CN101956117B - Nano zirconia and micron tungsten carbide toughened and enhanced metal ceramic die material and preparation method thereof - Google Patents

Nano zirconia and micron tungsten carbide toughened and enhanced metal ceramic die material and preparation method thereof Download PDF

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CN101956117B
CN101956117B CN201010516632A CN201010516632A CN101956117B CN 101956117 B CN101956117 B CN 101956117B CN 201010516632 A CN201010516632 A CN 201010516632A CN 201010516632 A CN201010516632 A CN 201010516632A CN 101956117 B CN101956117 B CN 101956117B
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CN101956117A (en
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许崇海
王兴海
张会发
张永莲
吴光永
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Shandong Institute of Light Industry
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Abstract

The invention relates to a metal ceramic die material and a preparation method thereof. The die material is formed by hot pressing and sintering micro TiC and TiN as matrix hard phases, added yttrium-stable nano ZrO2 and micro WC as enhanced phases, micro molybdenum and nickel as bonding phases and micro graphite and vanadium carbide as addictives. The preparation method comprises the following steps of: respectively dispersing the micro TiC, TiN, WC and micro ZrO2 powder; ball milling and drying to obtain the powder; and sintering by a hot pressing method. The method is beneficial to improving the strength and the toughness of the material and is simple in process and convenient in operation. The metal ceramic die material has favorable comprehensive mechanical properties and wear-resisting performance and can be used for fabricating squeezing dies, drawing dies, stamping dies and other wear-resisting parts.

Description

Nano zircite and the toughness reinforcing enhancing cermet mold material of micron wolfram varbide and preparation method thereof
Technical field
The present invention relates to a kind of cermet mold material and preparation method thereof, particularly a kind of nano zircite and the toughness reinforcing enhanced cermet mold material of micron wolfram varbide and preparation method thereof.
Background technology
A kind of matrix material that sintering metal is made of mutually ceramic hard and metal bonding.It has good mechanical performance and use properties, is the ideal structure material of making cutter, mould, wearing piece etc.
The Chinese patent file CN86107658 provide a kind of metallic ceramic moulding material for hot processing, and designed cermet material contains tungsten and ceramic phase aluminium sesquioxide, lanthanum sesquioxide, also contains metallic elements such as chromium, nickel (or iron, cobalt) simultaneously.As copper hot-extrusion mold material, be 1650/mould mean life, reach the highest work-ing life 3100/more than the mould.
The Chinese patent file CN1031258 provide a kind of moulding stock of molybdenum based metall-ceramic used for hot rolling, and designed cermet material is to be base with the metal molybdenum, has added ceramic phase and other metallic element simultaneously again.Because ceramic phase itself has good chemical stability and wear resistance in the material, hardness is more or less the same during simultaneously at high temperature with room temperature, can form sosoloid with metallic element again, therefore can improve the thermal shock resistance and the hot strength of material.
The Chinese patent file CN1332262A provide a kind of cermet mold material, and chemical ingredients (weight %) is: W10-60%, Cr38.5-80%, Al 2O 31-30%, La 2O 30-15%, any or any two above sum is 0.5-20% among Ni, Co, the Fe.Described material red hardness height, Heat stability is good, oxidation-resistance and high abrasion resistance, good toughness, anti-rapid heat cycle excellent performance.
Nano composite ceramic in the research of moulding stock application facet still less.With the compound 3Y-TZP micro mist of the 3Y-TZP nano powder of 3-10%, adopt isostatic pressing and sintering to prepare high performance compound TZP ceramic die.This research adopts the 3Y-TZP nano powder to strengthen ZrO 2Phase transformation enhancing and nanometer strengthen, and can significantly improve TZP ceramic die intensity, hardness, and firing temperature is reduced to 1480 ℃ from 1540 ℃.Referring to good page or leaf recklessly etc., the development of the multiple platform TZP ceramic die of nanometer, Foshan pottery, 2002, (6): 8-9.
Xu Li waits by force and has reported a kind of Ti (C that adds nano aluminium oxide 0.7N 0.3)/MgO/Al 2O 3(n)/Cr 2C 3/ Mo/Ni sintering metal adopts the pressure sintering preparation, its bending strength 900MPa, fracture toughness property 9.95MPam 1/2, referring to Xu Liqiang, Wang Suilian, yellow fax etc., nanometer Al 2O 3To Ti (C, N) based ceramic metal Effect on Performance, Rare Metals Materials and engineering, 2008,37 (4): 732-735.
Chinese patent file CN101164963A provides a kind of preparation method of micro-nano composite ceramic die material: with micron order Al 2O 3Pottery is a matrix, and (C, N) the ceramic hard particle forms as the sintering aid hot pressed sintering with Mo, Ni and MgO as disperse phase to add nano level Ti.The stupalith sample of gained carries out cutting processing and records mechanical property parameters and be: bending strength 743-789MPa, fracture toughness property 7.4-8.2MPam 1/2, hardness 19.5-20.4GPa (embodiment 1-3).
From existing report as can be seen, the performance advantage of nano composite ceramic especially its toughening effect still fail to be not fully exerted in the cermet mold field.Because toughness is on the low side, the metal current stupalith can only be used to not have or seldom have the mould of shock load, as hot extrusion, hot rolling mould etc.With regard to present general status, the kind of cermet mold material, performance and range of application all await further enlarging and improving.
Summary of the invention
In order to overcome the weak point of prior art, the invention provides the better nano zircite of a kind of toughness and the toughness reinforcing enhanced cermet mold material of micron wolfram varbide and preparation method thereof.
Cermet mold material of the present invention is a kind of by adding nano zircite and micron wolfram varbide realization nanometer, micron particle coordination plasticizing enhanced cermet mold material.
The term explanation:
Yttrium stabilized nano ZrO 2Be abbreviated as Y-ZrO 2
5mol% yttrium stabilized nano ZrO 2Be abbreviated as 5Y-ZrO 2
3mol% yttrium stabilized nano ZrO 2Be abbreviated as 3Y-ZrO 2
Technical solution of the present invention is as follows:
A kind of cermet mold material, be with a micron TiC and a micron TiN be the matrix hard mutually, add yttrium stabilized nano ZrO 2(Y-ZrO 2) and micron WC as wild phase, serve as to bond mutually with micron molybdenum (Mo) and micron nickel (Ni),, form as auxiliary agent with micron graphite (C) and micron vanadium carbide (VC) through vacuum heating-press sintering; Described yttrium stabilized nano ZrO 2Be 3-8mol% yttrium stabilized nano ZrO 2The feed composition mass percent is as follows:
TiN 10-25%, Y-ZrO 25-20%, WC5-20%, Mo 5-10%, Ni 5-15%, C 0.5-1.5%, VC 0.5-1.5%, all the other are TiC.
Preferably, the mass percent of described TiN is 12-20%.
Preferably, described yttrium stabilized nano ZrO 2Mass percent is 5-15%, is 5mol% yttrium stabilized nano zirconium white, below is abbreviated as 5Y-ZrO 2, use 5Y-ZrO 2Comprehensive mechanical property the best of gained moulding stock.
Preferably, the mass percent of described WC is 10-15%.
Preferably, the mass percent of described Mo is 6-8%.
Preferably, the mass percent of described Ni is 10-15%.
Preferably, the mass percent of described C is 0.6-1.0%.
Preferably, the mass percent of described VC is 0.6-1.0%.
Most preferred, micron composite ceramics tool die material of receiving of the present invention, the feed composition mass percent is as follows: TiC 37.4%, TiN16.6%, WC 14.4%, ZrO 210%, Mo 7%, and Ni 13%, and C 0.8%, and VC 0.8%.Described yttrium stabilized nano ZrO 2Be 5mol% yttrium stabilized nano ZrO 2
In above-mentioned each component, used raw material is the commercially available prod, and is preferred, the ZrO that yttrium is stable 2The nanometer powder median size is 80nm, and micron TiC, micron TiN, micron WC powder median size are respectively 3 μ m, 2 μ m and 1 μ m, and purity is all greater than 99%.
The preparation method of cermet mold material of the present invention, feed composition ratio comprise that step is as follows as mentioned above:
(1) takes by weighing TiC, TiN, WC micron powder in proportion, add dehydrated alcohol respectively and be made into TiC suspension, TiN suspension, WC suspension, stirring, ultra-sonic dispersion 20-30min respectively;
(2) take by weighing the stable ZrO of yttrium in proportion 2Nanometer powder is that 4000 polyoxyethylene glycol (PEG4000) is a dispersion agent with molecular weight, with the stable ZrO of yttrium 2The nanometer powder quality is the radix meter, and the addition of dispersion agent is 0.2-1.0wt%; With an amount of dehydrated alcohol is dispersion medium, is made into the stable ZrO of yttrium 2Suspension, with agitator fully stir, ultra-sonic dispersion 20-30min, the pH value of regulating suspension is to 3-4;
(3) take by weighing the powder of micron-sized Mo, Ni, graphite, VC in proportion respectively, add dehydrated alcohol respectively and be made into Mo suspension, Ni suspension, graphite suspension, VC suspension, stir respectively, ultra-sonic dispersion 20-30min;
(4) with TiC suspension, TiN suspension, WC suspension, the stable ZrO of yttrium of step (1)-(3) gained 2Suspension, Mo suspension, Ni suspension, graphite suspension and VC suspension mix, and obtain the complex phase mixing suspension, and fully stirring, ultra-sonic dispersion 20-30min mix;
(5) step (4) gained mixing suspension being poured in the ball grinder, is protective atmosphere with the rare gas element, is medium with the dehydrated alcohol, and the pellet weight ratio of each component raw material total amount and mill ball is 1: 10-12, ball milling 30-60h; Successive drying under 110-120 ℃ of temperature in the electric vacunm drying case sieves in inert gas flow behind the complete drying then, obtains mixed powder, seals standby;
(6) adopt the pressure sintering sintering, with powder pressing mold, the sinter molding of step (5) gained.
Dehydrated alcohol described in above-mentioned steps (1)-(3) is as the dispersion medium that is made into suspension, and consumption gets final product by conventional selection the in this area, and the present invention does not do special qualification.
Above-mentioned steps (2) is regulated the pH of suspension value with hydrochloric acid and ammoniacal liquor.
Preferably, the mill ball that ball milling is used in the step (5) is a sintered carbide ball.
Preferably, rare gas element is nitrogen or argon gas in the step (5).
Preferably, above-mentioned steps (6) pressure sintering agglomerating operation steps is as follows:
The graphite jig of earlier powder of step (5) gained being packed into carries out vacuum heating-press sintering then, and hot pressing parameters is: holding temperature 1400-1500 ℃, and hot pressing pressure 30-35MPa, soaking time 20-40min, temperature rise rate 10-20 ℃/min.
Excellent results of the present invention is as follows:
Cermet mold material of the present invention is by adding yttrium stabilized nano ZrO in cermet material 2Realize that with the micron wolfram varbide nanometer, micron particle coordination plasticizing strengthen, and by exclusive highly malleablized mechanism and the ZrO of nano ceramics 2The acting in conjunction of multiple toughened and reinforced mechanism such as transformation toughening, tiny crack are toughness reinforcing, the mechanical property of improving material is its intensity and toughness especially.Compare with existing cermet mold material, this cermet mold material has higher toughness, can be used for making ceramic overflow mould, drawing die and other wear-resisting spare parts.Because flexible significantly improves, this cermet mold material also can be used for making the press tool of bearing medium and small shock load.
Embodiment
The present invention will be further described below in conjunction with embodiment.In the component of each embodiment, used 3Y-ZrO 2And 5Y-ZrO 2The nanometer powder median size is 80nm, and purity is greater than 99%; Micron TiC, TiN, WC powder wood median size are respectively 3 μ m, 2 μ m and 1 μ m, and purity is all greater than 99%.The used vacuum heating-press sintering stove of vacuum heating-press sintering is Ji'nan Nonferrous Metal Castings Co., Ltd. of Shandong University's product, model ZR50B-8T.
Embodiment 1
Cermet mold material, the mass percent of feed composition is: TiC 37.4%, and TiN 16.6%, and WC 14.4%, 5Y-ZrO 210%, Mo 7%, and Ni 13%, and C 0.8%, and VC 0.8%.The preparation method is as follows:
Take by weighing TiC, TiN, WC micron powder in proportion, add the suspension that dehydrated alcohol is made into TiC, TiN, WC respectively, with agitator fully stir, ultra-sonic dispersion 30min.Get TiC suspension, TiN suspension and WC suspension.
Take by weighing 5Y-ZrO in proportion 2Nanometer powder is that 4000 polyoxyethylene glycol (PEG4000) is a dispersion agent with molecular weight, with 5Y-ZrO 2The nanometer powder quality is the radix meter, and the addition of dispersion agent is 0.6wt%; With an amount of dehydrated alcohol is dispersion medium, is made into 5Y-ZrO 2Suspension, with agitator fully stir, ultra-sonic dispersion 30min, the pH value to 3 of regulating suspension again with hydrochloric acid and ammoniacal liquor must the stable ZrO of yttrium 2Suspension.
Take by weighing a micron Mo, Ni, graphite, VC powder in proportion, add dehydrated alcohol respectively and be made into Mo, Ni, graphite, VC suspension, with agitator fully stir, ultra-sonic dispersion 30min.
With above gained TiC suspension, TiN suspension, WC suspension, the stable ZrO of yttrium 2Suspension, Mo suspension, Ni suspension, graphite suspension and VC suspension mix, with agitator fully stir, ultra-sonic dispersion 30min, mix; Get the complex phase mixing suspension.
The above-mentioned complex phase mixing suspension that makes is poured in the ball grinder, is protective atmosphere with nitrogen, is medium with the dehydrated alcohol, is grinding element with the sintered carbide ball, and the pellet weight ratio is 1: 10, ball milling 60h; Then in the electric vacunm drying case at 110 ℃ of following successive dryings of design temperature, in stream of nitrogen gas, sieve behind the complete drying, the graphite jig of then powder being packed into carries out vacuum heating-press sintering.Hot pressing parameters is: 1450 ℃ of holding temperatures, hot pressing pressure 35MPa, soaking time 30min, 15 ℃/min of temperature rise rate.
The stupalith sample that makes is carried out cutting processing, record its mechanical property parameters and be: bending strength 967MPa, fracture toughness property 13.62MPam 1/2, Vickers' hardness 14.24GPa.
Embodiment 2
Cermet mold material, the mass percent of feed composition is: TiC43.8%, TiN19.6%, WC10%, 5Y-ZrO 25%, Mo5%, Ni15%, C0.6%, VC1%.The preparation method is as follows:
Take by weighing TiC, TiN, WC micron powder in proportion, add the suspension that dehydrated alcohol is made into TiC, TiN, WC respectively, with agitator fully stir, ultra-sonic dispersion 20min.Take by weighing 5Y-ZrO in proportion 2Nanometer powder is that 4000 polyoxyethylene glycol (PEG4000) is a dispersion agent with molecular weight, with 5Y-ZrO 2The nanometer powder quality is the radix meter, and the addition of dispersion agent is 0.3wt%; With an amount of dehydrated alcohol is dispersion medium, is made into 5Y-ZrO 2Suspension, with agitator fully stir, ultra-sonic dispersion 20min, the pH value to 4 of regulating suspension again with hydrochloric acid and ammoniacal liquor.Take by weighing a micron Mo, Ni, graphite, VC powder in proportion, add dehydrated alcohol respectively and be made into Mo, Ni, graphite, VC suspension, with agitator fully stir, ultra-sonic dispersion 20min.Above gained suspension is mixed, and fully stirring, ultra-sonic dispersion 30min mix; Mixture is poured in the ball grinder, is protective atmosphere with the argon gas, is medium with the dehydrated alcohol, is grinding element with the sintered carbide ball, and the pellet weight ratio is 1: 12, ball milling 40h; Then in the electric vacunm drying case at 120 ℃ of following successive dryings of design temperature, in argon stream, sieve behind the complete drying, the graphite jig of then powder being packed into carries out vacuum heating-press sintering.Hot pressing parameters is: 1420 ℃ of holding temperatures, hot pressing pressure 35MPa, soaking time 40min, 20 ℃/min of temperature rise rate.
The stupalith sample that makes is carried out cutting processing, record its mechanical property parameters and be: bending strength 892MPa, fracture toughness property 11.38MPam 1/2, Vickers' hardness 15.1GPa.
Embodiment 3
Cermet mold material, the mass percent of feed composition is: TiC 28.1%, and TiN 12%, and WC 18.4%, 5Y-ZrO 220%, Mo 10%, and Ni 10%, and C 1.1%, and VC 0.4%.The preparation method is as follows:
Take by weighing TiC, TiN, WC micron powder in proportion, add the suspension that dehydrated alcohol is made into TiC, TiN, WC respectively, with agitator fully stir, ultra-sonic dispersion 25min.Take by weighing 5Y-ZrO in proportion 2Nanometer powder is that 4000 polyoxyethylene glycol (PEG4000) is a dispersion agent with molecular weight, with 5Y-ZrO 2The nanometer powder quality is the radix meter, and the addition of dispersion agent is 0.8wt%; With an amount of dehydrated alcohol is dispersion medium, is made into 5Y-ZrO 2Suspension, with agitator fully stir, ultra-sonic dispersion 25min, the pH value to 3 of regulating suspension again with hydrochloric acid and ammoniacal liquor.Take by weighing a micron Mo, Ni, graphite, VC powder in proportion, add dehydrated alcohol respectively and be made into Mo, Ni, graphite, VC suspension, with agitator fully stir, ultra-sonic dispersion 25min.Above gained suspension is mixed, with agitator fully stir, ultra-sonic dispersion 25min, mix; Mixture is poured in the ball grinder, is protective atmosphere with nitrogen, is medium with the dehydrated alcohol, is grinding element with the sintered carbide ball, and the pellet weight ratio is 1: 11, ball milling 50h; Then in the electric vacunm drying case at 110 ℃ of following successive dryings of design temperature, in stream of nitrogen gas, sieve behind the complete drying, the graphite jig of then powder being packed into carries out vacuum heating-press sintering.Hot pressing parameters is: 1480 ℃ of holding temperatures, hot pressing pressure 35MPa, soaking time 20min, 10 ℃/min of temperature rise rate.
The stupalith sample that makes is carried out cutting processing, record its mechanical property parameters and be: bending strength 944MPa, fracture toughness property 13.78MPam 1/2, Vickers' hardness 13.52GPa.
Embodiment 4
As described in embodiment 1, different is to use 3Y-ZrO 2Replace 5Y-ZrO 2, the mass percent of feed composition is: TiC37.4%, TiN16.6%, WC14.4%, 3Y-ZrO 210%, Mo7%, Ni13%, C0.8%, VC0.8%.The stupalith sample that makes is carried out cutting processing, record its mechanical property parameters and be: bending strength 913MPa, fracture toughness property 12.59MPam 1/2, Vickers' hardness 13.85GPa.
Compare with the micro-nano composite ceramic die material that patent of invention CN101164963A provided of same employing pressure sintering, the bending strength of cermet mold material of the present invention and fracture toughness property improve about 22.6-30.1% and 66.1-84.1% respectively.Ti (the C of the interpolation nano aluminium oxide made from the same employing pressure sintering of reports such as Xu Liqiang 0.7N 03)/MgO/Al 2O 3(n)/Cr 2C 3/ Mo/Ni sintering metal compare (referring to Xu Liqiang, Wang Suilian, yellow fax etc., nanometer Al 2O 3To Ti (C, N) based ceramic metal Effect on Performance, Rare Metals Materials and engineering, 2008,37 (4): 732-735), the bending strength of cermet mold material of the present invention and fracture toughness property improve about 7.4% and 36.9% respectively.Significantly improve just because of flexible, this cermet mold material not only can be used for making ceramic overflow mould, drawing die and other wear-resisting spare parts, also can be used for making existing cermet mold the press tool of bearing medium and small shock load that can not do.

Claims (9)

1. cermet mold material, be with a micron TiC and a micron TiN be the matrix hard mutually, add yttrium stabilized nano ZrO 2With micron WC as wild phase, with the micron molybdenum and the micron nickel serve as the bonding mutually, with micron graphite and the micron vanadium carbide as auxiliary agent, form through vacuum heating-press sintering; Described yttrium stabilized nano ZrO 2Be 3-8mol% yttrium stabilized nano ZrO 2The feed composition mass percent is as follows:
TiN 10-25%, yttrium stabilized nano ZrO 25-20%, WC 5-20%, Mo 5-10%, Ni 5-15%, C 0.5-1.5%, VC 0.5-1.5%, all the other are TiC.
2. cermet mold material according to claim 1 is characterized in that, the mass percent of described TiN is 12-20%, and the mass percent of described WC is 10-15%.
3. cermet mold material according to claim 1 is characterized in that, described yttrium stabilized nano ZrO 2Mass percent is 5-15%, is 5mol% yttrium stabilized nano zirconium white.
4. cermet mold material according to claim 1 is characterized in that, the mass percent of described Mo is 6-8%, and the mass percent of described Ni is 10-15%.
5. cermet mold material according to claim 1 is characterized in that, the mass percent of described C is 0.6-1.0%, and the mass percent of described VC is 0.6-1.0%.
6. cermet mold material according to claim 1 is characterized in that, the feed composition mass percent is as follows: TiC37.4%, and TiN 16.6%, and WC 14.4%, yttrium stabilized nano ZrO 210%, Mo 7%, and Ni 13%, and C 0.8%, and VC 0.8%; Described yttrium stabilized nano ZrO 2Be 5mol% yttrium stabilized nano ZrO 2
7. the preparation method of the arbitrary described cermet mold material of claim 1-6 comprises that step is as follows:
(1) takes by weighing TiC, TiN, WC micron powder in proportion, add dehydrated alcohol respectively and be made into TiC suspension, TiN suspension, WC suspension, stirring, ultra-sonic dispersion 20-30min respectively;
(2) take by weighing the stable ZrO of yttrium in proportion 2Nanometer powder is that 4000 polyoxyethylene glycol is a dispersion agent with molecular weight, with the stable ZrO of yttrium 2The nanometer powder quality is the radix meter, and the addition of dispersion agent is 0.2-1.0wt%; With an amount of dehydrated alcohol is dispersion medium, is made into the stable ZrO of yttrium 2Suspension, with agitator fully stir, ultra-sonic dispersion 20-30min, the pH value of regulating suspension is to 3-4;
(3) take by weighing the powder of micron-sized Mo, Ni, graphite, VC in proportion respectively, add dehydrated alcohol respectively and be made into Mo suspension, Ni suspension, graphite suspension, VC suspension, stir respectively, ultra-sonic dispersion 20-30min;
(4) with TiC suspension, TiN suspension, WC suspension, the stable ZrO of yttrium of step (1)-(3) gained 2Suspension, Mo suspension, Ni suspension, graphite suspension and VC suspension mix, and obtain the complex phase mixing suspension, and fully stirring, ultra-sonic dispersion 20-30min mix;
(5) step (4) gained mixing suspension being poured in the ball grinder, is protective atmosphere with nitrogen or argon gas, is medium with the dehydrated alcohol, and the pellet weight ratio of each component raw material total amount and mill ball is 1: 10-12, ball milling 30-60h; Successive drying under 110-120 ℃ of temperature in the electric vacunm drying case sieves in inert gas flow behind the complete drying then, obtains mixed powder, seals standby;
(6) adopt the pressure sintering sintering, with powder pressing mold, the sinter molding of step (5) gained.
8. the preparation method of cermet mold material according to claim 7, it is characterized in that, the operation steps of step (6) is as follows: the graphite jig of earlier powder of step (5) gained being packed into, carry out vacuum heating-press sintering then, hot pressing parameters is: holding temperature 1400-1500 ℃, hot pressing pressure 30-35MPa, soaking time 20-40min, temperature rise rate 10-20 ℃/min.
9. the preparation method of cermet mold material according to claim 7 is characterized in that, step (2) is regulated the pH of suspension value with hydrochloric acid and ammoniacal liquor.
CN201010516632A 2010-10-22 2010-10-22 Nano zirconia and micron tungsten carbide toughened and enhanced metal ceramic die material and preparation method thereof Expired - Fee Related CN101956117B (en)

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