Fabrication of Graphene-reinforced Alumina Ceramic Composites via Adsorption-precipitation Self-assembly Combined with Spark Plasma Sintering

doi:10.15541/jim20250140

Abstract

Abstract:

Alumina ceramics are widely utilized as structural materials, yet their inherent brittleness and monofunctionality limit their application in high-stress scenarios. Strategic integration of two-dimensional graphene sheets, characterized by their excellent mechanical, thermal and electrical properties, into ceramic matrix can facilitate grain refinement through interface engineering, thereby achieving performance optimization. Conventional physical blending methods result in poor uniformity and integrity of 2D sheets, thereby impeding advancements in graphene-ceramic composites. Herein, a novel adsorption-precipitation self-assembly (APSA) method was proposed for the nondestructive integration of graphene oxide (GO) sheets with submicron Al₂O₃ particles. A homogeneous precursor is obtained by uniform deposition of Al³⁺ ions adsorbed on GO surface, followed by low-temperature rapid densification via spark plasma sintering (SPS). For the resultant composites, the incorporated graphene is aligned parallel to the alumina grains, facilitating grain refinement and significantly enhancing the mechanical properties through synergistic effect of various toughening mechanisms, including pull-out, crack extension and bridging. In comparison to monolithic alumina ceramics, the ceramic composites exhibit a 43% enhancement in flexural strength ((428±87) MPa) and a 34% improvement in fracture toughness ((4.40±0.13) MPa·m^1/2). Furthermore, the strength and toughness values also increase by 15% respectively, compared to specimens made from the conventional ball-milling mixing process, confirming the efficacy and advancement of such a manufacturing approach.

Key words: graphene, alumina, ceramic composite, reinforcement, self-assembly

CLC Number:

TQ174

CHENG Aopeng, WANG Yuewen, XU Wentao, LIU Quanwei, ZHANG Haitao, ZHOU Youfu. Fabrication of Graphene-reinforced Alumina Ceramic Composites via Adsorption-precipitation Self-assembly Combined with Spark Plasma Sintering[J]. Journal of Inorganic Materials, 2026, 41(4): 536-544.

Figures/Tables 14

Fig. 1 Schematic illustration of preparing process for hybrid precursors by APSA method

Fig. 2 (a) Zeta potential of GO dispersion as a function of pH with inset showing the Zeta potentials for different Al3+ ions added to the GO solution; (b) XRD patterns of the precursors before and after calcination; (c, d) SEM images of 5rGO-Al2O3 precursor (c) before and (d) after calcinations

Fig. 3 Fracture surface morphologies of the SPSed ceramics (a) Monolithic Al2O3; (b) 1rGO-Al2O3; (c) 3rGO-Al2O3; (d) 5rGO-Al2O3

Fig. 4 Mechanical properties of rGO-Al2O3 ceramic composites (a) Density; (b) Vickers hardness; (c) Flexural strength; (d) Fracture toughness

Table 1 Characteristics and properties of the graphene-Al2O3 ceramic composites[11,28 -30]

Material	Filler loading/ % (in mass)	Sintering method	Vickers hardness/ GPa	Fracture toughness/ (MPa·m^1/2)	Flexural strength/ MPa	Reference
rGO-Al₂O₃	1.0	SPS	19.71	4.4	428	This work
rGO-Al₂O₃	3.0	HP	9.9	—	313.75	[11]
GO-Al₂O₃	0.5	SPS	18.3	5.4	—	[28]
FLG-Al₂O₃	1.0	SPS	20.1	3.3	310	[29]
GNP-Al₂O₃	0.5	HP	17	5.5	390	[30]

Fig. 5 Crack propagation and toughening mechanisms in rGO-Al2O3 ceramic composites

Fig. 6 (a) Electrical conductivity of rGO-Al2O3 composites as a function of filler fraction in two directions; (b) Fitting curves of electrical conductivity with inset showing the logarithmic plots of electrical conductivities against (Vh-Vh,c)

Fig. S1 (a) SEM image of obtained GO sheets; (b) XRD patterns of GO and original graphite powders

Fig. S2 TGA curves of GO and GO-Al2O3 precursor in N2 atmosphere

Fig. S3 (a-c) Sintering curves of 5rGO-Al2O3 composite ceramics and (d) bulk density of specimen sintered at different temperatures (a) 1300 ℃; (b) 1350 ℃; (c) 1400 ℃

Fig. S4 (a) XRD patterns of 5rGO-Al2O3 ceramics at different temperatures and (b) rGO-Al2O3 ceramics with different rGO contents sintered at 1350 ℃

Fig. S5 Raman spectra of rGO-Al2O3 ceramic composites

Fig. S6 EDS mappings of rGO-Al2O3 ceramic composites

Fig. S7 Thermal conductivities of rGO-Al2O3 ceramic composites

References 38

[1]	MUDRA E, HRUBOVCAKOVA M, SHEPA I, et al. Processing and characterization of fiber-reinforced and layered alumina- graphene composites. Journal of the European Ceramic Society, 2020, 40(14): 4808. DOI URL
[2]	GEVORKYAN E, RUCKI M, PANCHENKO S, et al. Effect of SiC addition to Al₂O₃ ceramics used in cutting tools. Materials, 2020, 13(22): 5195. DOI URL
[3]	WANG H Z, GAO L, GUO J K. Silicon carbide particle size effects in Al₂O₃-SiC nanocomposites. Journal of Inorganic Materials, 1999, 14(4): 679.
[4]	OJAIMI C L, FERREIRA J A, DOS SANTOS F A, et al. Mechanical characterization and hydrothermal degradation of Al₂O₃-15 vol% ZrO₂ nanocomposites consolidated by two-step sintering. Ceramics International, 2018, 44(14): 16128. DOI URL
[5]	XU C H, HUANG C Z, LI Z Q, et al. Toughening mechanisms of Al₂O₃/TiC ceramic composite with carbon additive. Journal of Inorganic Materials, 2001, 16(2): 256.
[6]	BAGHEL R, MALI H S, BISWAS S K. Micro hole fabrication in TiN-Al₂O₃ ceramic composite by SiC powder assisted micro-EDM. Engineering Research Express, 2020, 2(1): 15028. DOI
[7]	ZHU Y, MURALI S, CAI W, et al. Graphene and graphene oxide: synthesis, properties, and applications. Advanced Materials, 2010, 22(35): 3906. DOI URL
[8]	FARJADIAN F, ABBASPOUR S, SADATLU M A A, et al. Recent developments in graphene and graphene oxide: properties, synthesis, and modifications: a review. ChemistrySelect, 2020, 5(33): 10200. DOI URL
[9]	LI W, SIM H J, LU H, et al. Effect of reduced graphene oxide on the mechanical properties of rGO/Al₂O₃ composites. Ceramics International, 2022, 48(16): 24021. DOI URL
[10]	SHIN J H, CHOI J, KIM M, et al. Comparative study on carbon nanotube- and reduced graphene oxide-reinforced alumina ceramic composites. Ceramics International, 2018, 44(7): 8350. DOI URL
[11]	ZHOU L, QIU J, WANG X, et al. Mechanical and dielectric properties of reduced graphene oxide nanosheets/alumina composite ceramics. Ceramics International, 2020, 46(12): 19731. DOI URL
[12]	MARKANDAN K, CHIN J K, TAN M T T. Recent progress in graphene based ceramic composites: a review. Journal of Materials Research, 2016, 32(1): 84. DOI URL
[13]	BARTOLUCCI S F, PARAS J, RAFIEE M A, et al. Graphene- aluminum nanocomposites. Materials Science and Engineering: A, 2011, 528(27): 7933. DOI URL
[14]	SUN C, HUANG Y, SHEN Q, et al. Embedding two-dimensional graphene array in ceramic matrix. Science Advances, 2020, 6(39): eabb1338.
[15]	CHEN Y F, BI J Q, YIN C L, et al. Microstructure and fracture toughness of graphene nanosheets/alumina composites. Ceramics International, 2014, 40(9): 13883. DOI URL
[16]	NIETO A, HUANG L, HAN Y H, et al. Sintering behavior of spark plasma sintered alumina with graphene nanoplatelet reinforcement. Ceramics International, 2015, 41(4): 5926. DOI URL
[17]	DHAR S, DASH T, SAHU A K, et al. Study on the microstructure and microhardness behavior of reduced graphene oxide reinforced alumina nanocomposites. Journal of Materials Engineering and Performance, 2024, 33(11): 5446. DOI
[18]	WU J, XU W, DONG T, et al. Self-assembly of graphene reinforced ZrO₂ composites with deformation-sensing performance. Ceramics International, 2022, 48(21): 32131. DOI URL
[19]	DONG T, XU W, JIN M, et al. A self-assemble strategy toward conductive 2D MXene reinforced ZrO₂ composites with sensing performance. Journal of the European Ceramic Society, 2022, 42(3): 1102. DOI URL
[20]	ZHAO G K, ZHU H W. Cation-π interactions in graphene- containing systems for water treatment and beyond. Advanced Materials, 2020, 32(22): 1905756. DOI URL
[21]	LIU J, YAN H X, JIANG K. Mechanical properties of graphene platelet-reinforced alumina ceramic composites. Ceramics International, 2013, 39(6): 6215. DOI URL
[22]	MAZAHERI M, MARI D, SCHALLER R, et al. Processing of yttria stabilized zirconia reinforced with multi-walled carbon nanotubes with attractive mechanical properties. Journal of the European Ceramic Society, 2011, 31(14): 2691. DOI URL
[23]	BOBYLEV S V, SHEINERMAN A G. Effect of crack bridging on the toughening of ceramic/graphene composites. Reviews on Advanced Materials Science, 2018, 57(1): 54. DOI URL
[24]	WOZNIAK J, PETRUS M, CYGAN T, et al. Silicon carbide matrix composites reinforced with two-dimensional titanium carbide - manufacturing and properties. Ceramics International, 2019, 45(6): 6624. DOI URL
[25]	LU S, LI X Q, ZHOU Y F, et al. Synthesis and mechanical properties of TiB₂/Ti₂AlN composites fabricated by hot pressing sintering. Journal of the Ceramic Society of Japan, 2018, 126(11): 900. DOI URL
[26]	AHMOYE D, BUCEVAC D, KRSTIC V D. Mechanical properties of reaction sintered SiC-TiC composite. Ceramics International, 2018, 44(12): 14401. DOI URL
[27]	WANG G, KRSTIC V D. Roles of porosity, residual stresses and grain size in the fracture of brittle solids. Philosophical Magazine A, 1998, 78(5): 1125. DOI URL
[28]	WOZNIAK J, JASTRZĘBSKA A, CYGAN T, et al. Surface modification of graphene oxide nanoplatelets and its influence on mechanical properties of alumina matrix composites. Journal of the European Ceramic Society, 2017, 37(4): 1587. DOI URL
[29]	HRUBOVCAKOVA M, MUDRA E, BURES R, et al. Microstructure, fracture behaviour and mechanical properties of conductive alumina based composites manufactured by SPS from graphenated Al₂O₃ powders. Journal of the European Ceramic Society, 2020, 40(14): 4818. DOI URL
[30]	YAZDANI B, XU F, AHMAD I, et al. Tribological performance of graphene/carbon nanotube hybrid reinforced Al₂O₃ composites. Scientific Reports, 2015, 5: 11579. DOI
[31]	WALKER L S, MAROTTO V R, RAFIEE M A, et al. Toughening in graphene ceramic composites. ACS Nano, 2011, 5(4): 3182. DOI PMID
[32]	YAHYA N A, TODD R I. Influence of C doping on the fracture mode and abrasive wear of Al₂O₃. Journal of the European Ceramic Society, 2012, 32(16): 4003. DOI URL
[33]	MCALLISTER M J, LI J L, ADAMSON D H, et al. Single sheet functionalized graphene by oxidation and thermal expansion of graphite. Chemistry of Materials, 2007, 19(18): 4396. DOI URL
[34]	FAN Y, JIANG W, KAWASAKI A. Highly conductive few-layer graphene/Al₂O₃ nanocomposites with tunable charge carrier type. Advanced Functional Materials, 2012, 22(18): 3882. DOI URL
[35]	CINAR A, BASKUT S, SEYHAN A T, et al. Tailoring the properties of spark plasma sintered SiAlON containing graphene nanoplatelets by using different exfoliation and size reduction techniques: anisotropic mechanical and thermal properties. Journal of the European Ceramic Society, 2018, 38(4): 1299. DOI URL
[36]	FAN Y C, WANG L J, LI J L, et al. Preparation and electrical properties of graphene nanosheet/Al₂O₃ composites. Carbon, 2010, 48(6): 1743. DOI URL
[37]	KILBRIDE B E, COLEMAN J N, FRAYSSE J, et al. Experimental observation of scaling laws for alternating current and direct current conductivity in polymer-carbon nanotube composite thin films. Journal of Applied Physics, 2002, 92(7): 4024. DOI URL
[38]	AHMAD K, PAN W, SHI S L. Electrical conductivity and dielectric properties of multiwalled carbon nanotube and alumina composites. Applied Physics Letters, 2006, 89(13): 133122. DOI URL