Highly thermally conductive graphitic film(GF)materials have become a competitive solution for the thermal management of high-power electronic devices.However,their catastrophic structural failure under extreme altern...Highly thermally conductive graphitic film(GF)materials have become a competitive solution for the thermal management of high-power electronic devices.However,their catastrophic structural failure under extreme alternating thermal/cold shock poses a significant challenge to reliability and safety.Here,we present the first investigation into the structural failure mechanism of GF during cyclic liquid nitrogen shocks(LNS),which reveals a bubbling process characterized by“permeation-diffusion-deformation”phenomenon.To overcome this long-standing structural weakness,a novel metal-nanoarmor strategy is proposed to construct a Cu-modified graphitic film(GF@Cu)with seamless heterointerface.This well-designed interface ensures superior structural stability for GF@Cu after hundreds of LNS cycles from 77 to 300 K.Moreover,GF@Cu maintains high thermal conductivity up to 1088 W m^(−1)K^(−1)with degradation of less than 5%even after 150 LNS cycles,superior to that of pure GF(50%degradation).Our work not only offers an opportunity to improve the robustness of graphitic films by the rational structural design but also facilitates the applications of thermally conductive carbon-based materials for future extreme thermal management in complex aerospace electronics.展开更多
Effective thermal management is quite urgent for electronics owing to their ever-growing integration degree,operation frequency and power density,and the main strategy of thermal management is to remove excess energy ...Effective thermal management is quite urgent for electronics owing to their ever-growing integration degree,operation frequency and power density,and the main strategy of thermal management is to remove excess energy from electronics to outside by thermal conductive materials.Compared to the conventional thermal management materials,flexible thermally conductive films with high in-plane thermal conductivity,as emerging candidates,have aroused greater interest in the last decade,which show great potential in thermal management applications of next-generation devices.However,a comprehensive review of flexible thermally conductive films is rarely reported.Thus,we review recent advances of both intrinsic polymer films and polymer-based composite films with ultrahigh in-plane thermal conductivity,with deep understandings of heat transfer mechanism,processing methods to enhance thermal conductivity,optimization strategies to reduce interface thermal resistance and their potential applications.Lastly,challenges and opportunities for the future development of flexible thermally conductive films are also discussed.展开更多
Combining the mean field Pozhar-Gubbins(PG)theory and the weighted density approximation,a novel method for local thermal conductivity of inhomogeneous fluids is proposed.The correlation effect that is beyond the mean...Combining the mean field Pozhar-Gubbins(PG)theory and the weighted density approximation,a novel method for local thermal conductivity of inhomogeneous fluids is proposed.The correlation effect that is beyond the mean field treatment is taken into account by the simulation-based empirical correlations.The application of this method to confined argon in slit pore shows that its prediction agrees well with the simulation results,and that it performs better than the original PG theory as well as the local averaged density model(LADM).In its further application to the nano-fluidic films,the influences of fluid parameters and pore parameters on the thermal conductivity are calculated and investigated.It is found that both the local thermal conductivity and the overall thermal conductivity can be significantly modulated by these parameters.Specifically,in the supercritical states,the thermal conductivity of the confined fluid shows positive correlation to the bulk density as well as the temperature.However,when the bulk density is small,the thermal conductivity exhibits a decrease-increase transition as the temperature is increased.This is also the case in which the temperature is low.In fact,the decrease-increase transition in both the small-bulk-density and low-temperature cases arises from the capillary condensation in the pore.Furthermore,smaller pore width and/or stronger adsorption potential can raise the critical temperature for condensation,and then are beneficial to the enhancement of the thermal conductivity.These modulation behaviors of the local thermal conductivity lead immediately to the significant difference of the overall thermal conductivity in different phase regions.展开更多
Functional composite films were successfully prepared from cellulose, graphite(GP), and polyaniline(PANI) using a combination of physical and chemical processes. Cellulosewasdissolved in N-methylmorpholine-N-oxide mon...Functional composite films were successfully prepared from cellulose, graphite(GP), and polyaniline(PANI) using a combination of physical and chemical processes. Cellulosewasdissolved in N-methylmorpholine-N-oxide monohydrate(NMMO) and regenerated in water to form the matrix. GP was dispersed in the NMMO solvent prior to the dissolution of the cellulose, and PANI was deposited on the surfaces of the cellulose/GP films by in situ chemical polymerization. The structures of the PANI/cellusose/GP composite films were investigated using X-ray diffraction analysis, Fourier transform infrared spectroscopy, scanning electron microscopy(SEM), and SEM/energy-dispersive X-ray spectroscopy. The mechanical strengths, thermal stabilities, conductivities, and antibacterial activities of the films were studied in detail. The results showed that GP formed a multilayered structure in the cellulose matrix and that the PANI nanoparticles were tightly wrapped on the film surface. The film thickness increased from 40 mm to 100 mm after the addition of GP and PANI. The tensile strength of the composite films was 80~107 MPa, with the elongation at break being 3%~10%. The final residual weight of the composite films was as high as 65%, and the conductivity of the composite films reached 14.36 S/m. The cellulose matrix ensured that the films were flexible and exhibited desirable mechanical properties, while the GP filler significantly improved the thermal stability of the films. The PANI coating acted as a protective layer during burning and provided good electrical conductivity and antibacterial activity against Escherichia coli; both of these characteristics were slightly enhanced by the incorporation of GP. These PANI/cellulose/GP composite films should be suitable for use in electronics, antistatic packing, and numerous other applications.展开更多
Polymer-derived ceramic(PDC) thin films are promising wear-resistant coatings for protecting metals and carbon-carbon composites from corrosion and oxidation.However,the high pyrolysis temperature hinders the applicat...Polymer-derived ceramic(PDC) thin films are promising wear-resistant coatings for protecting metals and carbon-carbon composites from corrosion and oxidation.However,the high pyrolysis temperature hinders the applications on substrate materials with low melting points.We report a new synthesis route for PDC coatings using initiated chemical vapor deposited poly(1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane)(pV_3D_3) as the precurs or.We investigated the changes in siloxane moieties and the network topology,and proposed a three-stage mechanism for the thermal annealing process.The rise of the connectivity number for the structures obtained at increased annealing temperatures was found with strong correlation to the enhanced mechanical properties and thermal conductivity.Our PDC films obtained via annealing at 850℃ exhibit at least 14.6% higher hardness than prior reports for PDCs synthesized below 1100℃.Furthermore,thermal conductivity up to 1.02 W(mK)^(-1) was achieved at the annealing temperature as low as 700℃,which is on the same order of magnitude as PDCs obtained above 1100℃.Using minimum thermal conductivity models,we found that the thermal transport is dominated by diffusons in the films below the percolation of rigidity,while ultra-short mean-free path phonons contribute to the thermal conductivity of the films above the percolation threshold.The findings of this work provide new insights for the development of wear-resistant and thermally conductive PDC thin films for durable protection coatings.展开更多
Ag nanoparticles were in-situ grown on the surface of MXene nanosheets to prepare thermally conductive hetero-structured MXene@Ag fillers.With polyvinyl alcohol(PVA)as the polymer matrix,thermally conductive MXene@Ag/...Ag nanoparticles were in-situ grown on the surface of MXene nanosheets to prepare thermally conductive hetero-structured MXene@Ag fillers.With polyvinyl alcohol(PVA)as the polymer matrix,thermally conductive MXene@Ag/PVA composite films were fabricated by the processes of solution blending,pouring,evaporative self-assembly.With the same mass fraction,MXene@Ag-III(MXene/Ag,2:1,w/w)presents more significant improvement in thermal conductivity coefficient(λ)than MXene@Ag,single MXene,Ag,simply blending MXene/Ag.MXene@Ag-III/PVA composite films show dual functions of excellent thermal conductivity and electromagnetic interference(EMI)shielding.When the mass fraction of MXene@Ag-III is 60 wt.%,the in-planeλ(λ_(∥)),through-planeλ(λ_(⊥)),EMI shielding effectiveness(EMI SE)are 3.72 and 0.41 W/(m∙K),32 dB,which are increased by 3.1,1.3,105.7 times than those of pure PVA film(0.91 and 0.18 W/(m∙K),0.3 dB),respectively.The 60 wt.%MXene@Ag-III/PVA composite film also has satisfying mechanical and thermal properties,with Young’s modulus,glass transition temperature,heat resistance index of 3.8 GPa,58.5 and 175.3℃,respectively.展开更多
Polyimide-based composite films with high thermal conductivity,good mechanical property and electrical insulating performance are urgently needed in the electronics and microelectronics fields.As one of the key techni...Polyimide-based composite films with high thermal conductivity,good mechanical property and electrical insulating performance are urgently needed in the electronics and microelectronics fields.As one of the key technical challenges to be solved,interfacial compatibility between filler and matrix plays an important role for composite film.Herein,boron nitride was modified by grafting polyimide brushes via a twostep method,and a series of thermally conductive polyimide/boron nitride composite films were prepared.Both characterization and performance results proved that the interfacial interaction and compatibility was greatly enhanced,resulting in a significant reduction in defects and interfacial thermal resistance.The interphase width of transition zone between two phases was also efficiently enlarged due to polyimide brushes grafted on filler surface.As a result,composite films based on polyimide-grafted boron nitride exhibited significantly improved properties compared with those based on pristine filler.Tensile strength can reach up to 80 MPa even if the filler content is as high as 50 wt%.The out-of-plane and in-plane thermal conductivity of composite film increased to 0.841 and 0.850 W·m^(-1)·K^(-1),respectively.In addition,thermal and dielectric properties of composite films were also enhanced to some extent.The above results indicate that surface modification by chemically grafting polymer brushes is an effective method to improve two-phase interfacial compatibility so as to prepare composite film with enhanced properties.展开更多
基金the National Natural Science Foundation of China(Nos.52272046,52090030,52090031,52122301,51973191)the Natural Science Foundation of Zhejiang Province(LR23E020003)+4 种基金Shanxi-Zheda Institute of New Materials and Chemical Engineering(2021SZ-FR004,2022SZ-TD011,2022SZ-TD012,2022SZ-TD014)Hundred Talents Program of Zhejiang University(188020*194231701/113,112300+1944223R3/003,112300+1944223R3/004)the Fundamental Research Funds for the Central Universities(Nos.226-2023-00023,226-2023-00082,2021FZZX001-17,K20200060)National Key R&D Program of China(NO.2022YFA1205300,NO.2022YFA1205301,NO.2020YFF0204400,NO.2022YFF0609801)“Pioneer”and“Leading Goose”R&D Program of Zhejiang 2023C01190.
文摘Highly thermally conductive graphitic film(GF)materials have become a competitive solution for the thermal management of high-power electronic devices.However,their catastrophic structural failure under extreme alternating thermal/cold shock poses a significant challenge to reliability and safety.Here,we present the first investigation into the structural failure mechanism of GF during cyclic liquid nitrogen shocks(LNS),which reveals a bubbling process characterized by“permeation-diffusion-deformation”phenomenon.To overcome this long-standing structural weakness,a novel metal-nanoarmor strategy is proposed to construct a Cu-modified graphitic film(GF@Cu)with seamless heterointerface.This well-designed interface ensures superior structural stability for GF@Cu after hundreds of LNS cycles from 77 to 300 K.Moreover,GF@Cu maintains high thermal conductivity up to 1088 W m^(−1)K^(−1)with degradation of less than 5%even after 150 LNS cycles,superior to that of pure GF(50%degradation).Our work not only offers an opportunity to improve the robustness of graphitic films by the rational structural design but also facilitates the applications of thermally conductive carbon-based materials for future extreme thermal management in complex aerospace electronics.
基金funded by the National Natural Science Foundation of China (NNSFC grant nos. 52103034, 51873126, 52175331 and 52003170)Shandong Provincial Natural Science Foundation (ZR2021QE014, ZR2020ZD04)
文摘Effective thermal management is quite urgent for electronics owing to their ever-growing integration degree,operation frequency and power density,and the main strategy of thermal management is to remove excess energy from electronics to outside by thermal conductive materials.Compared to the conventional thermal management materials,flexible thermally conductive films with high in-plane thermal conductivity,as emerging candidates,have aroused greater interest in the last decade,which show great potential in thermal management applications of next-generation devices.However,a comprehensive review of flexible thermally conductive films is rarely reported.Thus,we review recent advances of both intrinsic polymer films and polymer-based composite films with ultrahigh in-plane thermal conductivity,with deep understandings of heat transfer mechanism,processing methods to enhance thermal conductivity,optimization strategies to reduce interface thermal resistance and their potential applications.Lastly,challenges and opportunities for the future development of flexible thermally conductive films are also discussed.
基金Project supported by the Fundamental Research Fund for the Central Universities of Chinathe Research Project for Independently Cultivate Talents of Hebei Agricultural University (Grant No.ZY2023007)。
文摘Combining the mean field Pozhar-Gubbins(PG)theory and the weighted density approximation,a novel method for local thermal conductivity of inhomogeneous fluids is proposed.The correlation effect that is beyond the mean field treatment is taken into account by the simulation-based empirical correlations.The application of this method to confined argon in slit pore shows that its prediction agrees well with the simulation results,and that it performs better than the original PG theory as well as the local averaged density model(LADM).In its further application to the nano-fluidic films,the influences of fluid parameters and pore parameters on the thermal conductivity are calculated and investigated.It is found that both the local thermal conductivity and the overall thermal conductivity can be significantly modulated by these parameters.Specifically,in the supercritical states,the thermal conductivity of the confined fluid shows positive correlation to the bulk density as well as the temperature.However,when the bulk density is small,the thermal conductivity exhibits a decrease-increase transition as the temperature is increased.This is also the case in which the temperature is low.In fact,the decrease-increase transition in both the small-bulk-density and low-temperature cases arises from the capillary condensation in the pore.Furthermore,smaller pore width and/or stronger adsorption potential can raise the critical temperature for condensation,and then are beneficial to the enhancement of the thermal conductivity.These modulation behaviors of the local thermal conductivity lead immediately to the significant difference of the overall thermal conductivity in different phase regions.
基金financial support from the International S&T Cooperation Program of China (No.2015DFG31860)the National Science Foundation of China for the Key Projects (Nos.31430092 and 31110103902)
文摘Functional composite films were successfully prepared from cellulose, graphite(GP), and polyaniline(PANI) using a combination of physical and chemical processes. Cellulosewasdissolved in N-methylmorpholine-N-oxide monohydrate(NMMO) and regenerated in water to form the matrix. GP was dispersed in the NMMO solvent prior to the dissolution of the cellulose, and PANI was deposited on the surfaces of the cellulose/GP films by in situ chemical polymerization. The structures of the PANI/cellusose/GP composite films were investigated using X-ray diffraction analysis, Fourier transform infrared spectroscopy, scanning electron microscopy(SEM), and SEM/energy-dispersive X-ray spectroscopy. The mechanical strengths, thermal stabilities, conductivities, and antibacterial activities of the films were studied in detail. The results showed that GP formed a multilayered structure in the cellulose matrix and that the PANI nanoparticles were tightly wrapped on the film surface. The film thickness increased from 40 mm to 100 mm after the addition of GP and PANI. The tensile strength of the composite films was 80~107 MPa, with the elongation at break being 3%~10%. The final residual weight of the composite films was as high as 65%, and the conductivity of the composite films reached 14.36 S/m. The cellulose matrix ensured that the films were flexible and exhibited desirable mechanical properties, while the GP filler significantly improved the thermal stability of the films. The PANI coating acted as a protective layer during burning and provided good electrical conductivity and antibacterial activity against Escherichia coli; both of these characteristics were slightly enhanced by the incorporation of GP. These PANI/cellulose/GP composite films should be suitable for use in electronics, antistatic packing, and numerous other applications.
基金funding from the National Natural Science Foundation of China (22178301,21938011,51876186and 52150410417)the funding from the Natural Science Foundation of Zhejiang Province (LR21B060003 and LZ19E060002)+1 种基金grant from Science Technology Department of Zhejiang Province (2023C01182)supported by Shanxi Institute of Zhejiang University for New Materials and Chemical Industry(2022SZ-TD005)。
文摘Polymer-derived ceramic(PDC) thin films are promising wear-resistant coatings for protecting metals and carbon-carbon composites from corrosion and oxidation.However,the high pyrolysis temperature hinders the applications on substrate materials with low melting points.We report a new synthesis route for PDC coatings using initiated chemical vapor deposited poly(1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane)(pV_3D_3) as the precurs or.We investigated the changes in siloxane moieties and the network topology,and proposed a three-stage mechanism for the thermal annealing process.The rise of the connectivity number for the structures obtained at increased annealing temperatures was found with strong correlation to the enhanced mechanical properties and thermal conductivity.Our PDC films obtained via annealing at 850℃ exhibit at least 14.6% higher hardness than prior reports for PDCs synthesized below 1100℃.Furthermore,thermal conductivity up to 1.02 W(mK)^(-1) was achieved at the annealing temperature as low as 700℃,which is on the same order of magnitude as PDCs obtained above 1100℃.Using minimum thermal conductivity models,we found that the thermal transport is dominated by diffusons in the films below the percolation of rigidity,while ultra-short mean-free path phonons contribute to the thermal conductivity of the films above the percolation threshold.The findings of this work provide new insights for the development of wear-resistant and thermally conductive PDC thin films for durable protection coatings.
基金the National Natural Science Foundation of China(Nos.U21A2093 and 51973173)the Technological Base Scientific Research Projects(Highly Thermally Conductive Nonmetal Materials)+1 种基金the Fundamental Research Funds for the Central Universities,the Undergraduate Innovation&Business Program in Northwestern Polytechnical University(Nos.S202210699381 and S202210699172)the Innovation Foundation for Doctor Dissertation of Northwestern Polytechnical University(No.CX2022073).
文摘Ag nanoparticles were in-situ grown on the surface of MXene nanosheets to prepare thermally conductive hetero-structured MXene@Ag fillers.With polyvinyl alcohol(PVA)as the polymer matrix,thermally conductive MXene@Ag/PVA composite films were fabricated by the processes of solution blending,pouring,evaporative self-assembly.With the same mass fraction,MXene@Ag-III(MXene/Ag,2:1,w/w)presents more significant improvement in thermal conductivity coefficient(λ)than MXene@Ag,single MXene,Ag,simply blending MXene/Ag.MXene@Ag-III/PVA composite films show dual functions of excellent thermal conductivity and electromagnetic interference(EMI)shielding.When the mass fraction of MXene@Ag-III is 60 wt.%,the in-planeλ(λ_(∥)),through-planeλ(λ_(⊥)),EMI shielding effectiveness(EMI SE)are 3.72 and 0.41 W/(m∙K),32 dB,which are increased by 3.1,1.3,105.7 times than those of pure PVA film(0.91 and 0.18 W/(m∙K),0.3 dB),respectively.The 60 wt.%MXene@Ag-III/PVA composite film also has satisfying mechanical and thermal properties,with Young’s modulus,glass transition temperature,heat resistance index of 3.8 GPa,58.5 and 175.3℃,respectively.
基金financially supported by the Natural Science Foundation of Beijing(No.2202068)the National Natural Science Foundation of China(No.51803221)National Key Research and Development Program(No.2022YFB3603105).
文摘Polyimide-based composite films with high thermal conductivity,good mechanical property and electrical insulating performance are urgently needed in the electronics and microelectronics fields.As one of the key technical challenges to be solved,interfacial compatibility between filler and matrix plays an important role for composite film.Herein,boron nitride was modified by grafting polyimide brushes via a twostep method,and a series of thermally conductive polyimide/boron nitride composite films were prepared.Both characterization and performance results proved that the interfacial interaction and compatibility was greatly enhanced,resulting in a significant reduction in defects and interfacial thermal resistance.The interphase width of transition zone between two phases was also efficiently enlarged due to polyimide brushes grafted on filler surface.As a result,composite films based on polyimide-grafted boron nitride exhibited significantly improved properties compared with those based on pristine filler.Tensile strength can reach up to 80 MPa even if the filler content is as high as 50 wt%.The out-of-plane and in-plane thermal conductivity of composite film increased to 0.841 and 0.850 W·m^(-1)·K^(-1),respectively.In addition,thermal and dielectric properties of composite films were also enhanced to some extent.The above results indicate that surface modification by chemically grafting polymer brushes is an effective method to improve two-phase interfacial compatibility so as to prepare composite film with enhanced properties.
