Materials Letters 65 (2011) 19921994

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Materials Letters
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / m a t l e t

Effect of microstructure and physical parameters of hollow glass microsphere on insulation performance
Bing Li a,b, Jing Yuan a,b, Zhenguo An a,b, Jingjie Zhang a,
a b

Technical Institute of Physics and Chemistry, Chinese Academy of Science, Beijing 100190, China Graduate University of Chinese Academy of Science, Beijing 100049, China

a r t i c l e

i n f o

a b s t r a c t
Hollow glass microsphere (HGM) is a special type of inorganic functional powder with wide applications. HGM can be applied in the insulation area as llers owing to the hollow structure that is not conductive to the transfer of heat. The mechanism of heat transfer in HGM is analyzed and the thermal conductivity is proved to be the main heat transfer. Then a simple model comprised of continuous solid phase and independent gas phase is proposed to study the methods for decreasing the thermal conductivity of the lled system through the methods of reducing the density of HGM or increasing the stacking coefcient of HGM. This work provides actual guidance for the design and controlled preparation of composite materials with hollow glass microspheres as functional ller. 2011 Elsevier B.V. All rights reserved.

Article history: Received 4 January 2011 Accepted 15 March 2011 Available online 21 March 2011 Keywords: Hollow glass microsphere Microstructure Thermal properties True density Stacking coefcient

1. Introduction Hollow glass microsphere (HGM) is nely dispersed, free-owing inorganic powder, exerting important prospects in aerospace [1], deep-sea exploration [2], and hydrogen storage [3,4] and so on. Besides, the hollow core endows HGM excellent thermal insulating property, which makes HGM a promising candidate in insulation elds [5,6]. Hollow glass microsphere can be used as an insulating material owing to its low thermal conductivity, a key factor for evaluating the thermal insulation of materials. But up to date, little work has been seen for the research of thermal conductivity of HGM independent of any matrixes or adhesives. In order to make the HGM better applied in the insulation area, it is urgent to carry out relevant study to understand the effect of structure and physical parameters on the insulation performance. In this work, the results of the effect of the microstructure and properties of HGM on the thermal conductivity have been studied and the heat transfer process of HGM has been analyzed in detail, aiming to nd out the relation between the density and thermal conductivity, and the relation between stacking coefcient and thermal conductivity for the HGM, laying an exceptional foundation for the actual applications in heat insulating.

0.60 g/cm3, stacking coefcient = 0.540.56), for studying the relation between thermal conductivity and density. In order to have a clearer understanding about the effect of stacking coefcient, HGM screened by 250-mesh standard sieve ( = 0.45 g/cm3, particle diameter 070 m) and oating microsphere of ash ash screened by 120mesh standard sieve ( = 0.80 g/cm3, particle diameter 85200 m) were chosen to study by using the method of xing the quality of oating microspheres and then continually adding small-size HGM into the system. All the microspheres were dried at 120 C for an hour before the experiments. As the insulation performance of microsphere is closely related to particle size, we used the LS 13 320 laser diffraction particle size analyzer (Beckman Coulter) to obtain the results of the statistical distribution of particle size by measuring the light scattering pattern of particles of the samples. The thermal conductivity was measured by QTM-500 rapid thermal conductivity meter. The temperature was kept at 23 C during the whole experiment.

3. Results and discussion 3.1. Structural characteristics

2. Experiments The ve samples of HGM selected were prepared by our laboratory via soft chemical method (True density t = 0.25, 0.32, 0.40, 0.46, and
Corresponding author. Tel./fax: + 86 10 82543691. E-mail addresses: bingli@mail.ipc.ac.cn (B. Li), jjzhang@mail.ipc.ac.cn (J. Zhang). 0167-577X/$ see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.matlet.2011.03.062

It is well known that the behavior of the HGM is strongly dependent on its microstructure. Typical SEM images of HGM involving full view and cross section are observed by scanning electron microscopy (SEM, HITACHI S-4300). Fig. 1(a) shows that most of the HGM are of spherical appearance with ne sphericity, possessing different size for several or tens of microns. Fig. 1(b) shows the clear hollow core and homogeneous wall thickness.

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Fig. 1. SEM image (a) the front view of HGM and (b) the cross section of HGM.

3.2. Mechanism of heat transfer The basic mechanisms of heat transfer are generally considered to be conduction, convection and radiation. Conduction is the most signicant means of heat transfer within a solid or between solid objects in contact. Fluids, especially gasses are less conductive, and Skochdopole [7] concluded that the natural convection would not occur when bubble diameter was less than 4 mm for porous materials, so convective heat transfer can be neglected since the diameter of HGM is only 0100 m. Thermal radiation refers to the transfer of heat energy through empty space by electromagnetic waves, it is usually signicant only at high temperature compared to other mechanisms of heat transfer. In conclusion, conduction is the main mechanism of heat transfer and the other two can be neglected for HGM. There are several factors affecting conduction including density, heat transfer path, and contact points and so on. 3.3. Methods for reducing thermal conductivity of system Fig. 2(a) shows the simple system containing continuous solid phase and independent gas phase. Thus,
s s + g g ; it is known that g s ; So g g s s ; and s s :

veried in the articles [8,9] that the glass density can be calculated according to glass compositions and there are tiny differences in the compositions of the samples, leading to similar 0 of them. So we can see from the above formula that t will vary signicantly as d/D changes, which means that mass will decrease per unit volume when d/D increases, thus leading to a decline in thermal conductivity of system. Fig. 3 shows that the thermal conductivity of HGM increases as the true density of HGM rises at 23 C in the real state. Besides, the ve samples essentially have the similar stacking coefcient, which means that they have the similar space utilization. So it can be inferred that there's a close relationship between thermal conductivity and true density. Therefore, using low-density HGM decreases thermal conductivity of both HGM and system for applying in the insulation area. 3.3.2. Relationship between and N The thermal conductivity of the simple system will decline when the stacking coefcient of HGM increases just as method II. The mode of classic stacking theory [10] is sphere just like HGM and it has been thought that the large particles constitute the framework, the middle grains ll in the gap within the large particles and ne powder lls in the gap between large particles and middle grains for the ideal state of close packing. When the ratio of diameter of large particles and ne particles is less than 3, it is not effective for matching the particles size and increasing free packing density of complexes compared to that of just large particles, because the gap size within large particles at this time is smaller than the diameter of ne particles and it is difcult for ne particles to ll the gap, leading to ineffective gradation matching. So HGM screened by 250-mesh standard sieve ( = 0.45 g/cm3) and oating microsphere screened by 120-mesh standard sieve ( = 0.80 g/cm3) were used for exploring binary system of accumulation. The ratio of the average diameters of the large and small sized HGM is about 4:1; Fig. 4 shows the relation between weight percentage of large size oating microsphere and thermal conductivity, and also the relation between weight percentage of large size oating microsphere and stacking coefcient. It can be seen that the stacking coefcient increased at rst, then it decreased with the increase of small size HGM, curve a reached a peak when the weight percentage of large size oating microsphere is about 0.7, which is similar with curve b. It

Wherein, thermal conductivity of the system, sthermal conductivity of the solid, gthermal conductivity of the gas, s volume percentage of the solid, gvolume percentage of the gas s and g are related to essence of materials (here, assuming they are constant). So can be reduced by increasing g and decreasing s through expanding the ratio of the internal diameter and the external diameter (the size of microspheres of raw system is constant) in method I, and increasing the stacking coefcient in method II as well. 3.3.1. Relationship between and t The theoretically true density of HGM t can be calculated as t = [1 (d/D)3] 0, wherein, d is the average internal diameter of microspheres, D is the average external diameter of microsphere, and 0 is the glass density of shell part excluding hollow part. It has been

I Gas Gas

II Gas

Solid (b)

Solid (a)

Solid (c)

Fig. 2. Method I for increasing the volume of hollow part of HGM; method II for increasing the amount of HGM.

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B. Li et al. / Materials Letters 65 (2011) 19921994

Fig. 3. Relationship between thermal conductivity and true density.

Fig. 4. Relationship between weight percentage of large size oating microspheres W and thermal conductivity , and stacking coefcient N.

proves that the close packing of HGM can be articially controlled and the thermal conductivity of HGM, together with the volume of gas will both increase as samples stack close. 4. Conclusions Hollow glass microsphere with hollow structure can be used in the insulation areas owing to its low thermal conductivity and conduction heat transfer is the most important means for transferring heat within the hollow glass microspheres according to the mechanism of heat transfer of HGM. In view of the simple system containing continuous solid phase and independent gas phase, two main methods are usually used to reduce the thermal conductivity of the system: increase the ratio of internal diameter and external diameter of HGM and increase the stacking coefcient of HGM, which also means to reduce the true density of HGM and increase the amount of HGM. The thermal conductivity of HGM and the system will be reduced by using the former method, and the thermal conductivity of the system will be reduced but the thermal conductivity of HGM will be increased by using the latter method. So the thermal conductivity of the system can be reduced by the combined use of the above two methods, which

provide effective guidance for hollow glass microspheres being used as llers to reduce the thermal conductivity of the system in practice. Acknowledgments This work has been supported by the National Natural Science Foundation of China (projects No. 04B7131801) and the State High Technology Development Program 863 (2006AA09Z209). References
[1] Geleil AS, Hall MM, Shelby JE. J NonCryst Solids 2006;352:6205. [2] Khimiya. Handbook of llers for polymeric composite materials; 1981 [Russian translation] Moscow. [3] Rapp DB, Shelby JE. J NonCryst Solids 2004;349:2549. [4] Brow Richard K, Schmitt Melodie L. J Eur Ceram Soc 2009;29:1193201. [5] Allen MS, Baumgartner RG, Fesmire JE, Augustynowicz SD. Cryogenic engineering conference; Sep. 2226, 2003. p. 18. [6] Allen M.S., Willen G.S., Mohling R.A. US Patent No. 6,858,280. 2005. [7] Skochdopole RE. Eng Prog 1961;57:558. [8] Huggins Maurice L, Sun Kuan-Han. J Amer Ceram Soc 1943;26:411. [9] Scholze H. Glas. natur, struktur and eigenschaften, glass. Nature, structure and properties. Berlin: Springer; 1977. [10] Westman AR, Hugill HR. J Amer Ceram Soc 1930:10.