scholarly journals Scission, Cross-Linking, and Physical Relaxation during Thermal Degradation of Elastomers

Polymers ◽  
2019 ◽  
Vol 11 (8) ◽  
pp. 1280 ◽  
Author(s):  
Zaghdoudi ◽  
Kömmling ◽  
Jaunich ◽  
Wolff

Elastomers are susceptible to chemical ageing, i.e., scission and cross-linking, at high temperatures. This thermally driven ageing process affects their mechanical properties and leads to limited operating time. Continuous and intermittent stress relaxation measurements were conducted on ethylene propylene diene rubber (EPDM) and hydrogenated nitrile butadiene rubber (HNBR) samples for different ageing times and an ageing temperature of 125 °C. The contributions of chain scission and cross-linking were analysed for both materials at different ageing states, elucidating the respective ageing mechanisms. Furthermore, compression set experiments were performed under various test conditions. Adopting the two-network model, compression set values were calculated and compared to the measured data. The additional effect of physical processes to scission and cross-linking during a long-term thermal exposure is quantified through the compression set analysis. The characteristic times relative to the degradation processes are also determined.

2021 ◽  
Vol 21 (8) ◽  
pp. 4444-4449
Author(s):  
Bongjin Chung ◽  
Shin Sungchul ◽  
Jaeho Shim ◽  
Seongwoo Ryu

Epoxy adhesive was analyzed under long term thermal aging and mechanical properties and chemical degradation were observed by X-ray photoelectron spectroscopy (XPS). Long term thermal exposure of epoxy causes a noticeable reduction in adhesive properties. We developed a predictive model of temperature and time dependent aging. The temperature dependent aging behavior of epoxy adhesive shows good agreement with conventional Arrhenius equations. Using XPS analysis, we also discovered a correlation between chemical degradation and the adhesive properties. Decay of C–C bonding ratio induced chain-scission of epoxy adhesive; increase of total numbers of C–O and C═O induced oxidation of epoxy adhesive during thermal exposure.


2013 ◽  
Vol 86 (4) ◽  
pp. 591-603 ◽  
Author(s):  
Jiaohong Zhao ◽  
Rui Yang ◽  
Rossana Iervolino ◽  
Stellario Barbera

ABSTRACT The accelerated thermo-oxidative aging of acrylonitrile–butadiene rubber (NBR) was studied at elevated temperatures. The chemical structure characterized by attenuated total reflectance–Fourier transform infrared spectroscopy (ATR-FTIR) and pyrolysis gas chromatography–mass spectroscopy (PGC-MS) showed the loss of low-molecular-weight additives, such as antioxidants and paraffin, and the formation of carbonyl groups and unsaturated double bonds. The cross-linking degree characterized by NMR and a swelling test showed that aging is a competitive process of cross-linking and chain scission. Cross-linking dominated the thermal aging of NBR most of the time, whereas chain scission began to increase after a long time at high temperatures. The changes of mechanical property magnitudes during thermal aging of NBR were studied by using the recovery from bending test (RFB) and tensile test. By comparing the physical property results and the structural changes, their relationship is discussed.


2005 ◽  
Vol 8 (1) ◽  
pp. 55 ◽  
Author(s):  
Azman Ates ◽  
Yahya �nl� ◽  
Ibrahim Yekeler ◽  
Bilgehan Erkut ◽  
Yavuz Balci ◽  
...  

Purpose: To evaluate long-term survival and valve-related complications as well as prognostic factors for mid- and long-term outcome after closed mitral commissurotomy, covering a follow-up period of 14 years. Material and Methods: Between 1989 and 2003, 36 patients (28 women and 8 men, mean age 28.8 6.1 years) underwent closed mitral commissurotomy at our institution. The majority of patients were in New York Heart Association (NYHA) functional class IIB, III, or IV. Indication for closed mitral commissurotomy was mitral stenosis. Closed mitral commissurotomy was undertaken with a Tubbs dilator in all cases. Median operating time was 2.5 hours 30 minutes. Results: After closed mitral commissurotomy, the mitral valve areas of these patients were increased substantially, from 0.9 to 2.11 cm2. No further operation after initial closed mitral commissurotomy was required in 86% of the patients (n = 31), and NYHA functional classification was improved in 94% (n = 34). Postoperative complications and operative mortality were not seen. Follow-up revealed restenosis in 8.5% (n = 3) of the patients, minimal mitral regurgitation in 22.2% (n = 8), and grade 3 mitral regurgitation in 5.5% (n = 2) patients. No early mortality occurred in closed mitral commissurotomy patients. Reoperation was essential for 5 patients following closed mitral commissurotomy; 2 procedures were open mitral commissurotomies and 3 were mitral valve replacements. No mortality occurred in these patients. Conclusions: The mitral valve area was significantly increased and the mean mitral valve gradient was reduced in patients after closed mitral commissurotomy. Closed mitral commissurotomy is a safe alternative to open mitral commissurotomy and balloon mitral commissurotomy in selected patients.


Atmosphere ◽  
2021 ◽  
Vol 12 (1) ◽  
pp. 65
Author(s):  
Maximilian Kerner ◽  
Kilian Schmidt ◽  
Stefan Schumacher ◽  
Christof Asbach ◽  
Sergiy Antonyuk

Electret filters are electrostatically charged nonwovens which are commonly used in aerosol filtration to remove fine particles from gases. It is known that the charge and thus also the filtration efficiency can degrade over time. Thus, many testing standards require to remove the charge by treatment with liquid isopropanol (IPA) or IPA-saturated air. However, the parameters influencing this discharge have not been completely clarified yet. The aim of this work was, on the one hand, to experimentally investigate the influence of the IPA treatment on different electret filters and, on the other hand, to show the optimization potential of electret filters with respect to efficiency and long-term stability by numerical simulations. The experiments revealed that the air permeability is a central influencing parameter. Small pores lead to a reduced discharge efficiency using liquid IPA, while both treatment methods are suitable for larger pores. The simulations showed that a homogeneous charge distribution within the filter depth is advantageous for the initial performance. In contrast, charge penetrating deeper in the filter medium delays the charge decay and thus increases the operating time, with the trade-off of a lower initial performance.


Polymers ◽  
2021 ◽  
Vol 13 (7) ◽  
pp. 1139
Author(s):  
Hans van Hoek ◽  
Jacques Noordermeer ◽  
Geert Heideman ◽  
Anke Blume ◽  
Wilma Dierkes

De-vulcanization of rubber has been shown to be a viable process to reuse this valuable material. The purpose of the de-vulcanization is to release the crosslinked nature of the highly elastic tire rubber granulate. For present day passenger car tires containing the synthetic rubbers Styrene-Butadiene Rubber (SBR) and Butadiene Rubber (BR) and a high amount of silica as reinforcing filler, producing high quality devulcanizate is a major challenge. In previous research a thermo-chemical mechanical approach was developed, using a twin-screw extruder and diphenyldisulfide (DPDS) as de-vulcanization agent.The screw configuration was designed for low shear in order to protect the polymers from chain scission, or uncontrolled spontaneuous recombination which is the largest problem involved in de-vulcanization of passenger car tire rubber. Because of disadvantages of DPDS for commercial use, 2-2′-dibenzamidodiphenyldisulfide (DBD) was used in the present study. Due to its high melting point of 140 °C the twin-screw extruder process needed to be redesigned. Subsequent milling of the devulcanizate at 60 °C with a narrow gap-width between the mill rolls greatly improved the quality of the devulcanizate in terms of coherence and tensile properties after renewed vulcanization. As the composition of passenger car tire granulate is very complex, the usefulness of the Horikx-Verbruggen analysis as optimization parameter for the de-vulcanization process was limited. Instead, stress-strain properties of re-vulcanized de-vulcanizates were used. The capacity of the twin-screw extruder was limited by the required residence time, implying a low screw speed. A best tensile strength of 8 MPa at a strain at break of 160% of the unblended renewed vulcanizate was found under optimal conditions.


2021 ◽  
pp. 112067212110183
Author(s):  
Yasin Cinar ◽  
Cagla Cilem Han ◽  
Alparslan Sahin ◽  
Zeba A Syed

Purpose: To evaluate the long term visual, refractive, and corneal tomographic outcomes of epithelium-off accelerated corneal collagen cross-linking (ACXL) in the management of pediatric keratoconus (KC). Methods: This retrospective study included patients under 18 years old with progressive KC who underwent ACXL between 2012 and 2019 at Dicle University Hospital. Complete ophthalmic examination was performed including uncorrected distance visual acuity (UDVA), best spectacle-corrected distance visual acuity (CDVA), manifest refraction, and corneal tomography. Evaluations were performed preoperatively and at 6 months intervals postoperatively. Results: Forty-nine eyes of 49 patients were included in the study. The mean age of patients at the time of ACXL was 14.2 ± 1.8 (range: 9.5–17.3) years. Mean follow up was 4.61 ± 1.90 (range: 2.0–8.1) years. The mean LogMAR UDVA improved from 0.94 ± 0.41 to 0.81 ± 0.43, 0.69 ± 0.41, and 0.67 ± 0.33 after 1, 3, and 5 years respectively ( p = 0.001). The mean LogMAR CDVA improved from 0.58 ± 0.36 to 0.46 ± 0.31, 0.34 ± 0.23, and 0.39 ± 0.27 after 1, 3, and 5 years respectively ( p = 0.015). The mean refractive cylinder improved significantly from 6.01 ± 2.07 diopters (D) to 5.46 ± 1.87, 5.38 ± 2.18, and 5.02 ± 2.31 D after 1, 3, and 5 years respectively ( p = 0.005). As compared to preoperative values, steep keratometry and maximum keratometry were not significantly different ( p = 0.805 and 0.448, respectively) following ACXL, while flat keratometry significantly improved after ACXL ( p = 0.012). Although central corneal thicknesses decreased significantly ( p = 0.029), the decrease in thinnest corneal thickness was not statistically significant ( p = 0.205). Conclusion: Epithelium-off ACXL seems to be effective for halting KC progression with long term clinical benefits in pediatric patients.


Author(s):  
Rafique Umer Harvitkar ◽  
Abhijit Joshi

Abstract Introduction Laparoscopic fundoplication (LF) has almost completely replaced the open procedure performed for gastroesophageal reflux disease (GERD) and hiatus hernia (HH). Several studies have suggested that long-term results with surgery for GERD are better than a medical line of management. In this retrospective study, we outline our experience with LF over 10 years. Also, we analyze the factors that would help us in better patient selection, thereby positively affecting the outcomes of surgery. Patients and Methods In this retrospective study, we identified 27 patients (14 females and 13 males) operated upon by a single surgeon from 2010 to 2020 at our institution. Out of these, 25 patients (12 females and 13 males) had GERD with type I HH and 2 (both females) had type II HH without GERD. The age range was 24 to 75 years. All patients had undergone oesophago-gastro-duodenoscopy (OGD scopy). A total of 25 patients had various degrees of esophagitis. Two patients had no esophagitis. These patients were analyzed for age, sex, symptoms, preoperative evaluation, exact procedure performed (Nissen’s vs. Toupet’s vs. cruroplasty + gastropexy), morbidity/mortality, and functional outcomes. They were also reviewed to examine the length of stay, length of procedure, complications, and recurrent symptoms on follow-up. Symptoms were assessed objectively with a score for six classical GERD symptoms preoperatively and on follow-up at 1-, 4- and 6-weeks postsurgery. Further evaluation was performed after 6 months and then annually for 2 years. Results 14 females (53%) and 13 males (48%) with a diagnosis of GERD (with type I HH) and type II HH were operated upon. The mean age was 46 years (24–75 years) and the mean body mass index (BMI) was 27 (18–32). The range of duration of the preoperative symptoms was 6 months to 2 years. The average operating time dropped from 130 minutes for the first 12 cases to 90 minutes for the last 15 cases. The mean hospital stay was 3 days (range: 2–4 days). In the immediate postoperative period, 72% (n = 18) of the patients reported improvement in the GERD symptoms, while 2 (8%) patients described heartburn (grade I, mild, daily) and 1 (4%) patient described bloating (grade I, daily). A total of 5 patients (20%) reported mild dysphagia to solids in the first 2 postoperative weeks. These symptoms settled down after 2 to 5 weeks of postoperative proton-pump inhibitor (PPI) therapy and by adjusting consistency of oral feeds. There was no conversion to open, and we observed no perioperative mortality. There were no patients who underwent redo surgeries in the series. Conclusion LF is a safe and highly effective procedure for a patient with symptoms of GERD, and it gives long-term relief from the symptoms. Stringent selection criteria are necessary to optimize the results of surgery. Experience is associated with a significant reduction of operating time.


2021 ◽  
Vol 19 (1) ◽  
Author(s):  
Claudio F. Feo ◽  
Giulia Deiana ◽  
Chiara Ninniri ◽  
Giuseppe Cherchi ◽  
Paola Crivelli ◽  
...  

Abstract Background Pancreatic ductal adenocarcinoma (PDAC) is an aggressive malignancy with poor prognosis. Radical surgery is the best option for cure and, nowadays, it is performed by many surgeons also in cases of vascular infiltration. Whether this aggressive approach to a locally advanced PDAC produces a survival benefit is under debate. Most data in the literature come from retrospective comparative studies; therefore, it is still unclear if such an extensive surgery for an advanced cancer is justified. Methods A retrospective review of patients with PDAC treated at our institution over a 12-year period was performed. Data concerning patients’ characteristics, operative details, postoperative course, and long-term survival were retrieved from prospective databases and analysed. Factors associated with poor survival were assessed via Cox regression analysis. Results A total of 173 patients with PDAC were included in the analysis, 41 subjects underwent pancreatectomy with vascular resection for locally advanced disease, and in 132 patients, only a pancreatic resection was undertaken. Demographics, major comorbidities, and tumour characteristics were similar between the two groups. Length of surgery (P=0.0006), intraoperative blood transfusions (P<0.0001), and overall complications (P<0.0001) were significantly higher in the vascular resection group. Length of hospital stay (P=0.684) and 90-day mortality (P=0.575) were comparable between groups. Overall median survival (P= 0.717) and survival rates at 1, 3, and 5 years (P=0.964, P=0.500, and P=0.445, respectively) did not differ significantly between groups. Age ≥70 years and postoperative complications were independent predictors of lower survival. Conclusions Our study confirms that pancreatectomy with vascular resection for a locally advanced PDAC is a complex operation associated with a significant longer operating time that may increase morbidity; however, in selected patients, R0 margins can be obtained with an acceptable long-term survival rate. Older patients are less likely to benefit from surgery.


2016 ◽  
Vol 89 (4) ◽  
pp. 671-688 ◽  
Author(s):  
M. A. L. Verbruggen ◽  
L. van der Does ◽  
W. K. Dierkes ◽  
J. W. M. Noordermeer

ABSTRACT The theoretical model developed by Charlesby to quantify the balance between cross-links creation of polymers and chain scission during radiation cross-linking and further modifications by Horikx to describe network breakdown from aging were merged to characterize the balance of both types of scission on the development of the sol content during de-vulcanization of rubber networks. There are, however, disturbing factors in these theoretical considerations vis-à-vis practical reality. Sulfur- and peroxide-cured NR and EPDM vulcanizates were de-vulcanized under conditions of selective cross-link and random main-chain scissions. Cross-link scission was obtained using thiol-amine reagents for selective cleavage of sulfur cross-links. Random main-chain scission was achieved by heating peroxide vulcanizates of NR with diphenyldisulfide, a method commonly employed for NR reclaiming. An important factor in the analyses of these experiments is the cross-linking index. Its value must be calculated using the sol fraction of the cross-linked network before de-vulcanization to obtain reliable results. The values for the cross-linking index calculated with sol-gel data before de-vulcanization appear to fit the experimentally determined modes of network scission during de-vulcanization very well. This study confirms that the treatment of de-vulcanization data with the merged Charlesby and Horikx models can be used satisfactorily to characterize the de-vulcanization of NR and EPDM vulcanizates.


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