- APTEOS , * hjkim68@kyonggi.ac.

gi.ac.kr The gas permeation properties of APTEOS film prepared by sol-gel process Kyoungmi Jang, Hyunjoon Kim* Major of Chemical Engineering, Division of Advanced Industrial Engineering, Kyonggi University hjkim68@kyonggi.ac.kr INTRODUCTION Polymer films have been widely used for barrier applications because of their transparency, easy processability, flexibility, lightness, and so on. However these films have poor thermal stability, high permeability of water vapor and variable gases, and UV transmission. On the other hand, inorganic materials have high thermal and mechanical strength and low gas permeability. It is thus possible to prepare new kinds of materials with excellent barrier properties that have advantages of both organic inorganic materials. One of the methods for preparing these kinds of materials is to form inorganic thin layers on polymer substrates or to make the organic-inorganic hybrids. The sol-gel process is reaching their full potential; enabling the preparation of new generations of advanced materials not easily accessible by other methods. And it is now widely accepted as the useful method for the coating of oxide thin films or organic-inorganic hybrid films on polymer substrates. It is reported that inorganic or hybrid materials forming a thin layer on polymer films reduce both oxygen and water vapor permeability [Tadanaga et al., 1996; Amberg-Scwab et al.,2000]. Most of these works have been done using polyethylene terephthalate(PET) or Nylon-6 as the substrate polymer film, because these polymer molecules have polar functional groups. However, these polymer films are too expensive to use as commercial packaging film, so that it is necessary to replace these with rather cheap substrate films such as polypropylene (PP) or polyethylene(PE). In this study, nonporous silica films were formed by a sol-gel process using 3-aminopropyltriethoxysilane (APTEOS). The PP film as substrate was modified by corona-plasma treatment to provide appropriate adhesion between the coating material and the polymer base film. The effects of the pH, water ratio and film storage time on the gas permeability were then investigated. Aminoalkoxysilane has been one of the most widely applied silane coupling agents or adhesion enhancers. Tadanaga et al.[1996] pretreated Nylon6 film with APTEOS sol to improve the affinity of tetraethoxysilane(TEOS) coating layers and the substrate. Smaihi et al.[1999] prepared hybrid imidesiloxane copolymers by sol-gel coreaction of pyromellitic dianhydride, aminoalkoxysilane and

tetramethoxysilane(TMOS). In that experiment, two types of aminoalkoxysilane were used to provide a bonding between the inorganic and organic phases. Although the pretreatment with aminoalkoxysilane or aminoalkoxysilane-modified oxide films are prospective materials for industrial applications such as membranes, thin films, coatings, and so on[Tadagana et al., 1996; Zumud and Sonnefeld, 1996; Gilberts and Tinnemans, 1998], their practical use is rather limited because of the lack of stability in humid atmosphere and the short gelation time. In the present work, only APTEOS was used as inorganic network former to examine an effect of aminoalkoxysilane on the physical and gas permeation properties. EXPERIMENAL 3-aminopropyl triethoxysilane(APTEOS)[Aldrich, 98%] was mixed in ethanol with molar ratio of 10. After acidic water was added to the mixture, this mixture was stirred for 24hrs at room temperature in a closed container. Hydrochloric acid in the acidic water was used as catalyst in the hydrolysis and condensation reaction. The molar ratio of water to APTEOS was varied from 1 to 3 to examine the effect of the amount of water. The coating was carried out on the corona-treated biaxially oriented polypropylene(BOPP) substrate. The coating film was dried at room temperature for 24hrs, and then kept in the desiccators before the characterizations. The coating sols were characterized by various methods, such as Fourier transform infrared(FT-IR, JASCO-430) and
29

Si nuclear magnetic

resonance(29Si-NMR, Varian UI-200) spectroscopy. The morphology of cross-section and surface of the coating films were characterized with the scanning electron microscopy (SEM, JEOL, JSM5310LV). A constant volume-variable pressure method was used to determine steady state permeability coefficients at 30 over a range of upstream pressure up to 1000torr. A coating film was mounted on the permeation cell and degassed by exposing both sides of the film to vacuum. The steady-state rate of pressure rise in a downstream receiving volume was used to determine the gas permeability coefficient. The permeation apparatus is shown schematically in Fig. 1. At steady state the following expression was used to calculate the permeability coefficient.

22,414V dp2 p1 P= RT dt l
Where V is the downstream reservoir volume, A is the cross-sectional area of the film, p 1 is the upstream pressure, and dp2/dt is the rate of change in downstream pressure. RESULT AND DISCUSSION It was reported that when only TEOS was used as inorganic precursor, microcracks were observed

Pressure read out Computer Vent

PT1 Gas input MFC

V2 V1

PT2

Vent V4 N2 O2 CO2 V3 Vacuum

TC

Temperature controller (set at T1)

Insulated enclosure

Fig.1 The schematic diagram of permeation apparatus

in the thin films on the polymer substrates[Iwashita et al., 1996]. However in case of APTEOS, homogeneous and uniform thin film without cracks are obtained in this study. Fig.2 and 3 represent permeability coefficient of oxygen and nitrogen, respectively, and show the amount of HCl dependence of the gas permeability coefficient of PP substrate coated with APTEOS. In fig.2 and 3, the permeability coefficient of PP bare film is 0.858Barrer[10 -10 cm3(STP)cm/cm2 s cmHg] for oxygen and 0.23Barrer for nitrogen. Open symbols in fig.2 and closed symbols in fig.3 represent that the coating of APTEOS is very effective to suppress the gas permeation. This may cause the formation of dense structure and good adhesion between APTEOS layer and PP substrate. APTEOS is a trifunctional inorganic precursor with amine group, and can hold to corona discharged PP substrate. The influence of storage time of coated film at ambient condition was also investigated. The results show that the gas permeability coefficient is not changed comparably to 15days. The contact angle is also not changed to 15days(the result of contact angle analysis not shown here). CONCLUSION Nonporous silica films with crack-free were formed on PP film by sol-gel process using APTEOS. The gas permeability coefficient of PP film was reduced considerably by the coating of APTEOS. It might be concluded that excellent barrier properties of coated film due to the formation of dense

Permeability coefficient of O2 (Barrer)

0.860

polypropylene

Permeability coefficient of N2 (Barrer)

0.230

polypropylene

0.855

0.225

0.850

0.220

0.010 0.005 0.000

0.010

storage time = 0 storage time = 15 days

0.005

storage time = 0 storage time = 15 days

0.000

0.00

0.01

0.02

0.03

0.00

0.01

0.02

0.03

amount of HCl (ml)

amount of HCl (ml)

Fig.2 Dependence of the permeability coefficient of oxygen on the amount of HCl

Fig.3 Dependence of the permeability coefficient of nitrogen on the amount of HCl

structure and food adhesion between APTEOS Thin layer and PP substrate. By storing the coating films, gas permeability coefficient is not changed comparably to 15days. REFERENCES Amberg-Schawb S., Katschorek H., Weber U., Hoffman M. and Burger A., Barrier Properties of Inorganic-Organic Polymers: Influence of Starting Compounds, Curing Conditions and StorageScaling-Up to Industrial Application J. Sol-Gel Sci. Tech., 19, 125 (2000) Gilbert J. and Tinnemans A.H.A, UV Curable Hard Transparent Hybrid Coatong Materials on Polycarbonate Prepared by the Sol-Gel Method , J. Sol-Gel Sci. Tech., 11, 153 (1998) Iwashita K., Tadanaga K., and Minami T., Water Permeation Properties of SiO2-RsiO3/2 (R=Methyl, Vinyl, Phenyl) Thin Films Prepared by the Sol-Gel Method on Nylon-6 Substrate J. Applied Poly. Sci. 61, 2173 (1996) Smihi M., Schrotter J., Lesimple C., Prevost I. and Guizard C. Gas Separation Properties of Hybrid Imide-Siloxane Copolymers with Various Silica Contents J. Membr. Sci., 161, 157 (1999) Tadanaga K., Iwashita K. and Minami T. Coating and Water permeation Properties of SiO2 Thin Films Prepared by the Sol-Gel Method on Nylon-6 Substrate J. Sol-Gel Sci. Tech., 6, 107 (1996) Zhumud B.Y. and Sonnefeld J. Aminopolysiloxane Gels: production and Properties J. Non-Cryst. Solids, 195, 16 (1996) Acknowledgement Kyoungmi Jang, one of the authors, is a research assistant. This work is supported by Research

Funds from Kyonggi University. (Grant No.:2002-020)