Thermal degradation of EVA and EBA—A comparison. I. Volatile decomposition products

This is the first in a series of papers in which structural changes during thermal degradation of ethylene-vinyl acetate (EVA) and ethylene-butyl acrylate (EBA) copolymers are compared. EVA, containing 11.4 mol% vinyl acetate (VA) and EBA, containing 5.4 mol% butyl acrylate (BA), were pyrolyzed at 280°C in nitrogen for 30 min. In another series of pyrolysis, EVA containing 1.2, 2.2, and 11.4 mol% VA were treated at 150–190°C for 3 h. The volatile decomposition products were collected in cooled traps respectively gas bags and then analysed with GC-MS and ion-chromatography. EVA is rather labile. The main volatile decomposition product is acetic acid. A linear decomposition rate was found already at the lowest investigated pyrolysis temperature, 150°C. After 30 min at 280°C every 15th of the acetate side groups had been eliminated. EBA is much more stable to pyrolysis. Thirty minutes at 280°C resulted in a decomposition of one out of 1500 BA groups. Butene is the main volatile decomposition product. Ester pyrolysis is supposed to account for the degradation of both types of polymers. The big difference in reactivity is presumably due to conformational differences. The ester pyrolysis mechanism will result in random unsaturations in EVA and carboxylic groups in EBA. To a minor extent acetaldehyde is formed when EVA is degraded. According to the mechanisms suggested, carbonyl groups remain in the main chain. Contrary to what is reported for poly(butyl acrylate), no alcohol was formed when pyrolysing EBA. This indicates that adjacent acrylate groups are needed for alcohol formation. For both types of polymer, scissions of the main chain results in hydrocarbon fragments mainly. In addition, acrylate containing fragments are observed when EBA is degraded. EVA, however, does not give any acetate-containing fragments.     

Distribution of Asellus aquaticus and microinvertebrates in a non-chlorinated drinking water supply system--effects of pipe material and sedimentation

Danish drinking water supplies based on ground water without chlorination were investigated for the presence of the water louse, Asellus aquaticus, microinvertebrates (<2 mm) and annelida. In total, 52 water samples were collected from fire hydrants at 31 locations, and two elevated tanks (6000 and 36,000 m³) as well as one clean water tank at a waterworks (700 m³) were inspected. Several types of invertebrates from the phyla: arthropoda, annelida (worms), plathyhelminthes (flatworms) and mollusca (snails) were found. Invertebrates were found at 94% of the sampling sites in the piped system with A. aquaticus present at 55% of the sampling sites. Populations of A. aquaticus were present in the two investigated elevated tanks but not in the clean water tank at a waterworks. Both adult and juvenile A. aquaticus (length of 2-10 mm) were found in tanks as well as in pipes. A. aquaticus was found only in samples collected from two of seven investigated distribution zones (zone 1 and 2), each supplied directly by one of the two investigated elevated tanks containing A. aquaticus. Microinvertebrates were distributed throughout all zones. The distribution pattern of A. aquaticus had not changed considerably over 20 years when compared to data from samples collected in 1988-89. Centrifugal pumps have separated the distribution zones during the whole period and may have functioned as physical barriers in the distribution systems, preventing large invertebrates such as A. aquaticus to pass alive. Another factor characterising zone 1 and 2 was the presence of cast iron pipes. The frequency of A. aquaticus was significantly higher in cast iron pipes than in plastic pipes. A. aquaticus caught from plastic pipes were mainly single living specimens or dead specimens, which may have been transported passively trough by the water flow, while cast iron pipes provided an environment suitable for relatively large populations of A. aquaticus. Sediment volume for each sample was measured and our study described for the first time a clear connection between sediment volume and living A. aquaticus since living A. aquaticus were nearly only found in samples with sediment contents higher than 100 ml/m³ sample. Presence of A. aquaticus was not correlated to turbidity of the water. Measurements by ATP, heterotrophic plate counting and Colilert^® showed that the microbial quality of the water was high at all locations with or without animals. Four other large Danish drinking water supplies were additionally sampled (nine pipe samples and one elevated tank), and invertebrates were found in all systems, three of four containing A. aquaticus, indicating a nationwide occurrence.     

The effect of enzymatic treatment on blackcurrant (Ribes nigrum) juice flavour and its stability

The effects of different enzymatic treatments on the sensory profile and chemical composition, especially various phenolic compounds, sugars and fruit acids, of blackcurrant juices were investigated. In addition to pectinolytic activities, the enzymes had different cellulolytic, hemicellulolytic and glycolytic activities. The enzymatic treatments improved significantly the yield of juice, but with more fermented and astringent characteristics than juices without enzymatic hydrolysis. Enzymes with higher glycosidase activity increased astringency and the content of phenolic compounds in the juice. When the incubation temperature was elevated the contents of fruit acids increased whereas sugars and the perceived sweetness were the highest in the juices without enzymatic treatments. Despite of the significant changes in chemical composition, the sensory properties did not change significantly during 6 weeks of storage. Optimisation of the enzymatic process is crucial for juice making as maximising the juice yield or the content of phenolic compounds may produce unwanted sensory properties to the juice.     

Survey of management practices on reproductive performance of dairy cattle on large US commercial farms

A survey regarding general management, sire selection, reproductive management, inseminator training and technique, heat abatement, body condition scoring, facility design and grouping, nutrition, employee training and management, and animal health and bio-security was carried out from March to September of 2004 in 153 herds in the Alta Genetics (Watertown, WI) Advantage Progeny Testing Program. A total of 103 herds (67.3%) completed the survey. Herd size was 613 ± 46 cows, with herds located in Wisconsin (26), California (12), New York (11), Minnesota (10), Michigan (7), Washington (6), Pennsylvania (6), Iowa (5), Idaho (5), Texas (4), Ohio (4), and other states (7). These farms sold 34.5 ± 0.3 kg of milk/d per cow, with an annual culling rate of 34 ± 1% and a calving interval of 13.8 ± 0.1 mo. Cows were observed for estrus 2.8 ± 0.3 times/d, for a duration of 27 ± 4 min, but 78% of the respondents admitted that detection of estrus was not the employee's sole responsibility at that time. Managers tried to achieve pregnancy until 8.8 ± 0.9 failed inseminations, 300 ± 26 d postpartum, or milk yield <17.7 ± 0.5 kg/d. Nonpregnant cows were culled at 326 ± 36 d postpartum or milk yield <16.4 ± 0.3 kg/d. Mean durations of the voluntary waiting period were 52 ± 1.3 and 53 ± 1.4 d for primiparous and multiparous cows, respectively. Hormonal synchronization or timed artificial insemination programs were used in 87% of the herds, with 86% synchronizing first services, 77% resynchronizing repeat services, and 59% treating cystic, anestrous, or anovular cows. Finding good employees was identified as the greatest labor challenge, followed by training and supervising employees. Mastitis and hairy heel warts were noted as the greatest animal health concerns, followed by lameness, abortions, and death losses, whereas the greatest reproductive challenges were artificial insemination service rate, conception rate, twinning, and retained placenta or metritis. Results of this study can provide a useful benchmark or reference with regard to commonly used management practices on large commercial US dairy farms at the present time.     

基于ANSYS的板料成型系统模内加热模块热分析

针对目前板料热成形过程中存在的能量浪费、板料氧化严重等缺点,文章对模内加热方案进行研究探讨,使用ANSYS-Icepack对板料冲压成形的模内加热温度场进行模拟分析,并以此基础做出实物并调试对比模拟状况。结果显示:对于该模架,上下模1 000 W的热源同时加热时,加热组块最高温度可达近400℃,中间板材可加热到300℃以上,10min之后散热和加热接近平衡。按该模型设计的实际加热系统的温度分布与模拟基本接近。该研究对模内加热模块的设计进行了模拟与初步的试验,将有助于板料热成形技术方面发展。     

Effect of very long chain fatty acids on peroxisomal β-oxidation in primary rat hepatocyte cultures

Previous studies have demonstrated that certain high fat diets can induce peroxisomal fatty acid β-oxidation in rodent liver and that this may be due to their content oftrans 22∶1 fatty acids. In this study we have examined the effects ofcis andtrans 22∶1 fatty acids (erucic and brassidic) and oleic acid (18∶1) on palmitoyl-CoA oxidation, carnitine acetyltransferase and carnitine palmitoyltransferase activities in primary rat hepatocyte cultures. Brassidic and erucic acid and, to a lesser extent, oleic acid were cytotoxic to rat hepatocytes. However, at a concentration of 0.1 mM, brassidic acid produced small increases in palmitoyl-CoA oxidation and carnitine acetyltransferase activities in hepatocytes cultured 70 hr. Treatment of cells with 0.1 and 0.3 mM of either erucic or oleic acid had no effect on any of the enzymes measured.     

Can spectroscopy in combination with chemometrics replace minks in digestibility tests?

One of the most relevant but expensive methods of assessing the quality of fish meal is the physiological digestibility test with minks. The purpose of this study was to determine whether spectroscopic and chemical analyses evaluated with chemometrics can replace minks in digestibility tests. The spectroscopic methods used were the two complementary techniques of fluorescence emission and near‐infrared reflectance. The investigation included 54 samples of high‐quality fish meal ranging from 89.6 to 93.9 on the mink digestibility index. The investigation also included determination of seven quality parameters in the fish meal to substantiate the spectroscopic models on the mink digestibility. These quality parameters include the content of protein, oil, water, water‐soluble protein, ash and the biogenic substance cadaverine as well as the titration value. The study demonstrates that the mink digestibility could be predicted from combining the two reference quality parameters oil and ash with a correlation coefficient of 0.89. The best spectroscopic calibration models on the mink digestibility resulted in a correlation coefficient of 0.94 and a prediction error of 0.5 using the near‐infrared spectral ensemble and a correlation coefficient of 0.92 and a prediction error of 0.5 using the fluorescence spectral ensemble. In addition, the seven reference quality parameters could be predicted from the spectroscopic ensembles with good precision. © 2000 Society of Chemical Industry     

Formation of anomalous structures in PVC and their influence on the thermal stability: 3. Internal chloroallylic groups

Internal double bonds were determined by oxidative cleavage in fractions of a commercial suspension PVC (S-PVC) and experimental PVC samples obtained at subsaturation conditions (U-PVC). The changes in molecular weight were measured by g.p.c. and viscometry. The oxidation was performed by ozonolysis in tetrachloroethane solution at ?20°C. Oxidation by potassium permanganate in dimethylacetamide solution at ?10° to +50°C was also studied. However, this method was found to give erratic results. With increasing monomer starvation the number of internal double bonds increased. In the original S-PVC sample the internal double bond content was $\text{0.2}\text{1000}\text{VC}$. The formation of double bonds is assumed to be the result of an increased tendency, by chlorine atoms, to attack on the methylene groups in the chain. Hydrolytic cleavage and ¹H n.m.r. measurements did not give any evidence of ketoallylic groups. With increasing chloroallylic group content the U-PVC samples showed an increased rate of dehydrochlorination at 190°C in nitrogen. The S-PVC fractions, however, showed a decreased rate. However, the thermal stability in both series of samples could be related to the tertiary chlorine content. Butyl and long chain points with tertiary chlorine are more frequent than the internal chloroallylic groups. It was assumed that tertiary chlorine is the most important labile structure not only in U-PVC but also in ordinary PVC.