Blectr Ene DOT 10,1007/400202.016-0898-7 ORIGINAL PAPER, Accelerated aging investigation of silicone rubber/silica composites for coating of high-voltage insulators ‘Muhammad Ai Received: 26 January 2016 / Accepted: 25 November 2016 (© Springer-Verlag Berlin Heidelberg 2016 Abstract Room temperature vulcanized silicone rubber (RTV-SiR) is a prominent polymeric material for coating of high-voltage insulators. Like other polymeric materials, silicone rubber also exhibits aging in outdoor applications. Silica is one of the most effective additives for properties" enhancement of polymeric materials. To analyze the effect of siliea on the aging behavior of RTV-SiR, we prepared its two silica-based composites with 10% micro +59% nano and 15% microsilca. Prepared samples are subjected to accelerated stresses such a8 ultraviolet radiation, acid rain, hacat, and fog for 9000h in a specially fabricated cham- ber. For timely analysis of the samples, scanning electron ajcroscopy (SEM), Fourier tansform infrared spectroscopy (FTIR), leakage current monitoring and Swedish Transmis- sion Reseatch Insitute hydrophobicity analyses are used along with continuous visual inspection. In the course of time, all samples showed gradual decrease in transparency. Incvease in leakage current was highestin case ofthe neat SiR (GiK-0) and lowest in case of the hybrid composite (SiR-2). Initial values of leakage current for SiR-0, SiR-I and SiR-2 4 Abra Khattak abraiz ke @ gmail com of Hlectrical Engineering, Ghulam Ishaq Khan KI) of Engineering Sciences and Technology, Topi, Pakistan 2 Department of Blectical Engineering, COMSATS Institute of fafermation Technology (CIT), Wah, Pakistan Department of Hlectical Engineering, City University of Secnce and TT (CUSIM), Peshawar, Pakistan Department of Elecvica Engineering, University of Engineering and Technology (VET), Taxila, Pakistan Published oaline: 03 December 2016 Abraiz Khattak®? . Muhammad Alit were 0.5, 0.5 and 0.31A, respectively, and after aging the increased leakage current values were 0.9, 0,8 and 0.6 KA, From FTIR, the lowest decrease in the intensities of absorp- tion peaks of important groups in SiR-2 were recorded. In ‘SiR-O, the peaks of symmetric C-H stretching of CH and Si- CH, symmettic bending after 9000h were 91.7 and 94.6% of virgin, respectively, In SiR-I and SiR-2, symmetric C- H stretching of CH, exhibited an increase which was 120 and 110%, respectively, while Si~CHy symmetric bending remained 95% of virgin in SiR-1 and nearly 97% in SiR-2 after 9000, Final hydrophobicities of SiR-O and SiR-1 were HC-2, while comparatively SiR-1 bad higher hydrophobicity class of HC-1. SEM results also exposed least changes in the surface of hybrid composite. Silica revealed great impact on the aging behavior of silicone rubber which was highest in the case of the hybrid composite. Keywords Composites FTIR TRI Leakage current Coating - Aging - SE 1 Introduction Usage of ceramic insulators dates back to 1880s, while they were implemented and commercially accessible dur- ing the last decade of nineteenth century [1,2]. Since the time, advancements in its various aspects for instance shape, design, dielectric strength, resistance against flashover, cost and improvements in other properties were made possible [2,3]. However, for improvement of surface hydrophobicity and to minimize leakage current, these insulators are coated ‘with polymeric material [4] Due to their organie nature, polymeric materials have the issue of aging specifically in outdoor environment. Ulra- violet (UV) radiations, heat, humidity, acid rain and fog D springerElectr Bog are some of the examples of environmental stresses [510]. ‘These stresses affect physical, chemical, electrical, thermal and mechanical properties of polymers [9, 11-15} Room temperature vuleanized silicone rubber (RTV-SiR) isa frequently recommended material for outdoor HV insu- Jators’ coatings in comparison to other polymeric materials due to ils excellent weathering and heat resistance. Its an elastomeric organo-siloxane polymer which mainly consists of silicon with carbon, oxygen and hydrogen, The presence of hydrocarbon groups makes it an acceptable rubber, while the Si-O bond imparts its inorganic properties [16-18]. Due {othis hybrid nature, ithas excellent insulating properties and ‘unique hydrophobic behavior [19,20]. RTV-SiR has differ- cnt applications in many fields, g., bio-medical engineering, industrials rolls and coatings of high-voltage insulators, ete [21-24]. As the name indicates, RTV-SiR is cured at room temperature. Its specifically fabricated to obtain SiR with special features such as flame retardancy. RTV-SiR is pre- pared by two components, i., base and curator [25] and itis ‘an important class of SiR used for coatings of ceramic insula tors to minimize leakage current and enhance hydrophobicity of overall insulator [26]. RTV-SiR is known for its better ‘weather resistance in comparison to other polymers and has ood insulating properties. However, it also degrades after some period in outdoor applications [27,28]. Weathering resistance of RTV-SiR is needed to be improved to attain it with extended service life. One of the most efficient ways to improve the life expectancy of silicone rubber isto obtain its composites using nano- and micro-filers. To obtain polymeric composites with their precise char- acteristics, they need careful preparation according to the standard procedures [29]. Moreover, for exploration of envi- ronmental aging these prepared composites need to be evaluated under uniform stresses along with neat SiR. In a review [8], contributions of many authors on aging of silicone rubber were highlighted; also aging techniques for polymeric insulators were described. Accelerated multstress weather- ing (AMW) is an efficient way for assessment of polymeric materials. AMW is an artificial weathering procedure and is performed in the Iboratory. In comparison to field/natural aging, AMW not only reduces operation time and cost but itis also helpful to readily examine the insulators through different analysis techniques in the laboratory [30] Few contributions were made on study characteristics and their improvements for RTV-SiR. However, there are still gaps in refining performance of RTV-SiR. In [31], only improvement of hydrophobic behavior for RTV-SiR was dis cussed by adding aluminium-tri-hydrate (ATH), and also stresses other than UV were not taken into account. While in [52] hydrophobicity, surface charge and flashover character- istics for only neat RTV-SiR were reported ‘There are many types of nano- and micro-filers that canbe used for properties’ enhancements of silicone rubber [33]. In D springer some cases, nano/micro-fillers can bring superior enhance- ‘ments in the required properties of polymers. Different types of reinforcing fillers can be used for this purpose. By many researchers, nanocomposites and hybrid composites were studied [34,35]. Improvements of properties of polymers depend on size, type and loading of fille. Therefore, further studies on type and concentration of fillers for SiR are still requited. Among wide range of these fillers, silica (SiO2) is an inorganic filler that provides resistance against thermal, ‘mechanical and electrical stresses and, thus, can slow the aging time and enhance the performance of SiR [12, 36,27] ‘The authors of [38] used up to 2 w1% nanosilica and electri- cal teeing characteristics of RTV-SiR were focused. Other studies such as (39—11] were conducted on RTV-SiR and its composites. However, they were specific to particular property, and also lacked the realistic practical conditions, Although the previous work done by many authors on RTV- Si is a contribution towards its durability, still long-term study ofthe silicone rubber in a multistress environment has rnot been done. The long-term study is important because degradation and recovery of polymers are random and unpre- dictable, and the results may not be reliable on the basis of short time explorations. Therefore, silicone rubber should be investigated under multi-stress weathering environment along with its composites for adequate long time. Keeping in view the above motivations, we prepared silica-based micro and micro/nanocomposites of RTV-SiR, ‘The composites and neat sample are degraded all together through multiple environmental stresses for 9000h in a spe- cially fabricated environmental chamber withreference to the neat RTV-SiR. Furthermore, leakage current analysis, STRI hydrophobicity classification, FTIR and SEM are used along. ‘with critical visual inspection to analyze different variations in the samples. 2 Experimental details 21 Preparation of samples RTY silicone rubber (RTV-615) was procured from Lanxess Chemicals Co,, Germany, microsilica was purchased from Waban Newseach chemicals Co., China and nanosilica (42mm) was procured from Degussa Chemicals Co., USA. ‘Composites were prepared according to the percentage weight (% wt) of the fillers and polymer. For example, 5% ‘wt, microsilica composites refer to samples that are made by iixing Sg of microsilica and 95g of RTV 615 silicone rubber ‘having 86.36 g RTV 615-A base polymer) and 8.64 g RTV. 615-B curator. The ratio of the base polymer to curator was kept 10:1 ina sample, The maximum amount of nano-fumed silica loading was restricted to 5% wt. in hybrid composite,Blecte Boe A Prepared SiR.0, SiR-1 2 amples Kalle Wr) ‘Table 1 Samples and their codes ple name ‘Sample code Filler concentration (wt) Newt silicone mbber SiR om Silicone rubber SiR 155 microsilica ierocomposit Silicone rubber nano’ SiR-2 10% microsite and microcomposite 5% nanoilica ‘Avhigh shear laboratory mixer with a sonicator was used for the preparation ofthe silicone rubber composites [42] ‘The silicone rubber composite samples were prepared in three steps. In first step, dry fillers were gently added to RTV. 615-A, while keeping the mixing speed low to wet out the fillers. After the fillers got properly wet, the mixing speeds ‘were gradually increased (o the maximum revolution per ‘minute (tpm) and were kept at the same maximum speed ‘ntl the mixture did not show any visible signs of lumps. In second step, after 2-3 min of cooling, RTV 615-B was added tothe mixture and mixed at low speed for 2min by a sonicator and then the mixture was degassed in a vacuum at 27 inHg until the bubbles were completely removed. In third step, the silicon rubber mixture was discharged into molds and allowed to cure at room temperature for 24h. Subsequently, the samples were post-cured for 4h in an oven at 90°C. List, of the prepared samples is given in Table 1. Photographs of prepared samples are given in Fig. 1. All the prepared sam- ples had 80 mm diameter and 3 mum thickness. 2.2 Accelerated aging setup Anenvironmental chamber with dimensions of Im x 2m x ‘Lm was fabricated in which the neat SiR and its composites were energized with 2.5 kV voltage through 220V/2.5kV. ‘wansformer having output current capacity of nearly 100 mA. Schematic diagram of accelerated weathering cham- ber is shown in Fig. 2a and b shows picture of chamber in ‘operating conditions, Different environmental stresses such as controlled ultra- violet (UV) radiations, temperature, humidity, acid rain and salt fog were applied timely along with the electrical stress. ‘To include variable heating stress, 1500 W (max.) heater was used, For ultraviolet radiations, (wo UV lights (xenon lamps) were used, each of 15W ie., 15 x 2 = 30W to make lumi- nous intensity ImWyem? as per IEC 61109. The samples position can be seen in Fig. 2. 11C1 dilute solution with pl 4,5 was used for acid rain purpose, Two accelerated weather cycles based on weather data of Hattar were followed during the experiment, ie., summer cycle which was of 11 days and winter cycle which was of 17 days. During summer cycle, temperature was kept 47.3 °C and in winter cycle it was 35.2 °C. The temperature was calculated by taking average of _maximum temperature of amonths’ cycle (May-October and April-September) and adding 11 °C as explained in [43,44] Sommer cycle (11 days) temperature 2A3°C4 11°C = 353°C Winter eycle (17 days) temperature 362°C+ 11°C = 472°C Specifications of accelerated weather eycles are shown in ‘Table 2. Values for other stresses such as pH for acid rain, salt fog and humidity were applied by finding the appropriate effect of these stresses in actual environment. Furthermore, {or preparation of this experimental setup, ASTM D286SM- 06, IEC 62217 ed2.0 and IEC-61 109 standards were used as uides. 2.3 Instruments and analysis techniques 2.3.1 Visual inspection To check the insulators for major degradation or cracking, each sample was analyzed through a lens under lamp. To record the surface condition of samples, their photographs ‘were taken in daylight using a high-resolution digital camera, 23.2 Hydrophobicity classification To measure the degree of water repellency after every weather cycle, each sample was examined using Swedish Transmission Research Institute (STRD hydrophobicity clas- sification method. A total of 28 hydrophobicity tests were D springerFig. 2. Accelerated mulstress @) avironmental chamber. a Schematic. b Photograph of, experimental setup Salt Fog Tenperature Control b) pesformed, Each sample was sprayed for 20s with tap ‘water and then its hydrophobicity was evaluated within 105 according to the STRI guide by comparing images of the samples with the standard images (HC1-1C7). The photos ‘of sprayed samples were taken with a high-resolution digital D Springer Wamp Energized Samples Electr Bog “Temperature, Humalty and UV radiations’ Sensors tap? Heater and Humidity Display (Connectedto chambes) 23.4 Leakage current measurement Alternating leakage current was measured directly using pre- cision micto-ammeter (UT-70B) after each weather cycle, ‘Thus, a total of 28 leakage current measurements were recorded during 9000h period.Blecte Boe ‘Table 2 Weathering cycles ‘applied sess Sommer Winter ‘Test volage 25kV, 25kV Length of eyele (days) n 0 “Temperature (°C) 472 353 UW.A dhiday) 10 8 ‘Acid rain 45 pt) 6 times Dimes Salt og (6000 Siem) ° “4 imes Relative humidity (%) 85 2.34 Fourier ransform infrared (FTIR) spectroscopy FTIR spectroscopy was performed to analyze structural changes in the samples from Oh (virgin) to 9000h, For this purpose, spectrographs of samples in absorption form were obtained through Perkin-Elmer Spectrum 2000 FTIR spec- trometer after each 1000h. A total of six were obtained for each sample during 9000h aging period. In all the tests, potassium bromide (KBr) powder was used as a transparent material 2.3.5 Scanning electron microscopy (SEM) To investigate the surface morphology of virgin and aged samples at micro-level, scanning electron microscopy (SEM), ‘was used before and after aging. Before subjecting to SEM, the materials were gold coated. The images were taken at Sym scale by applying 20 kV voltage, SEM-Hitachi (SU- 1500) was used for SEM analysis. 3 Results and discussion 3.1 Visual inspection “Major cracking or degradation was not recorded in any sam- ple during routine visual inspection. All hee samplesremain in acceptable condition and look adequate by examining them through lens under lamp, Opacity of samples increased ‘gradually with aging as can be seen virgin and 9000h aged samples of SiR-0, SiR-1, and SiR-2 from left to right in Fig 3aandb respectively. However, color fading of this level is considered normal in polymeric materials [45,46]. 3.2 Hydrophobicity analysis Hydrophobicity of each sample was recorded by matching the samples with standard images of STRI hydrophobicity ‘guide [47], and recorded as given in Table 3. Images of only virgin and 9000h aged samples after hydrophobicity tests are Fig. 3. Samples’ photographs: a vigin,b 90008 aged ‘Table 3 Hydeophobicty class of SIR-0, SIR-1 and SiR-2 from virgin Sino. Agingperiod STR hydrophobicity clase SRO SRI SRD 1 (virgin) wer HCL Hed 2 268 Het HE? HCA 3 on HEL HCl HCA 4 936 He. He2 HC 5 134 Hel HE2 Hea 6 1908 wea HED CL 1 2016 Hes HGS Hea 6 2280 He? HES HCA 9. 2688 Hel HC2 He 10. 2982 Hea HCI Hea in 3360 Hea HCL HCA n. 3028 HED? HGS HC BB. sz Ho2 HCD 14 4296 wea -HC2 He 15, 4708 Het HCL HCA 16. 4968 HEL HGS HCA 1. 5376 Hes HGS HC 18, 5640 Wel HGS He 18, 0s Hes HES Ha 2. os Hea WeSC 21 “m0 He? -HC2 HC 2. 6980 Hel? HCD HC 2, 02 wet HCI «Hea 24, 1656 Het HET He 2 068 HOI -HC2 HCA 2. 328 Hel HCL HCA 2. 8136 wea HCL CA 2. 000 wea He? HeElectr Bog Fig. 5 Images of SiR, SiR-I and SiR.2 for hydrophobicity test given in Figs. 4 and 5, respectively. Samples are arranged as, ‘SiR-O, SiR-1 and SiR-2 from left to tight, zexpectively. SiR-O starting from HC-2 showed clear variation in its hydropho- bicity in which recovery was observed at many points. This nature of silicone rubber has been previously reported by ‘many authors and is attributed to the rotation of backbone chain and transfer of low weight molecules to the surface [19], The maximum decrease inthe hyédrophabicity of SiR-O ‘was recorded at 6048 of aging and then recovered to HC-2 while showed HC-1 at 7656h and maintained this hydropho- bicity Gill 8328h, However, SiR-0 showed its initial value of hydrophobicity in last two tests, Le., HC-2. SiR-1 did not show much variation in hydrophobicity from SiR-O and it ended with IIC-2. During 4968 and 6048h, SiR-1 maintained its hydrophobicity at HC-3; this indicates thet microsilica has no significant influence on the improvement of hydrophobic behavior. During hydrophobicity analysis, SiR-2 performed differently than SiR-O and SiR-1. SiR-2 started from HC-1 and touched HC-2 only 7 times during entire 9000h aging. During rest of the tests, it maintained minimum hydropho- bicity class HC-1, Among all polymeric insulating materials, silicone rubber has best hydrophobicity property. The loss of hydrophobicity of SiR is comparatively ess, butitalso recov- ers with time. The reasons for this are high bond energy of siloxane which resist chain scission and also Si~CHy bond cchain length is greater than hydrocarbon methyl chain of other hydrocarbons. Furthermore, relatively higher mobil- ity of backbone chain in SiR also contributes to this unique behavior [48] ‘The SiR-2 sample's improved hydrophobic behavior over ‘SiR-O may be due to the strong interaction between silanol D springer = SIRO) ‘Leakage Current (uA) 2 0 4800" 3600” 4500" @d00” 7800” 9d00 Aging Period (Hours) Fig. 6. Variation in leakage current with increasing aging period ‘groups present in nanosilica and SiR network, due to which the main groups of SiR remain intact against stresses. How ver, this hydrophobicity may decrease with further increase in silica loading [49] 33 Leakage current analysis, ‘The trend in variations of leakage currents of the SiR-0, SiR- 1 and SiR-2 is given in Fig. 6, From Fig. 2, itean be observed that like hydrophobicity leakage current forall the samples varied in complex unpredictable manner. Although not linear Dbutall the three samples exhibited incvease in leakage current with the decrease in hydrophobicity ‘Among all three samples, SiR-0 showed highest values of LC followed by SiR-1. SiR-2 relatively had overall least Teakage current and at some points it also touched the initial value of leakage current, £¢0.3 LA. The maximum values of leakage current were recorded in all samples nearly 4000, ‘SiR-2 with both nano and microsilica ended with east value 0f 0.6 WA. Although SiR-1 showed little higher values of leakage current as compared to SiR-2, it performed better than SiR-O during leakage current analysis. The suppression of leakage current in composites may be due to the increase in over~ all resistance imparted by silica. Decrease in hydrophobicity causes higher surface resistivity and, thereby, lowers leakage current. Like hydrophobicity, the same reasons of changes at molecular level are responsible for reduced leakage currents in nanocomposites which are clear from hydrophobicity and leakage current relation explained in [50]. 3.4 Fourier transform infrared spectroscopy ‘Variation in all wavenumbers occurred which shows continu ‘ous chemical changes in both composites and SiR-0. Ina the {ests, potassium bromide (KBr) powder was used as a transBlecte Boe @ © @ - (sire 3000) ie i a a ) Aorta =] @) ® eran 2 snozs00% os . exe o LW Absoranes Fig. 7 Specteographs of SIR: a virgin, b 10008, € 2000, d 3000, € 4000, f 50008, g 60008, b 70001, i $000k, j 90001 2D springerElectr Bog ob) ll Avene aan © @ i. . © ©, 7" SIRT = 20087) (g)+2 (ny a ie Fig. § Spectrograph of SiR-I. a Vzgi, b 1000b, ¢ 2000, d 30008, ¢4000%, £0008, = 6000b, b 7000, $000k, j 90008 D springerBlecte Boe (a) Avo of oe = =n «e) Do» hes oe @ ow @ oe Fig. 9 Spectrographs of SiR-2: a virgin, b 10008, €2000h,d 3000, € 4000h,f 5000, g 60008, b 70001, § $000k, j 90001 2D springerElectr Bog Table 4 Important groups in Sif and relevant absorption bands Group ‘Wave number ear ‘Symmetiic CHT stretching of CH ~2963-2960 SACHS symmetric hending 1280-1255, Si0-c SiO-Si asymmetric stretching etching 1110-1050 30-1000 Si-0 of O-SUCHs)s ~s70-850 SiA0 of O-S4(CHs)-0 ~s40-390 Si-of SL(CHy)s ~00 parent material. Spectrographs of SiR-0, SiR-2 ate given in Figs. 7, 8 and 9, respectively, Important groups in SiR and relevant wavenumbers are given in Table . In SiR-0, loss in absorption peaks of symmetric C— Hi suetching of CH; and symmetric bending of Si~CH occurred at ~2963-2960 and ~1280-125Sem™', respec tively, tl $000h of aging, but afterwards increases in absorption peaks at these wavenumbers were recorded. ‘The peaks of symmetric C-H stretching of CH and Si- (CH; symmetric bending after 9000h were 91.7 and 94.6% of virgin, respectively. The increase in C-H bonds on the sutface is the indication of hydrophobicity recovery which is also evident from hydrophobicity analysis. The Si~O-C stretch- ing at ~1110-10S0cm~" exhibited decrease in absorption peak and remained 74.5% of the virgin sample, Similarly, Si-O-Si asymmetric stretching at ~1130-1000em7, Si-O (of O-Si(CHs)s at ~1130-1000em™!, Si-O of O-Si(CHs)- © at ~870-850em~! and Si-of Si(CHs)s at ~700em™! showed decrease in absorption peaks and at the end of 9000 ‘of aging their peaks recorded were 75, 70, 70 and 56% of vir- ain, respectively. Variation in absorption peaks can be seen through data extracted from FTIR spectrographs of virgin to 9000h aged samples of SiR-0 given in Table 5. FTIR analysis for SiR-1 showed that absorption peak at ~2963-2960cm™! exhibited gradual increase, which shows twansfer of hydrophobic methyl group from material bulk to the surface. Similstly, though initial decrease in Si-CH symmetric bending was greater, itrecovered and showed 5% decrease atthe end of 90008, Si-O-C stretching showed 23.7% decrease which is lesser in comparison to SIRO. At the end of 9000h, absorp- tion peaks at Si-O-Si asymmetric stretching at ~1130— 1000cm"t, Si-O of O-Si(CHs)s at ~1130—1000em~, Si-O of O-Si(CH3):~O at ~ 870-850em! and Si- of Si- (CHs)s at wavenumber ~700 were 80, 74, 74.5 and 75% ‘of visgin, zespectively. Variation in the absorption peaks can be seen through data extracted from FTIR graphs of virgin to 9000h aged samples of SiR-1 given in Table 6. SiR-2 showed slightly higher absorption peaks related to impor- tant groups as compared to SiR-1. Like SiR-1 at the end of D springer Table Absorption peaks in SIRO at elevant wavenumbers frm 0 (vitgin) to 90008 “Absorbance 2 30008 Percentage of 000% S000% 8 virgin afer 900h vepineter 50008 96 0.055 035 035 06 0055 03 oar 06 0 005 03s 005 03 333 865 ss 0.05 6. 0.05 032 005 0.325 04s 082 02 0.085 om oa 005 035 6 006 oat ©. é & 4 a ‘Symmetric CH setching of Cl Si-CHY symmetric bending SLO suetehing 45: 2 us in 45 065 oa oa 065 a7 i o75 os 09 S125 15 5 “0 on on os os2 ous os oat os 30-1000 -$70-850, ~840-790 700 Si-O-Si asymmetric stretching S-0 of O-Si(CHL)s ou 70 o7 1s oa7 ous ow: 02 1 1 o7s 1.05 02 Si-O of O-Si(CHs):-0 om 56 02 02. 02 025Blecte Bog sors 9r0 esto. tO «ss uu usro ovo vo tO eo o0L~ serra = LO THEO. SLO soLO eu 0 LO 6D -oh~ o-XCHDHS-020 078 Leie8L STO sstO ssrO zs of ur ss10 sro seo. 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LL SLO ALO 510 OUT-VETT~ —__-Sumnans omnoms ru sro wo sro two HIS SPO LPO SPO LO SPO S80 OSOI-U Sexprons rons ws wo seo co iro vs yO Seo. ae SED gO ea SeeI-ORTI~ Serpuog senacouks SH oo wo S00 S00 Ol ss00 40 SOD_——TTD $0 SoD ON6e-FB6E~ ATO Fo FuMprane Hp stHeUMAKS "10005 2g wna 1000 Fae | 382341025154 49006 Hoos —_YoOOL ones JAFMEDHA _YoONS HOOF HOOK OORT _HoOOT EEA ameqoray —_paRG-oneyg soup "70006 01 (HEN) 9 WoH soguTAKeM HRNETA UES ePOd uondosay 9 IgE Springer asElectr Bog Fig. 10 SEM images. a Samples before and alter 9000 aging. b Magnified SiR-0.SiR-1 and SiR-2 after 90008 9000, aging period hydrophobic methyl group at ~2963— 2960cm~! increased which is also clear from hydrophobic analysis and Si-CHy ~1280-125Sem™! remained almost 97% of the virgin, Variation in the absorption peaks can be seen through data extracted from FTIR spectrographs of vir- gin to 9000h aged samples of SiR-0 given in Table 7, ‘Only 11% loss in the absorption peak occurred at ~1110-1050em™! which represents Si-O-C stretching. ‘Other important groups also degraded lesser comparative to SiR-O and SiR-I. At the end of 9000h of aging absorp- tion peaks of Si-O-Si asymmettic suetching at ~1130- 1000em™!, Si-O of O-Si(CHs)s at ~1130-1000em~, Si-O of O-Si(CHs):O at ~870-850em™! and Si- of Si- (CH); at wavenumber ~700 were 77.9, 78.9, 72.16 and 765% ‘of virgin, respectively. Variation inthe absorption peaks can be seen through data extracted from FTIR graphs of virgin to 9000h aged samples of SiR-2. In composites, least loss ‘of important hydrocarbons and minimum impact of oxida- tion are due to the intactness provided by hydrogen bonding of silanol groups of silica and oxygen atom of backbone chain in SiR [51-53]. The second reason for good hydropho- bic behavior of nanocomposite is due to the interaction of acidic Si-OH group with polymer groups, which reduces the swelling of polymer and water resistive interface is formed between nanosilica and the main polymer [54,55]. D springer 3.5 Scanning electron microscopy (SEM) ‘To analyze the surface topography of samples at micro-level before and after aging, scanning electron microscopy (SEM) was used. SiR-0 which is neat RTV-SiR showed sigoiti- cant material loss and erosion a8 a response to application of stresses for 90008. SiR-1 which is a microcomposite showed less surface degradation in comparison to neat sam- ple. SiR.0 ended with loss of materials along with minor holes and ruptures. After 9000b of accelerated aging, sur- face of SiK-0 showed higher degradation in comparison to SiR-1 and SiR-2. Although SiR-1 affected less as compared to SiR-0, SiR-2 had better surface intactness than SiR-L In SiR-1 surface erosion was slightly higher than SiR-2. This is due to the fact that nanosilica has better interac- tion with polymer matrix in comparison to microsilica. After aging, illers in SiR-1 were relatively highly exposed in com- parison to SiR-2. In Fig. 10a, SEM images of virgin and 9000h aged samples are given. Figure 10b shows magni- fied SEM image of the samples after 9000h aging. Large specific surface atea of nanosilica with abundance of silanol (Si-OH) groups provides intactness to the functional groups of SiR, which may cause in lower loss of material from surface of the SiR-2 [56]. Among all the three samples, SEM results showed that surface ofthe sample without silicaBlecte Bog {(SiR-O) affected more in comparison to silica-based compos- 4 Conclusions To investigate the aging characteristics of silicone rubber composites, microsilica and nano/microsilica-hased com- posites were prepared and tested for 9000h in a specially Tubricated aging chamber under multiple stresses along with neat SiR. Silica was found effective in bringing improve- ments in aging behavior of silicone rubber. In case of addition of both nanosilica and microsilica, this improve- ‘ment was profound. Relatively best hydrophobic behavior ‘and least leakage currents were recorded for hybrid com- posite. Similarly, FTIR results also showed least reductions in intensities of important hydrocarbon groups of hybrid composite, SEM results also concurred with other investi- ‘atory techniques. Neat SiR was found with lower aging resistance in comparison to both composites, Microcompos- ite performed moderate. At the end of 9000h aging hybrid composite had Ieakage current of 0.6 4A, hydrophobicity class IC-1 and comparatively had less loss in methyl groups and organo-silicon bonding. In SiR-2, Si-CH; and Si-O- C reduced only 11 and 4%, respectively. From this work, it was found that decrease in the susface quality of SiR and its composites contribute to loss in hydrophobicity, loss ‘of important hydrocarbons and increase in leakage current, Promising results were obtained for SiR/silica composites aimed at their usage in high-voltage insulation. However, further exploration of influence of environmental stresses on, the mechanical, dielectric and other physical properties of these composites is necessary References 1. Hailey KA (1951) Development ofthe Porcelain Insulator Trans ‘Am Inst Blectr Bag SO(1:47-51 Mackevich J, Shab M (1997) Polymer outdoor insulating material Pat: comparison of porcelain and polymer cleczical insulation, IEEE Elect Tnsul Mag 1313)5-12, 3. Yang L, Hao ¥, Li L, Zhao ¥ (2012) Comparison of pollution ‘ushover performance of porelain long rod, dsc type, and com posite UHVDC insulators at high altitudes. IEEE Trans Dieleett Elect Tasul 19(3}:1053-1059 4. GorurRS, Chemey B, de Tourei!, DumoraD, Harmon 8, Hervig H, Tay R (1995) Protective coatings for improving contamina tion performance of ou\dor high voliage ceramic insulators. IEEE, ‘Trans Power Deliv 10(2}:924-933, 5. Tochiéek J, Vritaiékovi Z 2014) Polymer lifetime prediction: the role of temperstare in UV accelerated ageing of polypropylene andits copolymers, Polym Test 36:82-8 6, LiZ, Moon KS, Yao Y, Hansen K, Watkins K, Morato L, Wong. ‘CP (2013) Carbon nanotobe/polymer nanocomposites: sensing the thermal aging conditions of electrical insulation components. Car- bon 65:71-79 24, 2s 2. 2, ‘Wang W, Yue C, He D, Yang K, Chen S (2014) A comparative analysis of delete propenies of ol-paper insulation and polymer mattials before and afer thermal aging. Sei China Technol Sei S74) T38-746 Amin M, AminS (2014) Aging researchon SiR And TPE insulators (an overview) Rev Adv Mater Sci 36:29-39 Pickett IE, Coyle DJ 2013) Hyérolysis kineties of condensation polymers under humidity aging conditions. Polym Degrad Stab ‘98(7;1311-1320 Amin M, Akbar M, Matsuoka R (2006) Etfest of UY_sadiaton, temperature and SALT Fog on polymeric insulators. ni IBEE 8th intemational conference on properties & applications of dielectric materials, TEBE, pp 611-514 Deroiné M, Le Duigou A, Core YM. Le Gae PY, Daves P, César G, Braud S (2014) Accelerated ageing and lifetime prediction of poly (-hydroxybutyrate-co-3-hydroxyvalerae) in distied water Polym Test 39:70-78, Cangialos D, Boucher VM, Alegria A, Colmenero (2012) Physi ‘al aping in polymers and polymer nanocomposites: recent results and open questions. Soft Matte 9(36):8619-630 “Marzee A, Laskowska A, Boiteux G, Zaborsi M, Gain O, Sergbei ‘A 2014) Study on weather aging of ntl rubber composites con- ‘wining imidazolium ionie liquids. In: Macromolecular symposia, vol 42, No I, pp 25-34 Vilar G, Fesndndez-Rosas E, Puntes V, Jamiet V, Aubouy Ly Vazquez-Campos § (2013) Monitoring migration and tansforma. tion of nanomaterials in polymetie composites duing accelerated aging_J Phys Conf Ser 429(1):012044 OP Publishing) ‘Zia VI, Zhang J, ing B, Tax YB (2013) Ageing effect on steady rheological behavior in oilfield water of water-soluble, bydropho- bically associating polymer Ady Mater Res T8.431-435 (Trans ‘Tech Publications) ‘Manired W, Sieftied N (1961) US. Patent No. 299,077. US. Patent and Trademark Ottice, Washington, DC Guill A, Patel VV, Gates SM (2002) U.S. Patent US. Patent and Trademark Otice, Washington, DC Braley 5 (1968) The silicones a subdermal engineering material Ann NY Acad Set H6(1):188-157 Reynders JP, Jandel TR, Reynders SM (1999) Review of aging and recovery of silicone rubber insulation for outdoor use. IEEE ‘Trans Diclect Blect nsul 6(9):620-631 ‘Meguriya N (2003) US, Patent No, 6,352,096, U.S. Patent and “Trademark Ofice, Washington, DC [Nakamura Hirabayashi S (1996) US, PtentNo, 582,885. US. Patent and Trademark Office, Washington, DC Shimizu K, Watanabe T, Hamada M (i982) U.S. Pateat No. 4,360,566. US. Patent and Trademark Office, Washington, DC Browa JB, Fryer MP. Randall P. Lu M (1953) Silicones in plastic surgery laboratory and clinical investigations preliminary epor. last Reconste Surg 12(5)'374376 ‘Lotiongkam C, Siler D, Heidmann G, Plath R, Gockenbach E (2014) The influence of thermal aging on AC dicleetre strength 5 transparent silicone rubbers for HV ineulaon In: Proceedings ‘02014 international symposium on electrical insulating materials SEIN), TEBE, pp 46-349 Bian S,Jayaram 8, Cherney BA (2012) Blectospinning as a new ‘method of preparing nanofled silicone rubber composites. IEEE. ‘Trans Dielectr Blect Tnsul 19(3): 777-185 ‘Kim SH, Cherney HA, Hackam K (1991) Suppression mechanism ‘of leakage current on RTV costed porcelain and silicone rubber insulators. IEEE Trans Power Deliv 6(4):1549-1556 Vas V, Veakatsulu B, Thomas M) (2012) Tracking and erosion of| silicone robber nanocomposites under DC voltages of both polati- ties. IEEE Trans Dileet leer Intl 19() 91-98 Bian §, Jayaram SH, Cherney EA (2012) Improvements to the ctosion resistance of nanofled silicone rubber composites by 679,110. D springerElectr Bog 2, 50. at 3. 23 4 55, 3, M. 36 29, aL 2. lectrospining. In: 2012 Annual eport conference on electical insulation and dileese phenomena (CEIDP), IEEE, pp 741-744 Amin M (2013) Methods for preparation of nano-composies for ‘outdoor insulation applications. Rev Adv Mater Sei 34 173-184 Saldvae-Gversero R, Heréndes-Corona R, Lopez-Gonzale FA. [Rején-Gareia L, Romero-Baizabal V @014) Application of unusual techniques for characterizing ageing on polymeric elee- ‘weal insulation. Elect Power Syst Res 117-202-209 Seyedmehdi SA, Zhang H. Zbu } 2012) Supethydcopbobic RV silicone rubber insulator coatings. Appl Su Si 258(7) 2972-2976 Ds BX, Li ZL (2015) Hydcophobieiy, surface charge and DC ‘ashover characteristics ofdrest-fuorinted RTY silicone robber TEE Trans Delete Elet Ines 22(2)954-950 ‘Monen G, Farzanch M (2011) Survey of microlnano files use to improve silicone rubber fr outdoor insulators. Rev Adv Mater Sei 270}1-13, Fabiani D, Montanati GC, Krivda A, Schmidt LE, Holler: R (2010) Epoxy based materials contsining micro and nano sized hile fr improved elestcal characterises, Tn: 2010 10 TEER international conference on solid dielectrics, IEEE, pp | Anhall M, WeidenfellerB (2011) Influence of llr content, paticle size and temperature on thermal dlisivity of polypropylen-iton filicon composites. Appl Polym Sei 119(2).732-735, ELtag AH. Jayaram SH, Chemney EA (2008) Comparison between silicone rubber containing enicro-and nane-sie silica filets [ines- Jang materia applications), In: 2004 Annual report conference on ‘lectiealinvulation and dielectric phenomena, 2004, CEIDP 04, ERE, pp 385-385, El-Hag AH, Simon LC, Tayaram SH, Chemney BA (2005) Erosion resistence of nano-filled silicone robber. IEEE Trans Dielectr Electr Tnsul 13():122-128 Du BX, Han T, Su JG (2014) Tree characteristics in silicone rubber/Si0; nanocomposites under low temperate, IEEE Trans Dieletr Electr Insul 212:503-510 Du BX, Li ZI 2014) Surfuce charge and de Aashover character. istics of dixeet-luorinated SiR/SiO> nanocomposites, IEEE Trans DieleerHlet Inwul 21(6):2602-2610 Du BX, Han T, Su JG (2014) ktlect of low temperature on wee ‘haracteisis in silicone rubber with diferent power fequency. [BEE Trans Dielectr Elect Insul 21(4:1880-1886 Dimiuopoulou M, Pylarinos D, Siderakis K, Thalassinakis B, Damskas M (2015) Comparative investigation of polation accu lation and:natural cleaning for different HV inslatrs. Eng Technol ‘Appl Set Res 5(2}T64 Khatak A, Igbal M, Amin M, Aging analysis of high voltage sil icone rubbecisilica nanocomposites under accelerated wealbering ‘conditions. Sei Eng Compos Mater (in press) D springer 5 41. 4 50. 51. 53. ss 55. 58. Khutak A, Amin M (2016) Accelerated aging investigation of high voltage EPDMUsilica composite inslatrs. J Polym Eag. 36(2)199-209 Setncider HM, Guidi WW, Burnham JT, Gorur RS, Hall F (1993) Accelerated aging and Dashover test on 138 RV noneeramie ine post insulators. IEEE Trans Power Deliv §(1):325-336 Chen Z, Rao Z, Lin C, Chen C, fia Z, Lu H, Yang Z (2014) [Non-destrutive condition assessment of silicone ruber composite insulators n: 2014 IBEE conference on electeal insulation and ielecec phenomena (CEIDF), IEEE, pp 94-297 ‘Olave C, Trinidad P. Molina 1, Suadazarjan R (2005) Influence ‘of acid rain + mltetress condone on te long term performance ‘of 6 KV polymeric insulator, In; CEIDP'05, 2005 Annual report ‘conference on electrical neation and dielectric phenome, 2005, TREE, pp 41-344 ‘Guide STRI (1992) Hydrophobicty cassiication guide. Guide 192}:1 ‘Kim JH (1999) Hydrophoicity lots and recovery of silicone HV insulation, IEBE Trans Dicleei Beet Ins 65):95-102 ‘Meyer LH, Cabral SH, Arajo E, Cardoso G, Liesenfel N (2006) ‘Use of nanowilieain silicone rubber for ceramic insulators costings in coastal areas. In: Conference record ofthe 2006 IEEE intera- tional syenposiu on letriel insulation, 2006, IEEE, pp 474-477 ‘Kumagai S, Yoshimura N (2000) Evaluation of leakage cures on ‘arious types of polymeric materials used for HV outdoor isulae tioninsalt-fog condition Trane Inst lets Eng Ipa.A Publ Fundam Mater Soe 120(11):10511085 Rajni V, Udayakumar K (2008) Degredtion of silicone rubber under AC ot DC voltages in radon envionment. IEEE Trans DielectrHlet sul 16(3):834-841 Ramirez-Vazquer I, Nava R (2013) Application of nano particles {forthe modification of high voltage insulators. IEEE TransDielect Elect Insul 20(6):2262-2269, ‘Znuravley LT (1988) Structurally bound water and surface charac terization of amorphous silica Pare Appl Chen 61(11):1969-1976 ‘Khan Y, ALArsiny AA. Mabik NH, Qureshi ML, AbAmmar AE (2010) Loss and recovery of hydrophobicity of EPDM insulators in simulated aid desert enwironmient. In: Power and energy eng neering conference (AFPEEC), IEEE, pp 14 Rajsmar K, Dwivek C, ThavianiP Jeyanth P,Pashanisamy P (2013) Bfect of nanosilica on ethylene propylene Diene monomer rubber nanocomposites. It J Innov Res Dev 2(5): 831-841 ‘Okel TA, Waddell WH (1995) Eee of precipitated silica physical properties on silicone rubber pelormance, Rubber Chem Technol (68(1)59-76