WO2018072368A1 - Rare earth-copper alloy glass mold and preparation method therefor - Google Patents

Rare earth-copper alloy glass mold and preparation method therefor Download PDF

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WO2018072368A1
WO2018072368A1 PCT/CN2017/074497 CN2017074497W WO2018072368A1 WO 2018072368 A1 WO2018072368 A1 WO 2018072368A1 CN 2017074497 W CN2017074497 W CN 2017074497W WO 2018072368 A1 WO2018072368 A1 WO 2018072368A1
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rare earth
copper
glass mold
alloy
copper alloy
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PCT/CN2017/074497
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French (fr)
Chinese (zh)
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戈剑鸣
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苏州东方模具科技股份有限公司
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Priority to CN201610910458.X priority Critical
Priority to CN201610910458.XA priority patent/CN106566946A/en
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Publication of WO2018072368A1 publication Critical patent/WO2018072368A1/en

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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making alloys
    • C22C1/02Making alloys by melting
    • C22C1/03Making alloys by melting using master alloys
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C9/00Alloys based on copper
    • C22C9/01Alloys based on copper with aluminium as the next major constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C9/00Alloys based on copper
    • C22C9/04Alloys based on copper with zinc as the next major constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C9/00Alloys based on copper
    • C22C9/06Alloys based on copper with nickel or cobalt as the next major constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon

Abstract

A rare earth-copper alloy glass mold and preparation method therefor, belonging to the field of glass mold materials. The chemical element composition and mass fraction of the rare earth-copper alloy glass mold are: 9-12% of nickel, 7-10% of aluminum, 8-12% of zinc, less than 0.5% of iron and 0.01-0.5% of rare earth, the remainder being copper. Steps: preparing a brass alloy from zinc and electrolytic copper; putting weighed aluminum, nickel, iron and copper into a smelting furnace, adding the brass alloy, standing, floating impurities upward, carrying out slagging-off, adding a copper-rare earth intermediate alloy, and carrying out slagging-off again; increasing the temperature of rare earth-copper alloy glass mold melt to be poured, discharging out of the furnace and pouring into a resin sand casting mold; performing stress relief annealing on the obtained rare earth-copper alloy glass mold to be annealed, preserving heat and cooling to room temperature, thereby obtaining a finished product. The flowability and toughness of an alloy are improved; the strength and hardness of the alloy are improved, and abrasion resistance is enhanced; mechanical properties and impact corrosion resistance of materials are improved; and the toughness and thermal conductivity of the materials are improved.

Description

稀土铜合金玻璃模具及其制备方法Rare earth copper alloy glass mold and preparation method thereof 技术领域Technical field
本发明属于玻璃模具材料领域,具体涉及一种稀土铜合金玻璃模具,并且还涉及其制备方法。The invention belongs to the field of glass mold materials, in particular to a rare earth copper alloy glass mold, and also relates to a preparation method thereof.
背景技术Background technique
玻璃模具是生产玻璃制品的主要装备,其频繁的与600℃-1100℃的高温玻璃液接触,承受着氧化、生长、热交换、热疲劳等作用,同时由于频繁的开模合模,因此要求模具的接触面具有优异的耐磨损性能。具体而言,要求玻璃模具内腔表面具有良好的耐高温、耐磨性能、抗氧化性能和耐蚀性能而藉以延长使用寿命;要求玻璃模具的外圆具有优异的散热性能,模具整体具有良好的韧性以理想地适应高速生产需求。Glass mold is the main equipment for producing glass products. It is frequently contacted with high temperature glass liquid of 600 °C-1100 °C, and is subjected to oxidation, growth, heat exchange, thermal fatigue, etc., and is required due to frequent mold opening and closing. The contact surface of the mold has excellent wear resistance. Specifically, the inner surface of the glass mold is required to have good high temperature resistance, wear resistance, oxidation resistance and corrosion resistance, thereby prolonging the service life; the outer circle of the glass mold is required to have excellent heat dissipation performance, and the overall mold has good properties. Resilience is ideally suited to high speed production needs.
随着制瓶技术日新月异的发展,对于玻璃模具的要求越来越高,铜合金玻璃模具早已运用在大型工厂的生产车间中,其主要以普通锌铝白铜为主,如发明专利授权公告号CN102732745B推荐有“高镍铜合金玻璃模具及其制造方法”,其提供的化学元素组成及其质量百分比为:Al:8.5-10.5%、Ni:14-16%,Zn:7.5-9.5%,Si:0.8-1.2%、Fe:0.8-1.2%、Mn:0.08-0.15%,其余为铜,此类铜合金模具虽然含有较高的Ni含量,提高了材料的抗腐蚀、抗氧化性能,并通过Zn和Cu的固溶强化作用来提高铜合金的硬度,但是由于目前开发的铜合金玻璃模具普遍存在强度硬度与导热性两者难以甚至无法兼得的技术问题,具体而言:强度硬度高,则导热性能较差,反之同例,这是因为材料的强度和材料导热性是一对矛盾。With the rapid development of bottle making technology, the requirements for glass molds are getting higher and higher. Copper alloy glass molds have already been used in the production workshops of large factories, mainly based on ordinary zinc aluminum white copper, such as invention patent authorization announcement number CN102732745B It is recommended to have "high-nickel-copper alloy glass mold and its manufacturing method", which provides the chemical element composition and its mass percentage: Al: 8.5-10.5%, Ni: 14-16%, Zn: 7.5-9.5%, Si: 0.8-1.2%, Fe: 0.8-1.2%, Mn: 0.08-0.15%, and the rest is copper. Although such a copper alloy mold contains a high Ni content, the corrosion resistance and oxidation resistance of the material are improved, and Zn is passed. And solid solution strengthening of Cu to improve the hardness of copper alloy, but the copper alloy molds currently developed generally have technical problems that are difficult or impossible to achieve both strength and thermal conductivity, specifically: high strength and hardness The thermal conductivity is poor, and vice versa, because the strength of the material and the thermal conductivity of the material are a contradiction.
在冶金工业中,稀土常被称作金属材料的“维生素”。稀土在铜合金中的主要作用有:脱氧、脱硫、脱氢及脱除铅等有害元素,净化铜合金成分;消除枝状晶、细化晶粒,提高塑性和强度、减少表面裂纹和缺陷;改善和提高铜合金的热加工性能;提高铜合金的导热性、热强性、抗氧化性和焊接性能。稀土对铜合金性能的改善已被大量的实验所证实,如:在普通电解铜中加入一定量的稀土可生产出高导电率的铜排,其导电率、导热率、抗拉强度、延伸率、高温软化温度等指标均优于普通铜排。In the metallurgical industry, rare earths are often referred to as "vitamins" of metallic materials. The main functions of rare earths in copper alloys are: deoxidation, desulfurization, dehydrogenation and removal of lead and other harmful elements, purification of copper alloy components; elimination of dendrites, grain refinement, improvement of plasticity and strength, reduction of surface cracks and defects; Improve and improve the hot workability of copper alloys; improve the thermal conductivity, thermal strength, oxidation resistance and weldability of copper alloys. The improvement of the performance of rare earth on copper alloy has been confirmed by a large number of experiments. For example, adding a certain amount of rare earth to common electrolytic copper can produce a high conductivity copper row with conductivity, thermal conductivity, tensile strength and elongation. The high temperature softening temperature and other indicators are superior to ordinary copper bars.
同时添加适量稀土可改善合金的铸造性能,提高合金熔融液的流动性,减少铸造缩孔、气孔、偏析及裂纹的倾向,提高铸造成品率;同时稀土对金属表面具有改性作用,能明显提高合金的抗氧化性、抗氢脆、抗磨损、抗腐蚀性能,延长合金的使用寿命。At the same time, adding proper amount of rare earth can improve the casting performance of the alloy, improve the fluidity of the alloy melt, reduce the tendency of casting shrinkage, pore, segregation and crack, and improve the casting yield; at the same time, the rare earth has a modification effect on the metal surface, which can obviously improve The alloy's oxidation resistance, hydrogen embrittlement resistance, wear resistance and corrosion resistance extend the service life of the alloy.
虽然有关稀土在铜合金中的应用国内外均有报道,但是关于稀土在高性能铜合金玻璃模具材料中的应用,特别是钇基重稀土在高性能铜合金玻璃模具材料的应用却未见专 利文献和非专利文献报道,下面将要介绍的技术方案便是在这种背景下产生的。Although the application of rare earths in copper alloys has been reported at home and abroad, the application of rare earths in high performance copper alloy glass mold materials, especially the application of bismuth-based heavy rare earths in high-performance copper alloy glass mold materials, has not been seen. The literature and non-patent literature report that the technical solution to be described below is produced in this context.
发明内容Summary of the invention
本发明的首要任务在于提供一种具有高导热率、高强度、高韧性,同时具有良好的抗氧化耐腐蚀性能的以适应高速制瓶机高速化生产需要的稀土铜合金玻璃模具。The primary task of the present invention is to provide a rare earth copper alloy glass mold which has high thermal conductivity, high strength, high toughness and good anti-oxidation and corrosion resistance, and is suitable for high-speed production of high-speed bottle making machines.
发明的另一个任务在于提供一种稀土铜合金玻璃模具的制备方法,该方法有利于通过稀土的脱氧、脱硫作用净化铜合金成分,有助于消除枝状晶、细化晶粒,从而提高铜合金的强度、韧性,进而提高模具的使用寿命;通过稀土的加入,能够进一步提高铜水的流动性,提高铸造的成品率,降低模具的直接加工成本。Another object of the invention is to provide a method for preparing a rare earth copper alloy glass mold, which is advantageous for purifying copper alloy components by deoxidation and desulfurization of rare earth, thereby helping to eliminate dendrites and refine grains, thereby improving copper. The strength and toughness of the alloy, and thus the service life of the mold; through the addition of rare earth, the fluidity of the copper water can be further improved, the yield of the casting can be improved, and the direct processing cost of the mold can be reduced.
为完成本发明的首要任务,本发明提供的技术方案是:一种稀土铜合金玻璃模具,其化学元素组成及其质量%比为:9-12%的镍,7-10%的铝,8-12%的锌,<0.5%的铁,0.01-0.5%的稀土,其余为铜。In order to accomplish the primary task of the present invention, the technical solution provided by the present invention is: a rare earth copper alloy glass mold having a chemical element composition and a mass % ratio thereof: 9-12% nickel, 7-10% aluminum, 8 -12% zinc, <0.5% iron, 0.01-0.5% rare earth, and the balance is copper.
在本发明的一个具体的实施例中,一种稀土铜合金玻璃模具,其化学元素及其质量%比为:10%的镍,7%的铝,8%的锌,0.4%的铁,0.2%的稀土,其余为铜。In a specific embodiment of the present invention, a rare earth copper alloy glass mold has a chemical element and a mass ratio thereof of: 10% nickel, 7% aluminum, 8% zinc, 0.4% iron, 0.2. % of rare earths, the rest being copper.
在本发明的另一个具体的实施例中,一种稀土铜合金玻璃模具,其化学元素及其质量%比为:12%的镍,9%的铝,10%的锌,0.3%的铁,0.5%的稀土,其余为铜。In another specific embodiment of the present invention, a rare earth copper alloy glass mold has a chemical element and a mass ratio thereof of: 12% nickel, 9% aluminum, 10% zinc, and 0.3% iron. 0.5% rare earth, the rest is copper.
在本发明的又一个具体的实施例中,一种稀土铜合金玻璃模具,其化学元素及其质量%比为:9%的镍,10%的铝,12%的锌,0.35%的铁,0.01%的稀土,其余为铜。In still another specific embodiment of the present invention, a rare earth copper alloy glass mold has a chemical element and a mass ratio thereof of: 9% nickel, 10% aluminum, 12% zinc, and 0.35% iron. 0.01% rare earth, the rest is copper.
在本发明的再一个具体的实施例中,所述的稀土铜合金玻璃模具的硬度为190-250HBW,导热系数为282-302w/(m.k)。In still another specific embodiment of the present invention, the rare earth copper alloy glass mold has a hardness of 190-250 HBW and a thermal conductivity of 282-302 w/(m.k).
为完成本发明的另一任务,本发明提供的技术方案是;一种稀土铜合金玻璃模具的制备方法,包括以下步骤:In order to accomplish another task of the present invention, the technical solution provided by the present invention is: a method for preparing a rare earth copper alloy glass mold, comprising the following steps:
A)熔炼,首先准备由锌和电解铜制备的且锌与铜的质量比为45:55的黄铜合金,其次,依据稀土铜合金玻璃模具材料中各元素的质量%比,将称量好的铝、镍、铁和铜投入到熔炉中,待熔炼温度达到1200-1250℃时加入所述的黄铜合金,当熔炼温度达到1280-1300℃时,断电静置5-10min,使杂质上浮以净化铜水,然后进行扒渣,而后加入铜-稀土中间合金,待铜-稀土中间合金熔化后再次扒渣并且同时采用光谱分析调整化学元素的质量%含量,得到待浇注的稀土铜合金玻璃模具溶液;A) smelting, first preparing a brass alloy prepared from zinc and electrolytic copper and having a mass ratio of zinc to copper of 45:55, and secondly, weighing according to the mass% ratio of each element in the rare earth copper alloy glass mold material The aluminum, nickel, iron and copper are put into the furnace, and the brass alloy is added when the melting temperature reaches 1200-1250 ° C. When the melting temperature reaches 1280-1300 ° C, the electricity is allowed to stand for 5-10 min to make impurities. The upper part is floated to purify the copper water, and then the slag is slag, and then the copper-rare earth intermediate alloy is added. After the copper-rare earth intermediate alloy is melted, the slag is again slag and the mass analysis of the chemical element is adjusted by spectral analysis to obtain the rare earth copper alloy to be poured. Glass mold solution;
B)浇注成型,先将步骤A)所述的待浇注的稀土铜合金玻璃模具熔液升温至1280-1320℃,再出炉浇注到树脂砂铸型中,浇注之前,在树脂砂铸型的内腔中放置用于成型出玻璃模具的内腔的冷铁泥芯,浇注完成静置,而后撤去冷铁泥芯,得到待退火的 稀土铜合金玻璃模具;B) casting, firstly, the molten rare earth copper alloy glass mold melt to be poured in step A) is heated to 1280-1320 ° C, and then poured into a resin sand mold, before casting, in the resin sand mold A cold iron core for forming a cavity of the glass mold is placed in the cavity, the casting is completed, and then the cold iron core is removed to obtain an annealing to be annealed. Rare earth copper alloy glass mold;
C)退火,将由步骤B)得到的待退火的稀土铜合金玻璃模具进行去应力退火,去应力退火结束后保温并且在保温后冷却至室温,得到稀土铜合金玻璃模具。C) annealing, the rare earth copper alloy glass mold to be annealed obtained in step B) is subjected to stress relief annealing, after the stress relief annealing is completed, and after cooling, it is cooled to room temperature to obtain a rare earth copper alloy glass mold.
在本发明的还有一个具体的实施例中,步骤A)中所述的电解铜为1#电解铜,所述的镍为1#电解镍,所述的锌为1#锌。In still another specific embodiment of the present invention, the electrolytic copper described in the step A) is 1# electrolytic copper, the nickel is 1# electrolytic nickel, and the zinc is 1# zinc.
在本发明的更而一个具体的实施例中,步骤A)中所述的采用光谱分析调整化学元素的质量%含量是将化学元素的质量%含量调整为:9-12%的镍,7-10%的铝,8-12%的锌,<0.5%的铁,0.01-0.5%的稀土,其余为铜。In a further specific embodiment of the invention, the mass % content of the chemical element is adjusted by spectral analysis as described in step A) by adjusting the mass % content of the chemical element to: 9-12% nickel, 7- 10% aluminum, 8-12% zinc, <0.5% iron, 0.01-0.5% rare earth, and the balance copper.
在本发明的进而一个具体的实施例中,步骤A)中所述的铜-稀土中间合金为钇基重稀土并且以铜-钇中间合金的形式加入,该铜-钇中间合金的化学元素及其质量%为:ReO:1-11%,Cu:45-55%,Si:10-15%,Fe:20-25%,Mg:<5%,B:<5%。In still another specific embodiment of the present invention, the copper-rare earth intermediate alloy described in the step A) is a cerium-based heavy rare earth and is added in the form of a copper-bismuth intermediate alloy, the chemical element of the copper-bismuth intermediate alloy and The mass % thereof is: ReO: 1-11%, Cu: 45-55%, Si: 10-15%, Fe: 20-25%, Mg: <5%, B: <5%.
在本发明的又更而一个具体的实施例中,步骤B)中所述的静置的时间为40-60min;步骤C)中所述的去应力退火是在退火炉中进行的,并且去应力退火的温度为600-630℃,所述的去应力退火结束后保温的时间为4-6h,并且在保温4-6h后以≤50℃/h的冷却速度冷却至室温。In still another specific embodiment of the present invention, the standing time described in step B) is 40-60 min; the stress relief annealing described in step C) is carried out in an annealing furnace, and The stress annealing temperature is 600-630 ° C, the time after the stress relief annealing is 4-6 h, and after cooling for 4-6 h, it is cooled to room temperature at a cooling rate of ≤ 50 ° C / h.
本发明提供的技术方案的技术效果在于:其一,由于配方中的铝元素具有一定的脱氧作用,因而可改善合金的铸造性能,提高合金的流动性,同时其具有缩小铜合金中α相、增加β相,防止脆性γ相析出的作用,可以间接提高材料的韧性;其二,由于配方中的Ni元素作为一种与基体Cu可以无限互溶的元素,形成连续固溶体,因而可以改善合金的耐蚀性能,提高强度而不降低伸长率、韧性;其三,由于配方中的Zn元素不仅具有除气脱氧的作用,同时形成的α、β固溶体,因而能够提高合金的强度和硬度,增强模具的抗磨损性能;其四,由于配方中微量添加的Fe元素能够细化晶粒,因而得以提高材料的力学性能和抗冲击腐蚀性能;其五,配方中添加的稀土元素作为金属合金的维生素,改变了铜合金中微量的杂质元素在合金中的存在方式,使这些物质发生晶格畸变,改善这些微量元素在合金中分布的不均匀性,净化了合金的基体和晶界,提高了材料的韧性和导热率,进而提高了模具的使用寿命。The technical effects of the technical solution provided by the invention are as follows: First, since the aluminum element in the formulation has a certain deoxidation effect, the casting property of the alloy can be improved, the fluidity of the alloy can be improved, and the α phase in the copper alloy can be reduced, Increasing the β phase and preventing the precipitation of the brittle γ phase can indirectly improve the toughness of the material. Second, since the Ni element in the formulation acts as an element which can be infinitely miscible with the matrix Cu, forming a continuous solid solution, thereby improving the resistance of the alloy. Corrosion performance, improve strength without reducing elongation and toughness; Third, because the Zn element in the formulation not only has the function of degassing and deoxidation, but also forms the α, β solid solution, thereby improving the strength and hardness of the alloy and enhancing the mold. The anti-wear performance; Fourthly, since the Fe element added in the formula can refine the crystal grains, the mechanical properties and the impact corrosion resistance of the material can be improved; Fifth, the rare earth element added in the formula is used as the vitamin of the metal alloy, Changed the way in which trace elements of copper alloys exist in the alloy, causing them to crystallize Change, improving unevenness in the distribution of these trace elements in the alloy, purifying the alloy matrix and the grain boundaries and improves the toughness and thermal conductivity of the material, thereby increasing the life of the mold.
具体实施方式detailed description
下面结合实施例对本发明作进一步说明。The invention is further illustrated by the following examples.
实施例1:Example 1:
A)熔炼,首先准备由市售渠道购取的由锌和电解铜制备的且锌与铜的质量比为 45:55的黄铜合金,其次,依据稀土铜合金玻璃模具材料中各元素(即各化学元素)的质量%比将称量好的铝、镍、铁和铜投入到熔炉(即熔炼炉)中,待熔炼温度达到1230℃时加入所述的黄铜合金,当熔炼温度达到1280℃时,断电静置10min,使杂质充分上浮以净化铜水,然后进行扒渣,而后加入铜-稀土中间合金,待铜-稀土中间合金熔化后再次扒渣并且同时采用光谱分析调整化学元素的质量%含量为:10%的镍,7%的铝,8%的锌,0.4%的铁,0.2%的稀土,其余为铜,得到待浇注的稀土铜合金玻璃模具溶液,本步骤中所述的电解铜为1#电解铜,所述的镍为1#电解镍,所述的锌为1#锌,本步骤中所述的铜-稀土中间合金为钇基重稀土并且以铜-钇中间合金的形式加入,该铜-钇中间合金的化学元素及其质量%比为:ReO:1%,Cu:55%,Si:15%,Fe:25%,Mg:2%,B:2%;A) smelting, first prepared from commercially available channels, prepared from zinc and electrolytic copper and having a mass ratio of zinc to copper 45:55 brass alloy, and secondly, according to the mass% ratio of each element (ie, each chemical element) in the rare earth copper alloy glass mold material, the weighed aluminum, nickel, iron and copper are put into the furnace (ie, the melting furnace) The brass alloy is added when the temperature to be smelted reaches 1230 ° C. When the melting temperature reaches 1280 ° C, the electricity is allowed to stand for 10 min, the impurities are fully floated to purify the copper water, and then the slag is added, and then the copper-rare earth is added. The intermediate alloy, after the copper-rare earth intermediate alloy is melted, is slag again and at the same time the spectral analysis is used to adjust the mass % of the chemical element: 10% nickel, 7% aluminum, 8% zinc, 0.4% iron, 0.2% The rare earth, the rest is copper, and the rare earth copper alloy glass mold solution to be poured is obtained. The electrolytic copper described in this step is 1# electrolytic copper, the nickel is 1# electrolytic nickel, and the zinc is 1# zinc. The copper-rare earth intermediate alloy described in this step is a cerium-based heavy rare earth and is added in the form of a copper-rhenium intermediate alloy. The chemical element of the copper-bismuth intermediate alloy and its mass % ratio are: ReO: 1%, Cu : 55%, Si: 15%, Fe: 25%, Mg: 2%, B: 2% ;
B)浇注成型,先将步骤A)所述的待浇注的稀土铜合金玻璃模具熔液升温至1300℃,再出炉浇注到树脂砂铸型中,浇注之前,在树脂砂铸型的内腔中放置用于成型出玻璃模具的内腔的冷铁泥芯,浇注完成后静置40min,而后撤去冷铁泥芯,得到待退火的稀土铜合金玻璃模具;B) Casting, firstly, the rare earth copper alloy glass mold melt to be poured according to step A) is heated to 1300 ° C, and then poured into a resin sand mold, before pouring, in the inner cavity of the resin sand mold Place a cold iron core for forming the inner cavity of the glass mold, and then let stand for 40 minutes after the pouring is completed, and then remove the cold iron core to obtain a rare earth copper alloy glass mold to be annealed;
C)退火,将由步骤B)得到的待退火的稀土铜合金玻璃模具引入退火炉中进行去应力退火,去应力退火的温度为600℃,去应力退火结束后的保温时间为6h,保温6h后以≤50℃/h的冷却速度冷却至室温,得到稀土铜合金玻璃模具,经测试,该稀土铜合金玻璃模具的硬度为190HBW,导热系数为302W(m·k)。C) annealing, the rare earth copper alloy glass mold to be annealed obtained in step B) is introduced into the annealing furnace for stress relief annealing, the temperature of the stress relief annealing is 600 ° C, and the holding time after the stress relief annealing is 6 h, after 6 h of heat preservation The mixture was cooled to room temperature at a cooling rate of ≤50 ° C / h to obtain a rare earth copper alloy glass mold. The hardness of the rare earth copper alloy glass mold was 190 HBW and the thermal conductivity was 302 W (m·k).
实施例2:Example 2:
A)熔炼,首先准备由市售渠道购取的由锌和电解铜制备的且锌与铜的质量比为45:55的黄铜合金,其次,依据稀土铜合金玻璃模具材料中各元素(即各化学元素)的质量%比将称量好的铝、镍、铁和铜投入到熔炉(即熔炼炉)中,待熔炼温度达到1250℃时加入所述的黄铜合金,当熔炼温度达到1300℃时,断电静置5min,使杂质充分上浮以净化铜水,然后进行扒渣,而后加入铜-稀土中间合金,待铜-稀土中间合金熔化后再次扒渣并且同时采用光谱分析调整化学元素的质量%含量为:12%的镍,9%的铝,10%的锌,0.3%的铁,0.5%的稀土,其余为铜,得到待浇注的稀土铜合金玻璃模具溶液,本步骤中所述的电解铜为1#电解铜,所述的镍为1#电解镍,所述的锌为1#锌,本步骤中所述的铜-稀土中间合金为钇基重稀土并且以铜-钇中间合金的形式加入,该铜-钇中间合金的化学元素及其质量%比为:ReO:11%,Cu:45%,Si:13%,Fe:22%,Mg:4%,B:5%;A) smelting, first preparing a brass alloy prepared from zinc and electrolytic copper and having a mass ratio of zinc to copper of 45:55, and secondly, according to each element in the rare earth copper alloy glass mold material (ie, The mass % of each chemical element is put into the furnace (ie, the melting furnace) than the weighed aluminum, nickel, iron and copper, and the brass alloy is added when the melting temperature reaches 1250 ° C, when the melting temperature reaches 1300. At °C, the power is allowed to stand for 5min, the impurities are fully floated to purify the copper water, and then the slag is slag, and then the copper-rare earth intermediate alloy is added. After the copper-rare earth intermediate alloy is melted, the slag is again slag and the chemical elements are adjusted by spectral analysis. The mass% content is: 12% nickel, 9% aluminum, 10% zinc, 0.3% iron, 0.5% rare earth, and the balance is copper, and the rare earth copper alloy glass mold solution to be poured is obtained. The electrolytic copper is 1# electrolytic copper, the nickel is 1# electrolytic nickel, the zinc is 1# zinc, and the copper-rare earth intermediate alloy described in this step is a cerium-based heavy rare earth and is copper-cerium. In the form of an intermediate alloy, the chemistry of the copper-bismuth intermediate alloy Its mass% pigment ratio: ReO: 11%, Cu: 45%, Si: 13%, Fe: 22%, Mg: 4%, B: 5%;
B)浇注成型,先将步骤A)所述的待浇注的稀土铜合金玻璃模具熔液升温至1320℃,再出炉浇注到树脂砂铸型中,浇注之前,在树脂砂铸型的内腔中放置用于成型出玻璃模 具的内腔的冷铁泥芯,浇注完成后静置60min,而后撤去冷铁泥芯,得到待退火的稀土铜合金玻璃模具;B) Casting, firstly, the molten rare earth copper alloy glass mold melt to be poured in step A) is heated to 1320 ° C, and then poured into a resin sand mold, before pouring, in the inner cavity of the resin sand mold. Placed to form a glass mold The cold iron core of the inner cavity is allowed to stand for 60 minutes after the pouring is completed, and then the cold iron core is removed to obtain a rare earth copper alloy glass mold to be annealed;
C)退火,将由步骤B)得到的待退火的稀土铜合金玻璃模具引入退火炉中进行去应力退火,去应力退火的温度为630℃,去应力退火结束后的保温时间为4h,保温4h后以≤50℃/h的冷却速度冷却至室温,得到稀土铜合金玻璃模具,经测试,该稀土铜合金玻璃模具的硬度为250HBW,导热系数为282W(m·k)。C) annealing, the rare earth copper alloy glass mold to be annealed obtained in step B) is introduced into the annealing furnace for stress relief annealing, the temperature of the stress relief annealing is 630 ° C, the holding time after the stress relief annealing is 4 h, and after 4 h of heat preservation The mixture was cooled to room temperature at a cooling rate of ≤50 ° C / h to obtain a rare earth copper alloy glass mold. The hardness of the rare earth copper alloy glass mold was 250 HBW and the thermal conductivity was 282 W (m·k).
实施例3:Example 3:
A)熔炼,首先准备由市售渠道购取的由锌和电解铜制备的且锌与铜的质量比为45:55的黄铜合金,其次,依据稀土铜合金玻璃模具材料中各元素(即各化学元素)的质量%比将称量好的铝、镍、铁和铜投入到熔炉(即熔炼炉)中,待熔炼温度达到1200℃时加入所述的黄铜合金,当熔炼温度达到1290℃时,断电静置8min,使杂质充分上浮以净化铜水,然后进行扒渣,而后加入铜-稀土中间合金,待铜-稀土中间合金熔化后再次扒渣并且同时采用光谱分析调整化学元素的质量%含量为:9%的镍,10%的铝,12%的锌,0.35%的铁,0.01%的稀土,其余为铜,得到待浇注的稀土铜合金玻璃模具溶液,本步骤中所述的电解铜为1#电解铜,所述的镍为1#电解镍,所述的锌为1#锌,本步骤中所述的铜-稀土中间合金为钇基重稀土并且以铜-钇中间合金的形式加入,该铜-钇中间合金的化学元素及其质量%比为:ReO:6%,Cu:55%,Si:10%,Fe:20%,Mg:5%,B:4%;A) smelting, first preparing a brass alloy prepared from zinc and electrolytic copper and having a mass ratio of zinc to copper of 45:55, and secondly, according to each element in the rare earth copper alloy glass mold material (ie, The mass % of each chemical element is put into the furnace (ie, the melting furnace) than the weighed aluminum, nickel, iron and copper, and the brass alloy is added when the melting temperature reaches 1200 ° C, when the melting temperature reaches 1290 At °C, the power is allowed to stand for 8 minutes, the impurities are fully floated to purify the copper water, and then the slag is slag, and then the copper-rare earth intermediate alloy is added. After the copper-rare earth intermediate alloy is melted, the slag is again slag and the chemical elements are adjusted by spectral analysis. The mass% content is: 9% nickel, 10% aluminum, 12% zinc, 0.35% iron, 0.01% rare earth, and the balance is copper, and the rare earth copper alloy glass mold solution to be poured is obtained in this step. The electrolytic copper is 1# electrolytic copper, the nickel is 1# electrolytic nickel, the zinc is 1# zinc, and the copper-rare earth intermediate alloy described in this step is a cerium-based heavy rare earth and is copper-cerium. In the form of an intermediate alloy, the copper-bismuth intermediate alloy Its mass% elemental ratio: ReO: 6%, Cu: 55%, Si: 10%, Fe: 20%, Mg: 5%, B: 4%;
B)浇注成型,先将步骤A)所述的待浇注的稀土铜合金玻璃模具熔液升温至1295℃,再出炉浇注到树脂砂铸型中,浇注之前,在树脂砂铸型的内腔中放置用于成型出玻璃模具的内腔的冷铁泥芯,浇注完成后静置50min,而后撤去冷铁泥芯,得到待退火的稀土铜合金玻璃模具;B) Casting, firstly, the molten rare earth copper alloy glass mold melt to be poured in step A) is heated to 1295 ° C, and then poured into a resin sand mold, before casting, in the inner cavity of the resin sand mold. Place a cold iron core for forming the inner cavity of the glass mold, and let stand for 50 minutes after the pouring is completed, and then remove the cold iron core to obtain a rare earth copper alloy glass mold to be annealed;
C)退火,将由步骤B)得到的待退火的稀土铜合金玻璃模具引入退火炉中进行去应力退火,去应力退火的温度为615℃,去应力退火结束后的保温时间为5h,保温5h后以≤50℃/h的冷却速度冷却至室温,得到稀土铜合金玻璃模具,经测试,该稀土铜合金玻璃模具的硬度为230HBW,导热系数为294W(m·k)。 C) annealing, the rare earth copper alloy glass mold to be annealed obtained in step B) is introduced into the annealing furnace for stress relief annealing, the temperature of the stress relief annealing is 615 ° C, the holding time after the stress relief annealing is 5 h, and after 5 h of heat preservation The mixture was cooled to room temperature at a cooling rate of ≤50 ° C / h to obtain a rare earth copper alloy glass mold. The hardness of the rare earth copper alloy glass mold was 230 HBW and the thermal conductivity was 294 W (m·k).

Claims (10)

  1. 一种稀土铜合金玻璃模具,其特征在于其化学元素组成及其质量%比为:9-12%的镍,7-10%的铝,8-12%的锌,<0.5%的铁,0.01-0.5%的稀土,其余为铜。A rare earth copper alloy glass mold characterized in that its chemical element composition and its mass % ratio are: 9-12% nickel, 7-10% aluminum, 8-12% zinc, <0.5% iron, 0.01 -0.5% rare earth, the balance being copper.
  2. 根据权利要求1所述的稀土铜合金玻璃模具,其特征在于其化学元素及其质量%比为:10%的镍,7%的铝,8%的锌,0.4%的铁,0.2%的稀土,其余为铜。The rare earth copper alloy glass mold according to claim 1, wherein the chemical element and the mass % ratio thereof are: 10% nickel, 7% aluminum, 8% zinc, 0.4% iron, 0.2% rare earth. The rest is copper.
  3. 根据权利要求1所述的稀土铜合金玻璃模具,其特征在于其化学元素及其质量%比为:12%的镍,9%的铝,10%的锌,0.3%的铁,0.5%的稀土,其余为铜。The rare earth copper alloy glass mold according to claim 1, wherein the chemical element and the mass % ratio thereof are: 12% nickel, 9% aluminum, 10% zinc, 0.3% iron, 0.5% rare earth. The rest is copper.
  4. 根据权利要求1所述的稀土铜合金玻璃模具,其特征在于其化学元素及其质量%比为:9%的镍,10%的铝,12%的锌,0.35%的铁,0.01%的稀土,其余为铜。The rare earth copper alloy glass mold according to claim 1, wherein the chemical element and the mass ratio thereof are: 9% nickel, 10% aluminum, 12% zinc, 0.35% iron, and 0.01% rare earth. The rest is copper.
  5. 根据权利要求1至5任一权利要求所述的稀土铜合金玻璃模具,其特征在于所述的稀土铜合金玻璃模具的硬度为190-250HBW,导热系数为282-302w/(m.k)。The rare earth copper alloy glass mold according to any one of claims 1 to 5, wherein the rare earth copper alloy glass mold has a hardness of 190-250 HBW and a thermal conductivity of 282-302 w/(m.k).
  6. 一种如权利要求1所述的稀土铜合金玻璃模具的制备方法,其特征在于包括以下步骤:A method for preparing a rare earth copper alloy glass mold according to claim 1, comprising the steps of:
    A)熔炼,首先准备由锌和电解铜制备的且锌与铜的质量比为45:55的黄铜合金,其次,依据稀土铜合金玻璃模具材料中各元素的质量%比,将称量好的铝、镍、铁和铜投入到熔炉中,待熔炼温度达到1200-1250℃时加入所述的黄铜合金,当熔炼温度达到1280-1300℃时,断电静置5-10min,使杂质上浮以净化铜水,然后进行扒渣,而后加入铜-稀土中间合金,待铜-稀土中间合金熔化后再次扒渣并且同时采用光谱分析调整化学元素的质量%含量,得到待浇注的稀土铜合金玻璃模具溶液;A) smelting, first preparing a brass alloy prepared from zinc and electrolytic copper and having a mass ratio of zinc to copper of 45:55, and secondly, weighing according to the mass% ratio of each element in the rare earth copper alloy glass mold material The aluminum, nickel, iron and copper are put into the furnace, and the brass alloy is added when the melting temperature reaches 1200-1250 ° C. When the melting temperature reaches 1280-1300 ° C, the electricity is allowed to stand for 5-10 min to make impurities. The upper part is floated to purify the copper water, and then the slag is slag, and then the copper-rare earth intermediate alloy is added. After the copper-rare earth intermediate alloy is melted, the slag is again slag and the mass analysis of the chemical element is adjusted by spectral analysis to obtain the rare earth copper alloy to be poured. Glass mold solution;
    B)浇注成型,先将步骤A)所述的待浇注的稀土铜合金玻璃模具熔液升温至1280-1320℃,再出炉浇注到树脂砂铸型中,浇注之前,在树脂砂铸型的内腔中放置用于成型出玻璃模具的内腔的冷铁泥芯,浇注完成静置,而后撤去冷铁泥芯,得到待退火的稀土铜合金玻璃模具;B) casting, firstly, the molten rare earth copper alloy glass mold melt to be poured in step A) is heated to 1280-1320 ° C, and then poured into a resin sand mold, before casting, in the resin sand mold a cold iron core for forming a cavity of the glass mold is placed in the cavity, the casting is completed, and then the cold iron core is removed to obtain a rare earth copper alloy glass mold to be annealed;
    C)退火,将由步骤B)得到的待退火的稀土铜合金玻璃模具进行去应力退火,去应力退火结束后保温并且在保温后冷却至室温,得到稀土铜合金玻璃模具。C) annealing, the rare earth copper alloy glass mold to be annealed obtained in step B) is subjected to stress relief annealing, after the stress relief annealing is completed, and after cooling, it is cooled to room temperature to obtain a rare earth copper alloy glass mold.
  7. 根据权利要求6所述的稀土铜合金玻璃模具的制备方法,其特征在于步骤A)中所述的电解铜为1#电解铜,所述的镍为1#电解镍,所述的锌为1#锌。The method for preparing a rare earth copper alloy glass mold according to claim 6, wherein the electrolytic copper in the step A) is 1# electrolytic copper, the nickel is 1# electrolytic nickel, and the zinc is 1 #锌.
  8. 根据权利要求6所述的稀土铜合金玻璃模具的制备方法,其特征在于步骤A)中所述的采用光谱分析调整化学元素的质量%含量是将化学元素的质量%含量调整为:9-12%的镍,7-10%的铝,8-12%的锌,<0.5%的铁,0.01-0.5%的稀土,其余为铜。 The method for preparing a rare earth copper alloy glass mold according to claim 6, characterized in that the mass % content of the chemical element adjusted by the spectral analysis described in the step A) is adjusted to the mass % content of the chemical element: 9-12 % nickel, 7-10% aluminum, 8-12% zinc, <0.5% iron, 0.01-0.5% rare earth, and the balance copper.
  9. 根据权利要求6所述的稀土铜合金玻璃模具的制备方法,其特征在于步骤A)中所述的铜-稀土中间合金为钇基重稀土并且以铜-钇中间合金的形式加入,该铜-钇中间合金的化学元素及其质量%为:ReO:1-11%,Cu:45-55%,Si:10-15%,Fe:20-25%,Mg:<5%,B:<5%。The method for preparing a rare earth copper alloy glass mold according to claim 6, wherein the copper-rare earth intermediate alloy in the step A) is a cerium-based heavy rare earth and is added in the form of a copper-bismuth intermediate alloy, the copper- The chemical elements of the niobium intermediate alloy and the mass % thereof are: ReO: 1-11%, Cu: 45-55%, Si: 10-15%, Fe: 20-25%, Mg: <5%, B: <5 %.
  10. 根据权利要求6所述的稀土铜合金玻璃模具的制备方法,其特征在于步骤B)中所述的静置的时间为40-60min;步骤C)中所述的去应力退火是在退火炉中进行的,并且去应力退火的温度为600-630℃,所述的去应力退火结束后保温的时间为4-6h,并且在保温4-6h后以≤50℃/h的冷却速度冷却至室温。 The method for preparing a rare earth copper alloy glass mold according to claim 6, wherein the standing time in the step B) is 40-60 min; and the stress relief annealing in the step C) is in the annealing furnace. The temperature of the stress relief annealing is 600-630 ° C, the time of heat preservation after the end of the stress relief annealing is 4-6 h, and after cooling for 4-6 h, it is cooled to room temperature with a cooling rate of ≤ 50 ° C / h. .
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