CN-121992391-A - Method for constructing functional interface on metal surface by ultrasonic-assisted liquid gallium at low temperature

CN121992391ACN 121992391 ACN121992391 ACN 121992391ACN-121992391-A

Abstract

The invention discloses a method for constructing a functional interface on a metal surface by ultrasonic-assisted liquid gallium at a low temperature, and belongs to the field of material surface modification. The method comprises the steps of pretreating metal base materials such as copper, silver, nickel and the like, immersing the metal base materials in liquid gallium, applying low-power density ultrasonic waves at a low temperature of less than or equal to 50 ℃ for several minutes, overcoming solid atom diffusion barrier by utilizing ultrasonic cavitation effect, rapidly driving interface alloying reaction to form an intermetallic compound functional layer, and removing residual gallium through centrifugation and acid washing. The invention realizes the low-temperature, rapid and controllable construction of the metal surface function.

Inventors

ZHAO JUNFENG
XIAO FULAI
GUO XIAOTONG
BI XU
WANG BIN
SUN JUNFEI
YU JINFENG
ZHAN SHIFEN
DAI HAN

Assignees

烟台南山学院
山东南山科学技术研究院有限公司
山东南山铝业股份有限公司

Dates

Publication Date: 20260508
Application Date: 20260331

Claims (7)

1. The method for constructing the functional interface on the metal surface by using the ultrasonic-assisted liquid gallium is characterized by comprising the following steps of: (1) The pretreatment of the metal substrate, namely, carrying out surface pretreatment on the metal substrate to remove an oxide layer and clean the surface, wherein the metal substrate is one or more of Cu, ag and Ni; (2) Immersing the pretreated metal substrate in liquid gallium, placing in an ultrasonic treatment device, and applying 50-150W/L ultrasonic treatment 5-30 min under the condition that the reaction temperature is controlled to be less than or equal to 50 ℃ to enable the interface between the liquid gallium and the metal substrate to be subjected to rapid alloying reaction; (3) And (3) after the reaction is finished, taking out a sample, removing unreacted liquid gallium remained on the surface through centrifugation and/or selective acid washing, and washing with deionized water to obtain the modified metal substrate with the surface covered with the intermetallic compound functional layer.
2. The method according to claim 1, wherein the step (1) comprises the steps of subjecting the target metal substrate to a surface polishing treatment, immersing the target metal substrate in an acid solution to remove a surface oxide layer, ultrasonically cleaning the target metal substrate with deionized water and absolute ethyl alcohol, and drying the target metal substrate.
3. The method according to claim 1, wherein the reaction temperature in step (2) is 40±2 ℃.
4. The method of claim 1, wherein the ultrasonic treatment time of step (2) is 5 to 12 minutes.
5. The method of claim 1, wherein the liquid gallium in step (2) further comprises 5-15v/v% acetone, and the ultrasonic treatment time is 5-7min.
6. A surface functionalized metal material prepared by the method of any one of claims 1 to 5, wherein when the metal substrate is Cu, the functional layer has a composite morphology of irregular hexahedron and lamellar, the main phase being CuGa 2 , when the metal substrate is Ag, the functional layer has a regular needle-like crystal morphology, the main phase being Ag 2 Ga, and when the metal substrate is Ni, the functional layer has a micro-nano porous sponge morphology, the main phase being NiGa 4 .
7. Use of the surface-functionalized metal material according to claim 6, for the preparation of a thermal interface material, a surface-enhanced raman scattering substrate, a catalytic support or a functional coating.

Description

Method for constructing functional interface on metal surface by ultrasonic-assisted liquid gallium at low temperature Technical Field The invention belongs to the field of metal material surface modification and functional material preparation, and in particular relates to a method for quickly and controllably constructing a functional intermetallic compound interface on the surfaces of metals such as copper (Cu), silver (Ag), nickel (Ni) and the like at a low temperature (less than or equal to 50 ℃) by using low-power ultrasonic auxiliary liquid gallium (Ga) as an active solvent. Background Liquid metals, particularly gallium (Ga) and its alloys, have emerged as an emerging platform for material synthesis and surface modification due to their excellent flowability at room temperature, high thermal conductivity (20-30W m -1 K-1) and the ability to form intermetallic compounds with a variety of metals. By utilizing the interface reaction between the liquid Ga and the solid metal, a functional alloy layer or an intermetallic compound layer can be directly generated on the metal substrate at a lower temperature, which has important significance for developing high-performance thermal interface materials, functional coatings and the like. However, the reaction between conventional solid metal and liquid Ga relies mainly on a static thermal diffusion process, which is limited by the obstruction of the oxide layer on the surface of the solid metal and the extremely high energy barrier for solid atom diffusion. To achieve significant reaction and alloy layer growth, the prior art generally requires relatively high temperatures (> 100 ℃) or extremely long processing times (hours to days), which are not only energy consuming, inefficient, but can also cause thermal damage to heat sensitive substrates or precision electronic components, limiting the wide application of the technology. For example, nickel (Ni), while forming a stable compound with Ga thermodynamically (e.g., niGa 4), has little ability to react with liquid Ga at or near room temperature due to its extremely high melting point (1455 ℃) and low solid state diffusivity. In addition, the reaction products are often difficult to control, and controllable preparation of specific morphology and structure cannot be realized, so that specific requirements of different application scenes (such as high heat conduction, high specific surface area catalysis, SERS enhancement and the like) are met. To overcome these kinetic limitations, researchers have attempted to introduce external field interventions such as mechanical stirring, electric or magnetic fields. However, mechanical stirring is difficult to effectively activate a solid-liquid interface on a microscopic scale, and an electric field or a magnetic field has specific requirements on equipment and a material system, so that the universality is limited. Ultrasonic waves are used as a high-efficiency energy transmission and substance transportation means and are widely applied to the fields of welding, cleaning, nano material synthesis and the like. The cavitation effect (micro jet flow and shock wave) generated by the method can effectively peel off the passivation layer on the solid surface, and generates intense micro stirring and local high temperature and high pressure near the solid-liquid interface, which is expected to greatly promote interface atom exchange and break the limit of thermal diffusion. However, how to apply the low-power ultrasonic wave to the liquid metal/solid metal interface reaction system precisely and efficiently, realize the rapid and controllable surface functionalization of various metals at low temperature, and clarify the cooperative regulation and control rule of the ultrasonic external field and the intrinsic physical properties (melting point, formation enthalpy and solubility) of the metals on the morphology of the final interface structure is still one of the technical problems to be solved urgently by those skilled in the art. Disclosure of Invention In view of the above, in order to solve the technical bottlenecks of high reaction temperature, low speed and poor controllability of the liquid Ga and solid metal interface in the prior art, the invention provides a method for constructing a functional interface on the metal surface at a low temperature based on low-power ultrasonic assistance. The method overcomes the dynamic barrier of solid atom diffusion by the instantaneous high energy provided by the ultrasonic cavitation effect, rapidly activates and drives various metals (such as Cu, ag and Ni) and liquid Ga to generate interface reaction at a low temperature (such as 40 ℃) within a few minutes, and forms an intermetallic compound functional layer with specific microcosmic appearance (such as an irregular hexahedral-lamellar composite structure, a needle-shaped crystal and a porous sponge structure). The method has the advantages of universality, high efficiency,