High thermally conductive PLA based composites with tailored hybrid network of hexagonal boron nitride and graphene nanoplatelets

Bio‐based polymers and multifunctional polymeric composites are promising for the development of new environmentally sustainable materials and are becoming increasingly popular compared to their oil based counterparts. This research aims to develop new multifunctional bio‐based polymer composites with improved thermal conductivity and tailored electrical properties to be used as heat management materials in the electronics industry. A series of parametric studies were conducted to clarify the science behind the hybrid composites' behavior and their structure‐to‐property relationships. Using bio‐based polymers [e.g., polylactic acid (PLA)] as the matrix, heat transfer networks were developed and structured by embedding hexagonal boron nitride (hBN) and graphene nanoplatelets (GNP) in a PLA matrix. The effects of random uniform thermal hybrid networks of hBN‐GNP on improving the effective thermal conductivity (k_eff) of produced composites were studied and compared. Composites were characterized with respect to physical, thermal, electrical, and mechanical properties for practical application in the electronics industry. The use of high thermally conductive hybrid filler systems, with optimized filler content, was found to promote the composites' effective thermal conductivity to more than 12 times over neat PLA. The thermally conductive composite is expected to provide unique opportunities to injection mold three‐dimensional, net‐shape, lightweight, and eco‐friendly microelectronic enclosures with superior heat dissipation performance. POLYM. COMPOS., 37:2196–2205, 2016. © 2015 Society of Plastics Engineers     

ROMP‐based boron nitride composites

The present work focuses on the investigation of the thermal and dielectric properties of composites obtained by surface‐modified hexagonal boron nitride (hBN) and ring‐opening metathesis polymerization (ROMP) based polymer. A new kind of high performance composites was developed based on using amino silane functionalized hBN (AS‐hBN) and bromine functional group possessing homo and copolymers synthesized via ROMP pathway. Aminosilane capped boron nitride (BN) and bromine bearing polymer backbone enhance the interaction between filler and the polymer chains. The effects of surface‐modified BN (AS‐hBN) and its content on the dielectric properties, and thermal resistance of composites, are systematically investigated and discussed. The resultant composites possess high electrical break over voltages. While all of the ROMP‐based films exhibit low ?′ value in a wide frequency range, in the case of the composite with 20% AS‐hBN and poly(bromooxanorbornene‐co‐cyclooctadiene) (ROMP‐BN‐6) displays very low dielectric constants in around 1.5 up to 1 MHz at 20 °C. This value is significantly lower than that of common polymer dielectrics, which is usually in the range of 3–6. Besides the lowest dielectric constant of ROMP‐BN‐6, it has also the smallest dielectric loss tangent even at high temperatures. Tan δ of ROMP‐BN‐6 is 0.003 and 0.0067 at 10 Hz–1 MHz at 20 °C, respectively. Thermal stability of polymers was also improved by introducing surface‐modified hBN. Polymers bearing 20% AS‐hBN are highly thermally stable up to ～350 °C and gave 25% char yield at 800 °C. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45658.     

Development of thermally conductive polymer matrix composites by foaming‐assisted networking of micron‐ and submicron‐scale hexagonal boron nitride

Thermally conductive polymer matrix composite (PMC) foams with effective thermal conductivities (k_eff) higher than their solid counterparts have been developed for the first time. Using a material system consists of low density polyethylene and micron‐scale or submicron‐scale hexagon boron nitride platelets as a case example, this article demonstrates that foaming‐assisted filler networking is a feasible processing strategy to enhance PMC's k_eff, especially at a low hBN loading. Parametric studies were conducted to identify the structure‐to‐property relationships between foam morphology (e.g., cell population density, cell size, and foam expansion) and the PMC foam's k_eff. In particular, there exists an optimal cell size to maximize the PMC foam's k_eff for foams with up to 50% volume expansion. However, an optimal cell size is absent for PMC foams with higher volume expansion. X‐ray diffraction (XRD) analyses reveal that both the presence of hBN platelets and foam expansion promoted the crystallization of LDPE phase. Moreover, the XRD spectra also provide evidence for the effect of foam expansion on the orientation of hBN platelets. Overall, the findings provide new directions to design and fabricate thermally conductive PMC foams with low filler contents for heat management applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42910.     

Enhanced thermal conductivity of boron nitride epoxy‐matrix composite through multi‐modal particle size mixing

Castable particulate‐filled epoxy resins exhibiting excellent thermal conductivity have been prepared using hexagonal boron nitride (hBN) and cubic boron nitride (cBN) as fillers. The thermal conductivity of boron nitride filled epoxy matrix composites was enhanced up to 217% through silane surface treatment of fillers and multi‐modal particle size mixing (two different hBN particle sizes and one cBN particle size) prior to fabricating the composite. The measurements and interpretation of the curing kinetics of anhydride cured epoxies as continuous matrix, loaded with BN having multi‐modal particle size distribution, as heat conductive fillers, are highlighted. This study evidences the importance of surface engineering and multi‐modal mixing distribution applied in inorganic fillered epoxy‐matrix composite. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Synthesis and characterization of polyimide/hexagonal boron nitride composite

Polyimide (PI)/hexagonal boron nitride (h‐BN) composites were produced via the thermal imidization procedure from solution mixtures of a polyamicacid, which is prepared from 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride and 3,3′‐diaminodiphenyl sulfone (DADPS) in N‐methyl‐2‐pyrrolidone (NMP), and alkoxysilane functionalized h‐BN. The structure, thermostability, thermal behavior, and surface properties of the resulting materials were characterized by means of Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), scanning electron microscopy (SEM). The thermal characteristics of PI/h‐BN films were better than the pure PIs. The physical and mechanical properties of the films were evaluated by various techniques such as contact angle, chemical resistance, and tensile tests. The flame retardancy of the composite materials was also examined by the limiting oxygen index (LOI). The experiments showed that the LOI values of PIs increased from 32 to 43 for the materials containing hexagonal boron nitride. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Consolidation of cubic and hexagonal boron nitride composites

Consolidating cubic boron nitride (cBN) typically requires either a matrix of metal bearing materials that are undesirable for certain applications, or very high pressures within the cBN phase stability field that are prohibitive to manufacturing size and cost. We present new methodology for consolidating high stiffness cBN composites within a hexagonal boron nitride (hBN) matrix (15–25 vol%) with the aid of a binder phase (0–6 vol%) at moderate pressures (0.5–1.0 GPa) and temperatures (900–1300 °C). The composites are demonstrated to be highly tailorable with a range of compositions and resulting physical/mechanical properties. Ultrasonic measurements indicate that in some cases these composites have elastic mechanical properties that exceed those of the highest strength steel alloys. Two methods were identified to prevent phase transformation of the metastable cBN phase into hBN during consolidation: 1. removal of hydrocarbons, and 2. increased cBN particle size. Lithium tetraborate worked better as a binder than boron oxide, aiding consolidation without enhancing cBN to hBN phase transformation kinetics. These powder mixtures consolidated within error of their full theoretical mass densities at 1 GPa, and had only slightly lower densities at 0.5 GPa. This shows potential for consolidation of these composites into larger parts, in a variety of shapes, at even lower pressures using more conventional manufacturing methods, such as hot-pressing.     

Influence of molecular orientation direction on the in‐plane thermal conductivity of polymer/hexagonal boron nitride composites

The effect of the molecular orientation direction of a polymer matrix on the in‐plane thermal conductivity (TC) of injection‐molded polymer/hexagonal boron nitride (h‐BN) composites is investigated. In this system, the h‐BN platelets align in the in‐plane direction owing to injection shear flow. Three molecular orientations (perpendicular, random, and parallel to the h‐BN plane) are achieved using liquid crystalline polyesters and the in‐plane TCs are compared. Although a parallel orientation of the polymer chains provides the highest TC of the matrix in the injection direction, the TC of the composites is the lowest of the three systems for this orientation. The highest in‐plane TC is found in the perpendicularly oriented system, irrespective of the in‐plane direction. These results reveal that perpendicularly oriented molecular chains serve as effective heat paths between h‐BN platelets that are arranged one above the other, and consequently, a continuous thermal network is created in the in‐plane direction. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39768.     

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     

Tribological and thermal properties of hexagonal boron nitride filled high‐performance polymer nanocomposites

High‐performance polymer nanocomposites based on poly(aryletherketone) (PAEK) as matrix and hexagonal boron nitride (h‐BN) nanopowder as reinforcement were fabricated using planetary ball mill followed by hot pressing. The addition of h‐BN (0–5 wt %) to the matrix enhanced the microhardness and thermal stability compared to pure matrix. For a constant sliding speed, the wear rate of the nanocomposites determined by using Pin‐on‐Disk tribometer was reduced approximately 22 times compared to pure matrix. The coefficient of friction of the nanocomposites is slightly increased but it is stable compared to that of pure matrix. It was also investigated that the thermal stability of the debris of the nanocomposites was decreased compared to the pure matrix and its nanocomposites. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44409.     

Effect of time on microstructure and hardness of βSiAlON-cubic boron nitride composites during spark plasma sintering

βSiAlON-cubic boron nitride (cBN) composites were consolidated by spark plasma sintering, and the effects of holding time and heating rate on the phase transformation of cBN and Vickers hardness were investigated. The cBN phase transformed into hexagonal BN (hBN) and the hardness decreased with increasing holding time. The phase transformation from cBN to hBN was retarded by increasing the heating rate, resulting in increased hardness.     

Enhanced thermal conductivity and wear resistance of polytetrafluoroethylene composites through boron nitride and zinc oxide hybrid fillers

In this study, the thermal conductivity and wear resistance of the polytetrafluoroethylene (PTFE)/boron nitride (BN), PTFE/zinc oxide (ZnO), PTFE/tetra‐needle‐shaped zinc oxide whiskers (T‐ZnO), and PTFE/hybrid filler composites were investigated. Moreover, hot‐press molding was used to prepare the composites, and scanning electron microscopy was used to observe the morphology of the fillers and the friction interface of the composites. The results show that continuous thermally conductive paths could be formed in the PTFE/hybrid fillers (T‐ZnO and BN) composites so that the thermal conductivity of the PTFE was improved through addition of the hybrid fillers. Meanwhile, the synergistic effects of the hybrid fillers were useful for reducing the wear rate of the composites. In addition, for the pure PTFE, abrasive and adhesive wear was found. Compared to the worn surface of the pure PTFE, the worn surface of the PTFE composites filled with ZnO, T‐ZnO, BN, and hybrid fillers presented much smoother surfaces, and slighter ploughing occurred. Therefore, the hybrid fillers improved not only the thermal conductivity but also the wear resistance of the PTFE composites. The data obtained in this study contributed to the construction of a technical foundation for the preparation of composites with a high thermal conductivity and wear resistance. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42302.     

Study on thermal conductive PA6 composites with 3-dimensional structured boron nitride hybrids

To develop thermally conductive PA6 composites with the aim of decreasing filler content, structure-complexed fillers were fabricated. This research presented an effective approach by noncovalent functionalization of poly(dopamine) (PDA) followed by silver nanoparticles decoration to fabricate 3-dimensional (3-D) structured boron nitride hybrids (BN@PDA@AgNPs). BN hybrids were then introduced into PA6 to prepare thermally conductive PA6 composites. The results demonstrated that PA6/BN hybrids (PMB) composites exhibited higher thermal conducivity compared with PA6/BN composites, which revealed more effective construction of thermal conductive network in the composites with the addition of 3-D structured fillers. The effects of BN hybrids with different loadings on thermal stability, mechanical property, as well as electrical resistance of the composites were also analyzed. Overall, the prepared PMB composites exhibited outstanding performance in thermal conductivity, thermal stability, mechanical property, while retaining good electrical insulating property, which showed a potential application in electronic packaging fields. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47630.     

Heat propagation in thermally conductive polymers of PA6 and hexagonal boron nitride

Thermally conductive polymers offer new possibilities for the heat dissipation in electric and electronic components, for example, by a three‐dimensional shaping of the heat sinks. To face safety regulations, improved fire performance of those components is required. In contrast to unfilled polymers, those materials exhibit an entirely different thermal behavior. To investigate the flammability, a phosphorus flame retardant was incorporated into thermally conductive composites of polyamide 6 and hexagonal boron nitride. The flame retardant decreased the thermal conductivity only slightly. However, the burning behavior changed significantly, due to a different heat propagation, which was investigated using a thermographic camera. An optimum content of hexagonal boron nitride for a sufficient thermal conductivity and fire performance was found between 20 and 30 vol%. The improvement of the fire performance was due to a faster heat release out of the pyrolysis zone and an earlier decomposition of the flame retardant. For higher contents of hexagonal boron nitride, the heat was spread faster within the part, promoting an earlier ignition and increasing the decomposition rate of the flame retardant.     

Modification of hexagonal boron nitride nanoparticles with fluorosilane

Surfaces of hexagonal boron nitride (hBN) nanoparticles were modified with perfluorooctyl-triethoxysilane (FTS). Experiments were performed for 40–120 min in 70–150 °C range with FTS/hBN weight ratio in the range of 0.5–1.5. The products were analyzed by FT-IR, TGA, FESEM, HRTEM and EDX. Results of FT-IR analyses indicated that modification takes place in 80 min at 150 °C under reflux with a FTS/hBN ratio of 1.5. Presence of FTS on hBN nanoparticles was confirmed by the weight losses in TGA, and by TEM, TEM-EDX analyses.     

Thermal conductivity improvement in electrically insulating silicone rubber composites by the construction of hybrid three-dimensional filler networks with boron nitride and carbon nanotubes

In this study, we constructed hybrid three-dimensional (3D) filler networks by simply incorporating a relatively low content of one-dimensional carbon nanotubes (CNTs; 0.0005–0.25 vol %) and a certain content of two-dimensional boron nitride (BN; 30 phr) in a silicone rubber (SIR) matrix. As indicated by transmission electron microscopy observation, flexible CNTs can serve as bridges to connect BN platelets in different layers to form hybrid 3D thermally conductive networks; this results in an increase in thermally conductive pathways, and the isolation between CNTs can prevent the formation of electrically conductive networks. Compared to the SIR–BN composite with the same BN content, the SIR–BN–CNT composites exhibited improved thermal conductivity, slightly increased volume resistivity, and comparable breakdown strength without a largely decreased flexibility. When 0.25 vol % CNTs were incorporated, the SIR–BN–CNT composite exhibited 75 and 25% higher thermal conductivities relative to the neat SIR and SIR–BN composite with 30 phr BN, respectively, and a thermal conductivity that was even comparable to SIR–BN composite with 40 phr BN. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46929.     

Nanocoating individual cohesive boron nitride particles in a fluidized bed by ALD

Experiments are conducted with alumina (Al₂O₃) deposition on a wide size range of hexagonal boron nitride (BN) platelet-like particles. Successful deposition of alumina films on these particles, with film thickness controllable at the Angstrom level, is observed based upon TEM imaging, ICP-AES, particle size distributions, and surface area analysis. While fluidizing, fine BN particles aggregate in the bed. The aggregates are the entities fluidizing, not the primary particles. However, individual particles are coated using Atomic Layer Deposition (ALD), not aggregates. Since ALD is a surface chemistry phenomenon, the films grow uniformly on every primary particle. BN particles are small platelets with different functional groups on the basal planes and edge planes. A small exposure to reagents [2.5×10⁶ Langmuir (L) per reagent per cycle], will only coat the edge planes of uncoated BN particles. A larger dose of 1×10⁸ L will coat the entire uncoated BN particle (edge and basal planes). After 10 ALD cycles of the 1×10⁸ L dose, the exposures can be reduced to 1×10⁶ L as the film is then growing on alumina and not BN. Peel strength data indicate that adhesion between the coated particles and a cured epoxy in a filled composite is ∼25% stronger than that of uncoated particles and the epoxy. The overall thermal conductivity drops ∼17% for an identical filler loading as expected due to the additional thermal resistance added by the film. However, the viscosity of an epoxy resin loaded with coated BN is as much as five times lower than that of the resin loaded with the same amount of uncoated BN. These results indicate that the loading of Al₂O₃ nanocoated BN particles in an epoxy matrix can be substantially increased relative to that of uncoated particles. The thermal conductivity of the more highly filled composite will be increased without adversely impacting filled resin viscosity or the peel strength of the cured material. This is the first reported study indicating that cohesive primary particles that fluidize as aggregates in a fluidized bed can be individually coated with a nano-thick ceramic film using ALD.     

Preparation and properties of thermally conductive photosensitive polyimide/boron nitride nanocomposites

A new thermally conductive photoresist was developed. It was based on a dispersion of boron nitride (BN) nanoflakes in a negative‐tone photosensitive polyimide (PSPI) precursor. 3‐Mercaptopropionic acid was used as the surfactant to modify the BN nanoflake surface for the dispersion of BN nanoflakes in the polymer. The thermal conductivity of the composite films increased with increasing BN fraction. The thermal conductivity of the PSPI/BN nanocomposite was up to 0.47 W m⁻¹ K⁻¹ for a mixture containing 30 wt % nanosized BN filler in the polyimide matrix. Patterns with a resolution of 30 μm were obtained from the PSPI/BN nanocomposites. The PSPI/BN nanocomposites had excellent thermal properties. Their glass‐transition temperatures were above 360°C, and the thermal decomposition temperatures were over 460°C. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Lightweight and thermally conductive thermoplastic polyurethane/hollow glass bead/boron nitride composites with flame retardancy

Polymeric composites with low density and high thermal conductivity (TC) are greatly demanded in some specific applications such as aeronautics, astronautics, and deep-sea exploration. It is a great challenge to obtain lightweight and thermally conductive polymer composites because the heat fillers have high density (>2 g/cm³) Herein, lightweight and thermally conductive thermoplastic polyurethane/hollow glass bead/boron nitride composites (TPU/HGB/BN) were prepared with the construction of a 3D BN network under the assistance of ultralightweight HGB by a solution-mixing and hot-pressing method. A 3D BN heat network has been constructed in the TPU matrix due to the alignment of the BN platelets along with the HGB microspheres during hot-pressing, which leads to a higher TC (5.34 W/mK) of the TPU/HGB/BN composites with a low density of 1.23 g/cm³, which is close to the density of pure TPU (1.20 g/cm³). In addition, the TPU/HGB/BN composites show good thermal stability with TC losses of 4.24% and 2.22%, respectively, even after treated for 50 hot-cold cycles and heated at 80 °C for 50 h. Moreover, the limiting oxygen index (LOI) of the TPU/HGB/BN composites is 51%, and they can extinguish in 8 s after ignition and exhibit enhanced flame retardancy. This work presents a simple method to design and prepare lightweight, flame retardant and thermally conductive composite materials, which can be used as lightweight thermal management materials.     

Catalytic effect of potassium carbonate on carbothermic production of hexagonal boron nitride

Effect of potassium carbonate addition on the carbothermic formation of hexagonal boron nitride (hBN) was investigated by keeping the K₂CO₃ added B₂O₃+C mixtures in nitrogen atmosphere at 1400 °C for 40–160 min. K₂CO₃ amount was varied in the range of 10–60 wt% of the B₂O₃+C mixture. Products were subjected to XRD and quantitative analyses, SEM and TEM observations, and particle size measurement. Amount of hBN increased considerably with K₂CO₃ addition; also particle size and crystallinity improved. Catalytic role of K₂CO₃ was suggested as forming a potassium borate melt in which hBN particles form, in addition to carbothermic formation reaction. Effect of K₂CO₃ on increasing the hBN amount decreased when it was used over 40%. This was attributed to the rapid evaporation of the formed potassium borate liquid.     

Thermal conductivity of polyimide/boron nitride nanocomposite films

The thermal conductivity of polyimide/boron nitride (PI/BN) nanocomposite thin films has been studied for two sizes of BN nanofillers (40 and 120 nm) and for a wide range of content. A strong influence of BN particle size on the thermal conduction of PI has been identified. In the case of the largest nanoparticles (hexagonal‐BN), the thermal conductivity of PI/h‐BN (120 nm) increases from 0.21 W/mK (neat PI) up to 0.56 W/mK for 29.2 vol %. For the smaller nanoparticles (wurtzite‐BN), PI/w‐BN (40 nm), we observed two different behaviors. First, we see a decrease until 0.12 W/mK for 20 vol % before increasing for higher filler content. The initial phenomenon can be explained by the Kapitza theory describing the presence of an interfacial thermal resistance barrier between the nanoparticles and the polymer matrix. This is induced by the reduction in size of the nanoparticles. Modeling of the experimental results allowed us to determine the Kapitza radius a_K for both PI/h‐BN and PI/w‐BN nanocomposites. Values of a_K of 7 nm and >500 nm have been obtained for PI/h‐BN and PI/w‐BN nanocomposite films, respectively. The value obtained matches the Kapitza theory, particularly for PI/w‐BN, for which the thermal conductivity is expected to decrease compared to that of neat PI. The present work shows that it seems difficult to enhance the thermal conductivity of PI films with BN nanoparticles with a diameter <100 nm due to the presence of high interfacial thermal resistance at the BN/PI interfaces. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42461.