49 research outputs found
Environmental Stress Cracking of Polymers
Slow crack growth (SCG) is usually the most dominant failure mechanism in polymer products, typically occurring over extended periods under sustained low-stress conditions. This phenomenon is particularly critical in applications requiring long-term durability, such as gas pipes, water distribution systems, and storage tanks.
A phenomenon closely related to SCG is Environmental Stress Cracking (ESC), in which the progression of slow crack growth is accelerated when a polymer is exposed to surface-active agents under stress. These agents do not alter the polymer's chemical structure but drastically reduce the time to failure, by accelerating crack initiation and propagation. In ESC, the same crack growth mechanisms observed in SCG occur, but at a significantly accelerated rate due to environmental factors, making it a critical consideration in the design of polymer products intended for long-term use under stress.
The resistance to ESC is typically evaluated using standard methods, which unfortunately are quite limited in terms of both the amount of information provided (typically a single ranking parameter) and their accuracy, hindering the possibility of establishing clear structure-properties relationships for the materials under investigation. Over the years we developed an alternative approach, based on fracture mechanics (FM), which provides a much richer picture about the active ESC mechanisms and allows the identification of clear structure-properties relationships. These insights enable the optimization of the long-term performance of polymers under various stress conditions, at the same time providing reliable quantitative predictions of product lifetime, which can be of high interest for the industry
L’Omero tragico: luci e ombre nella parodo dell’Edipo Re di Sofocle
After a brief excursus about ancient sources helding Sophocles as the ‘Tragic Homer', the paper focuses on some case-studies of Epic vocabulary in the parodos of Sophocles' Oedipus Rex. The study presents various exploitation of Epic lexis by Sophocles such as epitheta ornantia, resemantization, and neologisms. In particular, specific attention is payed to thematic and intertextual links between the chorus and the Epic-Homeric tradition. The parodos of Oedipus Rex is traditionally considered a ‘peanic’ chorus, but within a dark setting. In addition to the ‘peanic’ influences, it is argued that the interference with the Epic genre is also crucial for a better understanding of the chorus as a whole. In fact, some Epic intertextual links help to highlight the two prevalent and conflicting feelings of the parodos: the hope in the help from the gods and a feeling of apprehension and fear. In particular, it is argued that some Epic features involving Apollo contribute to highlighting already from the opening song of the play two major conceptual themes of Oedipus Rex: the ambiguity of the role of the god and the extreme precariousness of human knowledge
Influence of morpho-structural parameters on environmental stress cracking in polyethylene
Polyethylene (PE) is widely utilized in several industries due to its versatility and mechanical strength, yet its long-term performance is often hindered by slow crack growth (SCG) and environmental stress cracking (ESC). This study quantitatively evaluates the influence of key morpho-structural parameters on SCG and ESC resistance in PE, using a linear elastic fracture mechanics (LEFM) approach to assess the effect of different comonomers on fracture toughness. Four PE materials were analyzed: two medium molecular weight, linear low-density polyethylenes (LLDPE) co-polymerized with 1-butene (Material A) and 1-hexene (Material B); a high molecular weight LLDPE copolymerized with 1-hexene (Material C); and a medium molecular weight, high-density polyethylene (HDPE) homopolymer (Material D). The results confirm that molecular weight is a dominant factor in enhancing stress cracking resistance, with the high molecular weight LLDPE (Material C) showing superior performance. Moreover, despite nearly identical structural parameters, Material B exhibited significantly higher SCG and ESC resistance compared to Material A, highlighting the critical role of the commoner type. The research identified three distinct environmental regimes influencing fracture behavior, each dependent on the applied stress intensity factor (K) and material properties. These regimes are: (1) no significant environmental effect at high K values, where fracture is dominated by the material's inherent properties; (2) partial plasticization of craze fibrils at intermediate K values, due to limited diffusion of environmental agents into the crack tip; and (3) full plasticization of craze fibrils at low K values, where extensive diffusion accelerates environmental stress cracking (ESC). By demonstrating how morpho-structural parameters and environmental conditions together influence polyethylene's resistance to SCG and ESC, this study improves our understanding of the underlying mechanisms and underscores the effectiveness of LEFM in evaluating long-term material performance. This knowledge can guide the design with polyethylene materials aimed at improving long-term durability for industrial applications
Influence of morpho-structural parameters on the environmental stress cracking of polyethylene
The environmental stress cracking resistance (ESCR) of four polyethylenes in active medium (10% Tergitol solution) was investigated.
The four materials were chosen to explore a broad range of performance and applications; they are listed according to increasing expected ESCR:
- an injection moulding, low-molecular weight (MW) HDPE homopolymer
- two rotomoulding LLDPE copolymers with a different comonomer (butene or hexene)
- a blown film extrusion high MW HDPE copolymer (hexene)
The fracture resistance of the hexene LLDPE copolymer was expected to be slightly higher than that of the butene one, because of the longer alkyl group. The two materials were chosen to challenge the ability of the different testing methods to discriminate between similar levels of ESCR.
Several analytical techniques were employed to obtain relevant morpho-structural parameters: density, degree of crystallinity, MW distribution, short chain branch content and average lamellar thickness.
ESCR was evaluated by employing three well-known but widely different approaches:
- the Bell Telephone test (ASTMD1693), performed on notched specimens immersed in the active environment at 50°C
- strain hardening modulus (SHM), obtained from tensile tests performed in air at 80°C
- fracture mechanics (FM) tests on three- and four-point bending notched specimens, performed at varying temperatures both in air and in the active environment; two different loading histories were considered (creep and constant displacement rate)
MW distribution seems to have a greater effect on ESCR behaviour with respect to other morpho-structural parameters. There was instead a strong consistency of the different ESCR testing methods, so that SHM could replace ASTMD1693 as an industrial test aimed at ranking ESCR of polyethylenes. FM, while being more complex to carry out, provides a wealth of additional information which could be used to actually predict the lifetime of products working in an ESC environment
An experimental, theoretical and numerical investigation of shape memory polymers
The present paper deals with the experimental analysis, constitutive modeling and numerical simulation of a class of polymers, exhibiting shape memory effects. We first present and discuss the results of an experimental traction-shrinkage campaign on semi-crystalline shape memory polymers, particularly, on low-density and high-density polyethylene-based polymers. Then, we develop a new one-dimensional phenomenological constitutive model, based on the so-called phase transition approach and formulated in a finite strain framework, in order to reproduce experimental observations. The model is treated through a numerical procedure, consisting in the replacement of the classical set of Kuhn-Tucker inequality conditions by the Fischer-Burmeister complementarity function. Numerical predictions reveal that the model is able to describe qualitative aspects of material behavior, involving both orientation and thermal retraction, as well as to predict experimental orientation processes for semi-crystalline polyethylene-based polymers with different densities
Modulation of soluble receptor for advanced glycation end products isoforms and advanced glycation end products in long-living individuals
Background: Circulating levels of soluble receptor for advanced glycation end products (sRAGE) and advanced glycation end products (AGEs) correlate with aging/cardiovascular risk, which is delayed in long-living individuals (LLIs). AGEs/sRAGE isoforms (cleaved RAGE [cRAGE] and secretory RAGE [esRAGE]) ratio is a valuable marker for disease risk. Results: We evaluated circulating sRAGE isoforms, and AGEs in LLIs (n = 95; 90-105 years) and controls (n = 94; 11-89 years). cRAGE decreased with age in controls and further declined in LLIs. esRAGE increased in LLIs. AGEs rose with age in controls and decreased in LLIs that were characterized by a lower AGEs/sRAGE ratio. Notably, cRAGE and AGE/esRAGE ratio better discriminated controls from LLIs. Conclusion: circulating cRAGE could be considered a reliable marker of chronological age while esRAGE a protective factor for longevity. Aging is the major risk factor for disease development. Long-living individuals (LLIs) are subjects older than 90 years that represent an invaluable model to study mechanisms underpinning longevity and healthy aging. Circulating levels of soluble receptor for advanced glycation end products (sRAGE) change with aging and can forecast the cardiovascular risk, which is reduced in centenarians. sRAGE is composed of two isoforms, the cleaved RAGE (cRAGE) and the secretory RAGE (esRAGE), that are known to inhibit the oxidative stress and inflammatory activities of their ligands such the advanced glycation end products (AGEs). In this study, we measured the plasmatic levels of both sRAGE isoforms and AGEs in LLIs (90-105 years) and control subjects (11-89 years). We found that cRAGE decreases with age in controls and LLIs. esRAGE increases in LLIs and AGEs increase in controls with age but decrease in LLIs. AGEs/esRAGE ratio and cRAGE were able to discriminate controls from LLIs. Hence, LLIs are characterized by a lower AGEs/sRAGE ratio, due to esRAGE increase and AGEs reduction that may explain their reduced cardiovascular and metabolic risk. Besides, circulating cRAGE could be considered a reliable marker of chronological age, while esRAGE a protective factor associated with longevity
Cardiometabolic Risk and Female Sexuality: Focus on Clitoral Vascular Resistance.
Introduction: The relation between sexual and cardiovascular health in women is not well defined. Clitoral color
Doppler ultrasound (CDU) with assessment of the pulsatility index (PI), reflecting resistance to blood flow, has
been proposed as an objective measurement of sexual functioning.
Aim: To investigate associations between clitoral PI and cardiometabolic risk factors, sexual and intrapsychic
parameters, and self-perception of body image.
Methods: Seventy-one adult heterosexual women in a stable relationship attending our clinic for sexual
dysfunction were consecutively recruited.
Main Outcome Measures: Patients underwent physical, laboratory, and clitoral color Doppler ultrasound
examinations and completed the Female Sexual Function Index, the Middlesex Hospital Questionnaire, and the
Body Uneasiness Test (BUT).
Results: Clitoral PI was positively correlated with body mass index (r 1⁄4 0.441, P < .0001), waist circumference
(r 1⁄4 0.474, P < .0001), glycemia (r 1⁄4 0.300, P 1⁄4 .029), insulin (r 1⁄4 0.628, P 1⁄4 .002), homeostatic model
assessment index (r 1⁄4 0.605, P 1⁄4 .005), triglycerides (r 1⁄4 0.340, P 1⁄4 .011), total cholesterol (r 1⁄4 0.346,
P 1⁄4 .010), and low-density lipoprotein cholesterol (r 1⁄4 0.334, P 1⁄4 .016). All relations, with the exception of
glycemia, retained statistical significance after adjusting for age, smoking habit, and years since menopause
(P < .0001 for body mass index, waist circumference, and triglycerides; P < .05 for all other associations).
Analysis of covariance, after adjusting for confounders, showed that women with obesity or metabolic syndrome
(MetS) showed significantly higher PI values (obesity: F 1⁄4 17.79, P 1⁄4 .001; MetS: F 1⁄4 7.37, P 1⁄4 .019).
In particular, a stepwise increase of PI was found as a function of increasing MetS components (b 1⁄4 0.434,
P 1⁄4 .007). Clitoral PI was negatively associated with Female Sexual Function Index arousal (b 1⁄4 0.321,
P 1⁄4 .014) and satisfaction (b 1⁄4 0.289, P 1⁄4 .026) scores and positively associated with Middlesex Hospital
Questionnaire somatized anxiety symptoms, even after adjusting for age, smoking habit, years since menopause,
and current use of psychiatric medication (b 1⁄4 0.354, P 1⁄4 .011). A positive association also was observed
between PI and the BUT positive symptom distress index (b 1⁄4 0.322, P 1⁄4 .039) and BUT for dislike of the
womb, genitals, and breast (b 1⁄4 0.538, P < .0001; b 1⁄4 0.642, P < .0001; b 1⁄4 0.549, P < .0001, respectively).
After introducing waist circumference as another covariate, the associations between clitoral PI and the BUT
positive symptom distress index and BUT dislike of the womb, genitals, and breast retained statistical significance
(P 1⁄4 .038 for positive symptom distress index; P < .0001 for dislike of womb, genitals, and breast).
Conclusion: Clitoral vascular resistance is positively associated with MetS (in particular insulin resistance),
decreased sexual arousal, body image concerns, and increased somatized anxiety symptoms. Further studies are
needed to establish whether treatment of metabolic abnormalities might improve clitoral color Doppler
ultrasound indices and sexual outcomes
Soluble receptor for advanced glycation end-products regulates age-associated cardiac fibrosis
Myocardial aging increases the cardiovascular risk in the elderly. The Receptor for Advanced Glycation End-products (RAGE) is involved in age-related disorders. The soluble isoform (sRAGE) acts as a scavenger blocking the membrane-bound receptor activation. This study aims at investigating RAGE contribution to age-related cardiac remodeling. We analyzed the cardiac function of three different age groups of female Rage-/-and C57BL/6N (WT) mice: 2.5-(Young), 12-(Middle-age, MA) and 21-months (Old) old. While aging, Rage-/-mice displayed an increase in left ventricle (LV) dimensions compared to age-matched WT animals, with the main differences observed in the MA groups. Rage-/-mice showed higher fibrosis and a larger number of α-Smooth Muscle Actin (SMA)+ cells with age, along with increased expression of pro-fibrotic Transforming Growth Factor (TGF)-β1 pathway components. RAGE isoforms were undetectable in LV of WT mice, nevertheless, circulating sRAGE declined with aging and inversely associated with LV diastolic dimensions. Human cardiac fibroblasts stimulated with sRAGE exhibited a reduction in proliferation, pro-fibrotic proteins and TGF-beta Receptor 1 (TGFbR1) expression and Smad2-3 activation. Finally, sRAGE administration to MA WT animals reduced cardiac fibrosis. Hence, our work shows that RAGE associates with age-dependent myocardial changes and indicates sRAGE as an inhibitor of cardiac fibroblasts differentiation and age-dependent cardiac fibrosis
Circulating Endothelial Stem Cells in Age-Matched Smokers with or without Mild-to-Moderate Pulmonary Emphysema
Previous studies have suggested a role for an increased apoptosis of the endothelial cells in the pulmonary capillaries of the alveolar septa in the pathogenesis of pulmonary emphysema. In animal models, circulating endothelial stem cells may contribute to the repair of lung damage. It is unknown if a decrease in the blood of these cells may contribute to the pathogenesis of pulmonary emphysema in humans. The aim of our study was to investigate by flow cytometry the number of total (CD34+) and endothelial stem (triple positive for CD34+/CD133/VEGF-R2) cells in the peripheral venous blood of age-matched smokers with or without pulmonary emphysema. The presence and the severity of pulmonary emphysema was determined using HRCT of the chest with density mask and the NETT score (0 to 4; NEJM 2001). All the subjects were free from concomitant diseases or drugs able to interfere with the number of circulating stem cells. Venous blood samples from 37 subjects (mean age: 66.8±1.4, 25M/12F, mean 33.11±3.2 pack-years, 12 current and 25 ex-smokers) were obtained. Their mean HRCT NETT score is 1.7±0.4.
Twenty-two subjects (59.5%) had chronic airflow obstruction (mean post-bronchodilator FEV1/FVC ratio=56.8%±2.7) whereas 39.5% (n=15) had normal lung function (FEV1/FVC ratio=77.1%±1.4).
We found a significant correlation between the absolute number of circulating CD34+ cells and the absolute number of circulating endothelial stem cells (r=0.593, p<0.0001). Also there was a significant correlation between the percentage of circulating endothelial stem cells and the number of pack-years smoked (r=0.42, p<0.05). No correlation was found between total and endothelial stem cells number and HRCT score of pulmonary emphysema or lung function data. These data suggest that the number of circulating endothelial stem cells is not related to pulmonary emphysema severity
Simplification to TDF+FTC fixed dose combination shows improved immunological response, adherence and patient-related outcomes while maintaining virological efficacy (the MULTIFACTORS Back Study)
Aim of this study was to assess the efficacy, adherence and patient-related outcomes of a simplification strategy in patients switching from a stable regimen containing tenofovir and lamivudine to fixed dose combination with tenofovir + emtricitabine
