Effects of pressure on poly(ether-ether-ketone) (PEEK) sintering mechanisms

This study deals with the understanding of the sintering mechanisms that occur during consolidation of an ultra-high-performance polymer: poly(ether-ether-ketone). In particular, we investigated the effects of uniaxial pressure during spark plasma sintering (SPS) processing. Glass-transition temperature (T_g) measurements under loading, stress–strain curves and scanning electron microscopy analysis allowed us to determine the role of pressure intensity and temperature of application on macromolecular chain mobility in both the bulk and the surface of the particles. First, a loss of chain mobility in the bulk of the particles was observed under high pressure. Second, it was shown that high pressure applied at low temperature leads to friction effects between the particles which enhances chain mobility in the particle shell through a local melting phenomenon. These experimental conditions favor the healing of particles and high cohesion was then observed in the resulting sintered samples. The level of friction is enhanced when pressure is applied at a low temperature since the powders are still in a glassy state. Finally, the achievement of cohesive grain boundaries was found to be related to the location and conformation of chain ends. Good healing between particles can only occur if a sufficient number of chain ends are available at the surface of the particle shell. We showed that the native powder state plays a significant role. The direct use of as-received powder leads to final material exhibiting good cohesion whereas pretreatments of the native powder are highly detrimental. It should be noted that this processing does not affect the high initial degree of crystallinity because no bulk melting is observed during consolidation by sintering. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47645.     

In vitro release kinetics and physical, chemical and mechanical characterization of a POVIAC ? /CaCO 3 /HAP-200 composite

Coralline calcium-hydroxyapatite and calcium carbonate from Porites Porites coral were added to a polymeric matrix based on polyvinyl acetate (POVIAC^?), to obtain a novel bone substitute composite as well as a system for the controlled drug (cephalexin) release. Composite samples with different compositions were characterized by physical–chemical and mechanical methods. Furthermore, the in vitro release profile of cephalexin and the kinetic behavior of its release from these composites were analyzed by appropriate mathematical models. It was shown that there is no chemical interaction between the inorganic filler and the polymer matrix, each conserving the original properties of the raw materials. The compressive mechanical strength and Young modulus of the composite with 17.5% of POVIAC^?, has better mechanical properties than those of cancellous bone. The variation of POVIAC^? content can affect the cephalexin release kinetic in the composite. The cephalexin release mechanism from the composites can be considered as the result of the joint contribution of a prevailing Fickian diffusion and of polymer chain relaxation. It was also demonstrated that cephalexin is occluded inside the composites and not on their surface.     

From contact angle titration to chemical force microscopy: a new route to assess the pH-dependent character of the stratum corneum

Despite of its complex multicomponent organization and its compact architecture, the Stratum corneum (SC) is not completely impermeable to substances directly applied on the skin surface. A huge number of works have been dedicated to the understanding of the mechanisms involved in substance permeation by exploring deeper layers than the SC itself. Surprisingly, there is a poor interest in studies relating to interactions which may occur in the near-surface region (i.e. approximately 1 nm depth) of the SC. In this work, equilibrium proton-transfer reactions have been used as probes to define in a fundamental point of view the nature of the SC interactions with its environment. Such titration curves are investigated on 'in vitro' SC (isolated SC from abdominal skin tissue) and on 'in vivo' volar forearm (a sebum poor area). The results are discussed in term of work of adhesion and surface pKa values. Because SC can 'reconstruct' under heating, influence of the temperature on titration curves is investigated and the role of the different components is discussed. Different sigmoidal transitions were observed. Two common pKa values (pKa(1) = 4 and pKa(2) = 11.5) were clearly identified in both cases and associated to an acid-base character. By playing with the temperature of 'in vitro' SC, the 'accessibility' of polar functions was increased, thus refining the results by revealing an amphoteric character with an acid-to-base transition at pH 3.5 and two acid transitions at pH = 6.5 and pH = 11.5. Adhesion forces between an Atomic Force Microscopy (AFM) tip and a single isolated corneocyte through buffered liquid media were also investigated to better understand the role of the individual corneocytes.     

Characterisation of the spoilage microbiota in raw salmon (Salmo salar) steaks stored under vacuum or modified atmosphere packaging combining conventional methods and PCR-TTGE

In order to characterise the spoilage related to microbiota of raw salmon, a combination of culture-dependent and -independent methods, including PCR–TTGE, was used to analyse 3 raw salmon batches stored for 3 days at chilled temperature in modified atmosphere packaging (MAP) (50% CO₂/50% N₂) or under vacuum. Sensory evaluation, microbiological enumeration and chemical analysis were performed after 3, 7 and 10 days of storage. At the onset of spoilage, 65 bacterial isolates were picked from the plates. Thus, 13 different genera or species were identified by phenotypic and molecular tests: Serratia spp., Photobacterium phosphoreum, Yersinia intermedia, Hafnia alvei, Buttiauxella gaviniae, Pseudomonas sp., Carnobacterium maltaromaticum, Carnobacterium divergens, Lactococcus piscium, Lactobacillus fuchuensis, Vagococcus carniphilus, Leuconostoc gasicomitatum and Brochothrix thermosphacta. The PCR–TTGE profiles and band identification enabled a shift of the dominant populations during the storage to be visualised for all the batches, probably due to the temperature change and the packaging. At the beginning of storage, Pseudomonas sp. dominated the raw salmon microbiota while in the following days (7 and 10), P. phosphoreum and L. piscium were identified as the main bacterial groups. This study enhances the knowledge of MAP and vacuum-packed raw salmon spoilage microbiota.     

Leachability and termite resistance of wood treated with a new preservative: ammonium borate oleate

Synthesis of a new chemical compound combining water-repellence of oleic acid and biocidal effect of boric acid linked by ammonia have been followed and validated by fourier transformed infra red (FTIR). This compound named ammonium borate oleate (ABO) has then been studied as a wood preservative. Different molar ratios of oleic acid have been involved in the synthesis of ABO and leachability of those mixes from wood observed according to Japanese industrial standard. The formulation one mole of boric acid and one of ammonia (1:1:4) for four moles of oleic acid has shown the best efficiency compared to formulations 1:1:1, 1:1:2 and 1:1:3 with about 52% of boron remaining after weathering when other formulations retained respectively 10%, 29% and 46% of boron in the case of an impregnation of Cryptomeria japonica. Seven solutions of 1:1:4 ABO in ethanol of different concentrations were then produced and sapwood blocks of C. japonica and Fagus crenata were impregnated. A toxicity threshold of around 2.0 kg/m³ for both species was determined in a termite resistance test to Coptotermes formosanus indicating the positive effect of combining water repellent and biocide. Termite mortality recording and microscopic observations complete this study indicating that the action mechanism of ABO is providing a water resistant inner coating.     

Hepatic lipid metabolism in transition dairy cows fed flaxseed

Thirty-three Holstein cows averaging 687 kg of body weight were allotted 6 wk before the expected date of parturition to 11 groups of 3 cows blocked within parity for similar calving dates to determine the effects of feeding different sources of fatty acids on blood parameters related to fatty liver and profile of fatty acids in plasma and liver. Cows were fed lipid supplements from 6 wk before the expected date of parturition until d 28 of lactation. Cows within each block were assigned to 1 of 3 isonitrogenous and isoenergetic dietary supplements: control with no added lipids (CO); unsaturated lipids supplied as whole flaxseed (FL; 3.3 and 11.0% of the dry matter in prepartum and postpartum diets, respectively); and saturated lipids supplied as Energy Booster (EB; 1.7 and 3.5% of the DM in prepartum and postpartum diets, respectively). Diets EB and FL had similar ether extract concentrations. Multiparous cows fed EB had lower dry matter intake and milk production, higher concentrations of nonesterified fatty acids and β-hydroxybutyrate in plasma and triglycerides (TG) and total lipids in liver, and lower concentrations of plasma glucose and liver glycogen than those fed FL and CO. Production of 4% fat-corrected milk was similar among treatments. Multiparous cows fed FL had the highest liver concentrations of glycogen on wk 2 and 4 after calving and lowest concentrations of TG on wk 4 after calving. Liver C16:0 relative percentages in multiparous cows increased after calving whereas those of C18:0 decreased. Relative percentages of liver C16:0 were higher in wk 2 and 4 postpartum for multiparous cows fed EB compared with those fed CO and FL; those of C18:0 were lower in wk 4 postpartum for cows fed EB compared with those fed CO and FL. Liver C18:1 relative percentages of multiparous cows increased after calving and were higher in wk 4 for cows fed EB compared with those fed CO and FL. The inverse was observed for liver C18:2 relative percentages. In general, diets had more significant effects on plasma concentrations of nonesterified fatty acids, β-hydroxybutyrate, and glucose and liver profiles of fatty acids, TG, total lipids, and glycogen of multiparous than primiparous cows. These data suggest that feeding a source of saturated fatty acids increased the risk of fatty liver in the transition cow compared with feeding no lipids or whole flaxseed. Feeding flaxseed compared with no lipids or a source of saturated fatty acids from 6 wk before calving could be a useful strategy to increase liver concentrations of glycogen and decrease liver concentrations of TG after calving, which may prevent the development of fatty liver in the transition dairy cow.     

High performance tannin resin-boron wood preservatives for outdoor end-uses

Fixation of boric acid as a low toxicity wood preservative to decrease markedly its leachability was undertaken. Preservative systems based on the cross-linking and hardening of condensed tannins by hexamine, where boric acid is complexed onto the network, were found to markedly slow down the leaching of boron. They significantly enhanced wood durability before and after leaching once tested towards basidiomycetes according to the guidelines of EN 113. A particularly virulent fungal species was used for the tests. Further immersion of the wood so treated in hot unsaturated vegetable oil does yield comparable results.     

Modulation of peroxisome proliferator-activated receptor delta and gamma transcripts in swine endometrial tissue during early gestation

Recent evidence points to a role for peroxisome proliferator-activated receptors (PPARs) delta and gamma in embryo implantation and survival. In this study, we report the porcine PPARdelta complete coding sequence and mRNA abundance of PPARdelta, PPARgamma1 and gamma2, angiopoietin-like protein 4 (ANGPTL4) and adipocyte determination and differentiation-dependent factor 1 (ADD1) genes in the pregnant sow endometrium. Real-time PCR analysis was used to study the effect of parity (Yorkshire-Landrace multiparous (YL) and nulliparous (YLn)), site of endometrial tissue sampling (between and at embryo attachment sites) in crossbred DurocxYorkshire-Landrace (DYL) sows and stages of pregnancy (non-pregnant, day 15 and day 25 after mating) in Meishan-Landrace (ML) on mRNA levels. Parity effects were observed for PPARdelta, ANGPTL4, and ADD1, with higher mRNA levels in YL than YLn sows. In DYL sows, lower mRNA levels were present at attachment sites compared to between attachment sites for PPARdelta, PPARgamma1, and ANGPTL4. Finally, day 15 pregnant ML sows had lower PPARdelta mRNA levels compared to day 15 cycling ML sows. A significant increase of PPARgamma1 mRNA levels was found on day 25 pregnant ML and DYL sows relative to day 15 ML or DYL pregnant sows. PPARdelta and gamma immunostaining was detected in endometrial tissue of day 15 cycling sows, day 15 and 25 pregnant sows and epithelial cells of day 25 embryos. Collectively, our results suggest a role for PPARdelta, PPARgamma1, and ANGPTL4, but not PPARgamma2, during the peri-implantation period in pregnant sows.     

The Clarifying Reagent, or how to make the analysis of milk and dairy products easier

Difficulties with the analysis of opaque milk and dairy products can be resolved by rendering the sample transparent. This allows direct photometric measurements of the reaction mixtures, and all sample pre-treatment steps become unnecessary. For this, several reagents have been reported in literature. Among them, the 'Clarifying Reagent' is mainly described here: its composition is given because it is now released from patenting restrictions. Its main property is a low absorbance between 340 and 800 nm. So it can be used in many chemical and enzymatic colorimetric measurements for estimating the quality of milk and dairy products.     

Effects of supplementary folic acid and vitamin B12 on hepatic metabolism of dairy cows according to methionine supply

The present experiment was undertaken to study the interactions between dietary supplements of rumen-protected methionine (RPM) and intramuscular injections of folic acid and vitamin B₁₂, given from 3 wk before calving to 16 wk of lactation, on hepatic metabolism of lactating dairy cows. Sixty multiparous Holstein cows were assigned to 10 blocks of 6 cows each according to their previous milk production. Within each block, 3 cows were fed a diet calculated to supply Met as 1.83% of metabolizable protein, whereas the 3 other cows were fed the same diet supplemented with 18 g of RPM calculated to provide Met as 2.23% of metabolizable protein. Within each level of Met, the cows received no vitamin supplement or weekly intramuscular injections of 160 mg of folic acid alone or combined with 10 mg of vitamin B₁₂. Liver biopsies were taken at 2, 4, 8, and 16 wk of lactation. Liver concentrations of folates and vitamin B₁₂ were increased by their respective supplements but this response to vitamin supplements was altered by methionine supply. Concentrations of total lipids and triglycerides increased in livers of cows fed RPM, whereas concentrations of cholesterol ester, cholesterol, diglycerides, phosphatidylethanolamine, and phosphatidylcholine were not affected. Folic acid, alone or combined with vitamin B₁₂, tended to increase the ratio of phosphatidylcholine to phosphatidylethanolamine. Gene expression of 5,10-methylene-tetrahydrofolate reductase, microsomal transfer protein, and phosphatidylethanolamine methyltransferase were higher in liver of cows fed RPM supplements. The relative mRNA abundance of 5,10-methylene-tetrahydrofolate reductase and methylmalonyl-CoA mutase were increased by the combined injections of folic acid and vitamin B₁₂, whereas those of methionine synthase and methionine synthase reductase were not affected by treatments. These results suggest that increasing supply of methyl groups, as preformed labile methyl groups or through methylneogenesis, affected the methylation cycle but had a limited effect on dairy cow performance. The observed effects of the combined supplement of folic acid and vitamin B₁₂ on lactational performance of dairy cows probably result from an improvement of energy metabolism during early lactation.