CN104878299B - Powder metallurgy wear-resistant and corrosion-resistant tool steel - Google Patents
Powder metallurgy wear-resistant and corrosion-resistant tool steel Download PDFInfo
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Abstract
The invention relates to powder metallurgy wear-resistant and corrosion-resistant tool steel. The powder metallurgy wear-resistant and corrosion-resistant tool steel comprises the following chemical components in percentage by mass: 1.8%-2.3% of C, 0.1%-1.0% of W, not more than 1.8% of Mo, 18.2%-24.0% of Cr, 3.0%-5.2% of V, 0.2%-1.8% of Nb, 0.1%-0.5% of Co, not more than 1.0% of Si, 0.2%-1.0% of Mn, 0.05%-0.5% of N and the balance of iron and impurities, wherein a carbide of the powder metallurgy wear-resistant and corrosion-resistant tool steel comprises an MC carbide and an M7C3 carbide; the type of the MC carbide is (V, Nb) (C, N); and the prepared powder metallurgy wear-resistant and corrosion-resistant tool steel is small in carbide size and uniform in distribution, has excellent overall performance, and especially has excellent wear-resisting property and corrosion resistance.
Description
Technical field
The present invention relates to a kind of tool steel, more particularly to a kind of powder metallurgy wear-and corrosion-resistant tool steel.
Background technology
Under the conditions of some special operation conditions, instrument or parts are subject not only to hard grinding in moving component or working media
Granule directly contact causes abrasion, is also subject to the corrosiveness of humidity, acid or other caustic, and the typical operating mode of such a is such as
The parts such as screw rod, screw rod head or the screw sleeve of injection molded are squeezed for plastics machinery, on the one hand due to adding big in plastics
Amount hard particles, such as glass fibre, carbon fiber etc. cause these parts wears to aggravate, in another aspect plastics corrosivity into
Divide and chemical attack is produced to parts.In order that the parts for being applied to these special operation conditions possess long service life, made
Must have high anti-wear performance and corrosion resisting property with tool steel, in addition to bearing working stress loading and impacting, tool steel
Need to possess certain hardness and toughness.The anti-wear performance of tool steel depends on hard second phase present in matrix hardness and steel
Content, form and particle size distribution.Hard second phase in steel includes M6C、M2C、M23C6、M7C3And MC etc., MC carbides
Microhardness be higher than other carbides, in operation process can preferably protect the substrate, so as to reduce the generation of abrasion, improve
The service life of tool and mould.The raising of tool steel corrosion resisting property depends on chromium solid solution in the base, it is believed that at least
It is necessary that 11% chromium is solid-solution in matrix.The toughness of tool steel depends on the distribution of matrix strength and the second phase, in steel
The presence of thick carbide causes stress concentration, reduces instrument steel toughness, causes that fracture occurs under relatively low external force loading,
In order to improve instrument steel toughness, it is important means to reduce carbide content or refined carbides granularity.Tool steel uses process
In occur in order to avoid plastic deformation, tool steel usually requires that hardness reaches more than HRC60.
Tool steel is mainly prepared using traditional cast forging process at present, prepares tool steel by technique mistake using cast forging process
The restriction of journey molten steel Slow cooling Solidification Characteristics, alloying component are susceptible to segregation in process of setting, form thick carbonization
Thing is organized, and even across the process of follow-up forging rolling, this harmful structure still can bring harmful effect to alloy property, cause casting forging
Include on instrument Steel Properties that intensity, toughness, anti-wear performance, grindability energy etc. are in low level, it is difficult to meet high-end processing
Requirement of the manufacture to materials'use performance and lifetime stability.Tool steel is prepared using powder metallurgical technique and solves alloying element
The problem of segregation, powder metallurgical technique prepares the key step of tool steel to be included：Powder by atomization → powder consolidation shaping, above-mentioned
Powder by atomization link, molten steel are cooled rapidly into powder, and in molten steel, alloying element has little time segregation and solidifies completely, powder consolidation
After becoming a useful person, fine microstructures are uniform, compare casting wrought alloy performance and have and are significantly lifted, height high for some performance requirements at present
Alloy tool steel is only prepared using powder metallurgical technique and could meet requirement.Tool steel is prepared using powder metallurgical technique
It has been reported that but steel grades design in part is not reasonable, and tissue and performance need further to be improved.
The content of the invention
To solve the deficiencies in the prior art, the invention provides a kind of powder metallurgy with excellent properties is wear-resisting
Anti-corrosion tool steel.
For achieving the above object, its chemical constituent of powder metallurgy wear-and corrosion-resistant tool steel of the invention is by mass percentage
Including：C：1.8%-2.3%, W：0.1%-1.0%, Mo：≤ 1.8%, Cr：18.2%-24.0%, V：3.0%-5.2%, Nb：0.2%-
1.8%, Co：0.1%-0.5%, Si：≤ 1.0%, Mn：0.2%-1.0%, N：0.05%-0.5%, balance of ferrum and impurity；The powder
The carbide of metallurgical wear-and corrosion-resistant tool steel consists of MC carbides and M7C3Carbide, the type of wherein MC carbides is（V、
Nb）（C、N）.
The present invention by the design of alloying component, to obtain a kind of tool steel with excellent wear and corrosion behavior.
C element part is solid-solution in matrix, improves matrix strength, meanwhile, C element is one of component of carbide, is contained
Amount can not be less than 1.8%, and to ensure that alloying element can fully participate in Carbide Precipitation, the maximum level of C is less than 2.3%, keeps away
Exempt from excessive C and be solid-solution in matrix to cause toughness to decline, in the range of C content 1.8%-2.3%, be obtained in that maximum abrasive resistance can be with
And the cooperation of obdurability.
W, Mo are solid-solution in matrix, improve matrix quenching degree, and W content scope of the present invention is 0.1%-1.0%, the content model of Mo
It is Mo≤1.8% to enclose.
On the one hand Cr is solid-solution in matrix, improves corrosion resisting property and quenching degree, and another aspect Cr is with M7C3Carbide form is analysed
Go out, it is contemplated that Cr is solid-solution in matrix and the balance to exist between carbide form precipitation, the Cr contents of the present invention are
18.2%-24.0%。
V is primarily used to form MC type carbides, improves the anti-wear performance of tool steel, and V content span of control is 3.0%-
5.2%。
The effect of Nb is similar with V, and participation forms MC carbides, and inventive article steel Nb is solid-solution in MC carbides, improves MC
Number of nuclei during Carbide Precipitation, promotes MC Carbide Precipitations and refinement, improves anti-wear performance；Nb adds upper content limit
Avoid the MC Carbide Precipitations of rich Nb；It is 0.2%-1.8% that the present invention controls the content range of Nb.
Co is mainly solid-solution in matrix, promotes the Carbide Precipitation, refined carbides granularity, the scope of Co contents of the present invention to be
0.1%-0.5%。
Si is not involved in carbide and is formed, and usually uses as a kind of deoxidizer and matrix strengthening unit, and Si can excessively make matrix
Toughness decline, therefore Si content ranges are defined to Si≤1.0%.
Mn is added as deoxidizer, can be consolidated sulfur and be reduced red brittleness, and manganese increases quenching degree, Mn content ranges of the present invention in addition
For 0.2%-1.0%.
N participates in forming MC carbides, and under condition of fast cooling, N promotes MC carbides forming core to separate out, while being not result in MC
Carbide is too grown up, and is conducive to improving anti-wear performance, and N simultaneously promotes the corrosion resisting property of steel to improve, limit N content scope as
0.05%-0.5%。
The alloying elements such as inventive article steel V, Nb, C, N form MC carbides（V、Nb）（C、N）, molten steel is quick
Under the conditions of cooled and solidified, the Nb and N of addition participate in MC carbides and are formed, and improve carbide nucleation rate and refinement MC carbides
Grain, improves instrument steel toughness.
Used as the restriction to aforesaid way, the impurity includes O, O≤0.01%.
O is too high to cause instrument steel toughness to decline, present invention control O content≤0.01%, to guarantee the premium properties of steel.
Used as the restriction to aforesaid way, its chemical constituent includes by mass percentage：C：1.8%-2.2%, W：0.1%-
0.8%, Mo：≤ 1.8%, Cr：18.2%-23.0%, V：3.0%-5.0%, Nb：0.2%-1.5%, Co：0.1%-0.4%, Si：≤
0.8%, Mn：0.2%-0.8%, N：0.05%-0.4%, O≤0.008%, balance of ferrum and impurity.
In order to reach more preferable combination property, each chemical constituent in powder metallurgy wear-and corrosion-resistant tool steel of the present invention should be controlled
System is within claimed range.
Used as the restriction to aforesaid way, the volume fraction of the MC carbides is 2%-6%.
Used as the restriction to aforesaid way, the MC carbides at least 80Vol% MC carbide sizes are 0.5-1.1 μm,
Maximum MC carbide sizes are less than 2.5 μm.
As the restriction to aforesaid way, the M7C3Carbide is richness Cr carbides.
As the restriction to aforesaid way, the M7C3The volume fraction of carbide is 18%-26%.
As the restriction to aforesaid way, the M7C3Carbide at least 80Vol% M7C3Carbide size is 1-5 μm, most
Big M7C3Carbide size is less than 10 μm.
The powder metallurgy wear-and corrosion-resistant tool steel of the present invention, can adopt and prepare with the following method, comprise the following steps：
A, tool steel molten steel is prepared by above-mentioned chemical composition requirement and be transferred to ladle；
The covering slag that b, electrified regulation molten steel ladle upper surface are covered, maintains the degree of superheat of molten steel；It is logical in ladle bottom
Enter noble gases to be stirred molten steel；
C, molten steel is flowed into into pre-warmed tundish with regime flow by the mozzle of ladle bottom, in treating that molten steel is entered
Between embedding covering slag is applied to molten steel upper surface when not having a mozzle lower surface；
D, continued compensation heating is carried out to tundish, maintain the degree of superheat of molten steel；
E, molten steel from tundish into aerochamber after carry out powder by atomization using noble gases, the sedimentation of the metal dust that obtains
To aerochamber bottom, the storage powder tank body with protective atmosphere is entered afterwards, metal dust is sieved by protecting screening plant
After enter back into storage powder tank body saving；
F, under inert gas shielding, will storage powder tank body in metal dust be transferred to high temperature insostatic pressing (HIP) jacket, treat metal powder
Evacuation degassing process is carried out to high temperature insostatic pressing (HIP) jacket after last vibration loading consolidation, soldering and sealing process is carried out to its end, with laggard
Row hip treatment makes the completely fine and close consolidation of metal dust, completes powder metallurgical technique.
Above-mentioned powder metallurgical technique includes non-vacuum melting powder by atomization and high temperature insostatic pressing (HIP) link, and process adopts whole process
Protection, to control oxygen content and carbide morphology, optimization tool Steel Properties.The covering slag of ladle possesses isolation air and conduction
Heating function；Ladle bottom is passed through noble gases by air-vent, makes diverse location molten steel temperature in ladle balanced, while accelerating
Harmful floating being mingled with is removed；On the one hand the mozzle of ladle bottom plays guide functions to molten steel, reduces molten steel circulation process
Produce turbulent flow, it is to avoid slag and prevent from being mingled with into next link, another aspect water conservancy diversion protection of pipe molten steel avoids exposure to air,
Prevent molten steel oxygen content from rising；The covering slag of tundish prevents from flowing through the molten steel of tundish directly and air contact, reduces molten steel
The rising of oxygen content；Molten steel is preheated to tundish into before tundish, is prevented molten steel into local coagulation during tundish or is led
Second is caused mutually to separate out in advance；There is atmosphere protection and forced cooling refrigerating function inside storage powder tank；Powder protects screening plant pair
Powder sieving process plays a protective role while preventing powder from waving；Storage powder tank body and high temperature insostatic pressing (HIP) jacket airtight connection, heat etc.
Static pressure is passed through noble gases air-out before being wrapped in dress powder, to control oxygen content.
In sum, using technical scheme, the powder metallurgy wear-and corrosion-resistant tool steel of acquisition possesses excellent
Combination property, especially possesses high anti-wear performance and corrosion resisting property, is adapted to using with abrasion and corrosive conditions occasion.This
The tool steel of invention is due to specific chemical composition and the quick cooled and solidified technique of powder metallurgy, the class of the MC carbides of formation
Type is（V、Nb）（C、N）, make the MC carbides of precipitation more tiny and be evenly distributed, in the higher situation of carbide content, have
Beneficial to high toughness and grindability energy is obtained, the hardness of more than HRC60 is obtained in that after heat treatment, different type can be met
Application demand, it is of many uses.Inventive article steel is prepared using powder metallurgical technique, and process is taken and various is effectively protected handss
Section prevents molten steel and powder to be contaminated, oxygen content increment≤30ppm, is finally to obtain high performance alloys to provide safeguard.
Specific embodiment
Embodiment one
The present embodiment is related to one group of powder metallurgy wear-and corrosion-resistant tool steel, and its chemical constituent is as shown in table 1.1：
The chemical constituent table of 1.1 embodiment of table, one powder metallurgy wear-and corrosion-resistant tool steel
Using following preparation process：
A, by inventive article steel molten steel load melting ladle in, molten steel Weight Loaded be 1.5-8 tons；
B, the covering slag electrified regulation covered to molten steel ladle upper surface using graphite electrode, ladle bottom air-vent are led to
Enter molten steel in argon or nitrogen gas stirring ladle, superheat of liquid steel opens molten steel mozzle when reaching 100 DEG C -150 DEG C；
C, the tundish that molten steel is preheated to 800 DEG C -1200 DEG C by the mozzle inflow of ladle bottom, control water conservancy diversion
Tube inlet size, makes molten steel flow for 10 kg/min -50 kg/min, and molten steel buries under molten steel mozzle into after tundish
Apply covering slag during end face；
D, powder by atomization process make superheat of liquid steel maintain 100 DEG C -150 DEG C the continuous compensation heating of middle holding；
E, molten steel leak eye by tundish bottom opening and enter aerochamber, open atomizing gas nozzle valve, using nitrogen
Powder by atomization is carried out as atomization gas, nitrogen gas purity >=99.999%, oxygen content≤2ppm, gas pressure are 1.0MPa-
5.0MPa；Molten steel is fractured into drop under noble gases percussion, while being quickly cooled to metal dust, flight is settled down to
Aerochamber bottom, enters storage powder tank body by aerochamber bottom；Powder by atomization powder tank in-vivo metal powder cooling to be stored up after terminating
To room temperature, sieved by protecting screening plant；Protection screening plant inside cavity is connected with malleation inert protective gas, Chu Fen
It is malleation inert gas shielding atmosphere inside tank；
F, will storage powder tank in-vivo metal powder packing to high temperature insostatic pressing (HIP) jacket, first to being passed through indifferent gas in high temperature insostatic pressing (HIP) jacket
Body excludes air, subsequent airtight connection high temperature insostatic pressing (HIP) jacket and storage powder tank body, and filling implementation Process vibration operation increases metal powder
The loading density at end；After the completion of evacuation degassing process is carried out to high temperature insostatic pressing (HIP) jacket, vacuum high temperature insostatic pressing (HIP) jacket adds
Heat insulation is deaerated to 0.01Pa and continues heating and thermal insulation >=2h, subsequently jacket end is carried out at soldering and sealing at 200 DEG C -600 DEG C
Reason, finally carries out hip treatment to jacket, and hip temperature is 1100 DEG C -1160 DEG C, protects under >=100MPa pressure
Hold the time >=1h after the completely fine and close consolidation of metal dust, furnace cooling.
Definite shape size is obtained to the further forging deformation of inventive article steel as needed, using different heat treatment system
Degree obtains different performance, and the heat treatment for being used includes annealing, quench and being tempered.The annealing is related to heat forging
To 860 DEG C -900 DEG C, temperature retention time 2 hours is subsequently cooled to 530 DEG C with≤15 DEG C/h of speed, and then stove is cold or static sky
Gas is air cooled to less than 50 DEG C；Quenching Treatment is related to the forging after annealing in 815 DEG C of -845 DEG C of preheating temperatures, puts after temperature is uniform
Enter at a temperature of 1000 DEG C -1200 DEG C insulation 15-40 minutes, be subsequently quenched to 530 DEG C -550 DEG C, be then air cooled to 50 DEG C with
Under；Temper is related to the forging after quenching is heated to 540-670 DEG C of temperature and 1.5-2 hours are incubated, and is subsequently air cooled to
Less than 50 DEG C, so repeat 2 to 3 times.
The powder metallurgy wear-and corrosion-resistant tool steel of embodiment 1.1-1.4 of acquisition, preparation process alloy oxygen content increase
Amount≤30ppm, obtains the complete fine and close tool steel that relative density is 100%, is made into the bar of Φ 50mm after thermal deformation.
Embodiment two
The present embodiment is related to the carbide content and granularity, heat treatment of the powder metallurgy wear-and corrosion-resistant tool steel of embodiment one
Hardness, anti-wear performance, the checking of corrosion resisting property, wherein carbide content and granularity obtain organization chart picture based on scanning electron microscope and carry out
Analysis, heat treatment hardness, anti-wear performance are tested with reference to GB/T 230.1, GB/T 12444-2006 respectively, corrosion resisting property
Using 5%HNO3+ 1%HCl corrosive solutions soaking at room temperature is tested.
Tool steel is forged in casting of the powder metallurgy wear-and corrosion-resistant tool steel of embodiment 1.1,1.2 with purchase（Alloy A）And powder
Last metallurgical tool steel（Alloy B）It is analyzed, its result is as follows：
2.1 embodiment 1.1,1.2 of table and alloy A, B are into being grouped into contrast
In upper table, N.A is represented and is not analyzed.
The powder metallurgy wear-and corrosion-resistant tool steel of embodiment 1.1,1.2, prepare before oxygen content be 50-60ppm, oxygen after preparation
Content be 60-80 ppm, preparation process oxygen content increment≤30ppm.
2.2 embodiment 1.1,1.2 of table is contrasted with the carbide content and granularity of alloy A, B
In upper table, Carbide size is the size of at least 80Vol% carbides.
To the present invention powder metallurgy wear-and corrosion-resistant Carbides in Tool Steels be analyzed, carbide consist of MC carbides and
M7C3Carbide, wherein MC carbides are（V、Nb）（C、N）, main component consists of V, Nb, C, N and a small amount of Fe, Cr etc.
Alloying element.M7C3Carbide is richness Cr type carbides.Can be seen that by table 2.2, inventive article steel MC carbides are very tiny,
At least 80Vol% is 0.5-1.1 μm, further measurement statistics MC carbide sizes, and maximum MC carbides are less than 2.5 μm, due to
MC carbides have high hardness, enable inventive article steel to possess excellent grindability, while being conducive to toughness to improve；MC
The volume fraction of carbide is 2%-6%, makes inventive article steel possess excellent anti-wear performance.M in inventive article steel7C3Carbon
Compound reaches 18%-26%, and at least 80Vol% is 1-5 μm, maximum M7C3Carbide size is less than 10 μm, M7C3Carbide size
Compare MC carbides bigger than normal, but still the tiny M in cast forging process prepares alloy A7C3Carbide size, comparative alloy B adopt powder
Prepared by last metallurgical technology, Carbide size is very tiny, and most of MC carbides are 0.5-1.5 μm, MC carbide volume fractions
For 3%-6%.
The heat treatment hardness of 2.3 embodiment 1.1,1.2 of table and alloy A, B, anti-wear performance contrast
By table 2.3 as can be seen that through suitable heat treatment, inventive article steel hardness reaches more than HRC60, Neng Gouman
Sufficient inventive article steel application demand, anti-wear performance comparing result show that inventive article steel has best wearability
Energy.
Using 5%HNO3+ 1%HCl solution carries out immersion corrosion at ambient temperature to inventive article steel, from height
The alloy A of Cr alloys composition is contrasted as corrosion resisting property, and both corrosion resisting property comparing results are as shown in table 2.4.
2.4 embodiment 1.1,1.2 of table is contrasted with the corrosion resisting property of alloy A
Inventive article steel can be seen that by the correction data of table 2.4 and show excellent corrosion resisting property.Need explanation
, according to different application scenarios to anti-wear performance and the demand of corrosion resisting property, suitable heat treating regime should to be selected, i.e., it is identical
Under quenching condition, during using relatively low tempering system, more Cr element solid solutions are obtained in that compared with high corrosion resistance, are adopted in matrix
During with higher tempering system, more Cr alloying elements are separated out with carbide form, and corrosion resisting property will reduce anti-wear performance simultaneously
To raise, in general, in the range of a wide heat treatment, inventive article steel can be provided simultaneously with excellent wear-resisting and resistance to
Corrosion energy, so as to meet the application with abrasion and corrosive conditions occasion.
In sum, powder metallurgy wear-and corrosion-resistant tool steel of the invention possesses excellent combination property, especially possesses
High anti-wear performance is provided simultaneously with high corrosion resisting property, is adapted to using with abrasion and corrosive conditions occasion.Due to the present invention
The specific chemical composition of tool steel and it is prepared using powder metallurgical technique, is carbonized in the case where carbide content is higher
Composition granule is maintained to tiny and is evenly distributed, and is conducive to obtaining high toughness and grindability energy, can after heat treatment
Obtain more than HRC60 hardness, disclosure satisfy that different types of application demand, it is of many uses, such as can be applicable to screw rod, screw sleeve,
Screw rod head, retaining ring etc. squeeze plastics machinery parts, food processing, medical surgical instrument, industrial shear-blade, wear-and corrosion-resistant
Parts etc..The powder metallurgy preparation technique of the present invention takes various means that are effectively protected to prevent molten steel and powder from preparing
Process is contaminated, oxygen content increment≤30ppm, is finally to obtain high performance alloys to provide safeguard.
Claims (10)
1. a kind of powder metallurgy wear-and corrosion-resistant tool steel, it is characterised in that its chemical constituent includes by mass percentage：C：
1.8%-2.3%, W：0.1%-1.0%, Mo：≤ 1.8%, Cr：18.2%-24.0%, V：3.0%-5.2%, Nb：0.2%-1.8%, Co：
0.1%-0.5%, Si：≤ 1.0%, Mn：0.2%-1.0%, N：0.05%-0.5%, balance of ferrum and impurity；The powder metallurgy is wear-resisting
The carbide of anti-corrosion tool steel consists of MC carbides and M7C3Carbide, the type of wherein MC carbides is（V、Nb）（C、N）.
2. powder metallurgy wear-and corrosion-resistant tool steel according to claim 1, it is characterised in that：The impurity includes O, O≤
0.01%。
3. powder metallurgy wear-and corrosion-resistant tool steel according to claim 2, it is characterised in that its chemical constituent presses quality hundred
Dividing includes than meter：C：1.8%-2.2%, W：0.1%-0.8%, Mo：≤ 1.8%, Cr：18.2%-23.0%, V：3.0%-5.0%, Nb：
0.2%-1.5%, Co：0.1%-0.4%, Si：≤ 0.8%, Mn：0.2%-0.8%, N：0.05%-0.4%, O≤0.008%, balance of ferrum
And impurity.
4. powder metallurgy wear-and corrosion-resistant tool steel according to claim 1, it is characterised in that：The impurity includes S, S≤
0.1%。
5. powder metallurgy according to claim 1 grinds anti-corrosion tool steel, it is characterised in that：The impurity includes P, P≤
0.03%。
6. powder metallurgy wear-and corrosion-resistant tool steel according to claim 1, it is characterised in that：The volume of the MC carbides
Fraction is 2%-6%.
7. powder metallurgy wear-and corrosion-resistant tool steel according to claim 1, it is characterised in that：The MC carbides are at least
80Vol%MC carbide sizes are 0.5-1.1 μm, and maximum MC carbide sizes are less than 2.5 μm.
8. powder metallurgy wear-and corrosion-resistant tool steel according to claim 1, it is characterised in that：The M7C3Carbide is richness
Cr carbides.
9. powder metallurgy wear-and corrosion-resistant tool steel according to claim 1, it is characterised in that：The M7C3The body of carbide
Fraction is 18%-26%.
10. powder metallurgy wear-and corrosion-resistant tool steel according to claim 1, it is characterised in that：The M7C3Carbide is at least
80Vol% M7C3Carbide size is 1-5 μm, maximum M7C3Carbide size is less than 10 μm.
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