Additive Manufacturing and Vulcanization of Carbon Black Filled Natural Rubber Based Components

Additive manufacturing of thermoplastics or metals is a well-approved sustainable process for obtaining rapidly precise and individual technical components. Except for crosslinked silicone rubber or thermoplastic elastomers, there is no method of additive manufacturing of elastomers. Based on the development of the additive manufacturing of elastomers (AME) process, the material group of rubber-based cured elastomers may gain first access to the process field of three-dimensional (3D) printing. Printing and crosslinking of rubber is separated into two steps. In the first step, printing is realized by extrusion of the rubber by using a twin-screw extruder, which works according to the derived fused-filament-fabrication principle. In the second step, the component is vulcanized in a high-pressure hot-air autoclave. Because of the plastic flow behavior of non–crosslinked rubber materials, a thermoplastic shell is probably needed to maintain the geometry and position of the additively manufactured rubber. In this way, one layer of thermoplastic and one layer of rubber are printed alternatingly until the component is finished. Afterward, the manufactured binary component is placed in an autoclave to obtain the elastomer after vulcanization under a hot-air and high-pressure atmosphere. Then, the thermoplastic shell is removed from the elastomer and can subsequently be recycled. As compared with conventional thermoplastics, the high viscosity of rubber during processing and its instable shape after extrusion are challenging factors in the development of the AME. This contribution will show a modified 3D printer; explain the printing process from the designed component, via shell generation, to the vulcanized component; and show first printed components

Tailoring the Curing Kinetics of NBR-Based Rubber Compounds for Additive Manufacturing of Rod Seals

The additive manufacturing (AM) of elastomeric parts based on high-viscosity reinforced rubbers has increasingly become a topic of scientific research in recent years. In addition to the viscosity, which is several decades higher during processing than the viscosities of thermoplastics, the flowability of the compound after the printing process and the necessary chemical crosslinking of the printed component play a decisive role in producing an elastic, high-quality, and geometrically stable part. After the first technological achievements using the so-called additive manufacturing of elastomers (AME) process, the knowledge gained has to be transferred first to concrete industrial parts. Therefore, in this study, the cure kinetics of a conventional rubber compound are tailored to match the specific requirements for scorch safety in the additive manufacturing of an industrial 2-component rod seal based on an acrylonitrile butadiene rubber O-ring in combination with a thermoplastic polyurethane as the base body. Experimental tests on a test rig for rod seals demonstrate the functionality of this additively manufactured 2-component rod seal

Impact of atherosclerotic plaque composition on coronary microembolization during percutaneous coronary interventions

BACKGROUND: Cardiac marker release after percutaneous coronary interventions (PCI) reflects myocardial necrosis which is usually the result of periprocedural (micro)embolization of atherothrombotic debris and associated with impaired left ventricular function and adverse outcome. METHODS: In this prospective study, we examined 55 patients treated by direct stenting of single de-novo lesions to assess the relationship between plaque composition, as determined by preinterventional intravascular ultrasound (IVUS) with radiofrequency data (IVUS-RF) analysis (so-called Virtual Histology) versus coronary microembolization, as determined by serial measurement of cardiac markers. IVUS was performed with an electronic system and 20-MHz IVUS catheters. Serum creatine kinase (CK) and cardiac troponin I (CTnI) were determined before PCI and after 6, 12, and 24 hours. RESULTS: Plaques had a volume of 99 +/- 63 mm(3) and were composed of fibrous (61 +/- 9%) and fibro-fatty tissue (27 +/- 12%), dense calcium (4 +/- 3%), and necrotic core (NC) (8 +/- 6%). NC volume per se, volume per 10 mm of segment length, and volume % were correlated (r = 0.64, 0.66, and 0.52 respectively; all P 10.8 mm(3)) had a particularly high increase in markers (P < 0.001). In contrast, total plaque volume and plaque components other than NC had no relation with cardiac markers (ns). CONCLUSIONS: Patients with large NC in culprit lesions may experience more myocardial injury from peri-interventional microembolization. IVUS-RF assessment before PCI has the potential to identify lesions at particular high risk which may help to tailor PCI

Relaxation Methods for Mixed-Integer Optimal Control of Partial Differential Equations

We consider integer-restricted optimal control of systems governed by abstract semilinear evolution equations. This includes the problem of optimal control design for certain distributed parameter systems endowed with multiple actuators, where the task is to minimize costs associated with the dynamics of the system by choosing, for each instant in time, one of the actuators together with ordinary controls. We consider relaxation techniques that are already used successfully for mixed-integer optimal control of ordinary differential equations. Our analysis yields sufficient conditions such that the optimal value and the optimal state of the relaxed problem can be approximated with arbitrary precision by a control satisfying the integer restrictions. The results are obtained by semigroup theory methods. The approach is constructive and gives rise to a numerical method. We supplement the analysis with numerical experiments

Synthesis of Alkaline Earth Diazenides MAEN2 (MAE = Ca, Sr, Ba) by Controlled Thermal Decomposition of Azides under High Pressure

The alkaline earth diazenides MAEN2 with MAE = Ca, Sr and Ba were synthesized by a novel synthetic approach, namely, a controlled decomposition of the corresponding azides in a multianvil press at highpressure/ high-temperature conditions. The crystal structure of hitherto unknown calcium diazenide (space group I4/mmm (no. 139), a = 3.5747(6) Å, c = 5.9844(9) Å, Z = 2, wRp = 0.078) was solved and refined on the basis of powder X-ray diffraction data as well as that of SrN2 and BaN2. Accordingly, CaN2 is isotypic with SrN2 (space group I4/mmm (no. 139), a = 3.8054(2) Å, c = 6.8961(4) Å, Z = 2, wRp = 0.057) and the corresponding alkaline earth acetylenides (MAEC2) crystallizing in a tetragonally distorted NaCl structure type. In accordance with literature data, BaN2 adopts a more distorted structure in space group C2/c (no. 15) with a = 7.1608(4) Å, b = 4.3776(3) Å, c = 7.2188(4) Å, β = 104.9679(33)°, Z = 4 and wRp = 0.049). The N−N bond lengths of 1.202(4) Å in CaN2 (SrN2 1.239(4) Å, BaN2 1.23(2) Å) correspond well with a double-bonded dinitrogen unit confirming a diazenide ion [N2]2−. Temperature-dependent in situ powder X-ray diffractometry of the three alkaline earth diazenides resulted in formation of the corresponding subnitrides MAE2N (MAE = Ca, Sr, Ba) at higher temperatures. FTIR spectroscopy revealed a band at about 1380 cm−1 assigned to the N−N stretching vibration of the diazenide unit. Electronic structure calculations support the metallic character of alkaline earth diazenides

Comparison of alternative versions of the job demand-control scales in 17 European cohort studies : the IPD-Work consortium

BACKGROUND: Job strain (i.e., high job demands combined with low job control) is a frequently used indicator of harmful work stress, but studies have often used partial versions of the complete multi-item job demands and control scales. Understanding whether the different instruments assess the same underlying concepts has crucial implications for the interpretation of findings across studies, harmonisation of multi-cohort data for pooled analyses, and design of future studies. As part of the 'IPD-Work' (Individual-participant-data meta-analysis in working populations) consortium, we compared different versions of the demands and control scales available in 17 European cohort studies. METHODS: Six of the 17 studies had information on the complete scales and 11 on partial scales. Here, we analyse individual level data from 70 751 participants of the studies which had complete scales (5 demand items, 6 job control items). RESULTS: We found high Pearson correlation coefficients between complete scales of job demands and control relative to scales with at least three items (r > 0.90) and for partial scales with two items only (r = 0.76-0.88). In comparison with scores from the complete scales, the agreement between job strain definitions was very good when only one item was missing in either the demands or the control scale (kappa > 0.80); good for job strain assessed with three demand items and all six control items (kappa > 0.68) and moderate to good when items were missing from both scales (kappa = 0.54-0.76). The sensitivity was >0.80 when only one item was missing from either scale, decreasing when several items were missing in one or both job strain subscales. CONCLUSIONS: Partial job demand and job control scales with at least half of the items of the complete scales, and job strain indices based on one complete and one partial scale, seemed to assess the same underlying concepts as the complete survey instruments.Peer reviewe

Monogenic variants in dystonia: an exome-wide sequencing study

Background Dystonia is a clinically and genetically heterogeneous condition that occurs in isolation (isolated dystonia), in combination with other movement disorders (combined dystonia), or in the context of multisymptomatic phenotypes (isolated or combined dystonia with other neurological involvement). However, our understanding of its aetiology is still incomplete. We aimed to elucidate the monogenic causes for the major clinical categories of dystonia. Methods For this exome-wide sequencing study, study participants were identified at 33 movement-disorder and neuropaediatric specialty centres in Austria, Czech Republic, France, Germany, Poland, Slovakia, and Switzerland. Each individual with dystonia was diagnosed in accordance with the dystonia consensus definition. Index cases were eligible for this study if they had no previous genetic diagnosis and no indication of an acquired cause of their illness. The second criterion was not applied to a subset of participants with a working clinical diagnosis of dystonic cerebral palsy. Genomic DNA was extracted from blood of participants and whole-exome sequenced. To find causative variants in known disorder-associated genes, all variants were filtered, and unreported variants were classified according to American College of Medical Genetics and Genomics guidelines. All considered variants were reviewed in expert round-table sessions to validate their clinical significance. Variants that survived filtering and interpretation procedures were defined as diagnostic variants. In the cases that went undiagnosed, candidate dystonia-causing genes were prioritised in a stepwise workflow. Findings We sequenced the exomes of 764 individuals with dystonia and 346 healthy parents who were recruited between June 1, 2015, and July 31, 2019. We identified causative or probable causative variants in 135 (19%) of 728 families, involving 78 distinct monogenic disorders. We observed a larger proportion of individuals with diagnostic variants in those with dystonia (either isolated or combined) with coexisting non-movement disorder-related neurological symptoms (100 [45%] of 222;excepting cases with evidence of perinatal brain injury) than in those with combined (19 [19%] of 98) or isolated (16 [4%] of 388) dystonia. Across all categories of dystonia, 104 (65%) of the 160 detected variants affected genes which are associated with neurodevelopmental disorders. We found diagnostic variants in 11 genes not previously linked to dystonia, and propose a predictive clinical score that could guide the implementation of exome sequencing in routine diagnostics. In cases without perinatal sentinel events, genomic alterations contributed substantively to the diagnosis of dystonic cerebral palsy. In 15 families, we delineated 12 candidate genes. These include IMPDH2, encoding a key purine biosynthetic enzyme, for which robust evidence existed for its involvement in a neurodevelopmental disorder with dystonia. We identified six variants in IMPDH2, collected from four independent cohorts, that were predicted to be deleterious de-novo variants and expected to result in deregulation of purine metabolism. Interpretation In this study, we have determined the role of monogenic variants across the range of dystonic disorders, providing guidance for the introduction of personalised care strategies and fostering follow-up pathophysiological explorations

Additive Fertigung und Vulkanisation von Natur- und Synthesekautschuken

Additive manufacturing of thermoplastics and metals is a sustainable and established process in industry for the rapid production of individual technical components. For a long time, this technology was not accessible for the group of elastomers, or only to a limited extent in the form of thermoplastic elastomers or silicone rubbers. The development of the Additive Manufacturing of Elastomers (AME)-process has enabled the additive manufacturing of high viscosity rubbers. In future, additively manufactured rubber components may be used in technical logistics in particular. On the one hand, the supply of spare parts such as sealing and damping elements is possible, and on the other hand, the production of individual geometries for grippers in handling technology. For the additive manufacturing of rubber, an industrial 3D-printer was modified by a twin screw extruder, which can process rubber filament and deposit it on a printing plate in strand form, similar to the thermoplastic Fused Filament Fabrication (FFF)-process. The use of a screw extruder is necessary because the viscosity of the rubber does not decrease sufficiently with heating, making it impossible to guide the filament through conventional print heads for thermoplastic filaments. The AME-process is a two-step manufacturing process. First, the components are additively manufactured, followed by vulcanization in a high-pressure autoclave or heating oven. Single-part production is a particular challenge in this case, as the vulcanization time depends on the rubber compound and the component geometry. In order to avoid waste, it is therefore necessary to know the optimum vulcanization time before vulcanization. For this purpose, a simulation was developed and validated that outputs the degree of crosslinking in the component as a function of the vulcanization temperature and time.Die additive Fertigung von Thermoplasten und Metallen ist ein nachhaltiges und in der Industrie zur schnellen Herstellung von individuellen technischen Bauteilen bewährtes Verfahren. Lange Zeit war diese Technologie für die Werkstoffgruppe der Elastomere nicht oder nur eingeschränkt in Form von Thermoplastischen Elastomeren oder Silikonkautschuken zugänglich. Durch die Entwicklung des Additive Manufacturing of Elastomers (AME)-Verfahrens ist nun auch die additive Fertigung von hochviskosen Kautschuken möglich. Besonders in der technischen Logistik können zukünftig additiv gefertigte Kautschukbauteile Einsatz finden. Einerseits ist die Bereitstellung von Ersatzteilen wie Dichtungs- und Dämpferelementen möglich, aber auch die Fertigung individueller Geometrien für Greifer in der Handhabungstechnik. Zur additiven Fertigung von Kautschuk wurde ein industrieller 3D-Drucker um einen Zweischneckenextruder erweitert, der Kautschukfilament verarbeiten und ähnlich zum thermoplastischen Fused Filament Fabrication (FFF)-Verfahren strangförmig auf eine Druckplatte auftragen kann. Der Einsatz eines Schneckenextruders ist notwendig, da die Viskosität des Kautschuks nicht ausreichend durch Erwärmung abnimmt und somit eine Führung des Filaments durch konventionelle Druckköpfe für thermoplastische Filamente nicht möglich ist. Das AME-Verfahren ist ein zweistufiges Fertigungsverfahren. Zuerst werden die Bauteile additiv gefertigt, anschließend folgt die Vulkanisation in einem Hochdruckautoklav oder Wärmeschrank. Hierbei ist besonders die Einzelteilfertigung eine Herausforderung, da die Vulkanisationszeit abhängig von der Kautschukmischung und der Bauteilgeometrie ist. Um keinen Ausschuss zu produzieren ist es daher notwendig die optimale Vulkanisationszeit vor der Vulkanisation zu kennen. Hierfür wurde eine Simulation, die den Vernetzungsgrad im Bauteil in Abhängigkeit von der Vulkanisationstemperatur und -zeit ausgibt, entwickelt und validiert

Numerical solution of a conspicuous consumption model with constant control delay☆

We derive optimal pricing strategies for conspicuous consumption products in periods of recession. To that end, we formulate and investigate a two-stage economic optimal control problem that takes uncertainty of the recession period length and delay effects of the pricing strategy into account