阅读说明：本技术 一种合金的回收方法 (Alloy recovery method ) 是由 李德坤 于 2018-06-29 设计创作，主要内容包括：本发明涉及金属处理领域,公开了一种合金的回收方法,包括如下步骤：a.机械破碎锆基非晶合金回收料,将回收料的尺寸控制在1-5cm；b.酸洗破碎后的回收料,然后超声波水洗至回收料1-2小时；c.在清洗液中超声清洗酸洗后的回收料,然后水洗至回收料,烘干；d.在清洗烘干后的回收料中添加亲氧性元素后在惰性气氛中熔炼；e.利用泡沫陶瓷过滤器过滤经步骤d处理后的回收料熔液；f.过滤后的回收料熔液在真空或惰性气氛下冷却、成型。(The invention relates to the field of metal treatment, and discloses an alloy recovery method, which comprises the following steps: a. mechanically crushing the zirconium-based amorphous alloy reclaimed material, and controlling the size of the reclaimed material to be 1-5 cm; b. pickling the crushed reclaimed materials, and then ultrasonically washing the reclaimed materials for 1 to 2 hours; c. ultrasonically cleaning the reclaimed materials after the acid cleaning in a cleaning solution, then washing the reclaimed materials with water, and drying; d. adding an oxophilic element into the cleaned and dried reclaimed material, and then smelting in an inert atmosphere; e. d, filtering the reclaimed material melt processed in the step d by using a foamed ceramic filter; f. and cooling and molding the filtered reclaimed material melt in vacuum or inert atmosphere.)

1. A method for recycling an alloy, characterized by comprising the steps of:

a. mechanically crushing the zirconium-based amorphous alloy reclaimed material, and controlling the size of the reclaimed material to be 1-5 cm;

b. pickling the crushed reclaimed materials, and then ultrasonically washing the reclaimed materials for 1 to 2 hours;

c. ultrasonically cleaning the reclaimed materials after the acid cleaning in a cleaning solution, then washing the reclaimed materials with water, and drying;

d. adding an oxophilic element into the cleaned and dried reclaimed material, and then smelting in an inert atmosphere;

e. d, filtering the reclaimed material melt processed in the step d by using a foamed ceramic filter;

f. and cooling and molding the filtered reclaimed material melt in vacuum or inert atmosphere.

2. A method of recycling an alloy according to claim 1, wherein: the acid washing adopts citric acid, oxalic acid, phosphoric acid, formic acid and acetic acid solution.

3. A method of recycling an alloy according to claim 1, wherein: the cleaning solution consists of alkaline solution and surfactant, the alkaline solution can be selected from 1 or more of sodium hydroxide, sodium carbonate, sodium phosphate, sodium silicate and sodium pyrophosphate, wherein the addition amount of the solid is 10-25 weight percent; the surfactant can be selected from 1 or more of sodium fatty alcohol polyoxyethylene ether sulfate, sodium dodecyl benzene sulfonate and sodium butyl naphthalene sulfonate, and the content of the surfactant accounts for 5-20 weight percent of the cleaning solution.

4. A method of recycling an alloy according to claim 1, wherein: the oxygen affinity element is preferably one or a mixture of Nd, Gd, Er, Sc and Y.

5. A method of recycling an alloy according to claim 1, wherein: the addition amount of the aerophilic element is 0.05-0.1% of the weight of the reclaimed material.

6. A method of recycling an alloy according to claim 1, wherein: the flow of the high-purity inert gas injected at the bottom of the smelting furnace is 0.001-0.05m³In terms of a/minute.

7. A method of recycling an alloy according to claim 1, wherein: the foamed ceramic filter is a zirconia foamed ceramic filter, and the pore size is 5-20 PPI.

8. A method of recycling an alloy according to claim 1, wherein: the foamed ceramic filter is a silicon carbide foamed ceramic filter, and the pore size is 5-20 PPI.

9. A method of recycling an alloy according to claim 1, wherein: the foamed ceramic filter is formed by compounding two layers of foamed ceramics which are made of the same materials and have different pore diameters, wherein the pore diameter of the upper layer of foamed ceramic is 5-10PPI, and the pore diameter of the lower layer of foamed ceramic is 20-50 PPI.

Technical Field

The invention relates to the field of metal treatment, in particular to a method for recovering an alloy.

Background

Amorphous alloys have received great attention for their high hardness, high strength, self-sharpening, high fracture toughness and excellent corrosion resistance due to their amorphous special structure. At present, more and more amorphous alloy systems are developed and applied, such as iron-based amorphous alloy, zirconium-based amorphous alloy, cobalt-based amorphous alloy, aluminum-based amorphous alloy and the like, wherein the zirconium-based amorphous alloy has high amorphous forming capability and good casting performance, and is widely applied in the fields of consumer electronics, medical devices, automobile industry, military industry and the like.

The zirconium-based amorphous alloy system has good amorphous forming capability, such as a Zr-Al-Ni-Cu quaternary alloy system, a Zr-Ti-Ni-Cu-Be quinary alloy system and the like, and can Be prepared by utilizing a traditional casting process at a low cooling rate. The preparation process of the zirconium-based amorphous alloy has strict requirements, and the purity of the component elements is very high except that the process needs to be strictly controlled, such as higher vacuum degree (preferably more than 10 < -3 > Pa) is required. Generally speaking, the purity of the raw material components of the zirconium-based amorphous alloy needs to be more than 99.9at%, the oxygen content in the raw material needs to be strictly controlled to be less than 0.025wt%, and the whole process of the smelting preparation process needs to be protected by high-purity inert gas. Such strict process and raw material limitations make the zirconium-based amorphous alloy product very costly. Meanwhile, once a defective product appears in the casting process, the product cannot be used any more and can only be discarded due to the exceeding of oxygen content and external pollution. How to effectively recycle the zirconium-based amorphous alloy to ensure that the recycled material of the alloy reaches the purity of the raw material grade again is a very important research.

For example, CN200910221643.8 discloses a method for recycling zirconium-based amorphous alloy scrap, which comprises mixing the zirconium-based amorphous alloy scrap with pure zirconium and yttrium oxide in a certain proportion, and then melting and cooling the mixture to remove oxygen in the scrap, thereby achieving the purpose of recycling the amorphous alloy.

Although the above-mentioned solutions can reduce the oxygen content in the zirconium-based amorphous alloy to a certain extent, they are still insufficient for improving the quality of the recovered zirconium-based amorphous alloy to a reusable purity level.

Disclosure of Invention

In order to solve the defects of the prior art, the invention provides an alloy recovery method, which not only can greatly reduce the oxygen content in the zirconium-based amorphous alloy, but also can remove impurities in the alloy so as to ensure that the zirconium-based amorphous alloy can achieve the purity capable of being reused. Meanwhile, the process method is simple, practical and easy to operate, and is suitable for popularization and application.

The technical problem to be solved by the invention is realized by the following technical scheme:

a method for recycling an alloy, characterized by comprising the steps of:

a. mechanically crushing the zirconium-based amorphous alloy reclaimed material, and controlling the size of the reclaimed material to be 1-5 cm;

the shape and size of the zirconium-based amorphous alloy reclaimed material which can be used for removing oxygen and impurities by using the method are not limited, and the zirconium-based amorphous alloy reclaimed material can comprise defective products generated in the amorphous alloy smelting process, defective products generated in the amorphous alloy product casting process and the like, and is not limited to the two types. The reclaimed materials are crushed by mechanical equipment, so that the reclaimed materials are convenient to carry and move among processes in the recovery process, the standardization of equipment, the using amount of cleaning liquid and process conditions in the subsequent process is facilitated, and the conditions of the subsequent process do not need to be changed frequently for reclaimed materials in different states. The mechanical equipment for crushing can be common crushing equipment, such as hammer crusher and roller crusher. The long-term practice of the inventor shows that the requirement can be met just by crushing the reclaimed materials to 1-5cm, which is beneficial to the subsequent processes.

b. Pickling the crushed reclaimed materials, and then ultrasonically washing the reclaimed materials for 1 to 2 hours;

the main element zirconium in the zirconium-based amorphous alloy is easy to react with oxygen, so that oxide is generated on the surface of the alloy. Most of the recycled materials are not processed by a subsequent process, the surface is rough, the surface oxidation and rusting are frequently caused due to the storage time, and iron impurities and iron rust which are brought into crushing equipment inevitably can be generated in the alloy recycled materials after the crushing in the step (1). Therefore, a pickling step is highly necessary, which can not only remove iron and oxides but also clean the surface of the recyclates. Strong acid can cause the dissolution of alloy elements, so the strong acid is not suitable for the acid washing step of the zirconium-based amorphous alloy, and the strong acid is suitable among citric acid, oxalic acid, phosphoric acid, formic acid, acetic acid and the like. The reclaimed materials need to be washed by water after the acid washing until no residue is left on the surface, so as to avoid acid corrosion of the amorphous alloy.

c. Ultrasonically cleaning the reclaimed materials after the acid cleaning in a cleaning solution, then washing the reclaimed materials with water, and drying;

the ultrasonic cleaning in the cleaning solution aims at removing oil and degreasing, can effectively clean oil stains on the surface of the reclaimed material, and can further avoid acid residues in the step (2), and the cleaning solution can be a commercially available cleaning solution. Through a large number of experiments and practices of the inventor, the cleaning solution in the invention adopts the combination of alkaline solution and surfactant, the alkaline solution can be selected from 1 or more aqueous solutions of sodium hydroxide, sodium carbonate, sodium phosphate, sodium silicate and sodium pyrophosphate, wherein the addition amount of solids is 10-25 weight percent; the surfactant can be selected from 1 or more of sodium fatty alcohol polyoxyethylene ether sulfate, sodium dodecyl benzene sulfonate and sodium butyl naphthalene sulfonate, and the content of the surfactant accounts for 5-20 weight percent of the cleaning solution. The composition, concentration and content of the surfactant of the alkaline solution are determined according to the conditions of different amorphous alloy reclaimed materials, for example, if the reclaimed materials are heavy in oil stain on the surface, the pH value of the alkaline solution can be increased or the content of the surfactant can be increased in a proper amount; if the aluminum content in the main component of the recovered material is high, sodium hydroxide is not suitable. The time of ultrasonic cleaning is determined according to the dirt condition of the surface of the reclaimed material, and if the dirt is too heavy, the time of ultrasonic cleaning can be prolonged or the ultrasonic cleaning step can be repeated for a plurality of times.

The water used in the acid washing and the ultrasonic cleaning can be tap water, or deionized water or distilled water, and has no obvious influence on the recovery effect.

d. Adding an oxophilic element into the cleaned and dried reclaimed material, and then smelting in an inert atmosphere;

in the forming process of the component of the zirconium-based amorphous alloy, if the oxygen content in the melt is high, the forming ability is low, and the brittleness of the obtained amorphous alloy component is increased. Meanwhile, stable endogenous oxide inclusions are easily formed in an alloy melt with high oxygen content, and the existence of the inclusions not only affects the macroscopic quality of an alloy product, such as appearance, strength and the like, but also often becomes a heterogeneous nucleation core in the forming process, so that the crystallization phenomenon is caused, and the formation of amorphous alloy is affected. In addition, the existing amorphous alloy smelting mostly adopts an oxide ceramic crucible, and because the activity of the zirconium-based amorphous alloy melt at high temperature is high, the crucible is easy to corrode, so that part of oxide ceramic particles forming the crucible enter the alloy melt to form foreign impurities. Therefore, how to remove oxygen and impurities is the most important problem for the reclaimed zirconium-based amorphous alloy.

In the invention, firstly, a proper amount of oxophilic element is added into the reclaimed materials, wherein the oxophilic element is one or a mixture of more than one of lanthanide and Y, Sc, and further preferably one or a mixture of more than one of Nd, Gd, Er, Sc and Y, and the addition amount of the oxophilic element is 0.05-0.1% of the weight of the reclaimed materials. After the addition of the oxophilic element, the oxophilic element can be actively combined with oxygen in the alloy melt in the smelting process to generate corresponding oxides, and the oxides are generally micron-sized particles and are easy to agglomerate in the amorphous melt to form larger impurity particles. Part of the oxophilic elements which do not form oxides can be preserved in the melt, and the lanthanide elements and Y, Sc are excellent additive elements in the process of forming the amorphous alloy, thereby being beneficial to the formation of the amorphous alloy and the improvement of macroscopic mechanical properties.

e. D, filtering the reclaimed material melt processed in the step d by using a foamed ceramic filter;

after the oxygen removal in the step (4), only residual particle impurities in the zirconium-based amorphous alloy melt can be filtered by using a ceramic foam filter, the pore size of the ceramic foam filter is preferably selected to be 5-20PPI, and a commercially available ceramic foam filter can be used. The foamed ceramic filter not only can filter larger impurities in the melt, but also has good adsorption effect on micro impurities, and can achieve the purpose of excellently removing the impurities in the amorphous alloy reclaimed material melt.

In the invention, a zirconium oxide ceramic foam filter can be preferably used, the zirconium oxide ceramic foam filter not only has high melting point, low enthalpy of formation and good chemical stability, but also has the most important that the zirconium oxide ceramic foam filter does not cause secondary pollution to the recovery of the zirconium-based amorphous alloy and does not introduce other impurity elements in the filtering process. Similarly, a silicon carbide ceramic filter is also preferred, and has high inertia and good stability, higher strength and better impact resistance. Furthermore, a foamed ceramic filter compounded by two layers of foamed ceramics made of the same material and having different pore diameters can be adopted, wherein the pore diameter of the upper layer of foamed ceramic is 5-10PPI, and the pore diameter of the lower layer of foamed ceramic is 20-50 PPI. The bigger granule can be filtered to the great foamed ceramic of upper pore diameter, and the slightly littleer foamed ceramic of lower floor's aperture filters more fine and close mingled with granule, and two-layer combined filtration can promote filtration efficiency. The foamed ceramic filter can be produced by adopting a common foamed ceramic production process, and the details are not repeated herein.

f. And cooling and molding the filtered reclaimed material melt in vacuum or inert atmosphere.

The invention has the following beneficial effects:

1. the oxygen content in the zirconium-based amorphous alloy is greatly reduced, and the oxygen removal rate can reach 95%.

2. Can remove impurities in the zirconium-based amorphous alloy, and enables the recycled zirconium-based amorphous alloy to reach the purity capable of being reused.

3. The process method is simple, practical and easy to operate, and is suitable for popularization and application.

Detailed Description

The components of the zirconium-based amorphous alloy which can Be recycled by the method of the invention are not limited, such as Zr-Al-Ni-Cu quaternary alloy, Zr-Al-Ti-Ni-Be quinary alloy and the like, and the recycled materials for treatment can Be unqualified smelting products, unqualified machining products, unqualified casting products or zirconium-based amorphous alloy products with high oxygen content and impurities, which are not limited.