WO2020118744A1

WO2020118744A1 - Rare earth-copper alloy lightweight glass mold and preparation method therefor

Info

Publication number: WO2020118744A1
Application number: PCT/CN2018/121932
Authority: WO
Inventors: 马建华; 苏秋君; 马伟刚; 王锦锋; 计水明; 夏建新
Original assignee: 常熟建华模具科技股份有限公司
Priority date: 2018-12-13
Filing date: 2018-12-19
Publication date: 2020-06-18
Also published as: CN109338155A; CN109338155B

Abstract

A rare earth-copper alloy lightweight glass mold and a preparation method therefor, relating to the field of glass mold materials. The method comprises: putting weighed nickel, silicon, chromium, 50% of copper, and rare earth into a smelting furnace; after melting, stopping the heating of the furnace and adding the remaining copper; after melting, adding a deslagging agent to cover the melt; performing heating and removing the slags; at the same time, adjusting the melt by means of spectral analysis to contain 4.0-9.5% of nickel, 0.5-3.5% of silicon, 0.5-3.5% of chromium, 0.01-0.5% of rare earth, with the balance being copper; pouring the obtained rare earth-copper alloy lightweight glass mold melt into a molding sand wall in which a cold iron core is provided, and removing the cold iron core after the pouring is completed; introducing the obtained rare earth-copper alloy lightweight glass mold into a solution treatment furnace to perform solution treatment; and then, putting into the furnace to perform aging treatment to obtain a finished product. The mold has high thermal conductivity, high tensile strength, high hardness, excellent oxidation resistance and corrosion resistance.

Description

Rare earth copper alloy lightweight glass mold and preparation method thereof

Technical field

The invention belongs to the technical field of glass mold materials, and particularly relates to a rare earth copper alloy lightweight glass mold, and also relates to a preparation method thereof.

Background technique

The above-mentioned lightweight glass mold substantially refers to a glass mold used for processing lightweight glass products (ie, containers). With the continuous maturity and development of lightweight glass products technology, the speed of bottle making machines is getting higher and higher, so that the thermal fatigue resistance and wear resistance of glass molds are increasingly strict. Manufacturers of high-end glass products are more inclined to choose copper alloys as glass mold materials when manufacturing high-end lightweight glass products. Although copper alloy has good heat dissipation, it can meet the requirements of high machine speed and high hardness, but because copper alloy belongs to the category of non-ferrous metals, smelting is difficult. In particular, the working conditions of the glass mold during service are cruel. Specifically, because of its frequent and rapid conversion in the temperature range of 500-1100 ℃, the material selection of the copper alloy glass mold and the preparation process If you can not strictly control the process conditions, it will affect its service life.

The main factors for considering the service life of copper alloy lightweight glass molds are: high thermal conductivity, high tensile strength, good hardness, good oxidation resistance and corrosion resistance.

Technical information about copper alloy glass molds and their preparation methods can be seen in the published Chinese and foreign patent documents. For example, Japanese Patent JP-A 10-219373A recommends "a copper alloy mold". The chemical element composition and its mass% ratio are : 6-20% nickel, 9-18% aluminum, 8% or less zinc, 6% or less iron and 6% or less manganese, the balance is copper and inevitable impurities (for details, please refer to the patent specification 9 paragraphs). Another example is CN106566946A which introduces "rare earth copper alloy glass mold and its preparation method". The chemical element composition and its mass% ratio are: 9-12% nickel, 7-10% aluminum, 8-12% zinc, <0.5 % Iron and 0.01-0.5% rare earth, the balance is copper.

Since it is not limited to the solutions disclosed in the above cited patent documents, the high thermal conductivity, high thermal fatigue resistance, high abrasion resistance, good oxidation resistance and corrosion resistance properties expected of the aforementioned lightweight glass mold cannot be fully achieved. Therefore, it is necessary to continue to explore. The technical solutions to be introduced below are generated under this background.

Summary of the invention

The primary task of the present invention is to provide a rare earth copper alloy lightweight glass mold with excellent high thermal conductivity, high tensile strength, good hardness, excellent oxidation resistance and corrosion resistance.

Another task of the present invention is to provide a method for preparing a rare earth copper alloy lightweight glass mold. This method helps to purify the copper alloy composition by means of the deoxidation and desulfurization of rare earth, which is conducive to ensuring the weight reduction of rare earth copper alloy The technical effect of the glass mold can be fully reflected.

The primary task of the present invention is accomplished in this way, a rare earth copper alloy lightweight glass mold whose chemical elements and its mass% ratio are: 4.0-9.5% nickel, 0.5-3.5% silicon, 0.5-3.5% Chromium, 0.01-0.5% rare earth, the rest is copper.

In a specific embodiment of the present invention, a rare earth copper alloy lightweight glass mold, the chemical elements and their mass% ratio are: 6.5% nickel, 2% silicon, 0.5% chromium, 0.5% rare earth , The rest is copper.

In another specific embodiment of the present invention, a rare earth copper alloy lightweight glass mold, the chemical elements and their mass% ratio are: 4.0% nickel, 3.5% silicon, 2.0% chromium, 0.01% Rare earth, the rest is copper.

In yet another specific embodiment of the present invention, a rare earth copper alloy lightweight glass mold, the chemical elements and their mass% ratio are: 9.5% nickel, 0.5% silicon, 3.5% chromium, 0.25% Rare earth, the rest is copper.

In yet another specific embodiment of the present invention, the nickel is electrolytic nickel with a grade of Ni9996, the silicon is industrial silicon with a grade of Si-1, and the copper is 1# electrolytic copper.

In still another specific embodiment of the present invention, the rare earth is a rare earth ferrosilicon alloy with a brand of 195032. The chemical elements and the mass% ratio of the rare earth ferrosilicon alloy are: 30-33% RE, greater than 46% Ce/RE, less than 40% Si, less than 2% Mn, less than 4% Ca and less than 1% Ti, the rest is Fe.

Another task of the present invention is accomplished in this way. A method for preparing a rare earth copper alloy lightweight glass mold includes the following steps:

A) Smelting, according to the mass% ratio of each chemical element in the light-weight rare earth copper alloy glass mold material, the weighed nickel, silicon, chromium and

The copper and rare earth are put into the smelting furnace. After melting, the temperature is raised to 1400-1550 ℃. The furnace is stopped and the remaining copper is added. After melting, the slag remover is added to cover. The temperature is raised to 1250-1350 ℃. Spectral analysis adjusts the mass% content of the chemical elements in the melt: 4.0-9.5% nickel, 0.5-3.5% silicon, 0.5-3.5% chromium, 0.01-0.5% rare earth, and the rest is copper. Rare earth copper alloy lightweight glass mold melt;

B) Casting molding, pouring the molten glass mold of rare earth copper alloy obtained in step A) into the molding sand wall with cold iron core placed, and removing the cold iron core after pouring to obtain rare earth to be solution treated Copper alloy lightweight glass mold;

C) Solution treatment, introducing the rare-earth copper alloy light-weight glass mold obtained in step B) into the solution treatment furnace for solution treatment, and controlling the temperature of the solution treatment and the time of the solution treatment, and leaving the furnace Water cooling to obtain lightweight glass mold of rare earth copper alloy to be aged;

D) Aging treatment, the rare earth copper alloy lightweight glass mold obtained in step C) to be aged is put into the furnace for aging treatment, and the temperature of the aging treatment and the time of the aging treatment are controlled, and the water is cooled in the furnace to obtain the rare earth copper alloy light Quantify glass molds.

In a more specific embodiment of the present invention, the temperature of the solution treatment described in step C) is to control the temperature of the solution treatment to 750-850°C, and the time to control the solution treatment is Control the time of solution treatment to 120-180min.

In a further specific embodiment of the present invention, the temperature of the aging treatment described in step D) is to control the temperature of the aging treatment to 200-350°C, and the time of the control aging treatment is to treat the aging treatment Time control is 120-180min.

In a more specific embodiment of the present invention, the hardness of the rare earth copper alloy lightweight glass mold in step D) is 280-300 HBW.

The technical solution provided by the present invention has the following technical effects: thermal conductivity λ (W/m*K) is 187 to 201, tensile strength Rm (MPa) is 890-920, and breaking elongation A (%) is 5-8 , The impact energy Ak(J) is 7-10, and the hardness (HBW) is 280-300; as the nickel element in the formula is an element that can be infinitely miscible with the base copper, forming a continuous solid solution, it can improve oxidation resistance and corrosion resistance Performance, and is conducive to improving the strength without reducing the elongation and toughness; the preparation method provided can purify the copper alloy composition and ensure that the technical effect of the rare earth copper alloy lightweight glass mold is fully reflected.

detailed description

Example 1:

A) Smelting, according to the mass% ratio of each chemical element in the light-weight rare earth copper alloy glass mold material, the electrolytic nickel with a good brand of Ni9996, industrial silicon with a brand of Si-1, and chromium (block chromium) with

The 1# electrolytic copper and rare earth are put into the smelting furnace. After melting, the temperature is raised to 1550 ℃, the furnace is stopped and the remaining 1# electrolytic copper is the remaining

The 1# electrolytic copper is added into the furnace and covered with a slag remover after melting. The temperature is raised to 1250°C, the slag is stripped, and the mass% content of the chemical elements in the melt is adjusted by spectral analysis: 6.5% nickel, 2% Silicon, 0.5% chromium and 0.5% rare earth, and the rest is copper, to obtain a lightweight glass mold melt of rare earth copper alloy to be cast, the rare earth ferrosilicon alloy of rare earth grade 195032 mentioned in this step, the rare earth ferrosilicon alloy The chemical elements and their mass% ratio are: 31.5% RE, 46% Ce/RE, 10% Si, 2% Mn, 3.5% Ca and 1% Ti, the balance is iron;

C) Solution treatment, the rare earth copper alloy light-weight glass mold obtained in step B) to be solution treated is introduced into a solution treatment furnace for solution treatment, and the temperature of the solution treatment is controlled to 750° C. The time is 180min, and the water is cooled in the furnace to obtain a lightweight glass mold of rare earth copper alloy to be aged;

D) Aging treatment, the rare earth copper alloy light-weight glass mold obtained in step C) to be aged is put into the furnace for aging treatment, and the temperature of the aging treatment is controlled to 200° C. and the time of the aging treatment is controlled to 180 min. A rare earth copper alloy lightweight glass mold with a hardness of 300HBW was obtained.

Example 2:

A) Smelting, according to the mass% ratio of each chemical element in the light-weight rare earth copper alloy glass mold material, weighed electrolytic nickel with a grade of Ni9996, industrial silicon with a grade of Si-1, and chromium (block chromium) with

The 1# electrolytic copper and rare earth are put into the smelting furnace. After melting, the temperature is raised to 1400 ℃, the furnace is stopped and the remaining 1# electrolytic copper is the remaining

The 1# electrolytic copper is added into the furnace and covered with a slag remover after being melted. The temperature is raised to 1300 ℃, the slag is stripped, and the mass% content of the chemical elements in the melt is adjusted by spectrum analysis: 4% nickel, 3.5% Silicon, 2% chromium and 0.01% rare earth, the rest is copper, to obtain the lightweight glass mold melt of the rare earth copper alloy to be cast, the rare earth ferrosilicon alloy with the rare earth brand of 195032 mentioned in this step, the rare earth ferrosilicon alloy The chemical elements and their mass% ratio are: 30% RE, 48% Ce/RE, 5% Si, 1% Mn, 4% Ca and 0.5% Ti, the balance is iron;

C) solution treatment, the rare earth copper alloy light-weight glass mold obtained in step B) to be solution treated is introduced into a solution treatment furnace for solution treatment, and the temperature of the solution treatment is controlled to 850° C. The time is 120min, and the water is cooled in the furnace to obtain a lightweight glass mold of rare earth copper alloy to be aged;

D) Aging treatment, the rare earth copper alloy light-weight glass mold obtained in step C) to be aged is put into the furnace for aging treatment, and the temperature of the aging treatment is controlled to 350° C. and the time of the aging treatment is controlled to 120 min. A rare-earth copper alloy lightweight glass mold with a hardness of 285 HBW was obtained.

Example 3:

The 1# electrolytic copper and rare earth are put into the smelting furnace. After melting, the temperature is raised to 1575 ℃, the furnace is stopped and the remaining 1# electrolytic copper is the remaining

The 1# electrolytic copper is added into the furnace and covered with a slag remover after melting. The temperature is raised to 1350 ℃, the slag is stripped, and the mass% content of the chemical elements in the melt is adjusted by spectral analysis: 9.5% nickel, 0.5% Silicon, 3.5% chromium and 0.25% rare earth, the rest is copper, to obtain the lightweight glass mold melt of the rare earth copper alloy to be cast, the rare earth ferrosilicon alloy of the rare earth brand mentioned in this step is 195032, the rare earth ferrosilicon alloy The chemical elements and their mass% ratio are: 33% RE, 47% Ce/RE, 7% Si, 2% Mn, 2% Ca and 0.2% Ti, the balance is iron;

C) Solution treatment, the rare earth copper alloy lightweight glass mold obtained in step B) to be solution treated is introduced into a solution treatment furnace for solution treatment, and the temperature of the solution treatment is controlled to 800° C. The time is 150min, and the water is cooled in the furnace to obtain a lightweight glass mold of rare earth copper alloy to be aged;

D) Aging treatment, the rare earth copper alloy lightweight glass mold obtained in step C) to be aged is put into the furnace for aging treatment, and the temperature of the aging treatment is controlled to 270°C and the time of the aging treatment is controlled to 150min, and the water is cooled. A rare-earth copper alloy lightweight glass mold with a hardness of 280 HBW was obtained.

The technical indicators of the rare earth copper alloy lightweight glass molds obtained from the above examples 1 to 3 are tested and shown in the table below:

Claims

A rare earth copper alloy lightweight glass mold, characterized by its chemical elements and its mass% ratio: 4.0-9.5% nickel, 0.5-3.5% silicon, 0.5-3.5% chromium, 0.01-0.5% rare earth , The rest is copper.
A rare earth copper alloy lightweight glass mold, characterized by its chemical elements and its mass% ratio: 6.5% nickel, 2% silicon, 0.5% chromium, 0.5% rare earth, and the rest is copper.
A rare earth copper alloy lightweight glass mold, characterized by its chemical elements and its mass% ratio: 4.0% nickel, 3.5% silicon, 2.0% chromium, 0.01% rare earth, and the rest is copper.
A rare earth copper alloy lightweight glass mold, characterized by its chemical elements and its mass% ratio: 9.5% nickel, 0.5% silicon, 3.5% chromium, 0.25% rare earth, and the rest is copper.
The rare earth copper alloy lightweight glass mold according to any one of claims 1 to 4, wherein the nickel is electrolytic nickel with a grade of Ni9996, and the silicon is industrial silicon with a grade of Si-1, The copper is 1# electrolytic copper.
The rare earth copper alloy lightweight glass mold according to any one of claims 1 to 4, characterized in that the rare earth is a rare earth ferrosilicon alloy with a brand of 195032, and the chemical elements of the rare earth ferrosilicon alloy and their mass% ratio are : 30-33% RE, greater than 46% Ce/RE, less than 40% Si, less than 2% Mn, less than 4% Ca and less than 1% Ti, the rest is Fe.
A method for manufacturing a rare earth copper alloy lightweight glass mold according to claim 1, characterized in that it includes the following steps:

A) Smelting, according to the mass% ratio of each chemical element in the light-weight rare earth copper alloy glass mold material, the weighed nickel, silicon, chromium and
The copper and rare earth are put into the smelting furnace. After melting, the temperature is raised to 1400-1550 ℃. The furnace is stopped and the remaining copper is added. After melting, the slag remover is added to cover. The temperature is raised to 1250-1350 ℃. Spectral analysis adjusts the mass% content of the chemical elements in the melt: 4.0-9.5% nickel, 0.5-3.5% silicon, 0.5-3.5% chromium, 0.01-0.5% rare earth, and the rest is copper. Rare earth copper alloy lightweight glass mold melt;

B) Casting molding, pouring the molten glass mold of rare earth copper alloy obtained in step A) into the molding sand wall with cold iron core placed, and removing the cold iron core after pouring to obtain rare earth to be solution treated Copper alloy lightweight glass mold;

C) Solution treatment, introducing the rare-earth copper alloy light-weight glass mold obtained in step B) into the solution treatment furnace for solution treatment, and controlling the temperature of the solution treatment and the time of the solution treatment, and leaving the furnace Water cooling to obtain lightweight glass mold of rare earth copper alloy to be aged;

D) Aging treatment, the rare earth copper alloy lightweight glass mold obtained in step C) to be aged is put into the furnace for aging treatment, and the temperature of the aging treatment and the time of the aging treatment are controlled, and the water is cooled in the furnace to obtain the rare earth copper alloy light Quantify glass molds.
The method for preparing a rare earth copper alloy lightweight glass mold according to claim 7, characterized in that the temperature of the solution treatment in step C) is to control the temperature of the solution treatment to 750-850°C, The control of the solution treatment time is to control the solution treatment time to 120-180min.
The method for preparing a rare earth copper alloy lightweight glass mold according to claim 7, characterized in that the temperature of the aging treatment in step D) is to control the temperature of the aging treatment to 200-350°C, and the control The time of aging treatment is to control the time of aging treatment to 120-180min.
The method for preparing a rare earth copper alloy lightweight glass mold according to claim 7, wherein the hardness of the rare earth copper alloy lightweight glass mold in step D) is 280-300HBW.