Skip to main content
NCBI home page
Nano-Micro Letters logoLink to Nano-Micro Letters
. 2025 Feb 6;17:134. doi: 10.1007/s40820-025-01669-5

Functionalized Aluminum Nitride for Improving Hydrolysis Resistances of Highly Thermally Conductive Polysiloxane Composites

Mukun He 1, Lei Zhang 1, Kunpeng Ruan 1, Junliang Zhang 1, Haitian Zhang 1, Peng Lv 3, Yongqiang Guo 1, Xuetao Shi 1, Hua Guo 1,✉, Jie Kong 1, Junwei Gu 1,2,✉
PMCID: PMC11799469  PMID: 39910001

Highlights

  • Copolymer of divinylphenyl-acryloyl chloride copolymers (PDVB-co-PACl) is designed and synthesized to graft on the surface of aluminum nitride (AlN) to improve its hydrolysis resistance.

  • AlN fillers functionalized by PDVB-co-PACl with the molecular weight of 5100 g mol-1 exhibits the highest hydrolysis resistance and the lowest interfacial thermal resistance.

  • When the mass fraction of AlN@PDVB-co-PACl is 75 wt% and the grafting density of PDVB-co-PACl is 0.8 wt%, the λ for AlN@PDVB-co-PACl/PMHS composites is 1.14 W m-1 K-1 and maintains 99.1% after soaking in 90 °C deionized water for 80 h.

Supplementary Information

The online version contains supplementary material available at 10.1007/s40820-025-01669-5.

Keywords: Polymethylhydrosiloxane, Aluminum nitride, Copolymer, Thermally conductive composites

Abstract

A series of divinylphenyl-acryloyl chloride copolymers (PDVB-co-PACl) is synthesized via atom transfer radical polymerization employing tert-butyl acrylate and divinylbenzene as monomers. PDVB-co-PACl is utilized to graft on the surface of spherical aluminum nitride (AlN) to prepare functionalized AlN (AlN@PDVB-co-PACl). Polymethylhydrosiloxane (PMHS) is then used as the matrix to prepare thermally conductive AlN@PDVB-co-PACl/PMHS composites with AlN@PDVB-co-PACl as fillers through blending and curing. The grafting of PDVB-co-PACl synchronously enhances the hydrolysis resistance of AlN and its interfacial compatibility with PMHS matrix. When the molecular weight of PDVB-co-PACl is 5100 g mol−1 and the grafting density is 0.8 wt%, the composites containing 75 wt% of AlN@PDVB-co-PACl exhibit the optimal comprehensive performance. The thermal conductivity (λ) of the composite is 1.14 W m−1 K−1, which enhances by 20% and 420% compared to the λ of simply physically blended AlN/PMHS composite and pure PMHS, respectively. Meanwhile, AlN@PDVB-co-PACl/PMHS composites display remarkable hydrothermal aging resistance by retaining 99.1% of its λ after soaking in 90 °C deionized water for 80 h, whereas the λ of the blended AlN/PMHS composites decreases sharply to 93.7%.graphic file with name 40820_2025_1669_Figa_HTML.jpg

Supplementary Information

The online version contains supplementary material available at 10.1007/s40820-025-01669-5.

Introduction

With the rapid development of electronic products toward high power and integration, the problems of heat accumulation and heat dissipation become more and more prominent [1–5], which puts forward higher requirements on the thermal conductivity, insulation, and heat resistance of the thermal interface materials [6–10]. Compared with traditional thermal interface materials (such as epoxy resin, polyurethane, etc. [11]), polymethylhydrosiloxane (PMHS) is an ideal matrix for the preparation of thermal interface materials because of its excellent insulating property, aging resistance, ease of molding, and compatibility with silicon substrates [12–14]. However, it is usually necessary to fill a large number of thermally conductive fillers into PMHS to obtain high thermal conductivity [15–17]. Aluminum nitride (AlN) as a material with high thermal conductivity (λ, 170 W m−1 K−1) and excellent electrical insulation, is an ideal filler for the preparation of PMHS composites with high thermal conductivity to be used as thermally conductive polysiloxane sheets, which play an effective role in heat dissipation to ensure the normal operation of the equipment [18–20]. However, the poor compatibility of AlN with PMHS is not beneficial to heat transfer, which limits the efficient improvement of thermal conductivity for AlN/PMHS composites [21, 22]. In addition, AlN is prone to hydrolysis in humid air, thus reducing its thermal conductivity and affects the stability of electronic devices after a long period of time with a rapid decline in performance [23–25].

The existing methods to modify the surface of AlN mainly involve physical coating and chemical grafting [26–28]. Physical coating is to combine functional substances on AlN surface by physical interaction [29–31]. Ganesh et al. [32] treated AlN powder by simultaneously using phosphoric acid and aluminum dihydrogen phosphate in ethanol solution. The treated AlN powder was found to remain stable after 72 h in water. However, physical coating suffers from low binding of the surface cladding layer to AlN and poor modification effect [33–35]. Chemical grafting is to graft small molecules or polymers onto the surface of AlN through chemical reaction with the modified layer firmly bound to AlN [36–38]. Lin et al. [39] prepared AlN-VTMS/PMHS composites using PMHS as matrix and vinyl trimethoxy-silane (VTMS) modified AlN (AlN-VTMS) as thermally conductive fillers. When the mass fraction of AlN-VTMS was 60 wt%, the thermal conductivity (λ) of AlN-VTMS/PMHS composites was 0.31 W m−1 K−1, which was higher than 0.24 W m−1 K−1 for unmodified AlN/PMHS composites with the same filler amount. Yang et al. [40] prepared AlN@(PEDOT:PSS)/PU composites using polyurethane (PU) as matrix and poly(3,4-vinyldioxthiophene):polystyrene sulfonic acid (PEDOT:PSS) modified AlN (AlN@(PEDOT:PSS)) as thermally conductive fillers. When the grafting density of PEDOT:PSS was 0.5 wt% and the mass fraction of fillers was 50 wt%, the λ of AlN@(PEDOT:PSS)/PU composites was 0.76 W m−1 K−1, which was higher than 0.48 W m−1 K−1 for the unmodified AlN/PU composites applying the same amount of fillers. However, the existing chemical grafting methods cannot simultaneously improve the hydrolysis resistance of AlN and its interfacial compatibility with PMHS matrix [41].

Copolymer contains abundant chemically reactive terminal groups [42–44], which can significantly improve the interfacial compatibility with the polymer matrix when grafted on the surface of thermally conductive fillers [45–47]. Meanwhile, copolymer polymers with branched structures have the advantages of small hydrodynamic radius and low viscosity, which provide excellent processing properties [48–50]. Hu et al. [51] prepared boron nitride fillers with the surface coated by copolymer of tea polyphenol and theophylline (BN@TPP) to make thermally conductive composites with polydimethylsiloxane as matrix (BN@TPP/PDMS). The λ of BN@TPP/PDMS composites with 40 wt% of BN@TPP increased to 0.46 from 0.35 W m−1 K−1 for the composite with the same amount of unmodified BN as fillers. Zhang et al. [52] applied 3-(Trimethoxysilyl)propyl methacrylate grafted poly(methylhydrosiloxane-co-dimethylsiloxane) (MPS-g-PHMS-PDMS) by hydrosilylation reaction. Further, Al2O3@MPS-g-PMHS-PDMS composites were prepared by blending and curing with SR as matrix and MPS-g-PMHS-PDMS modified Al2O3 (Al2O3@MPS-g-PMHS-PDMS) as thermally conductive fillers. When the mass fraction of Al2O3 was 83 wt% and the grafting density of MPS-g-PMHS-PDMS was 2.5 wt%, the Al2O3@MPS-g-PMHS-PDMS/SR composites exhibited an increased λ of 1.68 W m−1 K−1 and a decreased viscosity of 73.1 Pa s from 1.42 W m−1 K−1 to 85.0 Pa s for the Al2O3/SR composites with the same amount of unmodified Al2O3, respectively.

Herein, a series of copolymers with different molecular weight were synthesized by atom transfer radical polymerization (ATRP) using tert-butyl acrylate (tBA) and divinylbenzene (DVB) as monomers, followed by acylation of the tert-butyl group to afford PDVB-co-PACl. PDVB-co-PACl was then employed to graft on the surface of AlN to prepare (AlN@PDVB-co-PACl). Further, thermally conductive AlN@PDVB-co-PACl/PMHS composites were prepared with PMHS as matrix by blending and curing. PDVB-co-PACl was characterized and analyzed by nuclear magnetic resonance (NMR), Fourier transform infrared (FT-IR) spectroscopy and size exclusion chromatography (SEC). The surface structure and morphology of AlN@PDVB-co-PACl were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). Furthermore, the effects of molecular weight, grafting density, and mass fraction of AlN@PDVB-co-PACl on the thermal conductivity, viscosity, mechanical properties, and thermal properties of AlN@PDVB-co-PACl/PMHS composites were analyzed and investigated, and the thermal conductivity mechanism was analyzed simultaneously.

Experimental Section

Synthesis of PDVB-co-PACl

In argon atmosphere, tert-butyl acrylate (tBA, 35.75 mmol), cupric bromide (CuBr, 1.26 mmol), pentamethyldivinyltriamine (PMDETA, 0.81 mmol), methyl 2-bromopropionate (3.31 mmol), divinylbenzene (DVB, 3.31 mmol), and N,N-dimethylacetamide (DMAc, 22.99 mmol) were introduced to a Schlenk bottle and stirred evenly. The mixture reacted at 60 °C for 5 h and then poured into a large amount of deionized water to precipitate the polymer. The precipitated polymer was filtered, then dissolved in tetrahydrofuran (THF), and poured into deionized water again to precipitate the polymer, and repeated four times; then dried under vacuum to obtain PDVB-co-PtBA. Then, PDVB-co-PtBA (0.41 mmol), THF (12.47 mmol), and thionyl chloride (SOCl2, 0.031 mmol) were added into a single-necked flask with stirred and sealed, and then the reaction was carried out at room temperature for 2 h before THF was removed by rotary evaporation. The solid residue was dissolved with appropriate amount of THF, which was removed using rotary evaporation to afford PDVB-co-PACl with molecular weight of 2800, 5100, and 7900 g mol−1 realized by adjusting the amount of initiator, recorded as PDVB-co-PACl-1, PDVB-co-PACl-2, and PDVB-co-PACl-3, respectively.

Preparation of AlN@PDVB-co-PACl

PDVB-co-PACl (0.031 mmol), THF (0.28 mmol), and AlN (0.61 mmol) were added into a flask and stirred evenly. The reaction was carried out at 50 °C for 2 h. The functionally-modified AlN (AlN@PDVB-co-PACl) was obtained by filtration, washing, and vacuum drying. The preparation process is shown in Fig. 1a. AlN@0.4 wt% PDVB-co-PACl, AlN@0.8 wt% PDVB-co-PACl and AlN@1.2 wt% PDVB-co-PACl were prepared by adjusting the grafting density on AlN surface.

Fig. 1.

Fig. 1

Open in a new tab

Schemes for the preparation of a AlN@PDVB-co-PACl fillers and b AlN@PDVB-co-PACl/PMHS composites

Fabrication of AlN@PDVB-co-PACl/PMHS Composites

The PMHS matrix and AlN@PDVB-co-PACl fillers were added into a beaker according to the predetermined proportion and stirred evenly, then poured into a polytetrafluoroethylene mold. After vacuum defoaming, the thermally conductive AlN@PDVB-co-PACl/PMHS composites were fabricated by heat curing at 120 °C for 2 h, as shown in Fig. 1b.

Results and Discussion

Characterization of PDVB-co-PACl

Figure 2a shows a schematic diagram of the synthetic route for PDVB-co-PACl by ATRP using tert-butyl acrylate (tBA) and divinylbenzene (DVB) as monomers, meanwhile methyl 2-bromopropionate as initiators. The first step is a copolymerization reaction to prepare PDVB-co-PtBA. The second step is a chlorination reaction, which is prepared by chlorinating PDVB-co-PtBA using the chlorination reagent sulfoxide chloride to obtain PDVB-co-PACl. The sum of m and p is the number of moles for tBA divided by the number of moles for initiators. The sum of n and q is the number of moles for DVB divided by the number of moles for initiators. Figure 2b–e’’ display the 1H NMR spectra of tBA, DVB, PDVB-co-PtBA, and PDVB-co-PACl with different molecular weights. In Fig. 2b, the peaks at 6.38, 6.09, and 5.71 ppm correspond to the protons on the vinyl group of tBA. The peak at 1.48 ppm corresponds to the proton in the tert-butyl group of tBA. In Fig. 2c, the peaks at 7.38 and 6.54 ppm correspond to protons on the benzene ring of DVB, while the peaks at 5.72 and 5.28 ppm correspond to prbbotons on the ethenyl group of DVB. After copolymerization, in Fig. 2d, the peaks at 7.45 and 7.12 ppm correspond to protons on the benzene ring of DVB, while the peaks at 5.68 and 5.14 ppm correspond to protons on the vinyl group of DVB. Additionally, the peak at 1.48 ppm corresponds to the proton on the tert-butyl group of the tBA. Meanwhile, the integrations of the peaks of (a + b):(c + d):e:f:g are 3.88:1.00:0.97:0.94:94.32, which indicates the successful synthesis of PDVB-co-PtBA. The integration of the peaks of (a + b):(c + d):e:f:g are 3.81:1.00:1.09:0.55:12.56 (Fig. 2e), 3.85:1.00:0.95:0.43:13.78 (Fig. 2e’), 3.87:1.00:0.88:0.23:14.23 (Fig. 2e’’) for PDVB-co-PACl-1, PDVB-co-PACl-2 and PDVB-co-PACl-3, respectively. According to the integration difference of the tert-butyl group before and after acylation, the acylation degree for PDVB-co-PACl-1, PDVB-co-PACl-2, and PDVB-co-PACl-3 are found to be 81%, 79%, and 75%.

Fig. 2.

Fig. 2

Open in a new tab

a Schematic diagram of synthetic route of PDVB-co-PACl. 1H NMR spectra of b tBA, c DVB, d PDVB-co-PtBA, e PDVB-co-PACl with Mn of 2800, e’ PDVB-co-PACl with Mn of 5100 and e’’ PDVB-co-PACl with Mn of 7900

Size exclusion chromatography (SEC) is further employed to characterize the molecular weight and molecular weight distribution of PDVB-co-PACl (Fig. S1). The Mn of PDVB-co-PACl-1, PDVB-co-PACl-2, and PDVB-co-PACl-3 are 2800, 5100, and 7900 g mol−1, respectively. The SEC curves display relatively wide polydispersity (Ð) of 2.04, 1.94, and 2.17, respectively, which is mainly due to the fact that PDVB-co-PACl contains a large number of side chains. Figure S2 shows the FT-IR spectra of tBA, DVB, PDVB-co-PtBA and PDVB-co-PACl. After ATRP polymerization, the characteristic peak of tert-butyl group in PDVB-co-PtBA appears at 2960 cm−1, and the characteristic peak of carbonyl in tBA appears at 1736 cm−1. And the characteristic peaks of benzene ring skeleton vibration in DVB appear at 1600, 1580, 1500, and 1450 cm−1, indicating the successful synthesis of PDVB-co-PtBA. More importantly, the characteristic peak of carbon group in the chlorination group for PDVB-co-PACl appears at 1755 cm−1, which in combination with 1H NMR spectra and SEC spectra indicate the successful conduct of the chlorination reaction and the successful synthesis of PDVB-co-PACl.

Characterization and Hydrolysis Resistance of AlN@PDVB-co-PACl

FT-IR, XPS, TGA are applied to investigate the structure and physical properties of AlN@PDVB-co-PACl. Figure 3a shows the FT-IR spectra of AlN and AlN@PDVB-co-PACl. Both AlN and AlN@PDVB-co-PACl show strong characteristic absorption peak at 670 cm−1, corresponding to the stretching vibration of the AlN bond. Compared with AlN, AlN@PDVB-co-PACl shows a characteristic absorption peak of the carbonyl group at 1730 cm−1, corresponding to the carbonyl group in PDVB-co-PACl, indicating that PDVB-co-PACl is successfully grafted on the surface of AlN. At the same time, the characteristic absorption peak of AlN@PDVB-co-PACl at 670 cm−1 for the AlN bond broadens and the hydroxyl peak decreases. This is mainly attributed to the formation of covalent bonds by condensation reactions between the hydroxyl groups on the AlN surface and the chloride groups [53]. Figure 3b displays the XPS spectra of AlN and AlN@PDVB-co-PACl, the corresponding element content is shown in Fig. 3b’, and the corresponding O 1s spectrum is shown in Fig. S3. Compared with AlN, the content of C for AlN@PDVB-co-PACl increases, while the content of Al, O, and N decreases, mainly due to the higher C content of PDVB-co-PACl on AlN@PDVB-co-PACl surface. In addition, the O 1s characteristic peaks of AlN (Fig. S3a) appearing at 532.2 and 531.6 eV corresponds to Al-O–H and Al-O-N bonds, respectively. After the grafting of PDVB-co-PACl, the O 1s characteristic peaks of AlN@PDVB-co-PACl (Fig. S3b) appearing at 533.1, 531.8, and 531.3 eV correspond to the C = O, C-O, and Al-O-N bonds, respectively. The appearance of the C = O bond and the disappearance of the Al–O–H bond on the AlN surface indicate that the condensation reaction between the acyl chloride groups of PDVB-co-PACl and the hydroxyl groups successfully grafted on the AlN surface.

Fig. 3.

Fig. 3

Open in a new tab

a FT-IR spectra, b XPS spectra, b’ elements concentration and c TGA curves of AlN and AlN@PDVB-co-PACl. d pH and e XRD spectra of AlN and AlN@PDVB-co-PACl before and after hydrolysis. TEM images of f AlN and f’-f’’’ AlN@PDVB-co-PACl with different grafting density

As shown in Fig. 3c, there is only a slight mass loss of AlN before 350 °C and essentially no mass loss after 350 °C showing 99.9 wt% residual, which is mainly attributed to the evaporation of adsorbed water molecules on the AlN surface and the loss of hydroxyl groups. After grafting PDVB-co-PACl, the AlN@0.4 wt% PDVB-co-PACl, AlN@0.8 wt% PDVB-co-PACl and AlN@1.2 wt% PDVB-co-PACl exhibit weight loss at 100 ~ 460 °C. It is mainly attributed to the breakage of the covalent bond between AlN and PDVB-co-PACl and the cleavage of PDVB-co-PACl. However, no mass loss is observed for AlN@PDVB-co-PACl after 460 °C. In addition, AlN@PDVB-co-PACl presents 99.6, 99.2, and 98.8 wt% loss weight, suggesting the grafting density of PDVB-co-PACl are 0.4, 0.8, and 1.2 wt%, respectively. Figure 3d shows the pH values at different time for the mixture of AlN and AlN@PDVB-co-PACl in deionized water at 40 °C. As observed, the pH for AlN rise gradually and maintain at around 10.5 after 2 h. In contrast, the pH for AlN@PDVB-co-PACl barley changes and keeps constant between 6.8 and 7.2. In addition, PDVB-co-PACl prevents water molecules from penetrating into the internal AlN, which effectively prevents its hydrolysis. Figure 3e shows the XRD curves of AlN and AlN@PDVB-co-PACl before and after hydrolysis. The strong diffraction peaks at 33.3°, 36.1°, 37.8°, 49.8°, 59.8°, 66.0°, 69.8°, 71.7°, and 72.8° for AlN and AlN@PDVB-co-PACl correspond to the (100), (002), (101), (102), (110), (103), and (112) crystal planes, respectively. After hydrolysis, strong diffraction peaks at 18.6°, 21.8°, and 41.2° for AlN correspond to the (001), (110), and (201) crystal planes for Al(OH)3, respectively, indicating that AlN reacts with H2O. In contrast, no Al(OH)3 diffraction peaks in the XRD pattern of AlN@PDVB-co-PACl are observed after hydrolysis test, also indicating no obvious hydrolysis occurs for AlN@PDVB-co-PACl. This is ascribed to hydrophobic groups of benzene ring and abundant branched chain network in PDVB-co-PACl, which increase its hydrophobicity (Fig. S4). The above results demonstrate that the grafting of PDVB-co-PACl significantly increase the hydrolysis resistance of AlN. TEM is then applied to observe the surface morphology for AlN and AlN@PDVB-co-PACl (Fig. 3f–f’’’). As observed, the surface of AlN is smooth and free with other substances. By comparison, a grafting layer of PDVB-co-PACl is visible on the surface of AlN@PDVB-co-PACl, with the thickness increasing from 14.8 to 30.1 to 47.0 ~ 65.9 nm as the grafting density increases from 0.4 to 0.8 to 1.2 wt%. Because the thickness of the grafting layer becomes thicker with the increase in grafting density, but too much grafting can lead to agglomeration resulting in uneven thickness.

Thermal Conductivity of AlN@PDVB-co-PACl/PMHS Composites

The effects of different molecular weight and grafting density AlN@PDVB-co-PACl, as well as mass fraction AlN@PDVB-co-PACl on thermal conductivity (λ) and interfacial thermal resistance (ITR) are investigated. Figure 4a–b and 4a’–b’ shows the λ and ITR of AlN@PDVB-co-PACl/PMHS composites at different molecular weights of PDVB-co-PACl. Under the same grafting density of PDVB-co-PACl and the mass fraction of AlN@PDVB-co-PACl, the λ of AlN@PDVB-co-PACl/PMHS composite first increases and then decreases while the corresponding ITR first decreases and then increases with the increase in molecular weight of PDVB-co-PACl. When the molecular weight and grafting density of PDVB-co-PACl are 5100 g mol−1 and 0.8 wt% and the mass fraction of AlN@PDVB-co-PACl is 75 wt%, respectively, the λ of AlN@PDVB-co-PACl/PMHS composites reached the maximum of 1.14 W m−1 K−1, and the corresponding ITR is 1.36 × 10–7 m2 K W−1. Superior to the λ and ITR of AlN@PDVB-co-PACl/PMHS at the same mass fraction of AlN with PDVB-co-PACl molecular weight of 2800 g mol−1 (1.08 W m−1 K−1, 1.42 × 10–7 m2 K W−1) and PDVB-co-PACl molecular weight of 7900 g mol−1 (1.07 W m−1 K−1, 1.45 × 10–7 m2 K W−1). This is because PDVB-co-PACl-1 with the Mn of 2800 g mol−1 has fewer acyl chloride and vinyl functional groups, resulting in weak chemical bonding between AlN and PMHS matrix. Meanwhile, the relative shorter chains are difficult to form effective physical entanglements with the PMHS matrix. When the Mn of PDVB-co-PACl-2 is 5100 g mol−1, the length of main chains and branched chains of PDVB-co-PACl-2 is moderate, and it is easy to form physical entanglements with PMHS matrix. However, as the Mn increases further to 7900 g mol−1, the longer polymer chains make it difficult to diffuse within PMHS matrix to make AlN disperse well, which is not conducive to the efficient formation of AlN-AlN thermally conductive pathways. Therefore, PDVB-co-PACl-2 with the Mn of 5100 g mol−1 is selected for the following study. Figure 4c–c’ shows the λ and ITR of AlN@PDVB-co-PACl/PMHS composites with different PDVB-co-PACl grafting density. The λ of AlN@PDVB-co-PACl/PMHS composites tend to increase and then decrease with the increase in PDVB-co-PACl grafting density, and the corresponding ITR tends to decrease and then increase. When the grafting density of PDVB-co-PACl is 0.8 wt% and the mass fraction is 75 wt%, the λ of AlN@0.8 wt% PDVB-co-PACl/PMHS composites reaches the maximum, which is 1.14 W m−1 K−1, and the corresponding ITR is 1.36 × 10–7 m2 K W−1. It is better than the λ and corresponding ITR (1.12 W m−1 K−1 and 1.40 × 10–7 2 K W−1) of AlN@0.4 wt% PDVB-co-PACl/PMHS as well as λ and corresponding ITR (1.10 W m−1 K−1 and 1.43 × 10–7 m2 K W−1) of AlN@1.2 wt% PDVB-co-PACl/PMHS. When the grafting density of PDVB-co-PACl is 0.8 wt%, PDVB-co-PACl formed a complete and uniform thickness grafting layer on the AlN surface (Fig. 3f’’), which effectively improved the interfacial compatibility between AlN and PMHS matrix, reduced ITR, and conferred a higher λ to AlN@PDVB-co-PACl/PMHS composites. In contrast, the grafting layer of PDVB-co-PACl on the AlN surface is incomplete when the grafting density of PDVB-co-PACl is low (0.4 wt%, Fig. 3f’), and the thickness of the grafting layer of PDVB-co-PACl is not uniform when the grafting density is high (1.2 wt%, Fig. 3f’’’). All of them are unfavorable to the efficient interfacial bonding between AlN and PMHS matrix, and cannot improve the interfacial compatibility between AlN and PMHS matrix efficiently, and the λ of the corresponding PMHS composites is low. In summary, when the grafting density of PDVB-co-PACl is 0.8 wt%, AlN@PDVB-co-PACl/PMHS with the same amount of AlN has the best thermal conductivity, so 0.8 wt% is selected as the optimal grafting density.

Fig. 4.

Fig. 4

Open in a new tab

a-b λ and a’-b’ ITR of AlN@PDVB-co-PACl/PMHS composites with different molecular mass PDVB-co-PACl. c λ and c’ ITR of AlN@PDVB-co-PACl/PMHS composites with different grafting density of PDVB-co-PACl. d λ of AlN/PMHS and AlN@PDVB-co-PACl/PMHS composites. e Curves of logarithm of bound PMHS versus inverse temperature. f Curves of viscosity versus shear rate for AlN@PDVB-co-PACl/PMHS composites

Figure 4d shows λ of AlN/PMHS and AlN@PDVB-co-PACl/PMHS composites with different mass fraction. When the mass fraction of AlN@PDVB-co-PACl is 75 wt%, AlN@PDVB-co-PACl/PMHS composites have the best thermal conductivity, λ is 1.14 W m−1 K−1 and ITR is 1.36 × 10–7 m2 K W−1, which is better than that of λ and ITR for 75 wt% AlN/PMHS (0.95 W m−1 K−1 and 1.67 × 10–7 m2 K W−1). The λ of AlN/PMHS and AlN@PDVB-co-PACl/PMHS composites increases with the increase in the mass fraction of AlN. When the mass fraction of AlN@PDVB-co-PACl is 85 wt%, AlN@PDVB-co-PACl/PMHS composites have the best thermal conductivity, λ is 1.89 W m−1 K−1, which is better than that of λ for AlN/PMHS (1.58 W m−1 K−1). As the filler dosage increases, the overlapping of AlN in the PMHS matrix becomes more pronounced, facilitating the formation of continuous thermal conduction pathways. The thermal conductivity composites with AlN as fillers prepared by researchers over the most years are compared in Table S1. The AlN@PDVB-co-PACl/PMHS composites prepared from PDVB-co-PACl modified AlN have optimum thermal conductivity.

The effect of PDVB-co-PACl grafting on the compatibility of the AlN/PMHS interface is further investigated by testing the binding amount (β) of AlN and PMHS on the AlN@PDVB-co-PACl surface, and calculating the binding energy (Ea, Eq. S5) of AlN and AlN@PDVB-co-PACl to PMHS. The curves plot of the logarithmic versus inverse temperature fit to the amount of PMHS bound to the AlN surface is shown in Fig. 4e, and based on its slope the Ea of AlN and AlN@PDVB-co-PACl with PMHS can be calculated (Table S2). From Table S2, the interfacial binding energy of AlN@PDVB-co-PACl/PMHS is 17.13 J mol−1, which is higher than that of AlN/PMHS (6.73 J mol−1), indicating that AlN@PDVB-co-PACl/PMHS has relatively better interfacial compatibility. Because PDVB-co-PACl is a branched structure, it contains a large number of reactive vinyl groups at the end of the main chains and branched chains, which form bonds with PMHS matrix through silica-hydrogen addition reaction. Moreover, the PDVB-co-PACl contains a large number of branched chains, which are easier to diffuse and tangle with PMHS matrix, resulting in AlN@PDVB-co-PACl/PMHS better interface compatibility and greater interface binding energy. AlN@PDVB-co-PACl/PMHS composites not only incorporate the high thermal conductivity of AlN itself but also realize further performance enhancement through the modification of PDVB-co-PACl. With the increasing demand for efficient thermal management in modern electronic devices, new energy vehicles and aerospace industries, AlN@PDVB-co-PACl/PMHS composites will undoubtedly play an increasingly important role in the field of thermal interface materials and lead the new development of thermal management technology in the future. Figure 4f shows the viscosity versus shear rate curves for AlN@PDVB-co-PACl composites with different mass fraction. At the same shear rate, the viscosity of AlN@PDVB-co-PACl/PMHS composites increases with the increase in the mass fraction of fillers. Because PMHS molecular chains are flexible, intermolecular forces are small, and relative slip is easy [54]. In contrast, AlN is an irregular rigid solid, and the relative slip between AlN and PMHS molecular chains as well as AlN and AlN is difficult, which is not favorable for the flow of the composite system [55]. Therefore, the viscosity of AlN@PDVB-co-PACl/PMHS gradually increased with the increase in the mass fraction of fillers. When the mass fraction of AlN@PDVB-co-PACl is high (85 and 75 wt%), the viscosity of AlN@PDVB-co-PACl/PMHS composites show obvious shear thinning phenomenon [56]. The reason is that the molecular chains in the AlN@PDVB-co-PACl/PMHS are highly entangled with each other and the intermolecular forces are high when the system is not subjected to shear or at a low shear rate. And the molecular chains are in the dynamic equilibrium of entanglement and disentanglement, which is macroscopically manifested by the higher viscosity of the system. At high shear rate, the polymer system moves toward unentanglement due to the action of high shear force, and the degree of entanglement is small. Therefore, the intermolecular force decreases, the intermolecular slip is easy, and the macroscopic system viscosity decreases.

Mechanical and Thermal Properties of AlN@PDVB-co-PACl/PMHS Composites

Figure 5a shows the stress–strain curves of AlN@PDVB-co-PACl/PMHS composites. The stress of PMHS and AlN@PDVB-co-PACl/PMHS composites under tension increases linearly with the increasing strain until the PMHS and AlN@PDVB-co-PACl/PMHS composites break. The stress decreases rapidly after reaching the maximum value without any obvious yielding process. Figure 5a’–a’’ shows the tensile strength and elongation at break of AlN@PDVB-co-PACl/PMHS composites at different mass fraction of AlN@PDVB-co-PACl. Both tensile strength and elongation at break of AlN@PDVB-co-PACl/PMHS first increase and then decrease with the increasing amount of fillers. When the mass fraction of AlN@PDVB-co-PACl is 85 wt%, the tensile strength of AlN@PDVB-co-PACl/PMHS composites is 0.68 MPa, which is higher than that of pure PMHS (0.24 MPa), and the elongation at break is 7.9%, which is much lower than the elongation at break of pure PMHS (42%). When the mass fraction of AlN@PDVB-co-PACl is 75 wt%, the elongation at break and tensile strength of AlN@PDVB-co-PACl/PMHS are 53% and 1.81 MPa, respectively, which are both higher than that of pure PMHS (42% and 0.24 MPa). Both PDVB-co-PACl main chains and branched chains of end vinyl groups on the AlN@PDVB-co-PACl surface can participate in the curing of PMHS matrix, which enhances the mechanical properties of AlN@PDVB-co-PACl/PMHS composites. However, when the mass fraction of AlN@PDVB-co-PACl is too high (85 wt%), a large number of defects in the PMHS matrix, which significantly reduces its tensile strength and elongation at break.

Fig. 5.

Fig. 5

Open in a new tab

a Stress–strain curves, a’ tensile strength, a’’ elongation at break and b hardness of AlN@PDVB-co-PACl/PMHS composites. c DSC curves, c’ Tg and d TGA curves of AlN@PDVB-co-PACl/PMHS composites. e Water absorption and f λ of AlN/PMHS and AlN@PDVB-co-PACl/PMHS composites before and after the aging test

Figure 5b shows the hardness of AlN@PDVB-co-PACl/PMHS with different mass fraction of AlN@PDVB-co-PACl. As exhibited, the hardness improves with the increase in fillers. When the mass fraction of AlN@PDVB-co-PACl reaches 85 wt%, the hardness of AlN@PDVB-co-PACl/PMHS increased to the maximum of 87 HA from that of the pure PMHS matrix (36 HA). This is because AlN is a diamond-like structure, its deformation under pressure is very small [57], reducing the degree of deformation of AlN@PDVB-co-PACl/PMHS composites under pressure and revealing a greater hardness. Meanwhile, functional groups on the AlN@PDVB-co-PACl surface can participate in the curing of the PMHS matrix, which increases the density of the PMHS crosslinked network [58], resulting in increased hardness of the AlN@PDVB-co-PACl/PMHS composites. Figure 5c–c’ shows the DSC curves and corresponding glass transition temperatures (Tg) of the AlN@PDVB-co-PACl/PMHS composites at different mass fraction of AlN@PDVB-co-PACl. The Tg of AlN@PDVB-co-PACl/PMHS is proportional to the amount of fillers. When the mass fraction of AlN@PDVB-co-PACl is 85 wt%, the Tg of AlN@PDVB-co-PACl/PMHS is − 41.6 °C, which is 4.2 °C higher than that of pure PMHS matrix. The AlN@PDVB-co-PACl surface contains a large number of main chains and branched chains of end vinyl, which can participate in the curing reaction of PMHS matrix, increasing the cross-linking density of AlN@PDVB-co-PACl/PMHS composites. Therefore, the movement of PMHS molecular chains is limited, and the Tg of AlN@PDVB-co-PACl/PMHS is increased with the increasing amount of fillers. Figure 5d shows the TGA curves of AlN@PDVB-co-PACl/PMHS composites at different mass fraction of AlN@PDVB-co-PACl. Pure PMHS and AlN@PDVB-co-PACl/PMHS begin to lose weight at around 380 °C, and the mass equilibrates at around 560 °C, which is mainly attributed to thermal cleavage of the PMHS molecular chains at this temperature. In addition, when the mass fraction of AlN@PDVB-co-PACl is 55, 65, 75, and 85 wt%, the residual masses of AlN@PDVB-co-PACl/PMHS composites are 63.1, 71.6, 79.2, and 86.7 wt%, respectively, which are corresponding to the amount of fillers. The T5 of AlN@PDVB-co-PACl/PMHS (corresponding temperature at a weight loss of 5 wt%, Fig. S5) is proportional to the amount of fillers. When the mass fraction of AlN@PDVB-co-PACl is 85 wt%, the T5 of AlN@PDVB-co-PACl/PMHS is 449.2 °C, which is 61.5 °C higher than that of pure PMHS matrix (387.7 °C). Because a large number of main chains and branched chains of end vinyl on the AlN@PDVB-co-PACl surface can participate in the curing reaction of PMHS matrix. It helps to increase the cross-linking density of the curing network and improve the heat resistance of AlN@PDVB-co-PACl/PMHS composites.

Figure 5e illustrates the water absorption of AlN/PMHS and AlN@PDVB-co-PACl/PMHS composites when the mass fraction of AlN or AlN@PDVB-co-PACl is 75 wt%. The water absorption of AlN/PMHS and AlN@PDVB-co-PACl/PMHS composites increase with the extension of time, and reach saturation after 80 h. Because the rapid diffusion of water from the composites surface to the interface of AlN/PMHS or AlN@PDVB-co-PACl/PMHS increases the water absorption. When the water absorption at the internal interface of the composites tends to be saturated, the water absorption rate is gradually stable. After impregnating at room temperature for 80 h, the water absorption of AlN@PDVB-co-PACl/PMHS is 0.22%, which is significantly lower than that of AlN/PMHS (0.38%). Compared with AlN/PMHS, AlN@PDVB-co-PACl/PMHS composites have relatively better interfacial compatibility, with relatively fewer defects and pores at the interface, which is more conducive to hindering the entry of water molecules. In addition, PDVB-co-PACl results in a higher molecular chain network density at the interface of AlN@PDVB-co-PACl/PMHS composites, which makes it more difficult for water molecules to diffuse. This in turn provides the AlN@PDVB-co-PACl/PMHS composites with relatively lower water absorption and relatively better water resistance. Figure 5f shows the λ before and after the aging test of AlN/PMHS and AlN@PDVB-co-PACl/PMHS composites (80 h in 90 °C deionized water) when the mass fraction of AlN or AlN@PDVB-co-PACl is 75 wt%. After the aging test, the λ of AlN/PMHS composites decreases from 0.95 W to 0.89 W m−1 K−1. In contrast, the λ of AlN@PDVB-co-PACl/PMHS composites retain relatively constant of 1.13 compared to 1.14 W m−1 K−1 about retaining 99.1%, whereas the λ of the blended AlN/PMHS composites decreases sharply to 93.7%. Because the main chains and branched chains on the AlN@PDVB-co-PACl surface contain a large amount of reactive vinyl, which participate in PMHS matrix curing. Results in a higher molecular chain network density at the interface of AlN@PDVB-co-PACl/PMHS, and the more stable interface under hot and humid conditions. Therefore, the AlN@PDVB-co-PACl/PMHS composites have better aging resistance and more stable thermal conductivity. At the same time, the excellent aging resistance properties of AlN@PDVB-co-PACl/PMHS composites ensure the stability of the material in the long-term use of the process, extending the life of electronic equipment.

Conclusions

The copolymer of PDVB-co-PACl is synthesized by ATRP using tBA and DVB as the monomer. PDVB-co-PACl is utilized to graft on the surface of spherical AlN to prepare AlN@PDVB-co-PACl. PMHS is then used as the matrix to prepare thermally conductive AlN@PDVB-co-PACl/PMHS composites through blending and curing. The grafting of PDVB-co-PACl synchronously enhances the hydrolysis resistance of AlN and its interfacial compatibility with PMHS matrix. When the molecular weight of PDVB-co-PACl is 5100 g mol−1 and the grafting density is 0.8 wt%, the composites containing 75 wt% of AlN@PDVB-co-PACl exhibit the optimal comprehensive performance. The λ of the composites is 1.14 W m−1 K−1, which enhances by 20% and 420% compared to the λ of simply physically blended AlN/PMHS composites and pure PMHS, respectively. Meanwhile, AlN@PDVB-co-PACl/PMHS composites display remarkable hydrothermal aging resistance by retaining 99.1% of its λ after soaking in 90 °C deionized water for 80 h, whereas the λ of the blended AlN/PMHS composites decreases sharply to 93.7%.

Supplementary Information

Below is the link to the electronic supplementary material.

Supplementary file1 (DOCX 2770 KB) (2.7MB, docx)

Acknowledgements

The authors are grateful for the support from the National Natural Science Foundation of China (52473083 and 52403112), the Technological Base Scientific Research Projects (Highly Thermal conductivity Nonmetal Materials), the Natural Science Basic Research Program of Shaanxi (2024JC-TBZC-04), the Shaanxi Province Key Research and Development Plan Project (2023-YBGY-461), the Innovation Capability Support Program of Shaanxi (2024RS-CXTD-57), the Natural Science Foundation of Chongqing, China (2023NSCQ-MSX2547), the Fundamental Research Funds for the Central Universities (D5000240077 and D5000240067), the Innovation Foundation for Doctor Dissertation of Northwestern Polytechnical University (CX2024094), the Analytical & Testing Center of Northwestern Polytechnical University for FT-IR, XRD and TEM tests performed in this work.

Authors’ Contributions

Mukun He was involved in investigation, visualization, original draft writing. Lei Zhang was involved in investigation, original draft writing. Kunpeng Ruan contributed to conceptualization, review, funding acquisition. Junliang Zhang, Xuetao Shi, Jie Kong, and Peng Lv done review. Haitian Zhang helped in visualization. Yongqiang Guo helped in funding acquisition. Hua Guo helped in visualization, supervision. Junwei Gu helped in review, supervision, funding acquisition.

Declarations

Conflict of Interest

The authors declare no interest conflict. They have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. Junwei Gu is an editorial board member for Nano-Micro Letters and was not involved in the editorial review or the decision to publish this article. All authors declare that there are no competing interests.

Footnotes

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Mukun He and Lei Zhang contributed equally to this work.

Contributor Information

Hua Guo, Email: gh@nwpu.edu.cn.

Junwei Gu, Email: gjw@nwpu.edu.cn, Email: nwpugjw@163.com.

References

  • 1.K. Wu, Z. Dou, S. Deng, D. Wu, B. Zhang et al., Mechanochemistry-mediated colloidal liquid metals for electronic device cooling at kilowatt levels. Nat. Nanotechnol. 20, 104–111 (2025). 10.1038/s41565-024-01793-0 [DOI] [PubMed] [Google Scholar]
  • 2.J. Wu, Y. Wang, P. Song, M. Sang, Z. Fan et al., Asymmetric aramid aerogel composite with durable and covert thermal management via janus heat transfer structure. Nano Lett. 24, 14020–14027 (2024). 10.1021/acs.nanolett.4c03652 [DOI] [PubMed] [Google Scholar]
  • 3.Y. Guo, S. Wang, H. Zhang, H. Guo, M. He et al., Consistent thermal conductivities of spring-like structured polydimethylsiloxane composites under large deformation. Adv. Mater. 36, 2404648 (2024). 10.1002/adma.202404648 [DOI] [PubMed] [Google Scholar]
  • 4.P. Saechan, I. Dhuchakallaya, F.A.Z.M. Saat, Thermal performance improvement of forced-air cooling system combined with liquid spray for densely packed batteries of electric vehicle. Eng. Sci. 24, 886 (2023). 10.30919/es886 [Google Scholar]
  • 5.S. Sirikasemsuk, P. Vengsungnle, S. Eiamsa-ard, P. Naphon, Thermal management of prismatic LiFePO4 battery module with inversed-zigzag channeled ferrofluid flows. Eng. Sci. 27, 1017 (2024). 10.30919/es1017 [Google Scholar]
  • 6.K. Zhang, J. Zhang, L. Dang, Y. Wu, M. He et al., Highly intrinsic thermal conduction and low dielectric constant of liquid crystalline epoxy resins with fluorine-containing semi-IPN structures. Sci. China Chem. (2025). 10.1007/s11426-024-2504-y [Google Scholar]
  • 7.J. Yun, Y. Yoo, H. Kim, Y. Song, Recent progress in thermal management for flexible/wearable devices. Soft Sci. 3, 12 (2023). 10.20517/ss.2023.04 [Google Scholar]
  • 8.X. Kong, Y. Chen, R. Yang, Y. Wang, Z. Zhang et al., Large-scale production of boron nitride nanosheets for flexible thermal interface materials with highly thermally conductive and low dielectric constant. Compos. Part B-Eng. 271, 111164 (2024). 10.1016/j.compositesb.2023.111164 [Google Scholar]
  • 9.Z. Wu, X. Wang, S.H.K. Annamareddy, S. Gao, Q. Xu et al., Dielectric properties and thermal conductivity of polyvinylidene fluoride synergistically enhanced with silica@multi-walled carbon nanotubes and boron nitride. ES Mater. Manufact. 22, 847 (2023). 10.30919/esmm5f847 [Google Scholar]
  • 10.M. Arun Kumar, L.S. Jayakumari, Ramji Chandran, Enhanced mechanical and electrical properties of styrene butadiene rubber nanocomposites with graphene platelet nano-powder. J. Polym. Mater. 40, 141–156 (2023). 10.32381/JPM.2023.40.3-4.2 [Google Scholar]
  • 11.J. Zhang, L. Dang, F. Zhang, K. Zhang, Q. Kong et al., Effect of the structure of epoxy monomers and curing agents: toward making intrinsically highly thermally conductive and low-dielectric epoxy resins. JACS Au 3, 3424–3435 (2023). 10.1021/jacsau.3c00582 [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 12.Y. Bai, X. Wang, X. Wang, Q. Li, K. Yang et al., Study the intermolecular interaction of polymethylhydrosiloxane modifying acrylic resin and their application on anticorrosion area. Prog. Org. Coat. 195, 108632 (2024). 10.1016/j.porgcoat.2024.108632 [Google Scholar]
  • 13.Y. Xiao, J. Wu, Y. Zhang, Recent advances in the design, fabrication, actuation mechanisms and applications of liquid crystal elastomers. Soft Sci. 3, 11 (2023). 10.20517/ss.2023.03 [Google Scholar]
  • 14.Y. Guo, H. Qiu, K. Ruan, S. Wang, Y. Zhang et al., Flexible and insulating silicone rubber composites with sandwich structure for thermal management and electromagnetic interference shielding. Compos. Sci. Technol. 219, 109253 (2022). 10.1016/j.compscitech.2021.109253 [Google Scholar]
  • 15.M. Yang, Y. Pang, J. Li, W. Zhou, L. Ren et al., Grafted alkene chains: triggers for defeating contact thermal resistance in composite elastomers. Small 20, 2305090 (2024). 10.1002/smll.202305090 [DOI] [PubMed] [Google Scholar]
  • 16.M. He, J. Hu, H. Yan, X. Zhong, Y. Zhang et al., Shape anisotropic chain-like CoNi/polydimethylsiloxane composite films with excellent low-frequency microwave absorption and high thermal conductivity. Adv. Funct. Mater. 2316691, (2024). 10.1002/adfm.202316691 [Google Scholar]
  • 17.J. Wie, M. Kim, J. Kim, Enhanced thermal conductivity of a polysilazane-coated A-BN/epoxy composite following surface treatment with silane coupling agents. Appl. Surf. Sci. 529, 147091 (2020). 10.1016/j.apsusc.2020.147091 [Google Scholar]
  • 18.C. Perez, A.J. McLeod, M.E. Chen, S.I. Yi, S. Vaziri et al., High thermal conductivity of submicrometer aluminum nitride thin films sputter-deposited at low temperature. ACS Nano 17, 21240–21250 (2023). 10.1021/acsnano.3c05485 [DOI] [PubMed] [Google Scholar]
  • 19.S. Rao, X. Zeng, X. Cheng, J. Fan, D. He et al., Damping, soft, and thermally conductive composite elastomer via introducing bottlebrush chains. Chem. Eng. J. 474, 145847 (2023). 10.1016/j.cej.2023.145847 [Google Scholar]
  • 20.J. Du, W. Dai, H. Kou, P. Wu, W. Xing et al., AlN coatings with high thermal conductivity and excellent electrical properties for thermal management devices. Ceram. Int. 49, 16740–16752 (2023). 10.1016/j.ceramint.2023.02.035 [Google Scholar]
  • 21.N.T. Thuong, N.B. Lam, P.A. Son, N.B. Chien, N.P.D. Linh et al., Preparation and characterization of thermally conductive high impact polystyrene/AlN composite. Int. J. Polym. Sci. 2024, 2723981 (2024). 10.1155/2024/2723981 [Google Scholar]
  • 22.W. Yang, J. Kim, J. Kim, Improving thermal conductivity of epoxy composite by three-dimensional filler network constructed with two different diameters aluminum nitride and cellulose nanofiber. Cellulose 31, 2461–2474 (2024). 10.1007/s10570-024-05737-8 [Google Scholar]
  • 23.A. Mukhopadhyay, A. Pal, S. Sarkar, C.M. Megaridis, Laser-tuned surface wettability modification and incorporation of aluminum nitride (AlN) ceramics in thermal management devices. Adv. Funct. Mater. 34, 2313141 (2024). 10.1002/adfm.202313141 [Google Scholar]
  • 24.W.-K. Li, R.-Z. Zhang, J.-M. Wu, L. Guo, W.-H. Cai et al., Optimizing AlN hydrolysis process to fabricate coated modified powders for improving the properties of Si3N4/SiAlON ceramics prepared by Vat Photopolymerization. Addit. Manuf. 94, 104460 (2024). 10.1016/j.addma.2024.104460 [Google Scholar]
  • 25.F. Lü, R. Yang, H. Ruan, S. Wang, X. Yu, Effect of anti-hydrolysis AlN Microspheres on the electrical insulation and thermal conductivity of PMIA paper. IEEE T. Dielect. El. In. 30, 1674–1680 (2023). 10.1109/TDEI.2023.3243194 [Google Scholar]
  • 26.B.P. Sahoo, D. Das, P. Rath, S. Chakrabarty, S. Roy et al., Improving reinforcement properties of CNTs in aluminium matrix composites: a case of surface modification through AlN nano-particle grafting. Surf. Interfaces 36, 102571 (2023). 10.1016/j.surfin.2022.102571 [Google Scholar]
  • 27.X. Wang, Y. He, X. Xiao, W. Zhao, J. Leng, High-Tg shape memory polyimide composites with “spot-plane” directional thermally conduction structure based on AlN nanoparticles and acidified graphene. Compos. Struct. 330, 117846 (2024). 10.1016/j.compstruct.2023.117846 [Google Scholar]
  • 28.M.A. Saad, M.A.S. Sakr, N.H. Teleb, O.H. Abd-Elkader, H. Abdelsalam et al., Chemically functionalized AlN quantum dots for effective sensing and removal of methanol, ethanol, and formaldehyde: A first principle study. Chem. Phys. Impact 8, 100620 (2024). 10.1016/j.chphi.2024.100620 [Google Scholar]
  • 29.J. Hu, Z. Wei, B. Ge, L. Zhao, K. Peng et al., AlN micro-honeycomb reinforced stearic acid-based phase-change composites with high thermal conductivity for solar-thermal-electric conversion. J. Mater. Chem. A 11, 10727–10737 (2023). 10.1039/d2ta08748k [Google Scholar]
  • 30.A. Bekeshev, A. Mostovoy, A. Shcherbakov, L. Tastanova, M. Akhmetova et al., The influence of pristine and aminoacetic acid-treated aluminum nitride on the structure, curing processes, and properties of epoxy nanocomposites. J. Compos. Sci. 7, 482 (2023). 10.3390/jcs7120482 [Google Scholar]
  • 31.Z. Wang, Q. An, L. Jiao, P. Lu, Y. Qu et al., Preparation and properties of fluorosilicone composites with thermal conductivity and chemical resistance through modification of filler and matrix. Polym. Degrad. Stabil. 225, 110823 (2024). 10.1016/j.polymdegradstab.2024.110823 [Google Scholar]
  • 32.I. Ganesh, N. Thiyagarajan, G. Sundararajan, S.M. Olhero, J.M.F. Ferreira, A non-aqueous processing route for phosphate-protection of AlN powder against hydrolysis. J. Eur. Ceram. Soc. 28, 2281–2288 (2008). 10.1016/j.jeurceramsoc.2008.02.025 [Google Scholar]
  • 33.Y. Wang, S. Wang, G. Zhu, J. Xie, Z. Chen et al., Optimizing hydrolysis resistance and dispersion characteristics via surface modification of aluminum nitride powder coated with PVP-b-P(St-alt-ITA) copolymer. Molecules 27, 2457 (2022). 10.3390/molecules27082457 [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 34.M. Li, J. Ai, Z. Wang, Z. Xue, L. Cheng et al., HPMA modified aluminium nitride powder for aqueous tape casting of AlN ceramic substrates. J. Adv. Ceram. 12, 1701–1711 (2023). 10.26599/JAC.2023.9220780 [Google Scholar]
  • 35.S.-Y. Wu, Y.-L. Huang, C.-C.M. Ma, S.-M. Yuen, C.-C. Teng et al., Mechanical, thermal and electrical properties of aluminum nitride/polyetherimide composites. Compos. Part A-Appl. S. 42, 1573–1583 (2011). 10.1016/j.compositesa.2011.06.009 [Google Scholar]
  • 36.W. Tang, T. Zhao, K. Wang, T. Yu, R. Lv et al., Dendrite-free lithium metal batteries enabled by coordination chemistry in polymer-ceramic modified separators. Adv. Funct. Mater. 34, 2314045 (2024). 10.1002/adfm.202314045 [Google Scholar]
  • 37.G. Yu, J. Xie, S. Wang, Y. Wang, T. Wang et al., Non hydrolizable aluminum nitride powders surface modified by silicic acids. Ceram. Int. 47, 29253–29260 (2021). 10.1016/j.ceramint.2021.07.089 [Google Scholar]
  • 38.Y. Liu, Q. Lin, X. Long, S. Zhang, H. Dong et al., Effect of segment structure of monotrimethoxysilylethyl-terminated asymmetric polysiloxanes on the thermal management performance of AlN-filled silicone pastes. React. Funct. Polym. 198, 105889 (2024). 10.1016/j.reactfunctpolym.2024.105889 [Google Scholar]
  • 39.J. Zheng, S. He, J. Wang, W. Fang, Y. Xue et al., Performance of silicone rubber composites filled with aluminum nitride and alumina tri-hydrate. Materials 13, 2489 (2020). 10.3390/ma13112489 [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 40.C.-T. Yang, H.-I. Hsiang, T.-S. Huang, P.-C. Huang, Y.-K. Han, Thermal conductivity and dielectric properties of PEDOT:PSS-AlN filler reinforced water-soluble polymer composites. Ceram. Int. 43, S710–S716 (2017). 10.1016/j.ceramint.2017.05.271 [Google Scholar]
  • 41.Z. Lule, J. Kim, Surface modification of aluminum nitride to fabricate thermally conductive poly(butylene succinate) nanocomposite. Polymers 11, 148 (2019). 10.3390/polym11010148 [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 42.G. Shao, A. Li, Y. Liu, B. Yuan, W. Zhang, Branched polymers: synthesis and application. Macromolecules 57, 830–846 (2023). 10.1021/acs.macromol.3c01631 [Google Scholar]
  • 43.J.P. Coats, R. Cochereau, I.A. Dinu, D. Messmer, F. Sciortino et al., Trends in the synthesis of polymer nano- and microscale materials for bio-related applications. Macromol. Biosci. 23, 2200474 (2023). 10.1002/mabi.202200474 [DOI] [PubMed] [Google Scholar]
  • 44.B. Peng, X. Xu, Y. Wang, J. Zhang, J. Chen et al., Antifouling coating of membrane surface with branched poly(2-hydroxyethyl acrylate) brushes via aqueous reversible deactivation radical polymerization. Prog. Org. Coat. 184, 107868 (2023). 10.1016/j.porgcoat.2023.107868 [Google Scholar]
  • 45.J.-W. Zha, F. Wang, B. Wan, Polymer composites with high thermal conductivity: Theory, simulation, structure and interfacial regulation. Prog. Mater. Sci. 148, 101362 (2025). 10.1016/j.pmatsci.2024.101362 [Google Scholar]
  • 46.S. Liu, W. Liu, D. Ba, Y. Zhao, Y. Ye et al., Filler-integrated composite polymer electrolyte for solid-state lithium batteries. Adv. Mater. 35, 2110423 (2023). 10.1002/adma.202110423 [DOI] [PubMed] [Google Scholar]
  • 47.C. Yu, J. Feng, K. Feng, Z. Mo, Y. He et al., Effect of multi-epoxy compatibilizers with branched structures on enhancing mechanical and compatibility of PLA/starch composite. Polym. Advan. Technol. 34, 1622–1632 (2023). 10.1002/pat.5996 [Google Scholar]
  • 48.S.H. Jeong, J.M. Kim, C. Baig, Rheological influence of short-chain branching for polymeric materials under shear with variable branch density and branching architecture. Macromolecules 50, 4491–4500 (2017). 10.1021/acs.macromol.7b00544 [Google Scholar]
  • 49.D. Wang, X. Wen, D. Zhang, X. Tan, J. Tang, Single-polymer dynamics of starch-like branched ring polymers in steady shear flow. Int. J. Biol. Macromol. 227, 173–181 (2023). 10.1016/j.ijbiomac.2022.12.100 [DOI] [PubMed] [Google Scholar]
  • 50.M. Zhang, P. Yu, J. Xie, J. Li, Recent advances of zwitterionic-based topological polymers for biomedical applications. J. Mater. Chem. B 10, 2338–2356 (2022). 10.1039/d1tb02323c [DOI] [PubMed] [Google Scholar]
  • 51.Y. Zhang, C. Cai, T. Chen, C. Wu, X. Gong et al., Enhanced thermal conductivity of BN/SR composites via biomass-modification of BN. Electron. Mater. Lett. 19, 201–211 (2022). 10.1007/s13391-022-00387-z [Google Scholar]
  • 52.J. Song, Y. Zhang, Performance improvement of alumina/silicone rubber composites by adding 3-(trimethoxysilyl)propyl methacrylate grafted siloxane copolymer. Polym. Composites 41, 4842–4848 (2020). 10.1002/pc.25756 [Google Scholar]
  • 53.P. Jin, J. Zhu, S. Yuan, G. Zhang, A. Volodine et al., Erythritol-based polyester loose nanofiltration membrane with fast water transport for efficient dye/salt separation. Chem. Eng. J. 406, 126796 (2021). 10.1016/j.cej.2020.126796 [Google Scholar]
  • 54.B. Zhang, P. Zhang, H. Zhang, C. Yan, Z. Zheng et al., A transparent, highly stretchable, autonomous self-healing poly(dimethyl siloxane) elastomer. Macromol. Rapid Commun. 38, 1700110 (2017). 10.1002/marc.201700110 [DOI] [PubMed] [Google Scholar]
  • 55.S. Demski, D. Brzakalski, M. Gubernat, K. Dydek, P. Czaja et al., Nanocomposites based on thermoplastic acrylic resin with the addition of chemically modified multi-walled carbon nanotubes. Polymers 16, 422 (2024). 10.3390/polym16030422 [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 56.V.Y. Rudyak, A.V. Minakov, M.I. Pryazhnikov, Preparation, characterization, and viscosity studding the single-walled carbon nanotube nanofluids. J. Mol. Liq. 329, 115517 (2021). 10.1016/j.molliq.2021.115517 [Google Scholar]
  • 57.A. Iwata, J. Akedo, Hexagonal to cubic crystal structure transformation during aerosol deposition of aluminum nitride. J. Cryst. Growth 275, e1269–e1273 (2005). 10.1016/j.jcrysgro.2004.11.082 [Google Scholar]
  • 58.T. Hamada, Y. Nakanishi, K. Okada, J. Ohshita, Crack- and shrinkage-free ethylene-bridged polysilsesquioxane film prepared by a hydrosilylation reaction. ACS Omega 6, 8430–8437 (2021). 10.1021/acsomega.1c00183 [DOI] [PMC free article] [PubMed] [Google Scholar]

Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

Supplementary file1 (DOCX 2770 KB) (2.7MB, docx)

Articles from Nano-Micro Letters are provided here courtesy of Springer

RESOURCES