Effect of nanoparticles on the performance of thermally conductive epoxy adhesives

Microsized or nanosized α‐alumina (Al₂O₃) and boron nitride (BN) were effectively treated by silanes or diisocyanate, and then filled into the epoxy to prepare thermally conductive adhesives. The effects of surface modification and particle size on the performance of thermally conductive epoxy adhesives were investigated. It was revealed that epoxy adhesives filled with nanosized particles performed higher thermal conductivity, electrical insulation, and mechanical strength than those filled with microsized ones. It was also indicated that surface modification of the particles was beneficial for improving thermal conductivity of the epoxy composites, which was due to the decrease of thermal contact resistance of the filler‐matrix through the improvement of the interface between filler and matrix by surface treatment. A synergic effect was found when epoxy adhesives were filled with combination of Al₂O₃ nanoparticles and microsized BN platelets, that is, the thermal conductivity was higher than that of any sole particles filled epoxy composites at a constant loading content. The heat conductive mechanism was proposed that conductive networks easily formed among nano‐Al₂O₃ particles and micro‐BN platelets and the thermal resistance decreased due to the contact between the nano‐Al₂O₃ and BN, which resulted in improving the thermal conductivity. POLYM. ENG. SCI., 50:1809–1819, 2010. © 2010 Society of Plastics Engineers     

The influence of nano alumina additions on the coefficient of thermal expansion of a LZS glass–ceramic composition

In this work a 19.58Li₂O·11.10ZrO₂·69.32SiO₂ (mol%) glass–ceramic matrix was prepared and milled in order to determine its coefficient of thermal expansion (CTE) and to study how it is influenced by the addition of nanosized Al₂O₃ particles (1–5 vol%) and submicrometric Al₂O₃ particles (5 vol%). Comminution studies from the LZS parent glass frit showed that a powder with an adequate particle size (3.5 µm) is achieved after 120 min of dry milling followed by a second step of 60 h wet milling. The obtained LZS glass–ceramic samples (fired at 900 °C/30 min) showed an average relative density of ∼98% with zirconium silicate and lithium disilicate as main crystalline phases. Prepared composites with 1, 2.5 and 5 vol% of nanosized Al₂O₃ and 5 vol% submicrometric Al₂O₃ showed average relative densities varying from 97% to 94% as the alumina content increased. The formation of β-spodumene in the obtained composites leads to reduce the CTEs, whose values ranged from 9.5 to 4.4×10⁻⁶ °C⁻¹. Composites with 5% nanosized alumina showed a CTE lower than that of the equivalent formulation with submicrometric alumina.     

Effective thermal conductivity and thermal properties of phthalonitrile‐terminated poly(arylene ether nitriles) composites with hybrid functionalized alumina

A polymer‐based thermal conductive composite has been developed. It is based on a dispersion of micro‐ and nanosized alumina (Al₂O₃) in the phthalonitrile‐terminated poly (arylene ether nitriles) (PEN‐t‐ph) via solution casting method. The Al₂O₃ with different particle sizes were functionalized with phthalocyanine (Pc) which was used as coupling agent to improve the compatibility of Al₂O₃ and PEN‐t‐ph matrix. The content of microsized functionalized Al₂O₃ (m‐f‐Al₂O₃) maintained at 30 wt % to form the main thermally conductive path in the composites, and the nanosized functionalized Al₂O₃ (n‐f‐Al₂O₃) act as connection role to provide additional channels for the heat flow. The thermal conductivity of the f‐Al₂O₃/PEN‐t‐ph composites were investigated as a function of n‐f‐Al₂O₃ loading. Also, a remarkable improvement of the thermal conductivity from 0.206 to 0.467 W/mK was achieved at 30 wt % n‐f‐Al₂O₃ loading, which is nearly 2.7‐fold higher than that of pure PEN‐t‐ph polymer. Furthermore, the mechanical testing reveals that the tensile strength increased from 99 MPa for pure PEN‐t‐ph to 105 MPa for composites with 30 wt % m‐f‐Al₂O₃ filler loading. In addition, the PEN‐t‐ph composites possess excellent thermal properties with glass transition temperature (T_g) above 184°C, and initial degradation temperature (T_id) over 490°C. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41595.     

Development and evaluation of Al2O3–ZrO2 composite processed by digital light 3D printing

Digital Light Processing (DLP) is a promising approach to fabricate delicate ceramic components with high-fidelity structural features. In this work, the alumina and zirconia/alumina ceramic suspensions with low viscosity and high solid loading (40 vol%) were prepared specifically for DLP 3D printing. After debinding and sintering, the final parts were obtained without any defects. The surface morphologies and mechanical properties of alumina (Al₂O₃) and zirconia toughened alumina (ZTA) composites were investigated and the results showed that the final parts exhibited high relative densities and good interlayer combination at the sintering temperature of 1600 °C. Comparing with the Al₂O₃, the ZTA composites exhibited significantly enhanced density (99.4%), bending strength (516.7 MPa) and indentation fracture toughness (7.76 MPa m^1/2).     

Mechanical performance and microstructure of 3Y-TZP/Al2O3/GNPs medical ceramic surgical scalpel material prepared through SPS–HF dual sintering method

In this study, 3 mol% yttria-stabilized tetragonal zirconia polycrystal (3Y-TZP)/Al₂O₃/graphene nanoplatelets (GNPs) medical ceramic materials for manufacturing surgical scalpels were sintered in vacuum in an SPS–625HF furnace. The mechanical performances and microstructures of the composites were investigated, and the influence mechanisms of the sintering temperature and amount of added GNPs were studied. During the sintering process at 1400°C and 30 MPa for 5 min, the added GNPs enhanced the mechanical properties of the 3Y-TZP/Al₂O₃ composites. The results showed that the composite with .1 wt.% GNPs had 6.4% (910 ± 11 MPa) higher flexural strength than 3Y-TZP/Al₂O₃. The composite with .4 wt.% GNPs had 38.7% (12.95 ± .22 MPa m^1/2) greater fracture toughness than 3Y-TZP/Al₂O₃. The main toughening mechanisms of 3Y-TZP/Al₂O₃/GNPs were crack bridging, crack deflection, crack branching, GNPs bridging, transgranular fracture structures, and phase transformation of t-ZrO_1.95. The two-stage densification displacement curve appeared at the optimal sintering temperature of the materials, and the 3Y-TZP/Al₂O₃/GNPs composites with a two-stage densification displacement curve had excellent mechanical properties. The added GNPs can inhibit the grain growth during the sintering process, thereby refining the zirconia grains. With the increase in GNPs content, the grain size and flexural strength of the composites decreased gradually. However, higher content of GNPs was beneficial to improve the relative density and thermal diffusivity of 3Y-TZP/Al₂O₃/GNPs composite material.     

Mechanical and thermal properties of spark plasma sintered Al2O3-graphene-SiC hybrid composites

Monolithic Al₂O₃ and Al₂O₃-graphene-SiC hybrid composites were prepared by spark plasma sintering (SPS) under vacuum atmosphere. The results show that the hybrid composites were almost completely dense (>97%). SiC content has a significant effect on the microstructure of the composites. With the increase of SiC content, the average grain size of alumina decreased gradually. The addition of SiC to alumina changed fracture mode from inter-granular fracture to mixed fracture mode of inter-granular fracture and trans-granular fracture. The Al₂O₃-0.4 wt%graphene-5 wt% SiC hybrid composite has the highest bending strength and hardness, which were 57% and 19.22% higher than those of the monolithic alumina, respectively. The room temperature (RT) thermal conductivity of the monolithic Al₂O₃ (25.5 W/m·K) was the highest. The thermal conductivity and thermal diffusivity coefficient of the composites decreased with the increase in temperature, while the specific heat of monolithic alumina and composites increased with the increase in temperature and additives. These properties were related to the microstructure of materials and the possible transport mechanisms were discussed.     

Preparation and characterization of alumina/calcium-hexaluminate ceramic composites from ferrotitanium slag

Low-cost alumina/calcium-hexaluminate (Al₂O₃-CaAl₁₂O₁₉) ceramic composites were prepared using ferrotitanium slag in this paper. By making use of the TiO₂ and MgO originally existing in ferrotitanium slag, the sintering densification of Al₂O₃-CaAl₁₂O₁₉ composites was promoted. The results show that the optimum sintering temperature of the composites is 1500 ℃. The dominant sintering mechanism is the solid solution mechanism, i.e., Ti⁴⁺ and Mg²⁺ are dissolved in the CA₆ and Al₂O₃ lattices and generate numerous defects, which ultimately enhance the lattice diffusion coefficient and matter transport. Sintering densification improves the specific heat capacity, thermal conductivity, and thermal shock resistance of Al₂O₃-CaAl₁₂O₁₉ composites. Thermophysical properties analysis indicates that the composites can be potentially used for thermal storage and the slag-utilized ratio is about 60 wt.%. However, the layered cleavage of CA₆ limits further improvement of thermal shock resistance.     

High-temperature oxidation behaviour of vacuum hot-pressed WC-15 wt% Al2O3 composites

In this study, WC-15 wt% Al₂O₃ composites were prepared using the vacuum hot-pressing sintering method. The high-temperature (600–800 °C) oxidation behaviour of WC-15 wt% Al₂O₃ composites was investigated and compared with that of WC-6wt.%Co cemented carbides. The results showed that the oxidation resistance of WC-15 wt% Al₂O₃ composites was better than that of WC-6wt.%Co cemented carbides at relatively high temperatures (700–800 °C). At 800 °C, an oxide layer was formed on the surface of WC-15 wt% Al₂O₃ composites, which included WO₃ and Al₂O₃. The dispersion of alumina in the composites hindered the further diffusion of oxygen, thus improving the oxidation resistance. The Arrhenius activation energies of WC-15 wt% Al₂O₃ composites and WC-6wt.%Co cemented carbides were 110 ± 1 kJ/mol and 167 ± 2 kJ/mol at 600–800 °C, respectively.     

Near net-shape fabrication of alumina glass composites

The purpose of the present study is to fabricate alumina glass composites by melt infiltration with better dimensional control through reducing both the presintering and infiltration temperature. Main efforts were put to develop glasses that are chemically compatible with alumina. After extensive investigations, a glass of 21SiO₂–24B₂O₃–35Al₂O₃–15Li₂O–5CaO wt.% was successfully developed. The glass shows good chemical compatibility with alumina at elevated temperatures and low viscosity above 900 °C. Dense alumina glass composites can be fabricated by the melt infiltration process at 950 °C, which is 150 °C lower than the current state-of-art. Investigations showed improved net-shape capability for the newly developed composites, where the total linear shrinkage for the sintering and infiltration at 950 °C is less than 0.1%, as compared with the shrinkage of 0.5% induced by the presintering and infiltration at 1100 °C. Preliminary mechanical tests showed that the fracture strength and toughness of the composites are 303 MPa and 3.4 MPa m^1/2, respectively. The lower processing temperature and the better dimensional control are the major advantages for the newly developed alumina glass composites.     

Thermal stability and oxidation resistance of C/Al2O3 composites fabricated from a sol with high solid content

To improve fracture toughness of monolithic Al₂O₃ ceramics, three-dimensional carbon fiber preform was used as reinforcement, and the C/Al₂O₃ composites without interfacial coating were fabricated through vacuum impregnation-drying-heat treatment route with an Al₂O₃ sol as starting material. Characteristics of the Al₂O₃ sol with high solid content were firstly analyzed. Then thermal stability and oxidation resistance of the C/Al₂O₃ composites were investigated. It is found that the Al₂O₃ sol is an appropriate raw material for the fabrication of C/Al₂O₃ composites. The C/Al₂O₃ composites with a total porosity of 15.5% show a flexural strength of 208.5 MPa and a fracture toughness of 8.1 MPa m^1/2. Strength loss is observed after the composites were annealed at 1400 °C and 1600 °C under inert atmosphere. Oxidation resistance of the C/Al₂O₃ composites is unsatisfactory because of the existence of open pores and microcracks. When Al₂O₃ matrix was modified with SiO₂, the oxidation resistance is remarkably improved due to the viscous flow effect of SiO₂.     

Effect of glass additives on the strength and toughness of polycrystalline alumina

The effect of stress at grain boundaries on the mechanical properties of alumina ceramics was investigated. Residual stresses at grain-boundaries resulted from a mismatch in thermal expansion coefficient (TEC) between the alumina matrix and the glass-phase segregated at grain-boundaries. The BaO–Al₂O₃–SiO₂ (BAS) system and the Li₂O–Al₂O₃–SiO₂ (LAS) system glasses were chosen to have a higher and a lower TEC than that of alumina, respectively, resulting in microscopic tensile and compressive stresses at grain-boundaries for Al₂O₃/BAS and Al₂O₃/LAS composites, respectively. The experimental results showed that the Al₂O₃/BAS composite fractured intergranularly with a fracture toughness higher than that of monolithic alumina. On the other hand, the Al₂O₃/LAS composite experienced transgranular fracture and high bending strength despite its low toughness. Both composites could be sintered to full density at 1500°C for 2 h due to the presence of a liquid phase. It was concluded that strengthening and toughening of alumina ceramics could be tailored by designing their grain-boundary microstresses.     

The influence of different SiC amounts on the microstructure,densification, and mechanical properties of hot-pressed Al2O3-SiC composites

The hot pressing process of monolithic Al₂O₃ and Al₂O₃-SiC composites with 0-25 wt% of submicrometer silicon carbide was done in this paper. The presence of SiC particles prohibited the grain growth of the Al₂O₃ matrix during sintering at the temperatures of 1450°C and 1550°C for 1 h and under the pressure of 30 MPa in vacuum. The effect of SiC reinforcement on the mechanical properties of composite specimens like fracture toughness, flexural strength, and hardness was discussed. The results showed that the maximum values of fracture toughness (5.9 ± 0.5 MPa.m^1/2) and hardness (20.8 ± 0.4 GPa) were obtained for the Al₂O₃-5 wt% SiC composite specimens. The significant improvement in fracture toughness of composite specimens in comparison with the monolithic alumina (3.1 ± 0.4 MPa.m^1/2) could be attributed to crack deflection as one of the toughening mechanisms with regard to the presence of SiC particles. In addition, the flexural strength was improved by increasing SiC value up to 25 wt% and reached 395 ± 1.4 MPa. The scanning electron microscopy (SEM) observations verified that the increasing of flexural strength was related to the fine-grained microstructure.     

Synergistic thermal conductivity enhancement of PC/ABS composites containing alumina/magnesia/graphene nanoplatelets

Graphene nanoplatelets (GNPs) have attracted considerable attention in the field of thermal management materials due to their unique structure and exceptional thermal conductive properties. In this work, we demonstrate a significant synergistic effect of GNPs, alumina (Al₂O₃), and magnesia (MgO) in improving the thermal conductivity of polycarbonate/acrylonitrile‐butadiene‐styrene polymer alloy (PC/ABS) composites. The thermal conductivity of the composites prepared through partial replacement of Al₂O₃ and MgO with GNPs could increase dramatically compared with that without GNPs. The maximum thermal conductivity of the composite is 3.11 W mK⁻¹ at total mass fraction of 70% with 0.5 wt% GNPs loading. It increases 60% compared with that without GNPs (1.95 W mK⁻¹). The synergistic effect results from the compact packing structure formed by Al₂O₃/MgO and the bridging of GNPs with Al₂O₃/MgO, thus promoting the formation of effective thermal conduction pathways within PC/ABS matrix. More importantly, together with the intrinsically high thermal conductivity of GNPs, boosted and effective pathways for phonon transport can be created, thus decrease the thermal resistance at the interface between fillers and PC/ABS matrix and increase the thermal conductivity of composites. POLYM. COMPOS., 38:2221–2227, 2017. © 2015 Society of Plastics Engineers     

High-temperature mechanical property and thermal shock resistance of Al2O3f/Al2O3 composites

Continuous alumina fiber–reinforced alumina matrix composites (Al₂O_3f/Al₂O₃ composites) were produced via sol–gel process, then the high-temperature mechanical property and thermal shock resistance of Al₂O_3f/Al₂O₃ composites were investigated. The results showed that the composites exhibited excellent high-temperature properties. The mechanical property of the composites was affected by heat treatment (prepared at 1100°C exhibited the most desirable mechanical property). The tensile strength of the composites abruptly decreased at higher temperatures. Although the mechanical property of the composites deteriorated after the thermal shock test was conducted at high temperatures, they exhibited excellent thermal shock resistance. After 50 thermal shock tests conducted at 1300 and 1500°C, the flexural strength of the composites was found to be 124.34 and 93.04 MPa, thus showing a decrease in strength with the increasing temperature.     

Fabrication of Al2O3/AlN composite ceramics with enhanced performance via a heterogeneous precipitation coating process

To improve the thermal and mechanical properties of Al₂O₃/AlN composite ceramics, a novel heterogeneous precipitation coating (HPC) approach was introduced into the fabrication of Al₂O₃/AlN ceramics. For this approach, Al₂O₃ and AlN powders were coated with a layer of amorphous Y₂O₃, with the coated Al₂O₃ and AlN powders found to favor the formation of an interconnected YAG second phase along the grain boundaries. The interconnected YAG phase was designed to act as a diffusion barrier layer to minimize the detrimental interdiffusion between Al₂O₃ and AlN particles. Compared with samples prepared by a conventional ball-milling method, the HPC Al₂O₃/AlN composites exhibited less AlON formation, a higher relative density, a smaller grain size and a more homogeneous microstructure. The thermal conductivity, bending strength, fracture toughness and Weibull modulus of the HPC Al₂O₃/AlN composite ceramics were found to reach 34.21 ± 0.34 W m⁻¹ K⁻¹, 475.61 ± 21.56 MPa, 5.53 ± 0.29 MPa m^1/2 and 25.61, respectively, which are much higher than those for the Al₂O₃ and Al₂O₃/AlN samples prepared by the conventional ball-milling method. These results suggest that HPC is a more effective technique for preparing Al₂O₃/AlN composites with enhanced thermal and mechanical properties, and is probably applicable to other composite material systems as well.     

Alumina Toughened Zirconia Nanocomposite Incorporating Al2O3 Whiskers

We investigated the Vickers hardness and fracture toughness of an Al₂O_3(n) + 70 wt% ZrO₂ (TZ‐3Y)_n nanocomposite with addition of 2.5 wt% Al₂O₃ whiskers. Densities greater than 95% were reached after conventional sintering at 1500°C. The fracture toughness was increased 62% over pure Al₂O₃. Microcracking and crack deflection can be the mechanisms responsible to improve the fracture toughness. The use of ATZ composites with a low percent of whiskers can be a promising biomedical material for medical and dental applications given its large increase in fracture toughness over pure alumina and the observed relief from aging issues of zirconia.     

Effect of CeO2 addition on densification and microstructure of Al2O3-YSZ composites

Alumina (Al₂O₃) and alumina-yttria stabilized zirconia (YSZ) composites containing 3 and 5 mass% ceria (CeO₂) were prepared by spark plasma sintering (SPS) at temperatures of 1350-1400 °C for 300 s under a pressure of 40 MPa. Densification, microstructure and mechanical properties of the Al₂O₃ based composites were investigated. Fully dense composites with a relative density of approximately 99% were obtained. The grain growth of alumina was inhibited significantly by the addition of 10 vol% zirconia, and formation of elongated CeAl₁₁O₁₈ grains was observed in the ceria containing composites sintered at 1400 °C. Al₂O₃-YSZ composites without CeO₂ had higher hardness than monolithic Al₂O₃ sintered body and the hardness of Al₂O₃-YSZ composites decreased from 20.3 GPa to 18.5 GPa when the content of ZrO₂ increased from 10 to 30 vol%. The fracture toughness of Al₂O₃ increased from 2.8 MPa m^1/2 to 5.6 MPa m^1/2 with the addition of 10 vol% YSZ, and further addition resulted in higher fracture toughness values. The highest value of fracture toughness, 6.2 MPa m^1/2, was achieved with the addition of 30 vol% YSZ.     

Microstructure,fracture behaviour and mechanical properties of conductive alumina based composites manufactured by SPS from graphenated Al2O3 powders

Conductive Al₂O₃/graphene composites were manufactured by SPS from Al₂O₃ powders coated with a few graphene layers. Composite powders with a total carbon content of 0.1, 0.6 and 1.0 wt. % were manufactured by chemical vapour deposition. The effect of the graphene content on the microstructure, mechanical and electrical properties of the compacts were studied. Graphene, homogenously located along the grain boundaries, dramatically hindered the Al₂O₃ grain growth. The continuous interconnected graphene network enhanced electrical properties, achieving percolation threshold as low as 0.6 wt. % of graphene. The content of 1 wt. % of graphene increased electroconductivity by 13 orders of magnitude as compared to the monolithic alumina. The indentation fracture toughness increased by 20 % in specimens with 0.6 wt. % graphene content as compared to pure alumina. The presence of 1.0 wt. % of graphene resulted in a slight decrease of elastic modulus and hardness, but strength decreased by 40 %.     

Thermal Expansion Reduction in Alumina‐Toughened Zirconia by Incorporation of Zirconium Tungstate and Aluminum Tungstate

A series of composites containing yttria‐stabilized zirconia, Al₂O₃, and the thermomiotic (negative thermal expansion) materials ZrW₂O₈ and Al₂W₃O₁₂ were prepared by an in situ solid‐state reaction during sintering. Microstructural analysis of the composites indicated several sub‐micron sized components. ²⁷Al MAS NMR was used to characterize the aluminum‐containing phase distribution. Measurement of the coefficients of thermal expansion showed that the addition of thermomiotic components reduced the thermal expansivity of the alumina‐toughened zirconia matrix, but the reduction was considerably smaller than what would be predicted by the rule of mixtures. The Turner model was much more accurate in predicting the coefficients of thermal expansion of the composites due to the large differences in stiffness between the components.     

Effects of residual stress and intragranular particles on mechanical properties of hot-pressed Al2O3/SiC ceramic composites

Al₂O₃/SiC ceramic composites with different SiC contents have been prepared by powder metallurgy at 1600 °C for 120 min at 30 MPa pressure. The effect of second phase particles on the microstructure and mechanical properties of composites have been studied. The results show that SiC particle has a significant impact on the matrix subjected to residual stress, and on the microstructure of the composites as well. The average grain size of alumina matrix decreases as the SiC particle content increases. Simultaneously, it has been found that the mechanical properties of the material are significantly enhanced in comparison with monolithic Al₂O₃. The highest strength and toughness are obtained when the SiC content is 15 vol%, and the values are 1237 MPa and 5.68 MPa m^1/2, respectively. The mechanisms of strengthening and toughening have been discussed.