CN102242304A - Chromium-containing powder metallurgy low alloy steel and preparation method thereof - Google Patents
Chromium-containing powder metallurgy low alloy steel and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of chromium-containing powder metallurgy low alloy steel. The preparation method comprises the following steps of: mixing prealloyed Fe-Mo powder with Fe-Cr master alloyed powder to form Cr-Mo-containing iron-based alloy powder, mixing the Cr-Mo-containing iron-based alloy powder with copper powder, graphite powder and paraffin micro powder, dry-mixing and press forming, sintering and tempering to obtain powder metallurgy low alloy steel prepared by chromium-containing iron-based alloy powder. A microstructure of the prepared low alloy steel can be a lower bainite, a mixture of a lower bainite and a few pearlites or a mixture of a lower bainite and martensite, and the prepared material has medium and high hardness and medium and high strength. The preparation method disclosed by the invention is simple and convenient for operation, solves the problems that the traditional chromium-containing low alloy steel powder has poor press performance and high oxygen content, can provide powder metallurgy low alloy steel of parts with low production cost, high-strength and high hardness, and lays the foundation for improving the technical level of powder metallurgy ferrous parts for domestic automobiles , and is suitable for industrial production.
Description
Technical field
The invention discloses a kind of Cr of containing powder metallurgy low alloy steel and preparation method, belong to the mmaterial preparing technical field.
Background technology
Powder metallurgy technology can obtain to have the element of complicated shape, and has the characteristics of " near-net-shape ", and the utilization ratio that can improve metallic substance also significantly reduces the expense of follow-up machining
[1]Therefore powder metallurgy product is widely used in fields such as automobile, machinery, electronic apparatus.Along with the development of these industries, powder metallurgy product has also obtained application more and more widely, especially iron-base powder metallurgy material, is used for making component such as car engine, transmission, braking and all kinds of diesel engine connecting bars in a large number.
Usually the preparation of powder metallurgy low alloy steel be meant with the powder metallurgy process preparation based on iron (iron level is generally 90%～98%), add element such as a certain amount of Cu, Ni, Mo, Cr, Mn and control C content and the alloy system formed.Powder metallurgy low alloy steel is at first based on Fe-C, Fe-Cu, Fe-Cu-C, and tensile strength can be comparable with cast member performance at that time between 150～400MPa.The back is with outside the Fe-Ni-X (X=Cu, Mo) of Ni as main adding elements, and the alloy system that adds Cr, Mn with Fe-Mo prealloy powder has more not only reduced cost but also obtained preferable performance.The tensile strength of these low alloy steel generally can reach 500～1000MPa now, is higher than 1000MPa through Overheating Treatment back draft intensity.
The development high-performance is the powder metallurgy iron based articles of strong mechanical performance particularly, is the developing direction and the research emphasis of powder metallurgy.The mechanical property of mmaterial and its chemical ingredients, density, microstructure, porosity and pore morphology etc. have direct relation.The mechanical property that improves mmaterial mainly contains three approach, promptly improves density, alloying and sintering postheat treatment (containing sinter-hardened).
Alloying is the basic of development high-performance iron based articles, alloying can have influence on suppression performance and sintering densification process on the one hand, thereby influence the density of goods behind the density of pressed compact and the sintering, on the other hand, process of thermal treatment and heat treatment on microstructure, performance are also decided by the alloying composition.
The alloying element of steel powder except the C element, mainly contains Cu, Ni, Mo, Cr, Mn.These several alloying elements are followed successively by Mn, Cr, Mo, Ni, Cu from high to low to the influence of low alloy steel hardening capacity
[2,3]The Mo element can significantly improve the hardening capacity of iron powder, very little to the constrictive influence of iron powder, owing to costing an arm and a leg of Mo element, the add-on of Mo element is no more than 1.0%, and adopt complete alloyage process to join in the iron-based powder, to give full play to the alloying action of Mo element.But the price of Mo and Ni will be higher than the price of Cr far away, therefore as far back as the nineties in 20th century
It is the water atomization low alloyed steel powder of main alloy element that group just develops with Cr, and the trade mark is respectively Astaloy CrM
TMWith Astaloy CrL
TM[4]After this, the ATOMET 4701 of the Ancorsteel 4300 of U.S. Hoeganaes, Canadian QMP and the 94FDH of Japanese Kobe are arranged again.In China, also some researchs have been carried out to containing the Cr iron-base powder metallurgy material.On the basis of Fe-Ni-Mo-Cu system or reduced iron based powders, introduce alloying elements cr, its density and mechanical property are all increased, yet these are far from being enough aspect practical application in direct or indirect mode.
Although contain the existing aborning certain application of Cr prealloy comminuted steel shot, its weak point also arranged.In the water atomization process, form oxide compound as Cr, in nitrogen atmosphere, also be difficult to reduction, generally need the bigger vacuum reducing of use cost just can; In addition, the Cr element not directly adds in the iron powder, because can produce adverse influence to compactibility like this, generally need add with the form of alloy powder or with compound form.These have all limited its application aspect powder metallurgy.
It is raw material that the present invention adopts the low carbon ferrochromium alloy FeCr55C25 of market sale, solve existing technologic difficult point when Cr is element alloyed in the production of powder metallurgy iron-based part, be easy oxidation of Cr element and the problems such as compressible performance that reduce iron powder, replace the Ni element with Cr element at a low price, thereby reduce cost, improve the hardening capacity of powder simultaneously, form a kind of method that high-performance contains Cr powder metallurgy low alloy steel for preparing.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art and provide that a kind of processing method powder metallurgy low alloy steel simple, easy to operate, preparation possesses high strength, high rigidity contain Cr powder metallurgy low alloy steel and preparation method.
A kind of preparation method who contains Cr powder metallurgy low alloy steel of the present invention comprises the steps:
The first step: contain the preparation of Cr-Mo iron(-)base powder
Mixed by pre-alloyed Fe-Mo powder and Fe-Cr master alloyed powder, the Mo element is to adopt the method for water atomization to add in the Fe matrix in the described pre-alloyed Fe-Mo powder, and the mass percent that the Mo element accounts for described pre-alloyed Fe-Mo powder is 0.43-0.65%;
Described Fe-Cr master alloyed powder is to be raw material with the low carbon ferrochromium alloy; Mechanical Crushing to median size D (v, 0.5) be 1-30 μ m, obtain Fe-Cr master alloy powder;
Then, be that the Mo iron-based pre-alloyed powder that contains of 0.43-0.65% mixes with described Fe-Cr master alloy powder with Mo content, dried at least mixing 20 minutes, control Cr constituent content is 1.2-2.8%, obtains containing the Cr-Mo iron(-)base powder;
Second step: batching, mixing
Get the first step gained by mass percentage respectively and contain Cr-Mo iron(-)base powder 96.3-97.6%; Get the copper powder 1.4-2.0% of particle diameter≤74 μ m; Get the Graphite Powder 99 0.5-0.9% of particle diameter≤74 μ m, the paraffin micro mist 0.5-0.8% that gets particle diameter≤38 μ m mixes, dried at least mixing 20 minutes; Obtain mixed powder;
The 3rd step: press forming
The mixed powder that the first step is obtained with the pressure press forming of 500-700MPa, obtains green compact on hydropress;
The 4th step: sintering
Go on foot the green compact sintering under hydrogen shield that obtains, sintering temperature 1120-1180 ℃, sintering time 0.5-1.5 hour with second; Then, the rate of cooling with 0.5-5 ℃/s is cooled to room temperature; Obtain sintered blank;
The 5th step: tempering
The 3rd sintered blank that obtain of step is heated to air cooling behind the 150-200 ℃ of tempering 1h; Obtain following bainite structure for main form by the powder metallurgy low alloy steel that contains the preparation of Cr iron(-)base powder.
The present invention is a kind of to be contained among the preparation method of Cr powder metallurgy low alloy steel, and the Cr constituent content is 1.67-2.28% in the described Cr-Mo of the containing iron(-)base powder, and median size D (v, 0.5) is 1-10 μ m; Rate of cooling behind the sintering is 0.5-0.8 ℃/s.
The present invention is a kind of to be contained among the preparation method of Cr powder metallurgy low alloy steel, and the Cr constituent content is 1.25-1.87% in the described Cr-Mo of the containing iron(-)base powder, and median size D (v, 0.5) is 10-30 μ m; Rate of cooling behind the sintering is 0.5-0.8 ℃/s.
The present invention is a kind of to be contained among the preparation method of Cr powder metallurgy low alloy steel, and the Cr constituent content is 1.35-2.08% in the described Cr-Mo of the containing iron(-)base powder, and median size D (v, 0.5) is 10-20 μ m; Rate of cooling behind the sintering is 1-5 ℃/s.
The present invention is a kind of to be contained among the preparation method of Cr powder metallurgy low alloy steel, and described low carbon ferrochromium alloy is FeCr55C25; Described pre-alloyed Fe-Mo powder is LAP100.29A4.
Advantage of the present invention:
1. adopt the Cr element to replace the Ni element, greatly reduce cost;
2. introduce the Cr element by the mode of in the water atomization comminuted steel shot, adding the Fe-Cr powdered alloy, kept the high-compressibility of iron-based powder and low oxygen level;
3. the particle diameter of Fe-Cr powdered alloy is 1-30 μ m in the powder mix, just can obtain by mechanical ball milling, and method is easy;
4. in preparation process, only need carry out sinter-hardened processing, i.e. fast speed cooling behind the sintering, form martensitic stucture, just can reach the performance requriements after the thermal treatment, simplify technology, saved cost, the tensile strength of material can reach more than the 1000MPa, is up to 1210.14MPa; Hardness also can reach more than the HRC40, is up to HRC46.Substantially reach the service requirements of connecting rod, can save cost and manpower greatly;
5. the mixed powder sintered compact has very high hardening capacity, the Cr constituent content is 1.67-2.28% in the iron(-)base powder of employing the present invention preparation, median size D (v, 0.5) when being 1-10 μ m, adopt (0.5-0.8 ℃/the powder metallurgy low alloy steel that s) obtains of conventional cooling behind the sintering, can form with the lower bainite is the main microstructure of forming, and need not subsequent heat treatment and just has higher intensity and hardness.The Cr constituent content is 1.25-1.87% in the iron(-)base powder of preparation, when median size D (v, 0.5) is 10-30 μ m; Adopt (0.5-0.8 ℃/the powder metallurgy low alloy steel that s) obtains of conventional cooling behind the sintering, can form lower bainite+a small amount of pearlitic microstructure, this alloy has medium hardness (being not less than 20HRC), high intensity (tensile strength is higher than 820MPa, and yield strength is higher than 730MPa); Need not subsequent heat treatment, can satisfy multiple auto parts, as the performance requriements of sprocket wheel, gear level, automatic locking pin system planetary set etc.The Cr constituent content is 1.35-2.08% in the iron(-)base powder of preparation, and median size D (v, 0.5) is 10-20 μ m; Rate of cooling with 1-5 ℃/s behind the sintering is cooled to room temperature, can form the microstructure that lower bainite+martensite is formed, this low alloy steel has high hardness (being higher than 40HRC), medium tenacity (tensile strength is higher than 550MPa, and yield strength is higher than 350MPa); Need not subsequent heat treatment and just have higher hardness and medium tenacity.
The powder metallurgy low alloy steel of the present invention's preparation can be used for making the bigger component of working load and heavily loaded main shaft and heavy-duty gear etc., as some important transmitting gears, engine link etc. in the big unit type machine main shaft of working load, the wheel box; Or it is more serious to be used for wearing and tearing, needs certain wear resisting property, bears lathe and the automobile axle class and the gear part of medium load, as milling machine spindle, and the gear in main transmission system of machine tool and the feed system, automobile sprocket wheel etc.
In sum, processing method of the present invention is simple, easy to operate, solve the existing problem that Cr low alloyed steel powder suppression performance is poor, oxygen level is higher that contains, can provide a kind of powder metallurgy low alloy steel of producing low cost, high strength, high rigidity part for industries such as automobile, machineries, be suitable for suitability for industrialized production, lay a good foundation with the state of the art of powder metallurgy iron-based part for improving China's automobile.
Description of drawings
Fig. 1 is the microstructure of the bainite type high-strength powder metallurgical low alloy steel of embodiment 1 preparation.
Fig. 2 is the microstructure of the high-strength powder metallurgical low alloy steel of embodiment 2 preparations.
Fig. 3 is the microstructure of the high hardness powder metallurgy low alloy steel of embodiment 3 preparations.
Fig. 4 is the microstructure of the high hardness powder metallurgy low alloy steel of embodiment 4 preparations.
Fig. 5 is the microstructure of the high hardness powder metallurgy low alloy steel of embodiment 5 preparations.
Fig. 6 is the microstructure of the high hardness powder metallurgy low alloy steel of embodiment 6 preparations.
Fig. 7 is the microstructure of the high hardness powder metallurgy low alloy steel of embodiment 7 preparations.
Fig. 8 is the microstructure of the high hardness powder metallurgy low alloy steel of embodiment 8 preparations.
Fig. 9 is the microstructure of the high hardness powder metallurgy low alloy steel of embodiment 9 preparations.
Embodiment
The present invention will be further described below in conjunction with specific embodiment.
Preparation technology parameter of the present invention is basic identical, only be that the speed of cooling that contains behind Cr-Mo iron(-)base powder granularity, Cr constituent content and the sintering has different variations, therefore, describe preparation technology's engineering in detail with embodiment 1, embodiment 2-9 then only illustrates the parameter value that changes.
Embodiment 1:
A kind of preparation method who contains Cr powder metallurgy low alloy steel comprises the steps:
The first step: contain the preparation of Cr-Mo iron(-)base powder
Get the pre-alloyed Fe-Mo powder of LAP100.29A4, wherein the Mo element adopts the method for water atomization to add in the Fe matrix, and the mass percent that the Mo element accounts for described pre-alloyed Fe-Mo powder is 0.43-0.65%;
With low carbon ferrochromium alloy FeCr55C25 is raw material; Mechanical Crushing to median size D (v, 0.5) be 1-10 μ m, obtain Fe-Cr master alloy powder;
Then, be that the Mo iron-based pre-alloyed powder that contains of 0.43-0.65% mixes with described Fe-Cr master alloy powder with Mo content, dried at least mixing 20 minutes, control Cr constituent content is 1.67-1.7%, obtains containing the Cr-Mo iron(-)base powder.
The second step batching, mixing
Get the first step gained by mass percentage respectively and contain Cr-Mo iron(-)base powder 96.3-97.6%; Get the copper powder 1.4-2.0% of particle diameter≤74 μ m; Get the Graphite Powder 99 0.5-0.9% of particle diameter≤74 μ m, the paraffin micro mist 0.5-0.8% that gets particle diameter≤38 μ m mixes, and does and mixes 25 minutes; Obtain mixed powder;
Second step: press forming
The mixed powder that the first step is obtained with the pressure press forming of 500-700MPa, obtains green compact on hydropress;
The 3rd step: sintering
Go on foot the green compact sintering under hydrogen shield that obtains, sintering temperature 1120-1180 ℃, sintering time 0.5-1.5 hour with second; Then, the rate of cooling with 0.5-0.8 ℃/s is cooled to room temperature; Obtain sintered blank;
The 4th step: tempering
The 3rd sintered blank that obtain of step is heated to air cooling behind the 150-200 ℃ of tempering 1h; Acquisition is by the powder metallurgy low alloy steel that contains the preparation of Cr iron(-)base powder.
Referring to accompanying drawing 1, the microstructure of the powder metallurgy low alloy steel of embodiment 1 preparation is main the composition with the lower bainite.
The powder metallurgy low alloy steel hardness of present embodiment preparation is 34HRC, and tensile strength is 1210.1MPa, and yield strength is 1050.6MPa.
Embodiment 2
Embodiment 2 is with the difference of embodiment 1: contain that the Cr constituent content is 2.0-2.05% in the Cr-Mo iron(-)base powder;
Referring to accompanying drawing 2, the microstructure of the powder metallurgy low alloy steel of embodiment 2 preparations is main the composition with the lower bainite.
The powder metallurgy low alloy steel hardness of present embodiment preparation is 34HRC, and tensile strength is 1178.2MPa, and yield strength is 1043.8MPa.
Embodiment 3
Embodiment 3 is with the difference of embodiment 1: contain that the Cr constituent content is 2.25-2.28% in the Cr-Mo iron(-)base powder.
Referring to accompanying drawing 3, the microstructure of the powder metallurgy low alloy steel of embodiment 3 preparations is main the composition with the lower bainite.
The powder metallurgy low alloy steel hardness of present embodiment preparation is 36HRC, and tensile strength is 1002.5MPa, and yield strength is 987.3MPa.
Embodiment 4
Embodiment 4 is with the difference of embodiment 1: contain that the Cr constituent content is 1.25-1.3% in the Cr-Mo iron(-)base powder, it is 10-30 μ m that low carbon ferrochromium alloy FeCr55C25 is crushed to median size D (v, 0.5).
Sintering postcooling speed is 0.5-0.8 ℃/s
Referring to accompanying drawing 4, the microstructure of the powder metallurgy low alloy steel of embodiment 4 preparations serves as main the composition with lower bainite+a small amount of perlite.
The powder metallurgy low alloy steel hardness of present embodiment preparation is 97, and tensile strength is 1066.5MPa, and yield strength is 1060.3MPa.
Embodiment 5
Embodiment 5 is with the difference of embodiment 4: contain that the Cr constituent content is 1.5-1.55% in the Cr-Mo iron(-)base powder.
Referring to accompanying drawing 5, the microstructure of the powder metallurgy low alloy steel of embodiment 5 preparations serves as main the composition with lower bainite+a small amount of perlite.
The powder metallurgy low alloy steel hardness of present embodiment preparation is 30HRC, and tensile strength is 1128.6MPa, and yield strength is 1117.3MPa.
Embodiment 6
Embodiment 6 is with the difference of embodiment 4: contain that the Cr constituent content is 1.85-1.87% in the Cr-Mo iron(-)base powder.
Referring to accompanying drawing 6, the microstructure of the powder metallurgy low alloy steel of embodiment 6 preparations serves as main the composition with lower bainite+a small amount of perlite.
The powder metallurgy low alloy steel hardness of present embodiment preparation is 36HRC, and tensile strength is 1180.7MPa, and yield strength is 1172.5MPa.
Embodiment 7
Embodiment 7 is with the difference of embodiment 1: contain that the Cr constituent content is 1.35-1.4% in the Cr-Mo iron(-)base powder, it is 10-20 μ m that low carbon ferrochromium alloy FeCr55C25 is crushed to median size D (v, 0.5).
Sintering postcooling speed is 1-1.5 ℃/s.
Referring to accompanying drawing 7, the microstructure of the powder metallurgy low alloy steel of embodiment 7 preparations serves as main the composition with lower bainite+martensite.
The powder metallurgy low alloy steel hardness of present embodiment preparation is 40HRC, and tensile strength is 696.8MPa, and yield strength is 633.1MPa.
Embodiment 8
Embodiment 8 is with the difference of embodiment 7: contain that the Cr constituent content is 1.55-1.6% in the Cr-Mo iron(-)base powder.
Sintering postcooling speed is 2.0-3.0 ℃/s.
Referring to accompanying drawing 8, the microstructure of the powder metallurgy low alloy steel of embodiment 8 preparations serves as main the composition with lower bainite+martensite.
The powder metallurgy low alloy steel hardness of present embodiment preparation is 42HRC, and tensile strength is 838.8MPa, and yield strength is 819.9MPa.
Embodiment 9
Embodiment 9 is with the difference of embodiment 7: contain that the Cr constituent content is 2.0-2.08% in the Cr-Mo iron(-)base powder.
Sintering postcooling speed is 4.0-5.0 ℃/s.
Referring to accompanying drawing 9, the microstructure of the powder metallurgy low alloy steel of embodiment 9 preparations serves as main the composition with lower bainite+martensite.
The powder metallurgy low alloy steel hardness of present embodiment preparation is 46HRC, and tensile strength is 582.6MPa, and yield strength is 411.7MPa.
Claims (5)
1. a preparation method who contains Cr powder metallurgy low alloy steel comprises the steps:
The first step: contain the preparation of Cr-Mo iron(-)base powder
Mixed by pre-alloyed Fe-Mo powder and Fe-Cr master alloyed powder, the Mo element is to adopt the method for water atomization to add in the Fe matrix in the described pre-alloyed Fe-Mo powder, and the mass percent that the Mo element accounts for described pre-alloyed Fe-Mo powder is 0.43-0.65%;
Described Fe-Cr master alloyed powder is to be raw material with the low carbon ferrochromium alloy; Mechanical Crushing to median size D (v, 0.5) be 1-30 μ m, obtain Fe-Cr master alloy powder;
Then, be that the Mo iron-based pre-alloyed powder that contains of 0.43-0.65% mixes with described Fe-Cr master alloy powder with Mo content, dried at least mixing 20 minutes, control Cr constituent content is 1.2-2.8%, obtains containing the Cr-Mo iron(-)base powder;
Second step: batching, mixing
Get the first step gained by mass percentage respectively and contain Cr-Mo iron(-)base powder 96.3-97.6%; Get the copper powder 1.4-2.0% of particle diameter≤74 μ m; Get the Graphite Powder 99 0.5-0.9% of particle diameter≤74 μ m, the paraffin micro mist 0.5-0.8% that gets particle diameter≤38 μ m mixes, dried at least mixing 20 minutes; Obtain mixed powder;
The 3rd step: press forming
The mixed powder that the first step is obtained with the pressure press forming of 500-700MPa, obtains green compact on hydropress;
The 4th step: sintering
Go on foot the green compact sintering under hydrogen shield that obtains, sintering temperature 1120-1180 ℃, sintering time 0.5-1.5 hour with second; Then, the rate of cooling with 0.5-5 ℃/s is cooled to room temperature; Obtain sintered blank;
The 5th step: tempering
The 3rd sintered blank that obtain of step is heated to air cooling behind the 150-200 ℃ of tempering 1h; Obtain following bainite structure for main form by the powder metallurgy low alloy steel that contains the preparation of Cr iron(-)base powder.
2. a kind of preparation method who contains Cr powder metallurgy low alloy steel according to claim 1 is characterized in that: the Cr constituent content is 1.67-2.28% in the described Cr-Mo of the containing iron(-)base powder, and median size D (v, 0.5) is 1-10 μ m; Rate of cooling behind the sintering is 0.5-0.8 ℃/s.
3. a kind of preparation method who contains Cr powder metallurgy low alloy steel according to claim 1 is characterized in that: the Cr constituent content is 1.25-1.87% in the described Cr-Mo of the containing iron(-)base powder, and median size D (v, 0.5) is 10-30 μ m; Rate of cooling behind the sintering is 0.5-0.8 ℃/s.
4. a kind of preparation method who contains Cr powder metallurgy low alloy steel according to claim 1 is characterized in that: the Cr constituent content is 1.35-2.08% in the described Cr-Mo of the containing iron(-)base powder, and median size D (v, 0.5) is 10-20 μ m; Rate of cooling behind the sintering is 1-5 ℃/s.
5. a kind of preparation method who contains Cr powder metallurgy low alloy steel according to claim 1 is characterized in that: described low carbon ferrochromium alloy is FeCr55C25; Described pre-alloyed Fe-Mo powder is LAP100.29 A4.
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