CN105420587A - Preparation method for TiC high-boron low alloy high-speed steel-based steel bonded cemented alloy - Google Patents
Preparation method for TiC high-boron low alloy high-speed steel-based steel bonded cemented alloy Download PDFInfo
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Abstract
The invention discloses a preparation method for TiC high-boron low alloy high-speed steel-based steel bonded cemented alloy. Titanium and graphite powder are mixed with the mole ratio of atoms of C/Ti as 0.7-1.1 to form in-situ synthetic TiC mixed powder; vanadium iron powder, chromium iron powder, FeMo powder, boron iron powder, ferrosilicon powder, ferromanganese powder, iron powder, nickel powder, copper powder, aquadag and rare earth materials are mixed according to the needed proportion of the mass ratio of the bonding phase metal chemical components; and steel balls are put into for ball grinding, absolute ethyl alcohol serving as a medium and polyvinyl acetate are added, and slurry is dried after ball milling and then compressed to be molded and sintered to be the steel bonded cemented alloy. The in-situ reaction synthesis technology and the liquid phase sintering technology are combined, and the TiC high-boron low alloy high-speed steel-based steel bonded cemented alloy is prepared. The TiC is synthesized in an in-situ mode inside the base body through reaction in the sintering process, the size of reinforced particles is fine, and the base body interfaces are bonded better and clean. The preparation process is simple and convenient to implement, and the comprehensive mechanical performance of the alloy is improved.
Description
Technical field
The present invention relates to a kind of preparation method of TiC high-boron low-alloy high-speed steel base Steel Bond Hard Alloy, particularly produce a kind of preparation method of TiC high-boron low-alloy high-speed steel base Steel Bond Hard Alloy with reaction sintering.
Technical background
Steel Bond Hard Alloy (hereinafter referred to as steel-bonded carbide) take steel as matrix, wolfram varbide, titanium carbide etc. be hard phase adopt powder metallurgy process to produce between Wimet and the high life moulding stock between alloy tool steel, die steel and rapid steel and engineering materials.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 wear resistance suitable with high-cobalt hart metal; Rigidity high compared with steel, Young's modulus, bending strength and ultimate compression strength; Toughness high compared with Wimet; And good self lubricity and high damping characteristic etc.3) excellent chemical stability, as high temperature resistant, anti-oxidant, anti-various dielectric corrosions etc.Due to the over-all properties of the above-mentioned excellence of steel-bonded carbide, make it in tool die material, wear part, high temperature resistant and corrosion resistant member material etc., more and more occupy consequence, and be used widely in fields such as intermetallic composite coating, five metals electronics, automobile, machinery, metallurgy, chemical industry, boats and ships, aerospace and nuclear industry and obtain good result.As compared with alloy tool steel, die steel and rapid steel, steel-bonded carbide can make die life number increase substantially with ten times of ground, and economic benefit is also very remarkable.
Wolfram varbide steel-bonded carbide compared by titanium carbide Steel Bond Hard Alloy, and its cost is low, is applicable to marketing and uses.But the obdurability of its alloy is still lower, far can not meets more and more many power that withstands shocks comparatively large, use when in the higher situation of impact velocity.Therefore the titanium carbide Steel Bond Hard Alloy of Development and Production high-performance, low cost is necessary.Wherein, the obdurability improving titanium carbide steel-bonded carbide is the research direction of emphasis.
TiC has the physical and chemical performance of the excellences such as hardness is high, anti-oxidant, corrosion-resistant, proportion is little, Heat stability is good, is a kind of more satisfactory Steel Bond Hard Alloy hard phase material.V and Ti belongs to the transition metal of same period, and former ordinal number only differs 1, VC also has high-melting-point, high rigidity and high chemical stability, and the research about VC Steel Bond Hard Alloy also causes the interest of some investigators in recent years.
At present, the method mainly powder metallurgy lqiuid phase sintering method of Steel Bond Hard Alloy is prepared.Lqiuid phase sintering method can need to select suitable Binder Phase according to practical application and can adjust the content of hard phase in a big way, but due to the hard phase add mode introducing in addition usually of powder metallurgy lqiuid phase sintering method, material cost is high, particle is thick, the wettability of hard phase titanium carbide and Binder Phase is bad, interface vulnerable to pollution etc., therefore it is high that the Steel Bond Hard Alloy prepared by lqiuid phase sintering method has porosity, 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 that employing in-situ synthesis prepares Steel Bond Hard Alloy has been carried out both at home and abroad.Situ synthesis techniques is a kind of by alloy designs, and under certain condition, in matrix metal, reaction in－situ generates the advanced composite material technology of preparing of one or more thermodynamically stable hard phases.Compared with traditional material preparation method, the interface bond strength that this technology has wild phase and matrix is high, the kind of wild phase, size, distribution and quantity can control, preparation technology is simple, the wild phase of produced in situ is not contaminated, and interface bond strength is high, and cost is low, the intensity of material and Young's modulus high are the trend of Steel Bond Hard Alloy technology of preparing development.
But in-situ synthesis also has many deficiencies: enhanced granule is only limited to the thermodynamically stable grain in particular substrate; Comparing of generating is complicated, wayward; Granular size, shape are by the kinetic control of forming core, growth process; and after in-situ particle formed; often segregation gap or grain boundary can be asked in dendrite in castingprocesses; detrimentally affect is produced to material structure and performance; and manufacturability is poor; preparation cost is higher than existing technique, is unsuitable for large-scale production.Obviously, the key that situ synthesis techniques realizes industrialization must study rational homogenization process further, optimum synthesis technique, reduction production cost.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of preparation method of TiC high-boron low-alloy high-speed steel base Steel Bond Hard Alloy, in order to improve the performance of TiC Steel Bond Hard Alloy.
The preparation method of a kind of TiC high-boron low-alloy high-speed steel base Steel Bond Hard Alloy of the present invention, its by the following technical solutions:
(1) raw materials is titanium valve, vanadium iron powder, ferrochrome powder, ferrotungsten, molybdenum-iron powder, ferro-boron powder, iron powder, ferro-niobium, nickel powder, copper powder, ferrosilicon powder, ferromanganese powder, oildag, CeO
2, Y
3o
2, La
2o
3one of them or three kinds, PVA, powder size is all below 10 ~ 50 μm;
(2) material formulation:
1) in-situ synthesizing TiC mixed powder preparation: be 0.7 ~ 1.1 carry out being mixed with in-situ synthesizing TiC mixed powder by the atomic molar ratio of C/Ti by titanium (Ti) and Graphite Powder 99;
2) bonding phase matrix alloy powder preparation: bonding phase metal material chemical composition mass percent is: C0.2 ~ 0.6%, Cr5.0 ~ 7.0%, W2.5 ~ 3.0%, Mo1.5 ~ 3.0%, V1.5 ~ 2.5%, Nb0.5 ~ 1.0%, Si0.3 ~ 1.0%, Mn0.3 ~ 1.0%, B1.4 ~ 2.5%, Cu0.3 ~ 1.0%, Ni0.8 ~ 2.0%, S≤0.02, P≤0.02, CeO
2, Y
3o
2, La
2o
3combination≤0.8%, the surplus Fe of one of them or more than two kinds, and inevitable impurity element;
3) TiC Steel-bonded Cemented Carbide preparation: material chemical composition mass percent is: in-situ synthesizing TiC mixed powder 30 ~ 50%, bonding phase matrix alloy powder 70 ~ 50%;
(3) step of preparation process is:
1) material formulation:: be 0.7 ~ 1.1 carry out being mixed with in-situ synthesizing TiC mixed powder by titanium (Ti) and Graphite Powder 99 by the atomic molar ratio of C/Ti; By ferrochrome powder, molybdenum-iron powder, ferrosilicon powder, ferromanganese powder, ferro-boron powder converts according to required chemical composition mass percent, together with iron powder, nickel powder, copper powder, oildag, CeO
2, Y
3o
2, La
2o
3the combination raw materials of one of them or more than two kinds presses proportions needed for bonding phase metal material chemical composition mass percent;
2) bi-material mixes by the TiC particle needed for Steel-bonded Cemented Carbide and the ratio of body 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 refrigerant and dispersion agent, adopt vibrations ball mill ball milling 48 ~ 72 hours;
3) sieve after slip drying, then make the product of desired size shape at 350 ~ 500MPa pressure;
4) sinter under vacuum, sintering temperature is 1350 DEG C ~ 1420 DEG C, and sintering process is: rate of heating 10 DEG C/min, and sintering time is 30 ~ 40min, is incubated after 1 ~ 3 hour, and furnace cooling, to room temperature, obtains the high temperature steel bond hard alloy of required composition.
beneficial effect
Compared with prior art, tool of the present invention has the following advantages:
1, the present invention is with cheap titanium valve, vanadium iron powder, iron powder, ferrochrome powder, molybdenum-iron powder, ferrosilicon powder, ferromanganese powder, ferro-boron powder, nickel powder, copper powder, oildag is raw material, in-situ reactive synthesis technology is combined with liquid phase sintering technology, has prepared the TiC high-boron low-alloy high-speed steel base Steel Bond Hard Alloy that hard phase titanium carbide volume fraction is 30% ~ 50%.Its principal feature is: 1. because the TiC in Steel Bond Hard Alloy 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 degree of uniformity, basal body interface combines better and clean interfaces.2. fabricated in situ enhanced granule size is tiny, and surface without wedge angle, and is evenly distributed in the base, thus improves bending strength MPa and the properties of material.3. situ synthesis techniques and liquid phase sintering technology are combined together, simple process, cost are low.4. due to raw-material cheap, can greatly reduce costs.Not only can sinter in a vacuum in the technique of simultaneously this powder, also how can sinter in the atmosphere such as hydrogen, widen the means approach manufactured.5. due to the introducing of vanadium, make the form of TiC particle more regular than Ti, the form rounding more of TiC wild phase particle.
The present invention adopts high-energy ball milling mode to improve the activity of powder, and reaches the degree of titanium carbide and vanadium and steel matrix Mechanical Alloying, thus improves titanium carbide and vanadium and the affinity of steel matrix in sintering process, improves the obdurability of final alloy.In addition, have employed the lower ferro-molybdenum of price in the present invention as raw material, it improves the wettability of titanium carbide and vanadium 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, cost-saving.
2, the present invention is by adding CeO
2, Y
3o
2, La
2o
3inhibit growing up of crystal grain, and play the effect of dispersion-strengthened.Due to CeO
2, Y
3o
2, La
2o
3chemical property is active, at a sintering temperature, and CeO
2, Y
3o
2, La
2o
3can with the impurity on metal-powder interface and oxide film effect, play the effect at purification interface, contribute to the improvement of wettability, thus be conducive to the process of densification, reach the object of reduction holes porosity, and the reduction of porosity will contribute to the raising of bending strength.CeO
2, Y
3o
2, La
2o
3powder content is between 0.2% and 0.5%, rare earth reinforced effect can be played, therefore the intensity of Steel Bond Hard Alloy of the present invention and density are improved, bending strength can reach more than 1700MPa, density reaches more than 97.4%, hardness reaches about 90HRA, and wear resistance is 5 times and 6.5 times of rich chromium cast iron respectively.
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 improves titanium carbide and vanadium and the affinity of steel matrix in sintering process, improves the obdurability of final alloy.In addition, the lower iron alloy of price is have employed as raw material in the present invention, and after adding a certain amount of molybdenum and boron, it improves the wettability of titanium carbide and vanadium and steel matrix further in sintering process, the hard phase TiC of Steel Bond Hard Alloy situ Reactive Synthesis can be suppressed to grow up, TiC particle size is reduced, is evenly distributed.The wettability of Binder Phase to hard phase TiC is improved after adding molybdenum and boron, be conducive to liquid phase filling to hole in sintering process, porosity is low, the density of Steel Bond Hard Alloy is improved, crystal grain is tiny, homogeneous microstructure, thus make 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 for suitability for industrialized production.
Embodiment
Technical scheme of the present invention is further illustrated below in conjunction with embodiment:
Embodiment 1
A preparation method for TiC high-boron low-alloy high-speed steel base Steel Bond Hard Alloy, its by the following technical solutions:
(1) raw materials is titanium valve, vanadium iron powder, ferrochrome powder, molybdenum-iron powder, ferrosilicon powder, ferromanganese powder, ferro-boron powder, iron powder, nickel powder, copper powder, oildag, CeO
2, PVA, powder size is all below 10 ~ 50 μm;
(2) material formulation:
1) in-situ synthesizing TiC mixed powder preparation: be 0.8 carry out being mixed with in-situ synthesizing TiC mixed powder by the atomic molar ratio of C/Ti by titanium (Ti) and Graphite Powder 99;
2) bonding phase matrix alloy powder preparation: bonding phase metal material chemical composition mass percent is: C0.3%, Cr5.0%, W2.5%, Mo1.8%, V1.7%, Nb0.4%, Si0.5%, Mn0.5%, B1.6%, Cu0.5%, Ni0.9%, S≤0.02, P≤0.02, CeO
20.8%, surplus Fe, and inevitable impurity element;
3) 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) then material formulation: by titanium (Ti) and vanadium iron powder according to titanium: vanadium is that the ratio of 1:1 is prepared is 0.8 carry out being mixed with fabricated in situ 30%TiC mixed powder with Graphite Powder 99 by the atomic molar ratio of C/Ti; By ferrochrome powder, molybdenum-iron powder, ferrosilicon powder, ferromanganese powder, ferro-boron powder converts according to required chemical composition mass percent, together with iron powder, nickel powder, copper powder, oildag, CeO
2bonding phase metal material chemical composition mass percent 70% proportions pressed by raw material;
2) bi-material mixes by the TiC particle needed for Steel-bonded Cemented Carbide and the ratio of body material, load in ball milling bucket, load steel ball, ratio of grinding media to material 5:1, add dehydrated alcohol and make medium and 0.5%PVA as refrigerant and dispersion agent, adopt vibrations ball mill ball milling 48 hours;
3) sieve after slip drying, then make the product of desired size shape at 380MPa pressure;
4) sinter under vacuum, sintering temperature is 1380 DEG C, and sintering process is: rate of heating 10 DEG C/min, and sintering time is 30min, is incubated after 1.5 hours, and furnace cooling, to room temperature, obtains the high temperature steel bond hard alloy of required composition.
Embodiment 2
A preparation method for TiC high-boron low-alloy high-speed steel base Steel Bond Hard Alloy, its by the following technical solutions:
(1) raw materials is titanium valve, vanadium iron powder, ferrochrome powder, molybdenum-iron powder, ferrosilicon powder, ferromanganese powder, ferro-boron powder, iron powder, nickel powder, copper powder, oildag, CeO
2, Y
3o
2two kinds, PVA, powder size is all below 10 ~ 50 μm;
(2) material formulation:
1) then in-situ synthesizing TiC mixed powder preparation: by titanium (Ti) and vanadium iron powder according to titanium: vanadium is that the ratio of 1:1 is prepared is 0.8 carry out being mixed with in-situ synthesizing TiC mixed powder with Graphite Powder 99 by the atomic molar ratio of C/Ti;
2) bonding phase matrix alloy powder preparation: bonding phase metal material chemical composition mass percent is: C0.4%, Cr6.0%, W2.8%, Mo2.5%, V2.0%, Nb0.5%, Si0.6%, Mn0.6%, B2.0%, Cu0.6%, Ni1.2%, S≤0.02, P≤0.02, CeO
20.5%, Y
3o0.3%, surplus Fe, and inevitable impurity element;
3) TiC Steel-bonded Cemented Carbide preparation: material chemical composition mass percent is: in-situ synthesizing TiC mixed powder 40%, bonding phase matrix alloy powder 60%;
(3) step of preparation process is:
1) then material formulation: by titanium (Ti) and vanadium iron powder according to titanium: vanadium is that the ratio of 1:1 is prepared is 0.92 carry out being mixed with fabricated in situ 40%TiC mixed powder with Graphite Powder 99 by the atomic molar ratio of C/Ti; By ferrochrome powder, molybdenum-iron powder, ferrosilicon powder, ferromanganese powder, ferro-boron powder converts according to required chemical composition mass percent, together with iron powder, nickel powder, copper powder, oildag, CeO
2bonding phase metal material chemical composition mass percent 60% proportions pressed by raw material;
2) bi-material of the 40%TiC particle of fabricated in situ needed for Steel-bonded Cemented Carbide and the ratio of body material 60% is mixed, load in ball milling bucket, load steel ball, ratio of grinding media to material 8:1, add dehydrated alcohol and make medium and 0.8%PVA as refrigerant and dispersion agent, adopt vibrations ball mill ball milling 62 hours;
3) sieve after slip drying, then make the product of desired size shape at 450MPa pressure;
4) sinter under vacuum, sintering temperature is 1390 DEG C, and sintering process is: rate of heating 10 DEG C/min, and sintering time is 35min, is incubated after 2.3 hours, and furnace cooling, to room temperature, obtains the high temperature steel bond hard alloy of required composition.
Embodiment 3
A preparation method for TiC high-boron low-alloy high-speed steel base Steel Bond Hard Alloy, its by the following technical solutions:
(1) raw materials is titanium valve, vanadium iron powder, ferrochrome powder, molybdenum-iron powder, ferrosilicon powder, ferromanganese powder, ferro-boron powder, iron powder, nickel powder, copper powder, oildag, CeO
2, Y
3o
2, La
2o
3, PVA, powder size is all below 10 ~ 50 μm;
(2) material formulation:
1) in-situ synthesizing TiC mixed powder preparation: be 1.0 carry out being mixed with in-situ synthesizing TiC mixed powder by C/Ti atomic ratio by titanium (Ti) powder and Graphite Powder 99;
2) bonding phase matrix alloy powder preparation: bonding phase metal material chemical composition mass percent is: C0.5%, Cr7.0%, W3.0%, Mo3.0%, V2.5%, Nb1.0%, Si1.0%, Mn0.7%, B2.1%, Cu0.8%, Ni2.0%, S≤0.02, P≤0.02, CeO
20.3%, Y
3o
20.3%, La
2o
30.2%, surplus Fe, and inevitable impurity element;
3) (TiV) C Steel-bonded Cemented Carbide preparation: material chemical composition mass percent is: fabricated in situ (TiV) C mixed powder 50%, bonding phase matrix alloy powder 50%;
(3) step of preparation process is:
1) then material formulation: by titanium (Ti) and vanadium iron powder according to titanium: vanadium is that the ratio of 1:1 is prepared is 1.05 carry out being mixed with fabricated in situ 50%TiC mixed powder with Graphite Powder 99 by the atomic molar ratio of C/Ti; By ferrochrome powder, molybdenum-iron powder, ferrosilicon powder, ferromanganese powder, ferro-boron powder converts according to required chemical composition mass percent, together with iron powder, nickel powder, copper powder, oildag, CeO
2bonding phase metal material chemical composition mass percent 50% proportions pressed by raw material;
2) bi-material of the 50%TiC particle of fabricated in situ needed for Steel-bonded Cemented Carbide and the ratio of body material 50% 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 1.0%PVA as refrigerant and dispersion agent, adopt vibrations ball mill ball milling 72 hours;
3) sieve after slip drying, then make the product of desired size shape at 500MPa pressure;
4) sinter under vacuum, sintering temperature is 1420 DEG C, and sintering process is: rate of heating 10 DEG C/min, and sintering time is 40min, is incubated after 3 hours, and furnace cooling, to room temperature, obtains the high temperature steel bond hard alloy of required composition.
Claims (2)
1. a preparation method for TiC high-boron low-alloy high-speed steel base Steel Bond Hard Alloy, is characterized in that comprising following technical scheme:
(1) material formulation:
1) in-situ synthesizing TiC mixed powder preparation: be 0.7 ~ 1.1 carry out being mixed with in-situ synthesizing TiC mixed powder by the atomic molar ratio of C/Ti by titanium (Ti) and Graphite Powder 99;
2) bonding phase matrix alloy powder preparation: bonding phase metal material chemical composition mass percent is: C0.2 ~ 0.6%, Cr5.0 ~ 7.0%, W2.5 ~ 3.0%, Mo1.5 ~ 3.0%, V1.5 ~ 2.5%, Nb0.5 ~ 1.0%, Si0.3 ~ 1.0%, Mn0.3 ~ 1.0%, B1.4 ~ 2.5%, Cu0.3 ~ 1.0%, Ni0.8 ~ 2.0%, S≤0.02, P≤0.02, CeO
2, Y
3o
2, La
2o
3combination≤0.8%, the surplus Fe of one of them or more than two kinds, and inevitable impurity element;
3) TiC Steel-bonded Cemented Carbide preparation: material chemical composition mass percent is: in-situ synthesizing TiC mixed powder 30 ~ 50%, bonding phase matrix alloy powder 70 ~ 50%;
(2) step of preparation process is:
1) material formulation: be 0.7 ~ 1.1 carry out being mixed with in-situ synthesizing TiC mixed powder by the atomic molar ratio of C/Ti by titanium (Ti) and Graphite Powder 99; By ferrochrome powder, molybdenum-iron powder, ferrosilicon powder, ferromanganese powder, ferro-boron powder converts according to required chemical composition mass percent, together with iron powder, nickel powder, copper powder, oildag, CeO
2, Y
3o
2, La
2o
3the combination raw materials of one of them or more than two kinds presses proportions needed for bonding phase metal material chemical composition mass percent;
2) bi-material mixes by the TiC particle needed for Steel-bonded Cemented Carbide and the ratio of body 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 refrigerant and dispersion agent, adopt vibrations ball mill ball milling 48 ~ 72 hours;
3) sieve after slip drying, then make the product of desired size shape at 350 ~ 500MPa pressure;
4) sinter under vacuum, sintering temperature is 1350 DEG C ~ 1420 DEG C, and sintering process is: rate of heating 10 DEG C/min, and sintering time is 30 ~ 40min, is incubated after 1 ~ 3 hour, and furnace cooling, to room temperature, obtains the high temperature steel bond hard alloy of required composition.
2. the preparation method of a kind of TiC high-boron low-alloy high-speed steel base Steel Bond Hard Alloy according to claim 1, is characterized in that: raw materials is titanium valve, vanadium iron powder, ferrochrome powder, ferrotungsten, molybdenum-iron powder, ferro-boron powder, iron powder, ferro-niobium, nickel powder, copper powder, ferrosilicon powder, ferromanganese powder, oildag, CeO
2, Y
3o
2, La
2o
3one of them or three kinds, PVA, powder size is all below 10 ~ 50 μm.
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| CN106811701A (en) * | 2017-02-09 | 2017-06-09 | 江苏汇诚机械制造有限公司 | A kind of preparation method of high-toughness heat-resistant VC steel bonded carbide |
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