CN1818117A - Self-lubricating heat-resistnat and wear-resistant materials - Google Patents
Self-lubricating heat-resistnat and wear-resistant materials Download PDFInfo
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- CN1818117A CN1818117A CN 200610057539 CN200610057539A CN1818117A CN 1818117 A CN1818117 A CN 1818117A CN 200610057539 CN200610057539 CN 200610057539 CN 200610057539 A CN200610057539 A CN 200610057539A CN 1818117 A CN1818117 A CN 1818117A
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Abstract
The invention opened a heat-proof and wearing self-lubricating material. It can be used to the shafting bearing, bearing bush, axile bush and the other break-away friction parts of the metallurgy, mining area and machine, especially for the parts of the high temperature (350 DEG C-800 DEG C).the weight ration of the composition is C 2.6-3.%, S 0.35-0.49%, Si 0.5-1.0%, Cr 18-35%, Mo 0.8-1.5%, Cu 0.8-1.2%, Al 1.5-5.0%, V 0.1-0.25%, B 0.05-0.15%, RE 0.008-0.08%, P<=0.3%, Ni<=0.3%, Mn<=0.3%, the residue is Fe. The weight ratio of Cr/C is 5.5-10. The material has the good resistance to heat and wearing character, also it can resist the corrosion of the CO2 and SO2.
Description
Technical field
The invention belongs to metal self-lubricating material field, this self-lubricating material is applicable to the sliding friction parts of making bearing, bearing shell, axle sleeve and other kinds in the fields such as metallurgy, mine, machinery, is specially adapted to be manufactured on (350 ℃-800 ℃) employed heat-resistant antifriction self-lubricating material of military service component under the hot conditions.
Background technology
The industrial part of being on active service in industries such as metallurgy, machinery, mine is often because temperature height, load weight, dust pollution and oxidation have seriously influenced its life cycle greatly, particularly add difficulty at some high temperature greases (fat), refrigerating unit lost efficacy and the disadvantageous position of repair and maintenance, because the wearing and tearing of wearing piece can directly have influence on continuous production operating efficiency and quality product.
The material that is used to now to make bearing class wearing piece in the industries such as metallurgy, machinery, mine mainly contains GCr15 bearing steel, mmaterial and high-sulfur alloy steel material (chemical ingredients sees table 2 for details).Wherein GCr15 makes bearing (watt, cover) to wait the most general bearing steel material of wearing piece use at present.But this material is owing to must adopt the mode of grease lubrication to be lubricated, when working temperature reaches wearing piece self temperature to be higher than lubricating grease charing point temperature, lubricating oil generation charing, form a large amount of charing particles, the abrasive wear mode is changed into by border (or fluid) friction mode in the friction piece surface, frictional coefficient increases sharply, and causes the wearing piece running to be lost efficacy.And the bearing wearing piece that the mmaterial of introducing in the table 2 is made is applicable to that envrionment temperature uses below 500 ℃, use the identical use position of GCr15 material bearing now, such material has self-lubricating property (frictional coefficient is low) when short-term is used, but can appearring in wearing piece very soon that use such material to make under heavily loaded working conditions, abrasion loss increases, friction gap excess is because unbalance stress causes wearing piece to be lost efficacy by conquassation; Under the hot operation condition, MoS in the wearing piece that this material is made
2Can't obtain continuous supplementation Deng solid lubricant after separating out, the high temperature lubricating degradation, the surface enters metal to-metal contact because of promote the oxidation, so such material is shorter work-ing life.Another kind of high-sulfur alloy steel (major ingredient sees table 2 for details) according to relevant document introduction, when being used for the identical use of the wearing piece position of GCr15 material manufacturing, the high-sulfur sulfide that himself forms can be as solid lubricant, have and more significantly reduce the material friction coefficient acting, but such material bearing is discontinuous at fully loaded transportation condition lower surface solid lubricant film, and very fast surpassing of wearing clearance used design load; When using under hot conditions, the surface is easily oxidized, causes frictional coefficient to increase; Using such material to make wearing piece in addition needs bigger initial designs tolerance and running starting power, is not suitable for and makes accurate anti-friction bearing spare.
Summary of the invention
The object of the present invention is to provide a kind of more heat-resistingly, and have higher high temperature strong hardness, good wear-resisting and antifriction performance, high-temperature oxidation resistance and anti-industrial gasses (CO
2, SO
2Deng) corrosive nature, the self-lubricating material of long service life.
According to above-mentioned purpose, technical scheme of the present invention is:
Material of the present invention is to have designed a kind of conventional cast iron that is different from, but heat-resisting, the wear resistant alloy cast material that contain multiple High-Temperature Strengthening phase, wear-resisting phase, antifriction phase element and have the high-temperature self-lubrication function, it has excellent comprehensive performances under abominable working condition, finally reach to improve the material purpose in work-ing life.The basic ideas that design this alloy according to this purpose are by strengthening basic phase, add trace alloying element, improving the intensity under hot conditions of material self; Add by the antifriction element under the condition of hot strength guaranteeing, reduce the frictional coefficient of material and reach the purpose of material wear-resistant damage.
According to above-mentioned purpose and technical scheme, the concrete chemical ingredients of self-lubricating material of the present invention is formed (weight %) and is:
C 2.6-3.3%, S 0.35-0.49%, Si 0.5-1.0%, Cr 18-35%, Mo 0.8-1.5%, Cu 0.8-1.2%, Al 1.5-5.0%, V 0.1-0.25%, B 0.05-0.15%, RE 0.008-0.08%, P≤0.3%, Ni≤0.3%, Mn≤0.3%, Yu Weitie; Wherein the Cr/C weight ratio is 5.5-10.
The other technical scheme of the present invention is: the Cr/C weight ratio is 5.8-7.
The chemistry of above-mentioned each element is according to being: C (W%, down together) and Cr are the principal elements of this material structure of decision and performance, studies show that at M
23C
7, M
7C
3, M
3In the carbide of C several types, M
7C
3The type carbide is (the close-packed hexagonal dot matrix is strip and distributes) to have higher matrix strong hardness and fastness to wear.M
3C type carbide reticulates distribution, the reduction crystal boundary, and hardness is lower, and the abrasion resistance of material and toughness are descended thereupon.And M
23C
7The type carbide generally can form the sclerosis phase in the matrix, but in friction process, is easy to peel off from matrix.Therefore be mainly M for the wear-resisting phase (carbide) that this material is formed
7C
3Type, the Cr/C weight ratio should be controlled between the 5.8-7, and control M
3C type (cementite carbide size) increase M
3C will reduce and increase gradually usually with the Cr amount.
The control of carbide amount and carbide type plays crucial effects to the wear resisting property of this material, the simple carbon content raising matrix carbide amount that increases will make the chromium concn in the matrix reduce, cause material hardening capacity to descend, the back remained austenite content that quenches increases, and carbide is to M
3The structural changes of C type.So when selecting C, Cr content, must consider the chromium concn and the Cr/C ratio of carbide amount (wear resistance and toughness reguirements according to component are decided), matrix simultaneously.Cr/C is also higher than high matrix Cr concentration, and when the Cr/C ratio was 8-10, the chrome content in the matrix was about 12%--15%; For with martensite be the base cast alloy iron take off steady processing before, the Cr/C ratio should remain on more than 5.5 in the matrix.This material is can directly obtain high performance heat-resisting, high-abrasive material by adding the reinforced alloys element under as cast condition on the basis of matrix obtaining with martensite; When chromium content is brought up to more than 25%, the Cr/C ratio is 10 o'clock, can obtain to contain the rich chromium austenite of chromium about 15% behind the foundry goods air cooling, thereby makes matrix obtain good wear resisting property, toughness and high-temperature oxidation resistance.
Usually the matrix be made up of less carbide of colony and austenite of hypoeutectic structure mutually, in this material produce, should avoid bigger eutectic structure of colony and hypereutectic tissue occurring, studies show that: when chrome content improves within the specific limits in the matrix colony diameter diminish; When chromium content was constant, solidification rate reduced, and the colony diameter increases, and the shock resistance of material descends, thus should control the Cr/C ratio in process of production, and by adding complex element control solidification rate.When occurring eutectic and hypereutectic organizing in such material, be unfavorable for making the component that bear heavier shock load.In the manufacturing processed of the component that bear heavier load, the carbide amount in the body material can be selected between 20% to 28%; In bearing the component making processes of high impact loads, should reduce the carbide amount again.When the carbide amount reaches 35% when above, the toughness of material will descend.
Residual austenite is one of essentially consist phase in this material microstructure, it is generally acknowledged that residual austenite has that original hardness is low, characteristics such as good toughness, work hardening capacity are strong, its relative content has very important influence to the mechanical property and the resistance to abrasion of material, can be in the material composition design according to of the interpolation of different industrial and mineral conditions, with reference to Henin formula (martensitic cast iron M by C, Cr and other alloying element
sPut relation with chemical ingredients) calculate and the control residual austenite content.This material can obtain 15% to 38% residual austenite before thermal treatment.Residual austenite as softening phase, can alleviate the impact of external force to carbide in the matrix, prolong the time that carbide fracture takes place and comes off, simultaneously can avoid matrix and carbide junction crackle to occur, therefore under the situation of industrial and mineral conditions permit, increase the anti impact wear-proof that remained austenite content can improve material.The ratio that remained austenite content accounts for matrix directly influences the hardness of material matrix.The original structure of material is heated to M in actual production process
sThe part residual austenite was changed the effect of martensite generation secondary hardening into when the above temperature of point was cooled off, and had improved the hardness and the wear resistance of matrix.
Mo can effectively improve the hardening capacity of material, and for wear-resistant material, hardening capacity is the important process character of material.Material of the present invention is in order to improve fastness to wear, and therefore fully sclerosis under the condition of avoiding cracking adds molybdenum.In the hypoeutectic structure of this material, the molybdenum amount that contains of matrix is about alloy and always contains 10% to 25% of molybdenum amount.Molybdenum forms the molybdenum carbon compound in this material, its primary structure is Mo
2Compound between C and iron molybdenum.Molybdenum carbon compound hardness is very high, can effectively improve the wear-resistant grinding abrasion ability of matrix.Molybdenum can also effectively improve M
sThe point temperature reduces remained austenite content in the room temperature.Increase contains the martensite foundry goods equivalent depth increase that the molybdenum amount can make air cooling obtain, and this has higher practical value to thick big foundry goods.
Add Cu in the material of the present invention and be in order to cooperate the Mo element effectively to improve hardening capacity, and by the compound raising matrix of molybdenum copper strong hardness at high temperature.Studies show that: when Cu content reaches more than 0.5% to 1.0% the time, can the refinement carbide particle, it is more evenly distributed in matrix; Improve the hardening capacity of material, promptly to the useful influence of this material production; Copper is antifriction material, can improve the self-lubricating property of material, and effectively reduces the abrasive wear degree.When add-on surpassed 1.2%, effect weakened to the matrix microstructure thinning, increased with Cu content and formed soft phase, and matrix hardness descends on the contrary, generation is unfavorable for the effect of resistance to abrasion.
The purpose of adding Si in the material of the present invention is to reduce the oxidational losses of alloying elements such as chromium, vanadium, reduces the eutectic reaction temperature range, makes eutectic carbides become comparatively tiny and disperseization; Silicon reduces the eutectic carbon content, thereby matrix carbide amount is increased; Si helps to improve the hardness of martensite transformation product especially, when hypoeutectic alloy cast iron silicon content improves, will help M
7C
3The type compound increases.Studies show that when silicon content greater than 1% the time, will increase the fragility of material.
At Cr, Al is in the alloy material, when Al content greater than 4% the time, high temperature oxide film is mainly by Al
2O
3Form; When chromium is above greater than 15%, then form with Cr
2O
3Be main oxide film, also have higher oxidation-resistance,, then can better bring into play its antioxygenation if Cr, Al comprehensively use.(800 ℃) alloy surface forms firm alumina film under hot conditions, with the matrix metal mortise, and can be out of shape with matrix metal, plays the provide protection to matrix.Aluminium has the ability that forms high compactness and thermal oxidation resistance film than chromium greatly, therefore, adds a spot of aluminium in alloy of the present invention the resistance of oxidation of chromium is greatly improved, and the effect of equivalent aluminium is equivalent to the effect of 10 times of chromium.
Add micro-V and help generating V
2Secondary reinforced depositions such as C and VC improve the resistance to abrasion of material mutually.At high temperature the pinning effect of secondary reinforced deposition relative material crystal boundary can effectively improve the material at high temperature strong hardness.Add V and can also substitute Cr formation double carbide, thereby increase the chrome content in the matrix.
Add micro-B and can form ceramic particle in the matrix, improve matrix hardness, pertinent data is introduced boron and is had the effect that intensive is strengthened crystal boundary, can effectively suppress excessively growing up of crystal boundary under the high temperature, improves the high temperature abrasion resistance of material.
Add micro-Re and can obviously improve the shape of inclusion in the material, the interpolation of material middle-weight rare earths element of the present invention can make compound rare-earth sulfide be spherical, helps forming the antifriction phase.Rare earth can impel plate martensite to change to lath martensite.But the primary grain of rare earth refinement material improves the enrichment situation of crystal boundary place harmful element, makes material obtain fine and close fine grained texture; But rare earth is cleaning molten steel and improve its flowability also, thereby improves the quality of foundry goods.
Mn is the intensive austenite former, and material of the present invention is controlled at manganese content below 0.3% in order to obtain the martensitic matrix tissue.The affiliation that adds of manganese impels σ to separate out mutually; Manganese is the principal element that forms harmful inclusion in the material of the present invention, under the high temperature heavy load condition, easily forms formation of crack.The increase of manganese content can reduce the antioxidant property and the high-temperature gas corrosive nature of material.Because the adding of manganese and the S in the steel form the harmful inclusion of MnS, and consume in the steel for improving the lubricated S element that adds of antifriction, so the adding of control manganese in the material of the present invention.
Ni is valuable and rare metal, in order to reduce the cost of material, makes more economical being suitable for of component of making, and nickel content is the remaining nickel content in the steel-making selected materials in the material of the present invention.
S is the important interpolation element of in the material of the present invention.It is generally acknowledged in the material and should strictly control sulphur and sulfide, because sulphur and sulfide can have a negative impact to machinery, mechanics and other performance of material; But S also is the main adding elements in the free-cutting steel, because the effect of S makes its finished surface have self lubricity.In recent years some studies show that sulfide is a kind of good self-lubricating solid phase, and the adding by S in this investigation of materials forms MoS
2And compound rare-earth sulfide, its intensive hexagonal laminate structure can be used as a kind of self-lubricating solid phase, has good self-lubricating ability, particularly the fine metal particle lubricated granules that at high temperature forms between the friction idol can make the antifriction performance of material improve greatly, frictional coefficient reduces, thus the wear-resisting life cycle that has prolonged material.The sulphur content of determining in this material is 0.35% to 0.49%, smelting process and testing data show when sulphur content in the steel greater than 0.5% and the foundry goods type of cooling can not occur directly influencing the mechanical property of component in the cast structure at that time along grain-boundary crack.Sulfide in the material of the present invention is to be the polynary sulfide of base with moly-sulfide, iron, comprises chromic sulfide (Cr
3S
4), vanadium sulfide (VS) and three the sulfuration two aluminium (Al
2S
3) etc., its different tissues structure awaits further in depth studying to the antifriction of material, the influence of wear resisting property respectively.
The smelting technology of material of the present invention and conventional cast iron smelting technology are similar, comprise batching, smelt and cast three parts.Carrying out material in 500 kilograms of induction furnaces smelts and cast molding.This material can be according to the direct moldings formed therefrom of the design of bearing and wearing piece.The major ingredient of smelting is in proper order: the pig iron-steel scrap-ferrochrome-molybdenum-iron-electrolytic copper-ferrosilicon-electrolytic aluminum and slotting aluminium deoxidation, sulphur, rare earth are handled in the bag.Tapping temperature: 1550-1560 ℃; Pouring temperature: 1450-1460 ℃; The control casting rate.Casting is incubated die sinking after 5 to 8 hours after finishing.The casting gold phase constitution is martensite+carbide+residual austenite, HRC 〉=50.
Heat-resistant antifriction self-lubricating material of the present invention is compared with prior art more heat-resisting and have higher high temperature strong hardness, good wear-resisting and antifriction performance, high-temperature oxidation resistance and an anti-industrial gasses (CO
2, SO
2Deng) corrosive nature, the advantage of long service life.Specific as follows: material of the present invention is reasonably to have added C and Cr (determining different Cr/C ratios according to different industrial and mineral conditions) in the pig iron, forms body material; Utilize the compound action of Mo/Cu and add the high temperature strong hardness that V improves body material; Control carbide type is to guarantee strong hardness and the wear resistance of body material in the differing temps interval.By adjusting the ratio of C, Cr and other element, the content of control residual austenite is to guarantee the strong hardness and the shock resistance of material.By adding the sulfide (Cr that S forms
3S
4, VS, Al
2S
3) and compound rare-earth sulfide, improve the lubricity of material mutually as antifriction, reduce since frictional wear to the loss of material; By adding high temperature strong hardness and the antioxidant property that Al, Cu improve material, reduce the high temperature abrasive wear degree as antifriction material simultaneously, improve the work-ing life of material; By adding B and Re strengthening material crystal boundary, suppress material excessively growing up of crystal grain at high temperature, thereby guarantee having stable high-temperature performance of material, the compound rare-earth sulfide of formation helps improving the antifriction performance under the material at high temperature; Because the interpolation of S in the material, for avoiding forming too much MnS inclusion, material of the present invention is controlled at Mn content below 0.3%; Ni resource scarcity and costing an arm and a leg in order to reduce the cost of material, makes more economical being suitable for of component of making, and the nickel content of material of the present invention is the remaining nickel content in the selected materials in the steel-making.
Embodiment
According to chemical ingredients according to the present invention form with to the similar smelting technology of conventional cast iron smelting technology: comprise batching, smelt and cast three parts.Carrying out material in 500 kilograms of induction furnaces smelts and cast molding.This material can be according to the direct moldings formed therefrom of the design of bearing and wearing piece.The major ingredient of smelting is in proper order: the pig iron-steel scrap-ferrochrome-molybdenum-iron-electrolytic copper-ferrosilicon-electrolytic aluminum and slotting aluminium deoxidation, sulphur, rare earth are handled in the bag.Tapping temperature: 1550-1560 ℃; Pouring temperature: 1450-1460 ℃; The control casting rate.Casting is incubated die sinking after 5 to 8 hours (the casting gold phase constitution is martensite+carbide+residual austenite) and has prepared 5 batches of self-lubricating materials after finishing.In order to contrast conveniently, the bearing of material manufacturing of the present invention and the bearing of GCr15 material manufacturing, the bearing of typical mmaterial manufacturing and the service condition of bearing in industrial machinery of high-sulfur alloy steel manufacturing are compared simultaneously.Wherein, table 1 is the chemical composition table (weight %) of the embodiment of the invention, table 2 is the main chemical composition table (weight %) of material in the prior art, table 3 is material property embodiment of the present invention and prior art material correlated performance contrast table, and table 4 is the bearing of embodiment of the invention preparation and the on-the-spot service condition contrast table of bearing industry of other materials preparation.Sequence number 1-5# is the embodiment of the invention in the above-mentioned tabulation, and 6-8# is a prior art material contrast example.
The chemical composition table (weight %) of table 1 embodiment of the invention
Material main chemical compositions table in table 2 prior art
| Sequence number | The element steel grade | C | Si | Cr | Ni | Mn | P | S | Mo | Cu | Co | Fe | Remarks |
| 6# | The GCr15 bearing steel | 0.95-1.05 | 0.15-0.35 | 1.40-1.65 | ≤0.30 | 0.25-0.45 | ≤0.025 | 0.025 | ≤0.10 | ≤0.30 | Surplus | B00150 | |
| 7# | A kind of powder metallurgy self-lubricating material | 3-15 (graphite) | 1-3 | 2-7 | 3-6 (ferrophosphorus) | 2-5 molybdenumdisulphide | 2-7 | 5-30 (bronze) | Surplus (iron powder) | Nonstandard | |||
| 8# | A kind of high-sulfur alloy steel | 0.30-0.45 | 1.0-1.5 | 10-15 | 5-8 | 0.5-1 | 0.30 | 0.5-11 | 1.5 | 2 | 1-2 | Surplus | Nonstandard |
Table 3 self-lubricating material performance of the present invention embodiment and prior art material correlated performance contrast table
| Performance materials | Tensile strength sigma b/MPa | Hardness | Coefficientoffriction | Lubricating system |
| The GCr15 bearing steel | 588-716 (780 ℃ of annealing) | HRC60 (quenching) | 0.02-0.04 | Grease lubrication |
| Mmaterial | 250-340 | HB195-255 | 0.15-0.12 | Self-lubricating solid |
| High-sulfur alloy steel | HRC20-25 | 0.1-0.2 | Self-lubricating solid | |
| Material of the present invention | 950-1000 (slow cooling) | HRC52-55 | 0.06-0.1 | Self-lubricating solid |
The on-the-spot service condition contrast table of the bearing of table 4 embodiment of the invention preparation and other types bearing industry
Claims (2)
1, a kind of heat-resistant antifriction self-lubricating material is characterized in that the concrete chemical ingredients composition weight % of this self-lubricating material is: C 2.6-3.3%, S 0.35-0.49%, Si 0.5-1.0%, Cr 18-35%, Mo 0.8-1.5%, Cu 0.8-1.2%, Al 1.5-5.0%, V 0.1-0.25%, B 0.05-0.15%, RE 0.008-0.08%, P≤0.3%, Ni≤0.3%, Mn≤0.3%, Yu Weitie; Wherein the Cr/C weight ratio is 5.5-10.
2, heat-resistant antifriction self-lubricating material according to claim 1 is characterized in that the Cr/C weight ratio is 5.8-7.
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| CN105779863B (en) * | 2016-04-15 | 2018-01-05 | 芜湖德业摩擦材料有限公司 | A kind of preparation method of coating abrasion-proof bearing bush |
| CN108331838A (en) * | 2016-08-26 | 2018-07-27 | 杨帆 | A kind of self-lubricating internal combustion engine bearing |
| CN109514192A (en) * | 2018-11-19 | 2019-03-26 | 贵阳华丰航空科技有限公司 | A kind of corrosion-resistant screw processing and forming technology of aircraft utilization |
| CN109514192B (en) * | 2018-11-19 | 2020-06-23 | 贵阳华丰航空科技有限公司 | Machining and forming process for corrosion-resistant screw used for airplane |
| CN115369319A (en) * | 2022-08-05 | 2022-11-22 | 张家口三信同达机械制造有限公司 | Weldable high-strength high-toughness wear-resistant material and heat treatment process thereof |
| CN115369319B (en) * | 2022-08-05 | 2023-08-29 | 张家口三信同达机械制造有限公司 | Weldable high-strength high-toughness wear-resistant material and heat treatment process thereof |
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