WO2009086723A1 - A zirconium oxide and yttrium oxide dispersion-strengthened pd-au alloy and manufacturing method thereof - Google Patents
A zirconium oxide and yttrium oxide dispersion-strengthened pd-au alloy and manufacturing method thereof Download PDFInfo
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Abstract
A zirconium oxide and yttrium oxide dispersion-strengthened Pd-Au alloy comprises (in wt%): 0<Au≤7%, 0<Zr≤0.7%, 0<Y≤0.5% and balance Pd, in which Zr and Y are dispersed uniformly in the alloy in the form of zirconium oxide and yttrium oxide respectively. The alloy has high ability to endure stress at elevated temperature, and has a rupture life which is 35~55 times of that of conventional zirconium oxide dispersion-strengthened Pt-3Rh alloy. The alloy could be used in glass fiber, electric glass or optical glass industry instead of zirconium oxide dispersion-strengthened Pt-Rh alloy, so as to reduce production cost of glass.
Description
氧化锆氧化钇弥散强化钯金合金及其生产方法 技术领域 Zirconia yttria dispersion-strengthened palladium-gold alloy and production method thereof
本发明涉及一种贵金属合金，具体地说是一种氧化锆氧化钇弥散强化钯 金合金及其生产方法。 The present invention relates to a noble metal alloy, and more particularly to a zirconia yttria dispersion-strengthened palladium-gold alloy and a process for producing the same.
背景技术 Background technique
目前， 玻璃纤维， 电子玻璃 （CRT, TFT) 或光学玻璃工业的关键设备 使用氧化锆弥散强化铂铑合金， 成份为铑 Rh3~10%， 铂 Pt为余量， 锆 Zr含 量 <0.5%。这种合金的高温持久强度和承载能力超过 Pi-40Rh， 可在高温氧化 条件下使用， 但铂铑易挥发， 晶粒粗 ， 强度降低并发生蠕变， 使用寿命有 限， 且价格昂贵， 铂铑损耗大， 投资及使用成本高。 At present, the key equipment of glass fiber, electronic glass (CRT, TFT) or optical glass industry uses zirconia dispersion strengthened platinum-rhodium alloy, the composition is 3 Rh3~10%, platinum Pt is the balance, zirconium Zr content is <0.5%. This alloy has high temperature endurance and load carrying capacity over Pi-40Rh and can be used under high temperature oxidation conditions, but platinum rhodium is easy to volatilize, crystal grains are coarse, strength is reduced and creep occurs, life is limited, and expensive, platinum rhodium High loss, high investment and use costs.
发明内容 ； SUMMARY OF THE INVENTION;
本发明的目的在于提供一种氧化锆氧化钇弥散强化钯金合金及其生产 方法，以代替氧化锆弥散强化铂铑合 ，降低生产线的资金投入和使用损耗， 大幅降低玻璃的生产成本， 提高经济效益。 The object of the present invention is to provide a zirconia yttria dispersion-strengthened palladium-gold alloy and a production method thereof, which can replace the zirconia dispersion-strengthened platinum-ruthenium, reduce the capital investment and use loss of the production line, greatly reduce the production cost of the glass, and improve the economy. benefit.
本发明氧化锆氧化钇弥散强化钯金合金该合金包括： 钯、 金、 锆和钇； 各组份重量百分含量为：金大于 0、小于等于 7%，锆大于 0、小于等于 0.7%， 钇大于 0、 小于等于 0.5%， 钯为余量， ,其中的锆、 钇分别以氧化锆、 氧化钇 的形式均匀弥散在合金中。 The zirconia yttria dispersion-strengthened palladium-gold alloy comprises: palladium, gold, zirconium and hafnium; the weight percentage of each component is: gold is greater than 0, less than or equal to 7%, zirconium is greater than 0, less than or equal to 0.7%,钇 is greater than 0, less than or equal to 0.5%, palladium is the balance, and zirconium and hafnium are uniformly dispersed in the alloy in the form of zirconia and yttrium oxide, respectively.
所述合金中还含有铂， 铂的重量百分含量大于 0、 小于等于 12%。 The alloy further contains platinum, and the weight percentage of platinum is greater than 0 and less than or equal to 12%.
本发明提供述氧化锆氧化钇弥散强化钯金合金的生产方法， 歩骤如下： 将金、 钯、 锆、 钇加入真空感应炉中熔炼; 压力 2X l(T2〜l X l(T5Pa， 温 度 1700~1850°C，再浇注于铸模中形成铸锭;然后在轧机上轧制出 Pd-Au-Zr-Y 合金片材， 再将该合金片材在 800~1400°C下经 ^0〜120小时热处理， 将其中 的锆、 钇分别变成氧化锆和氧化钇， 并使氧化 氧化钇均匀弥散在合金中， 得到氧化锆氧化钇弥散强化钯金合金材料。氧化锆氧化钇起钉扎晶界并阻止 位错攀移的作用，同时也阻碍合金原子扩散，达到减小晶粒生长速度的目的，
氧化钇同时还提高氧的扩散速度，减少氧化处理时间，增强合金的高温性能。 在将金、 钯、 锆、 钇加入真空感应炉中熔炼时， 还可同时加入铂， 铂在 合金中的重量百分含量是大于： 0、 小于等于 12%。 The invention provides a method for producing a zirconia yttria dispersion-strengthened palladium-gold alloy, the steps are as follows: adding gold, palladium, zirconium and hafnium to a vacuum induction furnace for melting; pressure 2X l (T 2 〜 l X l (T 5 P a , the temperature is 1700~1850 °C, and then poured into the mold to form an ingot; then the Pd-Au-Zr-Y alloy sheet is rolled on the rolling mill, and the alloy sheet is then passed at 800~1400 °C. The heat treatment is carried out for 0 to 120 hours, and zirconium and hafnium are respectively changed into zirconium oxide and hafnium oxide, and the oxidized cerium oxide is uniformly dispersed in the alloy to obtain a zirconia yttria dispersion-strengthened palladium-gold alloy material. Pinning the grain boundary and preventing the dislocation from climbing, and also hindering the diffusion of the alloy atoms to achieve the purpose of reducing the grain growth rate. Cerium oxide also increases the diffusion rate of oxygen, reduces the oxidation treatment time, and enhances the high temperature performance of the alloy. When gold, palladium, zirconium, or hafnium is added to a vacuum induction furnace for melting, platinum may be simultaneously added, and the weight percentage of platinum in the alloy is greater than: 0, less than or equal to 12%.
所述铸模为水冷铜模。 The mold is a water-cooled copper mold.
这种合金具有优良的高温特性及很长的使用寿命， 耐髙温、 抗氧化、 抗 蠕变、 抗熔融玻璃腐蚀， 可在高温氧化条件下长期使用， 广泛用于玻璃纤维 工业用漏板、 旋转框、 套管； 光学玻璃熔化、 精整、 成型装置和搅拌器； 电 子玻璃 （CRT、 TFT) 制造等行业。 This alloy has excellent high temperature characteristics and long service life. It is resistant to enthalpy, oxidation, creep, and corrosion to molten glass. It can be used for a long time under high temperature oxidation conditions. It is widely used in glass fiber industrial leak boards. Rotating frame, casing; optical glass melting, finishing, forming equipment and agitator; manufacturing of electronic glass (CRT, TFT).
上述各成份的作用：钯的抗氧化性能良好、冶金学上与铂相容，熔点高， 延性与铂近似而价格便宜的钯作为主体； 金的加入提高了钯的抗熔融玻璃浸 润性， 但使用温度在钯的熔点,以下。 为了使钯-金合金有更高的使用温度， 可将铂添加于钯 -金合金中。 氧化锆氧化钇弥散强化钯金铂合金及氧化锆氧 化钇弥散强化钯金合金的高温性能远 于目前技术水平最领先的氧化锆弥 散强化铂铑 3合金 (ZGSPt-3Rh)0 且 Pd、 Au、 Pt不易挥发、 损耗小； 大幅 度降低使用者的生产成本， 显著提高绎济效益。 The role of the above components: palladium has good oxidation resistance, is metallurgically compatible with platinum, has a high melting point, palladium with a similar ductility and platinum, and is inexpensive; the addition of gold increases the infiltration resistance of palladium to molten glass, but The temperature used is below the melting point of palladium. In order to have a higher use temperature of the palladium-gold alloy, platinum may be added to the palladium-gold alloy. The high temperature performance of zirconia yttria dispersion strengthened palladium gold platinum alloy and zirconia yttria dispersion strengthened palladium alloy is far superior to the current state of the art zirconia dispersion strengthened platinum iridium 3 alloy (ZGSPt-3Rh) 0 and Pd, Au, Pt is not easy to volatilize and has low loss; it greatly reduces the production cost of users and significantly improves the economic benefits.
本合金主要性能是高温下能承受庳力的能力大提高，其断裂寿命为同类 产品氧化锆弥散强化铂铑 3合金的 35~55倍； 成份新颖、 高效节能、 完全可 靠、 造价成本低、 使用经济性好、 利于出口。 The main performance of this alloy is the ability to withstand high pressure at high temperature, and its fracture life is 35~55 times that of zirconia dispersion strengthened platinum-rhodium alloy of similar products; novel composition, high efficiency, energy saving, complete reliability, low cost, use Good economy and good for export.
具体实施方式 detailed description
本合金的熔炼方法如下- 将金 Au、钯 Pd、锆 Zr、钇 |Υ等加] \真空感应炉中熔炼， 压力 2 Χ 10_2〜1 X 10"5Pa, 温度 1700〜1850°C，：再浇注于铸模 Φ形成铸锭； 然后在轧机上轧 制出 Pd-Au-Zr-Y合金片材，再 该合金片材在 800〜1400°C下经 60〜120小时 热处理， 将其中的锆变成氧化锆， 钇变成氧化钇， 并使氧化锆和氧化钇均匀 弥散在合金中， 得到氧化锆与氧化钇弥散强化钯金合金材料。氧化锆与氧化 钇起钉扎晶界并阻止位错攀移的作用， 同时也阻碍合金原子扩散， 达到减小
晶粒生长速度的目的。氧化钇同时还可提高氧的扩散速度， 减少氧化处理时 间， 增强合金的高温性能。 The melting method of the alloy is as follows - gold Au, palladium Pd, zirconium Zr, 钇 | Υ, etc. are added in a vacuum induction furnace, pressure 2 Χ 10_ 2 〜 1 X 10" 5 Pa, temperature 1700~1850 ° C, : re-casting in the mold Φ to form an ingot; then rolling a Pd-Au-Zr-Y alloy sheet on the rolling mill, and then heat-treating the alloy sheet at 800 to 1400 ° C for 60 to 120 hours, Zirconium becomes zirconia, yttrium is turned into yttria, and zirconia and yttria are uniformly dispersed in the alloy to obtain a zirconia and yttria dispersion-strengthened palladium-gold alloy material. Zirconium oxide and yttrium oxide are used to pin the grain boundary and prevent The effect of dislocation climbing also hinders the diffusion of alloy atoms and reduces The purpose of grain growth rate. Cerium oxide can also increase the diffusion rate of oxygen, reduce the oxidation treatment time, and enhance the high temperature performance of the alloy.
在将金 Au、钯 Pd、锆 Zr、钇 Y加入真空感应炉中熔炼时， 同时还可以 加入铂 Pt，铂 Pt在合金中的含量是大于 0、小于等于 12%， 单位为重量百分 数。 所述铸模为水冷铜模。 When gold Au, palladium Pd, zirconium Zr, and yttrium Y are added to a vacuum induction furnace for melting, platinum Pt may also be added. The content of platinum Pt in the alloy is greater than 0, less than or equal to 12%, and the unit is weight percent. The mold is a water-cooled copper mold.
下面各实施例分别为纯钯或不同重量配比的合金的技术性，熔炼方法同 上。 The following examples are technically pure palladium or alloys of different weight ratios, and the melting method is the same as above.
实施例一： Pd l00%。 Example 1: Pd l00%.
技术性能： 在高温下承受同等应力时的断裂寿命为 ZGSPt-3Rh的 0.002 倍左右。 Technical performance: The fracture life at the same temperature under high temperature is about 0.002 times that of ZGSPt-3Rh.
实施例二： Au l.5%， Pd 96.3%, Pt 2.0%, Zr0.1%, Υ0·1%。 Example 2: Au l.5%, Pd 96.3%, Pt 2.0%, Zr 0.1%, Υ0·1%.
技术性能：在高温下承受同等应力时的断裂寿命为 ZGSPt-3Rh的 40倍左 右。 Technical performance: The fracture life at the same temperature under high temperature is about 40 times that of ZGSPt-3Rh.
实施例三： Au3.5%， Pd92:0%, Pt4.0%, Zr0.3%, Y0.2。/o。 Example 3: Au 3.5%, Pd 92: 0%, Pt 4.0%, Zr 0.3%, Y 0.2. / o .
技术性能：在高温下承受同等应力 的断裂寿命为 ZGSPt-3R 的 55倍左 右。 ；: ： Technical performance: The fracture life at the same temperature under high temperature is about 55 times that of ZGSPt-3R. ;: :
实施例四： Au5.0%， Pd88.2%, Pt6.0%, ZrO.5%, Y0.3%。 Example 4: Au 5.0%, Pd 88.2%, Pt 6.0%, ZrO.5%, Y 0.3%.
技术性能：在高温下承受同等应力时的断裂寿命为 ZGSPt-3Rh的 48倍左 右。 ： Technical performance: The fracture life at the same temperature under high temperature is about 48 times that of ZGSPt-3Rh. :
实施例五： Au6.00/0， Pd84.0%, Pt9.0%, ZrO.6%, Y0.4%。 Example 5: Au6.0 0 / 0 , Pd 84.0%, Pt 9.0%, ZrO.6%, Y0.4%.
技术性能：在高温下承受同等应力时的断裂寿命为 ZGSPt-3R 的 42倍左 右。 Technical performance: The fracture life at the same temperature under high temperature is about 42 times that of ZGSPt-3R.
实施例六： Au7.0%， Pd79.8%, Ptl2.0%, ZrO.7%, Y0.5%。 Example 6: Au7.0%, Pd79.8%, Ptl2.0%, ZrO.7%, Y0.5%.
技术性能：在高温下承受同等应力时的断裂寿命为 ZGSPt-3Rh的 39倍左 右。 Technical performance: The fracture life at the same temperature under high temperature is about 39 times that of ZGSPt-3Rh.
实施例七： Au l.0%， Pd 98.65%, ZrO.2%, Υ0.15ο/ο。
技术性能：在高温下承受同等应力时的断裂寿命为 ZGSPt-3R 的 36倍左 右。 Example 7: Au l.0%, Pd 98.65%, ZrO.2%, Υ0.15 ο /ο. Technical performance: The fracture life at the same temperature under high temperature is about 36 times that of ZGSPt-3R.
实施例八： Au2.5%， Pd96.85%, ZrO.4%, Y0.25%。 Example 8: Au 2.5%, Pd 96.85%, ZrO. 4%, Y 0.2%.
技术性能：在高温下承受同等应力时的断裂寿命为 ZGSPt-3Rh的 53倍左 右。 Technical performance: The fracture life at the same temperature under high temperature is about 53 times that of ZGSPt-3Rh.
实施例九： Au4.0°/o， Pd95.15%, ZrO.5%, Y0.35%。 Example 9: Au 4.0 ° / o, Pd 95.15%, ZrO. 5%, Y 0.35%.
技术性能：在高温下承受同等应力时的断裂寿命为 ZGSPt-3Rh的 46倍左 右。 Technical performance: The fracture life at the same temperature under high temperature is about 46 times that of ZGSPt-3Rh.
实施例十： Au5.5%, Pd93.45%, ZrO.6%, Y0.45。/o。 Example 10: Au 5.5%, Pd 93.45%, ZrO.6%, Y0.45. /o.
技术性能：在高温下承受同等应力时的断裂寿命为 ZGSPt-3R 的 45倍左 右。 Technical performance: The fracture life at the same temperature under high temperature is about 45 times that of ZGSPt-3R.
实施例"] "^―： AuO.1%, Pd98.7%, ZrO.7%, Y0.5%。 Example "] "^―: AuO.1%, Pd98.7%, ZrO.7%, Y0.5%.
技术性能：在高温下承受同等应力时的断裂寿命为 ZGSPt-3R 的 40倍左 右。
Technical performance: The fracture life at the same temperature under high temperature is about 40 times that of ZGSPt-3R.
Claims
1、 氧化锆氧化钇弥散强化钯金 金， 其特征是该合金包括： 钯、 金、 锆和钇； 各组份重量百分含量为： 金大于 0、 小于等于 7%， 锆大于 0、 小于 等于 0.7%， 钇大于 0、 小于等于 0.5%， 钯为余量， 其中的锆、 钇分别以氧 化锆、 氧化钇的形式均匀弥散在合金中。 1. Zirconium oxide yttrium oxide dispersion-strengthened palladium gold, characterized in that the alloy comprises: palladium, gold, zirconium and hafnium; the weight percentage of each component is: gold is greater than 0, less than or equal to 7%, zirconium is greater than 0, less than It is equal to 0.7%, 钇 is greater than 0, less than or equal to 0.5%, palladium is the balance, and zirconium and hafnium are uniformly dispersed in the alloy in the form of zirconia and yttrium oxide, respectively.
2、 如权利要求 1所述氧化锆氧化钇弥散强化钯金合金， 其特征是： 在 合金中还含有铂， 铂的含量大于 0、 小于等于 12%， 单位为重量百分数。 2. The zirconia yttria dispersion-strengthened palladium-gold alloy according to claim 1, wherein: the alloy further comprises platinum, and the platinum content is greater than 0, less than or equal to 12%, and the unit is weight percent.
3、 如权利要求《1所述氧化锆氧化钇弥散强化钯金合金的生产方法， 其 特征在于，将金、钯、锆、钇加入真空 应炉中熔炼，压力 2X 10_2〜1 X 10'5Pa, 温度 1700~1850°C， 再浇注 铸模中形成铸锭； 然后在轧机上轧制出 Pd-Au-Zr-Y合金片材，再将该合金片材在 800〜1400°C下经 60~120小时热处 理， 将其中的锆变成氧化锆， 某中的钇变成氧化钇， 并使氧化锆氧化钇均匀 弥散在合金中， 得到氧化锆钇弥散强化钯金合金材料。 3. The method for producing a zirconia yttria dispersion-strengthened palladium-gold alloy according to claim 1, wherein the gold, palladium, zirconium and hafnium are added to a vacuum furnace for melting, and the pressure is 2X 10_ 2 〜1 X 10' 5 Pa, temperature 1700~1850 °C, ingot is formed in the recasting mold; then Pd-Au-Zr-Y alloy sheet is rolled on the rolling mill, and then the alloy sheet is passed at 800~1400 °C After 60 to 120 hours of heat treatment, the zirconium is converted into zirconia, and the yttrium in one of them becomes yttrium oxide, and the zirconia yttria is uniformly dispersed in the alloy to obtain a zirconia ytterbium-dispersion-strengthened palladium-gold alloy material.
4、 如权利要求 3所述氧化锆氧化钇弥散强化钯金合金的生产方法， 其 特征是： 在将金、 钯、 锆、 钇加入真空感应炉中熔炼时， 同时还加入铂， 铂 在合金中的含量是大于 0、 小于等于 12%, 单位为重量百分数。 4. The method for producing a zirconia yttria dispersion-strengthened palladium-gold alloy according to claim 3, wherein: when gold, palladium, zirconium, and hafnium are added to a vacuum induction furnace for melting, platinum is also added, and platinum is alloyed. The content in the content is greater than 0, less than or equal to 12%, and the unit is weight percent.
5、 如权利要求 3所述氧化锆氧化钇弥散强化钯金合金的生产方法， 其 特征是： 所述铸模为水冷铜模。
A method for producing a zirconia yttria dispersion-strengthened palladium-gold alloy according to claim 3, wherein: said mold is a water-cooled copper mold.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810019452.9 | 2008-01-04 | ||
| CN2008100194529A CN101215652B (en) | 2008-01-04 | 2008-01-04 | Zirconium oxide dispersion strengthening palladium-gold alloy producing method |
| CN2008100218082A CN101386929B (en) | 2008-08-14 | 2008-08-14 | Zirconia and yttria dispersion strengthening palau alloy and producing method thereof |
| CN200810021808.2 | 2008-08-14 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115319424A (en) * | 2022-09-16 | 2022-11-11 | 咸阳三毅有岩科技有限公司 | Thin-wall iridium crucible and processing method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115319424A (en) * | 2022-09-16 | 2022-11-11 | 咸阳三毅有岩科技有限公司 | Thin-wall iridium crucible and processing method thereof |
| CN115319424B (en) * | 2022-09-16 | 2024-02-06 | 咸阳三毅有岩科技有限公司 | Processing method of thin-wall iridium crucible and thin-wall iridium crucible |
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