CN101239834B - Yttrium oxide doping zirconium oxide crucible and producing method thereof by using hot pressing sintering - Google Patents

Yttrium oxide doping zirconium oxide crucible and producing method thereof by using hot pressing sintering Download PDF

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CN101239834B
CN101239834B CN2008101017930A CN200810101793A CN101239834B CN 101239834 B CN101239834 B CN 101239834B CN 2008101017930 A CN2008101017930 A CN 2008101017930A CN 200810101793 A CN200810101793 A CN 200810101793A CN 101239834 B CN101239834 B CN 101239834B
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crucible
yttrium oxide
oxide
particle diameter
yttrium
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CN101239834A (en
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徐惠彬
高明
龚路杰
唐晓霞
张虎
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Beihang University
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Beihang University
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Abstract

The present invention discloses an yttrim oxide doping zirconium oxide crucible and a method adopting the hot pressing sintering crucible, the component of the yttrium oxide doping zirconium crucibleis that the zirconium oxide with 0.2-1.5g is doped in each 10g of yttrium oxide Y2O3. The grain diameter of the yttrim oxide Y2O3 for hot pressing sintering is 0.01-20 mu m, and the grain diameter ofyttrim oxide ZrO2 is 0.01-20 mu m. The using temperature of the yttrium oxide doping yttrim oxide crucible of the invention is 1600-2000 DEG C, and the crucible is taken as the apparatus of vacuum melting in the temperature surrounding, the inner surface of the crucible does not take part in the reaction of the active metal or alloy thereby increasing the purity of the flux.

Description

The method of Yttrium oxide doping zirconium oxide crucible and the hot pressed sintering system of employing crucible thereof
Technical field
The present invention relates to a kind of apparatus for melting metal, more particularly say, be meant a kind of method that can be used in the crucible and the hot pressed sintering system of the employing crucible thereof of vacuum melting high activity metal (metal or alloy such as Ti, Nb, Hf).
Background technology
The crucible material that existing vacuum melting high activity metal uses is mainly calcium oxide CaO, magnesium oxide MgO, boron nitride BN, Calcium Fluoride (Fluorspan) CaF 2Deng, the use temperature of crucible is generally 1200～1500 ℃, has certain difficulty for metal or alloy such as melting Ti, Nb, Hf.
Yttrium oxide (Y 2O 3) pottery is a kind of high-performance crystalline ceramics, has good heat-resisting, corrosion-resistant and high-temperature stability.The fusing point of yttrium oxide is greater than 2400 ℃, and at high temperature is difficult to react with some active metal (as titanium, aluminium etc.), uses with refractory materials so can be used as the potential melting.
But yttrium moulding difficulty in the industrial production, volume change is bigger during sintering, so yttrium oxide only is to exist with the additive form among traditional refractory materials preparation technology, solid volume fraction greatly reduces the use temperature of product less than 25% in yttrium.
General hot-press equipment (referring to shown in Figure 2) includes sealing-ring 1, stone mill felt 2, heater coil 3, body of heater 4, pressed compact 5, stone mill mould 6, power supply 7.(Hot-Pressing is to apply certain external force (general pressure between 10～40MPa, depend on the intensity that can bear with the stone mill moulding stock) in sintering process simultaneously HP) to hot pressed sintering, makes that material quickens to flow, rearrangement and densification.Usually the hot pressed sintering temperature is lower about 100 ℃ than normal pressure-sintered temperature, looks different objects and has or not the liquid phase generation and different.Can premolding or powder directly is loaded in the die cavity, technology is simple.The extrudate density that hot pressed sintering obtains usually is higher, can reach more than 99% of theoretical density, owing at lower sintering temperature, suppressed the growth of crystal grain, the sintered compact crystal grain of gained is thinner, and higher intensity is arranged.
Summary of the invention
The purpose of this invention is to provide a kind of Yttrium oxide doping zirconium oxide crucible that can be applicable to vacuum melting high activity metal or alloy, and adopt hot-pressing sintering method to prepare the technology of Yttrium oxide doping zirconium oxide crucible.
The composition of Yttrium oxide doping zirconium oxide crucible of the present invention is the yttrium oxide Y of every 10g 2O 3In be doped with the zirconium white of 0.2～1.5g.
It is as follows that the present invention adopts hot-pressing sintering method to prepare the concrete steps of Yttrium oxide doping zirconium oxide crucible:
The first step: slurrying material
The Y of particle diameter 0.01～20 μ m of assignment system will according to target be become 2O 3, particle diameter 0.01～20 μ m ZrO 2Make slurry after mixing with dehydrated alcohol;
The consumption of dehydrated alcohol is the yttrium oxide Y of every 100g 2O 3Middle 0.05～the 0.2L that adds.
Second step: oven dry base material
The slurry that makes in the first step dried in loft drier makes blank, 60～100 ℃ of drying temperatures, time of drying 8～15h;
The 3rd step: hot pressed sintering system crucible
Second blank that make of step is put into the die cavity of hot-press equipment, cover pressed compact;
Regulate pressure to 10～20MPa, 5～10 ℃/min of temperature rise rate, 1400～1800 ℃ of sintering temperatures, and under 1400～1800 ℃ of conditions of temperature, be incubated 5～10h; Finally demould makes the Yttrium oxide doping zirconium oxide crucible.
The advantage of Yttrium oxide doping zirconium oxide crucible of the present invention is: (1) spendable temperature is 1600～2000 ℃, is applicable to that vacuum melting prepares the melting equipment of reactive metal or alloy; (2) composition in this Yttrium oxide doping zirconium oxide crucible not with fusant reaction, can improve the purity of melt.
The present invention adopts the advantage of hot-pressing sintering technique oxygenerating yttrium doped zirconia crucible to be: (1) appearance is simple; (2) inner surface of crucible that makes is highly polished; (3) processing parameter is controlled in the sintering process.
Description of drawings
Fig. 1 is the XRD figure that adopts Yttrium oxide doping zirconium oxide crucible of the present invention Ti alloy of melting in vacuum heat treatment furnace.
Fig. 2 is the schematic diagram of hot-press equipment.
Embodiment
The present invention is described in further detail below in conjunction with drawings and Examples.
The composition of Yttrium oxide doping zirconium oxide crucible of the present invention is the yttrium oxide Y of every 10g 2O 3In be doped with the zirconium white of 0.2～1.5g.
In the present invention, the required yttrium oxide Y of preparation Yttrium oxide doping zirconium oxide crucible 2O 3Be the fine powder of particle diameter 0.01～20 μ m, zirconium white ZrO 2Fine powder for particle diameter 0.01～20 μ m.
In the present invention, it is as follows to adopt hot-pressing sintering method to prepare the concrete steps of Yttrium oxide doping zirconium oxide crucible:
The first step: slurrying material
The Y of particle diameter 0.01～20 μ m of assignment system will according to target be become 2O 3, particle diameter 0.01～20 μ m ZrO 2Make slurry after mixing with dehydrated alcohol;
The consumption of dehydrated alcohol is the yttrium oxide Y of every 100g 2O 3Middle 0.05～the 0.2L that adds.
Second step: oven dry base material
The slurry that makes in the first step dried in loft drier makes blank, 60～100 ℃ of drying temperatures, time of drying 8～15h;
The 3rd step: hot pressed sintering system crucible
Second blank that make of step is put into the die cavity of hot-press equipment, cover pressed compact;
Regulate pressure to 10～20MPa, 5～10 ℃/min of temperature rise rate, 1400～1800 ℃ of sintering temperatures, and under 1400～1800 ℃ of conditions of temperature, be incubated 5～10h; Finally demould makes the Yttrium oxide doping zirconium oxide crucible.
The above-mentioned Yttrium oxide doping zirconium oxide crucible that makes is put into vacuum melting equipment, and the reactive metal piece is put into crucible, in vacuum (vacuum tightness 10～1 * 10 -3Pa) or under the inert atmosphere (argon gas, helium, neon), under 1600～2000 ℃ of the smelting temperatures, metal or alloy such as melting high activity metal such as Ti, Nb, Hf.
In the present invention, the yttrium oxide Y of use 2O 3The powder material also can be the grating powder of multistage particle diameter, i.e. first step yttrium oxide Y 2O 3Powder material particle diameter is 0.01～0.5 μ m, second stage yttrium oxide Y 2O 3Powder material particle diameter is 0.5～2 μ m, third stage yttrium oxide Y 2O 3Powder material particle diameter is 2～6 μ m, fourth stage yttrium oxide Y 2O 3Powder material particle diameter is 6～20 μ m.Because the yttrium oxide Y of different-grain diameter 2O 3The powder material enters in the oarse-grained space in mixed preparing process small particles, thereby can increase density, has reduced the volume change of high temperature sintering.
Embodiment 1:
Make a Yttrium oxide doping zirconium oxide crucible that can melt 0.5Kg titanium Ti alloy
The target component of this Yttrium oxide doping zirconium oxide crucible is the yttrium oxide Y of 368g 2O 3In be doped with the zirconium white of 38g.
The crucible step that the employing hot pressed sintering prepares target component is as follows:
The first step: slurrying material
With the Y that according to target becomes 80% particle diameter of assignment system at 4.8 μ m 2O 3, 80% particle diameter, 5.0 μ m ZrO 2Make slurry after mixing with dehydrated alcohol; The consumption of dehydrated alcohol is 0.5L;
Second step: oven dry base material
The slurry that makes in the first step is made blank, 60 ℃ of bake out temperatures, drying time 15h in the oven dry of constant temperature drying case;
The 3rd step: hot pressed sintering system crucible
Second blank that make of step is put into the die cavity of hot-press equipment, cover pressed compact;
Regulate pressure to 15MPa, 10 ℃/min of temperature rise rate, 1600 ℃ of sintering temperatures, and under 1600 ℃ of conditions of temperature, be incubated 8h; Finally demould makes the Yttrium oxide doping zirconium oxide crucible of target component.
Adopt above-mentioned target component Yttrium oxide doping zirconium oxide crucible to carry out vacuum melting Ti alloy.The Ti alloy cube matherial of 0.5Kg is put into crucible, then crucible and material are installed in the vacuum heat treatment furnace (261W vacuum heat treatment furnace, general of Germany opens up general company) in the lump; Regulate the melting technology parameter: be evacuated to 2.4 * 10 -2Pa, 1600 ℃ of smelting temperatures, and behind insulation 20min under 1600 ℃ of temperature, cool to room temperature (25 ℃) back with the furnace and take out; And crucible detected, find that inner surface of crucible has neither part nor lot in the reaction of Ti alloy, through the Ti alloy being carried out the XRD test, wherein do not contain Y 2O 3Composition.As shown in fig. 1, do not contain Y element or Y 2O 3Diffraction peak.
Embodiment 2:
Make a multistage powder Yttrium oxide doping zirconium oxide crucible of joining that can melt 0.5Kg titanium Ti alloy
The target component of this Yttrium oxide doping zirconium oxide crucible is the yttrium oxide Y of 368g 2O 3In be doped with the zirconium white of 38g.
The crucible step that the employing hot pressed sintering prepares target component is as follows:
The first step: slurrying material
According to target become assignment system to choose 0.02 μ m first step Y 2O 3Fine powder, 1 μ m second stage Y 2O 3Fine powder, 5 μ m third stage Y 2O 3Fine powder, 15 μ m fourth stage Y 2O 3Fine powder, wherein, first step Y 2O 3Fine powder accounts for total Y 2O 35% of powder amount, second stage Y 2O 3Fine powder accounts for total Y 2O 320% of powder amount, third stage Y 2O 3Fine powder accounts for total Y 2O 330% of powder amount, fourth stage Y 2O 3Fine powder accounts for total Y 2O 345% of powder amount; The ZrO of 80% particle diameter, 5.0 μ m 2Make slurry after mixing with dehydrated alcohol; The consumption of dehydrated alcohol is 0.5L;
Second step: oven dry base material
The slurry that makes in the first step dried in loft drier makes blank, 80 ℃ of drying temperatures, time of drying 10h;
The 3rd step: hot pressed sintering system crucible
Second blank that make of step is put into the die cavity of hot-press equipment, cover pressed compact;
Regulate pressure to 10MPa, 6 ℃/min of temperature rise rate, 1700 ℃ of sintering temperatures, and under 1700 ℃ of conditions of temperature, be incubated 6h; Finally demould makes the Yttrium oxide doping zirconium oxide crucible of target component.
Adopt above-mentioned target component Yttrium oxide doping zirconium oxide crucible to carry out vacuum melting Ti alloy.The Ti alloy cube matherial of 0.5Kg is put into crucible, then crucible and material are installed in the vacuum heat treatment furnace (261W vacuum heat treatment furnace, general of Germany opens up general company) in the lump; Regulate the melting technology parameter: be evacuated to 2.4 * 10 -2Pa, 1600 ℃ of smelting temperatures, and behind insulation 20min under 1600 ℃ of temperature, cool to room temperature (25 ℃) back with the furnace and take out; And crucible detected, find that inner surface of crucible has neither part nor lot in the reaction of Ti alloy, does not contain Y in the Ti alloy 2O 3Composition.This example adopts the grating powder to carry out hot pressed sintering system crucible, and the crucible size behind the sintering reduces to some extent than the crucible deflection that embodiment 1 makes, and promptly the crucible shrinking percentage that makes of embodiment 2 is about 50% of the crucible shrinking percentage that makes of embodiment 1.
Embodiment 3:
Make a Yttrium oxide doping zirconium oxide crucible that can melt 1Kg hafnium Hf alloy
The target component of this Yttrium oxide doping zirconium oxide crucible is the yttrium oxide Y of 550g 2O 3In be doped with the zirconium white of 50g.
The crucible step that the employing hot pressed sintering prepares target component is as follows:
The first step: slurrying material
With the Y that according to target becomes 90% particle diameter of assignment system at 15 μ m 2O 3, 80% particle diameter, 10 μ m ZrO 2Make slurry after mixing with dehydrated alcohol; The consumption of dehydrated alcohol is 1L;
Second step: oven dry base material
The slurry that makes in the first step dried in loft drier makes blank, 80 ℃ of drying temperatures, time of drying 8h;
The 3rd step: hot pressed sintering system crucible
Second blank that make of step is put into the die cavity of hot-press equipment, cover pressed compact;
Regulate pressure to 15MPa, 5 ℃/min of temperature rise rate, 1750 ℃ of sintering temperatures, and under 1750 ℃ of conditions of temperature, be incubated 5h; Finally demould makes the Yttrium oxide doping zirconium oxide crucible of target component.
Adopt above-mentioned target component Yttrium oxide doping zirconium oxide crucible to carry out vacuum melting hafnium Hf alloy.The hafnium Hf alloy cube matherial of 0.5Kg is put into crucible, then crucible and material are installed in the vacuum heat treatment furnace (261W vacuum heat treatment furnace, general of Germany opens up general company) in the lump; Regulate the melting technology parameter: be evacuated to 1.9 * 10 -2Pa, 1700 ℃ of smelting temperatures, and behind insulation 15min under 1700 ℃ of temperature, cool to room temperature (25 ℃) back with the furnace and take out; And crucible detected, find that inner surface of crucible has neither part nor lot in the reaction of hafnium Hf alloy, through hafnium Hf alloy being carried out the XRD test, wherein do not contain Y 2O 3Composition.
Embodiment 4:
Make a Yttrium oxide doping zirconium oxide crucible that can melt 1Kg niobium Nb alloy
The target component of this Yttrium oxide doping zirconium oxide crucible is the yttrium oxide Y of 552g 2O 3In be doped with the zirconium white of 57g.
The crucible step that the employing hot pressed sintering prepares target component is as follows:
The first step: slurrying material
With the Y that according to target becomes 80% particle diameter of assignment system at 15 μ m 2O 3, 80% particle diameter, 10 μ m ZrO 2Make slurry after mixing with dehydrated alcohol; The consumption of dehydrated alcohol is 1L;
Second step: oven dry base material
The slurry that makes in the first step dried in loft drier makes blank, 100 ℃ of drying temperatures, time of drying 8h;
The 3rd step: hot pressed sintering system crucible
Second blank that make of step is put into the die cavity of hot-press equipment, cover pressed compact;
Regulate pressure to 19MPa, 5 ℃/min of temperature rise rate, 1750 ℃ of sintering temperatures, and under 1750 ℃ of conditions of temperature, be incubated 5h; Finally demould makes the Yttrium oxide doping zirconium oxide crucible of target component.
Adopt above-mentioned target component Yttrium oxide doping zirconium oxide crucible to carry out vacuum melting Nb alloy.The Nb alloy cube matherial of 0.5Kg is put into crucible, then crucible and material are installed in the vacuum heat treatment furnace (261W vacuum heat treatment furnace, general of Germany opens up general company) in the lump; Regulate the melting technology parameter: be evacuated to 1 * 10 -3Pa, 1950 ℃ of smelting temperatures, and behind insulation 30min under 1950 ℃ of temperature, cool to room temperature (25 ℃) back with the furnace and take out; And crucible detected, find that inner surface of crucible has neither part nor lot in the reaction of Nb alloy, through the Nb alloy being carried out the XRD test, wherein do not contain Y 2O 3Composition.

Claims (4)

1. Yttrium oxide doping zirconium oxide crucible, it is characterized in that: the composition of Yttrium oxide doping zirconium oxide crucible is the yttrium oxide Y of every 10g 2O 3In be doped with the zirconium white of 0.2～1.5g.
2. Yttrium oxide doping zirconium oxide crucible according to claim 1 is characterized in that: Yttrium oxide doping zirconium oxide crucible use temperature is 1600～2000 ℃.
3. adopt hot-pressing sintering technique to prepare the method for Yttrium oxide doping zirconium oxide crucible as claimed in claim 1, it is characterized in that the following step is arranged:
The first step: slurrying material
The Y of particle diameter 0.01～20 μ m of assignment system will according to target be become 2O 3, particle diameter 0.01～20 μ m ZrO 2Make slurry after mixing with dehydrated alcohol;
The consumption of dehydrated alcohol is the yttrium oxide Y of every 100g 2O 3Middle 0.05～the 0.2L that adds;
Second step: oven dry base material
The slurry that makes in the first step dried in loft drier makes blank, 60～100 ℃ of drying temperatures, time of drying 8～15h;
The 3rd step: hot pressed sintering system crucible
Second blank that make of step is put into the die cavity of hot-press equipment, cover pressed compact;
Regulate pressure to 10～20MPa, 5～10 ℃/min of temperature rise rate, 1400～1800 ℃ of sintering temperatures, and under 1400～1800 ℃ of conditions of temperature, be incubated 5～10h; Finally demould makes the Yttrium oxide doping zirconium oxide crucible.
4. the method for employing hot-pressing sintering technique oxygenerating yttrium doped zirconia crucible according to claim 3 is characterized in that: the yttrium oxide Y that uses in first step 2O 3The powder material is the grating powder of multistage particle diameter, i.e. first step yttrium oxide Y 2O 3Powder material particle diameter is 0.01～0.5 μ m, second stage yttrium oxide Y 2O 3Powder material particle diameter is 0.5～2 μ m, third stage yttrium oxide Y 2O 3Powder material particle diameter is 2～6 μ m, fourth stage yttrium oxide Y 2O 3Powder material particle diameter is 6～20 μ m.
CN2008101017930A 2008-03-12 2008-03-12 Yttrium oxide doping zirconium oxide crucible and producing method thereof by using hot pressing sintering Expired - Fee Related CN101239834B (en)

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CN101475392B (en) * 2009-01-21 2011-08-03 中国化工供销太原贵金属有限公司 Method for manufacturing noble metal smelting vessel
CN103224396B (en) * 2013-04-11 2014-11-19 哈尔滨工业大学 Composite crucible liner for vacuum anti-gravity casting of titanium and titanium alloys, and manufacturing method thereof
CN109928754B (en) * 2019-04-22 2021-07-06 郑州振中电熔新材料有限公司 Method for preparing modified yttrium oxide

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Publication number Priority date Publication date Assignee Title
CN1610814A (en) * 2001-11-16 2005-04-27 信越化学工业株式会社 Crucible for melting rare earth element alloy and rare earth element alloy

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Publication number Priority date Publication date Assignee Title
CN1610814A (en) * 2001-11-16 2005-04-27 信越化学工业株式会社 Crucible for melting rare earth element alloy and rare earth element alloy

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Title
易明.坩埚用钨-氧化钇合金.中国钨业 2.1994,(2),31.
易明.坩埚用钨-氧化钇合金.中国钨业 2.1994,(2),31. *

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