WO2019056595A1 - Germanium-containing nickel-free phosphorus-free large-sized palladium-based amorphous alloy and preparation method therefor - Google Patents

Germanium-containing nickel-free phosphorus-free large-sized palladium-based amorphous alloy and preparation method therefor Download PDF

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WO2019056595A1
WO2019056595A1 PCT/CN2017/115922 CN2017115922W WO2019056595A1 WO 2019056595 A1 WO2019056595 A1 WO 2019056595A1 CN 2017115922 W CN2017115922 W CN 2017115922W WO 2019056595 A1 WO2019056595 A1 WO 2019056595A1
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alloy
amorphous alloy
free
molybdenum
amorphous
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Chinese (zh)
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吕昭平
曹迪
周捷
吴渊
王辉
刘雄军
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北京科技大学
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/003—Amorphous alloys with one or more of the noble metals as major constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D18/00—Pressure casting; Vacuum casting
    • B22D18/06—Vacuum casting, i.e. making use of vacuum to fill the mould
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/11—Making amorphous alloys

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  • the invention belongs to the field of bulk amorphous alloys, and particularly relates to a large-sized palladium-based amorphous alloy containing bismuth, nickel-free and phosphorus-free, and a preparation method thereof.
  • the alloys involved have a critical dimension of 1-8 mm and a plastic deformation capability is not low. At 3%.
  • Amorphous alloys metal glass and conventional metal materials have long-range and orderly arrangements of atoms, have randomly arranged atomic structures, have long-range disordered short-range order, and have no grain boundaries in their microstructure. Defects such as dislocations are metal materials that have emerged in recent years as a new generation of structural and functional applications.
  • amorphous alloys Compared with conventional crystalline alloys, amorphous alloys have excellent properties such as high strength, high hardness, high elastic limit, low modulus, and corrosion resistance that cannot be achieved.
  • the amorphous alloy will enter the supercooled liquid region after being heated above the glass transition temperature, and the amorphous alloy exhibits viscous flow characteristics in the supercooled liquid region, exhibiting superplastic deformation characteristics. This unique property of amorphous alloys allows for precise press forming in the supercooled liquid region. These superior properties make amorphous alloys have broad application prospects in many fields such as medical devices, consumer electronics, microelectronics and even luxury goods.
  • the invention develops a large-sized palladium-based amorphous alloy containing bismuth, nickel-free and phosphorus-free, and aims to not only remove nickel elements having toxic side effects on living organisms, but also has good biocompatibility and no phosphorus, and the preparation process is relatively simple. It has strong amorphous forming ability and plastic deformation ability to obtain a good comprehensive effect of amorphous alloy in both safety and processability.
  • the atomic percentage expression of the amorphous alloy is Pd 74.5 Cu 3 Ge 16.5 .
  • the atomic percentage expression of the amorphous alloy is Pd 74.5 Cu 3 Si 8 Ge 8.5 .
  • the atomic percentage expression of the amorphous alloy is Pd 74.5 Cu 3 Si 12.5 Ge 4 Ag 3 Au 4 .
  • Another object of the present invention is to provide a method for preparing the above alloy, which method comprises the following steps:
  • Preparation method (1) preparing the mother alloy without glass coating and purifying, and preparing the amorphous alloy by copper die casting, the steps include: Step 1. Ingredients: metal Pd, Cu with a purity of 99.0 wt%-99.99 wt% , Ag and non-metal Si, Ge are converted into mass according to the atomic percentage of the above expression, the surface oxide of the raw material is removed, and the raw materials are washed with industrial ethanol and weighed according to the respective required qualities;
  • Step 2 Mother alloy smelting:
  • the raw materials processed in step 1 are stacked in a non-consumable vacuum arc furnace or a cold heading suspension furnace according to the melting point, and are filled with high-purity argon after the vacuum is less than 10 -3 Pa ( Not less than 99.99%) smelting, at least 4 times, so that the mother alloy is fully smelted uniformly;
  • Step 3 After grinding and removing the mother alloy prepared by smelting, put it into different size water-cooled copper molds of a vacuum arc furnace, and evacuate the arc furnace chamber to less than 10 -3 Pa and then charge 0.08 MPa high-purity argon gas. (not less than 99.99%), the mother alloy is melted at 150A, and heated for 15s, the arc current is raised to 200-250A, the suction vacuum valve is quickly opened, and the master alloy is pressed into the water-cooled copper mold by air pressure. Cooling is performed to obtain amorphous alloys of different sizes.
  • the preparation method (2) preparing the mother alloy by glass coating and purifying, and preparing the amorphous alloy by copper mold suction casting, the steps include:
  • Step 1 Ingredients: The metal Pd, Cu, Ag and non-metal Si, Ge with a purity of 99.0 wt%-99.99 wt% are converted into mass according to the atomic percentage of the above expression, the scale of the raw material surface is removed, and industrial ethanol is used. Cleaning the raw materials and weighing them according to their respective qualities;
  • Step 2 Mother alloy smelting:
  • the raw materials processed in step 1 are stacked in a non-consumable vacuum arc furnace or a cold heading suspension furnace according to the melting point, and are filled with high-purity argon after the vacuum is less than 10 -3 Pa ( Not less than 99.99%) smelting, at least 4 times, so that the mother alloy is fully smelted uniformly;
  • Step 3 Glass coating purification: The mother alloy and the dehydrated boron trioxide medium are placed in quartz tubes of different sizes, and the quartz tube is vacuumed to 10 Pa or less, and then the quartz tube is filled with 0.2 MPa high purity argon. Gas, and placed in an electric furnace at 1100 ° C for 24 hours, after which the melt is cooled with the furnace;
  • Step 4 Remove the coating medium adhered to the surface of the alloy ingot after glass coating and purifying with sandpaper, place it on the water-cooled copper mold of different sizes in the vacuum arc furnace, and evacuate the arc furnace chamber to less than 10 -3 Pa. After filling with 0.08MPa high purity argon (not less than 99.99%), the mother alloy is melted at 150A, and heated for 15s, the arc current is raised to 200-250A, and the suction vacuum valve is quickly opened. The master alloy is cooled by pressure into a water-cooled copper mold to obtain amorphous alloys of different sizes.
  • the preparation method (3) preparing the mother alloy by glass coating and purifying, and preparing the amorphous alloy by water quenching, the steps include:
  • Step 1 Ingredients: The metal Pd, Cu, Ag and non-metal Si, Ge with a purity of 99.0 wt%-99.99 wt% are converted into mass according to the atomic percentage of the above expression, the scale of the raw material surface is removed, and industrial ethanol is used. Cleaning the raw materials and weighing them according to their respective qualities;
  • Step 2 Mother alloy smelting:
  • the raw materials processed in step 1 are stacked in a non-consumable vacuum arc furnace or a cold heading suspension furnace according to the melting point, and are filled with high-purity argon after the vacuum is less than 10 -3 Pa ( Not less than 99.99%) smelting, at least 4 times, so that the mother alloy is fully smelted uniformly;
  • Step 3 Glass coating purification: The mother alloy and the dehydrated boron trioxide medium are placed in quartz tubes of different sizes, and the quartz tube is vacuumed to 10 Pa or less, and then the quartz tube is filled with 0.2 MPa high purity argon. Gas, and placed in an electric furnace at 1100 ° C for 24 hours;
  • Step 4 The alloy ingot purified by glass coating is directly quenched into a room temperature brine having a concentration of not less than 25% by weight in a molten state to prepare amorphous alloys of different sizes.
  • the atomic percentage expression of the amorphous alloy is Pd 74.5 Cu 3 Ge 16.5 , and an amorphous alloy having a critical dimension of not less than 1 mm can be prepared by the production method (3).
  • the atomic percentage expression of the amorphous alloy is Pd 77.5 Cu 6 Si c Ge 16.5-c , by the preparation method ( 3) An amorphous alloy having a critical dimension of not less than 1 mm can be prepared.
  • the atomic percentage expression of the amorphous alloy is Pd 74.5 Cu 3 Si 8 Ge 8.5 , and the critical dimension can be prepared by the preparation method (3).
  • the mother alloy can be prepared by preparing the amorphous alloy with a critical dimension of not less than 2 mm by preparation method (1);
  • an amorphous alloy having a critical dimension of not less than 4 mm can be prepared, and the supercooled liquid phase region has a width of 54K.
  • the preparation method (1) can prepare an amorphous alloy having a critical dimension of not less than 2 mm; the critical dimension capable of forming bulk amorphous by the preparation method (3) is not less than 8 mm, and the plastic strain is not less than 5%.
  • the atomic percentage expression of the amorphous alloy is Pd 77.5 Cu 3 Si 12.5 Ge 4 Ag 3 , and the master alloy is prepared (1)
  • An amorphous alloy having a critical dimension of not less than 4 mm can be prepared; the critical dimension capable of forming bulk amorphous by the preparation method (3) is not less than 8 mm, and the plastic strain is not less than 11%.
  • the atomic percentage expression of the amorphous alloy is Pd 74.5 Cu 3 Si 12.5 Ge 4 Ag 3 Au 4.
  • the critical dimension capable of forming bulk amorphous by the preparation method (3) is not less than 8 mm.
  • the critical size is the preparation method (1) ⁇ preparation mode (2) ⁇ preparation mode (3).
  • a series of palladium-based amorphous alloys according to the present invention which have excellent amorphous forming ability and a maximum critical dimension of not less than 8 mm.
  • a series of palladium-based amorphous alloys according to the present invention the main elements of which are Pd, Cu, Si, Ge, Ag, do not contain Ni or other toxic or bio-sensitizing elements, and have good biocompatibility. .
  • a series of palladium-based amorphous alloys according to the invention the main elements of the alloy are Pd, Cu, Si, Ge, Ag, and do not contain volatile P, and the preparation method of the smelting is simple.
  • a series of palladium-based amorphous alloys according to the present invention have strong plastic deformation ability and a maximum plastic deformation capacity of not less than 5%.
  • Figure 3 is a DSC curve of a Pd 77.5 Cu 6 Si 12.5 Ge 4 amorphous alloy.
  • Figure 7 is an XRD pattern of a Pd 77.5 Cu 3 Si 12.5 Ge 4 Ag 3 amorphous alloy.
  • Figure 8 is an SEM image of a Pd 77.5 Cu 3 Si 12.5 Ge 4 Ag 3 amorphous alloy.
  • Figure 10 is an XRD pattern of a Pd 74.5 Cu 3 Si 12.5 Ge 4 Ag 3 Au 4 amorphous alloy.
  • 11 is an XRD pattern of Pd 77.5 Cu 5 Si 12.5 Ge 4 Ag 1 , Pd 77.5 Cu 4 Si 12.5 Ge 4 Ag 2 , Pd 77.5 Cu 3 Si 12.5 Ge 4 Ag 3 , amorphous alloy.
  • the atomic percentage expression of the amorphous alloy is Pd 74.5 Cu 3 Ge 16.5 .
  • the atomic percentage expression of the amorphous alloy is Pd 74.5 Cu 3 Si 8 Ge 8.5 .
  • the atomic percentage expression of the amorphous alloy is Pd 74.5 Cu 3 Si 12.5 Ge 4 Ag 3 Au 4 .
  • Another object of the present invention is to provide a method for preparing the above alloy, which method comprises the following steps:
  • Preparation method (1) preparing the mother alloy without glass coating and purifying, and preparing the amorphous alloy by copper die casting, the steps include: Step 1. Ingredients: metal Pd, Cu with a purity of 99.0 wt%-99.99 wt% , Ag and non-metal Si, Ge are converted into mass according to the atomic percentage of the above expression, the surface oxide of the raw material is removed, and the raw materials are washed with industrial ethanol and weighed according to the respective required qualities;
  • Step 2 Mother alloy smelting:
  • the raw materials processed in step 1 are stacked in a non-consumable vacuum arc furnace or a cold heading suspension furnace according to the melting point, and are filled with high-purity argon after the vacuum is less than 10 -3 Pa ( Not less than 99.99%) smelting, at least 4 times, so that the mother alloy is fully smelted uniformly;
  • Step 3 After grinding and removing the mother alloy prepared by smelting, put it into different size water-cooled copper molds of a vacuum arc furnace, and evacuate the arc furnace chamber to less than 10 -3 Pa and then charge 0.08 MPa high-purity argon gas. (not less than 99.99%), the mother alloy is melted at 150A, and heated for 15s, the arc current is raised to 200-250A, the suction vacuum valve is quickly opened, and the master alloy is pressed into the water-cooled copper mold by air pressure. Cooling is performed to obtain amorphous alloys of different sizes.
  • the preparation method (2) preparing the mother alloy by glass coating and purifying, and preparing the amorphous alloy by copper mold suction casting, the steps include:
  • Step 1 Ingredients: The metal Pd, Cu, Ag and non-metal Si, Ge with a purity of 99.0 wt%-99.99 wt% are converted into mass according to the atomic percentage of the above expression, the scale of the raw material surface is removed, and industrial ethanol is used. Cleaning the raw materials and weighing them according to their respective qualities;
  • Step 2 Mother alloy smelting:
  • the raw materials processed in step 1 are stacked in a non-consumable vacuum arc furnace or a cold heading suspension furnace according to the melting point, and are filled with high-purity argon after the vacuum is less than 10 -3 Pa ( Not less than 99.99%) smelting, at least 4 times, so that the mother alloy is fully smelted uniformly;
  • Step 3 Glass coating purification: The mother alloy and the dehydrated boron trioxide medium are placed in quartz tubes of different sizes, and the quartz tube is vacuumed to 10 Pa or less, and then the quartz tube is filled with 0.2 MPa high purity argon. Gas, and placed in an electric furnace at 1100 ° C for 24 hours, after which the melt is cooled with the furnace;
  • Step 4 Remove the coating medium adhered to the surface of the alloy ingot after glass coating and purifying with sandpaper, place it on the water-cooled copper mold of different sizes in the vacuum arc furnace, and evacuate the arc furnace chamber to less than 10 -3 Pa. After filling with 0.08MPa high purity argon (not less than 99.99%), the mother alloy is melted at 150A, and heated for 15s, the arc current is raised to 200-250A, and the suction vacuum valve is quickly opened. The master alloy is cooled by pressure into a water-cooled copper mold to obtain amorphous alloys of different sizes.
  • the preparation method (3) preparing the mother alloy by glass coating and purifying, and preparing the amorphous alloy by water quenching, the steps include:
  • Step 1 Ingredients: The metal Pd, Cu, Ag and non-metal Si, Ge with a purity of 99.0 wt%-99.99 wt% are converted into mass according to the atomic percentage of the above expression, the scale of the raw material surface is removed, and industrial ethanol is used. Cleaning the raw materials and weighing them according to their respective qualities;
  • Step 2 Mother alloy smelting:
  • the raw materials processed in step 1 are stacked in a non-consumable vacuum arc furnace or a cold heading suspension furnace according to the melting point, and are filled with high-purity argon after the vacuum is less than 10 -3 Pa ( Not less than 99.99%) smelting, at least 4 times, so that the mother alloy is fully smelted uniformly;
  • Step 3 Glass coating purification: The mother alloy and the dehydrated boron trioxide medium are placed in quartz tubes of different sizes, and the quartz tube is vacuumed to 10 Pa or less, and then the quartz tube is filled with 0.2 MPa high purity argon. Gas, and placed in an electric furnace at 1100 ° C for 24 hours;
  • Step 4 The alloy ingot purified by glass coating is directly quenched into a room temperature brine having a concentration of not less than 25% by weight in a molten state to prepare amorphous alloys of different sizes.
  • An alloy having a composition of Pd 77.5 Cu 6 Ge 16.5 , Pd 77.5 Cu 6 Si 8 Ge 8.5 , and Pd 77.5 Cu 6 Si 12.5 Ge 4 was obtained.
  • FIG. 1 is an XRD pattern of a 2 mm sample prepared by the preparation method (3) of the alloy Pd 77.5 Cu 6 Ge 16.5 , Pd 77.5 Cu 6 Si 8 Ge 8.5
  • FIG. 2 is a preparation method of the alloy Pd 77.5 Cu 6 Si 12.5 Ge 4 ( 2)
  • the amorphous alloy, Pd 77.5 Cu 6 Si 12.5 Ge 4 alloy can be prepared by preparing the amorphous alloy with a critical dimension of not less than 4 mm by the preparation method (2), and has a strong amorphous forming ability.
  • Figure 3 is a DSC curve of the alloy Pd 77.5 Cu 6 Si 12.5 Ge 4 with a supercooled liquid phase interval of 54K.
  • An alloy having a composition of Pd 77.5 Cu 5 Si 12.5 Ge 4 Ag 1 , Pd 77.5 Cu 4 Si 12.5 Ge 4 Ag 2 and Pd 77.5 Cu 3 Si 12.5 Ge 4 Ag 3 was obtained.
  • FIG. 5 is an XRD pattern of an 8 mm sample prepared by the preparation method (3) of an alloy Pd 77.5 Cu 5 Si 12.5 Ge 4 Ag 1 , Pd 77.5 Cu 4 Si 12.5 Ge 4 Ag 2
  • FIG. 6 is a SEM corresponding to FIG. 5
  • Photo Fig. 7 is an 8 mm sample prepared by the preparation method (3) of the alloy Pd 77.5 Cu 3 Si 12.5 Ge 4 Ag 3
  • Fig. 8 corresponds to Fig.
  • the SEM photograph, XRD pattern only has a typical diffuse scattering peak of amorphous, and the corresponding SEM photograph also shows the single amorphous phase composition of the alloy, indicating that the prepared alloys are all amorphous phases, and the alloy is prepared by (3)
  • An amorphous alloy having a critical dimension of not less than 8 mm can be prepared, and an amorphous alloy having a critical dimension of not less than 2 mm can be prepared by preparing (1) Pd 77.5 Cu 5 Si 12.5 Ge 4 Ag 1 , Pd 77.5 Cu 4 Si 12.5 Ge 4 Ag 2 alloy.
  • the Pd 77.5 Cu 3 Si 12.5 Ge 4 Ag 3 alloy can prepare an amorphous alloy having a critical dimension of not less than 4 mm and has a strong amorphous forming ability.
  • alloy Pd 77.5 Cu 5 Si 12.5 Ge 4 Ag 1 is a compressive stress-strain curve of alloy Pd 77.5 Cu 5 Si 12.5 Ge 4 Ag 1 , Pd 77.5 Cu 4 Si 12.5 Ge 4 Ag 2 , Pd 77.5 Cu 3 Si 12.5 Ge 4 Ag 3 , wherein alloy Pd 77.5 Cu 5 Si 12.5 Ge 4 Ag 1 has a compression yield strength of 1602 MPa and a compression ductility of 11%.
  • Figure 5 is an XRD pattern of an 8 mm sample prepared by the preparation method (3) of Pd 74.5 Cu 3 Si 12.5 Ge 4 Ag 3 Au 4 alloy.
  • the XRD pattern has only a typical diffuse scattering peak of amorphous, indicating that the prepared alloy is amorphous.
  • Phase, an amorphous alloy having a critical dimension of not less than 8 mm can be prepared by the preparation method (3), and has a strong amorphous forming ability.
  • the invention relates to a niobium-free nickel-free and phosphorus-free large-sized palladium-based amorphous alloy and a preparation method thereof, wherein the atomic percentage of each component of the alloy is: Pd: 73-80%, Cu: 0 ⁇ b ⁇ 8%, Si: 0 -18%, Ge: 2-20%, Ag: 0-6%.
  • the main advantage of the invention is that it does not contain nickel element, the potential biological toxicity is greatly reduced, and the biocompatibility is improved; the method of smelting preparation is simple without containing phosphorus element; the amorphous amorphous forming ability is obtained, and the glass coating medium process is used for purification.
  • amorphous alloy with critical dimension of 1-8mm can be prepared by water quenching and rapid cooling.
  • the most intensive glass forming ability can be prepared by arc melting smelting copper die casting method to prepare amorphous alloy with critical dimension of not less than 4mm.
  • Mode 3 can prepare an amorphous alloy having a critical dimension of not less than 8 mm; having a plastic deformation ability of > 3%; and having a supercooled liquid phase range of 40 to 60 K.

Abstract

A germanium-containing nickel-free phosphorus-free large-sized palladium-based amorphous alloy and a preparation method therefor. The atomic percentages of each component of the alloy is: Pd: 73-80%, Cu: 0 < b≤ 8%, Si: 0-18%, Ge: 2-20%, and Ag: 0-6%. The alloy does not contain a nickel element, such that potential biotoxicity is greatly reduced, and biocompatibility is improved. The alloy does not contain a phosphorus element, such that a smelting preparation process is simple and the alloy has strong amorphous forming ability. A palladium-based amorphous alloy with a critical dimension of 1-8 mm can be prepared using an arc-melting copper mold die casting method, and an amorphous alloy having a critical dimension of no less than 4 mm can be prepared using components having the strongest glass forming ability. An amorphous alloy with a critical dimension of no less than 8 mm can be prepared by purifying a glass-coated medium and a water quenching and rapid cooling process; the prepared alloy has a plastic deformation ability of > 3% and a supercooled liquid region of 40-60K.

Description

一种含锗无镍无磷大尺寸钯基非晶合金及其制备方法Yttrium-free nickel-free and phosphorus-free large-size palladium-based amorphous alloy and preparation method thereof 技术领域Technical field
本发明属于块体非晶合金领域，具体涉及一种含锗无镍无磷大尺寸钯基非晶合金及其制备方法，所涉及的合金其临界尺寸介于1-8mm，塑性变形能力不低于3％。The invention belongs to the field of bulk amorphous alloys, and particularly relates to a large-sized palladium-based amorphous alloy containing bismuth, nickel-free and phosphorus-free, and a preparation method thereof. The alloys involved have a critical dimension of 1-8 mm and a plastic deformation capability is not low. At 3%.
技术背景technical background
非晶态合金(金属玻璃)和传统金属材料中原子具有长程有序的排列不同，具有无规排列的原子结构，具有长程无序短程有序的特征，在其微观组织中不存在晶界、位错等缺陷，是近年来出现的有望作为新一代结构和功能应用的金属材料。与传统晶态合金相比，非晶合金具有其无法实现的高强度、高硬度、高弹性极限、低模量以及耐腐蚀等优异的性能。另外，非晶合金加热至高于玻璃转变温度后将进入过冷液相区，在过冷液相区内非晶合金表现出黏性流动特征，呈现出超塑性变形特性。非晶合金的这种独有的性能使其在过冷液相区内可精确地压制成型。这些优越的性能使得非晶态合金在很多领域如医用器械、消费电子产品、微型电子元件甚至奢侈品等方面具有及其广阔的应用前景。Amorphous alloys (metal glass) and conventional metal materials have long-range and orderly arrangements of atoms, have randomly arranged atomic structures, have long-range disordered short-range order, and have no grain boundaries in their microstructure. Defects such as dislocations are metal materials that have emerged in recent years as a new generation of structural and functional applications. Compared with conventional crystalline alloys, amorphous alloys have excellent properties such as high strength, high hardness, high elastic limit, low modulus, and corrosion resistance that cannot be achieved. In addition, the amorphous alloy will enter the supercooled liquid region after being heated above the glass transition temperature, and the amorphous alloy exhibits viscous flow characteristics in the supercooled liquid region, exhibiting superplastic deformation characteristics. This unique property of amorphous alloys allows for precise press forming in the supercooled liquid region. These superior properties make amorphous alloys have broad application prospects in many fields such as medical devices, consumer electronics, microelectronics and even luxury goods.
近年来，研究者已在锆基、钯基、镧基、镁基、铁基、镍基等十余种合金体系中获得了块体非晶合金。虽然目前非晶合金最大的临界尺寸已经超过70mm，但是其适合的非晶成分往往仅仅局限于很窄的成分范围内；另外，非晶合金的独特的原子结构导致其在受力作用下往往表现出室温脆性的特征，在压缩状态下，其达到弹性极限后迅速发生灾难性断裂，塑性变形能力几乎为零。因此开发具有大玻璃形成能力及高塑性变形能力的非晶合金成分依旧是研究人员孜孜不倦的奋斗目标。目前钯基非晶合金成分的开发去得了一定的进展，Pd-Cu-Ni-P系合金的临界尺寸可以达到72mm；Pd-Cu-Si系合金在具有一定玻璃形成能力的基础上还兼具优异的塑性变形能力。但根据文献和专利检索，迄今尚未见公开报道兼具高玻璃形成能力和塑性变形能力含锗钯基非晶合金体系，同时设计体系中不含磷和镍的合金成分有助于简化钯基合金的制备工艺，并拓宽其在穿戴奢侈品以及生物医用材料上的应用前景。In recent years, researchers have obtained bulk amorphous alloys in more than ten kinds of alloy systems such as zirconium, palladium, sulfonium, magnesium, iron, and nickel. Although the maximum critical dimension of amorphous alloys has exceeded 70 mm, the suitable amorphous components are often limited to a narrow range of components. In addition, the unique atomic structure of amorphous alloys tends to behave under stress. The characteristic of brittleness at room temperature, in the state of compression, it rapidly catastrophic fracture after reaching the elastic limit, and the plastic deformation ability is almost zero. Therefore, the development of amorphous alloy composition with large glass forming ability and high plastic deformation ability is still a tireless goal of researchers. At present, the development of palladium-based amorphous alloy composition has made certain progress. The critical dimension of Pd-Cu-Ni-P alloy can reach 72mm; Pd-Cu-Si alloy has both glass forming ability and Excellent plastic deformation ability. However, according to the literature and patent search, it has not been reported so far that it has a high glass forming ability and plastic deformation ability. It contains a palladium-based amorphous alloy system, and the alloy composition containing no phosphorus and nickel in the design system helps to simplify the palladium-based alloy. The preparation process and broaden its application prospects in the wearing of luxury goods and biomedical materials.
发明内容Summary of the invention
本发明开发出一种含锗无镍无磷大尺寸钯基非晶合金，目的在于不仅去除对生物体具有毒副作用的镍元素，生物相容性好，而且不含磷，制备工艺相对简便，具有强非晶形成能力和塑性变形能力，以获得非晶合金在安全性和加工性两方面都良好的综合效果。The invention develops a large-sized palladium-based amorphous alloy containing bismuth, nickel-free and phosphorus-free, and aims to not only remove nickel elements having toxic side effects on living organisms, but also has good biocompatibility and no phosphorus, and the preparation process is relatively simple. It has strong amorphous forming ability and plastic deformation ability to obtain a good comprehensive effect of amorphous alloy in both safety and processability.
本发明的技术方案是：一种含锗无镍无磷大尺寸钯基非晶合金，该非晶合金的原子百分比表达式为PdaCubGec，式中a、b和c分别表示各对应元素的原子百分比，其中73≤a ≤80，0＜b≤8，2≤c≤20，且a+b+c＝100。The technical proposal of the present invention is: a ruthenium-free nickel-free and phosphorus-free large-sized palladium-based amorphous alloy, the atomic percentage expression of the amorphous alloy is Pd a Cu b Ge c , wherein a, b and c respectively represent The atomic percentage of the corresponding element, where 73 ≤ a ≤ 80, 0 < b ≤ 8, 2 ≤ c ≤ 20, and a + b + c = 100.
一种含锗无镍无磷大尺寸钯基非晶合金，，该非晶合金的原子百分比表达式为PdaCubGecSidAge，式中a、b、c和d分别表示各对应元素的原子百分比，其中73≤a≤80，0＜b≤8，2≤c≤20，0≤d≤18，0≤e≤6,且a+b+c+d+e＝100。A palladium-based amorphous alloy containing niobium, nickel-free and non-phosphorus, the atomic percentage expression of the amorphous alloy is Pd a Cu b Ge c Si d Ag e , wherein a, b, c and d respectively represent The atomic percentage of the corresponding element, where 73 ≤ a ≤ 80, 0 < b ≤ 8, 2 ≤ c ≤ 20, 0 ≤ d ≤ 18, 0 ≤ e ≤ 6, and a + b + c + d + e = 100.
一种含锗无镍无磷大尺寸钯基非晶合金，该非晶合金的原子百分比表达式为PdaCubGecSidAgeXf，且各组分：73≤a≤80，0＜b≤8，2≤c≤20，0≤d≤18，0≤e≤6，0≤f≤4且a+b+c+d+e+f＝100，其中X为Co、Au、Pt中的一种或多种。A niobium-free nickel-free and phosphorus-free large-sized palladium-based amorphous alloy having an atomic percentage expression of Pd a Cu b Ge c Si d Ag e X f and each component: 73 ≤ a ≤ 80, 0<b≤8, 2≤c≤20, 0≤d≤18, 0≤e≤6, 0≤f≤4 and a+b+c+d+e+f=100, where X is Co, Au One or more of Pt.
进一步，当a＝77.5，b＝6，c＝16.5，非晶合金的原子百分比表达式为Pd74.5Cu3Ge16.5。Further, when a = 77.5, b = 6, and c = 16.5, the atomic percentage expression of the amorphous alloy is Pd 74.5 Cu 3 Ge 16.5 .
进一步，当a＝77.5，b＝6，c＝8.5，d＝8，e＝0，非晶合金的原子百分比表达式为Pd74.5Cu3Si8Ge8.5。Further, when a = 77.5, b = 6, c = 8.5, d = 8, and e = 0, the atomic percentage expression of the amorphous alloy is Pd 74.5 Cu 3 Si 8 Ge 8.5 .
进一步，a＝77.5，b＝5，c＝12.5，d＝4，e＝1，非晶合金的原子百分比表达式为Pd74.5Cu5Si12.5Ge4Ag1；或者a＝77.5，b＝4，c＝4，d＝12.5，e＝2，非晶合金的原子百分比表达式为Pd74.5Cu4Si12.5Ge4Ag2；或者a＝77.5，b＝3，c＝4，d＝12.5，e＝3，非晶合金的原子百分比表达式为Pd74.5Cu3Si12.5Ge4Ag3。Pd74.5Cu3Si12.5Ge4Ag3。Further, a=77.5, b=5, c=12.5, d=4, e=1, the atomic percentage expression of the amorphous alloy is Pd 74.5 Cu 5 Si 12.5 Ge 4 Ag 1 ; or a=77.5, b=4 , c=4, d=12.5, e=2, the atomic percentage expression of the amorphous alloy is Pd 74.5 Cu 4 Si 12.5 Ge 4 Ag 2 ; or a=77.5, b=3, c=4, d=12.5, e=3, the atomic percentage expression of the amorphous alloy is Pd 74.5 Cu 3 Si 12.5 Ge 4 Ag 3 . Pd 74.5 Cu 3 Si 12.5 Ge 4 Ag 3 .
进一步，当X为Au，a＝73.5，b＝5，c＝4，d＝12.5，e＝1，f＝4,非晶合金的原子百分比表达式为Pd74.5Cu3Si12.5Ge4Ag3Au4。Further, when X is Au, a=73.5, b=5, c=4, d=12.5, e=1, f=4, the atomic percentage expression of the amorphous alloy is Pd 74.5 Cu 3 Si 12.5 Ge 4 Ag 3 Au 4 .
本发明的另一目的是提供上述合金的制备方法，该方法具体包括以下步骤：Another object of the present invention is to provide a method for preparing the above alloy, which method comprises the following steps:
制备方式(1)：未玻璃包覆提纯制备母合金，并以铜模吸铸方式制备非晶合金，步骤包括：步骤1.配料：以纯度为99.0wt％-99.99wt％的金属Pd，Cu，Ag以及非金属Si，Ge按照上述表达式的原子百分比换算成质量，将原料表面氧化皮去除，并使用工业乙醇清洗原料，并按各自所需质量称取；Preparation method (1): preparing the mother alloy without glass coating and purifying, and preparing the amorphous alloy by copper die casting, the steps include: Step 1. Ingredients: metal Pd, Cu with a purity of 99.0 wt%-99.99 wt% , Ag and non-metal Si, Ge are converted into mass according to the atomic percentage of the above expression, the surface oxide of the raw material is removed, and the raw materials are washed with industrial ethanol and weighed according to the respective required qualities;
步骤2.母合金熔炼：将步骤1处理后的原料按熔点高低顺序堆放在非自耗真空电弧炉或冷坩埚悬浮炉里，在真空低于10-3Pa后充入在高纯氩气(不低于99.99％)进行熔炼，至少熔炼4次，使母合金充分熔炼均匀； Step 2. Mother alloy smelting: The raw materials processed in step 1 are stacked in a non-consumable vacuum arc furnace or a cold heading suspension furnace according to the melting point, and are filled with high-purity argon after the vacuum is less than 10 -3 Pa ( Not less than 99.99%) smelting, at least 4 times, so that the mother alloy is fully smelted uniformly;
步骤3.将熔炼制备的母合金打磨去除氧化皮后放入真空电弧炉的不同尺寸水冷铜模上，将电弧炉腔体抽真空至低于10-3Pa后充入0.08MPa高纯氩气(不低于99.99％)，以150A电流将母合金熔化，并持续加热15s，将电弧电流升高至200-250A之间，迅速打开吸铸真空阀门，将母合金通过气压压入水冷铜模进行冷却，得到不同尺寸的非晶合金。Step 3. After grinding and removing the mother alloy prepared by smelting, put it into different size water-cooled copper molds of a vacuum arc furnace, and evacuate the arc furnace chamber to less than 10 -3 Pa and then charge 0.08 MPa high-purity argon gas. (not less than 99.99%), the mother alloy is melted at 150A, and heated for 15s, the arc current is raised to 200-250A, the suction vacuum valve is quickly opened, and the master alloy is pressed into the water-cooled copper mold by air pressure. Cooling is performed to obtain amorphous alloys of different sizes.
进一步，制备方式(2)：玻璃包覆提纯制备母合金，并以铜模吸铸方式制备非晶合金，步骤包括： Further, the preparation method (2): preparing the mother alloy by glass coating and purifying, and preparing the amorphous alloy by copper mold suction casting, the steps include:
步骤1.配料：以纯度为99.0wt％-99.99wt％的金属Pd，Cu，Ag以及非金属Si，Ge按照上述表达式的原子百分比换算成质量，将原料表面氧化皮去除，并使用工业乙醇清洗原料，并按各自所需质量称取；Step 1. Ingredients: The metal Pd, Cu, Ag and non-metal Si, Ge with a purity of 99.0 wt%-99.99 wt% are converted into mass according to the atomic percentage of the above expression, the scale of the raw material surface is removed, and industrial ethanol is used. Cleaning the raw materials and weighing them according to their respective qualities;
步骤2.母合金熔炼：将步骤1处理后的原料按熔点高低顺序堆放在非自耗真空电弧炉或冷坩埚悬浮炉里，在真空低于10-3Pa后充入在高纯氩气(不低于99.99％)进行熔炼，至少熔炼4次，使母合金充分熔炼均匀； Step 2. Mother alloy smelting: The raw materials processed in step 1 are stacked in a non-consumable vacuum arc furnace or a cold heading suspension furnace according to the melting point, and are filled with high-purity argon after the vacuum is less than 10 -3 Pa ( Not less than 99.99%) smelting, at least 4 times, so that the mother alloy is fully smelted uniformly;
步骤3.玻璃包覆提纯：将母合金和脱水后的三氧化二硼介质放置于不同尺寸的石英管中，将石英管中真空抽至10Pa以下后将石英管中充入0.2MPa高纯氩气，并放置于1100℃电炉中提纯24小时，之后将熔体随炉冷却；Step 3. Glass coating purification: The mother alloy and the dehydrated boron trioxide medium are placed in quartz tubes of different sizes, and the quartz tube is vacuumed to 10 Pa or less, and then the quartz tube is filled with 0.2 MPa high purity argon. Gas, and placed in an electric furnace at 1100 ° C for 24 hours, after which the melt is cooled with the furnace;
步骤4.用砂纸去除经玻璃包覆提纯后的合金锭表面附着的包覆介质后，放入真空电弧炉的不同尺寸水冷铜模上，将电弧炉腔体抽真空至低于10-3Pa后充入0.08MPa高纯氩气(不低于99.99％)，以150A电流将母合金熔化，并持续加热15s，将电弧电流升高至200-250A之间，迅速打开吸铸真空阀门，将母合金通过气压压入水冷铜模进行冷却，得到不同尺寸的非晶合金。Step 4. Remove the coating medium adhered to the surface of the alloy ingot after glass coating and purifying with sandpaper, place it on the water-cooled copper mold of different sizes in the vacuum arc furnace, and evacuate the arc furnace chamber to less than 10 -3 Pa. After filling with 0.08MPa high purity argon (not less than 99.99%), the mother alloy is melted at 150A, and heated for 15s, the arc current is raised to 200-250A, and the suction vacuum valve is quickly opened. The master alloy is cooled by pressure into a water-cooled copper mold to obtain amorphous alloys of different sizes.
进一步，制备方式(3)：玻璃包覆提纯制备母合金，并以水淬方式制备非晶合金，步骤包括：Further, the preparation method (3): preparing the mother alloy by glass coating and purifying, and preparing the amorphous alloy by water quenching, the steps include:
步骤1.配料：以纯度为99.0wt％-99.99wt％的金属Pd，Cu，Ag以及非金属Si，Ge按照上述表达式的原子百分比换算成质量，将原料表面氧化皮去除，并使用工业乙醇清洗原料，并按各自所需质量称取；Step 1. Ingredients: The metal Pd, Cu, Ag and non-metal Si, Ge with a purity of 99.0 wt%-99.99 wt% are converted into mass according to the atomic percentage of the above expression, the scale of the raw material surface is removed, and industrial ethanol is used. Cleaning the raw materials and weighing them according to their respective qualities;
步骤2.母合金熔炼：将步骤1处理后的原料按熔点高低顺序堆放在非自耗真空电弧炉或冷坩埚悬浮炉里，在真空低于10-3Pa后充入在高纯氩气(不低于99.99％)进行熔炼，至少熔炼4次，使母合金充分熔炼均匀； Step 2. Mother alloy smelting: The raw materials processed in step 1 are stacked in a non-consumable vacuum arc furnace or a cold heading suspension furnace according to the melting point, and are filled with high-purity argon after the vacuum is less than 10 -3 Pa ( Not less than 99.99%) smelting, at least 4 times, so that the mother alloy is fully smelted uniformly;
步骤3.玻璃包覆提纯：将母合金和脱水后的三氧化二硼介质放置于不同尺寸的石英管中，将石英管中真空抽至10Pa以下后将石英管中充入0.2MPa高纯氩气，并放置于1100℃电炉中提纯24小时；Step 3. Glass coating purification: The mother alloy and the dehydrated boron trioxide medium are placed in quartz tubes of different sizes, and the quartz tube is vacuumed to 10 Pa or less, and then the quartz tube is filled with 0.2 MPa high purity argon. Gas, and placed in an electric furnace at 1100 ° C for 24 hours;
步骤4.经玻璃包覆提纯后的合金锭在熔融状态下直接淬入浓度不低于25wt％的室温食盐水中，制备不同尺寸的非晶合金。Step 4. The alloy ingot purified by glass coating is directly quenched into a room temperature brine having a concentration of not less than 25% by weight in a molten state to prepare amorphous alloys of different sizes.
该非晶合金的原子百分比表达式为PdaCubGec，式中a、b和c分别表示各对应元素的原子百分比，其中73≤a≤80，0＜b≤8，2≤c≤20，且a+b+c＝100。The atomic percentage expression of the amorphous alloy is Pd a Cu b Ge c , where a, b and c respectively represent the atomic percentage of each corresponding element, wherein 73 ≤ a ≤ 80, 0 < b ≤ 8, 2 ≤ c ≤ 20, and a+b+c=100.
当a＝77.5，b＝6，c＝16.5时，非晶合金的原子百分比表达式为Pd74.5Cu3Ge16.5，通过 制备方式(3)可制备临界尺寸不小于1mm的非晶合金。When a = 77.5, b = 6, and c = 16.5, the atomic percentage expression of the amorphous alloy is Pd 74.5 Cu 3 Ge 16.5 , and an amorphous alloy having a critical dimension of not less than 1 mm can be prepared by the production method (3).
该非晶合金的原子百分比表达式为PdaCubGecSid，式中a、b、c和d分别表示各对应元素的原子百分比，其中73≤a≤80，0＜b≤8，2≤c≤20，0≤d≤18，且a+b+c+d＝100。The atomic percentage expression of the amorphous alloy is Pd a Cu b Ge c Si d , wherein a, b, c and d respectively represent the atomic percentage of each corresponding element, wherein 73 ≤ a ≤ 80, 0 < b ≤ 8, 2 ≤ c ≤ 20, 0 ≤ d ≤ 18, and a + b + c + d = 100.
当a＝77.5，b＝6，0≤d≤12.5，c＝16.5，4≤e≤16.5时，非晶合金的原子百分比表达式为Pd77.5Cu6SicGe16.5-c，通过制备方式(3)可制备临界尺寸不小于1mm的非晶合金。When a=77.5, b=6, 0≤d≤12.5, c=16.5, 4≤e≤16.5, the atomic percentage expression of the amorphous alloy is Pd 77.5 Cu 6 Si c Ge 16.5-c , by the preparation method ( 3) An amorphous alloy having a critical dimension of not less than 1 mm can be prepared.
当a＝77.5，b＝6，d＝8.5，c＝8，e＝0，非晶合金的原子百分比表达式为Pd74.5Cu3Si8Ge8.5，通过制备方式(3)可制备临界尺寸不小于2mm的非晶合金。When a=77.5, b=6, d=8.5, c=8, e=0, the atomic percentage expression of the amorphous alloy is Pd 74.5 Cu 3 Si 8 Ge 8.5 , and the critical dimension can be prepared by the preparation method (3). An amorphous alloy of less than 2 mm.
当a＝77.5，b＝6，c＝12.5，d＝4时，Pd77.5Cu6Si12.5Ge4合金，母合金经制备方式(1)可制备临界尺寸不小于2mm的非晶合金；通过制备方式(2)可制备临界尺寸不小于4mm的非晶合金，过冷液相区宽度54K。When a=77.5, b=6, c=12.5, d=4, Pd 77.5 Cu 6 Si 12.5 Ge 4 alloy, the mother alloy can be prepared by preparing the amorphous alloy with a critical dimension of not less than 2 mm by preparation method (1); In the mode (2), an amorphous alloy having a critical dimension of not less than 4 mm can be prepared, and the supercooled liquid phase region has a width of 54K.
该非晶合金的原子百分比表达式为PdaCubSicGedAge，式中a、b、c、d和e分别表示各对应元素的原子百分比，其中73≤a≤80，0＜b≤8，0≤d≤18，2≤c≤20，0≤e≤6，且a+b+c+d+e＝100。The atomic percentage expression of the amorphous alloy is Pd a Cu b Si c Ge d Ag e , wherein a, b, c, d and e respectively represent the atomic percentage of each corresponding element, wherein 73 ≤ a ≤ 80, 0 < b ≤ 8, 0 ≤ d ≤ 18, 2 ≤ c ≤ 20, 0 ≤ e ≤ 6, and a + b + c + d + e = 100.
当a＝77.5，4≤b≤6，c＝4，d＝12.5，1≤e≤2时，非晶合金的原子百分比表达式Pd77.5CubSi12.5Ge4Ag6-b，母合金经制备方式(1)可制备临界尺寸不小于2mm的非晶合金；通过制备方式(3)能够形成大块非晶的临界尺寸不小于8mm，塑性应变不小于5％。When a=77.5, 4≤b≤6, c=4, d=12.5, 1≤e≤2, the atomic percentage expression of amorphous alloy Pd 77.5 Cu b Si 12.5 Ge 4 Ag 6-b , mother alloy The preparation method (1) can prepare an amorphous alloy having a critical dimension of not less than 2 mm; the critical dimension capable of forming bulk amorphous by the preparation method (3) is not less than 8 mm, and the plastic strain is not less than 5%.
当a＝77.5，b＝3，c＝4，d＝12.5，e＝3时，非晶合金的原子百分比表达式为Pd77.5Cu3Si12.5Ge4Ag3，母合金经制备方式(1)可制备临界尺寸不小于4mm的非晶合金；通过制备方式(3)能够形成大块非晶的临界尺寸不小于8mm，塑性应变不小于11％。When a=77.5, b=3, c=4, d=12.5, e=3, the atomic percentage expression of the amorphous alloy is Pd 77.5 Cu 3 Si 12.5 Ge 4 Ag 3 , and the master alloy is prepared (1) An amorphous alloy having a critical dimension of not less than 4 mm can be prepared; the critical dimension capable of forming bulk amorphous by the preparation method (3) is not less than 8 mm, and the plastic strain is not less than 11%.
非晶合金的原子百分比表达PdaCubSicGedAgeXf，式中a、b、c、d和e分别表示各对应元素的原子百分比，其中73≤a≤80，0＜b≤8，0≤d≤18，2≤c≤20，1≤e≤6，0≤f≤4且a+b+c+d+e+f＝100，其中X为Co、Au、Pt中的一种或多种。The atomic percentage of the amorphous alloy expresses Pd a Cu b Si c Ge d Ag e X f , where a, b, c, d, and e represent the atomic percentage of each corresponding element, respectively, where 73 ≤ a ≤ 80, 0 < b ≤8,0≤d≤18,2≤c≤20,1≤e≤6,0≤f≤4 and a+b+c+d+e+f=100, where X is Co, Au, Pt One or more.
当X为Au，a＝73.5，b＝5，c＝4，d＝12.5，e＝1，f＝4时,非晶合金的原子百分比表达式为Pd74.5Cu3Si12.5Ge4Ag3Au4，通过制备方式(3)能够形成大块非晶的临界尺寸不小于8mm。When X is Au, a=73.5, b=5, c=4, d=12.5, e=1, f=4, the atomic percentage expression of the amorphous alloy is Pd 74.5 Cu 3 Si 12.5 Ge 4 Ag 3 Au 4. The critical dimension capable of forming bulk amorphous by the preparation method (3) is not less than 8 mm.
对比三种不同制备方式得到的非晶合金，其临界尺寸大小为制备方式(1)<制备方式(2)<制备方式(3)。Comparing the amorphous alloys obtained by three different preparation methods, the critical size is the preparation method (1) <preparation mode (2) <preparation mode (3).
本发明的优点在于：The advantages of the invention are:
1.本发明所涉及的一系列钯基非晶合金，具有优良的非晶形成能力，最大临界尺寸不低于8mm。 1. A series of palladium-based amorphous alloys according to the present invention, which have excellent amorphous forming ability and a maximum critical dimension of not less than 8 mm.
2.本发明所涉及的一系列钯基非晶合金，合金主要元素为Pd、Cu、Si、Ge、Ag，不含有Ni等有毒或对生物易致敏元素，有较好的生物相容性。2. A series of palladium-based amorphous alloys according to the present invention, the main elements of which are Pd, Cu, Si, Ge, Ag, do not contain Ni or other toxic or bio-sensitizing elements, and have good biocompatibility. .
3.本发明所涉及的一系列钯基非晶合金，合金主要元素为Pd、Cu、Si、Ge、Ag，不含有易挥发的P，熔炼制备方法简便。3. A series of palladium-based amorphous alloys according to the invention, the main elements of the alloy are Pd, Cu, Si, Ge, Ag, and do not contain volatile P, and the preparation method of the smelting is simple.
4.本发明所涉及的一系列钯基非晶合金，塑性变形能力强，最高塑性变形能力不小于5％。4. A series of palladium-based amorphous alloys according to the present invention have strong plastic deformation ability and a maximum plastic deformation capacity of not less than 5%.
附图说明DRAWINGS
图1为Pd77.5Cu6Si4Ge8.5或Pd77.5Cu6Si4Ge8.5非晶合金的XRD图谱。1 is an XRD pattern of a Pd 77.5 Cu 6 Si 4 Ge 8.5 or Pd 77.5 Cu 6 Si 4 Ge 8.5 amorphous alloy.
图2为Pd77.5Cu6Si12.5Ge4非晶合金的XRD图谱。2 is an XRD pattern of a Pd 77.5 Cu 6 Si 12.5 Ge 4 amorphous alloy.
图3为Pd77.5Cu6Si12.5Ge4非晶合金的DSC曲线。Figure 3 is a DSC curve of a Pd 77.5 Cu 6 Si 12.5 Ge 4 amorphous alloy.
图4为Pd77.5Cu6Si12.5Ge4非晶合金的压缩应力应变曲线。4 is a compressive stress-strain curve of a Pd 77.5 Cu 6 Si 12.5 Ge 4 amorphous alloy.
图5为Pd77.5Cu5Si12.5Ge4Ag1，Pd77.5Cu4Si12.5Ge4Ag2非晶合金的XRD图谱。5 is an XRD pattern of a Pd 77.5 Cu 5 Si 12.5 Ge 4 Ag 1 , Pd 77.5 Cu 4 Si 12.5 Ge 4 Ag 2 amorphous alloy.
图6为Pd77.5Cu5Si12.5Ge4Ag1，Pd77.5Cu4Si12.5Ge4Ag2非晶合金的SEM图。6 is an SEM image of a Pd 77.5 Cu 5 Si 12.5 Ge 4 Ag 1 , Pd 77.5 Cu 4 Si 12.5 Ge 4 Ag 2 amorphous alloy.
图7为Pd77.5Cu3Si12.5Ge4Ag3非晶合金的XRD图谱。Figure 7 is an XRD pattern of a Pd 77.5 Cu 3 Si 12.5 Ge 4 Ag 3 amorphous alloy.
图8为Pd77.5Cu3Si12.5Ge4Ag3非晶合金的SEM图。Figure 8 is an SEM image of a Pd 77.5 Cu 3 Si 12.5 Ge 4 Ag 3 amorphous alloy.
图9为Pd77.5Cu5Si12.5Ge4Ag1，Pd77.5Cu4Si12.5Ge4Ag2，Pd77.5Cu3Si12.5Ge4Ag3非晶合金的压缩应力应变曲线。9 is a compressive stress-strain curve of Pd 77.5 Cu 5 Si 12.5 Ge 4 Ag 1 , Pd 77.5 Cu 4 Si 12.5 Ge 4 Ag 2 , and Pd 77.5 Cu 3 Si 12.5 Ge 4 Ag 3 amorphous alloy.
图10为Pd74.5Cu3Si12.5Ge4Ag3Au4非晶合金的XRD图谱。Figure 10 is an XRD pattern of a Pd 74.5 Cu 3 Si 12.5 Ge 4 Ag 3 Au 4 amorphous alloy.
图11为Pd77.5Cu5Si12.5Ge4Ag1，Pd77.5Cu4Si12.5Ge4Ag2，Pd77.5Cu3Si12.5Ge4Ag3，非晶合金的XRD图谱。11 is an XRD pattern of Pd 77.5 Cu 5 Si 12.5 Ge 4 Ag 1 , Pd 77.5 Cu 4 Si 12.5 Ge 4 Ag 2 , Pd 77.5 Cu 3 Si 12.5 Ge 4 Ag 3 , amorphous alloy.
具体实施方式Detailed ways
下面结合具体实施例对本发明的技术方案做进一步说明。The technical solution of the present invention will be further described below in conjunction with specific embodiments.
本发明一种含锗无镍无磷大尺寸钯基非晶合金，该非晶合金的原子百分比表达式为PdaCubGec，式中a、b和c分别表示各对应元素的原子百分比，其中73≤a≤80，0＜b≤8，2≤c≤20，且a+b+c＝100。The invention relates to a niobium-free nickel-free and phosphorus-free large-sized palladium-based amorphous alloy, wherein the atomic percentage expression of the amorphous alloy is Pd a Cu b Ge c , wherein a, b and c respectively represent atomic percentages of corresponding elements Where 73 ≤ a ≤ 80, 0 < b ≤ 8, 2 ≤ c ≤ 20, and a + b + c = 100.
进一步，该非晶合金的原子百分比表达式为PdaCubGecSidAge，式中a、b、c和d分别表示各对应元素的原子百分比，其中73≤a≤80，0＜b≤8，2≤c≤20，0≤d≤18，0≤e≤6,且a+b+c+d+e＝100。Further, the atomic percentage expression of the amorphous alloy is Pd a Cu b Ge c Si d Ag e , wherein a, b, c and d respectively represent atomic percentages of the corresponding elements, wherein 73 ≤ a ≤ 80, 0 < b ≤ 8, 2 ≤ c ≤ 20, 0 ≤ d ≤ 18, 0 ≤ e ≤ 6, and a + b + c + d + e = 100.
进一步，该非晶合金的原子百分比表达式为PdaCubGecSidAgeXf，且各组分：73≤a≤80，0＜b≤8，2≤c≤20，0≤d≤18，0≤e≤6，0≤f≤4且a+b+c+d+e+f＝100，其中X为Co、 Au、Pt中的一种或多种。Further, the atomic percentage expression of the amorphous alloy is Pd a Cu b Ge c Si d Ag e X f , and each component: 73 ≤ a ≤ 80, 0 < b ≤ 8, 2 ≤ c ≤ 20, 0 ≤ d ≤ 18, 0 ≤ e ≤ 6, 0 ≤ f ≤ 4 and a + b + c + d + e + f = 100, where X is one or more of Co, Au, Pt.
进一步，当a＝77.5，b＝6，c＝16.5，非晶合金的原子百分比表达式为Pd74.5Cu3Ge16.5。Further, when a = 77.5, b = 6, and c = 16.5, the atomic percentage expression of the amorphous alloy is Pd 74.5 Cu 3 Ge 16.5 .
进一步，当a＝77.5，b＝6，c＝8.5，d＝8，e＝0，非晶合金的原子百分比表达式为Pd74.5Cu3Si8Ge8.5。Further, when a = 77.5, b = 6, c = 8.5, d = 8, and e = 0, the atomic percentage expression of the amorphous alloy is Pd 74.5 Cu 3 Si 8 Ge 8.5 .
进一步，a＝77.5，b＝5，c＝12.5，d＝4，e＝1，非晶合金的原子百分比表达式为Pd74.5Cu5Si12.5Ge4Ag1；或者a＝77.5，b＝4，c＝12.5，d＝4，e＝2，非晶合金的原子百分比表达式为Pd74.5Cu4Si12.5Ge4Ag2；或者a＝77.5，b＝3，c＝12.5，d＝4，e＝3，非晶合金的原子百分比表达式为Pd74.5Cu3Si12.5Ge4Ag3。Pd74.5Cu3Si12.5Ge4Ag3。Further, a=77.5, b=5, c=12.5, d=4, e=1, the atomic percentage expression of the amorphous alloy is Pd 74.5 Cu 5 Si 12.5 Ge 4 Ag 1 ; or a=77.5, b=4 , c = 12.5, d = 4, e = 2, the atomic percentage expression of the amorphous alloy is Pd 74.5 Cu 4 Si 12.5 Ge 4 Ag 2 ; or a = 77.5, b = 3, c = 12.5, d = 4, e=3, the atomic percentage expression of the amorphous alloy is Pd 74.5 Cu 3 Si 12.5 Ge 4 Ag 3 . Pd 74.5 Cu 3 Si 12.5 Ge 4 Ag 3 .
进一步，当X为Au，a＝73.5，b＝5，c＝12.5，d＝4，e＝1，f＝4,非晶合金的原子百分比表达式为Pd74.5Cu3Si12.5Ge4Ag3Au4。Further, when X is Au, a=73.5, b=5, c=12.5, d=4, e=1, f=4, the atomic percentage expression of the amorphous alloy is Pd 74.5 Cu 3 Si 12.5 Ge 4 Ag 3 Au 4 .
本发明的另一目的是提供上述合金的的制备方法，该方法具体包括以下步骤：Another object of the present invention is to provide a method for preparing the above alloy, which method comprises the following steps:
制备方式(1)：未玻璃包覆提纯制备母合金，并以铜模吸铸方式制备非晶合金，步骤包括：步骤1.配料：以纯度为99.0wt％-99.99wt％的金属Pd，Cu，Ag以及非金属Si，Ge按照上述表达式的原子百分比换算成质量，将原料表面氧化皮去除，并使用工业乙醇清洗原料，并按各自所需质量称取；Preparation method (1): preparing the mother alloy without glass coating and purifying, and preparing the amorphous alloy by copper die casting, the steps include: Step 1. Ingredients: metal Pd, Cu with a purity of 99.0 wt%-99.99 wt% , Ag and non-metal Si, Ge are converted into mass according to the atomic percentage of the above expression, the surface oxide of the raw material is removed, and the raw materials are washed with industrial ethanol and weighed according to the respective required qualities;
步骤2.母合金熔炼：将步骤1处理后的原料按熔点高低顺序堆放在非自耗真空电弧炉或冷坩埚悬浮炉里，在真空低于10-3Pa后充入在高纯氩气(不低于99.99％)进行熔炼，至少熔炼4次，使母合金充分熔炼均匀； Step 2. Mother alloy smelting: The raw materials processed in step 1 are stacked in a non-consumable vacuum arc furnace or a cold heading suspension furnace according to the melting point, and are filled with high-purity argon after the vacuum is less than 10 -3 Pa ( Not less than 99.99%) smelting, at least 4 times, so that the mother alloy is fully smelted uniformly;
步骤3.将熔炼制备的母合金打磨去除氧化皮后放入真空电弧炉的不同尺寸水冷铜模上，将电弧炉腔体抽真空至低于10-3Pa后充入0.08MPa高纯氩气(不低于99.99％)，以150A电流将母合金熔化，并持续加热15s，将电弧电流升高至200-250A之间，迅速打开吸铸真空阀门，将母合金通过气压压入水冷铜模进行冷却，得到不同尺寸的非晶合金。Step 3. After grinding and removing the mother alloy prepared by smelting, put it into different size water-cooled copper molds of a vacuum arc furnace, and evacuate the arc furnace chamber to less than 10 -3 Pa and then charge 0.08 MPa high-purity argon gas. (not less than 99.99%), the mother alloy is melted at 150A, and heated for 15s, the arc current is raised to 200-250A, the suction vacuum valve is quickly opened, and the master alloy is pressed into the water-cooled copper mold by air pressure. Cooling is performed to obtain amorphous alloys of different sizes.
进一步，制备方式(2)：玻璃包覆提纯制备母合金，并以铜模吸铸方式制备非晶合金，步骤包括：Further, the preparation method (2): preparing the mother alloy by glass coating and purifying, and preparing the amorphous alloy by copper mold suction casting, the steps include:
步骤1.配料：以纯度为99.0wt％-99.99wt％的金属Pd，Cu，Ag以及非金属Si，Ge按照上述表达式的原子百分比换算成质量，将原料表面氧化皮去除，并使用工业乙醇清洗原料，并按各自所需质量称取；Step 1. Ingredients: The metal Pd, Cu, Ag and non-metal Si, Ge with a purity of 99.0 wt%-99.99 wt% are converted into mass according to the atomic percentage of the above expression, the scale of the raw material surface is removed, and industrial ethanol is used. Cleaning the raw materials and weighing them according to their respective qualities;
步骤2.母合金熔炼：将步骤1处理后的原料按熔点高低顺序堆放在非自耗真空电弧炉或冷坩埚悬浮炉里，在真空低于10-3Pa后充入在高纯氩气(不低于99.99％)进行熔炼，至少熔炼4次，使母合金充分熔炼均匀； Step 2. Mother alloy smelting: The raw materials processed in step 1 are stacked in a non-consumable vacuum arc furnace or a cold heading suspension furnace according to the melting point, and are filled with high-purity argon after the vacuum is less than 10 -3 Pa ( Not less than 99.99%) smelting, at least 4 times, so that the mother alloy is fully smelted uniformly;
步骤3.玻璃包覆提纯：将母合金和脱水后的三氧化二硼介质放置于不同尺寸的石英管中，将石英管中真空抽至10Pa以下后将石英管中充入0.2MPa高纯氩气，并放置于1100℃电炉中提纯24小时，之后将熔体随炉冷却；Step 3. Glass coating purification: The mother alloy and the dehydrated boron trioxide medium are placed in quartz tubes of different sizes, and the quartz tube is vacuumed to 10 Pa or less, and then the quartz tube is filled with 0.2 MPa high purity argon. Gas, and placed in an electric furnace at 1100 ° C for 24 hours, after which the melt is cooled with the furnace;
步骤4.用砂纸去除经玻璃包覆提纯后的合金锭表面附着的包覆介质后，放入真空电弧炉的不同尺寸水冷铜模上，将电弧炉腔体抽真空至低于10-3Pa后充入0.08MPa高纯氩气(不低于99.99％)，以150A电流将母合金熔化，并持续加热15s，将电弧电流升高至200-250A之间，迅速打开吸铸真空阀门，将母合金通过气压压入水冷铜模进行冷却，得到不同尺寸的非晶合金。Step 4. Remove the coating medium adhered to the surface of the alloy ingot after glass coating and purifying with sandpaper, place it on the water-cooled copper mold of different sizes in the vacuum arc furnace, and evacuate the arc furnace chamber to less than 10 -3 Pa. After filling with 0.08MPa high purity argon (not less than 99.99%), the mother alloy is melted at 150A, and heated for 15s, the arc current is raised to 200-250A, and the suction vacuum valve is quickly opened. The master alloy is cooled by pressure into a water-cooled copper mold to obtain amorphous alloys of different sizes.
进一步，制备方式(3)：玻璃包覆提纯制备母合金，并以水淬方式制备非晶合金，步骤包括：Further, the preparation method (3): preparing the mother alloy by glass coating and purifying, and preparing the amorphous alloy by water quenching, the steps include:
步骤1.配料：以纯度为99.0wt％-99.99wt％的金属Pd，Cu，Ag以及非金属Si，Ge按照上述表达式的原子百分比换算成质量，将原料表面氧化皮去除，并使用工业乙醇清洗原料，并按各自所需质量称取；Step 1. Ingredients: The metal Pd, Cu, Ag and non-metal Si, Ge with a purity of 99.0 wt%-99.99 wt% are converted into mass according to the atomic percentage of the above expression, the scale of the raw material surface is removed, and industrial ethanol is used. Cleaning the raw materials and weighing them according to their respective qualities;
步骤2.母合金熔炼：将步骤1处理后的原料按熔点高低顺序堆放在非自耗真空电弧炉或冷坩埚悬浮炉里，在真空低于10-3Pa后充入在高纯氩气(不低于99.99％)进行熔炼，至少熔炼4次，使母合金充分熔炼均匀； Step 2. Mother alloy smelting: The raw materials processed in step 1 are stacked in a non-consumable vacuum arc furnace or a cold heading suspension furnace according to the melting point, and are filled with high-purity argon after the vacuum is less than 10 -3 Pa ( Not less than 99.99%) smelting, at least 4 times, so that the mother alloy is fully smelted uniformly;
步骤3.玻璃包覆提纯：将母合金和脱水后的三氧化二硼介质放置于不同尺寸的石英管中，将石英管中真空抽至10Pa以下后将石英管中充入0.2MPa高纯氩气，并放置于1100℃电炉中提纯24小时；Step 3. Glass coating purification: The mother alloy and the dehydrated boron trioxide medium are placed in quartz tubes of different sizes, and the quartz tube is vacuumed to 10 Pa or less, and then the quartz tube is filled with 0.2 MPa high purity argon. Gas, and placed in an electric furnace at 1100 ° C for 24 hours;
步骤4.经玻璃包覆提纯后的合金锭在熔融状态下直接淬入浓度不低于25wt％的室温食盐水中，制备不同尺寸的非晶合金。Step 4. The alloy ingot purified by glass coating is directly quenched into a room temperature brine having a concentration of not less than 25% by weight in a molten state to prepare amorphous alloys of different sizes.
实施例1：Pd-Cu-Si-Ge系非晶合金的制备：Example 1: Preparation of Pd-Cu-Si-Ge-based amorphous alloy:
设计PdaCubGecSidAge非晶合金成分，其中a＝77.5，b＝6，c＝16.5,8.5,4，8,12.5，d＝0，e＝0。得到成分为Pd77.5Cu6Ge16.5、Pd77.5Cu6Si8Ge8.5、Pd77.5Cu6Si12.5Ge4的合金。A Pd a Cu b Ge c Si d Ag e amorphous alloy composition was designed, where a = 77.5, b = 6, c = 16.5, 8.5, 4, 8, 12.5, d = 0, e = 0. An alloy having a composition of Pd 77.5 Cu 6 Ge 16.5 , Pd 77.5 Cu 6 Si 8 Ge 8.5 , and Pd 77.5 Cu 6 Si 12.5 Ge 4 was obtained.
图1为合金Pd77.5Cu6Ge16.5、Pd77.5Cu6Si8Ge8.5经过制备方式(3)制备的2mm试样的XRD图谱，图2为合金Pd77.5Cu6Si12.5Ge4经过制备方式(2)制备的2mm和4mm试样的XRD图谱，图谱只有非晶典型的漫散射峰，表明所制备的合金均为非晶相，该合金系通过制备方式(3)可制备临界尺寸不小于2mm的非晶合金，Pd77.5Cu6Si12.5Ge4合金通过制备方式(2)可制备临界尺寸不小于4mm的非晶合金，具有较强非晶形成能力。图3为合金Pd77.5Cu6Si12.5Ge4的DSC曲线，其过冷液相区间为54K。 1 is an XRD pattern of a 2 mm sample prepared by the preparation method (3) of the alloy Pd 77.5 Cu 6 Ge 16.5 , Pd 77.5 Cu 6 Si 8 Ge 8.5 , and FIG. 2 is a preparation method of the alloy Pd 77.5 Cu 6 Si 12.5 Ge 4 ( 2) The XRD patterns of the prepared 2mm and 4mm samples, the only typical diffuse scattering peaks of the amorphous, indicating that the prepared alloys are all amorphous phases, the alloy can be prepared by the preparation method (3) with a critical dimension of not less than 2 mm. The amorphous alloy, Pd 77.5 Cu 6 Si 12.5 Ge 4 alloy can be prepared by preparing the amorphous alloy with a critical dimension of not less than 4 mm by the preparation method (2), and has a strong amorphous forming ability. Figure 3 is a DSC curve of the alloy Pd 77.5 Cu 6 Si 12.5 Ge 4 with a supercooled liquid phase interval of 54K.
图4为Pd77.5Cu6Si12.5Ge4合金的压缩应力应变曲线，其压缩屈服强度为1650MPa，压缩塑性3.5％。4 is a compressive stress-strain curve of a Pd 77.5 Cu 6 Si 12.5 Ge 4 alloy having a compressive yield strength of 1650 MPa and a compression ductility of 3.5%.
实施例2：Pd-Cu-Si-Ge-Ag系非晶合金的制备：Example 2: Preparation of Pd-Cu-Si-Ge-Ag based amorphous alloy:
设计PdaCubGecSidAge非晶合金成分，其中a＝77.5，b＝5,4,3，c＝4，d＝12.5，e＝1,2,3。得到成分为Pd77.5Cu5Si12.5Ge4Ag1，Pd77.5Cu4Si12.5Ge4Ag2、Pd77.5Cu3Si12.5Ge4Ag3的合金。A Pd a Cu b Ge c Si d Ag e amorphous alloy composition was designed, wherein a = 77.5, b = 5, 4, 3, c = 4, d = 12.5, and e = 1, 2, 3. An alloy having a composition of Pd 77.5 Cu 5 Si 12.5 Ge 4 Ag 1 , Pd 77.5 Cu 4 Si 12.5 Ge 4 Ag 2 and Pd 77.5 Cu 3 Si 12.5 Ge 4 Ag 3 was obtained.
图5为合金Pd77.5Cu5Si12.5Ge4Ag1，Pd77.5Cu4Si12.5Ge4Ag2经过制备方式(3)制备的8mm试样的XRD图谱，图6为与图5相对应的SEM照片，图7为合金Pd77.5Cu3Si12.5Ge4Ag3经过制备方式(3)制备的8mm试样，以及制备方式(1)制备4mm试样的XRD图谱，图8为与图7相对应的SEM照片，XRD图谱只有非晶典型的漫散射峰，相对应的SEM照片也显示出合金单一的非晶相组成，表明所制备的合金均为非晶相，该合金通过制备方式(3)可制备临界尺寸不小于8mm的非晶，通过制备方式(1)Pd77.5Cu5Si12.5Ge4Ag1，Pd77.5Cu4Si12.5Ge4Ag2合金可制备临界尺寸不小于2mm的非晶合金，Pd77.5Cu3Si12.5Ge4Ag3合金可制备临界尺寸不小于4mm的非晶合金，具有强非晶形成能力。5 is an XRD pattern of an 8 mm sample prepared by the preparation method (3) of an alloy Pd 77.5 Cu 5 Si 12.5 Ge 4 Ag 1 , Pd 77.5 Cu 4 Si 12.5 Ge 4 Ag 2 , and FIG. 6 is a SEM corresponding to FIG. 5 . Photo, Fig. 7 is an 8 mm sample prepared by the preparation method (3) of the alloy Pd 77.5 Cu 3 Si 12.5 Ge 4 Ag 3 , and an XRD pattern of the preparation method (1) for preparing a 4 mm sample, and Fig. 8 corresponds to Fig. 7 The SEM photograph, XRD pattern only has a typical diffuse scattering peak of amorphous, and the corresponding SEM photograph also shows the single amorphous phase composition of the alloy, indicating that the prepared alloys are all amorphous phases, and the alloy is prepared by (3) An amorphous alloy having a critical dimension of not less than 8 mm can be prepared, and an amorphous alloy having a critical dimension of not less than 2 mm can be prepared by preparing (1) Pd 77.5 Cu 5 Si 12.5 Ge 4 Ag 1 , Pd 77.5 Cu 4 Si 12.5 Ge 4 Ag 2 alloy. The Pd 77.5 Cu 3 Si 12.5 Ge 4 Ag 3 alloy can prepare an amorphous alloy having a critical dimension of not less than 4 mm and has a strong amorphous forming ability.
图9为合金Pd77.5Cu5Si12.5Ge4Ag1，Pd77.5Cu4Si12.5Ge4Ag2、Pd77.5Cu3Si12.5Ge4Ag3的压缩应力应变曲线，其中合金Pd77.5Cu5Si12.5Ge4Ag1的压缩屈服强度为1602MPa，压缩塑性11％。9 is a compressive stress-strain curve of alloy Pd 77.5 Cu 5 Si 12.5 Ge 4 Ag 1 , Pd 77.5 Cu 4 Si 12.5 Ge 4 Ag 2 , Pd 77.5 Cu 3 Si 12.5 Ge 4 Ag 3 , wherein alloy Pd 77.5 Cu 5 Si 12.5 Ge 4 Ag 1 has a compression yield strength of 1602 MPa and a compression ductility of 11%.
实施例3：Pd-Cu-Si-Ge-Ag-X系非晶合金的制备：Example 3: Preparation of Pd-Cu-Si-Ge-Ag-X-based amorphous alloy:
设计PdaCubGecSidAgeXf的非晶合金成分，其中X为Au，a＝73.5，b＝5，c＝4，d＝12.5，e＝1，f＝4。得到成分为Pd74.5Cu3Si12.5Ge4Ag3Au4的合金。An amorphous alloy composition of Pd a Cu b Ge c Si d Ag e X f is designed, wherein X is Au, a = 73.5, b = 5, c = 4, d = 12.5, e = 1, f = 4. An alloy having a composition of Pd 74.5 Cu 3 Si 12.5 Ge 4 Ag 3 Au 4 was obtained.
图5为Pd74.5Cu3Si12.5Ge4Ag3Au4合金经过制备方式(3)制备的8mm试样的XRD图谱，XRD图谱只有非晶典型的漫散射峰，表明所制备的合金为非晶相，通过制备方式(3)可制备临界尺寸不小于8mm的非晶合金，具有强非晶形成能力。Figure 5 is an XRD pattern of an 8 mm sample prepared by the preparation method (3) of Pd 74.5 Cu 3 Si 12.5 Ge 4 Ag 3 Au 4 alloy. The XRD pattern has only a typical diffuse scattering peak of amorphous, indicating that the prepared alloy is amorphous. Phase, an amorphous alloy having a critical dimension of not less than 8 mm can be prepared by the preparation method (3), and has a strong amorphous forming ability.
本发明一种含锗无镍无磷大尺寸钯基非晶合金及其制备方法，该合金各成分的原子百分比为：Pd:73-80％，Cu:0＜b≤8％，Si:0-18％，Ge:2-20％，Ag:0-6％。本发明的主要优点是不含有镍元素，潜在的生物毒性大大降低，提高了生物相容性；不含有磷元素，熔炼制备的方法简便；具有强非晶形成能力，采用玻璃包覆介质工艺提纯并水淬快冷可制备出临界尺寸1-8mm的钯基非晶合金，其中玻璃形成能力最强成分采用电弧熔炼铜模吸铸的方法可制备临界尺寸不小于4mm的非晶合金，采用制备方式3可制备出临界尺寸不小于8mm的非晶合金；具有>3％的塑性变形能力；具有40-60K的过冷液相区范。 The invention relates to a niobium-free nickel-free and phosphorus-free large-sized palladium-based amorphous alloy and a preparation method thereof, wherein the atomic percentage of each component of the alloy is: Pd: 73-80%, Cu: 0 < b ≤ 8%, Si: 0 -18%, Ge: 2-20%, Ag: 0-6%. The main advantage of the invention is that it does not contain nickel element, the potential biological toxicity is greatly reduced, and the biocompatibility is improved; the method of smelting preparation is simple without containing phosphorus element; the amorphous amorphous forming ability is obtained, and the glass coating medium process is used for purification. And palladium-based amorphous alloy with critical dimension of 1-8mm can be prepared by water quenching and rapid cooling. The most intensive glass forming ability can be prepared by arc melting smelting copper die casting method to prepare amorphous alloy with critical dimension of not less than 4mm. Mode 3 can prepare an amorphous alloy having a critical dimension of not less than 8 mm; having a plastic deformation ability of > 3%; and having a supercooled liquid phase range of 40 to 60 K.

Claims (20)

  1. —种含锗无镍无磷大尺寸钯基非晶合金，其特征在于，该非晶合金的原子百分比表达式为PdaCubGec，式中a、b和c分别表示各对应元素的原子百分比，其中73≤ a≤ 80，0<b≤ 8，2≤ c≤ 20，且a+b+c=100。 - A nickel-free and phosphorus-free large-sized palladium-based amorphous alloy, characterized in that the atomic percentage expression of the amorphous alloy is PdaCubGec, wherein a, b and c respectively represent atomic percentages of corresponding elements, of which 73 ≤ a ≤ 80, 0 < b ≤ 8, 2 ≤ c ≤ 20, and a + b + c = 100.
  2. 一种含锗无镍无磷大尺寸钯基非晶合金，其特征在于，其特征在于，该非晶合金的原子百分比表达式为PdaCubGecSidAge，式中a、b、c、d和e分别表示各对应元素的原子百分比，其中73≤a≤80，0<b≤8，2≤c≤20，0≤d≤18，0≤e≤6，且a+b+c+d+e=100。 A palladium-based amorphous alloy containing niobium-free nickel-free and non-phosphorus, characterized in that the atomic percentage expression of the amorphous alloy is PdaCubGecSidAge, wherein a, b, c, d and e respectively represent The atomic percentage of the corresponding element, where 73 ≤ a ≤ 80, 0 < b ≤ 8, 2 ≤ c ≤ 20, 0 ≤ d ≤ 18, 0 ≤ e ≤ 6, and a + b + c + d + e = 100.
  3. 一种含锗无镍无磷大尺寸钯基非晶合金，其特征在于，该非晶合金的原子百分比表达式为PdaCubGecSidAgeXf，且各组分：73≤a≤80，0<b≤8，2≤c≤20，0≤d≤18，0≤e≤6，0≤f≤4，且a+b+c+d+e+f=100，其中X为Co、Au、Pt中的一种或多种。 A palladium-based amorphous alloy containing niobium-free nickel-free and non-phosphorus, characterized in that the atomic percentage expression of the amorphous alloy is PdaCubGecSidAgeXf, and each component: 73≤a≤80,0<b≤8,2 ≤ c ≤ 20, 0 ≤ d ≤ 18, 0 ≤ e ≤ 6, 0 ≤ f ≤ 4, and a + b + c + d + e + f = 100, where X is one of Co, Au, Pt Or a variety.
  4. 根据权利要求1所述含锗无镍无磷大尺寸钯基非晶合金，其特征在于，当a=77.5，b=6，c=16.5，非晶合金的原子百分比表达式为Pd74.5Cu3Ge16.5。The niobium-free nickel-free and phosphorus-free large-sized palladium-based amorphous alloy according to claim 1, wherein when a = 77.5, b = 6, c = 16.5, the atomic percentage expression of the amorphous alloy is Pd74.5Cu3Ge16. 5.
  5. 根据权利要求2所述含锗无镍无磷大尺寸钯基非晶合金,其特征在于，当a=77.5，b=6,c=8.5,d=8，e=0,非晶合金的原子百分比表达式为Pd74.5Cu3Si8Ge8.5。The niobium-free nickel-free and phosphorus-free large-sized palladium-based amorphous alloy according to claim 2, wherein when a = 77.5, b = 6, c = 8.5, d = 8, e = 0, the atom of the amorphous alloy The percentage expression is Pd74.5Cu3Si8Ge8.5.
  6. 根据权利要求2所述的含锗无镍无磷大尺寸钯基非晶合金，其特征在于，a=77.5，b=5，c=4,d=12.5，e=l,非晶合金的原子百分比表达式为Pd74.5Cu5Si12.5Ge4Ag1;或者a=77.5,b=4,c=12.5,d=4，e=2,非晶合金的原子百分比表达式为Pd74.5Cu4Si12.5Ge4Ag2;或者a=77.5，b=3,c=4,d=12.5，e=3，非晶合金的原子百分比表达式为Pd74.5Cu3Si12.5Ge4Ag3。The niobium-free nickel-free and phosphorus-free large-sized palladium-based amorphous alloy according to claim 2, wherein a = 77.5, b = 5, c = 4, d = 12.5, e = 1, atom of the amorphous alloy The percentage expression is Pd74.5Cu5Si12.5Ge4Ag1; or a=77.5, b=4, c=12.5, d=4, e=2, the atomic percentage expression of the amorphous alloy is Pd74.5Cu4Si12.5Ge4Ag2; or a=77.5 , b=3, c=4, d=12.5, e=3, and the atomic percentage expression of the amorphous alloy is Pd74.5Cu3Si12.5Ge4Ag3.
  7. 根据权利要求3所述的含锗无镍无磷大尺寸钯基非晶合金，其特征在于，当X为Au，a=73.5，b=5，c=4，d=12.5，e=l，f=4,非晶合金的原子百分比表达式为Pd74.5Cu3Si12.5Ge4Ag3Au4。The niobium-free nickel-free and phosphorus-free large-sized palladium-based amorphous alloy according to claim 3, wherein when X is Au, a = 73.5, b = 5, c = 4, d = 12.5, e = 1, f=4, the atomic percentage expression of the amorphous alloy is Pd74.5Cu3Si12.5Ge4Ag3Au4.
  8. 一种制备如权利要求1-7中任一所述的非晶合金的方法，其特征在于，具体包括以下：制备方式（1):未玻璃包覆提纯制备母合金，并以铜模吸铸方式制备非晶合金，步骤包括：步骤1.配料：以纯度为99.0wt%-99.99wt%的金属Pd，Cu，Ag以及非金属Si，Ge按照上述表达式的原子百分比换算成质量，将原料表面氧化皮去除，并使用工业乙醇清洗原料，并按各自所需质量称取；步骤2.母合金熔炼：将步骤1处理后的原料按熔点高低顺序堆放在非自耗真空电弧炉或冷坩埚悬浮炉里，在真空低于10-3Pa后充入在高纯氩气（纯度不低于99.99%)进行熔炼，至少熔炼4次，使母合金充分熔炼均匀；步骤3.将熔炼制备的母合金打磨去除氧化皮后放入真空电弧炉的不同尺寸水冷铜模上，将电弧炉腔体抽真空至低于10-3Pa后充入0.08MPa高纯氩气（纯度不低于99.99%)，以150A电流将母合金熔化，并持续加热15s，将电弧电流升髙至200-250A之间，迅速打开吸铸真空阀门，将母合金通过气压压入水冷铜模进行冷却，得到不同尺寸的非晶合金。A method for preparing an amorphous alloy according to any one of claims 1 to 7, which specifically comprises the following: preparation method (1): preparing a master alloy without glass coating and purifying, and casting with a copper mold The method for preparing an amorphous alloy comprises the following steps: Step 1. Ingredients: a metal having a purity of 99.0 wt% to 99.99 wt%, Cu, Ag, and a non-metal Si, Ge are converted into mass according to the atomic percentage of the above expression, and the raw material is used. The surface scale is removed, and the raw materials are cleaned with industrial ethanol and weighed according to the respective required quality; Step 2. Mother alloy smelting: The raw materials processed in step 1 are stacked in a non-consumable vacuum arc furnace or cold enthalpy according to the order of melting point. In the suspension furnace, after the vacuum is lower than 10-3 Pa, it is filled with high-purity argon gas (purity of not less than 99.99%) for melting, at least 4 times to make the mother alloy fully melted uniformly; Step 3. The mother prepared by melting The alloy is polished to remove the scale and placed in a different size water-cooled copper mold of the vacuum arc furnace, and the arc furnace chamber is evacuated to less than 10-3 Pa and then filled with 0.08 MPa high-purity argon gas (purity of not less than 99.99%). Melting the master alloy at a current of 150A and holding Heating 15s, the arc current to rise between Gao 200-250A, vacuum suction casting quickly open the valve, the water-cooled copper mold press master alloy is cooled by air pressure, to obtain amorphous alloys of different sizes.
  9. 一种制备如权利要求1-7中任一所述的非晶合金的方法，其特征在于，具体包括以下：制备方式（2）:玻璃包覆提纯制备母合金，并以铜模吸铸方式制备非晶合金，步骤包括：步骤1.配料：以纯度为99.0wt%-99.99wt%的金属Pd，Cu，Ag以及非金属Si，Ge按照上述表达式的原子百分比换算成质量，将原料表面氧化皮去除，并使用工业乙醇清洗原料，并按各自所需质量称取；步骤2.母合金熔炼：将步骤1处理后的原料按熔点高低顺序堆放在非自耗真空电弧炉或冷坩埚悬浮炉里，在真空低于10-3Pa后充入在高纯氩气（不低于99.99%）进行熔炼，至少熔炼4次，使母合金充分熔炼均匀；步骤3.玻璃包覆提纯：将母合金和脱水后的三氧化二硼介质放置于不同尺寸的石英管中，将石英管中真空抽至10Pa以下后将石英管中充入0.2MPa高纯氩气，并放置于1100°C电炉中提纯24小时，之后将熔体随炉冷却；步骤4.用砂纸去除经玻璃包覆提纯后的合金锭表面附着的包覆介质后，放入真空电弧炉的不同尺寸水冷铜模上，将电弧炉腔体抽真空至低于10-3Pa后充入0.08MPa高纯氩气（不低于99.99%），以150A电流将母合金熔化，并持续加热15s，将电弧电流升高至200-250A之间，迅速打开吸铸真空阀门，将母合金通过气压压入水冷铜模进行冷却，得到不同尺寸的非晶合金。A method for preparing an amorphous alloy according to any one of claims 1 to 7, which specifically comprises the following: preparation method (2): glass coating purification to prepare a master alloy, and copper mold suction casting method To prepare an amorphous alloy, the steps include: Step 1. Ingredients: a metal having a purity of 99.0 wt% to 99.99 wt%, Cu, Ag, and a non-metal Si, Ge, converted to a mass according to the atomic percentage of the above expression, and the raw material surface The scale is removed, and the raw materials are washed with industrial ethanol and weighed according to the respective required quality; Step 2. The mother alloy is smelted: the raw materials treated in step 1 are stacked in a non-consumable vacuum electric arc furnace or cold suspension in the order of melting point. In the furnace, after the vacuum is lower than 10-3 Pa, it is filled with high-purity argon (not less than 99.99%) for melting, and at least smelting 4 times to make the mother alloy fully melted uniformly; Step 3. Glass coating purification: The alloy and the dehydrated boron trioxide medium are placed in quartz tubes of different sizes. After vacuuming the quartz tube to 10 Pa or less, the quartz tube is filled with 0.2 MPa high purity argon gas and placed in an electric furnace at 1100 ° C. Purification for 24 hours, then melt Cooling with the furnace; Step 4. Using sandpaper to remove the coating medium adhered to the surface of the alloy ingot after glass coating and purging, put it into different size water-cooled copper molds of the vacuum arc furnace, and evacuate the arc furnace chamber to below After 10-3Pa, it is filled with 0.08MPa high purity argon (not less than 99.99%), the mother alloy is melted at 150A, and heated for 15s, the arc current is raised to 200-250A, and the suction vacuum is quickly opened. The valve is cooled by pressing the parent alloy into a water-cooled copper mold by air pressure to obtain amorphous alloys of different sizes.
  10. 一种制备如权利要求1-7中任一所述的非晶合金的方法，其特征在于，具体包括以下：制备方式（3）:玻璃包覆提纯制备母合金，并以水淬方式制备非晶合金，步骤包括：步骤1.配料：以纯度为99.0wt%-99.99wt%的金属Pd，Cu，Ag以及非金属Si，Ge按照上述表达式的原子百分比换算成质量，将原料表面氧化皮去除，并使用工业乙醇清洗原料，并毕各自所需质量称取；步骤2.母合金熔炼：将步骤1处理后的原料按熔点高低顺序堆放在非自耗真空电弧炉或冷坩埚悬浮炉里，在真空低于10-3Pa后充入在高纯氩气（不低于99.99%)进行熔炼，至少熔炼4次，使母合金充分熔炼均匀；步骤3.玻璃包覆提纯：将母合金和脱水后的三氧化二硼介质放置于不同尺寸的石英管中，将石英管中真空抽至10Pa以下后将石英管中充入0.2MPa高纯氩气，并放置于1100°C电炉中提纯24小时；步骤4.经玻璃包覆提纯后的合金锭在熔融状态下直接淬入浓度不低于25wt%的室温食盐水中，制备不同尺寸的非晶合金。A method for preparing an amorphous alloy according to any one of claims 1 to 7, which specifically comprises the following: preparation method (3): preparing a mother alloy by glass coating and purifying, and preparing the non-water quenching method The crystal alloy, the steps include: Step 1. Ingredients: the metal Pd, Cu, Ag and non-metal Si, Ge with a purity of 99.0 wt%-99.99 wt% are converted into mass according to the atomic percentage of the above expression, and the surface of the raw material is scaled. Remove and use industrial ethanol to clean the raw materials and weigh them according to the quality required; Step 2. Mother alloy smelting: The raw materials processed in step 1 are stacked in a non-consumable vacuum arc furnace or a cold-slipping suspension furnace according to the melting point. After the vacuum is lower than 10-3 Pa, it is filled with high-purity argon (not less than 99.99%) for melting, at least 4 times to make the mother alloy fully melted uniformly; Step 3. Glass coating purification: the mother alloy and The dehydrated boron trioxide medium is placed in a quartz tube of different sizes, and the quartz tube is vacuumed to 10 Pa or less, and then the quartz tube is filled with 0.2 MPa high-purity argon gas, and placed in an electric furnace at 1100 ° C for purification. Hour; step 4. coated with glass The purified alloy ingot is directly quenched into a room temperature brine having a concentration of not less than 25% by weight in a molten state to prepare amorphous alloys of different sizes.
  11. 一种应用非离子表面活性剂强化胶硫钼矿细菌浸出的方法，其特征在于，该方法先将胶硫钼矿型难选钼矿石破碎、研磨，作为浸矿试样；再将所述浸矿试样置于9K基础盐溶液中，添加一定量的Fe2+，接入经钼离子-钼矿物“两步法”驯化后的氧化亚铁硫杆菌或以氧化亚铁硫杆菌为优势菌的混合菌种，再加入Triton X-100，得到浸出液；将所述浸出液置于气浴恒温振荡器中进行摇瓶浸出，所述浸出液经离心去除沉淀杂质得上清液。A method for enhancing bacterial leaching of a sulphur-molybdenum ore by using a nonionic surfactant, characterized in that the method firstly crushes and grinds a sulphur-sulfur molybdenum-type refractory molybdenum ore as a leaching sample; The ore sample is placed in a 9K base salt solution, a certain amount of Fe 2+ is added , and the Thiobacillus ferrooxidans or the ferric bacteria of Thiobacillus ferrooxidans which are domesticated by the molybdenum ion-molybdenum mineral "two-step method" are added. The mixed bacteria were further added to Triton X-100 to obtain a leachate; the leachate was placed in a gas bath thermostat shake flask for leaching, and the leachate was centrifuged to remove precipitated impurities to obtain a supernatant.
  12. 如权利要求1所述的方法，其特征在于，具体包括如下步骤：The method of claim 1 further comprising the steps of:
    步骤一、将胶硫钼矿型难选钼矿石破碎、研磨至粒度为-0.074mm，再经真空高温灭菌后，作为浸矿试样；Step 1: crushing and grinding the sulphur-sulfur molybdenum-type refractory molybdenum ore to a particle size of -0.074 mm, and then sterilizing by vacuum high temperature as a leaching sample;
    步骤二、将步骤一中得到的所述浸矿试样置于高温灭菌后的9K基础盐溶液中，得到矿浆；所述矿浆浓度为2～10％(w/v)，在所述矿浆中加入0～9g/L Fe2+，接入经钼离子-钼矿物“两步法”驯化后的氧化亚铁硫杆菌或以氧化亚铁硫杆菌为优势菌的混合菌种，初始细菌浓度调节至(0.5～5)×107个/mL，再加入Triton X-100，Triton X-100的添加量为10～90mg/L，采用稀硫酸调节浸出液初始pH为1.5～3.5；Step 2, the leaching sample obtained in the first step is placed in a 9K base salt solution after high temperature sterilization to obtain a slurry; the slurry concentration is 2 to 10% (w/v), in the pulp Adding 0～9g/L Fe 2+ to the group , and connecting the ferrochemical-molybdenum mineral “two-step method” to domesticated Thiobacillus ferrooxidans or the mixed strain of Thiobacillus ferrooxidans as the dominant bacteria, the initial bacterial concentration Adjust to (0.5 ~ 5) × 10 7 / mL, then add Triton X-100, Triton X-100 is added in an amount of 10 ~ 90mg / L, using dilute sulfuric acid to adjust the initial pH of the leachate is 1.5 ~ 3.5;
    步骤三、将步骤二中得到的所述浸出液置于气浴恒温振荡器中进行摇瓶浸出30～60d，浸出结束后，浸出液样品经离心去除沉淀杂质后，取上清液检测钼离子的含量，测得Triton X-100的加入使胶硫钼矿中钼的浸出率提高20个百分点以上，可实现矿石中有价元素钼的有效回收。Step 3: The leaching solution obtained in the second step is placed in a gas bath thermostat shaker for 30 to 60 days. After the leaching is completed, the leaching solution sample is centrifuged to remove precipitated impurities, and the supernatant is taken to detect the content of molybdenum ions. The addition of Triton X-100 can increase the leaching rate of molybdenum in the sulphur-molybdenum ore by more than 20%, which can effectively recover the valuable element molybdenum in the ore.
  13. 如权利要求1或2所述的方法，其特征在于，所述的胶硫钼矿型难选钼矿是以胶硫钼矿为主要钼矿物的钼矿石。The method according to claim 1 or 2, wherein the sulphur-sulfur molybdenum-type refractory molybdenum ore is a molybdenum ore having a sulphur-sulfur molybdenum ore as a main molybdenum mineral.
  14. 如权利要求1或2所述的方法，其特征在于，所述的9 K基础盐溶液的组成为：(NH4)2SO4 3.0g/L，MgSO4·7H2O 0.5g/L，K2HPO4 0.5g/L，KCl 0.1g/L，Ca(NO3)2 0.01g/L，FeSO4·7H2O 44.2g/L，采用稀硫酸调节pH值至2.0。The method according to claim 1 or 2, wherein the composition of the 9 K base salt solution is: (NH 4 ) 2 SO 4 3.0 g/L, MgSO 4 · 7H 2 O 0.5 g/L, K 2 HPO 4 0.5 g/L, KCl 0.1 g/L, Ca(NO 3 ) 2 0.01 g/L, FeSO 4 ·7H 2 O 44.2 g/L, and the pH was adjusted to 2.0 with dilute sulfuric acid.
  15. 如权利要求1或2所述的方法，其特征在于，所述的钼离子-钼矿物“两步法”驯化菌种的具体步骤为：The method according to claim 1 or 2, wherein the specific steps of the "two-step" domesticated strain of the molybdenum ion-molybdenum mineral are:
    步骤1、在9K基础盐溶液培养基中添加一定浓度的Na2MoO4对细菌进行驯化培养，以细菌对培养基中Fe2+的氧化速率为判定依据，待细菌适应该浓度后，逐步提高Mo离子浓度以提高菌种对Mo的耐受能力； Step 1. Adding a certain concentration of Na 2 MoO 4 to the 9K basic salt solution culture medium to acclimate the bacteria, and determine the oxidation rate of Fe 2+ in the medium by bacteria. After the bacteria adapt to the concentration, gradually increase the bacteria. Mo ion concentration to increase the tolerance of the strain to Mo;
    步骤2、接种10mL细菌于含90mL的9K基础盐溶液培养基中，待细菌生长至对数期，随后加入5g粒度为-0.045mm的胶硫钼矿，置于气浴恒温振荡器中驯化培养7d，锥形瓶静置沉降后取出上清液10mL转接至90mL 9K基础盐溶液新鲜培养基中继续驯化，如此反复操作5次，以提高细菌对胶硫钼矿的浸出性能。Step 2: Inoculate 10 mL of bacteria in 90 mL of 9K basic salt solution medium, and wait until the bacteria grow to log phase, then add 5 g of sulphur-sulfur molybdenum with a particle size of -0.045 mm, and place it in a gas bath thermostat. 7d, after the conical flask was allowed to settle, 10 mL of the supernatant was taken and transferred to 90 mL of 9K basic salt solution to continue acclimatization in the fresh medium, and the operation was repeated 5 times to improve the leaching performance of the bacteria on the sulphur-sulfur molybdenum ore.
  16. 如权利要求1或2所述的方法，其特征在于，所述的非离子型表面活性剂Triton X-100，化合物名称为聚乙二醇对异辛基苯基醚，化学式为C34H62O11，分子结构式为：The method according to claim 1 or 2, wherein said nonionic surfactant Triton X-100 has a compound name of polyethylene glycol to isooctylphenyl ether and has a chemical formula of C 34 H 62 O 11 , the molecular structure is:
    Figure PCTCN2017115922-appb-100001
    Figure PCTCN2017115922-appb-100001
  17. 如权利要求1或2所述的方法，其特征在于，所述胶硫钼矿型难选钼矿石的矿样中Mo的含量为0.12-0.24％，矿样中的Mo主要以胶硫钼矿形式存在，脉石矿物主要为石英、钾长石、长石。The method according to claim 1 or 2, wherein the content of Mo in the ore sample of the sulphur-sulfur molybdenum type refractory molybdenum ore is 0.12-0.24%, and the Mo in the ore sample is mainly a sulphur-sulfur molybdenum ore. Forms exist, gangue minerals are mainly quartz, potassium feldspar, feldspar.
  18. 如权利要求1或2所述的方法，其特征在于，所述氧化亚铁硫杆菌为优势菌的混合菌种为At.ferrooxidans DB；该菌种是从酸性矿坑水中提取所得，具体提取过程是：将采取的酸性矿坑水10mL接种至90mL的9K基础盐溶液培养基中，置于温度为30℃、转速为160r/min的气浴恒温振荡器中进行富集培养；定期检测培养基Fe2+浓度，当培养基中Fe2+完全氧化时，进行转接培养，反复培养10次后即为目的菌种。The method according to claim 1 or 2, wherein the mixed strain of Thiobacillus ferrooxidans as the dominant bacteria is At. ferrooxidans DB; the strain is extracted from acidic pit water, and the specific extraction process is : 10 mL of acid pit water was inoculated into 90 mL of 9K basic salt solution medium, and enriched and cultured in a gas bath thermostat with a temperature of 30 ° C and a rotation speed of 160 r / min; the medium Fe 2 was periodically detected. + Concentration, when the Fe 2+ in the medium is completely oxidized, the transfer culture is carried out, and after repeated culture for 10 times, it is the target strain.
  19. 如权利要求1或2所述的方法，其特征在于，所述氧化亚铁硫杆菌为At.ferrooxidansstrain XZ11，为从西藏甲玛地区酸性矿坑水中富集、筛选、纯化所得，经16SrDNA测序为氧化亚铁硫杆菌，GenBank登录号为KJ573102。The method according to claim 1 or 2, wherein the Thiobacillus ferrooxidans is At. ferrooxidansstrain XZ11, which is obtained by enrichment, screening and purification from acidic pit water in Jiama, Tibet, and is oxidized by 16S rDNA sequencing. Thiobacillus ferrooxidans, GenBank accession number is KJ573102.
  20. 如权利要求1或2所述的方法，其特征在于，所述气浴恒温振荡器的型号为ZD-85A。 The method of claim 1 or 2 wherein said air bath thermostat is of the type ZD-85A.
PCT/CN2017/115922 2017-09-25 2018-02-27 Germanium-containing nickel-free phosphorus-free large-sized palladium-based amorphous alloy and preparation method therefor WO2019056595A1 (en)

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