WO2018072368A1

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

Info

Publication number: WO2018072368A1
Application number: PCT/CN2017/074497
Authority: WO
Inventors: 戈剑鸣
Original assignee: 苏州东方模具科技股份有限公司
Priority date: 2016-10-19
Filing date: 2017-02-23
Publication date: 2018-04-26
Also published as: CN106566946A

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

Rare earth copper alloy glass mold and preparation method thereof

Technical field

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.

Background technique

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.

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.

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.

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.

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.

Summary of the invention

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.

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.

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.

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.

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.

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.

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).

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) 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) 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) 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.

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.

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.

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%.

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.

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.

detailed description

The invention is further illustrated by the following examples.

Example 1:

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) 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) 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).

Example 2:

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) 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) 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).

Example 3:

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) 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) 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

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.
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.
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.
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.
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).
A method for preparing a rare earth copper alloy glass mold according to claim 1, comprising the steps of:

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) 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) 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.
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.
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.
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 %.
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. .