水热法制备高反射率TiO2壳层中空玻璃微球

以钛酸四丁酯、盐酸、去离子水、中空玻璃微球(HGM)为原料,乙醇为溶剂,采用水热合成法制备了高反射率的锐钛矿型TiO₂壳层HGM(HGM@TiO₂)。采用SEM、EDS、FTIR、XRD、UV-VIS-NIR、导热系数仪研究了钛酸四丁酯用量对微球的表面形貌、表面化学成分、物相结构、反射性能、导热系数的影响。结果表明:锐钛矿型TiO₂成功包覆于HGM表面,包覆形貌完整且均匀,并且包覆层厚度随着钛源用量的增加而变厚;与原始HGM相比,HGM@TiO₂的导热系数有小幅上升,最大上升幅度仅为0.007 W/(m·K),证明TiO₂的包覆对HGM的隔热性能的影响不大;包覆后的HGM的光谱反射率在可见光波段和近红外波段的反射率得到大幅提升,最大提升幅度为13%,HGM@TiO₂的最高反射率达到90%以上。      

Tailoring of thermal and dielectric properties of LDPE-matrix composites by the volume fraction,density, and surface modification of hollow glass microsphere filler

Hollow glass microsphere (HGM) filled low-density polyethylene (LDPE) composites were prepared, and the effects of density, content, and surface modification of HGM on the thermal and dielectric properties of the composites were investigated. It is found that the thermal conductivity of the composites decreases with increasing HGM content or decreasing HGM density. At the same HGM content and density, the composites filled with suitable amount of silane coupling agent (KH570) modified HGM exhibit higher thermal conductivity than unmodified-HGM filled composites. The dielectric constant at 1 MHz of the composites also decreases with increasing HGM content or decreasing HGM density, but their dielectric loss increases with increasing HGM content or increasing HGM density. By modifying the surface of HGM with suitable amount of KH570, the dielectric constant and loss at 1 MHz of the composites can be decreased at the same time. The results of microwave dielectric properties of the composites indicate that the dielectric constant decreases with increasing HGM content or decreasing HGM density, the quality factor (Q × f) decreases with increasing HGM content or increasing HGM density, but both dielectric constant and quality factor are slightly affected by the surface modification of HGM. Due to lower intrinsic thermal conductivity and dielectric constant but higher dielectric loss of HGM than LDPE, the thermal conductivity and dielectric properties of the composites can be controlled with adding HGM and varying its volume fraction. The surface modification of HGM improves the interface contact between HGM and LDPE in the composites, which is confirmed by the SEM observation, and thus the heat conduction and dielectric properties at low frequency are improved. Based on calculated thermal conductivity and dielectric constant of HGM, the experimental trends of thermal conductivity and dielectric constant at 1 MHz of the composites are analyzed by using different models, including typical models for particles-filled composites and special models developed for hollow microsphere filled composites. The results from suitable models show close correlation with the experimental values.     

Electrospun nanofiber composites with micro-/nano-particles for thermal insulation

Polyacrylonitrile (PAN) nanofiber and silica aerogel (SAG) laminated composites were prepared via electrospinning for thermal insulation. Conventional single nozzle and co-axial electrospinning were used to increase the fraction of aerogel particles in the composite sheets while maintaining the mechanical strength of the sheet. When the core-shell electrospinning technique with co-axial nozzle was applied, the proportion of aerogel particles increased two fold without a deterioration of the mechanical properties. The average thermal conductivity of the laminated composite sheet was reduced by approximately 12.5% as compared to the nanofiber composite prepared using the single-nozzle electrospinning technique. For additional reduction in thermal conductivity, hollow glass microspheres (HGM) was inserted between the interlayer spacing of the electrospun sheets to increase the interlayer spacing. When HGM particles were inserted, it was observed that the thermal conductivity decreased by approximately 20% compared to that of the specimen without particles.     

On a hybrid method to characterize the mechanical behavior of thin hollow glass microspheres

Hollow glass microspheres possess niche markets and future research areas due to their high strength-to-density ratio and low thermal conductivity. For example, these qualities make them a viable alternative insulation medium. For this study, Scotchlite^™ k1 hollow glass microspheres (HGMs) manufactured by 3M^™ were used; however, one of the challenges in investigating their mechanical properties was due to the limited availability of published data. Most importantly, the thickness (or the range of thicknesses) of produced thin hollow microspheres is not measured by the manufacturer, so the authors needed to develop a hybrid characterization method that depended on both experiments and simulations to estimate the HGMs mechanical properties. The experimental method utilizes a nano-indenter with a spherical sapphire tip of 500 μm in diameter. Each HGM was uniaxialy compressed under the indenter to yield the stiffness, diameter, and the force-displacement at fracture of each HGM tested. ABAQUS^™ was used to numerically model an HGM of mean diameter and stiffness to obtain a relation between the mechanical and geometrical properties of each HGM to its thickness, and investigate the development of stresses on an HGM during its uniaxial compression. The data show large scatter in the measured stiffness of each HGM as a function of diameter. The authors conjecture this is due to a large fluctuation of the microsphere thickness. Finally, the work necessary to deform an HGM was successfully correlated to its radius-to-thickness ratio. This gives us a unique insight on the force-displacement behavior against the geometrical features of HGMs.     

空心玻璃微球含量对环氧复合泡沫塑料性能的影响

以空心玻璃微球（HGM）填充环氧树脂制备了密度为0.56~0.91 g/cm3的HGM/环氧复合泡沫塑料。研究了HGM含量对复合泡沫塑料黏度、力学性能、动态力学性能及隔热性能的影响。结果表明:表面偶联处理后增加了HGM的表面亲油性,改善了其与基体树脂间的相容性和界面性能,有利于HGM/环氧复合泡沫塑料性能的提高;体系黏度与HGM含量呈正相关,与温度呈负相关;随着HGM含量的增加,HGM/环氧复合泡沫塑料的压缩强度、弯曲强度和拉伸强度均有一定程度的降低,但是比强度变化不大,材料得到很大程度的轻质化;HGM的引入使得HGM/环氧复合泡沫塑料玻璃化转变温度向低温方向偏移,储能模量呈现先减小后增加的趋势,导热系数由纯环氧树脂的0.203 W/（m·K）减小到HGM含量为40wt%时的0.126 W/（m·K）。HGM/环氧复合泡沫塑料阻尼性能和隔热性能均有所提高。      

Preparation and properties of hollow glass microsphere-filled epoxy-matrix composites

Hollow glass microsphere (HGM)–filled epoxy composites, with filler content ranging from 0 to 51.3 vol.%, were prepared in order to modify the dielectric properties of the epoxy. The results showed that the dielectric constant (D_k) and dielectric loss (D_f) of the composites decreased simultaneously with increasing HGM content, which was critical for the provision of superior high-frequency device performance. Other properties of the composite, such as the coefficient of thermal expansion (CTE) and the glass transition temperature (T_g), were also improved. The improvement in these properties was related to strong interaction between the HGM and epoxy, which was indicated by the formation of an interphase between the HGM and epoxy-matrix. It was unsatisfactory in this study that the thermal conductivity of the composites also decreased with HGM content. In order to obtain relatively high thermal conductivity and a low dielectric constant simultaneously, this paper suggests further adding other filler.     

空心玻璃微珠/硬质聚氨酯泡沫复合材料的制备及性能

以空心玻璃微珠(HGM)为添加剂,采用一步法全水发泡制备了一系列HGM/硬质聚氨酯泡沫(RPUF)复合材料。通过SEM、TG、极限氧指数(LOI)和水平燃烧,研究了HGM/RPUF复合材料的泡孔结构、炭层形貌、热稳定性及阻燃性能。采用万能材料试验机测试了HGM/RPUF复合材料的压缩强度和压缩弹性模量。采用热重-傅里叶红外光谱(TG-FTIR)研究了HGM/RPUF复合材料燃烧过程中的气相产物。研究表明,HGM有成核剂作用,可以缩小HGM/RPUF复合材料泡孔孔径。HGM在燃烧过程中迁移到炭层表面,促进形成致密厚实的炭层。当加入5.4wt% HGM时,HGM/RPUF复合材料的压缩强度及压缩弹性模量分别提高至0.14 MPa和4.53 MPa,相对RPUF,分别提高了37.30%和67.16%。同时发现,HGM能明显抑制HGM/RPUF复合材料在燃烧过程中CO的释放,有效提高了其火灾安全性。      

Investigation of thermal conductivity and dielectric properties of LDPE-matrix composites filled with hybrid filler of hollow glass microspheres and nitride particles

The hybrid filler of hollow glass microspheres (HGM) and nitride particles was filled into low-density polyethylene (LDPE) matrix via powder mixing and then hot pressing technology to obtain the composites with higher thermal conductivity as well as lower dielectric constant (D_k) and loss (D_f). The effects of surface modification of nitride particles and HGMs as well as volume ratio between them on the thermal conductivity and dielectric properties at 1 MHz of the composites were first investigated. The results indicate that the surface modification of the filler has a beneficial effect on thermal conductivity and dielectric properties of the composites due to the good interfacial adhesion between the filler and matrix. An optimal volume ratio of nitride particles to HGMs of 1:1 is determined on the basis of overall performance of the composites. The thermal conductivity as well as dielectric properties at 1 MHz and microwave frequency of the composites made from surface-modified fillers with the optimal nitride to HGM volume ratio were investigated as a function of the total volume fraction of hybrid filler. It is found that the thermal conductivity increases with filler volume fraction, and it is mainly related to the type of nitride particle other than HGM. The D_k values at 1 MHz and microwave frequency show an increasing trend with filler volume fraction and depend largely on the types of both nitride particles and HGMs. The D_f values at 1 MHz or quality factor (Q × f) at microwave frequency show an increasing or decreasing trend with filler volume fraction and also depend on the types of both nitride particle and HGM. Finally, optimal type of HGM and nitride particles as well as corresponding thermal conductivity and dielectric properties is obtained. SEM observations show that the hybrid filler particles are agglomerated around the LDPE matrix particles, and within the agglomerates the smaller-sized nitride particles in the hybrid filler can easily form thermally conductive networks to make the composites with high thermal conductivity. At the same time, the increase of the value D_k of the composites is restricted due to the presence of HGMs.     

高性能空心玻璃微球的力学特性研究

高性能空心玻璃微球具有许多优异的性能。作为复合材料的关键原料之一,其力学性质对复合材料的性能起决定性的作用。系统介绍了高性能空心玻璃微球抗压强度影响因素如粒径分布、壁厚和密度等基本物理力学性质的表征方法和手段。从统计研究和个体研究两个方面分别论述了空心玻璃微球统计与个体强度的研究方法。综述了壁厚、密度和表面修饰等对微球统计强度的影响,形状因子和抗拉强度对单个球体等静压强度的影响以及壁厚和直径对单个球体单轴压缩强度的影响。     

纳米胶囊潜热型功能流体制备及强化沸腾换热的实验研究

采用溶胶凝胶法制备了以软脂酸为芯材,二氧化硅为壳材的纳米相变胶囊,分析测试表明所合成的胶囊呈现为核壳结构分明的规则球形结构,且具有良好的储热能力。选用聚二甲基硅氧烷疏水改性,制备了稳定分散的丙酮基纳米胶囊潜热型功能流体,热导率及粘度测试表明其可以应用于强化换热。微小通道过冷流动沸腾实验研究发现,纳米相变胶囊的加入不但可以阻止气泡的合并,而且可以加速沸腾气泡的破裂,揭示了除提升热导率及提供潜热之外的另一强化沸腾换热的原因。     

脂肪酸相变材料导热系数测试及相变传热过程的数值模拟

相变材料在相变过程中由于材料本身状态的变化,其相变传热过程属于具有移动边界的非线性过程,针对相变材料相变传热过程中非线性传热特征,对月桂酸-癸酸混合脂肪酸相变材料的热性能进行了研究,利用差示扫描量热法(Differential Scanning Cal-orimetry)对相变材料的相变潜热和相变温度进行了测试,利用DRE-2C导热系数测定仪测试了不同摩尔比例脂肪酸相变材料以及相变材料在不同测试温度下的导热系数,通过将无机多孔材料硅藻土和脂肪酸相变材料混合制备了一种无机复合相变材料,并对其导热系数和蓄放热性能进行了测试,利用有限元法对相变材料的相变过程进行了数值模拟。研究表明,脂肪酸相变材料的导热系数和其相变温度呈反比关系,相变材料的相变温度越高,其导热系数越低。对于同一相变材料来说,相变材料的导热系数随着材料温度的升高而升高,硅藻土的掺入明显增加了相变材料的导热系数,复合相变材料蓄放热速率加快,改善了相变材料的传热性能。有限元模拟分析法可以较好地描述相变材料的传热过程,相变材料的导热性能需要强化以提高其蓄放热的速率和频率。     

Modeling of thermo-physical properties for FRP composites under elevated and high temperature

A decomposition model for resin in glass fiber-reinforced polymer composites (GFRP) under elevated and high temperature was derived from chemical kinetics. Kinetic parameters were determined by four different methods using thermal gravimetric data at different heating rates or only one heating rate. Temperature-dependent mass transfer was obtained based on the decomposition model of resin. Considering that FRP composites are constituted by two phases – undecomposed and decomposed material – temperature-dependent thermal conductivity was obtained based on a series model and the specific heat capacity was obtained based on the Einstein model and mixture approach. The content of each phase was directly obtained from the decomposition model and mass transfer model. The effects of endothermic decomposition of the resin on the specific heat capacity and the shielding effect of evolving voids in the resin on thermal conductivity are dependent on the rate of decomposition. They were also described by the decomposition model; the effective specific heat capacity and thermal conductivity models were subsequently obtained. Each model was compared with experimental data or previous models, and good agreements were found.     

Experimental evaluation of thermal properties of R134a clathrates based PCMs for cooling applications

The thermal properties of R134a clathrates with additives, which are treated as phase change materials (PCMs), are experimentally determined. The formation of refrigerant clathrates is investigated due to their potential use in active as well as in passive cooling applications. The PCMs are formed using R134a clathrate and distilled water with different refrigerant proportions and five different additives. The main objective of using additives is to study their potential for enhancing the clathrate thermal properties under direct contact heat transfer. PCMs are formed in glass tubes and their temperatures are recorded, at two different locations inside the tube, after regular intervals. The R134a percentages of 35% are used to form clathrate. For the additives, ethanol, sodium chloride, magnesium nitrate hexahydrate, copper and aluminum are used. PCMs are formed using a controllable constant energy water bath. The thermal properties determined are the liquid phase thermal conductivity, mushy phase thermal conductivity, and specific latent heat of the PCMs. A comparative study is conducted to compare the thermal properties of different PCMs using the suggested additives. The copper additive improves the thermal conductivity the most while sodium chloride reduces the thermal conductivity. Ethanol additive improves the specific latent heat the most while magnesium nitrate hexahydrate reduced the specific latent heat.     

等腰梯形蜂窝芯玻璃钢夹芯板的热性能

为研究等腰梯形蜂窝芯玻璃钢夹芯板传热机制,利用导热仪对夹芯板的传热性能进行了实验测试与模拟研究。结果表明:夹芯板稳态导热系数模拟结果与Swann and Pittman经验公式的计算结果相吻合,验证了数值计算胞体平面模型的合理性;Part2为夹芯板稳态传热的主要构件,Part2胞壁厚度与边长对夹芯板导热系数有显著影响,Part2高度、Part1与Part3厚度及面板厚度对夹芯板导热系数的影响偏弱;同时,若仅需降低夹芯板的导热系数,而忽略对夹芯板静力学性能要求,应该更换蜂窝芯层材料;若需夹芯板同时满足隔热性能与静力学性能,多层蜂窝芯夹芯板是很好的选择。      

Low dielectric permittivity and high thermal stability composites based on crosslinkable poly (arylene ether nitrile) and hollow glass microsphere

Crosslinkable poly (arylene ether nitrile)/hollow glass microsphere (PEN/HGM) composites with relative low dielectric permittivity and high thermal stability were prepared by a solution mixing and thermal compression method. For achieving this purpose, HGM were tight embedded in network, which were formed by crosslinking reaction of PEN end-capped with phthalonitrile. Compared to pure PEN, the dielectric constant of the resulting composite with 15 wt% of HGM reduced from 4.1 to 2.7 at 100 kHz, and the dielectric loss decreased from 2.0 × 10^?2 to 0.8 × 10^?2 at 100 kHz. Furthermore, the as-prepared composites showed significant enhancement in glass transition temperature (increased by 64 °C) and onset thermal degradation temperature (increased by 41 °C). Therefore, such composites were expected to find their applications area such as integrated circuit where needs low dielectric constant, low dielectric loss and high thermal stability.     

Application of Effective Media Theory for Determination of Thermal Properties of Hollow Bricks as a Function of Moisture Content

The effective thermal conductivity and effective specific heat capacity of hollow brick blocks are investigated as a function of moisture content. While the effective specific heat capacity as a heat storage parameter is calculated using the linear theory of mixtures, the effective thermal conductivity as a heat transport parameter is analyzed using the effective media theory. At first, the effective thermal conductivity of the dry hollow brick block is calculated using a combination of properties of the brick body and air cavities, and verified using experimental data. Then, the effective thermal conductivity of the brick body is analyzed as a function of moisture content both theoretically and experimentally, and appropriate homogenization formulas are identified. Finally, the effective thermal conductivity of the whole hollow bricks is expressed as a function of moisture content from the dry state to water saturation.     

空心玻璃微珠增强环氧树脂复合材料的动态力学性能

通过对空心玻璃微珠（HGM）/环氧树脂复合材料进行动态力学分析（DMA）,给出了环氧树脂基体在不同频率下的动态力学温度谱,利用时温等效原理,根据位移因子构建了HGM/环氧树脂复合材料在室温下的储能模量和损耗模量的频率主曲线。分析了温度和频率、体积比和粒径对HGM/环氧树脂复合材料储能模量和损耗模量的影响规律,并结合SEM图像分析其影响机制。结果表明,随着HGM体积分数的增加,HGM/环氧树脂复合材料储能模量和损耗模量呈增大趋势;储能模量随温度升高而降低,损耗模量随温度的增加先增大后减小,在玻璃化温度附近形成一个峰值,HGM低于10%的配比有利于提高其动态力学性能。颗粒的团聚及界面的黏合均对HGM/环氧树脂复合材料的动态力学性能产生较大影响。     

一种新型隔热涂料的制备及性能研究

以苯丙乳液为成膜剂,硅烷偶联剂处理后的中空玻璃微珠为功能隔热填料合成新型的隔热涂料。结果表明,用硅烷偶联剂预处理中空玻璃微珠后涂料附着力能提高1个级别;涂层导热系数随中空玻璃微珠粒径的增加呈现先减小后增大的趋势,当中空玻璃微珠的粒径为58μm左右时导热系数比其它粒径制得涂料的导热系数降低6%～28%;随涂膜厚度的增加,隔热效果增强,但当涂膜厚度增大到0.3mm时,继续增加涂膜厚度,隔热效果几乎不再增强;当中空玻璃微珠含量小于10%时,热反射率随中空玻璃微珠在隔热涂料中含量的增加显著增加,超过10%后,热反射率增加速率减缓,当达到12%时,涂料的热反射率值最高,继续增加玻璃微珠含量,热反射率几乎不增加。     

废胶粉/空心玻璃微珠改性环氧树脂的结构与性能

研究了微波辐射改性废胶粉(WRP)、偶联剂改性空心玻璃微珠(HGM)对环氧树脂复合材料的结构和性能的影响.采用差示扫描量热、热重分析等方法进行测试和表征,用扫描电镜观察了复合材料的断面形态.结果表明,少量合适粒径的改性WRP可以提高环氧树脂复合材料的冲击强度,适量的改性HGM可以提高复合材料的T<,g>和弯曲强度,并改...     

相变装置中填充泡沫金属的传热强化分析

通过对泡沫金属结构的分析，将泡沫金属结构简化为二维的循环扩展六边形网格形式，且传热单元被分为九个导热层。在此基础上以热阻分析推导出了在泡沫金属作为填充材料时其整体有效导热系数Koff与泡沫金属空隙率ε之间的数学关系式。分别以泡沫铜、泡沫铝填充石蜡为例与用铜、铝翅片并联和串联两种方式填充石蜡时的有效导热系数进行了计算对比，从计算结果可以明显看出采用泡沫金属作为填充材料，其整体效果要优于翅片，可显著改善相变储能装置的传热性能及储能效率。