CN101486098B - Method for preparing high-hardness wear-resistant powder metallurgical rolling sleeve - Google Patents
Method for preparing high-hardness wear-resistant powder metallurgical rolling sleeve Download PDFInfo
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Abstract
The invention relates to a method for preparing a high-hardness abrasion-resistant powder metallurgic roller sleeve, which is characterized in that the method adopts powder metallurgic technology for manufacture, and comprises the following steps: firstly, powder mixing, namely mixing iron powder, carbon powder, chromium powder or ferrochrome powder and a lubricant, and guaranteeing that the total composition comprises the following components in percentage by weight: 0.3 to 2 percent of carbon, 0.3 to 4 percent of chromium, not more than 2 percent of unavoidable impurities, and the balance being iron; secondly, forming, wherein the density after forming is more than 6.8g/cm<3>; thirdly, sintering; fourthly, machine processing; fifthly, quenching; sixthly, cold treatment; and seventhly, tempering. Compared with the prior art, the method has the advantages that the product mainly comprises the iron, the carbon and the chromium and does not comprise noble metal element such as nickel, molybdenum and tungsten, so that the cost is low; the mechanical properties such as the tensile strength, the hardness and the microhardness of the product are superior to those of products obtained bycasting technology; and both the thermal diffusivity and the thermal conductivity of the product are lower than those of the products obtained by the casting technology.
Description
Technical field
The present invention relates to a kind of method for preparing high-hardness wear-resistant powder metallurgical rolling sleeve, also can be applied to the axle sleeve field.
Background technology
Fields such as roll sleeve or axle sleeve extensive use compressor, pump, lathe, electric tool, automobile, it requires high strength, high rigidity, high-wearing feature.Roll sleeve or axle sleeve can adopt the alloy of casting to make, but alloying element contains precious metal elements such as nickel, molybdenum, referring to Chinese invention patent: ZL200410090214.9, a kind of " iron-based self-lubricating wear-resistant alloy " (Granted publication number: CN1276116C) is disclosed, the alloy material that this patent system gets has high-wear resistance and can be used for preparing roll sleeve or axle sleeve, but precious metals such as content nickel, molybdenum and tungsten in the raw material, and by melting, casting method production, its cost is high, has had a strong impact on its market competition.
The low alloy ferrous powdered metallurgical material of employing is also arranged, and this material generally also all contains alloying elements such as a large amount of molybdenums, vanadium, tungsten, chromium, cobalt and nickel, and the alloying element total amount belongs to high-alloy steel greater than 10%.Because international demand is vigorous, metal prices such as molybdenum, tungsten and nickel skyrocket in recent years, no matter be that traditional casting or low alloy ferrous powdered metallurgical material all directly causes the cost of raw material to rise.In order to solve cost of raw material problem, be necessary the low alloy material of developing low-cost.Powdered metal parts is a porous part again, and the existence of hole has reduced the macrohardness and the intensity of material, so the performance of general powder metallurgical rolling sleeve or axle sleeve is difficult to reach the instructions for use of compressor, pump, lathe, electric tool, automobile etc.
Open low cost, high performance powdered metallurgical material, and apply it on the axle sleeve of roll sleeve or like, the crucial consumption that will reduce precious metals such as molybdenum in the material, tungsten, nickel, but also need provide suitable technological requirement to solve powdered metal parts porous problem.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of low cost, method for preparing high-hardness wear-resistant powder metallurgical rolling sleeve at the above-mentioned state of the art.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: this a kind of method for preparing high-hardness wear-resistant powder metallurgical rolling sleeve, it is characterized in that adopting the powder metallurgical technique manufacturing, and specifically in turn include the following steps:
1. mix powder, with iron powder, carbon dust, chromium powder or ferrochrome powder, and mix lubricant, and guarantee percent by weight content in total component of iron, carbon, chromium: carbon is 0.3～2%, chromium is 0.5～4%, lubricant 0.1～2% is no more than 2% inevitable impurity, and surplus is an iron;
2. be shaped, the back density that is shaped is greater than 6.8g/cm
3
3. sintering, temperature is 1000～1350 ℃, the time is at least 20 minutes;
4. machined to being difficult to by bearing of die, adopts machining mode to handle;
5. quench, temperature is 800～950 ℃, and the time is 10～120 minutes;
6. cold treatment is quenched and is carried out in back 24 hours;
7. tempering, 170～300 ℃ of temperature, the time is 2～4 hours.
As preferably, step 1. in, percentage composition in total component of iron powder, carbon dust, chromium powder: carbon is 0.6%, chromium is 1.8%, lubricant 0.6% is no more than 2% inevitable impurity, surplus is an iron.
As preferably, step 1. in, described iron powder adopts atomized iron powder, carbon content is less than 0.02% in this atomized iron powder, oxygen content is less than 0.2%, compressibility under 490.3MPa greater than 6.9g/cm
3Described carbon dust adopts carbon content greater than 99% graphite powder or carbon black, and this graphite powder or carbon black ash content be less than 1%, and at least 90% particle diameter is less than 4 microns.Described lubricant adopts stearate or wax.
As preferably, step 3. in, the temperature of described sintering is 1150～1350 ℃.
As preferably, step 6. in, described cold treatment adopts temperature to be lower than subzero 60 ℃ industrial refrigerator, 20～300 minutes cool times, or in the liquid nitrogen environment, 5～120 minutes cool times.
Compared with prior art, the invention has the advantages that: mainly form, do not contain precious metal elemental nickel, molybdenum, tungsten etc. with iron, carbon and chromium, with low cost; Mechanical performance such as tensile strength, hardness, microhardness and casting technique products obtained therefrom are also superior, and thermal diffusion coefficient and thermal conductivity factor all than casting technique products obtained therefrom come low.Products obtained therefrom thermal coefficient of expansion of the present invention and all Application of composite requirements of dimensional stability also have HV in the products obtained therefrom structure of the present invention
0.01Surpass 2100 precipitation type carbide, the present invention also can be applied on the axle sleeve of high rigidity excellent abrasive resistance.。
Description of drawings
Fig. 1 is the cross-sectional view of roll sleeve.
Fig. 2 is the metallographic structure microphoto without cold treatment.
Fig. 3 is the metallographic structure microphoto through cold treatment.
Fig. 4 is the metallographic structure microphoto at casting technique roll sleeve edge.
Fig. 5 is the metallographic structure microphoto of casting technique roll sleeve heart portion.
Fig. 6 is the metallographic structure microphoto at embodiment roll sleeve edge.
Fig. 7 is the metallographic structure microphoto of embodiment roll sleeve heart portion.
Fig. 8 is the metallographic structure microphoto that the embodiment roll sleeve further amplifies.
Fig. 9 is the thermal coefficient of expansion (12.8472*10 of casting technique roll sleeve
-6) coordinate diagram.
Figure 10 is the thermal coefficient of expansion (12.2497*10 of embodiment roll sleeve
-6) coordinate diagram.
The specific embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
Embodiment: the method for preparing high-hardness wear-resistant powder metallurgical rolling sleeve in the present embodiment, adopt the powder metallurgical technique manufacturing, specifically in turn include the following steps:
1. mix powder, with iron powder, carbon dust, chromium powder or ferrochrome powder, and mix lubricant, and guarantee percent by weight content in total component of iron, carbon, chromium: carbon is 0.3～2%, chromium is 0.5～4%, lubricant 0.1～2% is no more than 2% inevitable impurity, and surplus is an iron;
2. be shaped, the back density that is shaped is greater than 6.8g/cm
3
3. sintering, temperature is 1000～1350 ℃, is preferably 1150～1350 ℃, the time is at least 20 minutes;
4. machined to being difficult to by bearing of die 100 (as shown in fig. 1), as mounting groove etc., adopts machining mode to handle, and machined can be for car, mill, grinding, brill, boring etc.;
5. quench, temperature is 800～950 ℃, and the time is 10～120 minutes;
6. cold treatment is quenched and is carried out in back 24 hours;
7. tempering, tempering insulation time is relevant with the thickness of product, 170～300 ℃ of temperature, the time is 2～4 hours.
Wherein, the step of present embodiment 1. in, percentage composition in total component of iron, carbon, chromium: carbon is 0.6%, chromium is 1.8%, lubricant 0.6% is no more than 2% inevitable impurity, surplus is an iron.Iron powder adopts atomized iron powder, and carbon content is less than 0.02% in this atomized iron powder, and oxygen content is less than 0.2%, compressibility under 490.3MPa greater than 6.9g/cm
3, carbon dust adopts carbon content greater than 99% graphite powder or carbon black, and this graphite powder or carbon black ash content be less than 1%, and at least 90% particle diameter is less than 4 microns, and described lubricant adopts stearate or wax.Step 6. in, cold treatment adopts temperature to be lower than subzero 60 ℃ industrial refrigerator, 20～300 minutes cool times, or in the liquid nitrogen environment, 5～120 minutes cool times.Mixed powder can carry out in the bipyramid batch mixer, and incorporation time is 60～90 minutes.
Step 2. in, be shaped to adopt common press.Green density has very big influence to the heat treatment and the sintering hardness of product.Density is 6.8g/cm
3Pressed compact, hardness only is HRB50 behind the sintering, and 7.1g/cm
3Pressed compact then be HRB73.7.1gcm after the heat treatment
3The pressed compact of pressed compact up to HRC50,6.8g/cm
3Only be HRC43.Shaping density is 6.7～7.3g/cm
3Density needs temperature and pressure or other modes to suppress greater than the shaping of the roll sleeve of 7.1g/cm3.Be compressed to the ordinary powder forming press in the present embodiment, shaping density is 7.0～7.1gcm
3, the pressure of shaping is 630MPa.
Step 3. in, sintering can adopt vacuum drying oven, meshbeltfurnace, push rod furnace or other sintering furnaces.Sintering atmosphere can be vacuum, nitrogen-based atmosphere, hydrogen etc., but can not use heat absorptivity atmosphere or exothermicity atmosphere.During sintering product is placed on guipure or the backing plate just passable.
Sintering temperature is directly connected to the inherent quality of powder metallurgy product.Heat treatment hardness, sintered density and sintering temperature influence are little, almost in same level.Influence not quite is more or less the same mainly due to the carbon content and the density of final products sintering temperature to heat treatment hardness.Sintering temperature mainly is the impact flexibility (ballistic work) of tensile strength and material to the parameter of performance impact maximum.Increase tensile strength and all significantly increases of ballistic work along with sintering temperature.Ballistic work is 5.9J during 1000～1150 ℃ of normal temperature sintering, is increased to 12J during 1150～1350 ℃ of high temperature sinterings, has increased by 103%, is 455MPa during tensile strength normal temperature sintering, and high temperature sintering is 619MPa then, has increased by 36%.
The raising of sintering temperature is strengthened in the diffusion of atom at high temperature the main mountain of the improvement of tensile strength and impact flexibility, has promoted sintering process, forms more bigger sintering necks.High temperature sintering is to improve intensity to get important measures.By high temperature sintering, can make a part of oxide reduction, improve the diffusion rate of atom, increase homogeneity of ingredients, can make the abundant nodularization of hole, the hole spacing is bigger.
The temperature of normal temperature sintering is 1000～1150 ℃, and best 1120 ℃, sintering time is at least 20 minutes.Present embodiment adopts high temperature sintering, and the temperature of high temperature sintering is 1150～1350 ℃, and best 1250 ℃, sintering time is at least 20 minutes.
Step 5. in, the heating of quenching is carried out in carburizing atmosphere, carbon potential is 0.4～2.0%.Hardness after the quenching is greater than HRC45.It is 7.0～7.1g/cm that the present invention manufactures experimently density
3The parts quenching temperature be 820 ℃, temperature retention time is 20 minutes.Hardening heat and temperature retention time are relevant with the density and the wall thickness of roll sleeve.The higher then temperature retention time of density is longer, and hardening heat is higher.
Step 6. in, the temperature retention time of cold treatment is relevant with the wall thickness of part, thicker part temperature retention time is longer.Cold treatment is the operation that the high-dimensional stability part necessarily requires.Hardness rises to some extent after low temperature cold treatment below-60 ℃, increases HRC1～2 approximately, and it is big that outside dimension becomes.This more or less all has a certain amount of retained austenite after quenching in the higher steel of general carbon content.The existence of retained austenite has following influence to product: the first, and retained austenite is unsettled phase, can decompose under certain condition, influences product size stability.The second, retained austenite hardness is lower, can influence the hardness and the wearability of product.
Retained austenite obviously reduces after the cold treatment, among Fig. 3 white be organized as retained austenite, and this white is organized obviously and is significantly reduced among Fig. 4.
Cold treatment is to the roll sleeve Effect on Performance:
| Technology | Hardness | Heat treatment external diameter situation of change |
| Quenching-tempering | HRC51～52 | +0.39％ |
| Quenching-cold treatment-tempering | HRC53～54 | +0.45％ |
| Quenching-tempering-cold treatment | HRC52～53 | +0.51％ |
Set of dispense in the present embodiment when preparation method also can be applied on the axle sleeve of high rigidity excellent abrasive resistance.
In actual generative process, the applicant has also made following contrast test:
Carbon content is to the roll sleeve Effect on Performance:
| Cr content, wt% | Allocate C content into, wt% | Sintering hardness | Heat treatment hardness | Sintered density (g/cm 3) |
| 0.5～4％ | ?1.0 | HRB88 | HRC46 | 6.83 |
| ?0.8 | HRB79 | HRC51 | 6.99 | |
| ?0.6 | HRB73 | HRC50 | 7.07 |
As can be seen from the above table, be 0.5～4% roll sleeve for Cr content, hardness increases with carbon content and reduces behind sintering, and carbon drops at 0.6% o'clock by 1%, and sintering hardness drops to HRB73 by HRB88.But this rule does not appear in the hardness of heat treatment state, and the roll sleeve hardness of high-carbon content is low than low carbon content also, and for example carbon content is that 1.0% roll sleeve hardness is HRC46, is HRC50 and carbon content is 0.6% hardness.This is mainly caused by following several respects reason:
The first, the product of three kinds of carbon contents puts together and quenches during heat treatment, and carbon potential is identical.Therefore, the carbon content of sintered state is little to the influence of the carbon content on final surface, so case hardness and previous carbon content do not have too big relation.
Because the density of graphite is lower, in pressed compact, account for bigger space when second, being shaped, thus the high product of content of graphite, green density is lower under same forming pressure, directly causes sintered density on the low side, and this point is confirmed by table 1.
Three, macrohardness is not only relevant with carbon content, and also the density in product is relevant.High more for the high more then macrohardness of the identical powder metallurgy product density of carbon content.
Chromium content increases, and the hardness of product and intensity and impact flexibility all can increase.Cr content increases to 2% by 0.5%, and tensile strength is increased to 619MPa by 558MPa, has increased by 10.9%, and impact flexibility is increased to 12J by 9J, has increased by 33%, and the hardness after the heat treatment then is increased to HRC40 by HRC36.
Present embodiment compares the chemical composition of two kinds of roll sleeves (wt%) with casting roll sleeve performance:
| Composition | Total carbon | Silicon | Manganese | Phosphorus | Sulphur | Nickel | Chromium | Molybdenum |
| Casting | 3.2～3.5 | 1.8～2.5 | 0.5～1.0 | 0.2～0.3 | 0.15max | 0.2～0.4 | 0.5～1.0 | 0.15～0.40 |
| Present embodiment | 0.3～2.0 | 0.5～4.0 |
The alloying element of casting contains noble elements such as Ni, Mo, and the exploitation present embodiment does not have the noble alloy element and can reduce certain production cost.
Mechanical performance compares:
| Project | The material standard of casting | Present embodiment | |
| Ballistic work (J) | Before the heat treatment | -- | 20 |
| After the heat treatment | -- | 4 | |
| Tensile strength (MPa) | Before the heat treatment | Greater than 300 | Greater than 500 |
| After the heat treatment | -- | Greater than 1000 | |
| Hardness | Before the heat treatment | HRB95 | HRB＞65 |
| After the heat treatment | HRC44～48 | HRC?45～60 | |
| Density (g/cm 3) | After the heat treatment | 7.2 | Greater than 7.1 |
As can be seen from the above table, the roll sleeve of powder metallurgical technique production reaches the performance of casting substantially at aspect of performance.
Microhardness compares:
| Microhardness HV 0.1 | |
| Casting | 728，752，749，654，699，752，770，860，637，761，741，730 |
| Present embodiment | 765，860，795，785，710，753，702，772，805，758，691，832 |
As can be seen from the above table, the present embodiment roll sleeve hardness of powder metallurgy exploitation is more stable, reaches the level of casting technique existing product fully.
The metallographic of the roll sleeve that casting and present embodiment are produced compares: with reference to figure 4 and shown in Figure 5, the metallographic of casting roll sleeve is mainly tempered martensite, carbide, free graphite and retained austenite.With reference to figure 6 and shown in Figure 7, the tissue of the product of present embodiment is mainly tempered martensite, a little retained austenite and carbide.The carbide of powder metallurgical technique development product is a granular carbide, by the test microhardness, finds that HV0.01 surpasses 2100, and this is the carbide (see figure 8) of precipitation type.And in cast article, do not find this carbide.
Thermophysical property compares:
| Temperature | Thermal diffusion coefficient mm 2/S | Standard deviation mm 2/S | Thermal conductivity factor W/ (m*k) | Cp J/g/K |
| Cast steel | 30℃ | 10.608 | 0.093 | 35.253 | 0.466 |
| 100℃ | 9.794 | 0.089 | 34.732 | 0.497 | |
| 180℃ | 9.053 | 0.131 | 33.882 | 0.525 | |
| Present embodiment | 30.1℃ | 9.336 | 0.038 | 32.040 | 0.486 |
| 100℃ | 8.634 | 0.12 | 29.965 | 0.491 | |
| 179.9℃ | 8.100 | 0.063 | 27.238 | 0.476 |
Last table is the thermophysical property of the product of cast steel and present embodiment.As can be seen from the table, the thermal diffusion coefficient of present embodiment and thermal conductivity factor are all low than cast steel, and the thermal diffusion coefficient of cast steel is 9.794mm in the time of 100 ℃
2/ S, and present embodiment is 8.634mm
2/ S reduces 1.16mm2/S; The thermal conductivity factor cast steel is 34.732W/ (m*k), and present embodiment is 29.965W/ (m*k), reduces 4.767W/ (m*k).Specific heat capacity is then comparatively complicated, and present embodiment is slightly high in the time of 30 ℃, and present embodiment is lower slightly when 100 ℃ and 180 ℃.The thermal diffusion coefficient and the thermal conductivity factor of present embodiment are lower slightly, and be main because contain certain hole in the present embodiment.Major part is gas or liquid (as quenching medium) in the hole, all is the non-conductor of heat, and cast steel then contains a large amount of graphite, is the good conductor of heat.This major reason that to be casting there are differences with the product thermophysical property of sintering process production.
Thermal coefficient of expansion compares: thermal coefficient of expansion is seen Fig. 9 and Figure 10 between 20～200 ℃.Wherein, the cast article specimen length of Fig. 9 is 25.14mm, and heating rate is 3k/mm, and mounting system is quartzy, standard sample is quartzy, and present embodiment specimen among Figure 10, length are 24.16mm, heating rate is 3k/mm, and mounting system is quartzy, and standard sample is quartzy.As seen from the figure, the difference of thermal expansion coefficients of cast steel and present embodiment is little, and present embodiment is approximately little by 4.65%.
Dimensional stability, after cold treatment, according to the test request of dimensional stability, present embodiment roll sleeve cold treatment change in size situation test result is as follows:
| Before the processing | After the processing |
| Ф31.900 | Ф31.900 |
| Ф31.828 | Ф31.827 |
| Ф31.850 | Ф31.849 |
Change in size reaches the level of cast steel fully.
Claims (6)
1. a method for preparing high-hardness wear-resistant powder metallurgical rolling sleeve is characterized in that adopting the powder metallurgical technique manufacturing, specifically in turn includes the following steps:
1. mix powder, with iron powder, carbon dust, chromium powder or ferrochrome powder, and mix lubricant, and guarantee percent by weight content in total component of iron, carbon, chromium: carbon is 0.3～2%, chromium is 0.5～4%, lubricant 0.1～2% is no more than 2% inevitable impurity, and surplus is an iron;
2. be compressed to the ordinary powder forming press, shaping density is 7.0～7.1g/cm
3, the pressure of shaping is 630MPa;
3. sintering, temperature is 1000～1350 ℃, the time is at least 20 minutes;
4. machined to being difficult to by bearing of die, adopts machining mode to handle;
5. quench, temperature is 800～950 ℃, and the time is 10～120 minutes;
6. cold treatment is quenched and is carried out in back 24 hours;
7. tempering, 170～300 ℃ of temperature, the time is 2～4 hours,
Described cold treatment adopts temperature to be lower than subzero 60 ℃ industrial refrigerator, 20～300 minutes cool times, or in the liquid nitrogen environment, 5～120 minutes cool times.
2. according to the preparation method described in the claim 1, it is characterized in that step is 1., percentage composition in total component of iron powder, carbon dust, chromium powder: carbon is 0.6%, and chromium is 1.8%, and lubricant 0.6% is no more than 2% inevitable impurity, and surplus is an iron.
3. according to the preparation method described in the claim 1, it is characterized in that step 1., described iron powder adopts atomized iron powder, carbon content is less than 0.02% in this atomized iron powder, oxygen content is less than 0.2%, compressibility under 490.3MPa greater than 6.9g/cm
3
4. according to the preparation method described in the claim 1, it is characterized in that step is 1., described carbon dust adopts carbon content greater than 99% graphite powder or carbon black, and this graphite powder or carbon black ash content be less than 1%, and at least 90% particle diameter is less than 4 microns.
5. according to the preparation method described in the claim 1, it is characterized in that step is 1., described lubricant adopts stearate or wax.
6. according to the preparation method described in the claim 1, it is characterized in that step is 3., the temperature of described sintering is 1150～1350 ℃.
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| CN102950278A (en) * | 2011-08-22 | 2013-03-06 | 六安市凯乐特新材料有限公司 | Iron-based low-alloy-steel powder for powder metallurgy and preparation method of iron-based low-alloy-steel powder |
| CN103386489A (en) * | 2012-05-09 | 2013-11-13 | 富瑞精密组件（昆山）有限公司 | Manufacturing method of shaft sleeve |
| CN102900670A (en) * | 2012-08-31 | 2013-01-30 | 珠海格力电器股份有限公司 | Horizontal compressor with symmetrical double cylinders |
| CN104084589B (en) * | 2014-06-06 | 2015-12-30 | 安徽吉思特智能装备有限公司 | A kind of powder metallurgy automobile hub-bearing unit |
| CN104674122B (en) * | 2015-03-19 | 2017-01-18 | 中南大学 | High-temperature wear-resistant Fe-Co-Cr-Mo iron-base alloy material and preparation method thereof |
| CN105041650B (en) * | 2015-08-06 | 2017-12-12 | 广东美芝制冷设备有限公司 | Twin-tub rotation-type compressor |
| CN109692951B (en) * | 2018-12-20 | 2022-03-01 | 东睦新材料集团股份有限公司 | Method for manufacturing powder metallurgy self-lubricating bearing |
| CN112538562A (en) * | 2019-09-23 | 2021-03-23 | 扬州祥帆重工科技有限公司 | Deformation-preventing machining method for pipe gallery steel structure plate |
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