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CN113430440B - Low-melting-point alloy and preparation method and application thereof - Google Patents

Low-melting-point alloy and preparation method and application thereof Download PDF

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CN113430440B
CN113430440B CN202010199485.7A CN202010199485A CN113430440B CN 113430440 B CN113430440 B CN 113430440B CN 202010199485 A CN202010199485 A CN 202010199485A CN 113430440 B CN113430440 B CN 113430440B
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melting
point alloy
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melting point
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CN113430440A (en
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曹宇
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Beijing Dream Ink Technology Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C28/00Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24Selection of soldering or welding materials proper
    • B23K35/26Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00Materials specially adapted for additive manufacturing
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C30/00Alloys containing less than 50% by weight of each constituent
    • C22C30/04Alloys containing less than 50% by weight of each constituent containing tin or lead
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys

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Abstract

The invention provides a low-melting-point alloy and a preparation method and application thereof, and relates to the technical field of new materials. The low-melting-point alloy provided by the invention comprises the following components in percentage by mass: 35 to 42 percent of tin, 8.5 to 11.5 percent of bismuth, 0.05 to 0.8 percent of gallium and 46 to 55.4 percent of indium; the melting point of the low-melting-point alloy is 80-110 ℃. The technical scheme of the invention can simultaneously meet the requirements of additive manufacturing of the electronic circuit based on the organic film material and firm welding of the electronic element.

Description

Low-melting-point alloy and preparation method and application thereof
Technical Field
The invention relates to the technical field of new materials, in particular to a low-melting-point alloy and a preparation method and application thereof.
Background
The additive manufacturing technology is a novel processing and manufacturing technology with development potential, and has the advantages of customizable processing, raw material saving, easy processing of complex structures and the like compared with the traditional processing technology. Through development for many years, the titanium alloy is widely applied to the fields of metal structural parts with complex structures, plastic structural part manufacturing, titanium alloy part manufacturing and the like.
In the field of electronic circuit manufacturing, a technology for directly manufacturing a circuit by adding materials on an organic film material substrate by using low-melting-point alloy materials has appeared at present, and compared with the traditional PCB (printed circuit board) manufacturing technology, the technology has the advantages of customizable processing, no need of chemical corrosion, quick realization and the like. The 'writing' type micro-channel control circuit manufacturing is a main technology of circuit additive manufacturing, controls the displacement of a micro-channel, simultaneously controls the molten low-melting-point alloy to flow out of the micro-channel and solidify on an organic film substrate, and the circuit manufacturing is completed.
The inventor finds that when electronic circuits are printed on the organic film material by using the low-melting-point alloy in the prior art, the organic film material is generally damaged or electronic components cannot be firmly welded.
Disclosure of Invention
The invention provides a low-melting-point alloy, a preparation method and application thereof, which can simultaneously meet the requirements of additive manufacturing of an electronic circuit based on an organic film material and firm welding of an electronic element.
In a first aspect, the invention provides a low melting point alloy, which adopts the following technical scheme:
the low melting point alloy comprises the following components in percentage by mass: 35 to 42 percent of tin, 8.5 to 11.5 percent of bismuth, 0.05 to 0.8 percent of gallium and 46 to 55.4 percent of indium; the melting point of the low-melting-point alloy is 80-110 ℃.
Optionally, the low melting point alloy further comprises 0.005-0.015% silver and 0.002-0.01% aluminum by mass fraction.
Optionally, the low melting point alloy further comprises 1-1.5% by mass of zinc.
In a second aspect, the present invention provides a method for preparing a low melting point alloy, which is used for preparing the low melting point alloy described in any one of the above aspects, and the method for preparing the low melting point alloy adopts the following technical scheme:
the preparation method of the low-melting-point alloy comprises the following steps:
step S1, pretreating the tin raw material, the bismuth raw material and the indium raw material to remove moisture and/or surface oxides adsorbed on the surfaces of the raw materials;
s2, weighing all the raw materials according to the mass fraction, and mixing the weighed raw materials;
step S3, carrying out vacuum high-frequency induction melting on the mixed raw materials;
and step S4, cooling to obtain the low-melting-point alloy.
Optionally, the purity of each raw material is above 99.95%.
Optionally, in step S1, the tin raw material, the bismuth raw material, and the indium raw material are heated and baked in a vacuum environment to remove moisture adsorbed on the surfaces thereof.
Further, in step S1, the baked tin raw material, bismuth raw material, and indium raw material are each separately placed in a barrel mill, and are subjected to barrel milling in an argon atmosphere to remove surface oxides.
Optionally, the preparation method of the low-melting-point alloy further comprises: and according to the application scene of the low-melting-point alloy, performing low-temperature casting on the low-melting-point alloy to obtain the low-melting-point alloy with the target shape.
Further, the mould used in the low-temperature casting process is a copper casting mould.
In a third aspect, the invention provides an application of a low melting point alloy, wherein the low melting point alloy is used as a printing consumable material in electronic circuit printing.
The invention provides a low-melting-point alloy and a preparation method and application thereof, wherein the low-melting-point alloy comprises the following components in percentage by mass: 35 to 42 percent of tin, 8.5 to 11.5 percent of bismuth, 0.05 to 0.8 percent of gallium and 46 to 55.4 percent of indium, and the melting point of the low-melting-point alloy with the components is 80 to 110 ℃, so that the low-melting-point alloy can simultaneously meet the requirements of additive manufacturing of electronic circuits based on organic film materials and firm welding of electronic elements.
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In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is a flowchart of a method for preparing a low melting point alloy according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the technical features in the embodiments of the present invention may be combined with each other without conflict.
The embodiment of the invention provides a low-melting-point alloy, which comprises the following components in percentage by mass: 35 to 42 percent of tin, 8.5 to 11.5 percent of bismuth, 0.05 to 0.8 percent of gallium and 46 to 55.4 percent of indium; the melting point of the low-melting-point alloy is 80-110 ℃.
Illustratively, the mass fraction of tin in the low melting point alloy may be 35%, 36%, 37%, 38%, 39%, 40%, 41%, or 42%; the mass fraction of bismuth in the low melting point alloy may be 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, or 11.5%; the mass fraction of gallium in the low melting point alloy may be 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, or 0.8%; the mass fraction of indium in the low melting point alloy may be 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, or 55.4%.
Among the above low melting point alloys, indium and tin are used to provide good electrical conductivity, and the addition of bismuth and gallium is mainly used to adjust the melting point of the low melting point alloy to a target range, i.e., 80 to 110 ℃. After the inventor carries out deep research on the low melting point alloy in the prior art, the analysis shows that: the reason for the damage of the organic film material is that the adopted low-melting point alloy is soldering tin alloy with the melting point within the range of 120-200 ℃, so that the temperature of the melted low-melting point alloy is too high, the organic film material is difficult to bear, and in addition, the alloy is easy to block a micro-channel in a printer in the printing process; the reason why the electronic component cannot be soldered is that the adopted low-melting-point alloy is low-melting-point soldering tin with the melting point within the range of 50-70 ℃, and the electronic circuit is melted in the soldering process due to the fact that the melting points of the soldering tin and the printed electronic circuit are close to or the same when the electronic component is soldered, and further firm soldering cannot be achieved.
In summary, the inventors propose the above-mentioned low melting point alloy with a melting point of 80-110 ℃, so that the low melting point alloy can simultaneously meet the requirements of additive manufacturing of electronic circuits based on organic film materials and firm welding of electronic components. In addition, the micro-channel in the printer is not easy to block, which is beneficial to improving the stability and the service life of the printer.
It should be noted that the low-melting-point alloy provided by the embodiment of the present invention has a significant advantage in an additive manufacturing process of an electronic circuit, but does not indicate that the low-melting-point alloy cannot be applied to other application scenarios.
Optionally, in the embodiment of the present invention, the low melting point alloy may further include 0.005% to 0.015% of silver and 0.002% to 0.01% of aluminum by mass fraction. The silver mainly plays a role in improving the fluidity and the conductivity of the low-melting-point alloy after being melted, and does not play a role if the content of the silver is too low, and high-melting-point components are easy to appear if the content of the silver is too high, so that the silver is difficult to melt and easy to block a micro-channel; aluminum mainly improves the oxidation resistance, has no effect when the content is too low, has adverse effect on the fluidity of the low-melting-point alloy after melting when the content is too high, and can generate high-melting-point components which are difficult to melt and easy to block a micro-channel. Illustratively, the mass fraction of silver in the low melting point alloy may be 0.005%, 0.007%, 0.009%, 0.011%, 0.013%, or 0.015%; the mass fraction of aluminum in the low melting point alloy may be 0.002%, 0.004%, 0.006%, 0.008%, or 0.01%.
Optionally, in the embodiment of the present invention, the low melting point alloy may further include zinc 1% to 1.5% by mass. The addition of zinc can properly reduce the melting point of the low-melting-point alloy and can also improve the oxidation resistance of the low-melting-point alloy to a certain extent. If the amount of the additive is too large, the fluidity of the low melting point alloy after melting is deteriorated. Illustratively, the mass fraction of zinc in the low melting point alloy may be 1%, 1.1%, 1.2%, 1.3%, 1.4%, or 1.5%.
It should be noted that, according to actual needs, those skilled in the art may add only silver and aluminum, or only zinc, or may add silver, aluminum, and zinc to the low-melting-point alloy at the same time.
In addition, an embodiment of the present invention further provides a method for preparing a low melting point alloy, which is used to prepare the low melting point alloy described in any one of the above embodiments, specifically, as shown in fig. 1, the method for preparing a low melting point alloy provided in fig. 1 for an embodiment of the present invention includes:
step S1, the tin raw material, the bismuth raw material, and the indium raw material are pretreated to remove moisture and/or surface oxides adsorbed on the surfaces thereof.
Exemplarily, in step S1, the tin raw material, the bismuth raw material, and the indium raw material are subjected to a heating bake in a vacuum environment to remove moisture adsorbed on the surfaces thereof. Illustratively, the vacuum pressure is not more than 10Pa, the heating and baking temperature is 120 ℃, and the heating and baking time is 20min to 60 min. Alternatively, in step S1, the tin raw material, the bismuth raw material, and the indium raw material are each separately put into a barrel mill and barrel-milled under an argon atmosphere to remove surface oxides.
When the pretreatment in step S1 is to remove moisture and surface oxides from the raw materials, in the embodiment of the present invention, it is preferable that the tin raw material, the bismuth raw material, and the indium raw material are heated and baked in a vacuum environment to remove moisture therefrom, and then the baked tin raw material, bismuth raw material, and indium raw material are individually placed in a barrel mill and are tumbled in an argon environment to remove surface oxides.
Preferably, the purities of the tin raw material, the bismuth raw material and the indium raw material in the embodiment of the invention are all more than 99.95%, so as to reduce the influence of impurities on the melting point of the prepared low-melting-point alloy.
And step S2, weighing all the raw materials according to the mass fraction, and mixing the weighed raw materials.
All the raw materials weighed in step S2 include the tin raw material, bismuth raw material, and indium raw material, which have been previously pretreated, and gallium raw material, and optionally silver raw material, aluminum raw material, and zinc raw material. The gallium, silver, aluminum and zinc feedstocks selected here are also preferably of a purity of 99.95% or more to reduce the influence of impurities on the melting point of the low melting point alloy produced.
And step S3, carrying out vacuum high-frequency induction melting on the mixed raw materials.
Illustratively, when the alloy is melted by using a vacuum high-frequency induction furnace, each raw material is placed in a crucible, and the vacuum high-frequency induction furnace is evacuated to a vacuum pressure of 10-3In order of Pa, melting is started, the raw materials of tin, bismuth and indium, gallium and optionally silver, aluminum and zinc are all melted, the crucible is maintained for 3 to 10 minutes, and the crucible is repeatedly tilted to make the componentsAnd (4) uniformity.
And step S4, cooling to obtain the low-melting-point alloy.
Illustratively, a smelting power supply of the vacuum high-frequency induction furnace is turned off, the vacuum degree is maintained, and the prepared low-melting-point alloy is waited to be cooled.
Optionally, the method for preparing a low melting point alloy in the embodiment of the present invention further includes: according to the application scene of the low-melting-point alloy, the low-melting-point alloy is cast at low temperature to obtain the low-melting-point alloy with the target shape. Specifically, when the alloy is melted by using a vacuum high-frequency induction furnace, the casting mold can be placed in a vacuum furnace bin of the vacuum high-frequency induction furnace, the temperature of the casting mold is kept at 15-20 ℃ through water circulation cooling, a ceramic filter block is placed at a mold gate, when the low-melting-point alloy is cooled to 150-170 ℃ in step S4, the low-melting-point alloy is cast, enters the casting mold through the ceramic filter block, and is rapidly cooled and solidified to obtain the low-melting-point alloy with uniform components and a target shape. In the casting process, the ceramic filter block can play a role in filtering and adsorbing impurities such as oxides, oxide films and other solid particles in the low-melting-point alloy.
Wherein, the material of the ceramic filter block can be alumina, zirconia or carborundum, and the thickness of the ceramic filter block is more than 20 mm. The mould used in the low-temperature casting process is a copper casting mould.
In addition, the embodiment of the invention also provides an application of the low-melting-point alloy, and the low-melting-point alloy is used as a printing consumable material to be applied to electronic circuit printing.
When the low-melting-point alloy is used as a printing consumable material, the main performance indexes of the low-melting-point alloy are the melting point, and the adhesion with a base material, the conductivity, the printing fluency, the printing service life and the like of the low-melting-point alloy are also considered. The indium and the tin provide good conductivity and basic printing performance, the bismuth is added to adjust the melting point and improve the printing fluency, and the gallium is added to improve the printing fluency and prolong the printing service life. The performance of the above low melting point alloy is deteriorated when the content of any one of the components exceeds the range. For example, if the content of tin exceeds the range, the melting point range is mainly influenced, and after exceeding the upper limit, the melting point is higher, and when the melting point is lower than the lower limit, different situations such as melting point reduction, different melting points of a plurality of components, melting point increase, and the like may occur according to the component situation; the content of gallium is lower than the lower limit, no improvement effect on the melting point is realized, and when the content of gallium is higher than the upper limit, a macroscopic visible liquid phase appears at room temperature, which is not beneficial to the storage and the use of the low-melting-point alloy and is not beneficial to the tight adhesion of a low-melting-point alloy printing circuit and an organic film material substrate; the content of bismuth is lower than the lower limit, the melting point is increased, and is higher than the upper limit, so that the melting point is reduced, the conductivity of bismuth is poor, and the conductivity of the low-melting-point alloy is unfavorable when the bismuth is added more.
In addition, to facilitate one of ordinary skill in the art to understand and practice the low melting point alloys of the embodiments of the present invention, a number of specific examples are provided below.
Example 1:
selecting high-purity metal raw materials In, Sn, Ga and Bi of which the purity is more than 99.95 percent, wherein In, Sn and Bi are heated and baked at 120 ℃ In a vacuum environment, the vacuum pressure is 5Pa, the heating and baking are carried out for 40min, the raw materials are respectively and independently placed into a tumbling mill after being baked, the rotating speed is 100 revolutions per minute, and argon is introduced for tumbling for 5 min. The treated raw materials are mixed according to the ratio of Sn: 37.5%, Bi: 10.0%, Ga: weighing 0.5% of the powder, and adding the rest In into a crucible, and placing the crucible into a vacuum high-frequency induction furnace. And (3) placing the copper casting mold into a vacuum furnace bin of a vacuum high-frequency induction furnace, and cooling by water circulation to keep the temperature of the copper casting mold at 18 ℃. And a ceramic filter block is arranged at the gate of the mold, and the ceramic filter block is made of zirconia and has the thickness of 20 mm. Vacuumizing until the vacuum pressure reaches 6 x 10-3And Pa, starting smelting. After the raw materials In, Sn, Ga and Bi are completely melted, keeping for 4 minutes, repeatedly tilting the crucible, then closing a smelting power supply, keeping the vacuum degree, and when the low-melting-point alloy is cooled to 150 ℃, casting the low-melting-point alloy into a copper casting mold through a ceramic filter block to obtain the low-melting-point alloy with the target shape. The low melting point alloy has a melting point of 98 deg.C and an electrical conductivity of 3.67 x 106S/m。
Example 2:
selecting high-purity metal raw materials of In, Sn, Ga, Bi and Zn with the purity of more than 99.95 percent, wherein In, Sn and Bi, heating and baking at 120 ℃ in a vacuum environment at the vacuum pressure of 6Pa for 45min, independently placing the baked materials into a tumbling mill respectively at the rotating speed of 100 rpm, and introducing argon for tumbling for 5 min. The treated raw materials are mixed according to the ratio of Sn: 40.5%, Bi: 8.5%, Ga: 0.8%, Zn: weighing 1.2% of the powder, and putting the rest In a crucible, and putting the crucible into a vacuum high-frequency induction furnace. And (3) placing the copper casting mold into a vacuum furnace bin of a vacuum high-frequency induction furnace, and cooling by water circulation to keep the temperature of the copper casting mold at 18 ℃. And a ceramic filter block is arranged at the gate of the mold, and the ceramic filter block is made of zirconia and has the thickness of 20 mm. Vacuumizing until the vacuum pressure reaches 7 x 10- 3And Pa, starting smelting. After the raw materials In, Sn, Ga, Bi and Zn are completely melted, keeping for 6 minutes, repeatedly tilting the crucible, then closing a smelting power supply, keeping the vacuum degree, and when the low-melting-point alloy is cooled to 150 ℃, casting the low-melting-point alloy into a copper casting mold through a ceramic filter block to obtain the low-melting-point alloy with the target shape. The low melting point alloy has a melting point of 100 deg.C and an electrical conductivity of 3.71 x 106S/m。
Example 3:
selecting high-purity metal raw materials In, Sn, Ga, Bi, Ag and Al with the purity of more than 99.95 percent, wherein In, Sn and Bi are heated and baked at 120 ℃ In a vacuum environment, the vacuum pressure is 5Pa, the heating and baking are carried out for 30min, the In, Sn and Bi are independently placed into a tumbling mill after being baked, the rotating speed is 100 revolutions per minute, and argon is introduced for tumbling for 5 min. The treated raw materials are mixed according to the ratio of Sn: 39.2%, Bi: 10.0%, Ga: 0.8%, Ag: 0.01%, Al: weighing 0.004%, and adding the rest In into a crucible, and placing the crucible into a vacuum high-frequency induction furnace. And (3) placing the copper casting mold into a vacuum furnace bin of a vacuum high-frequency induction furnace, and cooling by water circulation to keep the temperature of the copper casting mold at 18 ℃. And a ceramic filter block is arranged at the gate of the mold, and the ceramic filter block is made of zirconia and has the thickness of 20 mm. Vacuumizing until the vacuum pressure reaches 7 x 10-3And Pa, starting smelting. After the raw materials In, Sn, Ga, Bi, Ag and Al are completely melted, keeping for 5 minutes, repeatedly tilting the crucible, then closing a smelting power supply, keeping the vacuum degree, and when the low-melting-point alloy is cooled to 160 ℃, casting the low-melting-point alloy and passing through ceramicsAnd (4) putting the filter block into a copper casting mold to obtain the low-melting-point alloy with the target shape. The low melting point alloy has a melting point of 94 deg.C and an electrical conductivity of 3.86 x 106S/m。
Example 4:
selecting high-purity metal raw materials In, Sn, Ga, Bi, Ag and Al with the purity of more than 99.95 percent, wherein the In, Sn and Bi are heated and baked at the temperature of 120 ℃ In a vacuum environment, the vacuum pressure is 8Pa, the heating and baking are carried out for 40min, the In, Sn and Bi are independently placed into a tumbling mill after being baked, the rotating speed is 100 revolutions per minute, and argon is introduced for tumbling for 5 min. The treated raw materials are mixed according to the ratio of Sn: 40.5%, Bi: 10.3%, Ga: 0.2%, Ag: 0.008%, Al: weighing 0.007% of the powder, and adding the rest of In into a crucible, and placing the crucible into a vacuum high-frequency induction furnace. And (3) placing the copper casting mold into a vacuum furnace bin of a vacuum high-frequency induction furnace, and cooling by water circulation to keep the temperature of the copper casting mold at 16 ℃. And a ceramic filter block is arranged at the gate of the mold, and is made of aluminum oxide and has the thickness of 30 mm. Vacuumizing until the vacuum pressure reaches 6 x 10-3And Pa, starting smelting. After the raw materials In, Sn, Ga, Bi, Ag and Al are completely melted, keeping for 8 minutes, repeatedly tilting the crucible, then closing a smelting power supply, keeping the vacuum degree, and when the low-melting-point alloy is cooled to 165 ℃, casting the low-melting-point alloy into a copper casting mold through a ceramic filter block to obtain the low-melting-point alloy with the target shape. The low melting point alloy has a melting point of 97 deg.C and an electrical conductivity of 3.82 x 106S/m。
Example 5:
selecting high-purity metal raw materials In, Sn, Ga, Bi, Ag and Al with the purity of more than 99.95 percent, wherein the In, Sn and Bi are heated and baked at the temperature of 120 ℃ In a vacuum environment, the vacuum pressure is 10Pa, the heating and baking are carried out for 60min, the In, Sn and Bi are independently placed into a tumbling mill after being baked, the rotating speed is 100 revolutions per minute, and argon is introduced for tumbling for 5 min. The treated raw materials are mixed according to the ratio of Sn: 36%, Bi: 11.5%, Ga: 0.5%, Ag: 0.005%, Al: 0.009% of the powder was weighed, and the balance In was placed In a crucible, and the crucible was placed In a vacuum high-frequency induction furnace. And (3) placing the copper casting mold into a vacuum furnace bin of a vacuum high-frequency induction furnace, and cooling by water circulation to keep the temperature of the copper casting mold at 20 ℃. Placing ceramic at the mold gateThe filter block is made of silicon carbide and has a thickness of 40 mm. Vacuumizing until the vacuum pressure reaches 8 x 10-3And Pa, starting smelting. After the raw materials In, Sn, Ga, Bi, Ag and Al are completely melted, keeping for 10 minutes, repeatedly tilting the crucible, then closing a smelting power supply, keeping the vacuum degree, and when the low-melting-point alloy is cooled to 150 ℃, casting the low-melting-point alloy into a copper casting mold through a ceramic filter block to obtain the low-melting-point alloy with the target shape. The low melting point alloy has a melting point of 87 deg.C and an electrical conductivity of 3.73 x 106S/m。
Example 6:
selecting high-purity metal raw materials In, Sn, Ga, Bi, Ag and Al with the purity of more than 99.95 percent, wherein the In, Sn and Bi are heated and baked at 120 ℃ In a vacuum environment, the vacuum pressure is 7Pa, the heating and baking are carried out for 45min, the In, Sn and Bi are independently placed into a tumbling mill after being baked, the rotating speed is 100 revolutions per minute, and argon is introduced for tumbling for 5 min. The treated raw materials are mixed according to the ratio of Sn: 38.5%, Bi: 8.8%, Ga: 0.7%, Ag: 0.013%, Al: weighing 0.004%, and adding the rest In into a crucible, and placing the crucible into a vacuum high-frequency induction furnace. And (3) placing the copper casting mold into a vacuum furnace bin of a vacuum high-frequency induction furnace, and cooling by water circulation to keep the temperature of the copper casting mold at 20 ℃. And a ceramic filter block is arranged at the gate of the mold, and the ceramic filter block is made of zirconia and has the thickness of 20 mm. Vacuumizing until the vacuum pressure reaches 8 x 10-3And Pa, starting smelting. After the raw materials In, Sn, Ga, Bi, Ag and Al are completely melted, keeping for 7 minutes, repeatedly tilting the crucible, then closing a smelting power supply, keeping the vacuum degree, and when the low-melting-point alloy is cooled to 160 ℃, casting the low-melting-point alloy into a copper casting mold through a ceramic filter block to obtain the low-melting-point alloy with the target shape. The low melting point alloy has a melting point of 104 deg.C and an electrical conductivity of 3.90 x 106S/m。
Example 7:
selecting high-purity metal raw materials In, Sn, Ga, Bi, Ag, Al and Zn with the purity of more than 99.95 percent, wherein the In, Sn and Bi are heated and baked at 120 ℃ In a vacuum environment, the vacuum pressure is 7Pa, the heating and baking are carried out for 50min, the In, Sn and Bi are respectively and independently placed into a tumbling mill after being baked, the rotating speed is 100 r/min, and argon is introduced for tumbling for 5 min. Will be provided withThe raw materials after treatment are as follows: 37.5%, Bi: 8.5%, Ga: 0.4%, Zn: 1.3%, Ag: 0.012%, Al: weighing 0.005% of the powder, and the balance In, placing the powder into a crucible, and placing the crucible into a vacuum high-frequency induction furnace. And (3) placing the copper casting mold into a vacuum furnace bin of a vacuum high-frequency induction furnace, and cooling by water circulation to keep the temperature of the copper casting mold at 18 ℃. And a ceramic filter block is arranged at the gate of the mold, and the ceramic filter block is made of zirconia and has the thickness of 20 mm. Vacuumizing until the vacuum pressure reaches 8 x 10-3And Pa, starting smelting. After the raw materials In, Sn, Ga, Bi and Zn are completely melted, keeping for 5 minutes, repeatedly tilting the crucible, then closing a smelting power supply, keeping the vacuum degree, and when the low-melting-point alloy is cooled to 160 ℃, casting the low-melting-point alloy into a copper casting mold through a ceramic filter block to obtain the low-melting-point alloy with the target shape. The low melting point alloy has a melting point of 104 deg.C and an electrical conductivity of 3.87 × 106S/m。
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (9)

1. A low melting point alloy, comprising, in mass fractions: 35 to 42 percent of tin, 8.5 to 11.5 percent of bismuth, 0.05 to 0.8 percent of gallium, 46 to 55.4 percent of indium, 0.005 to 0.015 percent of silver and 0.002 to 0.01 percent of aluminum; the melting point of the low-melting-point alloy is 80-110 ℃.
2. A low melting point alloy as defined in claim 1, further comprising zinc in a range of 1 to 1.5% by mass.
3. A method for producing a low-melting-point alloy according to any one of claims 1 to 2, comprising:
step S1, pretreating the tin raw material, the bismuth raw material and the indium raw material to remove moisture and/or surface oxides adsorbed on the surfaces of the raw materials;
s2, weighing all the raw materials according to the mass fraction, and mixing the weighed raw materials;
step S3, carrying out vacuum high-frequency induction melting on the mixed raw materials;
and step S4, cooling to obtain the low-melting-point alloy.
4. A method for producing a low melting point alloy according to claim 3, wherein the purity of each raw material is 99.95% or more.
5. The method of claim 3, wherein in step S1, the tin material, the bismuth material, and the indium material are baked under vacuum to remove moisture adsorbed on the surfaces thereof.
6. The method of producing a low melting point alloy according to claim 5, wherein in step S1, the baked tin material, bismuth material and indium material are each separately placed in a barrel mill and are tumbled under argon atmosphere to remove surface oxides.
7. The method for producing a low-melting-point alloy according to any one of claims 3 to 6, further comprising: and according to the application scene of the low-melting-point alloy, performing low-temperature casting on the low-melting-point alloy to obtain the low-melting-point alloy with the target shape.
8. The method for producing a low melting point alloy according to claim 7, wherein the mold used in the low temperature casting process is a copper casting mold.
9. Use of a low melting point alloy according to any one of claims 1 to 2 as a printing consumable in electronic circuit printing.
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CN105483486A (en) * 2015-11-26 2016-04-13 苏州天脉导热科技有限公司 Low-melting-point alloy and thermal interface material made from low-melting-point alloy
CN109047768A (en) * 2018-08-30 2018-12-21 云南科威液态金属谷研发有限公司 A kind of low-melting-point metal wire rod for 3D printing

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105483486A (en) * 2015-11-26 2016-04-13 苏州天脉导热科技有限公司 Low-melting-point alloy and thermal interface material made from low-melting-point alloy
CN109047768A (en) * 2018-08-30 2018-12-21 云南科威液态金属谷研发有限公司 A kind of low-melting-point metal wire rod for 3D printing

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