CN106591711A - Preparation method for high strength and toughness modified high manganese steel based TiN steel bonded cemented carbide - Google Patents
Preparation method for high strength and toughness modified high manganese steel based TiN steel bonded cemented carbide Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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- C22C33/02—Making ferrous alloys by powder metallurgy
- C22C33/0207—Using a mixture of prealloyed powders or a master alloy
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- C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
- C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
- C22C33/0292—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5% with more than 5% preformed carbides, nitrides or borides
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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
Abstract
The invention relates to a preparation method for high strength and toughness modified high manganese steel based TiN steel bonded cemented carbide. The preparation method is characterized in that in-situ synthesis TiN powder is prepared, wherein one or three of TiO2 powder, TiH2 powder and Ti powder and urea ((NH2)2CO) are prepared into the in-situ synthesis TiN mixed powder according to the N/Ti atomic ratio being 0.4-1.1; molybdenum iron powder, vanadium iron powder, chrome iron powder, ferromanganese powder, ferrosilicon powder, iron powder, nickel powder, colloidal graphite and rare earth raw materials are prepared according to the required mass ratio of bonding-phase metal chemical compositions, the raw materials are put into a steel ball for ball milling, anhydrous ethanol are added to serve as a medium and PVA, slurry obtained after ball milling is dried to be pressed and formed, sintering is conducted, and the TiN steel bonded cemented carbide is obtained. According to the preparation method, an in-situ reaction synthesis technology is combined with a liquid-phase sintering technology, strengthening particles are wee in size, the surfaces of the particles are free of sharp corners, the base body interface bonding is good, and the interface is clean. By means of the preparation method for the steel bonded cemented carbide, the comprehensive mechanical performance of the cemented carbide can be improved, the cost is low, and the process is simple and convenient to implement.
Description
Invention field
The present invention relates to a kind of preparation method of high tough modified high manganese steel base TiN steel bonded carbide, particularly with anti-
Sintering process is answered to produce high tough modified high manganese steel base TiN steel bonded carbide technical fields.
Background of invention
Steel bonded carbide（Hereinafter referred to as steel-bonded carbide）It is that, based on steel, tungsten carbide, titanium carbide etc. are adopted for hard phase
The high life mold materials between hard alloy and alloy tool steel, mould steel and high-speed steel of powder metallurgy process production
And engineering material.Steel-bonded carbide steel matrix Binder Phase and the ratio range of hard phase are quite extensive, this just determine it possess as
Lower excellent properties：1）Extensive processing performance, mainly can forgeability and machinable performance and heat-treatability and
Weldability.2）Good physical and mechanical propertiess, are mainly manifested in the wearability suitable with high-cobalt hart metal；Compared with steel
High rigid, elastic modelling quantity, bending strength and comprcssive strength；The higher toughness compared with hard alloy；And good profit certainly
Slip and high damping characteristic etc..3）Excellent chemical stability, such as high temperature resistant, antioxidation, anti-various dielectric corrosions etc..Due to
The above-mentioned excellent combination property of steel-bonded carbide so that it is in tool die material, wear part, high temperature resistant and corrosion resistant member material
The aspects such as material more and more occupy consequence, and intermetallic composite coating, five metals electronics, automobile, machinery, metallurgy, chemical industry, ship,
It is used widely and obtains good result in the field such as Aero-Space and nuclear industry.Such as with alloy tool steel, mould steel and height
Fast steel is compared, and steel-bonded carbide can make die life number and be increased substantially with ten times of ground, and economic benefit is also extremely notable.
In recent years, be obtain steel bonded carbide some particular tissues and performance, and alleviate due to conventional rigid alloy
The problems such as material Main Resources W, Co are increasingly deficient, has been carried out to steel bonded carbide both at home and abroad and has more extensively been ground with deep
Study carefully, research particularly to the different New Rigid phases of addition (such as addition A1203, TiN, NbC, TiCN, TiB2, Mo2FeB2,
Mo2C, Cr3C2, VC, NV etc.).In recent years, some new hard phase steel-bonded carbides are continued to bring out.
TiB2 has heat-resisting quantity good, and density and resistivity are little, and conductivity is good, and metal adhesiveness is low and friction factor
It is low, the features such as non-oxidizability is strong, it is considered to be a kind of preferable steel-bonded carbide hard phase.Because of the solid solubility between Fe and TiB2
Low, wettability is good, and Mo can also improve its wettability, therefore the advantage of synthesis TiB2 and Fe, Mo, has made TiB.FeMo composite woods each
Material.
Japanese certain company develops and a kind of does not contain W, Co but the boride-based composite KMH of the M02FeB2 types containing Cr.
Such polynary boride-based alloy be prepared using water atomization Fe-Cr-B alloy powders, boride powder and Fe, Cr, Mo,
The metal dusts such as Ni make raw material, Jing wet grindings mixing, the method manufacture of compressing and vacuum-sintering.
In addition to above-mentioned new steel bonded carbide, Japanese some companies also utilize a variety of hard compounds (such as
TiC, VC, Cr3C2, SiC, ZrC, AlN etc.) and its mixing cpd make hard phase, make binding agent with various steel or ferrous alloy,
Develop some advanced composite material (ACM)s.
Meanwhile, people also in the combination for constantly seeking new hard phase and new Binder Phase, have most preferably to develop
The MC type particulate reinforced composites of tissue and performance.In steel-bonded carbide, the hard particulate carbide species as wear-resistant phase
Comparison is more, has the ceramic particles such as WC, TiC, Cr7C3, NbC, VC, SiC and alloy carbide and cementite.MC type carbides
Thermodynamic stability putting in order from high to low be：TiC ＞ NbC ＞ VC ＞ WC, putting in order for its hardness be：TiC ＞ VC
＞ WC ＞ NbC.It is known that TiC is poor with Fe intermiscibilities.Sintering temperature is high, and strength ratio WC is poor, and its advantage is light weight, thermally-stabilised
Property, frictional property are good；WC high temperature is bad with Fe intermiscibilities, is easily dissolved in Fe during high temperature, and high high-temp stability, calorific intensity are poor,
Separate out in cooling procedure so as to form bridge joint, deteriorate the mechanical performance of alloy；As carbide V element, with
Ti elements are similar to, and V is also a kind of very active alloying element, first with C, N etc. to have very strong affinity.The parent of V element and C
With power more than Cr elements and the affinity of C, two kinds of stable carbides of VC and V2C are easily formed.In carbide ceramics, VC's is hard
Degree highest, and have good heat stability, it is that a kind of preferable hard strengthens phase.
Ti base cemented carbides refer to the hard alloy based on TiC or Ti (C, N).Compared with WC base cemented carbides, Ti bases
The hardness of hard alloy is higher, and density is little, and high temperature resistant, wear-resistant, corrosion resistance are stronger, and has very good anti stick, resists
The ability of diffusive wear.Ti base cemented carbides can be divided into by composition and performance:（1）TiC based alloys；（2）Ti (C, N) based alloy.
As TiC based alloy toughness is very low, too many concern is never obtained.Until 20 century 70s, Kieffer et al. have found
In addition TiN to TiC-Mo-Ni series hard metals, hard phase crystal grain is significantly refined, the room temperature and high temperature power of hard alloy
Learning performance is also substantially improved, and adds appropriate TiN, can improve TiC steel bonded carbide into nuclear concentration, refinement is brilliant
Grain promotes homogeneous grain size, and the high temperature corrosion-resisting and non-oxidizability of hard alloy can be also significantly increased after adding TiN
Can, while improving the hardness and bending strength of material.In addition, the addition of TiN produces the effect that interfacial effect reduces crystal boundary, suppression
Dislocation motion in fracture process processed, plays pinning effect and can also improve intensity to breakaway poing.Therefore, Ti (C, N) bases hard is closed
Gold causes the great interest of researchers.TiN is strong as the little oxidation resistance of hard phase free energy, and it rubs and steel matrix between
Effect is little, and the wettability of its Binder Phase is better than TiC, and antisticking ability is more higher than TiC, and free energy is less, oxidation resistance temperature model
Enclose big.
Ai Te Vit of Germany have developed a kind of mono- ITE of steel bonded carbide CORO using TiN as hard phase.
TiN particle sizes in mono- ITE of hard alloy CORO are about 0.1 um, are evenly distributed in heat treatable steel matrix,
Therefore CORO-ITE is provided simultaneously with the high tenacity of the high rigidity and steel matrix of hard alloy.CORO-ITE hard alloys oneself successfully
Apply in many fields, show excellent performance the potentiality being improved.The milling cutter manufactured with CORO-ITE hard alloys is cut
The rate of cutting is 3 times of high-speed steel milling cutter, while its use time extends 2 times.
Sandvik AB of Sweden has developed a kind of new steel-bonded carbide CORONlTE based on TiN.They are using a kind of
Special process, the TiN powder of superfine (about 0.1 micron) is equably added in heat treatable steel matrix, its volume content
Can be from 35% to 60%, as TiN powder is thin and performance and its stable, obtained CORONITE alloys have concurrently by this method
The toughness of the wearability and high-speed steel of hard alloy.
Japan also using water atomization and sintering process develop with TiN as hard phase can machining and heat treatable steel
Bond hard alloy H34A.By the water atomization comminuted steel shot of tungsten, aluminum and high carbon content is mixed with 10wt%TiN powder, re-compacted molding
Sintering obtains H34A afterwards.H34A hardness after annealing reaches 46～48HRc, can carry out machining, and the tempering of H34A
Hardness is more up to more than 72HRc, this is because matrix is hardened due to possessing high-carbon quantity and WC, the disperse of MoC, TiN granule
Reinforcing, therefore the alloy possesses excellent cutting ability.During as the such as cutting element of drill bit, end mill(ing) cutter etc, performance is bright
It is aobvious to be better than high-speed steel and ordinary rigid alloy.
The presence of TiN can improve alloy eutectic temperature, hinder Ti and Mo to carry out counterdiffusion by liquid phase so that Mo in liquid phase
Content increases and the concentration of Ti reduces, and while the precipitation for suppressing crystal grain is grown up, also inhibits the formation of brittle mesophase, from
And make ceramic metal obtain higher toughness and wearability.By adding TiN, the nucleation that can improve TiC steel bonded carbide is dense
Degree, crystal grain thinning promote homogeneous grain size, while improving the hardness and bending strength of material.In addition, the addition of TiN is produced
Interfacial effect reduces the effect of crystal boundary, suppresses the dislocation motion in fracture process, pinning effect is played to breakaway poing and can also be carried
High intensity.Therefore, research and develop new TiN bases steel bonded carbide and there is good economic benefit, to widening hard alloy
Hard phase, saves precious alloy resource, improves its industrial value and using value, have great importance.
TiN based ceramic metals have density low, and hardness is high, wear-resistant, the excellent physical and mechanical propertiess such as resistance to high temperature oxidation,
And low production cost, there is high cost performance, conventional rigid alloy material can be substituted, be widely used at a high speed, high accuracy
Tool for cutting machining on.Meanwhile, this novel hard alloy can be replaced in industries such as automobile, metallurgy, mine, building materials and moulds
For traditional high-abrasive material, parts service life is increased substantially, is economized on resources, with good economic results in society.This
Outward, artificial with industrial wilderness demand and inevitably to waste, China or even worldwide W, Co resource are
Jing is quite poor, and price rises steadily, and each national capital Efforts To Develop seeks the research and development of the substitute material of W, Co.And China TiV
Ore resources enrich, and replace W to have very high feasibility in resource with Ti.Therefore, research and develop TiN bases steel bonded carbide without
In terms of being engineer applied, or all it is significant in terms of Technological Economy.
The obdurability of the alloy manufactured by steel bonded carbide manufacturing process developed at present is still relatively low, far from satisfaction
More and more many power that withstands shocks is larger, the use in the case of impact velocity is higher.Therefore Development and Production high-performance, low cost
Steel bonded carbide is necessary.Wherein, the obdurability for improving steel-bonded carbide is the research direction of emphasis.
At present, the method for preparing steel bonded carbide is mainly powder metallurgy lqiuid phase sintering method.Lqiuid phase sintering method can be with root
Need to select appropriate Binder Phase can be in the interior content for adjusting hard phase in a big way, but due to powder metallurgy according to practical application
The hard phase of lqiuid phase sintering method is generally introduced in the way of adding, cost of raw material height, thick granule, hard phase titanium carbide and bonding
Bad, interface vulnerable to pollution of wettability of phase etc., therefore the steel bonded carbide prepared by lqiuid phase sintering method has porosity
The shortcomings of height, low performance, high cost, for require higher application scenario often need through forging or hip treatment, material
The cost performance of material is further reduced.
In recent years, the research that steel bonded carbide is prepared using in-situ synthesis has been carried out both at home and abroad.Situ synthesis techniques
Be it is a kind of design by alloy, under certain condition in parent metal reaction in-situ to generate one or more thermodynamically stable
The advanced composite material (ACM) technology of preparing of hard phase.Compared with traditional material preparation method, the technology have preparation process is simple,
The enhancing of produced in situ is not mutually contaminated, the features such as interface bond strength is high, is becoming for steel bonded carbide technology of preparing development
Gesture.
But in-situ synthesis also have many deficiencies:Strengthen granule and be only limited to the thermodynamically stable grain in particular substrate；
Comparing for generating is more complicated, wayward；Granular size, shape receive forming core, the dynamics Controlling of growth process, and in-situ particle
After formation, the often meeting segregation in casting process asks gap or grain boundary in dendrite, produces bad shadow to material structure and performance
Ring, and manufacturability is poor, preparation cost is higher than existing process, is unsuitable for large-scale production.Obviously, situ synthesis techniques are realized producing
The key of industry is must further to study rational homogenization process, optimum synthesis technique, reduction production cost.
The content of the invention
For the deficiencies in the prior art, the invention provides a kind of high tough modified high manganese steel base TiN steel bonded carbide
Preparation method, to the performance for improving TiN steel bonded carbide.
The preparation method of a kind of high tough modified high manganese steel base TiN steel bonded carbide of the present invention, which adopts following skill
Art scheme：
(1) raw material：Raw materials are that Ti02 powder, TiH2 powder or Ti powder are one kind of or three kinds, ferrochrome powder, molybdenum-iron powder,
Vanadium iron powder, ferromanganese powder, ferrosilicon powder, iron powder, nikel powder, aquadag, industrial urea ((NH2) 2CO) or ammonia, CeO2, Y3O2,
One of La2O3 or three kinds, PVA, powder size is at 10～50 μm；
(2) material is prepared：
1）Fabricated in situ TiN powder is prepared：By Ti02 powder, TiH2 powder or Ti powder one kind of or three kinds and carbamide ((NH2)
2CO) carry out being configured to fabricated in situ TiN mixed-powders for 0.4～1.1 by N/Ti atomic ratios；
2）Bonding phase matrix alloy powder is prepared：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）High tough modified high manganese steel base Ti Steel-bonded Cemented Carbides are prepared：Material chemical composition mass percent is：It is in situ
Synthesis TiN powder 30～50%, bonding phase matrix alloy powder 70～50%；
(3) step of preparation process is：
1）TiN powder material is prepared：By Ti02 powder, TiH2 powder or Ti powder one kind of and industrial urea ((NH2) 2CO) by N/
Ti atomic ratios carry out being configured to fabricated in situ TiN mixed-powders for 0.4～1.1；Load in polyurethane ball milling bucket, load rustless steel
Steel ball, ratio of grinding media to material 10:1～20:1, add dehydrated alcohol to make medium and dispersant, carry out sealing ball milling 48 using vibrations ball mill
～72 hours, it is prepared into TiN powder；
2）Material is prepared：By the TiN powder for preparing and molybdenum-iron powder, ferrochrome powder, vanadium iron powder, ferromanganese powder, ferrosilicon powder, according to required
Chemical composition mass percent conversion, together with one of iron powder, nikel powder, aquadag, CeO2, Y3O2, La2O3 or two
The combination raw materials for planting the above press the preparation of bonding phase metal material chemical composition mass percent required ratio, wherein manganese carbon ratio >=3；
3）The ratio of fabricated in situ TiN mixed-powders and bonding phase matrix alloy powder according to needed for Steel-bonded Cemented Carbide
Bi-material is mixed, is loaded in ball milling bucket, is loaded steel ball, ratio of grinding media to material 5:1～10:1, add dehydrated alcohol make medium and
0.5～1%PVA adds 5～10% industrial ureas or ammonia as nitrogen source, using vibrations ball mill as coolant and dispersant
Carry out sealing ball milling 48～72 hours；
4）Sieve after slip is dried, the product of required size shape is then pressed under 350～500 MPa pressure；
5）Sinter under vacuum, sintering temperature is 1400 DEG C～1500 DEG C, sintering process is:10 DEG C/min of firing rate,
The Isothermal sinter of 2～5 hours is carried out after reaching sintering temperature, furnace cooling to room temperature obtains the high tough modified of required composition
High-manganese steel-base TiN steel bonded carbide.
Beneficial effect
Compared with prior art, the invention has the advantages that：
1st, the present invention is with cheap Ti02 powder, TiH2 powder or Ti powder, iron powder, ferrochrome powder, molybdenum-iron powder, ferrotungsten powder, vanadium iron powder,
Ferrosilicon powder, ferromanganese powder, aquadag are raw material, and in-situ reactive synthesis technology is combined with liquid phase sintering technology, are prepared for hard
Matter phase vanadium carbide volume fraction is 30%～50% high tough VC high-speed steel-bases steel bonded carbide.Which is mainly characterized by：1. by
In the VC in steel bonded carbide be by the reaction in sintering process and in intrinsic silicon fabricated in situ, it is possible to obtain general
The method of logical hardening phase powder mixing is be difficult to be reached, or even inaccessiable granular and uniformity coefficient, and basal body interface is combined
Preferable 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, so as to
Improve the bending strength and properties of material.3. situ synthesis techniques are combined together with liquid phase sintering technology, technique
Easy, low cost.4. it is cheap due to raw material, cost can be substantially reduced.Not only may be used in the technique of this powder simultaneously
To sinter in a vacuum, it is also possible to how sinter in the atmosphere such as hydrogen, widened the means approach manufactured.
The present invention improves the activity of powder using high-energy ball milling mode, and reaches titanium carbide with the machinery conjunction of steel matrix powder
The degree of aurification, so as to improve titanium carbide and affinity of the steel matrix in sintering process, improves the obdurability of final alloy.This
Outward, the present invention in employ the relatively low ferro-molybdenum of price as raw material, its further improve in sintering process titanium carbide with
The wettability of steel matrix, carries heavy alloyed obdurability.Therefore, the present invention prepares high-performance steel-bonded carbide method and can improve alloy
Comprehensive mechanical property, and process is easy, cost-effective.
2nd, the present invention mutually manufactures new steel bonded carbide to strengthen with TiN, and TiN and Fe has extraordinary intermiscibility,
The two joint interface is good, and high high-temp stability, red hardness are good, in carbide ceramics, the hardness highest of TiN, and have very
Good heat stability, is that a kind of preferable hard strengthens phase, is that TiC, WC substitute reinforcement well.TiN phases can pinning dislocation
With crystal boundary, dislocation and crystal boundary migration are hindered, improve the intensity of steel；The presence of TiN phases simultaneously can also improve the recrystallization temperature of material
Degree and high-temperature behavior.Using TiN do hard phase can also improve steel wearability, corrosion resistance, toughness, ductility and hardness and
The comprehensive mechanical performances such as thermal fatigue resistance, and make steel that there is good solderability, and play the effects such as elimination field trash extension.
3rd, the present invention is by adding CeO2、Y3O2、La2O3Growing up for crystal grain is inhibited, and plays a part of dispersion-strengtherning.By
In CeO2、Y3O2、La2O3Chemical property is active, at a sintering temperature, CeO2、Y3O2、La2O3Can with metal dust interface on
Impurity and oxide-film effect, play a part of to purify interface, contribute to the improvement of wettability, so as to be conducive to entering for densification
Journey, reaches the purpose for reducing 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 and act on, therefore the steel bonded carbide of the present invention
Intensity and consistency are improved, and bending strength can reach more than 1700MPa, and consistency reaches 97. more than 4%.
4th, the present invention improves the activity of powder using high-energy ball milling mode, and reaches vanadium carbide and steel matrix powder mechanical alloy
The degree of change, so as to improve vanadium carbide and affinity of the steel matrix in sintering process, improves the obdurability of final alloy.This
Outward, the relatively low ferroalloy of price is employed as raw material in the present invention, and after adding a certain amount of molybdenum, which is sintered
Further improve the wettability of vanadium carbide and steel matrix, the hard that steel bonded carbide situ can be suppressed to be synthesized in journey
Phase VC is grown up, and reduces VC particle sizes, is evenly distributed.Moistening of the Binder Phase to hard phase VC is improved after due to adding molybdenum
Property, being conducive to filling of the liquid phase to hole in sintering process, porosity is low, is improved the density of steel bonded carbide,
Crystal grain is tiny, even tissue, so that its hardness and bending strength and obdurability are also improved.Therefore, prepared by the present invention
High-performance steel-bonded carbide method can carry heavy alloyed comprehensive mechanical property, and process is easy, the easy to operate, sintering period
It is short, process costs are low, be suitable to industrialized production.
5th, the TiN base steel bonded carbide developed by the present invention has density low, and hardness and bending strength are high, wear-resistant,
The excellent physical and mechanical propertiess such as resistance to high temperature oxidation, and low production cost, have high cost performance, can substitute conventional rigid
Alloy material, is widely used at a high speed, high-precision tool for cutting machining, mould, high-temperature structural material etc., it is adaptable to machinery,
Many fields such as chemical industry, automobile making and Aero-Space.
6th, present invention saves the rare metal of costliness, reduces production cost.Mass production can be realized, is widened
The hard phase of hard alloy, it is often more important that solve the problems, such as scarcity of resources.With good economic and social benefit.
Specific embodiment
Technical scheme is further illustrated with reference to specific embodiment：
Embodiment 1
A kind of preparation method of high tough modified high manganese steel base TiN steel bonded carbide, which employs the following technical solutions：
(1) raw material：
Raw materials be Ti02 powder, ferrochrome powder, molybdenum-iron powder, vanadium iron powder, ferromanganese powder, ferrosilicon powder, iron powder, nikel powder, aquadag,
One of industrial urea ((NH2) 2CO) or ammonia, CeO2, Y3O2, La2O3 or three kinds, PVA, powder size is 10
～50 μm；
(2) material is prepared：
1）Fabricated in situ TiN powder is prepared：Ti02 powder and carbamide ((NH2) 2CO) are prepared for 0.4 by N/ Ti atomic ratios
Into fabricated in situ TiN mixed-powders；
2）Bonding phase matrix alloy powder is prepared：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 can not keep away
The impurity element exempted from；
3）High tough modified high manganese steel base TiN Steel-bonded Cemented Carbides are prepared：Material chemical composition mass percent is：It is in situ
Synthesis TiN powder 30%, bonding phase matrix alloy powder 70%；
(3) step of preparation process is：
1）TiN powder material is prepared：Ti02 powder and industrial urea ((NH2) 2CO) are prepared for 0.4 by N/ Ti atomic ratios
Into fabricated in situ TiN mixed-powders；Load in polyurethane ball milling bucket, load rustless steel steel ball, ratio of grinding media to material 10:1～20:1, add
Dehydrated alcohol makees medium and dispersant, carries out sealing ball milling 48～72 hours using vibrations ball mill, is prepared into TiN powder；
2）Material is prepared：By the TiN powder 30% for preparing and 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, CeO2Raw material presses bonding phase metal material
70% proportions of chemical composition mass percent；
3）The bi-material of fabricated in situ TiN powder 30% and matrix material 70% needed for Steel-bonded Cemented Carbide is mixed
Close, load in ball milling bucket, load steel ball, ratio of grinding media to material 5:1, add dehydrated alcohol to make medium and 0.6%PVA as coolant and divide
Powder, using vibrations ball mill ball milling 55 hours；
4）Sieve after slip is dried, the product of required size shape is then pressed under 400 MPa pressure；
5）Sinter under vacuum, sintering temperature is 1400 DEG C, sintering process is:10 DEG C/min of firing rate, reaches sintering
The heat preservation sintering of 2.5 hours is carried out after temperature, furnace cooling to room temperature obtains the high tough modified high manganese steel base of required composition
TiN steel bonded carbide.
Embodiment 2
A kind of preparation method of high tough modified high manganese steel base TiN steel bonded carbide, which employs the following technical solutions：
(1) raw material：
Raw materials be TiH2 powder, ferrochrome powder, molybdenum-iron powder, vanadium iron powder, ferromanganese powder, ferrosilicon powder, iron powder, nikel powder, aquadag,
One of industrial urea ((NH2) 2CO) or ammonia, CeO2, Y3O2, La2O3 or three kinds, PVA, powder size is 10
～50 μm；
(2) material is prepared：
1）Fabricated in situ TiN powder is prepared：IH2 powder and carbamide ((NH2) 2CO) are configured to for 0.9 by N/ Ti atomic ratios
Fabricated in situ TiN mixed-powders；
2）Bonding phase matrix alloy powder is prepared：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, CeO2 0.5%, Y3O2
0.3%th, surplus Fe, and inevitably impurity element；
4）High tough modified high manganese steel base TiN Steel-bonded Cemented Carbides are prepared：Material chemical composition mass percent is：It is in situ
Synthesis TiN powder 40%, bonding phase matrix alloy powder 60%；
(3) step of preparation process is：
1）TiN powder material is prepared：TiH2 powder and industrial urea ((NH2) 2CO) are prepared for 0.9 by N/ Ti atomic ratios
Into fabricated in situ TiN mixed-powders；Load in polyurethane ball milling bucket, load rustless steel steel ball, ratio of grinding media to material 10:1～20:1, add
Dehydrated alcohol makees medium and dispersant, carries out sealing ball milling 48～72 hours using vibrations ball mill, is prepared into TiN powder；
2）Material is prepared：By the TiN powder 40% for preparing and 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、Y3O2Raw material presses bonding phase metal
60% proportions of material chemical composition mass percent；
3）The bi-material of fabricated in situ TiN powder 40% and matrix material 60% needed for Steel-bonded Cemented Carbide is mixed
Close, load in ball milling bucket, load steel ball, ratio of grinding media to material 5:1, add dehydrated alcohol to make medium and 0.6%PVA as coolant and divide
Powder, using vibrations ball mill ball milling 55 hours；
4）Sieve after slip is dried, the product of required size shape is then pressed under 400 MPa pressure；
5）Sinter under vacuum, sintering temperature is 1400 DEG C, sintering process is:10 DEG C/min of firing rate, reaches sintering
The heat preservation sintering of 2.5 hours is carried out after temperature, furnace cooling to room temperature obtains the high tough modified high manganese steel base of required composition
TiN steel bonded carbide.
Embodiment 3
A kind of preparation method of high tough modified high manganese steel base TiN steel bonded carbide, which employs the following technical solutions：
(1) raw material：
Raw materials be Ti powder, ferrochrome powder, molybdenum-iron powder, vanadium iron powder, ferromanganese powder, ferrosilicon powder, iron powder, nikel powder, aquadag, work
One of industry carbamide ((NH2) 2CO) or ammonia, CeO2, Y3O2, La2O3 or three kinds, PVA, powder size 10～
50μm；
(2) material is prepared：
1）Fabricated in situ TiN powder is prepared：Ti powder and carbamide ((NH2) 2CO) are configured to for 1.0 by N/ Ti atomic ratios
Fabricated in situ TiN mixed-powders；
2）Bonding phase matrix alloy powder is prepared：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；
4）High tough modified high manganese steel base TiN Steel-bonded Cemented Carbides are prepared：Material chemical composition mass percent is：It is in situ
Synthesis TiN powder 50%, bonding phase matrix alloy powder 50%；
(3) step of preparation process is：
1）TiN powder material is prepared：Ti powder and industrial urea ((NH2) 2CO) are configured to for 1.0 by N/ Ti atomic ratios
Fabricated in situ TiN mixed-powders；Load in polyurethane ball milling bucket, load rustless steel steel ball, ratio of grinding media to material 10:1～20:1, add nothing
Water-ethanol makees medium and dispersant, carries out sealing ball milling 48～72 hours using vibrations ball mill, is prepared into TiN powder；
2）Material is prepared：By the TiN powder for preparing and 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, La2O3Raw material presses bonding phase metal
52% proportions of material chemical composition mass percent；
3）The bi-material of fabricated in situ TiN powder 50% and matrix material 50% needed for Steel-bonded Cemented Carbide is mixed
Close, load in ball milling bucket, load steel ball, ratio of grinding media to material 5:1, add dehydrated alcohol to make medium and 0.6%PVA as coolant and divide
Powder, using vibrations ball mill ball milling 55 hours；
4）Sieve after slip is dried, the product of required size shape is then pressed under 400 MPa pressure；
5）Sinter under vacuum, sintering temperature is 1400 DEG C, sintering process is:10 DEG C/min of firing rate, reaches sintering
The heat preservation sintering of 2.5 hours is carried out after temperature, furnace cooling to room temperature obtains the high tough modified high manganese steel base of required composition
TiN steel bonded carbide.
Claims (2)
1. a kind of preparation method of high tough modified high manganese steel base TiN steel bonded carbide, it is characterised in that including as follows：
(1) material is prepared：
1）Fabricated in situ TiN powder is prepared：By Ti02 powder, TiH2 powder or Ti powder one kind of or three kinds and carbamide ((NH2)
2CO) carry out being configured to fabricated in situ TiN mixed-powders for 0.4～1.1 by N/ Ti atomic ratios；
2）Bonding phase matrix alloy powder is prepared：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）High tough modified high manganese steel base TiN Steel-bonded Cemented Carbides are prepared：Material chemical composition mass percent is：It is in situ
Synthesis TiN powder 30～50%, bonding phase matrix alloy powder 70～50%；
(2) step of preparation process is：
1）TiN powder material is prepared：By Ti02 powder, TiH2 powder or Ti powder one kind of and industrial urea ((NH2) 2CO) by N/
Ti atomic ratios carry out being configured to fabricated in situ TiN mixed-powders for 0.4～1.1；Load in polyurethane ball milling bucket, load rustless steel
Steel ball, ratio of grinding media to material 10:1～20:1, add dehydrated alcohol to make medium and dispersant, carry out sealing ball milling 48 using vibrations ball mill
～72 hours, it is prepared into TiN powder；
2）Material is prepared：By the TiN powder for preparing and molybdenum-iron powder, ferrochrome powder, vanadium iron powder, ferromanganese powder, ferrosilicon powder, according to required
Chemical composition mass percent conversion, together with one of iron powder, nikel powder, aquadag, CeO2, Y3O2, La2O3 or two
The combination raw materials for planting the above press the preparation of bonding phase metal material chemical composition mass percent required ratio, wherein manganese carbon ratio >=3；
3）The ratio of fabricated in situ TiN mixed-powders and bonding phase matrix alloy powder according to needed for Steel-bonded Cemented Carbide
Bi-material is mixed, is loaded in ball milling bucket, is loaded steel ball, ratio of grinding media to material 5:1～10:1, add dehydrated alcohol make medium and
0.5～1%PVA adds 5～10% industrial ureas or ammonia as nitrogen source, using vibrations ball mill as coolant and dispersant
Carry out sealing ball milling 48～72 hours；
4）Sieve after slip is dried, the product of required size shape is then pressed under 350～500 MPa pressure；
5）Sinter under vacuum, sintering temperature is 1400 DEG C～1500 DEG C, sintering process is:10 DEG C/min of firing rate,
The Isothermal sinter of 2～5 hours is carried out after reaching sintering temperature, furnace cooling to room temperature obtains the high tough modified of required composition
High-manganese steel-base TiN steel bonded carbide.
2. the preparation method of a kind of high tough modified high manganese steel base TiN steel bonded carbide according to claim 1, which is special
Levy and be：Raw materials are that Ti02 powder, TiH2 powder or Ti powder are one kind of or three kinds, ferrochrome powder, molybdenum-iron powder, vanadium iron powder,
Ferromanganese powder, ferrosilicon powder, iron powder, nikel powder, aquadag, industrial urea ((NH2) 2CO) or ammonia, CeO2, Y3O2, La2O3
One of them or three kinds, PVA, powder size is at 10～50 μm.
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