CN-117778798-B - Graphene and diamond reinforced copper-based layered composite material and preparation method thereof

CN117778798BCN 117778798 BCN117778798 BCN 117778798BCN-117778798-B

Abstract

The invention discloses a graphene and diamond reinforced copper-based layered composite material and a preparation method thereof, wherein the composite material comprises 0.5-2.5 wt.% of surface modified nickel-plated graphene, 3-6 wt.% of core-shell structure nickel-plated diamond and the balance of copper sheets, wherein the total amount of the surface modified graphene is 100 wt wt.%, the surface modified graphene is prepared by adopting a rutin solution, the surface modified nickel-plated graphene and the surface nickel-plated diamond are prepared by adopting an electroless plating method, the core-shell structure nickel-plated diamond is realized by ball milling, the obtained composite material is more compact by forming compact cross interlocking bonding between a metal matrix and a reinforcing phase, the reinforcing phase of the core-shell structure enhances the comprehensive performance of the composite material by providing excellent performance of the composite material and prolonging a crack path, and the comprehensive performance of the layered composite material is finally improved.

Inventors

JIANG XIAOSONG
HE JUN
LIU CUILING
MO DEFENG
SUN HONGLIANG
JIANG JIAXIN
SHAO ZHENYI

Assignees

西南交通大学

Dates

Publication Date: 20260512
Application Date: 20231230

Claims (10)

1. The graphene and diamond reinforced copper-based layered composite material is characterized by comprising 0.5-2.5 wt.% of surface modified nickel-plated graphene, 3-6 wt.% of core-shell nickel-plated diamond and the balance of copper sheets, wherein the total amount of the nickel-plated graphene and the copper sheets is 100 wt wt.%; the method comprises the steps of adopting rutin solution to modify graphene to obtain surface modified graphene, and plating nickel on the surface of the surface modified graphene through chemical plating to obtain surface modified nickel-plated graphene; Plating nickel on the surface of the diamond through chemical plating to obtain the diamond with the nickel plated surface, mixing the diamond with the nickel plated surface with copper powder, and ball milling to obtain the nickel plated diamond with the core-shell structure; Ball milling is carried out on the copper powder to obtain a copper sheet; Mixing the nickel-plated graphene subjected to surface modification, nickel-plated diamond with a core-shell structure and a copper sheet, ball milling, freeze drying to obtain composite powder, performing vacuum hot-pressing sintering, cooling, performing hot isostatic pressing treatment, and performing pressure relief cooling to obtain a copper-based layered composite material; the nickel-plated diamond with the core-shell structure is positioned between two layers of copper sheets to form a layered unit, and the nickel-plated graphene subjected to surface modification is positioned between the two layered units to integrally form a layered structure.
2. The graphene and diamond reinforced copper-based layered composite material according to claim 1, wherein graphene is placed into a rutin solution, and subjected to ultrasonic stirring, standing, suction filtration and vacuum drying to obtain surface modified graphene; coarsening the surface-modified graphene in hydrochloric acid-alcohol solution, sensitizing and activating the surface-modified graphene in stannous chloride sensitizer and palladium chloride solution, plating nickel on the surface through chemical plating, ultrasonic dispersion, standing, suction filtration and vacuum drying to obtain the surface-modified nickel-plated graphene; And (3) coarsening the diamond in a hydrochloric acid-alcohol solution, sensitizing and activating the diamond in a stannous chloride sensitizer and a palladium chloride solution, plating nickel on the surface through chemical plating, performing ultrasonic dispersion, standing, performing suction filtration, and performing vacuum drying to obtain the diamond with the nickel plated surface.
3. The graphene and diamond enhanced copper-based layered composite material according to claim 2, wherein the concentration of the rutin solution is 0.02 ug/mL, and the volume ratio of the mass of graphene to the rutin solution is 0.05~0.4g:20~80 mL.
4. The graphene and diamond reinforced copper-based layered composite material according to claim 2, wherein the ultrasonic dispersion time is 20-40 min, the standing time is 12-36 h, the vacuum drying temperature is 60-80 ℃, and the vacuum drying time is 1-6 h.
5. The graphene and diamond reinforced copper-based layered composite material according to claim 2, wherein the stannous chloride sensitizer comprises 25-35 g/L, HCl of SnCl 2 -50-70 ml/L, and the palladium chloride activator comprises 0.1-0.3 g/L, HCl of PdCl 2 and 5-15 ml/L.
6. The graphene and diamond reinforced copper-based layered composite material according to claim 2, wherein the roughening time is 5-15 min, the ultrasonic dispersion time is 20-40 min, the standing time is 12-36 h, the drying temperature is 60-80 ℃, and the drying time is 1-6 h.
7. The graphene and diamond reinforced copper-based layered composite material according to claim 1, wherein when the diamond and copper powder with nickel plated surfaces are subjected to ball milling, a stainless steel ball and a stainless steel ball tank are adopted, a ball milling medium is tertiary butanol, the ball milling rotating speed is 100-150 rpm, and the ball milling time is 18-22 h.
8. The graphene and diamond reinforced copper-based layered composite material according to claim 1, wherein when copper powder is ball-milled, a stainless steel ball and a stainless steel ball tank are adopted, a ball milling medium is tert-butyl alcohol, the ball milling speed is 200-450 rpm, and the ball milling time is 4-8 hours.
9. The graphene and diamond reinforced copper-based layered composite material according to claim 1, wherein when the surface-modified nickel-plated graphene, the nickel-plated diamond with the core-shell structure and the copper sheet are mixed and ball-milled, a stainless steel ball and a stainless steel ball tank are adopted, the ball-milling medium is tertiary butanol, the ball-milling rotating speed is 100-150 rpm, and the ball-milling time is 1-2 h.
10. The graphene and diamond reinforced copper-based layered composite material according to claim 1, wherein the temperature of vacuum hot-press sintering is 800-1000 ℃, the pressure of vacuum hot-press sintering is 20-40 mpa, the heat preservation time of vacuum hot-press sintering is 1-3 h, the temperature of hot isostatic pressing is 800-1000 ℃, the pressure of hot isostatic pressing is 80-120 mpa, and the heat preservation and pressure maintaining time of hot isostatic pressing is 1-3 h.

Description

Graphene and diamond reinforced copper-based layered composite material and preparation method thereof Technical Field The invention relates to the technical field of composite materials, in particular to a graphene and diamond reinforced copper-based layered composite material and a preparation method thereof. Background Graphene is a novel nano carbon material, has an ultra-large specific surface area and stability, and is considered as an ideal catalytic material carrier. Graphene/copper composites have high thermal conductivity in the X-Y plane direction, but have limited thermal performance in the perpendicular plane direction. While diamond/copper composites have proven to be the best materials for efficient heat dissipation in integrated and miniaturized devices due to highly isotropic thermal conductivity. Thus, a composite of parallel oriented graphene, highly thermally conductive diamond particles, and a suitable proportion of copper can maintain all of the excellent thermophysical and mechanical properties of these three materials. The graphene and diamond reinforced metal matrix composite is superior to pure metal materials in performance, but has at least the problems of (1) large free energy of the surface of the graphene itself, (2) large difference in structure and performance between the graphene and diamond and the metal matrix, (3) non-uniform dispersion of the graphene and weak mechanical bonding of the graphene and the metal matrix, and (4) non-uniform dispersion of the diamond in the metal matrix and weak mechanical bonding of the diamond and the metal matrix. Disclosure of Invention It is therefore an objective of the claimed invention to provide a graphene and diamond reinforced copper-based layered composite material to solve the above-mentioned problems. In order to achieve the aim, the technical scheme adopted by the invention is that the graphene and diamond reinforced copper-based layered composite material comprises 0.5-2.5 wt.% of surface modified nickel-plated graphene, 3-6 wt.% of core-shell nickel-plated diamond and the balance of copper sheets, wherein the total weight of the composite material is 100wt.%; the surface modified graphene is graphene modified by rutin solution, the surface modified nickel-plated graphene and the surface nickel-plated diamond are prepared by adopting a chemical plating method, and the nickel-plated diamond with the core-shell structure is realized by ball milling; the nickel-plated diamond with the core-shell structure is positioned between two layers of copper sheets to form a layered unit, and the nickel-plated graphene subjected to surface modification is positioned between the two layered units to integrally form a layered structure. Preferably, the nickel-plated diamond reinforced copper-based layered composite material with the surface-modified nickel-plated graphene and the core-shell structure comprises, by weight, 0.5-1.5% of the surface-modified nickel-plated graphene, 3% of the nickel-plated diamond with the core-shell structure and the balance of copper sheets. Preferably, the nickel-plated diamond reinforced copper-based layered composite material with the surface-modified nickel-plated graphene and the core-shell structure comprises the following components in percentage by weight of 1.5wt.% of the surface-modified nickel-plated graphene, 3wt.% of the surface-plated nickel-plated diamond and the balance of copper sheets. In order to solve the above problems, the problems of dispersion and interfacial connection of graphene and diamond in a metal matrix are improved. A layer of metal film can be plated on the surface of the reinforcing phase, so that when the reinforcing phase and a matrix interface interact, the plating layer transfers a stress concentration area to the area, and further expansion of cracks is prevented, thereby improving the interfacial adhesion of the composite material. Ni has been studied on the surface of copper-based composites using electroless plating, and the results indicate that the presence of Cu/Ni can make the bond between the reinforcement and the matrix tighter. This is because the crystal structure of the reinforcing phase itself is greatly different from that of the matrix, and Cu and Ni are both FCC structures, and the surface of the reinforcing phase is similar to that of the matrix after being plated with a layer of Ni, which results in improved wettability of the interface and improved interfacial bonding. The addition of graphene and diamond reinforcement to the matrix can significantly improve the strength of the composite, but the toughness improvement effect is less pronounced, and may even be reduced. The core-shell structure can well solve the problem, the strength and the ductility are enhanced at the same time, and the comprehensive toughening efficiency is superior to that of the prior heterostructure. The graphene and the diamond have excellent strengthening effect, the graphene an