CN104294073B - A kind of preparation method of modified high manganese steel base TiC steel bonded carbide - Google Patents
A kind of preparation method of modified high manganese steel base TiC steel bonded carbide Download PDFInfo
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Abstract
The preparation method that the present invention relates to a kind of modified high manganese steel base TiC steel bonded carbide, it is characterised in that be 0.8～1.0 in-situ synthesizing TiC powder being configured to required ratio in C/Ti atomic ratio by titanium valve and graphite powder；By molybdenum-iron powder, vanadium iron powder, ferrochrome powder, ferromanganese powder, ferrosilicon powder, iron powder, nikel powder, aquadag and rare earths material press proportions needed for bonding phase metal chemical composition mass ratio, load steel ball ball milling, wherein add dehydrated alcohol and make medium and PVA, after ball milling, slip compressing, sintering after drying is obtained steel-bonded carbide。In-situ reactive synthesis technology is combined by the present invention with liquid phase sintering technology, is prepared for modified high manganese steel base TiC steel bonded carbide。Owing to TiC is at intrinsic silicon fabricated in situ by the reaction in sintering process, strengthening particle size tiny, surface is without wedge angle, and basal body interface combines better and clean interfaces。Prepared steel-bonded carbide method can carry heavy alloyed comprehensive mechanical property, and cheap, simple process。
Description
Technical field
The preparation method that the present invention relates to a kind of modified high manganese steel base TiC steel bonded carbide, particularly produces modified high manganese steel base TiC steel bonded carbide technical field with reaction sintering。
Background technology
Steel bonded carbide (hereinafter referred to as steel-bonded carbide) is with steel for matrix, and tungsten carbide, titanium carbide etc. adopt the high life mold materials between hard alloy and alloy tool steel, mould steel and high-speed steel and the engineering material of powder metallurgy process production for hard phase。The ratio range of steel-bonded carbide steel matrix Binder Phase and hard phase is quite extensive, and this just determines it and possesses following excellent properties: 1) processing performance widely, mainly can forgeability and machinable performance and heat-treatability and weldability。2) good physical and mechanical properties, is mainly manifested in the wearability suitable with high-cobalt hart metal；Rigidity high compared with steel, elastic modelling quantity, bending strength and comprcssive strength；Toughness high compared with hard alloy；And good self lubricity and high damping characteristic etc.。3) excellent chemical stability, such as high temperature resistant, antioxidation, anti-various dielectric corrosions etc.。Combination property due to the above-mentioned excellence of steel-bonded carbide, make it more and more occupy consequence in tool die material, wear part, high temperature resistant and corrosion resistant member material etc., and be used widely in fields such as intermetallic composite coating, five metals electronics, automobile, machinery, metallurgy, chemical industry, boats and ships, Aero-Space and nuclear industry and obtain good result。As compared with alloy tool steel, mould steel and high-speed steel, steel-bonded carbide can make die life number increase substantially with ten times of ground, and economic benefit is also extremely notable。
Tungsten carbide steel-bonded carbide compared by titanium carbide steel bonded carbide, and its cost is low, is suitable for marketing and uses。But the obdurability of its alloy is still relatively low, relatively big far from meeting more and more many power that withstands shocks, the use in the higher situation of impact velocity。Therefore Development and Production high-performance, low cost titanium carbide steel bonded carbide necessary。Wherein, the obdurability improving titanium carbide steel-bonded carbide is the research direction of emphasis。
At present, the method preparing TiC steel bonded carbide is mainly powder metallurgy lqiuid phase sintering method。Lqiuid phase sintering method can need select suitable Binder Phase and can adjust the content of hard phase in a big way according to practical application, but owing to the hard phase add mode generally in addition of powder metallurgy lqiuid phase sintering method introduces, the cost of raw material is high, granule is thick, hard phase titanium carbide is bad with the wettability of Binder Phase, interface vulnerable to pollution etc., therefore the steel bonded carbide prepared by lqiuid phase sintering method has porosity height, performance is low, high in cost of production shortcoming, for requiring that higher application scenario often needs through forging or hip treatment, the cost performance of material reduces further。
In recent years, the research adopting in-situ synthesis to prepare steel bonded carbide has been carried out both at home and abroad。Situ synthesis techniques is a kind of by alloy design, and under certain condition, in parent metal, reaction in-situ generates the advanced composite material (ACM) technology of preparing of one or more thermodynamically stable hard phases。Compared with traditional material preparation method, it is not contaminated mutually that this technology has preparation technology enhancing simple, produced in situ, and interface bond strength high, is the trend of steel bonded carbide technology of preparing development。
But in-situ synthesis also has many deficiencies: strengthen granule and be only limited to the thermodynamically stable grain in particular substrate；Comparing of generating is complicated, wayward；Granular size, shape are by the dynamics Controlling of forming core, growth process; and after in-situ particle formed; casting process often segregation can ask gap or grain boundary in dendrite; material structure and performance are produced harmful effect; and manufacturability is poor; preparation cost is higher than existing technique, is unsuitable for large-scale production。Obviously, situ synthesis techniques realize industrialization it is crucial that rational homogenization process must be studied further, optimum synthesis technique, reduce production cost。
Summary of the invention
For the deficiencies in the prior art, the preparation method that the invention provides a kind of modified high manganese steel base TiC steel bonded carbide, in order to improve the performance of TiC high-manganese steel-base steel bonded carbide。
A kind of preparation method of the modified high manganese steel base TiC steel bonded carbide of the present invention, its by the following technical solutions:
(1) raw material:
Raw materials is titanium valve, molybdenum-iron powder, ferrochrome powder, vanadium iron powder, ferromanganese powder, ferrosilicon powder, iron powder, nikel powder, aquadag, CeO2、Y3O2、La2O3One of them or three kinds, PVA, powder size is all below 10～50 μm；
(2) material preparation:
1) in-situ synthesizing TiC mixed-powder preparation: be 0.8～1.0 carry out being configured to in-situ synthesizing TiC mixed-powder by C/Ti atomic ratio by titanium (Ti) powder and graphite powder；
2) bonding phase matrix alloy powder preparation: bonding phase metal material chemical composition mass percent is: C1.0～1.5%, Cr1.8～2.5%, Mo0.6～2.0%, V0.5～2.0%, Si0.6～0.9%, Mn10～14%, Ni0.5～2.0%, S≤0.02, P≤0.02, CeO2、Y3O2、La2O3Combination≤0.8% of one of them or more than two kinds, surplus Fe, and inevitable impurity element；
3) modified high manganese steel base TiC Steel-bonded Cemented Carbide preparation: material chemical composition mass percent is: in-situ synthesizing TiC mixed-powder 30～60%, bonding phase matrix alloy powder 70～40%；
(3) step of preparation process is:
1) material preparation: be 0.8～1.0 in-situ synthesizing TiC mixed-powder carrying out being configured to required ratio in C/Ti atomic ratio by titanium (Ti) powder and graphite powder；By molybdenum-iron powder, ferrochrome powder, vanadium iron powder, ferromanganese powder, ferrosilicon powder, according to required chemical composition mass percent conversion, together with iron powder, nikel powder, aquadag, CeO2、Y3O2、La2O3The combination raw materials of one of them or more than two kinds presses proportions, wherein manganese carbon ratio >=3 needed for bonding phase metal material chemical composition mass percent；
2) bi-material is mixed by the ratio according to the TiC granule needed for Steel-bonded Cemented Carbide and matrix material, load in ball milling bucket, load steel ball, ratio of grinding media to material 5:1～10:1, add dehydrated alcohol and make medium and 0.5-1%PVA as coolant and dispersant, adopt vibrations ball mill ball milling 48-72 hour；
3) slip is sieved after drying, then make the product of required size shape at 350～500MPa pressure；
4) sintering under vacuum, sintering temperature is 1350 DEG C～1400 DEG C, and sintering process is: 10 DEG C/min of firing rate, sintering time is 30～40min, after being incubated 1～3 hour, furnace cooling, to room temperature, obtains the modified high manganese steel base TiC steel bonded carbide of required composition。
Beneficial effect
Compared with prior art, present invention have the advantage that
1, the present invention is with cheap titanium valve molybdenum-iron powder, ferrochrome powder, vanadium iron powder, ferromanganese powder, ferrosilicon powder, iron powder, nikel powder, aquadag is raw material, in-situ reactive synthesis technology is combined with liquid phase sintering technology, is prepared for the TiC High wear-resistant steel bond hard alloy that hard phase titanium carbide volume fraction is 30% one 50%。It is mainly characterized by: 1. owing to the TiC in steel bonded carbide is at intrinsic silicon fabricated in situ by the reaction in sintering process, so the method that can obtain the mixing of Ordinary hardening phase powder is difficult to reach, even inaccessiable granular and uniformity coefficient, basal body interface combines better and clean interfaces。2. fabricated in situ enhancing particle size is tiny, and surface is without wedge angle, and is evenly distributed in the base, thus improve bending strength and the properties of material。3. situ synthesis techniques and liquid phase sintering technology being combined together, simple process, cost are low。4. due to raw-material cheap, it is possible to be substantially reduced cost。Simultaneously the technique of this powder is possible not only to sinter in a vacuum, it is also possible to how sintering in the atmosphere such as hydrogen, has widened the means approach manufactured。
The present invention adopts high-energy ball milling mode to improve the activity of powder, and reaches the degree of titanium carbide and steel matrix Mechanical Alloying, thus improving titanium carbide and steel matrix affinity in sintering process, improves the obdurability of final alloy。Additionally, have employed the relatively low ferro-molybdenum of price in the present invention as raw material, it improves the wettability of titanium carbide and steel matrix further in sintering process, carries heavy alloyed obdurability。Therefore, the present invention prepares high-performance steel-bonded carbide method can carry heavy alloyed comprehensive mechanical property, and process is easy, saves cost。
2, the present invention is by adding CeO2、Y3O2、La2O3Inhibit growing up of crystal grain, and play the effect of dispersion-strengtherning。Due to CeO2、Y3O2、La2O3Chemical property is active, at a sintering temperature, and CeO2、Y3O2、La2O3Can with the impurity on metal dust interface and oxide-film effect, playing the effect purifying interface, contributing to the improvement of wettability, thus being conducive to the process of densification, reach to reduce the purpose of porosity, and the reduction of porosity will contribute to the raising of bending strength。CeO2、Y3O2、La2O3Powder content, between 0.2% and 0.5%, can play rare earth reinforced effect, and therefore the intensity of the steel bonded carbide of the present invention and consistency are improved, and bending strength can reach more than 1700MPa, and consistency reaches more than 97.4%。
3, the present invention adopts high-energy ball milling mode to improve the activity of powder, and reaches the degree of titanium carbide and steel matrix Mechanical Alloying, thus improving titanium carbide and steel matrix affinity in sintering process, improves the obdurability of final alloy。In addition, the present invention have employed the relatively low ferroalloy of price as raw material, and after adding a certain amount of molybdenum, it improves the wettability of titanium carbide and steel matrix further in sintering process, the hard phase TiC that steel bonded carbide situ is synthesized can be suppressed to grow up, make TiC particle size reduce, be evenly distributed。Improving the Binder Phase wettability to hard phase TiC owing to adding after molybdenum, be conducive to liquid phase filling to hole in sintering process, porosity is low, the density making steel bonded carbide is improved, crystal grain is tiny, even tissue, so that its hardness and bending strength and obdurability have also been obtained raising。Therefore, the present invention prepares high-performance steel-bonded carbide method can carry heavy alloyed comprehensive mechanical property, and process is easy, easy to operate, the sintering period is short, process costs is low, be suitable to industrialized production。
Detailed description of the invention
Technical scheme is further illustrated below in conjunction with detailed description of the invention:
Embodiment 1
A kind of preparation method of modified high manganese steel base TiC steel bonded carbide, its by the following technical solutions:
(1) raw material:
Raw materials is titanium valve, molybdenum-iron powder, ferrochrome powder, vanadium iron powder, ferromanganese powder, ferrosilicon powder, iron powder, nikel powder, aquadag, CeO2, PVA, powder size is all below 10～50 μm；
(2) material preparation:
1) in-situ synthesizing TiC mixed-powder preparation: be 0.85 carry out being configured to in-situ synthesizing TiC mixed-powder by C/Ti atomic ratio by titanium (Ti) powder and graphite powder；
2) bonding phase matrix alloy powder preparation: bonding phase metal material chemical composition mass percent is: C1.0%, Cr2.0%, Mo1.4%, V0.8%, Si0.6%, Mn11%, Ni1.2%, S≤0.02, P≤0.02, CeO2≤ 0.8%, surplus Fe, and inevitable impurity element；
3) modified high manganese steel base TiC Steel-bonded Cemented Carbide preparation: material chemical composition mass percent is: in-situ synthesizing TiC mixed-powder 30%, bonding phase matrix alloy powder 70%；
(3) step of preparation process is:
1) material preparation: be 0.85 carry out being configured to fabricated in situ 30%TiC mixed-powder by C/Ti atomic ratio by titanium (Ti) powder and graphite powder；By molybdenum-iron powder, ferrochrome powder, vanadium iron powder, ferromanganese powder, ferrosilicon powder, according to required chemical composition mass percent conversion, together with iron powder, nikel powder, aquadag, CeO2Bonding phase metal material chemical composition mass percent 70% proportions pressed by raw material；
2) bi-material of the fabricated in situ 30%TiC granule needed for Steel-bonded Cemented Carbide and matrix material 70% is mixed, load in ball milling bucket, load steel ball, ratio of grinding media to material 5:1, add dehydrated alcohol and make medium and 0.6%PVA as coolant and dispersant, adopt vibrations ball mill ball milling 55 hours；
3) slip is sieved after drying, then make the product of required size shape at 400MPa pressure；
4) sintering under vacuum, sintering temperature is 1370 DEG C, and sintering process is: 10 DEG C/min of firing rate, and sintering time is 30min, and after being incubated 1.5 hours, furnace cooling, to room temperature, obtains the modified high manganese steel base TiC steel bonded carbide of required composition。
Embodiment 2
A kind of preparation method of modified high manganese steel base TiC steel bonded carbide, its by the following technical solutions:
(1) raw material:
Raw materials is titanium valve, molybdenum-iron powder, ferrochrome powder, vanadium iron powder, ferromanganese powder, ferrosilicon powder, iron powder, nikel powder, aquadag, CeO2、Y3O2Two kinds, PVA, powder size is all below 10～50 μm；
(2) material preparation:
1) in-situ synthesizing TiC mixed-powder preparation: be 0.9 carry out being configured to in-situ synthesizing TiC mixed-powder by C/Ti atomic ratio by titanium (Ti) powder and graphite powder；
2) bonding phase matrix alloy powder preparation: bonding phase metal material chemical composition mass percent is: C1.3%, Cr2.2%, Mo1.8%, V1.5%, Si0.7%, Mn12%, Ni1.6%, S≤0.02, P≤0.02, CeO20.5%, Y3O20.3%, surplus Fe, and inevitable impurity element；
3) TiC high-manganese steel-base Steel-bonded Cemented Carbide preparation: material chemical composition mass percent is: fabricated in situ 40%TiC mixed-powder, bonding phase matrix alloy powder 60%；
(3) step of preparation process is:
1) material preparation: be 0.9 carry out being configured to institute's fabricated in situ 40%TiC mixed-powder by C/Ti atomic ratio by titanium (Ti) powder and graphite powder；By ferrochrome powder, molybdenum-iron powder, ferrosilicon powder, ferromanganese powder, vanadium iron powder, according to required chemical composition mass percent conversion, together with iron powder, nikel powder, aquadag, CeO2、Y3O2Bonding phase metal material chemical composition mass percent 60% proportions pressed by raw material；
2) bi-material of the 40%TiC granule of fabricated in situ needed for Steel-bonded Cemented Carbide and the ratio of matrix material 60% is mixed, load in ball milling bucket, load steel ball, ratio of grinding media to material 7:1, add dehydrated alcohol and make medium and 0.8%PVA as coolant and dispersant, adopt vibrations ball mill ball milling 62 hours；
3) slip is sieved after drying, then make the product of required size shape at 450MPa pressure；
4) sintering under vacuum, sintering temperature is 1390 DEG C, and sintering process is: 10 DEG C/min of firing rate, and sintering time is 35min, and after being incubated 2.3 hours, furnace cooling, to room temperature, obtains the modified high manganese steel base TiC steel bonded carbide of required composition。
Embodiment 3
A kind of preparation method of modified high manganese steel base TiC steel bonded carbide, its by the following technical solutions:
(1) raw material:
Raw materials is titanium valve, molybdenum-iron powder, ferrochrome powder, vanadium iron powder, ferromanganese powder, ferrosilicon powder, iron powder, nikel powder, aquadag, CeO2、Y3O2、La2O3, PVA, powder size is all below 10～50 μm；
(2) material preparation:
1) in-situ synthesizing TiC mixed-powder preparation: be 1.0 carry out being configured to in-situ synthesizing TiC mixed-powder by C/Ti atomic ratio by titanium (Ti) powder and graphite powder；
2) bonding phase matrix alloy powder preparation: bonding phase metal material chemical composition mass percent is: C1.0～1.5%, Cr1.8～2.5%, Mo0.6～2.0%, V0.5～2.0%, Si0.6～0.9%, Mn10～14%, Ni0.5～2.0%, S≤0.02, P≤0.02, CeO2、Y3O2、La2O3Combination≤0.8% of one of them or more than two kinds, surplus Fe, and inevitable impurity element；
2) bonding phase matrix alloy powder preparation: bonding phase metal material chemical composition mass percent is: C1.5%, Cr2.5%, Mo2.0%, V1.8%, Si0.8%, Mn13%, Ni2.0%, S≤0.02, P≤0.02, CeO20.3%, Y3O20.3%, La2O30.2%, surplus Fe, and inevitable impurity element；
3) TiC high-manganese steel-base Steel-bonded Cemented Carbide preparation: material chemical composition mass percent is: in-situ synthesizing TiC mixed-powder 48%, bonding phase matrix alloy powder 52%；
(3) step of preparation process is:
1) material preparation: be 1.0 carry out being configured to institute's fabricated in situ 48%TiC mixed-powder by C/Ti atomic ratio by titanium (Ti) powder and graphite powder；By molybdenum-iron powder, ferrochrome powder, vanadium iron powder, ferromanganese powder, ferrosilicon powder, according to required chemical composition mass percent conversion, together with iron powder, nikel powder, aquadag, CeO2、Y3O2, La2O3Bonding phase metal material chemical composition mass percent 52% proportions pressed by raw material；
2) bi-material of the 52%TiC granule of fabricated in situ needed for Steel-bonded Cemented Carbide and the ratio of matrix material 48% is mixed, load in ball milling bucket, load steel ball, ratio of grinding media to material 10:1, add dehydrated alcohol and make medium and 1%PVA as coolant and dispersant, adopt vibrations ball mill ball milling 72 hours；
3) slip is sieved after drying, then make the product of required size shape at 500MPa pressure；
4) sintering under vacuum, sintering temperature is 1420 DEG C, and sintering process is: 10 DEG C/min of firing rate, and sintering time is 40min, and after being incubated 3 hours, furnace cooling, to room temperature, obtains the modified high manganese steel base TiC steel bonded carbide of required composition。
Claims (2)
1. the preparation method of a modified high manganese steel base TiC steel bonded carbide, it is characterised in that include following technical scheme:
(1) material preparation:
1) in-situ synthesizing TiC mixed-powder preparation: be 0.8～1.0 carry out being configured to in-situ synthesizing TiC mixed-powder by C/Ti atomic ratio by titanium (Ti) powder and graphite powder；
2) bonding phase matrix alloy powder preparation: bonding phase metal material chemical composition mass percent is: C1.0～1.5%, Cr1.8～2.5%, Mo0.6～2.0%, V0.5～2.0%, Si0.6～0.9%, Mn10～14%, Ni0.5～2.0%, S≤0.02, P≤0.02, CeO2、Y3O2、La2O3Combination≤0.8% of one of them or more than two kinds, surplus Fe, and inevitable impurity element；
3) modified high manganese steel base TiC Steel-bonded Cemented Carbide preparation: material chemical composition mass percent is: in-situ synthesizing TiC mixed-powder 30～60%, bonding phase matrix alloy powder 70～40%；
(2) step of preparation process is:
1) material preparation: be 0.8～1.0 in-situ synthesizing TiC mixed-powder carrying out being configured to required ratio in C/Ti atomic ratio by titanium (Ti) powder and graphite powder；By molybdenum-iron powder, ferrochrome powder, vanadium iron powder, ferromanganese powder, ferrosilicon powder, according to required chemical composition mass percent conversion, together with iron powder, nikel powder, aquadag, CeO2、Y3O2、La2O3The combination raw materials of one of them or more than two kinds presses proportions, wherein manganese carbon ratio >=3 needed for bonding phase metal material chemical composition mass percent；
2) bi-material is mixed by the ratio according to the TiC granule needed for Steel-bonded Cemented Carbide and matrix material, load in ball milling bucket, load steel ball, ratio of grinding media to material 5: 1～10: 1, add dehydrated alcohol and make medium and 0.5-1%PVA as coolant and dispersant, adopt vibrations ball mill ball milling 48-72 hour；
3) slip is sieved after drying, then make the product of required size shape at 350～500MPa pressure；
4) sintering under vacuum, sintering temperature is 1350 DEG C～1400 DEG C, and sintering process is: 10 DEG C/min of firing rate, sintering time is 30～40min, after being incubated 1～3 hour, furnace cooling, to room temperature, obtains the high-manganese steel-base steel bonded carbide of required composition。
2. the preparation method of a kind of modified high manganese steel base TiC steel bonded carbide according to claim 1, it is characterised in that: powder size is all at 10～50 μm。
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| CN109898004A (en) * | 2019-03-20 | 2019-06-18 | 莱芜职业技术学院 | A kind of high tough titanium carbide-high manganese steel bonded carbide and preparation method and application |
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| CN112195388B (en) * | 2020-09-23 | 2022-02-18 | 湖南省冶金材料研究院有限公司 | Titanium carbide-based composite material and preparation method thereof |
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| CN103114232A (en) * | 2013-03-21 | 2013-05-22 | 湖南省冶金材料研究所 | Rare-earth modified steel-bonded hard alloy and preparation method |
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