CN102503489A - BaZrO3 refractory material for smelting titanium alloy and preparation method of crucibles - Google Patents
BaZrO3 refractory material for smelting titanium alloy and preparation method of crucibles Download PDFInfo
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- CN102503489A CN102503489A CN2011103504641A CN201110350464A CN102503489A CN 102503489 A CN102503489 A CN 102503489A CN 2011103504641 A CN2011103504641 A CN 2011103504641A CN 201110350464 A CN201110350464 A CN 201110350464A CN 102503489 A CN102503489 A CN 102503489A
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Abstract
The invention discloses a BaZrO3 refractory material of a titanium and titanium alloy smelting crucible and a crucible preparation method. The preparation method comprises the steps of: using BaCO3 and ZrO2 as raw materials, repeatedly sintering the raw materials at 1200-1400 DEG C to synthesize barium zirconate (BaZrO3) crystal powder; adding a proper dosage of additive and adhesive in the barium zirconate material, performing such procedures as pre-treating, forming, pre-sintering and sintering, and the like to prepare a crucible. The BaZrO3 crucible is used as a container for smelting titanium alloy at a temperature of 1650-1750 DEG C in a vacuum environment; the internal and external surfaces of the crucible are intact after the smelting process and no reaction is generated with the titanium alloy, no obvious interface layer exists, and as shown in the detection, no crucible material exists on the external surface of the metal, and the oxygen content in the alloy is low, so that the purity and performance of the titanium alloy are guaranteed.
Description
Technical field
The present invention relates to a kind of preparation method who is used for the refractory materials and the crucible of titanium or titanium alloy smelting pot, belong to the high melt technical field of refractory materials.
Technical background
Titanium alloy has a series of good characteristics such as specific tenacity height, density be little, corrosion-resistant, is widely used in the modern industry fields such as biological example science, engineering in medicine, aerospace industry, the energy, ocean, war industry.Titanium alloy can not be widely used, and mainly is for fear of its fancy price.Among its cost structure, the melting expense accounts for 30%～40%.
At present, consumable electrode arc furnace commonly used matches water jacketed copper crucible as the device of smelting titanium alloy in the industry.But water jacketed copper crucible is taken away a large amount of heats, the serious waste energy, and cause thermal field inhomogeneous, and make titanium alloy tissue odds even, influence its use properties.
Someone adopts graphite as the crucible material of smelting titanium or titanium alloy.After using plumbago crucible to carry out Ti alloy, the carburetting of titanium ingot is serious, generates the big scale brittle layer, reduces the titanium alloy performance.
The oxide refractories of employing crucible is arranged in addition as melting container.But the fusing point of metal titanium is high; Under molten state, the chemically reactive of titanium is big, under present melting condition; Can reaction in various degree take place with all refractory materialss commonly used almost; Therefore common refractory materials like aluminum oxide, Natural manganese dioxide and silicon oxide etc., all is not suitable for as the crucible material of smelting titanium alloy.Adopt lime crucible in addition, but lime crucible does not reach titanium alloy on the one hand to the control of Oxygen Content requirement, lime crucible is difficult for sinter molding on the other hand, and in air, is prone to aquation, is difficult for preserving.Report that yttrium oxide is less as the reaction of the refractory materials of smelting titanium alloy and titanium alloy, can form the middle layer, suppresses the further reaction of titanium alloy and refractory materials effectively, is ideal Ti alloy refractory materials.But its price is too high, directly improves the cost of titanium alloy, is not suitable for extensive use.
Pass through calphad and consult related data, provide as drawing a conclusion: compd B aZrO
3Fusing point can reach 2600 ℃, has good hot shock resistance, cubic perovskite structure, and density is 5.652g/cm
3And price is lower.Nowadays be not used to melting titanium and alloy thereof as yet though barium zirconate is existing, it is used as refractory materials in some melting, and it is the most stable crucible material in the present high-quality single crystal yttrium barium copper oxygen superconductive material of melting.This novel crucible material is used for yttrium barium copper oxygen superconductive material has several advantages: form the back crystal in crystallization and no longer contain the impurity from crucible; Because the variation that corrosion of crucible brought no longer influences the fused alloy composition, so just can avoid those uncontrollable resultants simultaneously.In all cubic perovskite materials, the lattice parameter of barium zirconate is maximum.Thus, BaZrO
3Be more stable crucible material, during high temperature, with the active metal reaction, stable performance is a kind of refractory materials of potential titanium or titanium alloy smelting pot hardly.
Summary of the invention
The purpose of this invention is to provide a kind of BaZrO that is used for titanium or titanium alloy
3The preparation method of refractory materials and crucible thereof.
A kind of BaZrO that is used for Ti alloy of the present invention
3The preparation method of refractory materials is characterized in that having following process and step:
Adopting highly purified barium carbonate and zirconium white is raw material, and the mol ratio that both cooperate is BaCO
3: ZrO
2=1:1; The TiO that adds 0.5 ~ 5.0 mol% in addition again
2With this admixtion sintering repeatedly under 1200 ~ 1400 ℃ of temperature, process BaZrO
3Refractory materials.
A kind of BaZrO that is used for Ti alloy of the present invention
3The preparation method of crucible is characterized in that it being that following process and step are arranged:
A) batching: adopting highly purified barium carbonate and zirconium white is raw material, and the mol ratio that both cooperate is BaCO
3: ZrO
2=1:1; The TiO that adds 0.5 ~ 5.0 mol% in addition again
2
B) ball milling: in above-mentioned admixtion, add an amount of absolute ethyl alcohol, and add zirconia ball, ball milling is 10 ~ 24 hours in ball mill, gets powder;
C) drying: the powder that ball milling is good places drying baker, in 80 ~ 120 ℃ of oven dry down;
D) moulding: in the powder of oven dry, add sticker, in homemade mould, be pressed into the crucible base; Sticker is a paraffin, USP Kosher, and at least a in the absolute ethyl alcohol, the add-on of sticker is 1 ~ 5% of a powder quality;
E) presintering: above-mentioned crucible base heated up at a slow speed is heated to 800 ~ 1200 ℃, is incubated 4 ~ 10 hours, obtains biscuit;
F) sintering: above-mentioned biscuit is rapidly heated to 1650 ~ 1750 ℃, and sintering 5 ~ 10 hours naturally cools to room temperature then, promptly makes finished product BaZrO
3Crucible.
Description of drawings
Crucible sample drawing before and after Fig. 1 sintering is accomplished (left side is that sample drawing before the sintering, the right side are sample drawing behind the sintering).
Crucible state graph behind Fig. 2 vacuum condition, 1500 ± 10 ℃ of following smelting titanium alloys.
The smelting apparatus general illustration of the conventional that Fig. 3 the present invention is used.
Embodiment
After specific embodiment of the present invention being described at present
Embodiment:
(1) BaZrO
3The preparation of refractory materials
Adopting highly purified barium carbonate and zirconium white is raw material, and both mole proportionings are BaCO
3: ZrO
2=1:1; The TiO that adds 0.5 ~ 5.0 mol% in addition again
2The sintering aids of fluxing; With this admixtion sintering repeatedly under 1300 ℃ of temperature, process BaZrO
3Refractory materials.
(2) BaZrO
3The preparation of smelting pot
Smelting pot manufacturing processed and step are described below:
1) batching: adopting high-pruity barium carbonate and zirconium white is raw material, and both mole proportionings are 1:1, add the TiO of 2.0 mol% in addition
2
2) ball milling: add an amount of absolute ethyl alcohol in the material for preparing, add zirconia ball, ball milling 20 hours;
3) drying: the material that ball milling is good places drying baker, 100 ~ 110 ℃ of oven dry;
4) moulding: in the material of having dried, add sticker, sticker is a paraffin, and add-on is 4wt%, in molding jig, is being pressed into the crucible base;
5) presintering: base substrate heated up at a slow speed is heated to 800 ~ 1200 ℃, is incubated 4 ~ 10 hours, obtains biscuit;
6) sintering: biscuit is warming up to 1200 ℃, sintering 10 hours; Be rapidly heated to 1650 ~ 1750 ℃, sintering 10 hours is cooled to room temperature, obtains the finished product crucible again.
Above-mentioned sample is analyzed through X-ray diffractometer (XRD), and gained XRD figure stave is bright: its phase composite is mainly BaZrO
3
The volume density of above-mentioned sample is measured, and the volume density of the sample of embodiment is 6.054g/cm
3
The crucible for smelting Ti-Ni alloy that utilization is processed through this operation, no significant reaction layer, metal energy spectrum analysis display surface does not have the crucible element and infects after the melting, and alloy property is good.
Use this BaZrO
3Crucible in induction furnace, vacuum condition, 1500 ± 10 ℃ of an amount of titanium alloys of following melting, inner surface of crucible is reactionless; Alloying constituent does not change after the melting, stable performance.What present embodiment adopted is the smelting apparatus of conventional, and equipment is as shown in Figure 3, mainly is made up of high frequency electric source, vacuum unit, infrared measurement of temperature and supporting PC system thereof and induction vacuum melting furnace four parts.
Claims (2)
1. BaZrO who is used for Ti alloy
3The preparation method of refractory materials is characterized in that having following process and step:
Adopting highly purified barium carbonate and zirconium white is raw material, and the mol ratio that both cooperate is BaCO
3: ZrO
2=1:1; The TiO that adds 0.5 ~ 5.0 mol% in addition again
2This admixtion is fired under 1200 ~ 1400 ℃ of temperature repeatedly, processed BaZrO
3Refractory materials.
2. BaZrO who is used for Ti alloy
3The preparation method of crucible is characterized in that it being that following process and step are arranged:
A) batching: adopting highly purified barium carbonate and zirconium white is raw material, and the mol ratio that both cooperate is BaCO
3: ZrO
2=1:1; The TiO that adds 0.5 ~ 5.0 mol% in addition again
2
B) ball milling: in above-mentioned admixtion, add an amount of absolute ethyl alcohol, and add zirconia ball, ball milling is 10 ~ 24 hours in ball mill, gets powder;
C) drying: the powder that ball milling is good places drying baker, in 80 ~ 120 ℃ of oven dry down;
D) moulding: in the powder of oven dry, add sticker, in homemade mould, be pressed into the crucible base; Sticker is a paraffin, USP Kosher, and at least a in the absolute ethyl alcohol, the add-on of sticker is 1 ~ 5% of a powder quality;
E) presintering: above-mentioned crucible base heated up at a slow speed is heated to 800 ~ 1200 ℃, is incubated 4 ~ 10 hours, obtains biscuit;
F) sintering: above-mentioned biscuit is rapidly heated to 1650 ~ 1750 ℃, and sintering 5 ~ 10 hours naturally cools to room temperature then, promptly makes finished product BaZrO
3Crucible.
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102990006A (en) * | 2012-11-30 | 2013-03-27 | 上海大学 | Shell for titanium and titanium alloy precision casting and preparation method thereof |
| CN102994785A (en) * | 2012-11-30 | 2013-03-27 | 上海大学 | Method for smelting hydrogen storage alloy containing titanium from BaZrO3 refractory material by vacuum induction |
| CN103864419A (en) * | 2014-03-12 | 2014-06-18 | 华东师范大学 | Preparation method of highly compact barium zirconate ceramic |
| CN103898610A (en) * | 2014-03-31 | 2014-07-02 | 上海大学 | Shell mold for directional solidification of highly active alloys and application of shell mold |
| CN103922769A (en) * | 2014-03-31 | 2014-07-16 | 上海大学 | Molten titanium and titanium alloy crucible and preparation method thereof |
| CN103979979A (en) * | 2014-05-05 | 2014-08-13 | 华东师范大学 | Method for preparing barium zirconate crucible by slip casting |
| CN105716902A (en) * | 2014-12-01 | 2016-06-29 | 鞍钢股份有限公司 | Sampler and preparation method thereof |
| CN105777162A (en) * | 2016-03-19 | 2016-07-20 | 上海大学 | Y2O3 doped BaZrO3 refractory material |
| CN106086520A (en) * | 2016-08-30 | 2016-11-09 | 上海大学 | Zircaloy smelting technology |
| CN109574661A (en) * | 2018-12-13 | 2019-04-05 | 沃尔曼科技张家港有限公司 | A kind of preparation method and application of barium zirconate ceramic core |
| CN109592709A (en) * | 2018-12-26 | 2019-04-09 | 郑州振中电熔新材料有限公司 | A kind of preparation method of electric smelting barium zirconate |
| CN110156463A (en) * | 2019-07-18 | 2019-08-23 | 湖南三五二环保科技有限公司 | A kind of compound refractory material and preparation method thereof |
| US10407349B2 (en) | 2015-04-24 | 2019-09-10 | Corning Incorporated | Bonded zirconia refractories and methods for making the same |
| CN114011483A (en) * | 2021-11-10 | 2022-02-08 | 中国核动力研究设计院 | Container for zirconium alloy molten pool and cooling water test and preparation method thereof |
| CN114166023A (en) * | 2021-11-05 | 2022-03-11 | 华中科技大学 | Ceramic crucible for induction melting of titanium and titanium alloy and integrated preparation method thereof |
| CN114436648A (en) * | 2021-12-15 | 2022-05-06 | 上海大学 | Barium-yttrium-zirconium-oxygen-fluorine multi-perovskite structure material and preparation method thereof |
| CN117383950A (en) * | 2023-12-11 | 2024-01-12 | 中国航发北京航空材料研究院 | Non-calcareous refractory crucible for nickel-based superalloy desulfurization and preparation method thereof |
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Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102994785A (en) * | 2012-11-30 | 2013-03-27 | 上海大学 | Method for smelting hydrogen storage alloy containing titanium from BaZrO3 refractory material by vacuum induction |
| CN102994785B (en) * | 2012-11-30 | 2015-05-27 | 上海大学 | Method for smelting hydrogen storage alloy containing titanium from BaZrO3 refractory material by vacuum induction |
| CN102990006B (en) * | 2012-11-30 | 2016-01-20 | 上海大学 | A kind of shell for titanium or titanium alloy hot investment casting and preparation method thereof |
| CN102990006A (en) * | 2012-11-30 | 2013-03-27 | 上海大学 | Shell for titanium and titanium alloy precision casting and preparation method thereof |
| CN103864419A (en) * | 2014-03-12 | 2014-06-18 | 华东师范大学 | Preparation method of highly compact barium zirconate ceramic |
| CN103898610A (en) * | 2014-03-31 | 2014-07-02 | 上海大学 | Shell mold for directional solidification of highly active alloys and application of shell mold |
| CN103922769A (en) * | 2014-03-31 | 2014-07-16 | 上海大学 | Molten titanium and titanium alloy crucible and preparation method thereof |
| CN103979979A (en) * | 2014-05-05 | 2014-08-13 | 华东师范大学 | Method for preparing barium zirconate crucible by slip casting |
| CN105716902A (en) * | 2014-12-01 | 2016-06-29 | 鞍钢股份有限公司 | Sampler and preparation method thereof |
| US10407349B2 (en) | 2015-04-24 | 2019-09-10 | Corning Incorporated | Bonded zirconia refractories and methods for making the same |
| CN105777162A (en) * | 2016-03-19 | 2016-07-20 | 上海大学 | Y2O3 doped BaZrO3 refractory material |
| CN106086520A (en) * | 2016-08-30 | 2016-11-09 | 上海大学 | Zircaloy smelting technology |
| CN109574661A (en) * | 2018-12-13 | 2019-04-05 | 沃尔曼科技张家港有限公司 | A kind of preparation method and application of barium zirconate ceramic core |
| CN109592709A (en) * | 2018-12-26 | 2019-04-09 | 郑州振中电熔新材料有限公司 | A kind of preparation method of electric smelting barium zirconate |
| CN109592709B (en) * | 2018-12-26 | 2021-05-25 | 郑州振中电熔新材料有限公司 | Preparation method of electric-melting barium zirconate |
| CN110156463A (en) * | 2019-07-18 | 2019-08-23 | 湖南三五二环保科技有限公司 | A kind of compound refractory material and preparation method thereof |
| CN110156463B (en) * | 2019-07-18 | 2019-10-15 | 湖南三五二环保科技有限公司 | A kind of compound refractory material and preparation method thereof |
| CN114166023A (en) * | 2021-11-05 | 2022-03-11 | 华中科技大学 | Ceramic crucible for induction melting of titanium and titanium alloy and integrated preparation method thereof |
| CN114011483A (en) * | 2021-11-10 | 2022-02-08 | 中国核动力研究设计院 | Container for zirconium alloy molten pool and cooling water test and preparation method thereof |
| CN114011483B (en) * | 2021-11-10 | 2023-03-14 | 中国核动力研究设计院 | Container for zirconium alloy molten pool and cooling water test and preparation method thereof |
| CN114436648A (en) * | 2021-12-15 | 2022-05-06 | 上海大学 | Barium-yttrium-zirconium-oxygen-fluorine multi-perovskite structure material and preparation method thereof |
| CN117383950A (en) * | 2023-12-11 | 2024-01-12 | 中国航发北京航空材料研究院 | Non-calcareous refractory crucible for nickel-based superalloy desulfurization and preparation method thereof |
| CN117383950B (en) * | 2023-12-11 | 2024-03-05 | 中国航发北京航空材料研究院 | Non-calcareous refractory crucible for nickel-based superalloy desulfurization and preparation method thereof |
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Application publication date: 20120620 |