Calcium Carbonate as a Functional Filler in Polyamide 12 – Manipulation of the thermal and mechanical properties

Controlling and adjusting the thermal response properties of a polymeric compound is a key driver for improving its usability for an additive manufacturing process such as selective laser sintering, optimising the final part density as well as hardness. Adding mineral fillers to polymers was originally aimed at cost reduction. However, fillers are often used to fulfil a functional role, such as improved thermal or mechanical properties of the polymer composite. The influence of particle size distribution, filler morphology and filler amount of calcium carbonate as a mineral functional filler particle on the thermal properties in a compression-moulded polyamide 12 matrix was investigated. The possibility to combine precisely defined particle size distributions, thereby combining the benefits which each particle size range within the chosen material size distribution contributes to the matrix, was evaluated. The loss of ductility, occurring as a common downside of the introduction of a non-flexing mineral filler, has been investigated. The effect of an optimised coupling agent on the mechanical properties of a compression-moulded compound, containing polyamide 12 filled with surface modified calcium carbonate was also determined. Mineral filler modifier, namely 6- -caprolactam, L-arginine and glutamic acid, were chosen to investigate their coupling effect. The melt flowability at 190°C, the melting speed, melting and crystallisation point, degradation temperature, crystallisation time at 170 and 172°C, as well as the elongation at break were analysed. The melt properties of a polyamide 12 matrix show a significant dependency on the filler volume-based particle size. The finer and the narrower the particle size distribution of the calcium carbonate particles in the polymer matrix become, the less influence the filler has on the melting properties, influencing the melt flow less significantly than the same surface amount of broad size distribution coarse calcium carbonate filler particles. However, due to increased nucleation, the crystallisation behaviour on cooling showed a markedly more rapid onset in the case of fine sub-micrometre filler particle size. The overall thermal and flow properties can be optimised, by adjusting the morphology and particle size distribution of a coarse and fine calcium carbonate filler, blended in an optimised functional filler ratio. With an optimised surface modifying agent and/or filler morphology, the tensile strength as well as elongation at break can be improved in comparison with uncoated filler implementation, such that up to 60% of the loss of ductility and toughness of a final part when using an untreated filler could be regained using the correct amount of an optimised surface modifier. The improvements were demonstrated with a twin-screw extruded compound, indicating the potential for the usage of a functional filler within a polymer matrix as an optimised composite for additive manufacturing

Influence of the Surface Modification of Calcium Carbonate on Polyamide 12 Composites

In previous investigations, it was found that the thermal properties of a polyamide 12 compound can be manipulated, using a designed filler, to improve the melting as well as crystallization behavior, determined for selective laser sintering. A common downside of the introduction of a non-flexing mineral filler is the reduction of the mechanical properties, such as ductility. This paper investigates the influence of content and surface modification of limestone on the mechanical properties. The aim is to understand the effect of an optimized coupling agent on the properties of a compound, containing polyamide 12 filled with 10 wt % of surface modified calcium carbonate. A range of four mineral filler modifications was chosen to investigate their coupling effect, namely 6-amino hexanoic acid, ε-caprolactam, l-arginine or glutamic acid. The in advance surface modified fillers were then each used in combination with the polyamide 12 in a twin-screw extrusion process. With an optimized surface modifying agent, the tensile strength as well as elongation at break can be improved in comparison with uncoated filler implementation, such that up to 60% of the loss of ductility and toughness of a final part when using an untreated filler could be regained using an optimized surface modifier at a correct amount. With the tested filler grade and the specific tested filler amount, the optimized amount of 6-amino hexanoic acid was approx. 2.5 mmol of treatment agent per 100 m2 of CaCO3. These found improvements in a twin-screw extruded polyamide 12 compound show the possible usage of modified calcium carbonate as a functional filler in additive manufacturing and can potentially be transferred in a subsequent investigation in the selective laser sintering process

Impact of Bimodal Particle Size Distribution Ratio of Functional Calcium Carbonate Filler on Thermal and Flowability Properties of Polyamide 12

In previous investigations, it was shown that the melting, as well as crystallization behavior of polyamide 12, could be manipulated by adjusting the particle size distribution of calcium carbonate as a functional filler. It was demonstrated that the melt properties of this compound show a significant dependency on the filler volume-based particle size. As finer and narrower the calcium carbonate particles in the polymer matrix become, the less influence the filler has on the melting properties, influencing the melt flow less significantly than the same surface amount of broad size distribution coarse calcium carbonate filler particles. However, due to increased nucleation, the crystallization behavior on cooling showed a markedly more rapid onset in the case of fine sub-micrometer filler particle size. To control further and optimize the thermal response properties of a filling compound for improved properties in additive manufacturing processing through selective laser sintering, the possibility to combine precisely defined particle size distributions has been studied, thereby combining the benefits of each particle size range within the chosen material size distribution contributes to the matrix. The melt flow at 190 °C, the melting speed, melting and crystallization point as well as crystallization time at 170 °C were analyzed. The thermal and flow properties of a polyamide 12 matrix can potentially be optimized with a combination of a precise amount of coarse and fine calcium carbonate filler. The improvements were exemplified using a twin-screw extruder for compounding, indicating the potential for optimizing functionally filled polymer in additive manufacturing

The p50 NF-\u3baB subunit is a prognostic regulator of colorectal cancer-associated inflammation

In most tumors, tumor associated macrophages (TAMs) express an M2-skewed phenotype and are therefore associated with unfavorable prognosis. However, the impact of TAMs in colorectal cancer (CRC) development and outcome is still controversial. We first demonstrate, by parallel studies in colitis-associated cancer (CAC) and in genetically driven ApcMin mouse models, that p50 NF-\u3baB is essential for CRC development by restraining M1-dependent antitumor response. In absence of p50 mice developed fewer and smaller CRC lesions which express enhanced levels of M1/Th1 cytokines/chemokines including IL-12 and CXCL10, whose administration restrained CAC development in vivo. Moreover colons from p50-/- tumor bearers showed a reduced number of TAMs, as opposed to increased NK, NKT, CD8+ T cells and apoptotic cancer cells. Consistently, in CRC patients, high burden of p50+ TAMs was associated with decreased M1/Th1 inflammation and worse outcome indicating p50 as a new candidate for prognostic and target therapeutic intervention

Alteration of colonic excitatory tachykininergic motility and enteric inflammation following dopaminergic nigrostriatal neurodegeneration

Background: Parkinson's disease (PD) is frequently associated with gastrointestinal (GI) symptoms, including constipation and defecatory dysfunctions. The mechanisms underlying such disorders are still largely unknown, although the occurrence of a bowel inflammatory condition has been hypothesized. This study examined the impact of central dopaminergic degeneration, induced by intranigral injection of 6-hydroxydopamine (6-OHDA), on distal colonic excitatory tachykininergic motility in rats. Methods: Animals were euthanized 4 and 8 weeks after 6-OHDA injection. Tachykininergic contractions, elicited by electrical stimulation or exogenous substance P (SP), were recorded in vitro from longitudinal muscle colonic preparations. SP, tachykininergic NK1 receptor, and glial fibrillary acidic protein (GFAP) expression, as well as the density of eosinophils and mast cells in the colonic wall, were examined by immunohistochemical analysis. Malondialdehyde (MDA, colorimetric assay), TNF, and IL-1 beta (ELISA assay) levels were also examined. The polarization of peritoneal macrophages was evaluated by real-time PCR. Results: In colonic preparations, electrically and SP-evoked tachykininergic contractions were increased in 6-OHDA rats. Immunohistochemistry displayed an increase in SP and GFAP levels in the myenteric plexus, as well as NK1 receptor expression in the colonic muscle layer of 6-OHDA rats. MDA, TNF, and IL-1 beta levels were increased also in colonic tissues from 6-OHDA rats. In 6-OHDA rats, the number of eosinophils and mast cells was increased as compared with control animals, and peritoneal macrophages polarized towards a pro-inflammatory phenotype. Conclusions: The results indicate that the induction of central nigrostriatal dopaminergic degeneration is followed by bowel inflammation associated with increased oxidative stress, increase in pro-inflammatory cytokine levels, activation of enteric glia and inflammatory cells, and enhancement of colonic excitatory tachykininergic motility

Enteric dysfunctions in experimental Parkinson's disease: alterations of excitatory cholinergic neurotransmission regulating colonic motility in rats

Parkinson's disease (PD) is frequently associated with gastrointestinal symptoms, mostly represented by constipation and defecatory dysfunctions. This study examined the impact of central dopaminergic denervation, induced by injection of 6-hydroxydopamine (6-OHDA) into the medial forebrain bundle, on distal colonic excitatory cholinergic neuromotor activity in rats. Animals were euthanized 4 and 8 weeks after 6-OHDA injection. In vivo colonic transit was evaluated by radiological assay. Electrically and carbachol-induced cholinergic contractions were recorded in vitro from longitudinal and circular muscle colonic preparations, while acetylcholine levels were assayed in their incubation media. Choline acetyltransferase (ChAT), HuC/D (pan-neuronal marker), muscarinic M2 and M3 receptors. As compared with control rats, at week 4 6-OHDA-treated animals displayed the following changes: decreased in vivo colonic transit rate; impaired electrically evoked neurogenic cholinergic contractions; enhanced carbachol-induced contractions; decreased basal and electrically stimulated acetylcholine release from colonic tissues; decreased ChAT immunopositivity in the neuromuscular layer; unchanged density of HuC/D immunoreactive myenteric neurons; increased expression of colonic muscarinic M2 and M3 receptors. The majority of such alterations were detected also at week 8 post-6-OHDA injection. These findings indicate that central nigrostriatal dopaminergic denervation is associated with an impaired excitatory neurotransmission characterized by a loss of myenteric neuronal ChAT positivity and decrease in acetylcholine release, resulting in a dysregulated smooth muscle motor activity, which likely contributes to the concomitant decrease in colonic transit rate

Burnout in cardiac anesthesiologists. results from a national survey in italy

Objective: There is increasing burnout incidence among medical disciplines, and physicians working in emergency settings seem at higher risk. Cardiac anesthesiology is a stressful anesthesiology subspecialty dealing with high-risk patients. The authors hypothesized a high risk of burnout in cardiac anesthesiologists. Design: National survey conducted on burnout Setting: Italian cardiac centers. Participants: Cardiac anesthesiologists. Interventions: The authors administered via email an anonymous questionnaire divided into 3 parts. The first 2 parts evaluated workload and private life. The third part consisted of the Maslach Burnout Inventory test with its 3 constituents: high emotional exhaustion, high depersonalization, and low personal accomplishment. Measurements and Main Results: The authors measured the prevalence and risk of burnout through the Maslach Burnout Inventory questionnaire and analyzed factors influencing burnout. Among 670 contacts from 71 centers, 382 cardiac anesthesiologists completed the survey (57%). The authors found the following mean Maslach Burnout Inventory values: 14.5 ± 9.7 (emotional exhaustion), 9.1 ± 7.1 (depersonalization), and 33.7 ± 8.9 (personal accomplishment). A rate of 34%, 54%, and 66% of respondents scored in “high” or “moderate-high” risk of burnout (emotional exhaustion, depersonalization, and personal accomplishment, respectively). The authors found that, if offered to change subspecialty, 76% of respondents would prefer to remain in cardiac anesthesiology. This preference and parenthood were the only 2 investigated factors with a protective effect against all components of burnout. Significantly lower burnout scores were found in more experienced anesthesiologists. Conclusion: A relatively high incidence of burnout was found in cardiac anesthesiologists, especially regarding high depersonalization and low personal accomplishment. Nonetheless, most of the respondents would choose to remain in cardiac anesthesiology

Analysis of urban greening scenarios for improving outdoor thermal comfort in neighbourhoods of Lecce (Southern Italy)

This study analyses the interactions and impacts between multiple factors i.e., urban greening, building layout, and meteorological conditions that characterise the urban microclimate and thermal comfort in the urban environment. The focus was on two neighbourhoods of Lecce city (southern Italy) characterised through field campaigns and modelling simulations on a typical hot summer day. Field campaigns were performed to collect greening, building geometry, and microclimate data, which were employed in numerical simulations of several greening scenarios using the Computational Fluid Dynamics-based and microclimate model ENVI-met. Results show that, on a typical summer day, trees may lead to an average daily decrease of air temperature by up to 1.00 °C and an improvement of thermal comfort in terms of Mean Radiant Temperature (MRT) by up to 5.53 °C and Predicted Mean Vote (PMV) by up to 0.53. This decrease is more evident when the urban greening (in terms of green surfaces and trees) is increased by 1266 m2 in the first neighbourhood and 1988 m2 in the second one, with respect to the current scenario, proving that shading effect mainly contributes to improving the urban microclimate during daytime. On the contrary, the trapping effect of heat, stored by the surfaces during the day and released during the evening, induces an increase of the spatially averaged MRT by up to 2 °C during the evenings and a slight deterioration of thermal comfort, but only locally where the concentration of high LAD trees is higher. This study contributes to a better understanding of the ecosystem services provided by greening with regard to microclimate and thermal comfort within an urban environment for several hours of the day. It adds knowledge about the role of green areas in a Mediterranean city, an important hot spot of climate change, and thus it can be a guide for important urban regeneration plans

Interactions between Natural Health Products and Oral Anticoagulants: Spontaneous Reports in the Italian Surveillance System of Natural Health Products

Introduction. The safety of vitamin K antagonists (VKA) use can be compromised by many popular herbal supplements taken by individuals. The literature reports that 30% of warfarin-treated patients self-medicates with herbs. Possible interactions represent an health risk. We aimed to identify all herbs-oral anticoagulants interactions collected in the Italian database of suspected adverse reactions to “natural health” products. Methods. The Italian database of spontaneous reports of suspected adverse reactions to natural products was analyzed to address herb-VKAs interactions. Results. From 2002 to 2009, we identified 12 reports with 7 cases of INR reduction in patients treated with warfarin (n = 3) and acenocoumarol (n = 4), and 5 cases of INR increase (all warfarin associated). It was reported 8 different herbal products as possibly interacting. Discussion. Our study confirms the risk of interactions, highlighting the difficulty to characterize them and their mechanisms and, finally, prevent their onset. The reported data underline the urgent need of healthcare providers being aware of the possible interaction between natural products and VKA, also because of the critical clinical conditions affecting patients. This is the first step to have the best approach to understand possible INR alterations linked to herb-VKA interaction and to rightly educate patients in treatment with VKA