WO2016112507A1

WO2016112507A1 - Watch case of amorphous alloy, watch and manufacturing method therefor

Info

Publication number: WO2016112507A1
Application number: PCT/CN2015/070713
Authority: WO
Inventors: 李奉珪
Original assignee: 东莞帕姆蒂昊宇液态金属有限公司
Priority date: 2015-01-14
Filing date: 2015-01-14
Publication date: 2016-07-21

Abstract

A watch case of amorphous alloy, a watch and a manufacturing method therefor. The watch case is made of zirconium-based amorphous alloy, copper-based amorphous alloy, titanium-based amorphous alloy, nickel-based amorphous alloy or iron-based amorphous alloy. The watch case has Vickers hardness of 400-600, yield strength of 1000-3000MPa, Nickel release of 0-0.015mg/cm 2/week. There is no corrosion on the surface of the watch case after a salt-mist test for 340-480 hours. The manufacturing method for the watch case is processing amorphous alloy raw material with die-casting molding, machining and/or thermoplastic forming or quick discharge forming, in coordination with surface treatment to prepare the amorphous alloy watch case. The amorphous alloy watch case obtained has the properties of high quality, high strength, scratching resistance, corrosion resistance and not easy to catch irritability for human skin.

Description

一种非晶合金手表外壳及手表及其制造方法Amorphous alloy watch case and watch and manufacturing method thereof

技术领域Technical field

本发明涉及非晶合金的应用技术领域，特别是涉及一种非晶合金手表外壳及手表及其制造方法。The invention relates to the technical field of application of amorphous alloys, in particular to an amorphous alloy watch case and a watch and a manufacturing method thereof.

背景技术Background technique

近年来，手表外壳的珍贵性、功能性备受瞩目，智能手表的出世将会使这种以性能为主的应用方式越来越广泛。In recent years, the preciousness and functionality of the watch case have attracted attention, and the birth of smart watches will make this performance-based application more and more widely.

目前，关于手表外壳的材质，比较常见的有：不锈钢表壳、陶瓷表壳、钛合金表壳、白金表壳、玫瑰金表壳、铂金表壳、精钢表壳、镀金表壳、黄铜表壳、青铜表壳、钨钢表壳、铝质表壳、铜表壳、锌合金表壳、塑料表壳等；不太常见的还有：木质表壳、铁表壳、纤维表壳、纯银表壳、纯金或K金表壳等。上述材质的手表外壳均存在表面硬度低，容易被刮伤或受外部冲击而变形，且外观容易褪色的缺点。另外，部分材质的手表外壳还存在因汗液或外界因素的腐蚀而使用寿命短的缺陷。At present, the material of the watch case is more common: stainless steel case, ceramic case, titanium case, white gold case, rose gold case, platinum case, steel case, gold-plated case, brass Case, bronze case, tungsten steel case, aluminum case, copper case, zinc alloy case, plastic case, etc.; less common are: wooden case, iron case, fiber case, Sterling silver case, pure gold or K gold case. The watch case of the above materials has the disadvantages of low surface hardness, easy to be scratched or deformed by external impact, and the appearance is easily faded. In addition, the watch case of some materials also has the defect of short service life due to corrosion of sweat or external factors.

另外，现有技术中的手表外壳或手表，多存在镍释放量大的问题。镍是一种容易导致接触性过敏的元素。镍元素通过一些含镍材料的释放并长期与皮肤接触后会被皮肤吸收，从而对部分个体导致过敏；进一步暴露在可溶性镍盐中会导致国民性接触性过敏。据统计，20％的人对镍有很明显的过敏反应症状。如利用钛合金或不锈钢材质制造的手表外壳或手表，均会释放镍，且镍释放量较大，容易使配戴者造成皮肤过敏。In addition, in the watch case or the wristwatch of the prior art, there is a problem that the amount of nickel released is large. Nickel is an element that easily causes contact allergy. Nickel is caused by the release of some nickel-containing materials and is absorbed by the skin after prolonged contact with the skin, thereby causing allergies to some individuals; further exposure to soluble nickel salts can lead to national contact allergy. According to statistics, 20% of people have obvious allergic reactions to nickel. For example, a watch case or watch made of titanium alloy or stainless steel will release nickel, and the release of nickel is large, which may cause skin irritation to the wearer.

另外，现有技术中的部分手表外壳或手表，由于含有带毒性的铍元素，在长期配戴的过程中会释放出带毒性的铍而渗透到配戴者的皮肤中，从而对人体健康不利。In addition, some watch cases or watches in the prior art, due to the presence of toxic strontium elements, release toxic sputum during long-term wear and penetrate into the wearer's skin, thereby being detrimental to human health. .

手表外壳一般以功能性、实用性、加工性等为优先考虑因素而设计并制造的表壳。现有技术中，手表外壳的制造多采用CNC(数控机床)进行加工制造。少部分手表外壳是通过手工加工的方式以制造出高价、奢侈的产品。现有技术采用CNC进行加工制造手表外壳的方式，存在机械加工量大、加工时间长、生产效率低且生产成本高的缺点。现有技术通过手工加工制造手表外壳的方式，存在生产效率低、市场需求小、难以产业化的缺点。The watch case is generally designed and manufactured with the functional, practical, and processability as a priority. In the prior art, the manufacture of the watch case is mostly manufactured by CNC (CNC machine tool). A small number of watch cases are manufactured by hand to create high-priced, extravagant products. The prior art adopts the CNC to process the manufacturing of the watch case, and has the disadvantages of large machining volume, long processing time, low production efficiency, and high production cost. In the prior art, a method of manufacturing a watch case by hand processing has the disadvantages of low production efficiency, small market demand, and difficulty in industrialization.

发明内容Summary of the invention

本发明的目的之一在于针对现有技术中的不足之处而提供一种表面硬度高、不易刮伤或变形、且外观不易褪色的非晶合金手表外壳。One of the objects of the present invention is to provide a surface hardness high and difficult to address the deficiencies in the prior art. Amorphous alloy watch case that is scratched or deformed and has a non-fading appearance.

本发明的目的之二在于针对现有技术中的不足之处而提供一种非晶合金手表，该非晶合金手表的外壳具有表面硬度高、不易刮伤或变形、且外观不易褪色的优点。A second object of the present invention is to provide an amorphous alloy wristwatch having an advantage of high surface hardness, being less likely to be scratched or deformed, and having an appearance that is not easily faded, in view of deficiencies in the prior art.

本发明的目的之三在于针对现有技术中的不足之处而提供一种机械加工量小、加工时间短、生产效率高且生产成本低的非晶合金手表外壳的制造方法。A third object of the present invention is to provide a method for manufacturing an amorphous alloy watch case having a small amount of machining, a short processing time, high production efficiency, and low production cost in view of the deficiencies in the prior art.

为达到上述目的之一，本发明通过以下技术方案来实现。In order to achieve the above object, the present invention is achieved by the following technical solutions.

提供一种非晶合金手表外壳，所述手表外壳是采用锆基非晶合金、铜基非晶合金、钛基非晶合金、镍基非晶合金或铁基非晶合金而制造的非晶合金手表外壳，其中所述非晶合金手表外壳包括智能手表外壳和传统手表外壳；Provided is an amorphous alloy watch case, which is an amorphous alloy made of a zirconium-based amorphous alloy, a copper-based amorphous alloy, a titanium-based amorphous alloy, a nickel-based amorphous alloy or an iron-based amorphous alloy. a watch case, wherein the amorphous alloy watch case comprises a smart watch case and a conventional watch case;

所述锆基非晶合金包括Zr-Cu-(Ni/Co)-Al+(Nb/Ti/Sn)系合金、Zr-Cu-Ni-Co-Al+(Nb/Ti/Sn)系合金；所述铜基非晶合金包括Cu-Ti-Zr-(Ni/Co)+(Sn)系合金、Cu-Ti-Zr-Ni-Co+(Sn)系合金。The zirconium-based amorphous alloy includes a Zr-Cu-(Ni/Co)-Al+(Nb/Ti/Sn)-based alloy, and a Zr-Cu-Ni-Co-Al+(Nb/Ti/Sn)-based alloy; The copper-based amorphous alloy includes a Cu-Ti-Zr-(Ni/Co)+(Sn)-based alloy and a Cu-Ti-Zr-Ni-Co+(Sn)-based alloy.

优选的，所述Zr-Cu-(Ni/Co)-Al+(Nb/Ti/Sn)系锆基非晶合金的原子百分比为：Zr(50～60)-Cu(12～20)-(Ni/Co)(10～15)-Al(7～15)+(Nb/Ti/Sn)(2～8)；Preferably, the atomic percentage of the Zr-Cu-(Ni/Co)-Al+(Nb/Ti/Sn)-based zirconium-based amorphous alloy is: Zr(50-60)-Cu(12-20)-(Ni /Co)(10~15)-Al(7~15)+(Nb/Ti/Sn)(2~8);

所述Zr-Cu-Ni-Co-Al+(Nb/Ti/Sn)系锆基非晶合金的原子百分比为：Zr(50～60)-Cu(12～20)-Ni(3～8)-Co(6～10)-Al(7～15)+(Nb/Ti/Sn)(2～8)；The atomic percentage of the Zr-Cu-Ni-Co-Al+(Nb/Ti/Sn)-based zirconium-based amorphous alloy is: Zr(50-60)-Cu(12-20)-Ni(3-8)- Co(6～10)-Al(7～15)+(Nb/Ti/Sn)(2～8);

所述Cu-Ti-Zr-(Ni/Co)+(Sn)系铜基非晶合金的原子百分比为：Cu(40～45)-Ti(30～40)-Zr(7～15)-(Ni/Co)(5～12)+(Sn)(2～8)；The atomic percentage of the Cu-Ti-Zr-(Ni/Co)+(Sn) copper-based amorphous alloy is: Cu(40-45)-Ti(30-40)-Zr(7-15)-( Ni/Co) (5 to 12) + (Sn) (2 to 8);

所述Cu-Ti-Zr-Ni-Co+(Sn)系铜基非晶合金的原子百分比为：Cu(40～45)-Ti(30～40)-Zr(7～15)-Ni(2～6)-Co(3～6)+(Sn)(2～8)。The atomic percentage of the Cu-Ti-Zr-Ni-Co+(Sn)-based copper-based amorphous alloy is: Cu(40-45)-Ti(30-40)-Zr(7-15)-Ni(2~ 6) - Co (3 ~ 6) + (Sn) (2 ~ 8).

更为优选的，所述Zr-Cu-(Ni/Co)-Al+(Nb/Ti/Sn)系锆基非晶合金的原子百分比为：Zr(54.75)-Cu(16.65)-(Ni/Co)(13.6)-Al(10)+(Nb/Ti/Sn)(5)；More preferably, the atomic percentage of the Zr-Cu-(Ni/Co)-Al+(Nb/Ti/Sn)-based zirconium-based amorphous alloy is: Zr(54.75)-Cu(16.65)-(Ni/Co (13.6)-Al(10)+(Nb/Ti/Sn)(5);

所述Zr-Cu-Ni-Co-Al+(Nb/Ti/Sn)系锆基非晶合金的原子百分比为：Zr(54.75)-Cu(16.65)-Ni(5.6)-Co(8)-Al(10)+(Nb/Ti/Sn)(5)；The atomic percentage of the Zr-Cu-Ni-Co-Al+(Nb/Ti/Sn)-based zirconium-based amorphous alloy is: Zr(54.75)-Cu(16.65)-Ni(5.6)-Co(8)-Al (10) + (Nb / Ti / Sn) (5);

所述Cu-Ti-Zr-(Ni/Co)+(Sn)系铜基非晶合金的原子百分比为：Cu(42)-Ti(34)-Zr(11)-(Ni/Co)(8)+(Sn)(5)；The atomic percentage of the Cu-Ti-Zr-(Ni/Co)+(Sn)-based copper-based amorphous alloy is: Cu(42)-Ti(34)-Zr(11)-(Ni/Co)(8 )+(Sn)(5);

所述Cu-Ti-Zr-Ni-Co+(Sn)系铜基非晶合金的原子百分比为：Cu(42)-Ti(34)-Zr(11)-Ni(3)-Co(5)+(Sn)(5)。The atomic percentage of the Cu-Ti-Zr-Ni-Co+(Sn)-based copper-based amorphous alloy is: Cu(42)-Ti(34)-Zr(11)-Ni(3)-Co(5)+ (Sn) (5).

所述非晶合金手表外壳的维氏硬度为400～600，降伏强度为1000MPa～3000MPa，镍释放量为0mg/cm²/week～0.015mg/cm²/week，经受340小时～480小时的盐雾测试后其表面仍然良好无腐蚀。The amorphous alloy wristwatch case a Vickers hardness of 400 to 600, yield strength of 1000MPa ~ 3000MPa, nickel release of ^{^{0mg / cm 2 /week~0.015mg/cm 2 / week}} , subjected to 340 hours to 480 hours salt After the fog test, the surface was still good and non-corrosive.

所述非晶合金手表外壳的厚度为0.5mm～3mm。The amorphous alloy watch case has a thickness of 0.5 mm to 3 mm.

所述非晶合金手表外壳包括表壳、表盘和后盖；所述表壳和/或所述表盘和/或所述后盖采用所述锆基非晶合金、所述铜基非晶合金、所述钛基非晶合金、所述镍基非晶合金或所述铁基非晶合金而制造。The amorphous alloy watch case includes a watch case, a dial and a back cover; the case and/or the dial and/or the back cover adopt the zirconium-based amorphous alloy, the copper-based amorphous alloy, The titanium-based amorphous alloy, the nickel-based amorphous alloy, or the iron-based amorphous alloy is produced.

为达到上述目的之二，本发明通过以下技术方案来实现。In order to achieve the above object, the present invention is achieved by the following technical solutions.

提供一种非晶合金手表，所述非晶合金手表包括上述所述的非晶合金手表外壳。An amorphous alloy watch is provided, the amorphous alloy watch comprising the amorphous alloy watch case described above.

为达到上述目的之三，本发明通过以下技术方案来实现。In order to achieve the above third object, the present invention is achieved by the following technical solutions.

提供一种非晶合金手表外壳的制造方法，在真空状态或惰性气氛的保护下，利用锆基非晶合金、铜基非晶合金、钛基非晶合金、镍基非晶合金或铁基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳。Providing a method for manufacturing an amorphous alloy watch case, using a zirconium-based amorphous alloy, a copper-based amorphous alloy, a titanium-based amorphous alloy, a nickel-based amorphous alloy or an iron-based non-protection under vacuum or an inert atmosphere The raw material of the crystal alloy is prepared by a die-casting method to prepare an amorphous alloy watch case.

进一步的，在真空状态或惰性气氛的保护下，利用锆基非晶合金、铜基非晶合金、钛基非晶合金、镍基非晶合金或铁基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳，包括如下步骤：Further, under the protection of a vacuum state or an inert atmosphere, a raw material of a zirconium-based amorphous alloy, a copper-based amorphous alloy, a titanium-based amorphous alloy, a nickel-based amorphous alloy or an iron-based amorphous alloy is prepared by a die-casting method. The amorphous alloy watch case includes the following steps:

步骤一，投料：将非晶合金原材料放入立式或卧式压铸机的供料装置，并由所述供料装置投入到立式或卧式压铸机的熔融装置中；Step one, feeding: placing the amorphous alloy raw material into the feeding device of the vertical or horizontal die casting machine, and inputting the feeding device into the melting device of the vertical or horizontal die casting machine;

步骤二，熔融：利用感应加热的方式将非晶合金原材料熔融并形成熔汤，所述熔汤的温度为900℃～1200℃；Step two, melting: using an induction heating method to melt the amorphous alloy raw material and forming a melt, the temperature of the melt is 900 ° C ~ 1200 ° C;

步骤三，倒汤：将步骤二得到的熔汤倒入手表外壳模具浇口套中，然后以冲头将熔汤注入手表外壳模具中；其中，冲头的速度为0.1m/s～5m/s；手表外壳模具的温度为200℃～250℃；Step 3: Pour the soup: pour the molten soup obtained in the second step into the mold cover of the watch case, and then inject the molten soup into the mold of the watch case with a punch; wherein the speed of the punch is 0.1 m/s to 5 m/ s; the temperature of the watch case mold is 200 ° C ~ 250 ° C;

步骤四，冷却：对步骤三中注入了熔汤的手表外壳模具进行冷却成型，得到非晶合金手表外壳，冷却速度为10⁰K/s～10⁶K/s；冷却时间为15秒～30秒；Step 4, cooling: cooling the watch case mold into which the molten soup is poured in the third step, and obtaining an amorphous alloy watch case, the cooling rate is 10 ⁰ K/s to 10 ⁶ K/s; the cooling time is 15 seconds to 30. second;

步骤五，产品取出：利用产品取出装置接住由手表外壳模具顶出的非晶合金手表外壳后再输送到产品出口，得到非晶合金手表外壳。Step 5, the product is taken out: the amorphous alloy watch case that is ejected from the mold of the watch case is caught by the product take-out device, and then transported to the product outlet to obtain an amorphous alloy watch case.

上述技术方案中，所述步骤一中，所述立式或卧式压铸机的真空度为10^-1torr～10^-3torr。In the above technical solution, in the first step, the vacuum degree of the vertical or horizontal die casting machine is 10 ^-1 torr to 10 ^-3 torr.

上述技术方案中，所述步骤三中，所述倒汤过程中，利用喷枪向所述手表外壳模具表面喷射惰性气氛以达到清洁所述手表外壳模具表面的熔汤碎屑的目的。In the above technical solution, in the step (3), during the pouring process, an inert atmosphere is sprayed onto the surface of the watch casing mold by using a spray gun to achieve the purpose of cleaning the melted chips on the surface of the watch outer casing mold.

上述技术方案中，所述步骤五后，还包括步骤六，将步骤五得到的非晶合金手表外壳进行切割浇铸口和溢流口。In the above technical solution, after the step 5, the method further includes the step 6 and the amorphous alloy watch obtained in the step 5 The outer casing cuts the casting port and the overflow port.

上述技术方案中，对所述步骤六中完成切割浇铸口和溢流口的非晶合金手表外壳，进行机加工以达到结构和精度的要求；In the above technical solution, the amorphous alloy watch case which cuts the casting port and the overflow port in the step 6 is machined to meet the requirements of structure and precision;

或，进行热塑成型(TPF)以达到结构、精度和表面品质的要求；Or, perform thermoforming (TPF) to achieve structural, precision, and surface quality requirements;

或，进行快速放电成型(RDF)以达到结构、精度和表面品质的要求；Or, perform rapid discharge molding (RDF) to achieve structural, precision, and surface quality requirements;

或，进行机加工以达到结构和精度的要求，然后进行热塑成型(TPF)以达到结构、精度和表面品质的要求；Or, machining to achieve structural and precision requirements, followed by thermoforming (TPF) to achieve structural, precision, and surface quality requirements;

或，进行机加工以达到结构和精度的要求，然后进行快速放电成型(RDF)以达到结构、精度和表面品质的要求；Or, machining to achieve structural and precision requirements, followed by rapid discharge forming (RDF) to achieve structural, precision, and surface quality requirements;

或，进行机加工以达到结构和精度的要求，然后进行热塑成型(TPF)和快速放电成型(RDF)以达到结构、精度和表面品质的要求。Or, machining to achieve structural and precision requirements, followed by thermoplastic forming (TPF) and rapid discharge forming (RDF) to achieve structural, precision and surface quality requirements.

上述技术方案中，在对所述非晶合金手表外壳进行机加工、热塑成型(TPF)和快速放电成型(RDF)的过程中，使用惰性气体或氮气对所述非晶合金手表外壳进行保护。In the above technical solution, the amorphous alloy watch case is protected by inert gas or nitrogen during machining, thermoforming (TPF) and rapid discharge forming (RDF) of the amorphous alloy watch case. .

上述技术方案中，对所述非晶合金手表外壳进行滚筒研磨和/或磁力研磨和/或抛光处理和/或拉丝处理和/或喷砂处理和/或PVD处理和/或喷涂处理。In the above technical solution, the amorphous alloy watch case is subjected to barrel grinding and/or magnetic grinding and/or polishing treatment and/or wire drawing treatment and/or sandblasting treatment and/or PVD treatment and/or spray treatment.

本发明的有益效果：The beneficial effects of the invention:

(1)本发明提供的一种非晶合金手表外壳，由于是采用锆基非晶合金、铜基非晶合金、钛基非晶合金、镍基非晶合金或铁基非晶合金而制造的非晶合金手表外壳，使得所制造的非晶合金手表外壳具有高精品质感、高强度、耐刮、抗腐蚀、人体皮肤不产生过敏反应的性能，即具有表面硬度高、不易刮伤或变形、外观不易褪色、且不易受汗液或外界因素而腐蚀的优点；其中，该非晶合金手表外壳的维氏硬度为400～600，降伏强度为1000MPa～3000MPa，经受340小时～480小时的盐雾测试后其表面仍然良好无腐蚀。(1) An amorphous alloy watch case provided by the present invention is manufactured by using a zirconium-based amorphous alloy, a copper-based amorphous alloy, a titanium-based amorphous alloy, a nickel-based amorphous alloy or an iron-based amorphous alloy. The amorphous alloy watch case makes the amorphous alloy watch case have high-quality texture, high strength, scratch resistance, corrosion resistance, and the skin does not produce allergic reaction, that is, it has high surface hardness, is not easy to scratch or deform, The appearance is not easy to fade, and is not easily corroded by sweat or external factors; wherein, the amorphous alloy watch case has a Vickers hardness of 400 to 600, a relief strength of 1000 MPa to 3000 MPa, and a salt spray test of 340 hours to 480 hours. After that the surface is still good and non-corrosive.

(2)本发明提供的一种非晶合金手表外壳，由于采用不含或只含极少量镍元素锆基非晶合金、铜基非晶合金、钛基非晶合金、镍基非晶合金或铁基非晶合金制造非晶合金手表外壳，使得所制造的非晶合金手表外壳的镍释放量为0mg/cm²/week～0.015mg/cm²/week，即无镍释放或镍释放量极小，当镍释放量为0.015mg/cm2/week，该镍释放量相当于利用不锈钢制备的手表外壳的镍释放量的1/10；而且，镍释放量为0.015mg/cm2/week以下，能够使得配戴者长时间配戴而不发生镍过敏反应。(2) An amorphous alloy watch case provided by the present invention adopts a zirconium-based amorphous alloy containing no or only a small amount of nickel element, a copper-based amorphous alloy, a titanium-based amorphous alloy, a nickel-based amorphous alloy or Fe-based amorphous alloy for producing the amorphous alloy wristwatch case, wristwatch case such that the amorphous alloy produced nickel release of ^{^{0mg / cm 2 /week~0.015mg/cm 2 / week}} , i.e., no release of nickel or a nickel electrode release Small, when the amount of nickel released is 0.015 mg/cm2/week, the amount of nickel released is equivalent to 1/10 of the amount of nickel released from the watch case made of stainless steel; and the amount of nickel released is 0.015 mg/cm2/week or less. Allows the wearer to wear for a long time without a nickel allergic reaction.

(3)本发明提供的一种非晶合金手表外壳，所采用的锆基非晶合金、铜基非晶合金、钛基非晶合金、镍基非晶合金或铁基非晶合金由于均不含有铍元素，因此，所制造的非晶合金手表外壳在长期配戴的过程中均不会释放出铍，从而能够避免铍的毒性对皮肤的影响。(3) An amorphous alloy watch case provided by the present invention, which uses a zirconium-based amorphous alloy, a copper-based amorphous alloy, a titanium-based amorphous alloy, a nickel-based amorphous alloy or an iron-based amorphous alloy Containing antimony, the amorphous alloy watch case produced will not release flaws during long-term wear, thus avoiding the effects of barium toxicity on the skin.

(4)本发明提供的一种非晶合金手表外壳，相对于钛合金手表外壳或不锈钢手表外壳，具有耐刮性和光泽度极佳的优点。(4) An amorphous alloy watch case provided by the present invention has an advantage of excellent scratch resistance and glossiness with respect to a titanium alloy watch case or a stainless steel watch case.

(5)本发明提供的一种非晶合金手表外壳的制造方法，由于是利用压铸成型法制造非晶合金手表外壳，相对于现有技术利用CNC(数控机床)进行加工制造手表外壳的方式，具有机械加工量小、加工时间短、生产效率高且生产成本低的优点。其中，由于本发明采用的压铸成型法为连续生产的工艺，该真空压铸的总工艺时间为10分钟，而现有技术利用CNC进行加工的工艺时间却需要1小时以上，因此，本发明提供的非晶合金手表外壳的制造方法能够大大缩短生产加工时间的优点。另外，现有技术利用CNC进行加工手表外壳的生产成本是本发明利用压铸成型法制造非晶合金手表外壳的生产成本的3倍，因此，本发明提供的一种非晶合金手表外壳的制造方法具有能够大大降低生产成本的优点。(5) The method for manufacturing an amorphous alloy watch case provided by the present invention is a method of manufacturing an amorphous alloy watch case by a die-casting method, and manufacturing a watch case by using a CNC (CNC machine tool) in comparison with the prior art. The utility model has the advantages of small machining amount, short processing time, high production efficiency and low production cost. Wherein, since the die casting molding method adopted by the present invention is a continuous production process, the total process time of the vacuum die casting is 10 minutes, and the process time of the prior art processing by using the CNC takes more than 1 hour, and therefore, the present invention provides The manufacturing method of the amorphous alloy watch case can greatly shorten the advantages of production processing time. In addition, the production cost of the watch case by using the CNC in the prior art is three times the production cost of the amorphous alloy watch case manufactured by the die casting method of the present invention, and therefore, the method for manufacturing the amorphous alloy watch case provided by the present invention It has the advantage of being able to greatly reduce production costs.

(6)本发明提供的一种非晶合金手表外壳的制造方法，由于利用压铸成型法来成型非晶合金手表外壳，因此，能够成型精密的结构，并能够避免大量的后续机械加工工序(例如如CNC加工、放电加工)，从而使得本发明能够以相对低的成本成型出精密且高质量的非晶合金手表外壳。(6) A method for manufacturing an amorphous alloy watch case provided by the present invention, since the amorphous alloy watch case is formed by a die-casting method, a precise structure can be formed, and a large number of subsequent machining processes can be avoided (for example, Such as CNC machining, electrical discharge machining, so that the present invention can form a precision and high quality amorphous alloy watch case at a relatively low cost.

(7)本发明提供的一种非晶合金手表外壳的制造方法，由于利用锆基非晶合金、铜基非晶合金、钛基非晶合金、镍基非晶合金或铁基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳，能够使得所制备的非晶合金手表外壳具有优异的表面硬度，因此使得非晶合金手表外壳不易刮伤或变形，且其具有外观不易褪色、不易受汗液或外界因素而腐蚀的优点。(7) A method for manufacturing an amorphous alloy watch case provided by the present invention, which utilizes a zirconium-based amorphous alloy, a copper-based amorphous alloy, a titanium-based amorphous alloy, a nickel-based amorphous alloy or an iron-based amorphous alloy The amorphous alloy watch case is prepared by the die-casting method, which can make the prepared amorphous alloy watch case have excellent surface hardness, so that the amorphous alloy watch case is not easy to be scratched or deformed, and its appearance is not easy to fade and is not easily affected. The advantage of sweat or external factors.

(8)本发明提供的一种非晶合金手表外壳的制造方法，利用锆基非晶合金、铜基非晶合金、钛基非晶合金、镍基非晶合金或铁基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳，具有压铸净成型的优点；且在真空压铸成型的过程中，由于锆基非晶合金、铜基非晶合金、钛基非晶合金、镍基非晶合金或铁基非晶合金不存在液态转固态的相变阶段，因此，锆基非晶合金、铜基非晶合金、钛基非晶合金、镍基非晶合金或铁基非晶合金的缩水率非常低(缩水率仅有0.17％左右)，因此，能够利用锆基非晶合金、铜基非晶合金、钛基非晶合金、镍基非晶合金或铁基非晶合金的原材料通过压铸成型法一次性成型，并且能够省去大量的后续加工工艺，具有易于成型、制备工艺简单，并且适用于大规模生产的优点。(8) A method for manufacturing an amorphous alloy watch case provided by the present invention, which utilizes a raw material of a zirconium-based amorphous alloy, a copper-based amorphous alloy, a titanium-based amorphous alloy, a nickel-based amorphous alloy or an iron-based amorphous alloy The amorphous alloy watch case is prepared by the die-casting method, and has the advantages of die-casting and forming; and in the process of vacuum die-casting, due to zirconium-based amorphous alloy, copper-based amorphous alloy, titanium-based amorphous alloy, and nickel-based amorphous Alloy or iron-based amorphous alloys do not have a liquid-to-solid phase transition phase, therefore, zirconium-based amorphous alloys, copper-based amorphous alloys, titanium-based amorphous alloys, and nickel-based alloys Amorphous alloy or iron-based amorphous alloy has a very low shrinkage rate (shrinkage rate is only about 0.17%), and therefore, a zirconium-based amorphous alloy, a copper-based amorphous alloy, a titanium-based amorphous alloy, a nickel-based amorphous alloy can be utilized. The raw materials of the alloy or the iron-based amorphous alloy are molded at one time by the die-casting method, and a large number of subsequent processing processes can be omitted, and the advantages of easy molding, simple preparation process, and large-scale production are available.

(9)本发明提供的一种非晶合金手表外壳的制造方法，在真空状态或惰性气氛的保护下，是利用锆基非晶合金、铜基非晶合金、钛基非晶合金、镍基非晶合金或铁基非晶合金的原材料通过压铸成型法以及通过机加工和/或热塑成型法(TPF，Thermalplastic Forming)或快速放电成型法(RDF，Rapid Discharge Forming)并配合表面处理制备非晶合金手表外壳，从而使得所制备的非晶合金手表外壳达到最终精度与表面品质要求。由于利用压铸成型法制备非晶合金手表外壳，所制备的非晶合金手表外壳一般多少会存在一些微孔，对步骤六中完成切割浇铸口和溢流口的非晶合金手表外壳，能够通过热塑成型法(TPF，Thermalplastic Forming)或快速放电成型法再进一步加热成型同时使结构更紧密并去除这些微孔。(9) The method for manufacturing an amorphous alloy watch case provided by the present invention is a zirconium-based amorphous alloy, a copper-based amorphous alloy, a titanium-based amorphous alloy, or a nickel base under the protection of a vacuum state or an inert atmosphere. Raw materials of amorphous alloys or iron-based amorphous alloys are prepared by die-casting and by mechanical processing and/or thermoplastic molding (TPF, Thermal Plastic Forming) or Rapid Discharge Forming (RDF). The crystal alloy watch case makes the prepared amorphous alloy watch case meet the final precision and surface quality requirements. Since the amorphous alloy watch case is prepared by the die-casting method, the prepared amorphous alloy watch case generally has some micropores, and the amorphous alloy watch case which cuts the casting port and the overflow port in step 6 can pass the heat. Plastic molding (TPF, Thermalplastic Forming) or rapid discharge molding is further heated to form the structure more tightly and to remove the micropores.

(10)本发明提供的一种非晶合金手表外壳的制造方法，在真空状态或惰性气氛的保护下，利用锆基非晶合金、铜基非晶合金、钛基非晶合金、镍基非晶合金或铁基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳时，步骤三中，在倒汤过程中，直接倒汤完成，利用喷枪向手表外壳模具表面喷射惰性气氛以达到清洁手表外壳模具表面的熔汤碎屑的目的，因为，在倒汤的过程中，会出现少许熔汤溅到手表外壳模具表面的情况而在手表外壳模具表面形成熔汤碎屑，如果不对手表外壳模具表面的熔汤碎屑进行清洁去除，则在后续制程的合模过程中，这些熔汤碎屑容易夹伤手表外壳模具表面，从而损坏手表外壳模具；本发明通过利用喷枪向手表外壳模具表面喷射惰性气氛以达到清洁手表外壳模具表面的熔汤碎屑的目的，从而避免熔汤碎屑夹伤手表模具表面，从而大大延长了手表模具的使用寿命。(10) A method for manufacturing an amorphous alloy watch case provided by the present invention, using a zirconium-based amorphous alloy, a copper-based amorphous alloy, a titanium-based amorphous alloy, or a nickel-based non-ferrous alloy under the protection of a vacuum state or an inert atmosphere When the raw material of the crystal alloy or the iron-based amorphous alloy is prepared by the die-casting method to prepare the amorphous alloy watch case, in the third step, in the process of pouring the soup, the soup is directly poured, and the inert atmosphere of the surface of the watch case is sprayed by the spray gun to achieve cleaning. The purpose of melting the crumb on the surface of the mold of the watch case, because in the process of pouring the soup, a little molten soup will splash on the surface of the mold of the watch case, and melted debris will be formed on the surface of the mold of the watch case, if not on the watch case. The melted chips on the surface of the mold are cleaned and removed, and in the process of clamping in the subsequent process, the melted chips easily pinch the surface of the mold of the watch case, thereby damaging the mold of the watch case; the invention uses the spray gun to face the mold of the watch case Injecting an inert atmosphere to achieve the purpose of cleaning the melted chips on the surface of the mold of the watch case, thereby preventing the melted chips from damaging the watch mold table. The surface thus greatly extends the life of the watch mold.

(11)本发明提供的一种非晶合金手表外壳的制造方法，由于利用锆基非晶合金、铜基非晶合金、钛基非晶合金、镍基非晶合金或铁基非晶合金的原材料通过压铸成型法在制备非晶合金手表外壳时，是在真空状态或惰性气氛的保护下进行的，从而能够避免在制备非晶合金手表外壳的过程中非晶合金发生氧化反应或结晶化反应。(11) A method for manufacturing an amorphous alloy watch case provided by the present invention, which utilizes a zirconium-based amorphous alloy, a copper-based amorphous alloy, a titanium-based amorphous alloy, a nickel-based amorphous alloy or an iron-based amorphous alloy The raw material is processed by a die-casting method in the preparation of an amorphous alloy watch case under the protection of a vacuum state or an inert atmosphere, thereby avoiding oxidation reaction or crystallization reaction of the amorphous alloy in the process of preparing the amorphous alloy watch case. .

附图说明DRAWINGS

图1是本发明的一种非晶合金手表外壳及手表及其制造方法的压铸成型的第一TTT图。 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a first TTT diagram of a die-cast molding of an amorphous alloy watch case and watch of the present invention and a method of manufacturing the same.

图2是本发明的一种非晶合金手表外壳及手表及其制造方法的热塑成型(TPF)的第二TTT图。2 is a second TTT diagram of a thermoplastic molding (TPF) of an amorphous alloy watch case and watch of the present invention and a method of manufacturing the same.

图3是本发明的一种非晶合金手表外壳及手表及其制造方法的快速放电成型(RDF)的第三TTT图。3 is a third TTT diagram of rapid discharge forming (RDF) of an amorphous alloy watch case and watch of the present invention and a method of manufacturing the same.

在图1至图3中包括有：Included in Figures 1 to 3 are:

1——晶化区域、1 - crystallized area,

2——非晶化区域、2 - amorphized area,

3——时间温度曲线、3 - time temperature curve,

Tg——玻璃化转变温度、Tg - glass transition temperature,

T₁——熔融温度、T ₁ - melting temperature,

T_x——结晶温度。T _x - crystallization temperature.

具体实施方式detailed description

为了使本发明所解决的技术问题、技术方案及有益效果更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。In order to make the technical problems, technical solutions and beneficial effects of the present invention more clear, the present invention will be further described in detail below with reference to the embodiments. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

其中，本发明提及的惰性气氛为氮气、氦气、氖气、氩气、氪气或氙气中的一种。Among them, the inert atmosphere mentioned in the present invention is one of nitrogen, helium, neon, argon, helium or neon.

其中，本发明测量维氏硬度是根据ASTM E92-82的标准测定的；本发明的盐雾测试是根据ASTM B117-2011的标准测定的。Here, the Vickers hardness of the present invention is measured in accordance with the standard of ASTM E92-82; the salt spray test of the present invention is determined in accordance with the standards of ASTM B117-2011.

其中，本发明的非晶合金手表外壳或非晶合金手表的结构及壁厚是根据所采用的非晶合金材料的玻璃成型能力(GFA,Glass Forming Ability)来设计，以保证所制备的非晶合金手表外壳或非晶合金手表为非晶结构。Wherein, the structure and wall thickness of the amorphous alloy watch case or the amorphous alloy watch of the present invention are designed according to the glass forming ability (GFA) of the amorphous alloy material used to ensure the prepared amorphous The alloy watch case or the amorphous alloy watch has an amorphous structure.

其中，本发明的压铸成型过程以第一TTT图为基准，使时间温度曲线不碰触到第一TTT图中的晶化区。Wherein, the die casting molding process of the present invention uses the first TTT map as a reference so that the time temperature curve does not touch the crystallization zone in the first TTT map.

实施例1。Example 1.

本实施例的一种非晶合金手表外壳，具体为，在真空度为10^-1torr的真空状态的保护下，利用Zr-Cu-Ni-Al-Nb系锆基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳。本实施例中，Zr-Cu-Ni-Al-Nb系锆基非晶合金的原子百分比为Zr(54.75)-Cu(16.65)-Ni(13.6)-Al(10)-Nb(5)。所制备的非晶合金手表外壳的维氏硬度为530，降伏强度为1400MPa，镍释放量为0.015mg/cm²/week，经受340小时的盐雾测试后非晶合金手表外壳的表面仍然良好无腐蚀。其中，本实施例的非晶合金手表外壳为智能手表外壳。An amorphous alloy watch case of the present embodiment, specifically, a die-casting material using a Zr-Cu-Ni-Al-Nb-based zirconium-based amorphous alloy under the protection of a vacuum of 10 ^-1 torr vacuum The amorphous alloy watch case is prepared by a molding method. In the present embodiment, the atomic percentage of the Zr-Cu-Ni-Al-Nb-based zirconium-based amorphous alloy is Zr(54.75)-Cu(16.65)-Ni(13.6)-Al(10)-Nb(5). The prepared amorphous alloy watch case has a Vickers hardness of 530, a relief strength of 1400 MPa, and a nickel release of 0.015 mg/cm ² /week. The surface of the amorphous alloy watch case is still good after being subjected to a salt spray test of 340 hours. corrosion. Wherein, the amorphous alloy watch case of the embodiment is a smart watch case.

本实施例中非晶合金手表外壳包括表壳、表盘和后盖；表壳、表盘和后盖采用Zr-Cu-Ni-Al-Nb系锆基非晶合金而制造。In the present embodiment, the amorphous alloy watch case includes a case, a dial and a back cover; and the case, the dial and the back cover are made of a Zr-Cu-Ni-Al-Nb-based zirconium-based amorphous alloy.

本实施例中，该非晶合金手表外壳设置为均一厚度，且其厚度为2mm。In this embodiment, the amorphous alloy watch case is provided with a uniform thickness and a thickness of 2 mm.

本实施例中，利用Zr-Cu-Ni-Al-Nb系锆基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳，包括如下步骤：In this embodiment, an amorphous alloy watch case is prepared by a die-casting method using a raw material of a Zr-Cu-Ni-Al-Nb-based zirconium-based amorphous alloy, including the following steps:

步骤一，投料：将Zr-Cu-Ni-Al-Nb系锆基非晶合金原材料放入立式压铸机的供料装置，并由供料装置投入到立式压铸机的熔融装置中；立式压铸机的真空度为10^-1torr；本实施例中，Zr-Cu-Ni-Al-Nb系锆基非晶合金原材料为Zr金属、Cu金属、Ni金属、Al金属和Ab金属，且Zr金属、Cu金属、Ni金属、Al金属和Ab金属的纯度均为99.9％以上。Step one, feeding: placing the Zr-Cu-Ni-Al-Nb zirconium-based amorphous alloy raw material into the feeding device of the vertical die casting machine, and feeding it into the melting device of the vertical die casting machine by the feeding device; The vacuum degree of the die casting machine is 10 ^-1 torr; in this embodiment, the raw materials of the Zr-Cu-Ni-Al-Nb-based zirconium-based amorphous alloy are Zr metal, Cu metal, Ni metal, Al metal and Ab metal, and The purity of Zr metal, Cu metal, Ni metal, Al metal and Ab metal is 99.9% or more.

步骤二，熔融：利用感应加热的方式将Zr-Cu-Ni-Al-Nb系锆基非晶合金原材料熔融并形成熔汤，熔汤的温度为900℃； Step 2, melting: the Zr-Cu-Ni-Al-Nb-based zirconium-based amorphous alloy raw material is melted by induction heating to form a melt, the temperature of the melt is 900 ° C;

步骤三，倒汤：将步骤二得到的熔汤倒入手表外壳模具浇口套中，然后以冲头将熔汤注入手表外壳模具中；其中，冲头的速度为0.1m/s；手表外壳模具的温度为200℃；其中，在倒汤过程中，利用喷枪向手表外壳模具表面喷射氩气以达到清洁手表外壳模具表面的熔汤碎屑的目的；Step 3: Pour the soup: pour the molten soup obtained in the second step into the mold cover of the watch case, and then inject the molten soup into the mold of the watch case with a punch; wherein the speed of the punch is 0.1 m/s; the watch case The temperature of the mold is 200 ° C; wherein, during the pouring process, the argon gas is sprayed onto the surface of the mold shell of the watch by the spray gun to achieve the purpose of cleaning the melted chips on the surface of the mold of the watch case;

步骤四，冷却：对步骤三中注入了熔汤的手表外壳模具进行冷却成型，得到非晶合金手表外壳，冷却速度为10⁰K/s；冷却时间为30秒；Step 4, cooling: cooling the watch case mold into which the molten soup is poured in the third step, obtaining an amorphous alloy watch case, the cooling rate is 10 ⁰ K/s; the cooling time is 30 seconds;

其中，步骤三中的手表外壳模具为一模多穴的模具。Among them, the watch shell mold in the third step is a mold with multiple holes.

其中，步骤五后，还包括步骤六，将步骤五得到的非晶合金手表外壳进行切割浇铸口和溢流口。Wherein, after step 5, step 6 is further included, and the amorphous alloy watch case obtained in step 5 is cut into a casting port and an overflow port.

本实施例中，在氮气的保护下，对步骤六中完成切割浇铸口和溢流口的非晶合金手表外壳，进行机加工以达到结构和精度的要求；其中机加工包括CNC铣和/或CNC切削。In this embodiment, under the protection of nitrogen, the amorphous alloy watch casing that cuts the casting port and the overflow port in step 6 is machined to meet the structural and precision requirements; wherein the machining includes CNC milling and/or CNC cutting.

本实施例中，对机加工后的非晶合金手表外壳进行滚筒研磨和抛光处理。其中，抛光处理为镜面抛光处理。In this embodiment, the machined amorphous alloy watch case is subjected to barrel grinding and polishing treatment. Among them, the polishing treatment is a mirror polishing treatment.

本实施例1制得的非晶合金手表外壳相对于利用钛合金或不锈钢制备的手表外壳，均具有优异的维氏硬度、降伏强度和抗腐蚀的性能；而且，利用Zr-Cu-Ni-Al-Nb 系锆基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳具有机械加工量小、加工时间短、生产效率高、生产成本低、易于成型、且制备工艺简单的优点。The amorphous alloy watch case obtained in the first embodiment has excellent Vickers hardness, lodging strength and corrosion resistance with respect to the watch case prepared by using titanium alloy or stainless steel; and, by using Zr-Cu-Ni-Al -Nb The raw material of the zirconium-based amorphous alloy is prepared by the die-casting method. The amorphous alloy watch casing has the advantages of small machining amount, short processing time, high production efficiency, low production cost, easy molding, and simple preparation process.

实施例2。Example 2.

本实施例的一种非晶合金手表外壳，具体为，在氦气的保护下，利用Zr-Cu-Ni-Al-Ti系锆基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳。本实施例中，Zr-Cu-Ni-Al-Ti系锆基非晶合金的原子百分比为Zr(50)-Cu(20)-Ni(15)-Al(7)-Ti(8)。所制备的非晶合金手表外壳的维氏硬度为400，降伏强度为1800MPa，镍释放量为0.01mg/cm²/week，经受400小时的盐雾测试后非晶合金手表外壳的表面仍然良好无腐蚀。其中，本实施例的非晶合金手表外壳为传统手表外壳。An amorphous alloy watch case of the embodiment, in particular, an amorphous alloy watch case is prepared by a die casting method using a raw material of a Zr-Cu-Ni-Al-Ti zirconium-based amorphous alloy under the protection of helium . In the present embodiment, the atomic percentage of the Zr-Cu-Ni-Al-Ti-based zirconium-based amorphous alloy is Zr(50)-Cu(20)-Ni(15)-Al(7)-Ti(8). The prepared amorphous alloy watch case has a Vickers hardness of 400, a relief strength of 1800 MPa, and a nickel release amount of 0.01 mg/cm ² /week. The surface of the amorphous alloy watch case is still good after being subjected to a salt spray test for 400 hours. corrosion. Wherein, the amorphous alloy watch case of the embodiment is a traditional watch case.

本实施例中非晶合金手表外壳包括表壳、表盘和后盖；表壳和表盘采用Zr-Cu-Ni-Al-Ti系锆基非晶合金而制造。In the present embodiment, the amorphous alloy watch case comprises a case, a dial and a back cover; and the case and the dial are manufactured using a Zr-Cu-Ni-Al-Ti-based zirconium-based amorphous alloy.

本实施例中，该非晶合金手表外壳设置为均一厚度，且其厚度为1mm。In this embodiment, the amorphous alloy watch case is provided with a uniform thickness and a thickness of 1 mm.

本实施例中，利用Zr-Cu-Ni-Al-Ti系锆基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳，包括如下步骤：In this embodiment, the amorphous alloy watch case is prepared by a die casting method using a raw material of a Zr-Cu-Ni-Al-Ti-based zirconium-based amorphous alloy, and includes the following steps:

步骤一，投料：将Zr-Cu-Ni-Al-Ti系锆基非晶合金原材料放入卧式压铸机的供料装置，并由供料装置投入到卧式压铸机的熔融装置中；本实施例中，卧式压铸机充入氦气进行保护；本实施例中，Zr-Cu-Ni-Al-Ti系锆基非晶合金原材料为Zr金属、Cu金属、Ni金属、Al金属和Ti金属，且Zr金属、Cu金属、Ni金属、Al金属和Ti金属的纯度均为99.9％以上。Step one, feeding: the Zr-Cu-Ni-Al-Ti-based zirconium-based amorphous alloy raw material is placed in the feeding device of the horizontal die-casting machine, and is fed into the melting device of the horizontal die-casting machine by the feeding device; In the embodiment, the horizontal die casting machine is filled with helium gas for protection; in the embodiment, the Zr-Cu-Ni-Al-Ti-based zirconium-based amorphous alloy raw material is Zr metal, Cu metal, Ni metal, Al metal and Ti. The metal, and the purity of the Zr metal, the Cu metal, the Ni metal, the Al metal, and the Ti metal are all 99.9% or more.

步骤二，熔融：利用感应加热的方式将Zr-Cu-Ni-Al-Ti系锆基非晶合金原材料熔融并形成熔汤，熔汤的温度为950℃；Step two, melting: the Zr-Cu-Ni-Al-Ti-based zirconium-based amorphous alloy raw material is melted by induction heating to form a melt, the temperature of the melt is 950 ° C;

步骤三，倒汤：将步骤二得到的熔汤倒入手表外壳模具浇口套中，然后以冲头将熔汤注入手表外壳模具中；其中，冲头的速度为0.5m/s；手表外壳模具的温度为210℃；其中，在倒汤过程中，利用喷枪向手表外壳模具表面喷射氮气以达到清洁手表外壳模具表面的熔汤碎屑的目的；Step 3: pouring the soup: pouring the molten soup obtained in the second step into the mold cover of the watch case, and then injecting the molten soup into the mold of the watch case with a punch; wherein the speed of the punch is 0.5 m/s; the watch case The temperature of the mold is 210 ° C; wherein, during the pouring process, the spray gun is used to spray nitrogen gas onto the surface of the mold shell of the watch to achieve the purpose of cleaning the molten scrap on the surface of the mold of the watch case;

步骤四，冷却：对步骤三中注入了熔汤的手表外壳模具进行冷却成型，得到非晶合金手表外壳，冷却速度为10¹K/s；冷却时间为28秒；Step 4, cooling: cooling the watch case mold into which the molten soup is poured in the third step, obtaining an amorphous alloy watch case, the cooling rate is 10 ¹ K/s; the cooling time is 28 seconds;

其中，步骤三中的手表外壳模具为一模多穴的模具。 Among them, the watch shell mold in the third step is a mold with multiple holes.

本实施例中，在氦气的保护下，对步骤六中完成切割浇铸口和溢流口的非晶合金手表外壳，进行热塑成型(TPF)以达到结构、精度和表面品质的要求。In the present embodiment, under the protection of helium, the amorphous alloy watch casing which cuts the casting port and the overflow port in step 6 is subjected to thermoforming (TPF) to achieve the requirements of structure, precision and surface quality.

其中，热塑成型(TPF)的具体步骤如下：Among them, the specific steps of thermoplastic molding (TPF) are as follows:

(1)对步骤六中完成切割浇铸口和溢流口的非晶合金手表外壳中需要进一步加工的位置进行加热(例如感应加热、电阻丝加热等方式)，并且加热到过冷液相区(即玻璃化转变温度Tg与结晶温度Tx之间)以使所需加工的位置达到较低粘度而能够自由型塑的目的；(1) Heating the position of the amorphous alloy watch case in which the cutting casting port and the overflow port are completed in step 6 to be further processed (for example, induction heating, resistance wire heating, etc.), and heating to the supercooled liquid region ( That is, between the glass transition temperature Tg and the crystallization temperature Tx), so that the desired processing position can reach a lower viscosity and can be freely molded;

(2)利用根据所述非晶合金手表外壳的构造而设计的小型模具或压头加压于所述非晶合金外壳中需要进一步加工的位置，从而成型出所需的结构；(2) using a small mold or ram designed according to the configuration of the amorphous alloy watch case to pressurize a position in the amorphous alloy case that requires further processing, thereby molding a desired structure;

(3)利用氮气对步骤(2)中成型出的结构进行冷却。(3) The structure formed in the step (2) is cooled by nitrogen gas.

其中，上述热塑成型(TPF)的整体加工期间的时间温度曲线不碰触到第二TTT图中的晶化区。Wherein, the time temperature curve during the overall processing of the above thermoplastic molding (TPF) does not touch the crystallization zone in the second TTT diagram.

本实施例中，对完成热塑成型(TPF)的非晶合金手表外壳进行拉丝处理。In this embodiment, the amorphous alloy watch case that has been subjected to thermoforming (TPF) is subjected to a wire drawing process.

本实施例2制得的非晶合金手表外壳相对于利用钛合金或不锈钢制备的手表外壳，均具有优异的维氏硬度、降伏强度和抗腐蚀的性能；而且，利用Zr-Cu-Ni-Al-Ti系锆基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳具有机械加工量小、加工时间短、生产效率高、生产成本低、易于成型、且制备工艺简单的优点。The amorphous alloy watch case obtained in the second embodiment has excellent Vickers hardness, lodging strength and corrosion resistance with respect to a watch case made of titanium alloy or stainless steel; and, by using Zr-Cu-Ni-Al The raw material of the Ti-based zirconium-based amorphous alloy is prepared by the die-casting method. The amorphous alloy watch outer casing has the advantages of small machining amount, short processing time, high production efficiency, low production cost, easy molding, and simple preparation process.

实施例3。Example 3.

本实施例的一种非晶合金手表外壳，具体为，在氖气的保护下，利用Zr-Cu-Co-Al-Nb系锆基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳。本实施例中，Zr-Cu-Co-Al-Nb系锆基非晶合金的原子百分比为Zr(60)-Cu(12)-Co(10)-Al(15)-Nb(3)。所制备的非晶合金手表外壳的维氏硬度为600，降伏强度为2000MPa，镍释放量为0mg/cm²/week，经受420小时的盐雾测试后非晶合金手表外壳的表面仍然良好无腐蚀。其中，本实施例的非晶合金手表外壳为智能手表外壳。The amorphous alloy watch case of the embodiment is specifically prepared by using a raw material of a Zr-Cu-Co-Al-Nb zirconium-based amorphous alloy by a die casting method to prepare an amorphous alloy watch case under the protection of helium. . In the present embodiment, the atomic percentage of the Zr-Cu-Co-Al-Nb-based zirconium-based amorphous alloy is Zr(60)-Cu(12)-Co(10)-Al(15)-Nb(3). The prepared amorphous alloy watch case has a Vickers hardness of 600, a relief strength of 2000 MPa, and a nickel release of 0 mg/cm ² /week. The surface of the amorphous alloy watch case is still good and non-corrosive after being subjected to a salt spray test for 420 hours. . Wherein, the amorphous alloy watch case of the embodiment is a smart watch case.

本实施例中非晶合金手表外壳包括表壳、表盘和后盖；表壳和后盖采用Zr-Cu-Co-Al-Nb系锆基非晶合金而制造。In the present embodiment, the amorphous alloy watch case includes a case, a dial and a back cover; and the case and the back cover are made of a Zr-Cu-Co-Al-Nb-based zirconium-based amorphous alloy.

本实施例中，该非晶合金手表外壳设置为均一厚度，且其厚度为3mm。In this embodiment, the amorphous alloy watch case is provided with a uniform thickness and a thickness of 3 mm.

本实施例中，利用Zr-Cu-Co-Al-Nb系锆基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳，包括如下步骤：In this embodiment, a raw material of a Zr-Cu-Co-Al-Nb-based zirconium-based amorphous alloy is produced by a die-casting method. An amorphous alloy watch case includes the following steps:

步骤一，投料：将Zr-Cu-Co-Al-Nb系锆基非晶合金原材料放入卧式压铸机的供料装置，并由供料装置投入到卧式压铸机的熔融装置中；本实施中，卧式压铸机充入氖气进行保护；本实施例中，Zr-Cu-Co-Al-Nb系锆基非晶合金原材料为Zr金属、Cu金属、Co金属、Al金属和Nb金属，且Zr金属、Cu金属、Co金属、Al金属和Nb金属的纯度均为99.9％以上。Step one, feeding: the Zr-Cu-Co-Al-Nb-based zirconium-based amorphous alloy raw material is placed in the feeding device of the horizontal die-casting machine, and is fed into the melting device of the horizontal die-casting machine by the feeding device; In the implementation, the horizontal die casting machine is filled with helium gas for protection; in this embodiment, the Zr-Cu-Co-Al-Nb zirconium-based amorphous alloy raw materials are Zr metal, Cu metal, Co metal, Al metal and Nb metal. The purity of the Zr metal, the Cu metal, the Co metal, the Al metal, and the Nb metal is 99.9% or more.

步骤二，熔融：利用感应加热的方式将Zr-Cu-Co-Al-Nb系锆基非晶合金原材料熔融并形成熔汤，熔汤的温度为1000℃； Step 2, melting: the Zr-Cu-Co-Al-Nb-based zirconium-based amorphous alloy raw material is melted by induction heating to form a melt, the temperature of the melt is 1000 ° C;

步骤三，倒汤：将步骤二得到的熔汤倒入手表外壳模具浇口套中，然后以冲头将熔汤注入手表外壳模具中；其中，冲头的速度为5m/s；手表外壳模具的温度为250℃；其中，在倒汤过程中，利用喷枪向手表外壳模具表面喷射氦气以达到清洁手表外壳模具表面的熔汤碎屑的目的；Step 3: Pour the soup: pour the molten soup obtained in the second step into the mold cover of the watch case, and then inject the molten soup into the mold of the watch case with a punch; wherein the speed of the punch is 5 m/s; the watch case mold The temperature is 250 ° C; wherein, in the process of pouring the soup, the spray gun is used to spray the helium gas on the surface of the mold shell of the watch to achieve the purpose of cleaning the melted debris on the surface of the mold shell of the watch;

步骤四，冷却：对步骤三中注入了熔汤的手表外壳模具进行冷却成型，得到非晶合金手表外壳，冷却速度为10⁶K/s；冷却时间为15秒；Step 4, cooling: cooling the watch case mold into which the molten soup is poured in the third step to obtain an amorphous alloy watch case, the cooling rate is 10 ⁶ K/s; the cooling time is 15 seconds;

本实施例中，在氖气的保护下，对步骤六中完成切割浇铸口和溢流口的非晶合金手表外壳，进行快速放电成型(RDF)以达到结构、精度和表面品质的要求。In the present embodiment, under the protection of helium, the amorphous alloy watch casing that cuts the casting port and the overflow port in step 6 is subjected to rapid discharge forming (RDF) to meet the requirements of structure, precision and surface quality.

其中，快速放电成型(RDF)的具体步骤如下：Among them, the specific steps of rapid discharge molding (RDF) are as follows:

(1)对步骤六中完成切割浇铸口和溢流口的非晶合金手表外壳中需要进一步加工的位置利用电容放电快速加热，并且加热到玻璃化转变温度(Tg)与熔点(Tm)之间以使所需加工的位置达到较低粘度而能够自由型塑的目的；(1) Rapidly heating the position of the amorphous alloy watch case that completes the cutting of the casting port and the overflow port in step 6 by means of capacitor discharge, and heating to between the glass transition temperature (Tg) and the melting point (Tm) The purpose of free molding is to achieve a lower viscosity at the desired processing position;

(2)利用根据所述非晶合金手表外壳的结构设计的电极加压于所述非晶合金外壳中需要进一步加工的位置，从而成型出所需的结构；(2) using an electrode designed according to the structure of the amorphous alloy watch case to pressurize a position in the amorphous alloy case that requires further processing, thereby molding a desired structure;

其中，上述快速放电成型(RDF)的整体加工期间的时间温度曲线不碰触到第三TTT图中的晶化区。 Wherein, the time temperature curve during the overall processing of the above rapid discharge molding (RDF) does not touch the crystallization zone in the third TTT diagram.

其中，快速放电成型(RDF)优点是能够快速并均匀地成型。Among them, the advantage of rapid discharge molding (RDF) is that it can be formed quickly and uniformly.

本实施例中，对完成快速放电成型(RDF)的非晶合金手表外壳进行PVD处理。In this embodiment, a PVD process is performed on an amorphous alloy watch case that is completed by rapid discharge molding (RDF).

本实施例3制得的非晶合金手表外壳相对于利用钛合金或不锈钢制备的手表外壳，均具有优异的维氏硬度、降伏强度和抗腐蚀的性能；而且，利用Zr-Cu-Co-Al-Nb系锆基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳具有机械加工量小、加工时间短、生产效率高、生产成本低、易于成型、且制备工艺简单的优点。The amorphous alloy watch case obtained in the third embodiment has excellent Vickers hardness, lodging strength and corrosion resistance with respect to a watch case made of titanium alloy or stainless steel; and, by using Zr-Cu-Co-Al The raw material of the -Nb zirconium-based amorphous alloy is prepared by the die-casting method. The amorphous alloy watch casing has the advantages of small machining amount, short processing time, high production efficiency, low production cost, easy molding, and simple preparation process.

实施例4。Example 4.

本实施例的一种非晶合金手表外壳，具体为，在氩气的保护下，利用Zr-Cu-Co-Al-Ti系锆基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳。本实施例中，Zr-Cu-Co-Al-Ti系锆基非晶合金的原子百分比为Zr(58)-Cu(14)-Co(13)-Al(13)-Ti(2)。所制备的非晶合金手表外壳的维氏硬度为500，降伏强度为2300MPa，镍释放量为0mg/cm²/week，经受480小时的盐雾测试后非晶合金手表外壳的表面仍然良好无腐蚀。其中，本实施例的非晶合金手表外壳为智能手表外壳。An amorphous alloy watch case of the present embodiment, specifically, an amorphous alloy watch case is prepared by a die casting method using a raw material of a Zr-Cu-Co-Al-Ti zirconium-based amorphous alloy under the protection of argon gas. . In the present embodiment, the atomic percentage of the Zr-Cu-Co-Al-Ti-based zirconium-based amorphous alloy is Zr(58)-Cu(14)-Co(13)-Al(13)-Ti(2). The prepared amorphous alloy watch case has a Vickers hardness of 500, a relief strength of 2300 MPa, and a nickel release amount of 0 mg/cm ² /week. The surface of the amorphous alloy watch case is still good and non-corrosive after being subjected to a salt spray test of 480 hours. . Wherein, the amorphous alloy watch case of the embodiment is a smart watch case.

本实施例中非晶合金手表外壳包括表壳、表盘和后盖；表盘和后盖采用Zr-Cu-Co-Al-Ti系锆基非晶合金而制造。In the present embodiment, the amorphous alloy watch case includes a case, a dial, and a back cover; and the dial and the back cover are made of a Zr-Cu-Co-Al-Ti-based zirconium-based amorphous alloy.

本实施例中，该非晶合金手表外壳设置为均一厚度，且其厚度为1.5mm。In this embodiment, the amorphous alloy watch case is provided with a uniform thickness and a thickness of 1.5 mm.

本实施例中，利用Zr-Cu-Co-Al-Ti系锆基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳，包括如下步骤：In this embodiment, an amorphous alloy watch case is prepared by a die-casting method using a raw material of a Zr-Cu-Co-Al-Ti-based zirconium-based amorphous alloy, including the following steps:

步骤一，投料：将Zr-Cu-Co-Al-Ti系锆基非晶合金原材料放入立式压铸机的供料装置，并由供料装置投入到立式压铸机的熔融装置中；本实施例中，立式压铸机充入氩气进行保护；本实施例中，Zr-Cu-Co-Al-Ti系锆基非晶合金原材料为Zr金属、Cu金属、Co金属、Al金属和Ti金属，且Zr金属、Cu金属、Co金属、Al金属和Ti金属的纯度均为99.9％以上。Step one, feeding: placing the Zr-Cu-Co-Al-Ti zirconium-based amorphous alloy raw material into the feeding device of the vertical die casting machine, and feeding it into the melting device of the vertical die casting machine by the feeding device; In the embodiment, the vertical die casting machine is filled with argon gas for protection; in this embodiment, the Zr-Cu-Co-Al-Ti-based zirconium-based amorphous alloy raw material is Zr metal, Cu metal, Co metal, Al metal and Ti. The metal, and the purity of the Zr metal, the Cu metal, the Co metal, the Al metal, and the Ti metal are all 99.9% or more.

步骤二，熔融：利用感应加热的方式将Zr-Cu-Co-Al-Ti系锆基非晶合金原材料熔融并形成熔汤，熔汤的温度为1100℃； Step 2, melting: the Zr-Cu-Co-Al-Ti-based zirconium-based amorphous alloy raw material is melted by induction heating to form a melt, the temperature of the melt is 1100 ° C;

步骤三，倒汤：将步骤二得到的熔汤倒入手表外壳模具浇口套中，然后以冲头将熔汤注入手表外壳模具中；其中，冲头的速度为2m/s；手表外壳模具的温度为230℃；其中，在倒汤过程中，利用喷枪向手表外壳模具表面喷射氖气以达到清洁手表外壳模具表面的熔汤碎屑的目的；Step 3: Pour the soup: pour the molten soup obtained in the second step into the mold cover of the watch case, and then inject the molten soup into the mold of the watch case with a punch; wherein the speed of the punch is 2 m/s; the watch case mold The temperature is 230 ° C; wherein, in the process of pouring the soup, the spray gun is used to spray the helium gas on the surface of the mold shell of the watch to achieve the purpose of cleaning the melted debris on the surface of the mold shell of the watch;

步骤四，冷却：对步骤三中注入了熔汤的手表外壳模具进行冷却成型，得到非晶合金手表外壳，冷却速度为10⁵K/s；冷却时间为17秒；Step 4, cooling: cooling the watch case mold into which the molten soup is poured in the third step to obtain an amorphous alloy watch case, the cooling rate is 10 ⁵ K/s; the cooling time is 17 seconds;

本实施例中，在氩气的保护下，对步骤六中完成切割浇铸口和溢流口的非晶合金手表外壳，进行机加工以达到结构和精度的要求，然后进行热塑成型(TPF)以达到结构、精度和表面品质的要求。其中机加工包括CNC铣和/或CNC切削。In this embodiment, under the protection of argon, the amorphous alloy watch casing which cuts the casting port and the overflow port in step 6 is machined to meet the structural and precision requirements, and then subjected to thermoforming (TPF). To meet the requirements of structure, precision and surface quality. Machining includes CNC milling and/or CNC cutting.

本实施例中，对完成热塑成型(TPF)的非晶合金手表外壳先进行拉丝处理，再进行PVD处理。In this embodiment, the amorphous alloy watch case that has been subjected to thermoforming (TPF) is subjected to wire drawing treatment and then subjected to PVD treatment.

本实施例4制得的非晶合金手表外壳相对于利用钛合金或不锈钢制备的手表外壳，均具有优异的维氏硬度、降伏强度和抗腐蚀的性能；而且，利用Zr-Cu-Co-Al-Ti系锆基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳具有机械加工量小、加工时间短、生产效率高、生产成本低、易于成型、且制备工艺简单的优点。The amorphous alloy watch case obtained in the fourth embodiment has excellent Vickers hardness, lodging strength and corrosion resistance with respect to a watch case made of titanium alloy or stainless steel; and, by using Zr-Cu-Co-Al The raw material of the Ti-based zirconium-based amorphous alloy is prepared by the die-casting method. The amorphous alloy watch outer casing has the advantages of small machining amount, short processing time, high production efficiency, low production cost, easy molding, and simple preparation process.

实施例5。Example 5.

本实施例的一种非晶合金手表外壳，具体为，在氮气的保护下，利用Zr-Cu-Co-Al-Sn系锆基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳，其中机加工包括CNC铣和/或CNC切削。本实施例中，Zr-Cu-Co-Al-Sn系锆基非晶合金的原子百分比为Zr(54.75)-Cu(16.65)-Co(13.6)-Al(10)-Sn(5)。所制备的非晶合金手表外壳的维氏硬度为500，降伏强度为2300MPa，镍释放量为0mg/cm²/week，经受480小时的盐雾测试后非晶合金手表外壳的表面仍然良好无腐蚀。其中，本实施例的非晶合金手表外壳为传统手表外壳。An amorphous alloy watch case of the embodiment, in particular, an amorphous alloy watch case is prepared by a die casting method using a raw material of a Zr-Cu-Co-Al-Sn-based zirconium-based amorphous alloy under the protection of nitrogen gas. Machining includes CNC milling and/or CNC cutting. In the present embodiment, the atomic percentage of the Zr-Cu-Co-Al-Sn-based zirconium-based amorphous alloy is Zr(54.75)-Cu(16.65)-Co(13.6)-Al(10)-Sn(5). The prepared amorphous alloy watch case has a Vickers hardness of 500, a drop strength of 2300 MPa, and a nickel release of 0 mg/cm ² /week. The surface of the amorphous alloy watch case is still good and non-corrosive after being subjected to a salt spray test of 480 hours. . Wherein, the amorphous alloy watch case of the embodiment is a traditional watch case.

本实施例中非晶合金手表外壳包括表壳、表盘和后盖；表壳采用Zr-Cu-Co-Al-Sn系锆基非晶合金而制造。In the present embodiment, the amorphous alloy watch case includes a case, a dial, and a back cover; and the case is made of a Zr-Cu-Co-Al-Sn-based zirconium-based amorphous alloy.

本实施例中，该非晶合金手表外壳设置为均一厚度，且其厚度为0.5mm。In this embodiment, the amorphous alloy watch case is provided with a uniform thickness and a thickness of 0.5 mm.

本实施例中，利用Zr-Cu-Co-Al-Sn系锆基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳，包括如下步骤：In this embodiment, an amorphous alloy watch case is prepared by a die casting method using a raw material of a Zr-Cu-Co-Al-Sn-based zirconium-based amorphous alloy, including the following steps:

步骤一，投料：将Zr-Cu-Co-Al-Sn系锆基非晶合金原材料放入立式压铸机的供料装置，并由供料装置投入到立式压铸机的熔融装置中；本实施例中，立式压铸机充入氮气进行保护；本实施例中，Zr-Cu-Co-Al-Sn系锆基非晶合金原材料为Zr金属、Cu金属、Co金属、Al金属和Sn金属，且Zr金属、Cu金属、Co金属、Al金属和Sn金属的纯度均为99.9％以上。Step one, feeding: the Zr-Cu-Co-Al-Sn-based zirconium-based amorphous alloy raw material is placed in the feeding device of the vertical die casting machine, and is fed into the melting device of the vertical die casting machine by the feeding device; In the embodiment, the vertical die casting machine is filled with nitrogen gas for protection; in this embodiment, the Zr-Cu-Co-Al-Sn-based zirconium-based amorphous alloy raw material is Zr metal, Cu metal, Co metal, Al metal, and Sn metal. And the purity of Zr metal, Cu metal, Co metal, Al metal, and Sn metal is 99.9% or more.

步骤二，熔融：利用感应加热的方式将Zr-Cu-Co-Al-Sn系锆基非晶合金原材料熔融并形成熔汤，熔汤的温度为1200℃； Step 2, melting: the Zr-Cu-Co-Al-Sn-based zirconium-based amorphous alloy raw material is melted by induction heating to form a melt, the temperature of the melt is 1200 ° C;

步骤三，倒汤：将步骤二得到的熔汤倒入手表外壳模具浇口套中，然后以冲头将熔汤注入手表外壳模具中；其中，冲头的速度为2m/s；手表外壳模具的温度为230℃；其中，在倒汤过程中，利用喷枪向手表外壳模具表面喷射氪气以达到清洁手表外壳模具表面的熔汤碎屑的目的；Step 3: Pour the soup: pour the molten soup obtained in the second step into the mold cover of the watch case, and then inject the molten soup into the mold of the watch case with a punch; wherein the speed of the punch is 2 m/s; the watch case mold The temperature is 230 ° C; wherein, in the process of pouring the soup, the spray gun is used to spray the helium gas on the surface of the mold shell of the watch to achieve the purpose of cleaning the melted debris on the surface of the mold shell of the watch;

步骤四，冷却：对步骤三中注入了熔汤的手表外壳模具进行冷却成型，得到非晶合金手表外壳，冷却速度为10⁵K/s；冷却时间为17秒；Step 4, cooling: cooling the watch case mold into which the molten soup is poured in the third step, and obtaining an amorphous alloy watch case, the cooling rate is 10 ⁵ K/s; the cooling time is 17 seconds;

本实施例中，在氮气的保护下，对步骤六中完成切割浇铸口和溢流口的非晶合金手表外壳，进行机加工以达到结构和精度的要求，然后进行快速放电成型(RDF)以达到结构、精度和表面品质的要求。其中机加工包括CNC铣和/或CNC切削。In the present embodiment, under the protection of nitrogen, the amorphous alloy watch case which cuts the casting port and the overflow port in step 6 is machined to meet the structural and precision requirements, and then subjected to rapid discharge molding (RDF). Meet the requirements of structure, precision and surface quality. Machining includes CNC milling and/or CNC cutting.

其中，快速放电成型(RDF)的具体步骤如下： Among them, the specific steps of rapid discharge molding (RDF) are as follows:

其中，上述快速放电成型(RDF)的整体加工期间的时间温度曲线不碰触到第三TTT图中的晶化区。Wherein, the time temperature curve during the overall processing of the above rapid discharge molding (RDF) does not touch the crystallization zone in the third TTT diagram.

本实施例中，对完成快速放电成型(RDF)的非晶合金手表外壳进行喷砂处理。In this embodiment, an amorphous alloy watch case that is subjected to rapid discharge forming (RDF) is subjected to sand blasting.

本实施例5制得的非晶合金手表外壳相对于利用钛合金或不锈钢制备的手表外壳，均具有优异的维氏硬度、降伏强度和抗腐蚀的性能；而且，利用Zr-Cu-Co-Al-Sn系锆基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳具有机械加工量小、加工时间短、生产效率高、生产成本低、易于成型、且制备工艺简单的优点。The amorphous alloy watch case obtained in the fifth embodiment has excellent Vickers hardness, lodging strength and corrosion resistance with respect to a watch case made of titanium alloy or stainless steel; and, by using Zr-Cu-Co-Al The raw material of the Sn-based zirconium-based amorphous alloy has the advantages of small machining amount, short processing time, high production efficiency, low production cost, easy molding, and simple preparation process by the die-casting method.

实施例6。Example 6.

本实施例的一种非晶合金手表外壳，具体为，在氩气的保护下，利用Zr-Cu-Ni-Al-Sn系锆基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳，其中机加工包括CNC铣和/或CNC切削。本实施例中，Zr-Cu-Ni-Al-Sn系锆基非晶合金的原子百分比为：Zr(50)-Cu(20)-Ni(15)-Al(7)-Sn(8)。所制备的非晶合金手表外壳的维氏硬度为500，降伏强度为2300MPa，镍释放量为0mg/cm²/week，经受480小时的盐雾测试后非晶合金手表外壳的表面仍然良好无腐蚀。An amorphous alloy watch case of the present embodiment, specifically, an amorphous alloy watch case is prepared by a die casting method using a raw material of a Zr-Cu-Ni-Al-Sn-based zirconium-based amorphous alloy under the protection of argon gas. , where machining includes CNC milling and/or CNC cutting. In the present embodiment, the atomic percentage of the Zr-Cu-Ni-Al-Sn-based zirconium-based amorphous alloy is: Zr(50)-Cu(20)-Ni(15)-Al(7)-Sn(8). The prepared amorphous alloy watch case has a Vickers hardness of 500, a relief strength of 2300 MPa, and a nickel release amount of 0 mg/cm ² /week. The surface of the amorphous alloy watch case is still good and non-corrosive after being subjected to a salt spray test of 480 hours. .

本实施例中非晶合金手表外壳包括表壳、表盘和后盖；表盘采用Zr-Cu-Ni-Al-Sn系锆基非晶合金而制造。In the present embodiment, the amorphous alloy watch case comprises a case, a dial and a back cover; and the dial is made of a Zr-Cu-Ni-Al-Sn-based zirconium-based amorphous alloy.

本实施例中，该非晶合金手表外壳设置为均一厚度，且其厚度为0.8mm。其中，本实施例的非晶合金手表外壳为传统手表外壳。In this embodiment, the amorphous alloy watch case is provided in a uniform thickness and has a thickness of 0.8 mm. Wherein, the amorphous alloy watch case of the embodiment is a traditional watch case.

本实施例中，利用Zr-Cu-Ni-Al-Sn系锆基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳，包括如下步骤：In this embodiment, an amorphous alloy watch case is prepared by a die casting method using a raw material of a Zr-Cu-Ni-Al-Sn-based zirconium-based amorphous alloy, including the following steps:

步骤一，投料：将Zr-Cu-Ni-Al-Sn系锆基非晶合金原材料放入立式压铸机的供料装置，并由供料装置投入到立式压铸机的熔融装置中；本实施例中，立式压铸机充入氩气进行保护；本实施例中，Zr-Cu-Ni-Al-Sn系锆基非晶合金原材料为Zr金属、 Cu金属、Ni金属、Al金属和Sn金属，且Zr金属、Cu金属、Ni金属、Al金属和Sn金属的纯度均为99.9％以上。Step one, feeding: the Zr-Cu-Ni-Al-Sn-based zirconium-based amorphous alloy raw material is placed in the feeding device of the vertical die casting machine, and is fed into the melting device of the vertical die casting machine by the feeding device; In the embodiment, the vertical die casting machine is filled with argon gas for protection; in this embodiment, the Zr-Cu-Ni-Al-Sn zirconium-based amorphous alloy raw material is Zr metal, Cu metal, Ni metal, Al metal, and Sn metal, and the purity of Zr metal, Cu metal, Ni metal, Al metal, and Sn metal are all 99.9% or more.

步骤二，熔融：利用感应加热的方式将Zr-Cu-Ni-Al-Sn系锆基非晶合金原材料熔融并形成熔汤，熔汤的温度为1150℃； Step 2, melting: the Zr-Cu-Ni-Al-Sn-based zirconium-based amorphous alloy raw material is melted by induction heating to form a melt, the temperature of the melt is 1150 ° C;

步骤三，倒汤：将步骤二得到的熔汤倒入手表外壳模具浇口套中，然后以冲头将熔汤注入手表外壳模具中；其中，冲头的速度为2m/s；手表外壳模具的温度为230℃；其中，在倒汤过程中，利用喷枪向手表外壳模具表面喷射氙气以达到清洁手表外壳模具表面的熔汤碎屑的目的；Step 3: Pour the soup: pour the molten soup obtained in the second step into the mold cover of the watch case, and then inject the molten soup into the mold of the watch case with a punch; wherein the speed of the punch is 2 m/s; the watch case mold The temperature is 230 ° C; wherein, in the process of pouring the soup, the spray gun is used to spray the helium gas on the surface of the mold shell of the watch to achieve the purpose of cleaning the melted debris on the surface of the mold shell of the watch;

本实施例中，在氩气的保护下，对步骤六中完成切割浇铸口和溢流口的非晶合金手表外壳，进行机加工以达到结构和精度的要求；其中机加工包括CNC铣和/或CNC切削。In this embodiment, under the protection of argon, the amorphous alloy watch casing that cuts the casting port and the overflow port in step 6 is machined to meet the structural and precision requirements; wherein the machining includes CNC milling and/or Or CNC cutting.

本实施例中，对机加工后的非晶合金手表外壳进行磁力研磨、拉丝处理和喷砂处理。In this embodiment, the machined amorphous alloy watch case is subjected to magnetic grinding, wire drawing, and sand blasting.

本实施例6制得的非晶合金手表外壳相对于利用钛合金或不锈钢制备的手表外壳，均具有优异的维氏硬度、降伏强度和抗腐蚀的性能；而且，利用Zr-Cu-Ni-Al-Sn系锆基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳具有机械加工量小、加工时间短、生产效率高、生产成本低、易于成型、且制备工艺简单的优点。The amorphous alloy watch case obtained in the sixth embodiment has excellent Vickers hardness, lodging strength and corrosion resistance with respect to a watch case made of titanium alloy or stainless steel; and, by using Zr-Cu-Ni-Al The raw material of the Sn-based zirconium-based amorphous alloy has the advantages of small machining amount, short processing time, high production efficiency, low production cost, easy molding, and simple preparation process by the die-casting method.

实施例7。Example 7.

本实施例的一种非晶合金手表外壳，具体为，在真空度为10^-2torr的真空状态的保护下，利用Zr-Cu-Ni-Co-Al-Nb系锆基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳。本实施例中，Zr-Cu-Ni-Co-Al-Nb系锆基非晶合金的原子百分比为：Zr(54.75)-Cu(16.65)-Ni(5.6)-Co(8)-Al(10)-Nb(5)。所制备的非晶合金手表外壳的维氏硬度为500，降伏强度为2300MPa，镍释放量为0.015mg/cm²/week，经受480小时的盐雾测试后非晶合金手表外壳的表面仍然良好无腐蚀。其中，本实施例的非晶合金手表外壳为传统手表外壳。The amorphous alloy watch case of the embodiment is specifically a raw material of Zr-Cu-Ni-Co-Al-Nb-based zirconium-based amorphous alloy under the protection of a vacuum of 10 ^-2 torr. An amorphous alloy watch case is prepared by a die casting method. In this embodiment, the atomic percentage of the Zr-Cu-Ni-Co-Al-Nb-based zirconium-based amorphous alloy is: Zr(54.75)-Cu(16.65)-Ni(5.6)-Co(8)-Al(10) )-Nb(5). The prepared amorphous alloy watch case has a Vickers hardness of 500, a relief strength of 2300 MPa, and a nickel release amount of 0.015 mg/cm ² /week. The surface of the amorphous alloy watch case is still good after being subjected to a salt spray test of 480 hours. corrosion. Among them, the amorphous alloy watch case of this embodiment is a conventional watch case.

本实施例中非晶合金手表外壳包括表壳、表盘和后盖；后盖采用Zr-Cu-Ni-Co-Al-Nb系锆基非晶合金而制造。In the present embodiment, the amorphous alloy watch case includes a case, a dial and a back cover; and the back cover is made of a Zr-Cu-Ni-Co-Al-Nb zirconium-based amorphous alloy.

本实施例中，该非晶合金手表外壳设置为均一厚度，且其厚度为1.2mm。In this embodiment, the amorphous alloy watch case is provided with a uniform thickness and a thickness of 1.2 mm.

本实施例中，利用Zr-Cu-Ni-Co-Al-Nb系锆基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳，包括如下步骤：In this embodiment, an amorphous alloy watch case is prepared by a die casting method using a raw material of a Zr-Cu-Ni-Co-Al-Nb-based zirconium-based amorphous alloy, including the following steps:

步骤一，投料：将Zr-Cu-Ni-Co-Al-Nb系锆基非晶合金原材料放入立式压铸机的供料装置，并由供料装置投入到立式压铸机的熔融装置中；立式压铸机的真空度为10^-2torr；本实施例中，Zr-Cu-Ni-Co-Al-Nb系锆基非晶合金原材料为Zr金属、Cu金属、Ni金属、Co金属、Al金属和Nb金属，且Zr金属、Cu金属、Ni金属、Co金属、Al金属和Nb金属的纯度均为99.9％以上。Step one, feeding: the Zr-Cu-Ni-Co-Al-Nb zirconium-based amorphous alloy raw material is placed in the feeding device of the vertical die casting machine, and is fed into the melting device of the vertical die casting machine by the feeding device. The vacuum degree of the vertical die casting machine is 10 ^-2 torr; in this embodiment, the raw material of the Zr-Cu-Ni-Co-Al-Nb zirconium-based amorphous alloy is Zr metal, Cu metal, Ni metal, Co metal, The Al metal and the Nb metal, and the purity of the Zr metal, the Cu metal, the Ni metal, the Co metal, the Al metal, and the Nb metal are all 99.9% or more.

步骤二，熔融：利用感应加热的方式将Zr-Cu-Ni-Co-Al-Nb系锆基非晶合金原材料熔融并形成熔汤，熔汤的温度为1180℃； Step 2, melting: the Zr-Cu-Ni-Co-Al-Nb-based zirconium-based amorphous alloy raw material is melted by induction heating to form a melt, the temperature of the melt is 1180 ° C;

步骤三，倒汤：将步骤二得到的熔汤倒入手表外壳模具浇口套中，然后以冲头将熔汤注入手表外壳模具中；其中，冲头的速度为2m/s；手表外壳模具的温度为230℃；其中，在倒汤过程中，利用喷枪向手表外壳模具表面喷射氩气以达到清洁手表外壳模具表面的熔汤碎屑的目的；Step 3: Pour the soup: pour the molten soup obtained in the second step into the mold cover of the watch case, and then inject the molten soup into the mold of the watch case with a punch; wherein the speed of the punch is 2 m/s; the watch case mold The temperature is 230 ° C; wherein, during the pouring process, the argon gas is sprayed onto the surface of the mold shell of the watch by the spray gun to achieve the purpose of cleaning the molten scrap on the surface of the mold of the watch case;

本实施例中，对机加工后的非晶合金手表外壳进行抛光处理。In this embodiment, the machined amorphous alloy watch case is polished.

本实施例7制得的非晶合金手表外壳相对于利用钛合金或不锈钢制备的手表外壳，均具有优异的维氏硬度、降伏强度和抗腐蚀的性能；而且，利用Zr-Cu-Ni-Co-Al-Nb系锆基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳具有机械加工量小、加工时间短、生产效率高、生产成本低、易于成型、且制备工艺简单的优点。The amorphous alloy watch case obtained in the seventh embodiment has excellent Vickers hardness, lodging strength and corrosion resistance with respect to a watch case made of titanium alloy or stainless steel; and, by using Zr-Cu-Ni-Co -The raw material of the Al-Nb-based zirconium-based amorphous alloy is prepared by a die-casting method to prepare an amorphous alloy watch case having a small amount of mechanical processing. The processing time is short, the production efficiency is high, the production cost is low, the molding is easy, and the preparation process is simple.

实施例8。Example 8.

本实施例的一种非晶合金手表外壳，具体为，在氩气的保护下，利用Zr-Cu-Ni-Co-Al-Ti系锆基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳。本实施例中，Zr-Cu-Ni-Co-Al-Ti系锆基非晶合金的原子百分比为：Zr(50)-Cu(20)-Ni(8)-Co(7)-Al(7)-Ti(8)。所制备的非晶合金手表外壳的维氏硬度为500，降伏强度为2300MPa，镍释放量为0mg/cm²/week，经受480小时的盐雾测试后非晶合金手表外壳的表面仍然良好无腐蚀。其中，本实施例的非晶合金手表外壳为智能手表外壳。An amorphous alloy watch case of the present embodiment, specifically, an amorphous alloy is prepared by a die casting method using a raw material of a Zr-Cu-Ni-Co-Al-Ti zirconium-based amorphous alloy under the protection of argon gas. Watch case. In this embodiment, the atomic percentage of the Zr-Cu-Ni-Co-Al-Ti-based zirconium-based amorphous alloy is: Zr(50)-Cu(20)-Ni(8)-Co(7)-Al(7) )-Ti(8). The prepared amorphous alloy watch case has a Vickers hardness of 500, a relief strength of 2300 MPa, and a nickel release amount of 0 mg/cm ² /week. The surface of the amorphous alloy watch case is still good and non-corrosive after being subjected to a salt spray test of 480 hours. . Wherein, the amorphous alloy watch case of the embodiment is a smart watch case.

本实施例中非晶合金手表外壳包括表壳、表盘和后盖；表壳、表盘和后盖均采用Zr-Cu-Ni-Co-Al-Ti系锆基非晶合金而制造。In the present embodiment, the amorphous alloy watch case includes a case, a dial and a back cover; and the case, the dial and the back cover are both made of a Zr-Cu-Ni-Co-Al-Ti-based zirconium-based amorphous alloy.

本实施例中，该非晶合金手表外壳设置为均一厚度，且其厚度为2.3mm。In this embodiment, the amorphous alloy watch case is provided with a uniform thickness and a thickness of 2.3 mm.

本实施例中，利用Zr-Cu-Ni-Co-Al-Ti系锆基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳，包括如下步骤：In this embodiment, an amorphous alloy watch case is prepared by a die casting method using a raw material of a Zr-Cu-Ni-Co-Al-Ti-based zirconium-based amorphous alloy, and includes the following steps:

步骤一，投料：将Zr-Cu-Ni-Co-Al-Ti系锆基非晶合金原材料放入立式压铸机的供料装置，并由供料装置投入到立式压铸机的熔融装置中；本实施例中，立式压铸机充入氩气进行保护；本实施例中，Zr-Cu-Ni-Co-Al-Ti系锆基非晶合金原材料为Zr金属、Cu金属、Ni金属、Co金属、Al金属和Ti金属，且Zr金属、Cu金属、Ni金属、Co金属、Al金属和Ti金属的纯度均为99.9％以上。Step one, feeding: the Zr-Cu-Ni-Co-Al-Ti-based zirconium-based amorphous alloy raw material is placed in the feeding device of the vertical die casting machine, and is fed into the melting device of the vertical die casting machine by the feeding device. In this embodiment, the vertical die casting machine is filled with argon gas for protection; in this embodiment, the Zr-Cu-Ni-Co-Al-Ti zirconium-based amorphous alloy raw material is Zr metal, Cu metal, Ni metal, Co metal, Al metal and Ti metal, and the purity of Zr metal, Cu metal, Ni metal, Co metal, Al metal and Ti metal are all 99.9% or more.

步骤二，熔融：利用感应加热的方式将Zr-Cu-Ni-Co-Al-Ti系锆基非晶合金原材料熔融并形成熔汤，熔汤的温度为1130℃； Step 2, melting: the Zr-Cu-Ni-Co-Al-Ti-based zirconium-based amorphous alloy raw material is melted by induction heating to form a melt, the temperature of the melt is 1130 ° C;

本实施例中，对机加工后的非晶合金手表外壳进行喷涂处理，本实施例的喷涂处理是进行防指纹漆的喷涂处理。In the present embodiment, the machined amorphous alloy watch case is subjected to a spray coating process, and the spray process of the present embodiment is a spray process for performing an anti-fingerprint paint.

本实施例8制得的非晶合金手表外壳相对于利用钛合金或不锈钢制备的手表外壳，均具有优异的维氏硬度、降伏强度和抗腐蚀的性能；而且，利用Zr-Cu-Ni-Co-Al-Ti系锆基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳具有机械加工量小、加工时间短、生产效率高、生产成本低、易于成型、且制备工艺简单的优点。The amorphous alloy watch case obtained in the eighth embodiment has excellent Vickers hardness, lodging strength and corrosion resistance with respect to a watch case made of titanium alloy or stainless steel; and, by using Zr-Cu-Ni-Co The raw material of the Al-Ti-based zirconium-based amorphous alloy is prepared by the die-casting method. The amorphous alloy watch casing has the advantages of small machining amount, short processing time, high production efficiency, low production cost, easy molding, and simple preparation process.

实施例9。Example 9.

本实施例的一种非晶合金手表外壳，具体为，在氩气的保护下，利用Zr-Cu-Ni-Co-Al-Sn系锆基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳。本实施例中，Zr-Cu-Ni-Co-Al-Sn系锆基非晶合金的原子百分比为：Zr(60)-Cu(12)-Ni(4)-Co(6)-Al(15)-Sn(3)。所制备的非晶合金手表外壳的维氏硬度为500，降伏强度为2300MPa，镍释放量为0mg/cm²/week，经受480小时的盐雾测试后非晶合金手表外壳的表面仍然良好无腐蚀。其中，本实施例的非晶合金手表外壳为智能手表外壳。An amorphous alloy watch case of the present embodiment, specifically, an amorphous alloy is prepared by a die casting method using a raw material of a Zr-Cu-Ni-Co-Al-Sn-based zirconium-based amorphous alloy under the protection of argon gas. Watch case. In this embodiment, the atomic percentage of the Zr-Cu-Ni-Co-Al-Sn-based zirconium-based amorphous alloy is: Zr(60)-Cu(12)-Ni(4)-Co(6)-Al(15) )-Sn(3). The prepared amorphous alloy watch case has a Vickers hardness of 500, a relief strength of 2300 MPa, and a nickel release amount of 0 mg/cm ² /week. The surface of the amorphous alloy watch case is still good and non-corrosive after being subjected to a salt spray test of 480 hours. . Wherein, the amorphous alloy watch case of the embodiment is a smart watch case.

本实施例中非晶合金手表外壳包括表壳、表盘和后盖；表壳、表盘和后盖均采用Zr-Cu-Ni-Co-Al-Sn系锆基非晶合金而制造。In the present embodiment, the amorphous alloy watch case includes a case, a dial and a back cover; and the case, the dial and the back cover are both made of a Zr-Cu-Ni-Co-Al-Sn-based zirconium-based amorphous alloy.

本实施例中，该非晶合金手表外壳设置为均一厚度，且其厚度为2.7mm。In this embodiment, the amorphous alloy watch case is provided with a uniform thickness and a thickness of 2.7 mm.

本实施例中，利用Zr-Cu-Ni-Co-Al-Sn系锆基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳，包括如下步骤：In this embodiment, an amorphous alloy watch case is prepared by a die casting method using a raw material of a Zr-Cu-Ni-Co-Al-Sn-based zirconium-based amorphous alloy, including the following steps:

步骤一，投料：将Zr-Cu-Ni-Co-Al-Sn系锆基非晶合金原材料放入立式压铸机的供料装置，并由供料装置投入到立式压铸机的熔融装置中；本实施例中，立式压铸机充入氩气进行保护；本实施例中，Zr-Cu-Ni-Co-Al-Sn系锆基非晶合金原材料为Zr金属、Cu金属、Ni金属、Co金属、Al金属和Sn金属，且Zr金属、Cu金属、Ni金属、Co金属、Al金属和Sn金属的纯度均为99.9％以上。Step one, feeding: the Zr-Cu-Ni-Co-Al-Sn-based zirconium-based amorphous alloy raw material is placed in the feeding device of the vertical die casting machine, and is fed into the melting device of the vertical die casting machine by the feeding device. In this embodiment, the vertical die casting machine is filled with argon gas for protection; in this embodiment, the Zr-Cu-Ni-Co-Al-Sn-based zirconium-based amorphous alloy raw material is Zr metal, Cu metal, Ni metal, Co metal, Al metal, and Sn metal, and the purity of Zr metal, Cu metal, Ni metal, Co metal, Al metal, and Sn metal are all 99.9% or more.

步骤二，熔融：利用感应加热的方式将Zr-Cu-Ni-Co-Al-Sn系锆基非晶合金原材料熔融并形成熔汤，熔汤的温度为1160℃； Step 2, melting: the Zr-Cu-Ni-Co-Al-Sn-based zirconium-based amorphous alloy raw material is melted by induction heating to form a melt, the temperature of the melt is 1160 ° C;

本实施例中，在氩气的保护下，对步骤六中完成切割浇铸口和溢流口的非晶合金手表外壳，进行热塑成型(TPF)以达到结构、精度和表面品质的要求。In this embodiment, under the protection of argon, the amorphous alloy watch case which cuts the casting port and the overflow port in step 6 is subjected to thermoforming (TPF) to achieve the requirements of structure, precision and surface quality.

本实施例中，对完成热塑成型(TPF)的非晶合金手表外壳先进行PVD处理。In this embodiment, the amorphous alloy watch case that has been subjected to thermoforming (TPF) is first subjected to PVD treatment.

本实施例9制得的非晶合金手表外壳相对于利用钛合金或不锈钢制备的手表外壳，均具有优异的维氏硬度、降伏强度和抗腐蚀的性能；而且，利用Zr-Cu-Ni-Co-Al-Sn系锆基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳具有机械加工量小、加工时间短、生产效率高、生产成本低、易于成型、且制备工艺简单的优点。The amorphous alloy watch case obtained in the embodiment 9 has excellent Vickers hardness, lodging strength and corrosion resistance with respect to the watch case prepared by using titanium alloy or stainless steel; and, by using Zr-Cu-Ni-Co The raw material of the Al-Sn-based zirconium-based amorphous alloy is prepared by the die-casting method. The amorphous alloy watch casing has the advantages of small machining amount, short processing time, high production efficiency, low production cost, easy molding, and simple preparation process.

实施例10。Example 10.

本实施例的一种非晶合金手表外壳，具体为，在氩气的保护下，利用 Zr-Cu-Ni-Co-Al-Sn系锆基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳。本实施例中，Zr-Cu-Ni-Co-Al-Sn系锆基非晶合金的原子百分比为：Zr(58)-Cu(14)-Ni(3)-Co(10)-Al(13)-Sn(2)。所制备的非晶合金手表外壳的维氏硬度为500，降伏强度为2300MPa，镍释放量为0mg/cm²/week，经受480小时的盐雾测试后非晶合金手表外壳的表面仍然良好无腐蚀。其中，本实施例的非晶合金手表外壳为智能手表外壳。An amorphous alloy watch case of the present embodiment, specifically, an amorphous alloy is prepared by a die casting method using a raw material of a Zr-Cu-Ni-Co-Al-Sn-based zirconium-based amorphous alloy under the protection of argon gas. Watch case. In this embodiment, the atomic percentage of the Zr-Cu-Ni-Co-Al-Sn-based zirconium-based amorphous alloy is: Zr(58)-Cu(14)-Ni(3)-Co(10)-Al(13) )-Sn(2). The prepared amorphous alloy watch case has a Vickers hardness of 500, a relief strength of 2300 MPa, and a nickel release amount of 0 mg/cm ² /week. The surface of the amorphous alloy watch case is still good and non-corrosive after being subjected to a salt spray test of 480 hours. . Wherein, the amorphous alloy watch case of the embodiment is a smart watch case.

本实施例中，在氩气的保护下，对步骤六中完成切割浇铸口和溢流口的非晶合金手表外壳，进行热塑成型(TPF)以达到结构、精度和表面品质的要求。In this embodiment, under the protection of argon, the amorphous alloy hand for cutting the casting port and the overflow port is completed in step 6. The watch case is thermoformed (TPF) for structural, precision and surface quality requirements.

本实施例中，对完成热塑成型(TPF)的非晶合金手表外壳先进行喷砂处理，再进行PVD处理。In this embodiment, the amorphous alloy watch case that has completed the thermoforming (TPF) is sandblasted first, and then subjected to PVD treatment.

本实施例10制得的非晶合金手表外壳相对于利用钛合金或不锈钢制备的手表外壳，均具有优异的维氏硬度、降伏强度和抗腐蚀的性能；而且，利用Zr-Cu-Ni-Co-Al-Sn系锆基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳具有机械加工量小、加工时间短、生产效率高、生产成本低、易于成型、且制备工艺简单的优点。The amorphous alloy watch case obtained in the tenth embodiment has excellent Vickers hardness, lodging strength and corrosion resistance with respect to a watch case made of titanium alloy or stainless steel; and, by using Zr-Cu-Ni-Co The raw material of the Al-Sn-based zirconium-based amorphous alloy is prepared by the die-casting method. The amorphous alloy watch casing has the advantages of small machining amount, short processing time, high production efficiency, low production cost, easy molding, and simple preparation process.

实施例11。Example 11.

本实施例的一种非晶合金手表外壳，具体为，在氪气的保护下，利用Cu-Ti-Zr-Ni-Sn系铜基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳。本实施例中，Cu-Ti-Zr-Ni-Sn系铜基非晶合金的原子百分比为：Cu(42)-Ti(34)-Zr(11)-Ni(8)-Sn(5)。所制备的非晶合金手表外壳的维氏硬度为550，降伏强度为3000MPa，镍释放量为0.005mg/cm²/week，经受360小时的盐雾测试后非晶合金手表外壳的表面仍然良好无腐蚀。其中，本实施例的非晶合金手表外壳为传统手表外壳。An amorphous alloy watch case of the embodiment, in particular, an amorphous alloy watch case is prepared by a die casting method using a raw material of a Cu-Ti-Zr-Ni-Sn-based copper-based amorphous alloy under the protection of helium . In the present embodiment, the atomic percentage of the Cu-Ti-Zr-Ni-Sn-based copper-based amorphous alloy is: Cu(42)-Ti(34)-Zr(11)-Ni(8)-Sn(5). The prepared amorphous alloy watch case has a Vickers hardness of 550, a relief strength of 3000 MPa, and a nickel release amount of 0.005 mg/cm ² /week. The surface of the amorphous alloy watch case is still good after being subjected to a salt spray test for 360 hours. corrosion. Wherein, the amorphous alloy watch case of the embodiment is a traditional watch case.

本实施例中非晶合金手表外壳包括表壳、表盘和后盖；表壳、表盘和后盖均采用Cu-Ti-Zr-Ni-Sn系铜基非晶合金而制造。In the present embodiment, the amorphous alloy watch case includes a case, a dial and a back cover; and the case, the dial and the back cover are both made of Cu-Ti-Zr-Ni-Sn-based copper-based amorphous alloy.

本实施例中，该非晶合金手表外壳设置为均一厚度，且其厚度为2.5mm。In this embodiment, the amorphous alloy watch case is provided with a uniform thickness and a thickness of 2.5 mm.

本实施例中，利用Cu-Ti-Zr-Ni-Sn系铜基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳，包括如下步骤：In this embodiment, an amorphous alloy watch case is prepared by a die-casting method using a raw material of a Cu-Ti-Zr-Ni-Sn-based copper-based amorphous alloy, including the following steps:

步骤一，投料：将Cu-Ti-Zr-Ni-Sn系铜基非晶合金原材料放入立式压铸机的供料装置，并由供料装置投入到立式压铸机的熔融装置中；本实施例中，立式压铸机充入氪气进行保护；本实施例中，Cu-Ti-Zr-Ni-Sn系铜基非晶合金原材料为Cu金属、Ti金属、Zr金属、Ni金属和Sn金属，且Cu金属、Ti金属、Zr金属、Ni金属和Sn金属的纯度均为99.9％以上。Step one, feeding: Put the Cu-Ti-Zr-Ni-Sn copper-based amorphous alloy raw material into the vertical die casting machine The material device is put into the melting device of the vertical die casting machine by the feeding device; in the embodiment, the vertical die casting machine is filled with helium gas for protection; in this embodiment, the Cu-Ti-Zr-Ni-Sn system The copper-based amorphous alloy raw materials are Cu metal, Ti metal, Zr metal, Ni metal, and Sn metal, and the purity of Cu metal, Ti metal, Zr metal, Ni metal, and Sn metal is 99.9% or more.

步骤二，熔融：利用感应加热的方式将Cu-Ti-Zr-Ni-Sn系铜基非晶合金原材料熔融并形成熔汤，熔汤的温度为1050℃； Step 2, melting: the Cu-Ti-Zr-Ni-Sn-based copper-based amorphous alloy raw material is melted by induction heating to form a melt, the temperature of the melt is 1050 ° C;

步骤三，倒汤：将步骤二得到的熔汤倒入手表外壳模具浇口套中，然后以冲头将熔汤注入手表外壳模具中；其中，冲头的速度为4m/s；手表外壳模具的温度为220℃；其中，在倒汤过程中，利用喷枪向手表外壳模具表面喷射氩气以达到清洁手表外壳模具表面的熔汤碎屑的目的；Step 3: Pour the soup: pour the molten soup obtained in the second step into the mold cover of the watch case, and then inject the molten soup into the mold of the watch case with a punch; wherein the speed of the punch is 4 m/s; the watch case mold The temperature is 220 ° C; wherein, during the pouring process, the argon gas is sprayed onto the surface of the mold shell of the watch by the spray gun to achieve the purpose of cleaning the molten scrap on the surface of the mold shell of the watch;

步骤四，冷却：对步骤三中注入了熔汤的手表外壳模具进行冷却成型，得到非晶合金手表外壳，冷却速度为10⁴K/s；冷却时间为20秒；Step 4, cooling: cooling the watch case mold into which the molten soup is poured in the third step, obtaining an amorphous alloy watch case, the cooling rate is 10 ⁴ K/s; the cooling time is 20 seconds;

本实施例中，在氪气的保护下，对步骤六中完成切割浇铸口和溢流口的非晶合金手表外壳，进行热塑成型(TPF)以达到结构、精度和表面品质的要求。In the present embodiment, under the protection of helium, the amorphous alloy watch casing which cuts the casting port and the overflow port in step 6 is subjected to thermoforming (TPF) to achieve the requirements of structure, precision and surface quality.

本实施例中，对完成热塑成型(TPF)的非晶合金手表外壳先进行喷砂处理，再进行喷涂处理。In this embodiment, the amorphous alloy watch case that completes the thermoforming (TPF) is sandblasted first, and then Spray treatment.

本实施例11制得的非晶合金手表外壳相对于利用钛合金或不锈钢制备的手表外壳，均具有优异的维氏硬度、降伏强度和抗腐蚀的性能；而且，利用Cu-Ti-Zr-Ni-Sn系铜基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳具有机械加工量小、加工时间短、生产效率高、生产成本低、易于成型、且制备工艺简单的优点。The amorphous alloy watch case prepared in the present embodiment 11 has excellent Vickers hardness, lodging strength and corrosion resistance with respect to a watch case made of titanium alloy or stainless steel; and, by using Cu-Ti-Zr-Ni The raw material of the Sn-based copper-based amorphous alloy is prepared by the die-casting method. The amorphous alloy watch case has the advantages of small machining amount, short processing time, high production efficiency, low production cost, easy molding, and simple preparation process.

实施例12。Example 12.

本实施例的一种非晶合金手表外壳，具体为，在氙气的保护下，利用Cu-Ti-Zr-Co-Sn系铜基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳。本实施例中，Cu-Ti-Zr-Co-Sn的原子百分比为：Cu(40)-Ti(40)-Zr(7)-Co(5)-Sn(8)。所制备的非晶合金手表外壳的维氏硬度为450，降伏强度为1000MPa，镍释放量为0.003mg/cm²/week，经受380小时的盐雾测试后非晶合金手表外壳的表面仍然良好无腐蚀。其中，本实施例的非晶合金手表外壳为智能手表外壳。In an amorphous alloy watch case of the present embodiment, specifically, an amorphous alloy watch case is prepared by a die casting method using a raw material of a Cu-Ti-Zr-Co-Sn-based copper-based amorphous alloy under the protection of helium. In the present embodiment, the atomic percentage of Cu-Ti-Zr-Co-Sn is: Cu(40)-Ti(40)-Zr(7)-Co(5)-Sn(8). The prepared amorphous alloy watch case has a Vickers hardness of 450, a relief strength of 1000 MPa, and a nickel release amount of 0.003 mg/cm ² /week. The surface of the amorphous alloy watch case is still good after being subjected to a salt spray test of 380 hours. corrosion. Wherein, the amorphous alloy watch case of the embodiment is a smart watch case.

本实施例中非晶合金手表外壳包括表壳、表盘和后盖；表壳、表盘和后盖均采用Cu-Ti-Zr-Co-Sn系铜基非晶合金而制造。In the present embodiment, the amorphous alloy watch case includes a case, a dial and a back cover; and the case, the dial and the back cover are both made of Cu-Ti-Zr-Co-Sn-based copper-based amorphous alloy.

本实施例中，该非晶合金手表外壳设置为均一厚度，且其厚度为1.8mm。In this embodiment, the amorphous alloy watch case is provided with a uniform thickness and a thickness of 1.8 mm.

本实施例中，利用Cu-Ti-Zr-Co-Sn系铜基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳，包括如下步骤：In this embodiment, an amorphous alloy watch case is prepared by a die-casting method using a raw material of a Cu-Ti-Zr-Co-Sn-based copper-based amorphous alloy, including the following steps:

步骤一，投料：将Cu-Ti-Zr-Co-Sn系铜基非晶合金原材料放入立式压铸机的供料装置，并由供料装置投入到立式压铸机的熔融装置中；本实施例中，立式压铸机充入氙气进行保护；本实施例中，Cu-Ti-Zr-Co-Sn系铜基非晶合金原材料为Cu金属、Ti金属、Zr金属、Co金属和Sn金属，且Cu金属、Ti金属、Zr金属、Co金属和Sn金属的纯度均为99.9％以上。Step one, feeding: the Cu-Ti-Zr-Co-Sn copper-based amorphous alloy raw material is placed in the feeding device of the vertical die casting machine, and is fed into the melting device of the vertical die casting machine by the feeding device; In the embodiment, the vertical die casting machine is filled with helium gas for protection; in this embodiment, the Cu-Ti-Zr-Co-Sn copper-based amorphous alloy raw materials are Cu metal, Ti metal, Zr metal, Co metal, and Sn metal. The purity of Cu metal, Ti metal, Zr metal, Co metal, and Sn metal is 99.9% or more.

步骤二，熔融：利用感应加热的方式将Cu-Ti-Zr-Co-Sn系铜基非晶合金原材料熔融并形成熔汤，熔汤的温度为980℃； Step 2, melting: the Cu-Ti-Zr-Co-Sn-based copper-based amorphous alloy raw material is melted by induction heating to form a melt, the temperature of the melt is 980 ° C;

步骤三，倒汤：将步骤二得到的熔汤倒入手表外壳模具浇口套中，然后以冲头将熔汤注入手表外壳模具中；其中，冲头的速度为3m/s；手表外壳模具的温度为240℃；其中，在倒汤过程中，利用喷枪向手表外壳模具表面喷射氩气以达到清洁手表外壳模具表面的熔汤碎屑的目的；Step 3: Pour the soup: pour the molten soup obtained in the second step into the mold cover of the watch case, and then inject the molten soup into the mold of the watch case with a punch; wherein the speed of the punch is 3 m/s; the watch case mold The temperature is 240 ° C; wherein, during the pouring process, the argon gas is sprayed onto the surface of the mold shell of the watch by the spray gun to achieve the purpose of cleaning the molten scrap on the surface of the mold of the watch case;

步骤四，冷却：对步骤三中注入了熔汤的手表外壳模具进行冷却成型，得到非晶合金手表外壳，冷却速度为10³K/s；冷却时间为22秒； Step 4, cooling: cooling the watch case mold into which the molten soup is poured in the third step, obtaining an amorphous alloy watch case, the cooling rate is 10 ³ K/s; the cooling time is 22 seconds;

本实施例中，在氙气的保护下，对步骤六中完成切割浇铸口和溢流口的非晶合金手表外壳，进行快速放电成型(RDF)以达到结构、精度和表面品质的要求。In the present embodiment, under the protection of helium, the amorphous alloy watch casing that cuts the casting port and the overflow port in step 6 is subjected to rapid discharge forming (RDF) to meet the requirements of structure, precision and surface quality.

本实施例中，对完成快速放电成型(RDF)的非晶合金手表外壳进行镜面抛光处理。In this embodiment, the amorphous alloy watch case that has completed rapid discharge forming (RDF) is mirror-polished.

本实施例12制得的非晶合金手表外壳相对于利用钛合金或不锈钢制备的手表外壳，均具有优异的维氏硬度、降伏强度和抗腐蚀的性能；而且，利用Cu-Ti-Zr-Co-Sn系铜基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳具有机械加工量小、加工时间短、生产效率高、生产成本低、易于成型、且制备工艺简单的优点。The amorphous alloy watch case obtained in the embodiment 12 has excellent Vickers hardness, lodging strength and corrosion resistance with respect to a watch case made of titanium alloy or stainless steel; and, by using Cu-Ti-Zr-Co The raw material of the Sn-based copper-based amorphous alloy is prepared by the die-casting method. The amorphous alloy watch case has the advantages of small machining amount, short processing time, high production efficiency, low production cost, easy molding, and simple preparation process.

实施例13。Example 13.

本实施例的一种非晶合金手表外壳，具体为，在氙气的保护下，利用Cu-Ti-Zr-Ni-Co-Sn系铜基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳。本实施例中，Cu-Ti-Zr-Ni-Co-Sn的原子百分比为：Cu(43)-Ti(36)-Zr(7)-Ni(6)-Co(6)-Sn(2)。所制备的非晶合金手表外壳的维氏硬度为450，降伏强度为1000MPa，镍释放量为0.005mg/cm²/week，经受380小时的盐雾测试后非晶合金手表外壳的表面仍然良好无腐蚀。其中，本实施例的非晶合金手表外壳为传统手表外壳。An amorphous alloy watch case of the embodiment, in particular, an amorphous alloy watch prepared by a die casting method using a raw material of a Cu-Ti-Zr-Ni-Co-Sn-based copper-based amorphous alloy under the protection of helium shell. In this embodiment, the atomic percentage of Cu-Ti-Zr-Ni-Co-Sn is: Cu(43)-Ti(36)-Zr(7)-Ni(6)-Co(6)-Sn(2) . The prepared amorphous alloy watch case has a Vickers hardness of 450, a relief strength of 1000 MPa, and a nickel release amount of 0.005 mg/cm ² /week. The surface of the amorphous alloy watch case is still good after being subjected to a salt spray test of 380 hours. corrosion. Wherein, the amorphous alloy watch case of the embodiment is a conventional watch case.

本实施例中非晶合金手表外壳包括表壳、表盘和后盖；表壳、表盘和后盖均采用Cu-Ti-Zr-Ni-Co-Sn系铜基非晶合金而制造。In the present embodiment, the amorphous alloy watch case includes a case, a dial and a back cover; and the case, the dial and the back cover are both made of Cu-Ti-Zr-Ni-Co-Sn-based copper-based amorphous alloy.

本实施例中，该非晶合金手表外壳设置为均一厚度，且其厚度为1.6mm。In this embodiment, the amorphous alloy watch case is provided with a uniform thickness and a thickness of 1.6 mm.

本实施例中，利用Cu-Ti-Zr-Ni-Co-Sn系铜基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳，包括如下步骤：In this embodiment, an amorphous alloy watch case is prepared by a die casting method using a raw material of a Cu-Ti-Zr-Ni-Co-Sn-based copper-based amorphous alloy, including the following steps:

步骤一，投料：将Cu-Ti-Zr-Ni-Co-Sn系铜基非晶合金原材料放入立式压铸机的供料装置，并由供料装置投入到立式压铸机的熔融装置中；本实施例中，立式压铸机充入氙气进行保护；本实施例中，Cu-Ti-Zr-Ni-Co-Sn系铜基非晶合金原材料为Cu金属、Ti金属、Zr金属、Ni金属、Co金属和Sn金属，且Cu金属、Ti金属、Zr金属、Ni金属、Co金属和Sn金属的纯度均为99.9％以上。Step one, feeding: the Cu-Ti-Zr-Ni-Co-Sn copper-based amorphous alloy raw material is placed in the feeding device of the vertical die casting machine, and is fed into the melting device of the vertical die casting machine by the feeding device. In this embodiment, the vertical die casting machine is filled with helium gas for protection; in this embodiment, the Cu-Ti-Zr-Ni-Co-Sn copper-based amorphous alloy raw material is Cu metal, Ti metal, Zr metal, Ni The metal, the Co metal, and the Sn metal, and the purity of the Cu metal, the Ti metal, the Zr metal, the Ni metal, the Co metal, and the Sn metal are all 99.9% or more.

步骤二，熔融：利用感应加热的方式将Cu-Ti-Zr-Ni-Co-Sn系铜基非晶合金原材料熔融并形成熔汤，熔汤的温度为970℃； Step 2, melting: the Cu-Ti-Zr-Ni-Co-Sn-based copper-based amorphous alloy raw material is melted by induction heating to form a melt, the temperature of the melt is 970 ° C;

步骤四，冷却：对步骤三中注入了熔汤的手表外壳模具进行冷却成型，得到非晶合金手表外壳，冷却速度为10³K/s；冷却时间为22秒；Step 4, cooling: cooling the watch case mold into which the molten soup is poured in the third step, obtaining an amorphous alloy watch case, the cooling rate is 10 ³ K/s; the cooling time is 22 seconds;

(1)对步骤六中完成切割浇铸口和溢流口的非晶合金手表外壳中需要进一步加工的位置利用电容放电快速加热，并且加热到玻璃化转变温度(Tg)与熔点(Tm)之间以使所需加工的位置达到较低粘度而能够自由型塑的目的； (1) Rapidly heating the position of the amorphous alloy watch case that completes the cutting of the casting port and the overflow port in step 6 by means of capacitor discharge, and heating to between the glass transition temperature (Tg) and the melting point (Tm) The purpose of free molding is to achieve a lower viscosity at the desired processing position;

本实施例中，对完成快速放电成型(RDF)的非晶合金手表外壳先进行滚筒研磨，再进行抛光处理。In this embodiment, the amorphous alloy watch case that completes the rapid discharge forming (RDF) is first subjected to barrel grinding and then polished.

本实施例13制得的非晶合金手表外壳相对于利用钛合金或不锈钢制备的手表外壳，均具有优异的维氏硬度、降伏强度和抗腐蚀的性能；而且，利用Cu-Ti-Zr-Ni-Co-Sn系铜基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳具有机械加工量小、加工时间短、生产效率高、生产成本低、易于成型、且制备工艺简单的优点。The amorphous alloy watch case obtained in the present embodiment 13 has excellent Vickers hardness, lodging strength and corrosion resistance with respect to a watch case made of titanium alloy or stainless steel; and, by using Cu-Ti-Zr-Ni The raw material of the -Co-Sn copper-based amorphous alloy is prepared by the die-casting method. The amorphous alloy watch casing has the advantages of small machining amount, short processing time, high production efficiency, low production cost, easy molding, and simple preparation process.

实施例14。Example 14.

本实施例的一种非晶合金手表外壳，具体为，在氩气的保护下，利用钛基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳，所制备的非晶合金手表外壳的维氏硬度为570，降伏强度为2800MPa，镍释放量为0mg/cm²/week，经受450小时的盐雾测试后非晶合金手表外壳的表面仍然良好无腐蚀。其中，本实施例的非晶合金手表外壳为智能手表外壳。An amorphous alloy watch case of the present embodiment, specifically, an amorphous alloy watch case is prepared by a die-casting method using a raw material of a titanium-based amorphous alloy under the protection of argon gas, and the prepared amorphous alloy watch case is The Vickers hardness is 570, the lodging strength is 2800 MPa, and the nickel release amount is 0 mg/cm ² /week. After the 450 hour salt spray test, the surface of the amorphous alloy watch case is still good and non-corrosive. Wherein, the amorphous alloy watch case of the embodiment is a smart watch case.

本实施例中非晶合金手表外壳包括表壳、表盘和后盖；表壳、表盘和后盖均采用钛基非晶合金而制造。In the present embodiment, the amorphous alloy watch case includes a case, a dial and a back cover; and the case, the dial and the back cover are both made of a titanium-based amorphous alloy.

本实施例中，该非晶合金手表外壳设置为均一厚度，且其厚度为2.4mm。In this embodiment, the amorphous alloy watch case is provided with a uniform thickness and a thickness of 2.4 mm.

本实施例中，利用钛基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳，包括如下步骤：In this embodiment, the amorphous alloy watch case is prepared by a die casting method using a raw material of a titanium-based amorphous alloy, and includes the following steps:

步骤一，投料：将钛基非晶合金原材料放入立式压铸机的供料装置，并由供料装置投入到立式压铸机的熔融装置中；本实施例中，立式压铸机充入氩气进行保护；Step one, feeding: placing the titanium-based amorphous alloy raw material into the feeding device of the vertical die casting machine, and feeding it into the melting device of the vertical die casting machine by the feeding device; in this embodiment, the vertical die casting machine is charged Argon gas protection;

步骤二，熔融：利用感应加热的方式将钛基非晶合金原材料熔融并形成熔汤，熔汤的温度为1080℃； Step 2, melting: using a method of induction heating to melt the titanium-based amorphous alloy raw material and forming a melt, the temperature of the melt is 1080 ° C;

步骤三，倒汤：将步骤二得到的熔汤倒入手表外壳模具浇口套中，然后以冲头将熔汤注入手表外壳模具中；其中，冲头的速度为1m/s；手表外壳模具的温度为205℃；其中，在倒汤过程中，利用喷枪向手表外壳模具表面喷射氩气以达到清洁手表外壳模具表面的熔汤碎屑的目的；Step 3: Pour the soup: pour the molten soup obtained in the second step into the mold cover of the watch case, and then inject the molten soup into the mold of the watch case with a punch; wherein the speed of the punch is 1 m/s; the watch case mold The temperature is 205 ° C; wherein, during the pouring process, the argon gas is sprayed onto the surface of the mold shell of the watch by the spray gun to clean the watch. The purpose of melting the crumb on the surface of the shell mold;

步骤四，冷却：对步骤三中注入了熔汤的手表外壳模具进行冷却成型，得到非晶合金手表外壳，冷却速度为10²K/s；冷却时间为25秒；Step 4, cooling: cooling the watch case mold into which the molten soup is poured in the third step, obtaining an amorphous alloy watch case, the cooling rate is 10 ² K/s; the cooling time is 25 seconds;

本实施例中，在氩气的保护下，对步骤六中完成切割浇铸口和溢流口的非晶合金手表外壳，进行机加工以达到结构和精度的要求，然后进行热塑成型(TPF)和快速放电成型(RDF)以达到结构、精度和表面品质的要求。其中机加工包括CNC铣和/或CNC切削。In this embodiment, under the protection of argon, the amorphous alloy watch casing which cuts the casting port and the overflow port in step 6 is machined to meet the structural and precision requirements, and then subjected to thermoforming (TPF). And rapid discharge molding (RDF) to achieve structural, precision and surface quality requirements. Machining includes CNC milling and/or CNC cutting.

其中，上述快速放电成型(RDF)的整体加工期间的时间温度曲线不碰触到第三 TTT图中的晶化区。Wherein, the time-temperature curve during the overall processing of the above rapid discharge forming (RDF) does not touch the third Crystallization zone in the TTT diagram.

本实施例中，对完成热塑成型(TPF)和快速放电成型(RDF)的非晶合金手表外壳进行PVD处理。In this embodiment, a PVD process is performed on an amorphous alloy watch case that is completed by thermoforming (TPF) and rapid discharge forming (RDF).

本实施例14制得的非晶合金手表外壳相对于利用钛合金或不锈钢制备的手表外壳，均具有优异的维氏硬度、降伏强度和抗腐蚀的性能；而且，利用钛基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳具有机械加工量小、加工时间短、生产效率高、生产成本低、易于成型、且制备工艺简单的优点。The amorphous alloy watch case obtained in the embodiment 14 has excellent Vickers hardness, lodging strength and corrosion resistance with respect to the watch case prepared by using titanium alloy or stainless steel; and, the raw material using the titanium-based amorphous alloy The amorphous alloy watch casing prepared by the die-casting method has the advantages of small machining amount, short processing time, high production efficiency, low production cost, easy molding, and simple preparation process.

实施例15。Example 15.

本实施例的一种非晶合金手表外壳，具体为，在氮气的保护下，利用镍基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳。所制备的非晶合金手表外壳的维氏硬度为480，降伏强度为1700MPa，镍释放量为0.015mg/cm²/week，经受470小时的盐雾测试后非晶合金手表外壳的表面仍然良好无腐蚀。其中，本实施例的非晶合金手表外壳为传统手表外壳。In the amorphous alloy watch case of the embodiment, specifically, the amorphous alloy watch case is prepared by a die casting method using a raw material of a nickel-based amorphous alloy under the protection of nitrogen. The prepared amorphous alloy watch case has a Vickers hardness of 480, a relief strength of 1700 MPa, and a nickel release of 0.015 mg/cm ² /week. The surface of the amorphous alloy watch case is still good after being subjected to a salt spray test of 470 hours. corrosion. Wherein, the amorphous alloy watch case of the embodiment is a traditional watch case.

本实施例中非晶合金手表外壳包括表壳、表盘和后盖；表壳、表盘和后盖均采用镍基非晶合金而制造。In this embodiment, the amorphous alloy watch case includes a case, a dial and a back cover; and the case, the dial and the back cover are both made of a nickel-based amorphous alloy.

本实施例中，该非晶合金手表外壳设置为均一厚度，且其厚度为0.7mm。In this embodiment, the amorphous alloy watch case is provided with a uniform thickness and a thickness of 0.7 mm.

本实施例中，利用镍基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳，包括如下步骤：In this embodiment, an amorphous alloy watch case is prepared by a die-casting method using a raw material of a nickel-based amorphous alloy, including the following steps:

步骤一，投料：将镍基非晶合金原材料放入卧式压铸机的供料装置，并由供料装置投入到卧式压铸机的熔融装置中；本实施例中，卧式压铸机充入氮气进行保护；Step 1: Feeding: The nickel-based amorphous alloy raw material is placed in the feeding device of the horizontal die casting machine, and is fed into the melting device of the horizontal die casting machine by the feeding device; in this embodiment, the horizontal die casting machine is charged Nitrogen for protection;

步骤二，熔融：利用感应加热的方式将镍基非晶合金原材料熔融并形成熔汤，熔汤的温度为1090℃；Step two, melting: using a method of induction heating to melt the nickel-based amorphous alloy raw material and forming a melt, the temperature of the melt is 1090 ° C;

步骤三，倒汤：将步骤二得到的熔汤倒入手表外壳模具浇口套中，然后以冲头将熔汤注入手表外壳模具中；其中，冲头的速度为0.8m/s；手表外壳模具的温度为225℃；其中，在倒汤过程中，利用喷枪向手表外壳模具表面喷射氩气以达到清洁手表外壳模具表面的熔汤碎屑的目的；Step 3: pouring the soup: pouring the molten soup obtained in the second step into the mold cover of the watch case, and then injecting the molten soup into the mold of the watch case with a punch; wherein the speed of the punch is 0.8 m/s; the watch case The temperature of the mold is 225 ° C; wherein, during the pouring process, the argon gas is sprayed onto the surface of the mold shell of the watch by the spray gun to achieve the purpose of cleaning the melted chips on the surface of the mold of the watch case;

步骤五，产品取出：利用产品取出装置接住由手表外壳模具顶出的非晶合金手表外壳后再输送到产品出口，得到非晶合金手表外壳。Step 5, product removal: use the product extraction device to catch the amorphous alloy watch that is ejected from the mold of the watch case. The outer casing is then transported to the product outlet to obtain an amorphous alloy watch casing.

本实施例中，在氮气的保护下，对步骤六中完成切割浇铸口和溢流口的非晶合金手表外壳，进行机加工以达到结构和精度的要求，然后进行热塑成型(TPF)以达到结构、精度和表面品质的要求。其中机加工包括CNC铣和/或CNC切削。In this embodiment, under the protection of nitrogen, the amorphous alloy watch case which cuts the casting port and the overflow port in step 6 is machined to meet the structural and precision requirements, and then subjected to thermoforming (TPF). Meet the requirements of structure, precision and surface quality. Machining includes CNC milling and/or CNC cutting.

本实施例中，对完成热塑成型(TPF)的非晶合金手表外壳进行PVD处理。In this embodiment, a PVD process is performed on an amorphous alloy watch case that is subjected to thermoforming (TPF).

本实施例15制得的非晶合金手表外壳相对于利用钛合金或不锈钢制备的手表外壳，均具有优异的维氏硬度、降伏强度和抗腐蚀的性能；而且，利用镍基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳具有机械加工量小、加工时间短、生产效率高、生产成本低、易于成型、且制备工艺简单的优点。The amorphous alloy watch case obtained in the embodiment 15 has excellent Vickers hardness, lodging strength and corrosion resistance with respect to a watch case made of titanium alloy or stainless steel; and, a raw material using a nickel-based amorphous alloy The amorphous alloy watch casing prepared by the die-casting method has the advantages of small machining amount, short processing time, high production efficiency, low production cost, easy molding, and simple preparation process.

实施例16。Example 16.

本实施例的一种非晶合金手表外壳，具体为，在真空度为10^-3torr的真空状态的保护下，利用铁基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳，所制备的非晶合金手表外壳的维氏硬度为420，降伏强度为1200MPa，镍释放量为0mg/cm²/week，经受410小时的盐雾测试后非晶合金手表外壳的表面仍然良好无腐蚀。其中，本实施例的非晶合金手表外壳为智能手表外壳。An amorphous alloy watch case of the embodiment, specifically, under the protection of a vacuum state of a vacuum of 10 ^-3 torr, an amorphous alloy watch case is prepared by a die casting method using a raw material of an iron-based amorphous alloy. The prepared amorphous alloy watch case has a Vickers hardness of 420, a relief strength of 1200 MPa, and a nickel release amount of 0 mg/cm ² /week. The surface of the amorphous alloy watch case is still well corrosion-free after being subjected to a salt spray test for 410 hours. Wherein, the amorphous alloy watch case of the embodiment is a smart watch case.

本实施例中非晶合金手表外壳包括表壳、表盘和后盖；表壳、表盘和后盖均采用铁基非晶合金而制造。 In the present embodiment, the amorphous alloy watch case includes a case, a dial and a back cover; and the case, the dial and the back cover are both made of an iron-based amorphous alloy.

本实施例中，该非晶合金手表外壳设置为均一厚度，且其厚度为1.4mm。In this embodiment, the amorphous alloy watch case is provided with a uniform thickness and a thickness of 1.4 mm.

本实施例中，利用铁基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳，包括如下步骤：In this embodiment, an amorphous alloy watch case is prepared by a die casting method using a raw material of an iron-based amorphous alloy, and includes the following steps:

步骤一，投料：将铁基非晶合金原材料放入卧式压铸机的供料装置，并由供料装置投入到卧式压铸机的熔融装置中；卧式压铸机的真空度为10^-3torr；Step 1: Feeding: The iron-based amorphous alloy raw material is placed in the feeding device of the horizontal die-casting machine, and is fed into the melting device of the horizontal die-casting machine by the feeding device; the vacuum degree of the horizontal die-casting machine is 10 ^-3 Torr;

步骤二，熔融：利用感应加热的方式将铁基非晶合金原材料熔融并形成熔汤，熔汤的温度为930℃； Step 2, melting: using an induction heating method to melt the iron-based amorphous alloy raw material and forming a melt, the temperature of the melt is 930 ° C;

步骤三，倒汤：将步骤二得到的熔汤倒入手表外壳模具浇口套中，然后以冲头将熔汤注入手表外壳模具中；其中，冲头的速度为2.5m/s；手表外壳模具的温度为235℃；其中，在倒汤过程中，利用喷枪向手表外壳模具表面喷射氩气以达到清洁手表外壳模具表面的熔汤碎屑的目的；Step 3: Pour the soup: pour the molten soup obtained in the second step into the mold cover of the watch case, and then inject the molten soup into the mold of the watch case with a punch; wherein the speed of the punch is 2.5 m/s; the watch case The temperature of the mold is 235 ° C; wherein, during the pouring process, the argon gas is sprayed onto the surface of the mold shell of the watch by the spray gun to achieve the purpose of cleaning the molten scrap on the surface of the mold of the watch case;

其中，上述热塑成型(TPF)的整体加工期间的时间温度曲线不碰触到第二TTT 图中的晶化区。Wherein, the time temperature curve during the overall processing of the above thermoplastic molding (TPF) does not touch the second TTT The crystallized area in the figure.

本实施例16制得的非晶合金手表外壳相对于利用钛合金或不锈钢制备的手表外壳，均具有优异的维氏硬度、降伏强度和抗腐蚀的性能；而且，利用铁基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳具有机械加工量小、加工时间短、生产效率高、生产成本低、易于成型、且制备工艺简单的优点。The amorphous alloy watch case obtained in the embodiment 16 has excellent Vickers hardness, lodging strength and corrosion resistance with respect to the watch case prepared by using titanium alloy or stainless steel; and, the raw material using the iron-based amorphous alloy The amorphous alloy watch casing prepared by the die-casting method has the advantages of small machining amount, short processing time, high production efficiency, low production cost, easy molding, and simple preparation process.

实施例17。Example 17.

本实施例的一种非晶合金手表外壳，具体为，在氩气的保护下，利用利用Zr-Cu-Co-Al-Nb系锆基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳。本实施例中，Zr-Cu-Co-Al-Nb系锆基非晶合金的原子百分比为：Zr(54.75)-Cu(16.65)-Co(13.6)-Al(10)-Nb(5)。所制备的非晶合金手表外壳的维氏硬度为410，降伏强度为1090MPa，镍释放量为0mg/cm²/week，经受415小时的盐雾测试后非晶合金手表外壳的表面仍然良好无腐蚀。其中，本实施例的非晶合金手表外壳为智能手表外壳。An amorphous alloy watch case of the embodiment, in particular, an amorphous alloy watch prepared by a die casting method using a raw material of a Zr-Cu-Co-Al-Nb zirconium-based amorphous alloy under the protection of argon gas shell. In the present embodiment, the atomic percentage of the Zr-Cu-Co-Al-Nb-based zirconium-based amorphous alloy is: Zr(54.75)-Cu(16.65)-Co(13.6)-Al(10)-Nb(5). The prepared amorphous alloy watch case has a Vickers hardness of 410, a relief strength of 1090 MPa, and a nickel release of 0 mg/cm ² /week. The surface of the amorphous alloy watch case is still good and non-corrosive after being subjected to a salt spray test of 415 hours. . Wherein, the amorphous alloy watch case of the embodiment is a smart watch case.

本实施例中非晶合金手表外壳包括表壳、表盘和后盖；表壳、表盘和后盖均采用Zr-Cu-Co-Al-Nb系锆基非晶合金而制造。In the present embodiment, the amorphous alloy watch case includes a case, a dial and a back cover; and the case, the dial and the back cover are both made of a Zr-Cu-Co-Al-Nb zirconium-based amorphous alloy.

本实施例中，该非晶合金手表外壳设置为均一厚度，且其厚度为0.6mm。In this embodiment, the amorphous alloy watch case is provided with a uniform thickness and a thickness of 0.6 mm.

实施例18。Example 18.

本实施例的一种非晶合金手表外壳，具体为，在氩气的保护下，利用利用Cu-Ti-Zr-Co-Sn系铜基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳。本实施例中，Cu-Ti-Zr-Co-Sn系铜基非晶合金的原子百分比为：Cu(45)-Ti(30)-Zr(15)-Co(8)-Sn(2)。所制备的非晶合金手表外壳的维氏硬度为530，降伏强度为2090MPa，镍释放量为0.003mg/cm²/week，经受435小时的盐雾测试后非晶合金手表外壳的表面仍然良好无腐蚀。其中，本实施例的非晶合金手表外壳为传统手表外壳。An amorphous alloy watch case of the embodiment, in particular, an amorphous alloy watch prepared by a die casting method using a raw material of a Cu-Ti-Zr-Co-Sn-based copper-based amorphous alloy under the protection of argon gas shell. In the present embodiment, the atomic percentage of the Cu-Ti-Zr-Co-Sn-based copper-based amorphous alloy is: Cu(45)-Ti(30)-Zr(15)-Co(8)-Sn(2). The prepared amorphous alloy watch case has a Vickers hardness of 530, a relief strength of 2090 MPa, and a nickel release amount of 0.003 mg/cm ² /week. The surface of the amorphous alloy watch case is still good after being subjected to a salt spray test of 435 hours. corrosion. Wherein, the amorphous alloy watch case of the embodiment is a traditional watch case.

实施例19。Example 19.

本实施例的一种非晶合金手表外壳，具体为，在氮气的保护下，利用Cu-Ti-Zr-Ni-Co-Sn系铜基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳。本实施例中，Cu-Ti-Zr-Ni-Co-Sn的原子百分比为：Cu(45)-Ti(30)-Zr(15)-Ni(2)-Co(6)-Sn(2)。所制备的非晶合金手表外壳的维氏硬度为530，降伏强度为2090MPa，镍释放量为0.003mg/cm²/week，经受435小时的盐雾测试后非晶合金手表外壳的表面仍然良好无腐蚀。其中，本实施例的非晶合金手表外壳为传统手表外壳。An amorphous alloy watch case of the embodiment, in particular, an amorphous alloy watch prepared by a die casting method using a raw material of a Cu-Ti-Zr-Ni-Co-Sn-based copper-based amorphous alloy under the protection of nitrogen shell. In this embodiment, the atomic percentage of Cu-Ti-Zr-Ni-Co-Sn is: Cu(45)-Ti(30)-Zr(15)-Ni(2)-Co(6)-Sn(2) . The prepared amorphous alloy watch case has a Vickers hardness of 530, a relief strength of 2090 MPa, and a nickel release amount of 0.003 mg/cm ² /week. The surface of the amorphous alloy watch case is still good after being subjected to a salt spray test of 435 hours. corrosion. Wherein, the amorphous alloy watch case of the embodiment is a traditional watch case.

本实施例中，该非晶合金手表外壳设置为均一厚度，且其厚度为1.7mm。In this embodiment, the amorphous alloy watch case is provided with a uniform thickness and a thickness of 1.7 mm.

实施例20。Example 20.

本实施例用实施例1的Zr-Cu-Ni-Al-Nb系锆基非晶合金手表外壳制备手表。In this embodiment, a wristwatch was prepared using the Zr-Cu-Ni-Al-Nb-based zirconium-based amorphous alloy watch case of Example 1.

实施例21。Example 21.

本实施例用实施例2的Zr-Cu-Ni-Al-Ti系锆基非晶合金手表外壳制备手表。In this embodiment, a wristwatch was prepared using the Zr-Cu-Ni-Al-Ti-based zirconium-based amorphous alloy watch case of Example 2.

实施例22。Example 22.

本实施例用实施例3的Zr-Cu-Co-Al-Nb系锆基非晶合金手表外壳制备手表。In this embodiment, a wristwatch was prepared using the Zr-Cu-Co-Al-Nb-based zirconium-based amorphous alloy watch case of Example 3.

实施例23。Example 23.

本实施例用实施例4的Zr-Cu-Co-Al-Ti系锆基非晶合金手表外壳制备手表。In this embodiment, a wristwatch was prepared using the Zr-Cu-Co-Al-Ti-based zirconium-based amorphous alloy watch case of Example 4.

实施例24。Example 24.

本实施例用实施例5的Zr-Cu-Co-Al-Sn系锆基非晶合金手表外壳制备手表。In this embodiment, a wristwatch was prepared using the Zr-Cu-Co-Al-Sn-based zirconium-based amorphous alloy watch case of Example 5.

实施例25。Example 25.

本实施例用实施例6的Zr-Cu-Ni-Al-Sn系锆基非晶合金手表外壳制备手表。In this embodiment, a wristwatch was prepared using the Zr-Cu-Ni-Al-Sn-based zirconium-based amorphous alloy watch case of Example 6.

实施例26。Example 26.

本实施例用实施例7的Zr-Cu-Ni-Co-Al-Nb系锆基非晶合金手表外壳制备手表。In this embodiment, a wristwatch was prepared using the Zr-Cu-Ni-Co-Al-Nb-based zirconium-based amorphous alloy watch case of Example 7.

实施例27。Example 27.

本实施例用实施例8的Zr-Cu-Ni-Co-Al-Ti系锆基非晶合金手表外壳制备手表。In this embodiment, a wristwatch was prepared using the Zr-Cu-Ni-Co-Al-Ti-based zirconium-based amorphous alloy watch case of Example 8.

实施例28。Example 28.

本实施例用实施例9的Zr-Cu-Ni-Co-Al-Sn系锆基非晶合金手表外壳制备手表。In this embodiment, a wristwatch was prepared using the Zr-Cu-Ni-Co-Al-Sn-based zirconium-based amorphous alloy watch case of Example 9.

实施例29。Example 29.

本实施例用实施例10的Zr-Cu-Ni-Co-Al-Sn系锆基非晶合金手表外壳制备手表。In this embodiment, a wristwatch was prepared using the Zr-Cu-Ni-Co-Al-Sn-based zirconium-based amorphous alloy watch case of Example 10.

实施例30。Example 30.

本实施例用实施例11的Cu-Ti-Zr-Ni-Sn系铜基非晶合金手表外壳制备手表。 In this embodiment, a watch was prepared using the Cu-Ti-Zr-Ni-Sn-based copper-based amorphous alloy watch case of Example 11.

实施例31。Example 31.

本实施例用实施例12的Cu-Ti-Zr-Co-Sn系铜基非晶合金手表外壳制备手表。In this embodiment, a watch was prepared using the Cu-Ti-Zr-Co-Sn-based copper-based amorphous alloy watch case of Example 12.

实施例32。Example 32.

本实施例用实施例13的Cu-Ti-Zr-Ni-Co-Sn系铜基非晶合金手表外壳制备手表。In this embodiment, a watch was prepared using the Cu-Ti-Zr-Ni-Co-Sn-based copper-based amorphous alloy watch case of Example 13.

实施例33。Example 33.

本实施例用实施例14的钛基非晶合金手表外壳制备手表。In this embodiment, a watch was prepared using the titanium-based amorphous alloy watch case of Example 14.

实施例34。Example 34.

本实施例用实施例15的镍基非晶合金手表外壳制备手表。In this embodiment, a watch was prepared using the nickel-based amorphous alloy watch case of Example 15.

实施例35。Example 35.

本实施例用实施例16的铁基非晶合金手表外壳制备手表。In this embodiment, a watch was prepared using the iron-based amorphous alloy watch case of Example 16.

实施例36。Example 36.

本实施例用实施例17的Zr-Cu-Co-Al-Nb系锆基非晶合金手表外壳制备手表。In this embodiment, a wrist watch was prepared using the Zr-Cu-Co-Al-Nb-based zirconium-based amorphous alloy watch case of Example 17.

实施例37。Example 37.

本实施例用实施例18的Cu-Ti-Zr-Co-Sn系铜基非晶合金手表外壳制备手表。In this embodiment, a watch was prepared using the Cu-Ti-Zr-Co-Sn-based copper-based amorphous alloy watch case of Example 18.

实施例38。Example 38.

本实施例用实施例19的Cu-Ti-Zr-Ni-Co-Sn系铜基非晶合金手表外壳制备手表。In this embodiment, a watch was prepared using the Cu-Ti-Zr-Ni-Co-Sn-based copper-based amorphous alloy watch case of Example 19.

性能测试对比实验Performance test comparison experiment

将实施例7中利用Zr-Cu-Ni-Co-Al-Nb系锆基非晶合金制备的手表外壳，实施例13中利用Cu-Ti-Zr-Ni-Co-Sn系铜基非晶合金制备的手表外壳，与现有技术中利用钛合金(Ti6Al4V)制备的手表外壳、利用不锈钢(SUS304)制备的手表外壳进行性能测试对比实验，所测试的性能包括维氏硬度、降伏强度、抗腐蚀性能(盐雾测试)、耐刮性和光泽度，所测试的实验数据见表1。A watch case prepared by using a Zr-Cu-Ni-Co-Al-Nb-based zirconium-based amorphous alloy in Example 7 and a Cu-Ti-Zr-Ni-Co-Sn-based copper-based amorphous alloy in Example 13 The prepared watch case is compared with the watch case prepared by using titanium alloy (Ti6Al4V) in the prior art and the watch case prepared by using stainless steel (SUS304). The tested properties include Vickers hardness, lodging strength, corrosion resistance. Performance (salt spray test), scratch resistance and gloss, the experimental data tested are shown in Table 1.

表1四种材质的手表外壳的性能测试对比数据表Table 1 Performance test comparison data table of four material watch cases

根据表1的实验数据表明，实施例7中利用Zr-Cu-Ni-Co-Al-Nb系锆基非晶合金制备的手表外壳，实施例13利用Cu-Ti-Zr-Ni-Co-Sn系铜基非晶合金制备的手表外壳，相对于现有技术中利用钛合金制备的手表外壳、利用不锈钢制备的手表外壳，均具有更加优异的维氏硬度、降伏强度、抗腐蚀、耐刮性和光泽度的性能。另外，其它实施例制备的非晶合金手表外壳，相对于现有技术中利用钛合金制备的手表外壳、利用不锈钢制备的手表外壳，也均具有更加优异的维氏硬度、降伏强度、抗腐蚀、耐刮性和光泽度的性能。According to the experimental data of Table 1, the watch case prepared by using the Zr-Cu-Ni-Co-Al-Nb-based zirconium-based amorphous alloy in Example 7 was used, and Example 13 utilized Cu-Ti-Zr-Ni-Co-Sn. The watch case prepared by the copper-based amorphous alloy has better Vickers hardness, lodging strength, corrosion resistance and scratch resistance than the watch case prepared by using the titanium alloy in the prior art and the watch case made of stainless steel. And gloss performance. In addition, the amorphous alloy watch case prepared by other embodiments has better Vickers hardness, lodging strength, corrosion resistance, and the like, compared with the watch case prepared by using the titanium alloy in the prior art and the watch case made of stainless steel. Scratch resistance and gloss performance.

而且，采用Zr-Cu-Ni-Co-Al-Nb系锆基非晶合金制备的手表外壳，镍释放量为0.015mg/cm2/week，该镍释放量相当于利用不锈钢制备的手表外壳的镍释放量的1/10；采用Cu-Ti-Zr-Ni-Co-Sn系铜基非晶合金制备的手表外壳，镍释放量为0.005mg/cm2/week，该镍释放量相当于利用钛合金制备的手表外壳的镍释放量的1/10；0.015mg/cm²/week以下的镍释放量范围均使得该Zr-Cu-Ni-Co-Al-Nb系锆基非晶合金和Cu-Ti-Zr-Ni-Co-Sn系铜基非晶合金适合制作手表外壳，并使得配戴者长时间配戴而不引起任何过敏反应。Moreover, the watch case prepared by using a Zr-Cu-Ni-Co-Al-Nb-based zirconium-based amorphous alloy has a nickel release amount of 0.015 mg/cm2/week, which is equivalent to the nickel of the watch case made of stainless steel. 1/10 of the release amount; a watch case prepared using a Cu-Ti-Zr-Ni-Co-Sn-based copper-based amorphous alloy, the nickel release amount is 0.005 mg/cm 2 /week, and the release amount of nickel is equivalent to using a titanium alloy The prepared watch case has a nickel release amount of 1/10; the nickel release amount of 0.015 mg/cm ² /week or less makes the Zr-Cu-Ni-Co-Al-Nb-based zirconium-based amorphous alloy and Cu-Ti The -Zr-Ni-Co-Sn copper-based amorphous alloy is suitable for the manufacture of the watch case and allows the wearer to wear it for a long time without causing any allergic reaction.

其中，上述性能测试的项目中，抗腐蚀(盐雾测试)的详细实验结果如表2所示。Among them, the detailed experimental results of corrosion resistance (salt spray test) in the above performance test items are shown in Table 2.

表2四种材质的手表外壳的盐雾测试数据表Table 2 Salt spray test data sheet of four material watch cases

由表2的测试数据可知，实施例7中利用Zr-Cu-Ni-Co-Al-Nb系锆基非晶合金制备的手表外壳，实施例13利用Cu-Ti-Zr-Ni-Co-Sn系铜基非晶合金制备的手表外壳，相对于现有技术中利用钛合金(Ti6Al4V)制备的手表外壳、利用不锈钢(SUS304)制备的手表外壳，具有更好的抗腐蚀性能。From the test data of Table 2, the watch case prepared by using Zr-Cu-Ni-Co-Al-Nb-based zirconium-based amorphous alloy in Example 7 was used, and Example 13 utilized Cu-Ti-Zr-Ni-Co-Sn. The watch case prepared by the copper-based amorphous alloy has better corrosion resistance than the watch case prepared by using the titanium alloy (Ti6Al4V) in the prior art and the watch case prepared by using stainless steel (SUS304).

最后应当说明的是，以上实施例仅用于说明本发明的技术方案而非对本发明保护范围的限制，尽管参照较佳实施例对本发明作了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的实质和范围。 It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of the present invention. Although the present invention is described in detail with reference to the preferred embodiments, those skilled in the art The technical solutions of the present invention are modified or equivalently substituted without departing from the spirit and scope of the technical solutions of the present invention.

Claims

一种非晶合金手表外壳，其特征在于：所述手表外壳是采用锆基非晶合金、铜基非晶合金、钛基非晶合金、镍基非晶合金或铁基非晶合金而制造的非晶合金手表外壳，其中所述非晶合金手表外壳包括智能手表外壳和传统手表外壳；An amorphous alloy watch case, characterized in that the watch case is made of a zirconium-based amorphous alloy, a copper-based amorphous alloy, a titanium-based amorphous alloy, a nickel-based amorphous alloy or an iron-based amorphous alloy. An amorphous alloy watch case, wherein the amorphous alloy watch case comprises a smart watch case and a conventional watch case;

所述锆基非晶合金包括Zr-Cu-(Ni/Co)-Al+(Nb/Ti/Sn)系合金、Zr-Cu-Ni-Co-Al+(Nb/Ti/Sn)系合金；所述铜基非晶合金包括Cu-Ti-Zr-(Ni/Co)+(Sn)系合金、Cu-Ti-Zr-Ni-Co+(Sn)系合金。The zirconium-based amorphous alloy includes a Zr-Cu-(Ni/Co)-Al+(Nb/Ti/Sn)-based alloy, and a Zr-Cu-Ni-Co-Al+(Nb/Ti/Sn)-based alloy; The copper-based amorphous alloy includes a Cu-Ti-Zr-(Ni/Co)+(Sn)-based alloy and a Cu-Ti-Zr-Ni-Co+(Sn)-based alloy.
根据权利要求1所述的一种非晶合金手表外壳，其特征在于：所述Zr-Cu-(Ni/Co)-Al+(Nb/Ti/Sn)系锆基非晶合金的原子百分比为：Zr(50～60)-Cu(12～20)-(Ni/Co)(10～15)-Al(7～15)+(Nb/Ti/Sn)(2～8)；The amorphous alloy watch case according to claim 1, wherein the atomic percentage of the Zr-Cu-(Ni/Co)-Al+(Nb/Ti/Sn)-based zirconium-based amorphous alloy is: Zr(50～60)-Cu(12～20)-(Ni/Co)(10～15)-Al(7～15)+(Nb/Ti/Sn)(2～8);

所述Zr-Cu-Ni-Co-Al+(Nb/Ti/Sn)系锆基非晶合金的原子百分比为：Zr(50～60)-Cu(12～20)-Ni(3～8)-Co(6～10)-Al(7～15)+(Nb/Ti/Sn)(2～8)；The atomic percentage of the Zr-Cu-Ni-Co-Al+(Nb/Ti/Sn)-based zirconium-based amorphous alloy is: Zr(50-60)-Cu(12-20)-Ni(3-8)- Co(6～10)-Al(7～15)+(Nb/Ti/Sn)(2～8);

所述Cu-Ti-Zr-(Ni/Co)+(Sn)系铜基非晶合金的原子百分比为：Cu(40～45)-Ti(30～40)-Zr(7～15)-(Ni/Co)(5～12)+(Sn)(2～8)；The atomic percentage of the Cu-Ti-Zr-(Ni/Co)+(Sn) copper-based amorphous alloy is: Cu(40-45)-Ti(30-40)-Zr(7-15)-( Ni/Co) (5 to 12) + (Sn) (2 to 8);

所述Cu-Ti-Zr-Ni-Co+(Sn)系铜基非晶合金的原子百分比为：Cu(40～45)-Ti(30～40)-Zr(7～15)-Ni(2～6)-Co(3～6)+(Sn)(2～8)。The atomic percentage of the Cu-Ti-Zr-Ni-Co+(Sn)-based copper-based amorphous alloy is: Cu(40-45)-Ti(30-40)-Zr(7-15)-Ni(2~ 6) - Co (3 ~ 6) + (Sn) (2 ~ 8).
根据权利要求2所述的一种非晶合金手表外壳，其特征在于：所述Zr-Cu-(Ni/Co)-Al+(Nb/Ti/Sn)系锆基非晶合金的原子百分比为：Zr(54.75)-Cu(16.65)-(Ni/Co)(13.6)-Al(10)+(Nb/Ti/Sn)(5)；The amorphous alloy watch case according to claim 2, wherein the atomic percentage of the Zr-Cu-(Ni/Co)-Al+(Nb/Ti/Sn)-based zirconium-based amorphous alloy is: Zr(54.75)-Cu(16.65)-(Ni/Co)(13.6)-Al(10)+(Nb/Ti/Sn)(5);

所述Zr-Cu-Ni-Co-Al+(Nb/Ti/Sn)系锆基非晶合金的原子百分比为：Zr(54.75)-Cu(16.65)-Ni(5.6)-Co(8)-Al(10)+(Nb/Ti/Sn)(5)；The atomic percentage of the Zr-Cu-Ni-Co-Al+(Nb/Ti/Sn)-based zirconium-based amorphous alloy is: Zr(54.75)-Cu(16.65)-Ni(5.6)-Co(8)-Al (10) + (Nb / Ti / Sn) (5);

所述Cu-Ti-Zr-(Ni/Co)+(Sn)系铜基非晶合金的原子百分比为：Cu(42)-Ti(34)-Zr(11)-(Ni/Co)(8)+(Sn)(5)；The atomic percentage of the Cu-Ti-Zr-(Ni/Co)+(Sn)-based copper-based amorphous alloy is: Cu(42)-Ti(34)-Zr(11)-(Ni/Co)(8 )+(Sn)(5);

所述Cu-Ti-Zr-Ni-Co+(Sn)系铜基非晶合金的原子百分比为：Cu(42)-Ti(34)-Zr(11)-Ni(3)-Co(5)+(Sn)(5)。The atomic percentage of the Cu-Ti-Zr-Ni-Co+(Sn)-based copper-based amorphous alloy is: Cu(42)-Ti(34)-Zr(11)-Ni(3)-Co(5)+ (Sn) (5).
根据权利要求1所述的一种非晶合金手表外壳，其特征在于：所述非晶合金手表外壳的维氏硬度为400～600，降伏强度为1000MPa～3000MPa，镍释放量为0mg/cm²/week～0.015mg/cm²/week，经受340小时～480小时的盐雾测试后其表面仍然良好无腐蚀。 The amorphous alloy watch case according to claim 1, wherein the amorphous alloy watch case has a Vickers hardness of 400 to 600, a relief strength of 1000 MPa to 3000 MPa, and a nickel release amount of 0 mg/cm ^{2 .} /week~0.015mg/cm ² /week, after being subjected to a salt spray test of 340 hours to 480 hours, the surface is still good and non-corrosive.
根据权利要求1所述的一种非晶合金手表外壳，其特征在于：所述非晶合金手表外壳的厚度为0.5mm～3mm。The amorphous alloy watch case according to claim 1, wherein the amorphous alloy watch case has a thickness of 0.5 mm to 3 mm.
根据权利要求1所述的一种非晶合金手表外壳，其特征在于：所述非晶合金手表外壳包括表壳、表盘和后盖；所述表壳和/或所述表盘和/或所述后盖采用所述锆基非晶合金、所述铜基非晶合金、所述钛基非晶合金、所述镍基非晶合金或所述铁基非晶合金而制造。An amorphous alloy watch case according to claim 1, wherein said amorphous alloy watch case comprises a watch case, a dial and a back cover; said case and/or said dial and/or said The back cover is manufactured using the zirconium-based amorphous alloy, the copper-based amorphous alloy, the titanium-based amorphous alloy, the nickel-based amorphous alloy, or the iron-based amorphous alloy.
一种非晶合金手表，其特征在于：所述非晶合金手表包括权利要求1至6任意一项所述的非晶合金手表外壳。An amorphous alloy watch characterized by comprising the amorphous alloy watch case according to any one of claims 1 to 6.
权利要求1至6任意一项所述的一种非晶合金手表外壳的制造方法，其特征在于：在真空状态或惰性气氛的保护下，利用锆基非晶合金、铜基非晶合金、钛基非晶合金、镍基非晶合金或铁基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳。A method of manufacturing an amorphous alloy watch case according to any one of claims 1 to 6, wherein the zirconium-based amorphous alloy, the copper-based amorphous alloy, and the titanium are used under the protection of a vacuum or an inert atmosphere. A raw material of a base alloy, a nickel-based amorphous alloy or an iron-based amorphous alloy is prepared by a die-casting method.
根据权利要求8所述的一种非晶合金手表外壳的制造方法，其特征在于：在真空状态或惰性气氛的保护下，利用锆基非晶合金、铜基非晶合金、钛基非晶合金、镍基非晶合金或铁基非晶合金的原材料通过压铸成型法制备非晶合金手表外壳，包括如下步骤：The method of manufacturing an amorphous alloy watch case according to claim 8, wherein the zirconium-based amorphous alloy, the copper-based amorphous alloy, and the titanium-based amorphous alloy are used under the protection of a vacuum state or an inert atmosphere. The raw material of the nickel-based amorphous alloy or the iron-based amorphous alloy is prepared by a die-casting method, and includes the following steps:

步骤一，投料：将非晶合金原材料放入立式或卧式压铸机的供料装置，并由所述供料装置投入到立式或卧式压铸机的熔融装置中；Step one, feeding: placing the amorphous alloy raw material into the feeding device of the vertical or horizontal die casting machine, and inputting the feeding device into the melting device of the vertical or horizontal die casting machine;

步骤二，熔融：利用感应加热的方式将非晶合金原材料熔融并形成熔汤，所述熔汤的温度为900℃～1200℃；Step two, melting: using an induction heating method to melt the amorphous alloy raw material and forming a melt, the temperature of the melt is 900 ° C ~ 1200 ° C;

步骤三，倒汤：将步骤二得到的熔汤倒入手表外壳模具浇口套中，然后以冲头将熔汤注入手表外壳模具中；其中，冲头的速度为0.1m/s～5m/s；手表外壳模具的温度为200℃～250℃；Step 3: Pour the soup: pour the molten soup obtained in the second step into the mold cover of the watch case, and then inject the molten soup into the mold of the watch case with a punch; wherein the speed of the punch is 0.1 m/s to 5 m/ s; the temperature of the watch case mold is 200 ° C ~ 250 ° C;

步骤四，冷却：对步骤三中注入了熔汤的手表外壳模具进行冷却成型，得到非晶合金手表外壳，冷却速度为10⁰K/s～10⁶K/s；冷却时间为15秒～30秒；Step 4, cooling: cooling the watch case mold into which the molten soup is poured in the third step, and obtaining an amorphous alloy watch case, the cooling rate is 10 ⁰ K/s to 10 ⁶ K/s; the cooling time is 15 seconds to 30. second;

步骤五，产品取出：利用产品取出装置接住由手表外壳模具顶出的非晶合金手表外壳后再输送到产品出口，得到非晶合金手表外壳。Step 5, the product is taken out: the amorphous alloy watch case that is ejected from the mold of the watch case is caught by the product take-out device, and then transported to the product outlet to obtain an amorphous alloy watch case.
根据权利要求9所述的一种非晶合金手表外壳的制造方法，其特征在于：所述步骤一中，所述立式或卧式压铸机的真空度为10^-1torr～10^-3torr。The method of manufacturing an amorphous alloy watch case according to claim 9, wherein in the first step, the vacuum degree of the vertical or horizontal die casting machine is 10 ^-1 torr to 10 ^-3 torr .
根据权利要求9所述的一种非晶合金手表外壳的制造方法，其特征在于：所述步骤三中，所述倒汤过程中，利用喷枪向所述手表外壳模具表面喷射惰性气氛以达到清洁所述手表外壳模具表面的熔汤碎屑的目的。A method of manufacturing an amorphous alloy watch case according to claim 9, wherein: In the third step, during the pouring process, an inert atmosphere is sprayed onto the surface of the watch case mold by using a spray gun to achieve the purpose of cleaning the melted chips on the surface of the watch case mold.
根据权利要求9所述的一种非晶合金手表外壳的制造方法，其特征在于：所述步骤五后，还包括步骤六，将步骤五得到的非晶合金手表外壳进行切割浇铸口和溢流口。The method of manufacturing an amorphous alloy watch case according to claim 9, wherein after the step five, the method further comprises the step of: cutting the casting alloy inlet and the overflow of the amorphous alloy watch case obtained in the fifth step. mouth.
根据权利要求12所述的一种非晶合金手表外壳的制造方法，其特征在于：对所述步骤六中完成切割浇铸口和溢流口的非晶合金手表外壳，进行机加工以达到结构和精度的要求；The method of manufacturing an amorphous alloy watch case according to claim 12, wherein the amorphous alloy watch case in which the cutting port and the overflow port are cut in the step 6 is machined to achieve the structure and Precision requirements;

或，进行热塑成型(TPF)以达到结构、精度和表面品质的要求；Or, perform thermoforming (TPF) to achieve structural, precision, and surface quality requirements;

或，进行快速放电成型(RDF)以达到结构、精度和表面品质的要求；Or, perform rapid discharge molding (RDF) to achieve structural, precision, and surface quality requirements;

或，进行机加工以达到结构和精度的要求，然后进行热塑成型(TPF)以达到结构、精度和表面品质的要求；Or, machining to achieve structural and precision requirements, followed by thermoforming (TPF) to achieve structural, precision, and surface quality requirements;

或，进行机加工以达到结构和精度的要求，然后进行快速放电成型(RDF)以达到结构、精度和表面品质的要求；Or, machining to achieve structural and precision requirements, followed by rapid discharge forming (RDF) to achieve structural, precision, and surface quality requirements;

或，进行机加工以达到结构和精度的要求，然后进行热塑成型(TPF)和快速放电成型(RDF)以达到结构、精度和表面品质的要求。Or, machining to achieve structural and precision requirements, followed by thermoplastic forming (TPF) and rapid discharge forming (RDF) to achieve structural, precision and surface quality requirements.
根据权利要求13所述的一种非晶合金手表外壳的制造方法，其特征在于：在对所述非晶合金手表外壳进行机加工、热塑成型(TPF)和快速放电成型(RDF)的过程中，使用惰性气体或氮气对所述非晶合金手表外壳进行保护。A method of manufacturing an amorphous alloy watch case according to claim 13, wherein the process of machining, thermoforming (TPF) and rapid discharge forming (RDF) of said amorphous alloy watch case is performed The amorphous alloy watch case is protected with an inert gas or nitrogen.
根据权利要求12或13或14所述的一种非晶合金手表外壳的制造方法，其特征在于：对所述非晶合金手表外壳进行滚筒研磨和/或磁力研磨和/或抛光处理和/或拉丝处理和/或喷砂处理和/或PVD处理和/或喷涂处理。 A method of manufacturing an amorphous alloy watch case according to claim 12 or 13 or 14, wherein the amorphous alloy watch case is subjected to barrel grinding and/or magnetic grinding and/or polishing treatment and/or Wire drawing and/or sandblasting and/or PVD and/or spray processing.