Detection of stress whitening in plastics with the help of X-ray dark field imaging

The processing of thermoplastics can induce a wide range of defects such as stress whitening, cavitation and porosity, which can adversely affect the reliability of the final products. Hence, fast and effective non-destructive detection methods for such defects are highly important for quality assurance on production lines. In this paper, X-ray dark field imaging is presented as a new non-destructive testing method that allows the visualization of stress whitening or cavitation efficiently. The performance of the method is demonstrated for the case of an injection-moulded polyvinylidene fluoride part that exhibits stress whitening. Whereas the stress whitening could not be detected by conventional X-ray imaging, it was localized by an X-ray dark field image acquired within a few minutes. Once the precise location of the stress whitening was known, it was possible to verify the result by local micro X-ray computed tomography and by a micro section image.     

Thermal Oxidative Stability of Heat-Stabilised Polyamide 66 by Differential Scanning Calorimetry

The thermal stability of heat-stabilised polyamide 66 in an oxidative environment is evaluated by DSC. The oxidative stability of the polyamide decreases as a result of repeated injection moulding. The results also indicate that the presence of glass fibres in the polyamide has a negative influence on the oxidative stability. Both isothermal and dynamic DSC measurements seem to be useful tools for assessing the stability of polyamides and there is a relationship between data determined using both procedures. This revised version was published online in July 2006 with corrections to the Cover Date.     

The phase behavior of a polymer‐fullerene bulk heterojunction system that contains bimolecular crystals

Polymer:fullerene blends have been widely studied as an inexpensive alternative to traditional silicon solar cells. Some polymer:fullerene blends, such as blends of poly(2,5‐bis(3‐tetradecylthiophen‐2‐yl)thieno[3,2‐b]thiophene (pBTTT) with phenyl‐c71‐butyric acid methyl ester (PC₇₁BM), form bimolecular crystals due to fullerene intercalation between the polymer side chains. Here we present the determination of the eutectic pBTTT:PC₇₁BM phase diagram using differential scanning calorimetry (DSC) and two‐dimensional grazing incidence X‐ray scattering (2D GIXS) with in‐situ thermal annealing. The phase diagram explains why the most efficient pBTTT:PC₇₁BM solar cells have 75–80 wt % PC₇₁BM since these blends lie in the center of the only room‐temperature phase region containing both electron‐conducting (PC₇₁BM) and hole‐conducting (bimolecular crystal) phases. We show that intercalation can be suppressed in 50:50 pBTTT:PC₇₁BM blends by using rapid thermal annealing to heat the blends above the eutectic temperature, which forces PC₇₁BM out of the bimolecular crystal, followed by quick cooling to kinetically trap the pure PC₇₁BM phase. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Unequal siblings: Adverse characteristics of naphtalene‐based hoveyda‐type second generation initiators in ring opening metathesis polymerization

A family of four different Hoveyda‐type initiators bearing a π‐extended carbene ligand was characterized regarding the activity in ring opening metathesis polymerization. One of the initiators shows high activity at ambient temperature, similar to the second generation Hoveyda–Grubbs catalyst and is even suited for the controlled polymerization of certain norbornene derivatives. The other family members exhibit a pronounced latency at room temperature, and polymerization can be triggered by heat. The scope of these initiators in the thermally triggered polymerizations of norbornene derivatives in general and dicyclopentadiene in particular was disclosed. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.     

The Thermal Degradation of Poly(dimethyl Itaconate-co-4-vinylpyridine)

Copolymers of dimethyl itaconate (DMI) and 4-vinylpyridine (4VP) were synthetized in toluene at 60°C with0.26 mol% of AIBN as initiator. Their compositions were determined by differential refractometry and by differential scanning calorimetry. The 4VP contents of the copolymer samples ranged between 7 and 75 mol%. The reactivity ratios calculated via the Fineman-Ross method were r ₁=0.24 (DMI) and r ₂=0.57 (4VP). The thermal degradations of these copolymers were studied. The results of thermogravimetric measurements indicated that the copolymers degrade at lower temperatures than those of their parent homopolymers. A possible explanation of this anomalous behaviour is the formation of thermally unstable structures during the copolymerisation. This revised version was published online in July 2006 with corrections to the Cover Date.     

Chemical and Photochemical Water Oxidation Catalyzed by Mononuclear Ruthenium Complexes with a Negatively Charged Tridentate Ligand

Two mononuclear ruthenium complexes [RuL(pic)₃] ( 1 ) and [RuL(bpy)(pic)] ( 2 ) (H₂L=2,6‐pyridinedicarboxylic acid, pic=4‐picoline, bpy=2,2′‐bipyridine) have been synthesized and fully characterized. Both complexes could promote water oxidation chemically and photochemically. Compared with other known ruthenium‐based water oxidation catalysts using [Ce(NH₄)₂(NO₃)₆] (Ce^IV) as the oxidant in solution at pH 1.0, complex 1 is one of the most active catalysts yet reported with an initial rate of 0.23 turnover s^?1. Under acidic conditions, the equatorial 4‐picoline in complex 1 dissociates first. In addition, ligand exchange in 1 occurs when the Ru^III state is reached. Based on the above observations and MS measurements of the intermediates during water oxidation by 1 using Ce^IV as oxidant, [RuL(pic)₂(H₂O)]⁺ is proposed as the real water oxidation catalyst.