Comparison of alumina and magnesia filled PTFE composites for microwave substrate applications K.P. Muralia, b, S.

Rajesha, Om Prakashb, A.R. Kulkarnib and R. Ratheesha,

a ,

Centre for Materials for Electronics Technology (C-MET), M.G. Kavu, Athani, Thrissur 680 771, India

Department of Metallurgical Engineering and Materials Science, I.I.T. Bombay, Powai, Mumbai 400076, India Received 25 February 2008; revised 11 July 2008; accepted 17 July 2008. Available online 30 August 2008.

Abstract Flexible microwave substrates have been fabricated using micron size powders of -Al2O3 and MgO filled in polytetrafluoroethylene (PTFE) matrix through SMECH process, comprising of sigma mixing (SM), extrusion (E), calendering (C) followed by hot pressing (H). Prior to fabrication of the composites, silane coating on the fillers was done to preclude moisture absorption. Filler loading in the PTFE matrix was varied in steps (10 70 wt.%) and their effects on the microwave dielectric properties ( r and tan ) at Xband (8.2 12.4 GHz) were evaluated using waveguide cavity perturbation technique. Optimum filler loading for both alumina and magnesia filled composites were found out by systematically varying the filler concentration. SEM microgrpahs revealed uniform distribution of filler in the matrix without any delamintaion of stacked calendered tapes. A comparative study of the magnesia filled samples with and without silane coating is also carried out to ascertain the effects of brucite phase formed during silane coating process on the dielectric and moisture absorption properties of composite substrates. Keywords: Polymers; Composite materials; Ceramics; Dielectric properties Article Outline 1. Introduction 2. Experimental 2.1. Materials 2.2. Silane coating process 2.3. Fabrication of composites

2.4. Characterization studies 3. Results and discussion 4. Conclusion Acknowledgements References 1. Introduction The lower regions of microwave spectrum (0.5 1 GHz) are increasingly getting overcrowded in the communication sector with the advent of modern communication systems such as mobile phones, global positioning system, LAN, etc. Exploring higher frequencies has, therefore, become essential to meet the future progressively growing requirements. This has necessitated microwave dielectric materials with superior electrical, thermal and mechanical properties. Although many ceramic and polymer composite materials are presently available for communication applications, fluoropolymerbased dielectric materials are generally preferred for applications viz. digital printed circuit boards, patch antennas and flex cables because of their ease of fabrication and excellent electrical properties [1]. Polytetrafluoroethylene (PTFE) is the commonly used fluoropolymer because of its low dielectric constant ( r 2.1) which is stable over a wide frequency range (up to 20 GHz), very low loss tangent (tan 3 10 4), high operating temperature ( 250 C), low moisture absorption and good chemical resistance. However it has serious drawback of high coefficient of thermal expansion (CTE 109 ppm C 1) which limits its application in microwave circuits [1], [2], [3] and [4]. To alleviate this adversely affecting property, suitable filler materials are incorporated into the PTFE matrix to significantly reduce the thermal expansion coefficient matching with that of the metal conducting layer and also to tailor dielectric properties, which makes these materials ideal candidates for the fabrication of extremely reliable electronic packages operating at high frequencies. PTFE filled with low dielectric material, fused quartz ( r 3.78) is used as flexible microwave substrate having effective dielectric constant ( r 2.94) for improved propagation speeds, low attenuation at high frequencies [5]. Although many commercial PTFE-based substrate materials are presently available in the market, published literature on the processing as well as property evaluation of these technologically important class of materials is limited. The industrial research approaches were mostly focused on the fabrication of planar PTFE laminates filled with titania or fused quartz materials. Effect of filler size and content on the properties of PTFE/SiO2 composites were reported by Chen et al. [3]. In this work, authors have used PTFE suspension (colloidal PTFE) as starting material and fused quartz of size 25 and 5 m as particulate fillers to study the variation of dielectric, thermal and mechanical properties with respect to filler loading. Arthur et al. have disclosed effect of silane coating on the particulate fillers such as distribution of the fillers in the PTFE matrix, mechanical strength, moisture absorption, etc. for circuit applications [5]. -Alumina ( -Al2O3) and magnesia (MgO) are well known materials for dielectric applications owing to their stable dielectric constant and low loss tangent. Both alumina and magnesia have almost similar

dielectric constants 9.96 and 9.80, respectively, whereas magnesia has a slightly inferior loss tangent (tan 5 10 4) than alumina (tan 1 10 4) [6] and [7]. In the present work, micron size alumina and magnesia particulate fillers with almost identical dielectric properties (both have comparable particle size distribution), have been incorporated in the PTFE matrix through a proprietary process to study the variation of dielectric, structural, microstructure and moisture absorption properties of the composite substrates. 2. Experimental 2.1. Materials The starting materials PTFE, 50 m powder, H71 grade (m/s. Hindustan Fluoro Carbons, India), 3 m Al2O3 powder, 99.99% pure (m/s. Sumitomo Corporation, Japan), 2 m MgO powder, >99% pure (m/s. Dead Sea Bromine Group (DSBG), France) and short E-glass fiber (filament size 10 m, length 4 6 mm) (m/s. Binani Glass, India). Phenyl trimethoxy silane (PTMS) (m/s. Sigma Aldrich, USA) and dipropyleneglycol (m/s. Merck, Germany) were used as silane coating agent and lubricant, respectively. 2.2. Silane coating process Prior to filling in the PTFE matrix, both the fillers -Al2O3 and MgO were silane-coated to preclude hydrophilic nature of the fillers. Silane coating was carried out following the reference [5]. Initially, the pH of water was adjusted to 3 using acetic acid. 63 ml of this acidified water was added to 100 g of the ceramic filler. The concentrated slurry was vigorously agitated using a heavy duty mixer. After 1 h of mixing, PTMS was added drop-wise and continued mixing for about 30 min. The volume of the PTMS was calculated to obtain 1 wt.% silane coating over the filler. The resulting mixture thus obtained was transferred to a glass container and dried at 120 C for 12 h to obtain silane-coated filler. 2.3. Fabrication of composites Since PTFE has very high melt viscosity (>1011 Pa s), common processing techniques used for the fabrication of thermoplastics such as injection molding, melt extrusion, etc. could not be employed for the fabrication of PTFE products. The performance of PTFE-based microwave circuit materials largely depends on the distribution of the particulate filler in the matrix. This is particularly important while loading high permittivity filler materials, which in turn induce fringing capacitance due to non-uniform filler distribution [5] and [8]. Hence, the fabrication process employed for PTFE-based composite substrate must ensure uniformity of the filler distribution in the PTFE matrix so as to minimize the dielectric anisotropy of the heterogeneous composite system. So a process comprising of Sigma Mixing, Extrusion, Calendering followed by Hot pressing (SMECH process) [9] and [10] was employed to obtain dense, nearly isotropic and dimensionally stable composite substrates of size 100 mm (L) 100 mm (B) 625 m (T). The role of E-glass fiber in the composite matrix is to impart mechanical strength and to control surface properties of substrate for Cu-cladding. Since we obtained desirable mechanical and surface properties for composites filled with 2 wt.% of chopped E-glass fiber [10], the same amount of Eglass fiber is retained in all other composite samples. 2.4. Characterization studies The microwave dielectric properties of the hot pressed samples were studied using X-band waveguide cavity perturbation technique [11] and [12]. The advantage of waveguide cavity perturbation technique is that it requires only thin rectangular samples and measurements are possible at several discrete frequencies in a single setting covering the whole frequency band. Agilent make PNA E8362B Vector

Network Analyzer was used in the X-band (8.2 12.4 GHz) region. The dielectric constant and loss tangent are average of values obtained for five discrete frequencies in the entire X-band range. The uncertainty in rand r using waveguide cavity perturbation is estimated to be 2% [11]. Dimensional method was used to find out the density of the PTFE composites. Moisture absorption of the composite substrate samples was carried out as per IPC-TM-650.2.6.2.1 method. Surface morphology and filler distribution in the composite samples were analyzed using m/s. Philips, The Netherlands make SEM (Philips XL-30) with an accelerating voltage of 15 kV. Samples were sputtered with gold layer and both the planar and the brittle fractured cross-section surfaces were analyzed. 3. Results and discussion The heterogeneous composites prepared in the present study comprise of PTFE/alumina and PTFE/magnesia composites reinforced with short E-glass fiber. Planar and cross-sectional SEM micrographs of PTFE composites loaded with alumina and magnesia fillers are shown in Fig. 1(a d). From the micrographs, it can be seen that the particulate fillers are homogeneously distributed throughout the polymer matrix in alumina filled composite whereas non-uniform filler distribution and porosity are observed in the samples filled with magnesia powder.

Full-size image (135K) Fig. 1. SEM micrographs of (a) planar PTFE/alumina substrate, (b) cross-sectional PTFE/alumina substrate, (c) planar magnesia filled PTFE substrate and (d) cross-sectional magnesia filled PTFE substrate.

Calendering is a decisive step in SMECH process where in the particulate fillers are uniformly distributed through out the matrix once the green tape reaches <100 m thickness. In general 625 10 m or higher thick planar laminates are used for microwave circuit fabrication. In the present study, 625 m thick hot pressed samples are prepared by stacking 10 layers of <100 m thick calendered tapes. In view of this, cross-sectional micrographs of composites are of particular importance owing to the possibility of delamination of stacked calendered green tapes during hot pressing. It is clear from the crosssectional SEM micrograph of the composite samples that the stacked green tapes are well fused without any delamination after hot pressing thereby ensuring the efficacy of the SMECH process employed for the fabrication of flexible PTFE-based laminates. Dielectric constant and density of the constituent phases are 9.96 and 3.96 g cc 1 for alumina, 9.80 and 3.58 g cc 1 for MgO, 2.10 and 2.17 g cc 1 for PTFE, 6.26 and 2.55 g cc 1 for short E-glass fiber

respectively[4], [7] and [13]. Thus, the bulk densities of the composites are found to have substantial influence on the amount of the particulate filler in the polymer matrix since the ceramic fillers have relatively high density and dielectric constant compared to that of polymer matrix. Variation of density and dielectric constant of the PTFE composites, >99% pure with respect to wt.% of alumina and magnesia fillers are shown in Fig. 3. As the filler loading increases, the density of the composite system increases linearly for both the fillers. The particle size of magnesia and alumina fillers is almost similar and has comparable particle size distribution which is given in Fig. 2. Recently we have reported that up to 66 wt.% of 3 m alumina can be loaded in the PTFE matrix to form dense composite substrates whereas only 56 wt.% loading was only possible with 0.4 m alumina, beyond which porosity is introduced in the hot pressed composites [10]. It is inferred that one of the factors that influences filling fraction of a composite is the surface area of filler because adequate polymer is required for encapsulating the filler surface to form a pore free and dimensionally stable laminate. Since both alumina and magnesia have comparable particle size and surface area, it was expected that both would have similar packing fraction. Contradictory to the expected results, the density of the magnesia filled samples is observed to be comparatively less and shows a decreasing trend after 50 wt.% loading (Fig. 3). Whereas, in the case of alumina filled composites, higher densities are attained and unlike for MgO filled composites, an increase in composite density is noticed even after 50 wt.% filler loading. The high porosity seen in the SEM micrograph further establishes the relatively low density values of magnesia filled samples (Fig. 1(c and d)).

Full-size image (82K) Fig. 2. Particle size distributions of (a) -alumina and (b) MgO fillers.

Full-size image (16K) Fig. 3. Comparison of density of silane-coated alumina and magnesia filled PTFE substrates.

The measured X-band dielectric constant values for the alumina and magnesia filled PTFE samples are given in Fig. 4. The plotted dielectric constants and loss tangents are average values calculated corresponding to five discrete frequencies in the X-band. It is seen from the figure that the dielectric constant of the composites shows an increasing trend with respect to filler loading up to nearly 60 wt.%, since the polarizability of the ceramic fillers are higher than that of the matrix. It is interesting to note fromFig. 4 that although the permittivity of both alumina and magnesia fillers are nearly equal, the

composite systems show different characteristics while loaded in the PTFE matrix. Alumina filled composites exhibit higher permittivity values compared to that of magnesia filled samples. Similarly, the loss tangent of the composite systems also shows remarkable difference (Fig. 5). The magnesia filled samples exhibit high loss tangent values compared to those filled with alumina.

Full-size image (13K) Fig. 4. Comparison of dielectric constant of silane-coated alumina and magnesia filled PTFE substrates at X-band.

Full-size image (14K) Fig. 5. Comparison of loss tangent of silane-coated alumina and magnesia filled PTFE substrates at Xband.

In order to understand the unexpected microwave dielectric properties of magnesia filled samples, X-ray diffraction pattern of the magnesia filled composite was recorded which is given in Fig. 6. XRD pattern shows peaks corresponding to Mg(OH)2 (Brucite phase) in addition to the expected PTFE and MgO reflections. The presence of brucite phase in the magnesia filler can influence considerably the end properties of the composite system since brucite phase has low density, low dielectric constant and high loss tangent compared to that of magnesia. Hence, it is inferred that the reason for the low filling fraction and inferior dielectric properties of magnesia filled PTFE composites are more likely due to the influence of brucite phase. In order to probe the evolution of brucite phase in the composite system, the powder XRD pattern of as received MgO was recorded which did not show the presence of any mixed phase (Fig. 7). However, the XRD pattern of the magnesia powder after silane coating treatment clearly shows the presence of brucite secondary phase (JCPDS 07-0239) together with MgO (periclase) major phase (JCPDS 45-0946). Hence it is concluded that the brucite phase has essentially formed during the silane coating process.

Full-size image (12K) Fig. 6. XRD pattern of magnesia filled PTFE composite. Peaks due to impurity brucite peaks are seen.

Full-size image (14K) Fig. 7. Powder XRD pattern of (a) as received MgO and (b) silane-coated MgO indicating presence of brucite phase.

Under filled composite laminates will have better mechanical properties, but suffer from dielectric anisotropy due to random orientation of the particulate fillers. It will also have the disadvantage of higher coefficient of thermal expansion. Whereas higher loading fraction induces porosity in the final product which in turn adversely affects its moisture absorption characteristics. It is ideal to have optimum filler loading for better control over the critical properties and the reproducibility of the same. Composites were prepared using silane-coated alumina and magnesia fillers with 2 wt.% loading interval in the PTFE matrix to arrive at optimum filler loading. Fig. 8, Fig. 9 and Fig. 10 show density, dielectric constant and loss tangent of silane-coated alumina and magnesia filled PTFE composites at optimum loading level. Since silane-coated magnesia samples have deleterious microwave dielectric properties due to the presence of brucite phase, the as received brucite free magnesia powder was filled in the PTFE matrix through SMECH process to obtain optimum filler loading.

Full-size image (18K) Fig. 8. Comparison of densities of the as received magnesia filled PTFE with silane-coated magnesia and alumina filled PTFE samples.

Full-size image (18K) Fig. 9. Comparison of dielectric constant of the as received magnesia filled PTFE with silane-coated magnesia and alumina filled PTFE samples.

Full-size image (19K) Fig. 10. Comparison of loss tangent of the as received magnesia filled PTFE with silane-coated magnesia and alumina filled PTFE samples.

Comparison of density, dielectric constant and loss tangent values of silane-coated magnesia, the as received magnesia and alumina filled composite samples are given in Fig. 8, Fig. 9 and Fig. 10respectively. It can be seen from Fig. 8 that compared to silane-coated magnesia, the as received magnesia could be filled up to a high filling fraction of 64 wt.% as against 56 wt.% in the case of silanecoated magnesia filled composites. The density of the as received magnesia filled composite system has considerably improved (2.45 g cc 1) at optimum loading which was compared with that of silane-coated magnesia filled composites (2.0 g cc 1). The improvement in density for the as received magnesia filled composites can be attributed to the absence of brucite phase. In addition to density, dielectric properties also show considerable improvement while loading brucite free magnesia in PTFE matrix. A comparison of the dielectric constant values at X-band of the as received magnesia, silane-coated magnesia and alumina filled samples is shown in Fig. 9 for comparison. The dielectric constant of the as received magnesia filled samples shows a definite improvement in comparison with that of the silane-coated composites. Again the improvement in dielectric constant can be attributed to the brucite free magnesia used as particulate filler. Moreover, the loss tangent of the as received MgO filled composites are better than that of silane-coated ones (Fig. 10) However, it is to be noted that both dielectric constant and loss tangent of the as received magnesia filled samples are not at par with the alumina filled composite system at the same loading fractions. Bare minimum moisture absorption (preferably <0.1%) is one of the important parameter for any composite materials to be used as microwave substrate [14]. Although most of the ceramic fillers are hydrophilic in nature, often silane coating is employed to prevent moisture absorption while incorporating ceramic fillers in the polymer matrix to tailor dielectric and mechanical properties for microwave applications. In the present study, both alumina and magnesia fillers are silane-coated to prevent the moisture absorption. Fig. 11 shows the variation of moisture absorption with filler loading for silane-coated alumina and magnesia filled PTFE composites. It is clear from Fig. 11 that as the filler

loading increases, moisture absorption also goes up due to porosity for both the composites under study. Silane-coated alumina filled samples exhibit very low moisture absorption characteristics (0.06% for 66 wt.% loading) whereas silane-coated magnesia filled composites exhibit moisture absorption as high as 2% at a filler loading of 56 wt.%. Interestingly, the as received magnesia filled samples have better moisture absorption characteristics (0.8% at 64 wt.% filler loading) than that of silane-coated one (Table 1). Although the moisture absorption characteristics of the as received magnesia filled samples are much desirable than that of silane-coated ones, further improvement is definitely needed to bring down the moisture absorption characteristics for device applications. Since water-based silane coating process helps in the formation of brucite secondary phase in MgO, water free silane coating techniques are being attempted for nanoscale silane coating over magnesia fillers which can provide substrates with better microwave dielectric and moisture absorption characteristics. A comparison of density, dielectric properties and moisture absorption of alumina, silane-coated MgO and the as-received MgO filled PTFE composites at optimum filler loading is shown in Table 1. The present study however shows that alumina filled PTFE substrates can be commercially exploited owing to their superior microwave dielectric and moisture absorption properties.

Full-size image (14K) Fig. 11. Comparison of moisture absorption of the silane-coated alumina and magnesia filled PTFE samples.

Table 1. Density, dielectric properties and moisture absorption of optimum filled composites Properties -Alumina Silane-coated MgO As-received MgO

Optimum filler fraction (%) 66 Density (g/cc) 2.8

56 2.0 3.35 0.015 2.0

64 2.45 3.98 0.0079 0.8

Dielectric constant (X-band) 4.3 Loss tangent (X-band) Moisture absorption (%) 0.0021 0.06

4. Conclusion -alumina and MgO filled planar PTFE composite substrates were successfully fabricated through the SMECH process. The ceramic fillers have been silane-coated to preclude the moisture absorption. SEM micrographs of the composites revealed homogeneous filler distribution throughout the polymer matrix. The effects of filler loading on the microwave dielectric properties of alumina and magnesia filled composite substrates were compared. Silane-coated magnesia filled composite samples showed low density, low dielectric constant and high loss tangent compared to alumina filled samples. PTFE/Al2O3composite has a dielectric constant of 4.30 and a loss tangent of 0.0021 whereas PTFE/MgO composite has a dielectric constant of 3.35 and a loss tangent of 0.015 respectively at optimum filler loading. Brucite phase formation during silane coating is expected to be the reason for the inferior dielectric properties of silane-coated magnesia filled PTFE composites. The as received MgO filler was also incorporated in the PTFE matrix through SMECH process to compare the properties. Although better filling fraction, density and microwave dielectric properties were obtained for the as received brucite free magnesia filled PTFE composites, the moisture absorption characteristics were inferior compared to that of alumina filled composites. On the other hand, present study concludes that alumina filled PTFE composites have excellent microwave dielectric properties, superior moisture absorption characteristics and hence can be exploited for microwave substrates applications. Acknowledgements The authors are grateful to m/s. Sumitomo Corporation, Japan for providing alumina powder and m/s. DSBG, France for providing MgO powder. We are also thankful to Dr. K.R. Dayas, Director, C-MET, Thrissur for extending facilities to carry out this work. References [1] D.N. Light and J.R. Wilcox, IEEE Trans. Compon. Pack. Manuf. Technol. 18 (1995), p. 118. Full Text via CrossRef | View Record in Scopus | Cited By in Scopus (9) [2] B. Daigle, Proceedings of the IEEE ECTC Florida, USA (1996), p. 354. Full Text via CrossRef | View Record in Scopus | Cited By in Scopus (3) [3] Y. Chen, H. Lin and Y. Lee, J. Polym. Res. 10 (2003), p. 247. Full Text via CrossRef | View Record in Scopus | Cited By in Scopus (33) [4] L.A. Wall, Fluropolymers (1st ed.), Wiley Interscience, New York (1972). [5] D.J. Arthur, J.C Mosko, C.S Jackson, G.R Traut, US Patent No. 4849284 (1989). [6] L.M. Walpita and M.R. Ahern, IEE Proc. Microw. Anten. Propag. 147 (2000), p. 285. Full Text via CrossRef | View Record in Scopus | Cited By in Scopus (4) [7] J. Krupka, G. Richard, M. Kuhn and H.J. Heyan, IEEE Trans. Microw. Theory 42 (1994), p. 1886. Full Text via CrossRef | View Record in Scopus | Cited By in Scopus (95) [8] V.S. Nisa, S. Rajesh, K.P. Murali, V. Priyadarsini, S.N. Potty and R. Ratheesh, Compos. Sci. Technol. 68(2008), p. 106. Article | PDF (360 K) | View Record in Scopus | Cited By in Scopus (15)

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Materials Chemistry and Physics Volume 113, Issue 1, 15 January 2009, Pages 290-295