Fabrication and thermal expansion properties of ZrW2O8/Zr2WP2O12 composites

ZrW₂O₈/Zr₂WP₂O₁₂ composites were fabricated by sintering ZrW₂O₈–Zr₂WP₂O₁₂ powder mixtures at 1473 K for 1 h, and their negative thermal expansion properties were investigated. The relative density of sintered pure-phase ZrW₂O₈ was 72.3%, while that of the sintered composites was 88.4–92.3%. In the composites, the observed hysteresis in the thermal expansion data was small because of the small difference between the CTEs of ZrW₂O₈ and Zr₂WP₂O₁₂. The CTE of the composites was negative and increased with the Zr₂WP₂O₁₂ content. When the Zr₂WP₂O₁₂ volume fraction in the composites was increased from 0 to 75 vol%, the CTEs of the composites increased from ?9.1 × 10^?6 to ?3.1 × 10^?6 K^?1 and from ?5.0 × 10^?6 to ?1.9 × 10^?6 K^?1 over the temperature ranges of 323–373 and 473–673 K, respectively. In composites with Zr₂WP₂O₁₂ volume fractions of 0–25 vol%, the experimentally obtained CTE values were in good agreement with the calculated values obtained by assuming mixed law behavior.     

Improved dispersion and interfacial interaction of SiO2@polydopamine fillers in polytetrafluoroethylene composites for reduced thermal expansion and suppressed dielectric deterioration

Copper-clad laminate (CCL) comprised of copper foil and polytetrafluoroethylene (PTFE) faces severe thermal expansion mismatch due to the discrepancy in coefficient of thermal expansion (CTE) between the two components. Incorporating inorganic fillers with low CTE into PTFE has been proved to be a promising way to achieve the goal. However, it is a challenge to achieve homogeneous distribution and good interfacial interaction of fillers in PTFE composites owing to the characteristics of PTFE emulsion. In this work, core@shell structured SiO₂@polydopamine fillers (SiO₂@PDA) were synthesized and incorporated into PTFE matrix to form SiO₂@PDA/PTFE composites. Due to the presence of PDA shell, SiO₂@PDA exhibited improved dispersion and interfacial interaction, contributing to the reduced CTE and suppressed dielectric deterioration of SiO₂@PDA/PTFE composites. With 40 vol% of filler, the CTE of SiO₂@PDA/PTFE composite was efficiently reduced (50%), coupled with a limited sacrifice of only 2% and 40% of increments for dielectric constant (D_k, 2.3) and dielectric loss (D_f, 2.4 × 10⁻³), respectively (@40 GHz), as compared with that of the corresponding SiO₂/PTFE composite. The fillers and composites were comprehensively characterized to verify the mechanism of CTE and dielectric properties of the composites.     

Avoiding the intermediate phase Zr2WP2O12 to develop a larger-negative-thermal-expansion-coefficient material Zr2W2P2O15

Zr₂W₂P₂O₁₅ with larger-negative-thermal-expansion-coefficient (NTEC, −4.01×10⁻⁶ K⁻¹, 143–673 K) is developed by controlling reaction process to avoid the intermediate phase of Zr₂WP₂O₁₂, whose smaller NTEC limits its application. From 1473 K to1573 K, Zr₂WP₂O₁₂ forms easily but the reaction between Zr₂WP₂O₁₂ and WO₃ to generate Zr₂W₂P₂O₁₅ is difficult even followed by heating up to 1673 K. However, putting raw materials of ZrO₂, WO₃ and NH₄H₂PO₄ into a pipe furnace at sintering temperature 1673 K directly, the Zr₂W₂P₂O₁₅ is formed avoiding the intermediate phase of Zr₂WP₂O₁₂.     

Mechanical properties of silicon carbide—in situ zirconium carbonitride composites

SiC–Zr₂CN composites were fabricated by conventional hot pressing from β-SiC and ZrN powders with 2 vol% equimolar Y₂O₃–Sc₂O₃ as a sintering additive. The effects of the ZrN addition on the room-temperature (RT) mechanical properties and high-temperature flexural strength of the SiC–Zr₂CN composites were investigated. The fracture toughness gradually increased from 4.2 ± 0.3 MPa·m^1/2 for monolithic SiC to 6.3 ± 0.2 MPa·m^1/2 for a SiC–20 vol% ZrN composite, whereas the RT flexural strength (546 ± 32 MPa for the monolithic SiC) reached its maximum of 644 ± 87 MPa for the SiC–10 vol% ZrN composite. The monolithic SiC had improved strength at 1200°C, whereas the SiC–Zr₂CN composites could not retain their RT strengths at 1200°C. The typical flexural strength values of the SiC–0, 10, and 20 vol% ZrN composites at 1200°C were 650 ± 53, 448 ± 31, and 386 ± 19 MPa, whereas their RT strength values were 546 ± 32, 644 ± 87, and 528 ± 117 MPa, respectively.     

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.     

Effect of Al2O3 addition on thermo‐electrical properties of polymer composites: An experimental investigation

To develop a new class of composites with adequately high thermal conductivity and suitably controlled dielectric constant for electronic packages and printed circuit board applications, polymer composites are prepared with microsized Al₂O₃ particle as filler having an average particle size of 80–100 μm. Epoxy and polypropylene (PP) are chosen as matrix materials for this study. Fabrication of epoxy‐based composite is done by hand lay‐up technique and its counterpart PP‐based composite are fabricated by compression molding technique with filler content ranging from 2.5–25 vol%. Effects of filler loading on various thermal properties like effective thermal conductivity (k_eff), glass transition temperature (T_g), coefficient of thermal expansion (CTE) and electrical property like dielectric constant (ε_c) of composites are investigated experimentally. In addition, physical properties like density and void fraction of the composites along with there morphological features are also studied. The experimental findings obtained under controlled laboratory conditions are interpreted using appropriate theoretical models. Results show that with addition of 25 vol% of Al₂O₃, k_eff of epoxy and PP improve by 482% and 498% respectively, T_g of epoxy increases from 98°C to 116°C and that of PP increases from −14.9°C to 3.4°C. For maximum filler loading of 25 vol% the CTE decreases by 14.8% and 26.4% for epoxy and PP respectively whereas the dielectric constants of the composites get suitably controlled simultaneously. POLYM. COMPOS., 36:102–112, 2015. © 2014 Society of Plastics Engineers     

Dielectric constant and energy density of poly(vinylidene fluoride) nanocomposites filled with core-shell structured BaTiO3@Al2O3 nanoparticles

Ceramics-polymer nanocomposites consisting of core-shell structured BaTiO₃@Al₂O₃ (BT@Al₂O₃) nanoparticles as the filler and poly(vinylidene fluoride) (PVDF) as the polymer matrix were fabricated by solution casting. At the same volume fraction, the BT@Al₂O₃/PVDF nanocomposites, with larger dielectric constant and higher energy density, outperformed the BT/PVDF nanocomposites. The 2.5 vol% BT@Al₂O₃/PVDF nanocomposites at 360 MV/m had a double more energy density than pure PVDF at 400 MV/m (6.19 vs. 2.30 J/cm³), and a remarkably 42% lower remnant polarization than the 2.5 vol% BT/PVDF nanocomposites (0.99 vs. 1.69 μC/cm² at 300 MV/m). Such significant enhancement was closely related to the surface modification by Al₂O₃, which improved the insulation of BT nanoparticles and reduced the contrast of dielectric constant between the filler and the PVDF matrix.     

Dielectric Properties of Ultra‐Low Sintering Temperature Al2O3–BBSZ Glass Composite

Ceramic composites of B₂O₃–Bi₂O₃–SiO₂–ZnO (BBSZ) glass mixed with Al₂O₃ (10–50 vol%) were sintered at 450°C, and their microstructural and dielectric properties investigated. Dense structures were obtained when the Al₂O₃ content was lower than 30 vol%. Raman, XRD, and FESEM showed the existence of a secondary phase, Bi₂₄Si₂O₄₀, in all samples. The dielectric properties of the composite with 30 vol% addition of Al₂O₃ showed good dielectric properties with ε_r of 14.8 and 20.8 and 32.5 at 100 kHz and 100 MHz and 1 GHz, respectively. The tanδ values at the same frequencies were 0.004 and 0.006 and 0.016. The results show that BBSZ glass with different amounts of Al₂O₃ exhibit widely applicable relative permittivity values and affordable loss and are thus promising candidates for ultra‐low sintering temperature applications.     

0D surface modification and 3D silicon carbide network construction for improving the thermal conductivity of epoxy resins

With rapid advances in electronic device miniaturization and increasing power density, high thermal conductivity polymer composites with excellent properties are becoming increasingly significant for the progress of next-generation electronic apparatuses. In this work, a new type of three-dimensional (3D) network silicon carbide (SiC) frame and core-shell SiC@SiO₂ (SiC@SiO₂) were successfully prepared. The effects of different filler forms (dispersed particle filler and three-dimensional continuous filler network) on the thermal conductivity of the composites were compared. The composites based on the three-dimensional filler network exhibited evidently better thermal conductivity improvement rates, compared to their traditional counterparts. The thermal conductivity of the epoxy/SiC@SiO₂ composite having a total filler content of 17.0 vol% was 0.857 W/m/K, 328.5% higher than that of pure epoxy resin. Similarly, the thermal conductivity of the EP/3D-SiC composite having a total filler content of 13.8 vol% was 1.032 W/m/K, 416.0% higher than that of pure epoxy resin. The abovementioned stats were proven via molecular simulations. We estimated the interfacial thermal resistance (ITR) of the EP/3D-SiC composite to be 5.98 × 10^?8 m² K/W, which was an order of magnitude lower than that of the epoxy composites without a 3D network. Simultaneously, computerized molecular simulation technology was used to verify the feasibility of the experiment, which provided new ideas for the preparation of other highly thermally conductive materials.     

Polymer-derived yttrium silicate coatings on 2D C/SiC composites

Yttrium silicate environmental barrier coatings (EBCs) on C/SiC composites were fabricated by using polysiloxanes-derived ceramic process. In order to reduce the free silica in the resultant ceramic coatings, Y₂O₃ was added as an active filler. The materials with different weight ratios of polysiloxanes to Y₂O₃ were synthesized. Their coefficient of thermal expansion (CTE) and water-vapor resistance were tested. The results indicated that the composition of 50% Y₂O₃–50% polysiloxanes (Y50) was suitable to be the EBCs for C/SiC composites. The C/SiC composites coated with Y50 were tested in the water-vapor environments at 1400 °C for 200 h. The results revealed that such a coating could effectively protect the C/SiC composites.     

Electrical and thermal properties of SiC-Zr2CN composites sintered with Y2O3-Sc2O3 additives

SiC-Zr₂CN composites were fabricated from β-SiC and ZrN powders with 2 vol% equimolar Y₂O₃-Sc₂O₃ additives via conventional hot pressing at 2000 °C for 3 h in a nitrogen atmosphere. The electrical and thermal properties of the SiC-Zr₂CN composites were investigated as a function of initial ZrN content. Relative densities above 98% were obtained for all samples. The electrical conductivity of Zr₂CN composites increased continuously from 3.8 × 10³ (Ωm)⁻¹ to 2.3 × 10⁵ (Ωm)⁻¹ with increasing ZrN content from 0 to 35 vol%. In contrast, the thermal conductivity of the composites decreased from 200 W/mK to 81 W/mK with increasing ZrN content from 0 to 35 vol%. Typical electrical and thermal conductivity values of the SiC-Zr₂CN composites fabricated from a SiC-10 vol% ZrN mixture were 2.6 × 10⁴ (Ωm)⁻¹ and 168 W/m K, respectively.     

Electrical and thermal properties of low permittivity Sr2Al2SiO7 ceramic filled HDPE composites

The feasibility of low permittivity Sr₂Al₂SiO₇ (SAS) ceramic filled high density polyethylene (HDPE) composites for substrate and packaging applications has been investigated in this paper. The composites were prepared by the melt mixing and hot pressing techniques. Scanning electron microscopic images of SAS filled HDPE showed the increased connectivity with filler loading. The composites showed excellent relative density (>98%) with low bulk density (<2.40 g cm^?3) and very low moisture absorption (<0.10 wt%). The relative permittivity (ε_r) and the dielectric loss (tan δ) at 1 MHz and at 5 GHz were found to be low and found to increase with filler volume fraction (V_f). The experimentally observed relative permittivity at 5 GHz was correlated with the values proposed by different theoretical models. Among them, effective medium theory (EMT) gave better fit with experimental values except at the highest filler loading (0.50 V_f). Improvement in the thermal properties was also observed with filler content. The coefficient of linear thermal expansion (CTE) was found to decrease with filler content. Thermal conductivity (TC) of the composite was greatly enhanced as a function of filler volume fraction. The composite with 0.50 filler volume fraction showed balanced thermal and dielectric properties with ε_r=4.2, tan δ=3.9×10^?3, TC=2.2 W m^?1 K^?1 and CTE=101 ppm/°C.     

Modified BCZN particles filled PTFE composites with high dielectric constant and low loss for microwave substrate applications

The modified 0.7Ba (Co_1/3Nb_2/3)O₃-0.3Ba(Zn_1/3Nb_2/3)O₃ (BCZN) powders filled PTFE composites were synthesized by hot-pressing. The influences of BCZN content on the microstructure, dielectric, thermal, mechanical properties and moisture absorption were investigated systematically. The modified BCZN powders filled PTFE composites exhibited better microstructure and dielectric properties compared with untreated powders. Various mathematic models were utilized to predict the dielectric constant of different composites and the effective medium theory (EMT) showed perfect consistency with the experimental results. The modified BCZN/PTFE composites possess the best comprehensive properties at the powders content of 50 vol% with high dielectric constant (ε_r) of 7.7, low loss (tanδ) of 0.0014, acceptable temperature coefficient of dielectric constant (τ_ε) of −125.6 ppm/°C and temperature coefficient of resonant frequency (τ_f) of 29.4 ppm/°C at 7 GHz, low moisture absorption of 0.07% and low coefficient of thermal expansion (CTE) of 33 ppm/°C. All the results show modified BCZN/PTFE composites are the potential materials for microwave substrate applications.     

C/SiC composite-Ti6Al4V joints brazed with negative thermal expansion ZrP2WO12 nanoparticle reinforced AgCu alloy

Brazing C/SiC composites to Ti6Al4V alloy is associated with the problem of high residual stress inducing low joining strength. To overcome this problem, negative thermal expansion Zr₂P₂WO₁₂ (ZWP) nanoparticles were introduced into AgCu brazing alloy to obtain robust C/SiC-Ti6Al4V joints. Microstructures and mechanical properties of the joints brazed with different ZWP contents were investigated. Results indicated that 3 wt% ZWP nanoparticles dispersed homogeneously among brazing seam and compatible with brazing alloy. The width of reaction layer at C/SiC side was reduced sharply. Meanwhile, the finite element analysis showed that residual stress was reduced by 52.9 MPa and stress concentration among reaction layer was eliminated. The average shear strength of the joints brazed with AgCu + 3 wt% ZWP increased to 146.2 MPa, which was 70.8% higher than that of joints brazed without ZWP.     

Low dielectric loss LNT/PEEK composites with high mechanical strength and dielectric thermal stability

(3-Aminopropyl)triethoxysilane treated La_(2−x)/3Na_0.06TiO₃ (x = 0.06) (LNT) microparticles filled polyetheretherketone (PEEK) composites were prepared using hot pressing process. The effects of variation of LNT ceramic filling fraction on dielectric properties, water absorption, thermal stability and mechanical strength were investigated. All composites demonstrate low water absorption (less than 0.4%) when the ceramic filling fraction is lower than 0.6V_f. The obtained composites exhibited dielectric permittivities varying from ~4 to ~22 as the ceramic fillers increased from 0.1 to 0.8V_f and low losses (~10⁻⁴ @1 MHz, 3~5 × 10⁻³ at the frequencies of microwave (10 GHz) and millimeter wave (29-50 GHz), respectively). The mechanical strength, dimensional and dielectric thermal stability of the composite are remarkably improved by the addition of LNT ceramic fillers. A composite with near zero temperature coefficients of dielectric permittivity or resonant frequency and flexural strength of ~140 MPa could be obtained. The out-of-plane coefficient of thermal expansion (CTE) could be reduced to ~20 ppm/°C as the ceramic filler loading reached 0.7V_f.     

Microcellular foams of glass–fiber reinforced poly(phenylene sulfide) composites generated using supercritical carbon dioxide

Microcellular foaming of poly(phenylene sulfide) (PPS) and its glass–fiber (GF) reinforced composites using supercritical CO₂ as a blowing agent presents a promising approach to produce novel cellular materials with tailored microstructures. This study investigated the effects of the material composition and process conditions on the foaming behaviors and final morphologies of the microcellular foamed PPS and PPS/GF composites. The rheological and thermal properties as well as the saturation and desorption behaviors of CO₂ in the pure PPS and PPS/GF composites were also detailedly discussed. The results show that microcellular foams with various relative densities, cell sizes, cell‐size distributions, and cell densities can be attained by tailoring the fiber content and key process parameters. At low foaming temperatures below the cold crystallization temperature, the microcellular foamed PPS and PPS/GF composites both present a unimodal cell‐size distribution. At elevated temperatures, the generated crystalline superstructures including spherulites in the polymer matrix and transcrystals around the GF will cause a secondary heterogeneous cell nucleation. This leads to the observations of bimodal and trimodal cell‐size distributions in the pure PPS and the PPS/GF composites, respectively. The mechanisms for the solid‐state foaming behaviors of pure PPS and PPS/GF composites have been illustrated by establishing theoretical models. POLYM. COMPOS., 37:2527–2540, 2016. © 2015 Society of Plastics Engineers     

Simultaneously Improved Thermal Conductivity and Dielectric Properties of NBR Composites by Constructing 3D Hybrid Filler Networks

This work aims to address the heat accumulation issue in electronic components during high-frequency operation through the preparation of novel thermally conductive composites. First, polydopamine (PDA) and in-situ growth of silver (Ag) nanoparticles are applied for the surface modification of graphene oxide (GO) and carbon nanotube (CNT) to prepare pGO@Ag and pCNT@Ag hybrid filler, respectively. Then, nitrile butadiene rubber (NBR) is chosen as the polymeric matrix and simultaneously incorporated with both pGO@Ag and pCNT@Ag to prepare polymeric composites with excellent thermal conductivity (TC) and dielectric constant (ɛ_r). Due to the construction of 3D heat conduction networks by utilizing 2D pGO@Ag and 1D pCNT@Ag, the fabricated NBR composites achieved the maximum TC of 1.0112 W/(mK), which is 636% higher than that of neat NBR (0.1373 W (mK)⁻¹). At the filler loading of 9 vol%, the TC of pGO@Ag/pCNT@Ag/NBR composite is 152% that of GO/CNT/NBR composite (0.6660 W (mK)⁻¹). Moreover, due to electron polarization effect of GO and CNT and micro-capacitor effect of Ag nanoparticles, a large ɛ_r of 147.12 is attained at 10 Hz for NBR composites. Overall, the development of dielectric polymer materials with high TC is beneficial for enhancing the service life and safety stability of the electronic components.     

Bimodal distribution of filler on viscosity and thermal expansion of glass composites

This paper investigates the bimodal oxide filler system to study the viscous behavior and thermal expansion properties of glass composites. Zinc oxide and cordierite, which are two types of filler, with different average diameters (10 μm and 1 μm, respectively), were considered in a Bi2O3 containing glass with various volume fractions (up to 40 vol%). The experimental results for the composites with the bimodal filler distribution show a reduced viscosity. The viscosity increased from fine particles to coarse particles with an increase in the volume fraction of the composite. Both viscosity and coefficient of thermal expansion (CTE) decreased significantly in the composite with the cordierite filler. The CTE is determined from the volume fraction with respect to particle size and distribution. On the other hand, viscosity is dependent on the particle distribution, particle size, and volume fraction of the composite.     

Design and preparation of BaO–Al2O3–SiO2–B2O3/Quartz LTCC composites with tailored coefficient of thermal expansion

In this work, by focusing on widespread problem of thermal mismatch caused by different coefficients of thermal expansion (CTE) in electronic packaging materials, low-temperature co-fired ceramic (LTCC) materials with tunable CTE values were designed. By substituting Ba²⁺ with Sr²⁺ and replacing quartz with alumina and zirconia, respectively, BaO–Al₂O₃–SiO₂–B₂O₃/quartz LTCC composites with CTE of 7.05–9.52 × 10^?6/°C were developed. Results show that major crystalline phases of LTCC composite materials are quartz and hexacelsian. By replacing quartz with alumina or zirconia, sintering behavior and subsequently thermal expansion and dielectric properties were modulated. On the other hand, substituting Ba²⁺ with Sr²⁺ can be beneficial to the densification of composite materials. The introduction of Sr²⁺ triggered mixed alkali effect and hindered the crystallization of hexacelsian phase, which can further improve mechanical properties. Finally, sandwich structure module of BaO–Al₂O₃–SiO₂–B₂O₃/quartz with gradient CTE values was obtained, which showed potential for electronic packaging with sustained thermal compatibility under cyclic temperatures.     

Cyclic thermal shock resistance of h-BN composite ceramics with La2O3–Al2O3–SiO2 addition

The effects of La₂O₃–Al₂O₃–SiO₂ addition on the thermal conductivity, coefficient of thermal expansion (CTE), Young's modulus and cyclic thermal shock resistance of hot-pressed h-BN composite ceramics were investigated. The samples were heated to 1000 °C and then quenched to room temperature with 1–50 cycles, and the residual flexural strength was used to evaluate cyclic thermal shock resistance. h-BN composite ceramics containing 10 vol% La₂O₃–Al₂O₃ and 20 vol% SiO₂ addition exhibited the highest flexural strength, thermal conductivity and relatively low CTE, which were beneficial to the excellent thermal shock resistance. In addition, the viscous amorphous phase of ternary La₂O₃–Al₂O₃–SiO₂ system could accommodate and relax thermal stress contributing to the high thermal shock resistance. Therefore, the residual flexural strength still maintained the value of 234.3 MPa (86.9% of initial strength) after 50 cycles of thermal shock.