Stabilizers in crosslinked polydimethylsiloxane

Sammanfattning: The loss and recovery of the surface hydrophobicity areimportant phenomena when highvoltage insulators, with a shedmaterial composed of polydimethylsiloxane (PDMS), are used. Theloss of hydrophobicity is mostly due to the oxidativecrosslinking which takes place on the PDMS surface duringexposure to electrical discharges, e. g. corona discharges. Thecrosslinking reaction leads to the formation of anoxygen-enriched, silica-like layer, which is brittle and henceprone to cracking, either spontaneously or upon mechanicaldeformation. Repetitive cracking leads to the propagation ofcracks into the core of the material, which is believed todeteriorate the insulator’s performance and reduce itsservice-life. Hence, an approach to make PDMS more resistant tothe build-up of the silica-like layer is beneficial for theperformance of PDMS in high voltage insulators.In this work the effect of antioxidative stabilizers on thecorona- and air-plasma-induced surface oxidation of PDMS isstudied. Three commercial stabilizers, a hindered phenol(Irganox® 1076), a hindered amine light stabilizer(Tinuvin® 770) and a bifunctional stabilizer withchainbreaking hindered phenol and secondary amine andhydroperoxide-decomposing sulfide moieties (Irganox® 565),have been used. Surface oxidation was achieved by exposure of amodel crosslinked PDMS to an air plasma or a corona discharge,and the surface characteristics of the exposed samples wereassessed by contact angle measurements, X-ray photoelectronspectroscopy, optical and scanning electron microscopy, andsurface profilometry before and after uniaxial stretching.A reliable rapid method for the assessment of stabilizerconcentration in PDMS was established. PDMS samples containingknown stabilizer concentrations of a phenolic antioxidant(Irganox® 1010) and a hindered amine stabilizer(Tinuvin® 144) were prepared. It was shown that thestabilizer concentration in PDMS could be determined by highperformance liquid chromatography (HPLC) of the microwaveassisted solvent extracts (MAE) of stabilized PDMS samplesusing acetone (a non-swelling solvent). This method wasemployed to measure the stabilizer concentration in PDMSsamples exposed to air plasma and corona discharges. Thestabilizer concentration in PDMS was varied by using diluteswelling solutions (0.005 wt% to 0.2 wt%) of the stabilizers inhexane. Samples stabilized with Irganox 565 showed stabilizerprecipitation on the surface after swelling in solutions with astabilizer concentration greater than 0.05 wt%. Samplescontaining Irganox 1076 and Tinuvin 770 showed no surfaceprecipitation except after swelling in a solution of 0.2 wt%stabilizer concentration.The air plasma and corona exposure time required for theformation of the silica-like surface layer increased,essentially, in a linear fashion with increasing stabilizerconcentration. Tinuvin 770 showed the strongest overallprotecting effect during, as well air plasma as coronaexposures, whereas Irganox 565 showed the strongest protectingeffect per mass fraction stabilizer during air plasmaexposures. Irganox 1076 was of moderate efficiency. The resultssuggest that efficient protection towards discharge-inducedsurface oxidation is achieved with hindered amine stabilizersor with stabilizers combining chain-breaking andhydroperoxide-decomposing functions.The diffusion of the stabilizers Irganox 1010 and Tinuvin144 from PDMS to water at elevated temperatures (75 °C and95 °C for Irganox 1010 and 95 °C for Tinuvin 144) wasstudied. For Irganox 1010 the diffusion constant (D), accordingto Fick’s second law for uni-dimensional penetrantdiffusion was assessed to 3.1 X 10-9cm2s-1at 95 °C and to 5.46 X 10-10cm2s-1at 75 °C. An estimate for the activationenergy for the diffusion of Irganox 1010 to the surroundingmedia was obtained (Ea=93 kJ mol-1), on the basis of the diffusion data. For Tinuvin144, no diffusion constant could be calculated due to poorseparation of the stabilizer peak from the impurities in theextract when using the HPLC method developed earlier.