy-Ag-graphite solid self-lubricating material 0.32 of people such as Ou Yangjinlin report.Frictional coefficient has reduced by 53% and 59% respectively.Also be lower than the frictional coefficient of other kind Ni base-graphite alloy.
(2). (the atomic ratio concise representation is Ni to adopt Ni-8.13%Al-3.5%C
5The Al-graphite alloy) solid self-lubricant material of proportioning and GCr15 bearing steel are to mill, frictional coefficient is 0.25, with the 45# annealed steel to the mill, frictional coefficient is 0.26 (seeing Table 2), be lower than Niu Shuqin, the Pei of Zhu family, the friction co-efficient value of Ni (Cr) alloy-Ag-graphite solid self-lubricating material 0.32 of people such as Ou Yangjinlin report, frictional coefficient has reduced by 20% approximately.
(3), adopting Ni-12.73%Al-3.5%C (is compound N i
3The Al-graphite alloy) solid self-lubricant material of proportioning and GCr15 bearing steel are to mill, frictional coefficient is 0.4 (seeing Table 2), with the 45# annealed steel to the mill, frictional coefficient is 0.4 (seeing Table 2), be higher than Niu Shuqin, the Pei of Zhu family, the friction co-efficient value (seeing Table 1) of the best values 0.32 of Ni (Cr) alloy-Ag-graphite solid self-lubricating material of people such as Ou Yangjinlin report, but the matrix of this alloy is fully by Ni
3The Al intermetallic compound is formed, its hardness height, and wear resistance is good, exceeds much than the hot strength and the high-temperature oxidation resistance of Ni (Cr) alloy-Ag-graphite self-lubricating material, also be that other material is beyond one's reach.Therefore this material performance self-lubricating function that can in hyperthermal environments, (be up to 1200 ℃), and keep high strength, this is the material science long-term aim.
2. with the Ni-Al-graphite alloy of the above-mentioned smelting method for preparing solid self-lubricant material with respect to the powder metallurgic method preparation, have dense structure, do not have tissue defects such as empty, non-microcracked, graphite and matrix bond be tight, be evenly distributed.
(1) Fig. 1 is Ni-12.73%Al-3.5%C alloy organizing pattern, i.e. atomic percent Ni
3The tissue topography of Al-graphite alloy.Al adds back insulation 3.5 minutes, is poured in the graphite mould mould, and crystalline graphite is pattern in the form of sheets, and the long-width ratio of graphite is about 8: 1, and is identical with II type graphite form in the graphitic cast iron.Remaining shred shape graphite is the eutectic graphite that changes in eutectic temperature subsequently.White base is Ni
3Al compound phase.Show and adopt smelting process successfully to obtain Ni
3Al/ graphite two-phase structure.Graphite Distribution is even, dense structure.Fig. 2 is the graphite structure pattern that adds the Ni-8.13%Al-3.5%C alloy of 8.13%Al in sense melt furnace, i.e. atomic percent Ni
5The Al-graphite alloy.Al adds back insulation 3 minutes, is cast in the graphite jig, and crystalline graphite is form in the form of sheets, and is identical with II type graphite form in the graphitic cast iron.White base is Ni (Al) sosoloid and Ni
3Two phase composites of Al compound.Graphite Distribution is even, dense structure.Fig. 3 is Ni-4.33%Al-3.5%C alloy organizing pattern, i.e. atomic percent Ni
10The Al-graphite alloy.Al adds back insulation 3 minutes, is poured in the graphite mould mould, and crystalline primary phase graphite is pattern in the form of sheets, and is identical with II type graphite form in the graphitic cast iron.White base is Ni (Al) solid solution alloy.Graphite Distribution is even, dense structure.
(2) the Ni-Al-graphite alloy solid self-lubricant material of smelting method for preparing have the advantage that dense structure, graphite and matrix bond are tight, be evenly distributed, thereby the impelling strength of material is higher.As the Ni-4.33%Al-3.5%C solid self-lubricant material of the present invention's development, impelling strength has reached 9.8J/cm
2(seeing Table 2), the impelling strength for preparing Ni (Cr) alloy-Ag-graphite alloy than the powder metallurgic method of having reported is high 2.5 times; The Ni-8.13%Al-3.5%C solid self-lubricant material of the present invention's development, impelling strength has reached 8.35J/cm
2(seeing Table 2), the impelling strength for preparing Ni (Cr) alloy-Ag-graphite alloy than the powder metallurgic method of having reported is high about 2 times; The intermetallic compound Ni of the present invention's preparation
3This hard brittle material of Al is after adding graphite, and its impelling strength is 2.3J/cm
2(seeing Table 2), identical with the impelling strength of the Ni alloy-Ag-graphite of powder metallurgic method preparation.
3. studies show that originally that the performance of Ni-Al-graphite series alloy has different performances along with the variation of Al content.Along with the increase of Al content, the hardness of material, intensity, wear resistance improve, and the content of graphite in impelling strength and the matrix decreases, and frictional coefficient increases to some extent.Therefore can select material according to working conditions.
(1). about 900 ℃-1200 ℃ for operating ambient temperature, the military service part that oxidation corrosion is serious can be selected Ni
3The Al-graphite alloy; The high temperature oxidation resistance of Ni-Al-graphite alloy is better than the high temperature oxidation resistance of other kind Ni base-graphite alloy, as with intermetallic compound Ni
3Al high temperature is the alloy of base mutually, and its use temperature can reach 1000 ℃-1200 ℃.This is because the adding of one side Al has strengthened the bonding force of matrix, has formed intermetallic compound Ni
3Al high temperature phase contains covalent linkage.Aluminium and oxygen have at high temperature generated the Al of one deck densification at alloy surface on the other hand
2O
3Film can stop the further generation of oxidation.Though the present invention does not provide the high temperature oxidation resistance data, the high temperature oxidation resistance of this material is putative already, and relevant research can obtain in other document.
(2). little for requiring frictional coefficient, 0.15～0.25, use temperature can be selected Ni at the alloy below 900 ℃ as the μ value
10Al-graphite alloy and Ni
5The Al-graphite alloy.
The performance of table 1 document [1] Ni alloy-Ag-graphite solid self-lubricating material
| Form wt% | Density g/cm 3 | Hardness HB/MPa | Impelling strength J/m 2(×10 4) | Crushing strength MPa | Coefficientoffriction in the time of 20 ℃ |
| Ni alloy: Ag: graphite=84: 10: 6 Ni alloy: Ag: graphite=80: 10: 10 Ni alloy: Ag: graphite=75: 10: 15 Ni alloy: Ag: graphite=73: 10: 17 Ni alloy: Ag: graphite=70: 10: 20 | 7.07 6.47 5.84 5.63 5.33 | 140 86 76 69 40 | 2.88 2.16 1.60 1.35 1.08 | 693 443 290 210 148 | 0.32 0.36 0.38 0.41 0.43 |
The performance of table 2 Ni-Al-graphite alloy solid self-lubricant material
| Form wt% | Density g/cm 3 | Hardness HB/MPa | Impelling strength J/m 2(×10 4) | Bending strength σ bb/MPa | Coefficientoffriction in the time of 20 ℃/45# steel/GCr15 | Abrasion loss kg/Nm (* 10 -11) |
| Ni-4.33％Al-3.5％C Ni-8.13％Al-3.5％C Ni-12.73％Al-3.5％C | 7.32 7.20 7.03 | 145 234 383 | 9.82 8.35 2.30 | 165 182.5 215 | 0.13 0.15 0.26 0.25 0.40 0.40 | 11.51 9.84 0.59 |
Although the present invention has done detailed explanation and exemplified out some object lessons, the present invention is not limited to these scopes, and the Ni-Al-graphite self-lubricating material of every employing smelting method for preparing all belongs to protection scope of the present invention.
Claims (2)
1, one group of high-temperature self-lubrication Ni-Al alloy material is characterized in that having added in this series alloy the constituent element graphite with lubrication, and the mass percent of this alloy material set of dispense ratio is Ni-4.33～12.73%Al-3.5%C.
2, the preparation method of the described one group of high-temperature self-lubrication Ni-Al alloy material of a kind of claim 1, its step is as follows:
(1). the pure plumbago crucible of heating melting crucibles, raw material employing purity is 99.8% electrolytic nickel, and purity is 98% commercial-purity aluminium, and purity is 99% Graphite Powder 99;
(2). the configuration alloy compositions claims above-mentioned Ni, Al, graphite to join by ratio requirement;
(3). with claiming the Graphite Powder 99 for preparing to be positioned over the bottom of vacuum medium frequency induction melting furnace smelting pot, the Ni piece for preparing is placed on it earlier, with claiming the aluminium block for preparing to be contained in the loading hopper, to be added;
(4). before melting earlier with mechanical pump to extracting rough vacuum to 1.25 * 10 in the stove
-1Pa charges into argon gas to 1.01 * 10 then
5Pa normal atmosphere protected;
(5). the melting Heating temperature was higher than 1650 ℃, to temperature back insulation 5-8 minute;
(6). treat after the Ni-C liquid alloy reaction evenly again that with aluminium block by pouring in the loading hopper in the liquid alloy, after insulation 2-4 minute, powered-down pours into liquid alloy in the casting mold.
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| CN101857925B (en) * | 2010-07-07 | 2011-07-13 | 哈尔滨工业大学 | Preparation method of ultrafine grained Ni-Al alloy |
| CN102041466B (en) * | 2010-07-30 | 2012-11-07 | 中国科学院金属研究所 | Preparation method of high-performance high temperature solid self-lubricating coating |
| CN107177758B (en) * | 2017-05-26 | 2019-02-19 | 东北大学 | A kind of metal-based self-lubricating composite material of fire-resistant oxidation resistant and preparation method thereof |
| CN111020297A (en) * | 2019-12-18 | 2020-04-17 | 陕西易莱德新材料科技有限公司 | Nickel-chromium alloy material and preparation method thereof |
| CN114293133B (en) * | 2021-12-31 | 2022-11-04 | 西安交通大学 | Spraying material of wide-temperature-range self-lubricating coating, preparation method and application thereof |
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