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Organisationseinheit der BAM
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- 4 Material und Umwelt (1)
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Eingeladener Vortrag
- nein (4)
Durch die Auswahl einer geeigneten Rezeptur werden hochzähe Polyethylen/Polypropylen- Mischungen mit Haftvermittlerzusatz entwickelt, deren Morphologie analysiert sowie die für die hohe Kerbschlagzähigkeit verantwortlichen Deformations- und Bruchmechanismen erläutert. Im Vordergrund der Betrachtungen stehen dabei werkstoffseitige Einflussfaktoren auf das Zähigkeitsverhalten der PE/PP-Mischungen, wobei die Abhängigkeit vom Volumenanteil der einzelnen Komponenten, der Einfluss der Phasenmorphologie und der Beitrag der Phasenhaftung untersucht werden. Zum Einsatz kommen u.a. die Elektronenmikroskopie, mechanische und bruchmechanische Prüfmethoden sowie die Schallemission. Durch die Zugabe eines Haftvermittlers werden feindisperse Morphologien und bessere Phasenhaftung in der Grenzschicht erzielt. Damit werden Zähigkeitsverbesserungen gegenüber den Homopolymeren um den Faktor 5 bis 8 erreicht.
Die zum Vergleich der Polyethylenformstoffe für eine Bauart in der DIN EN 15507: 2009 – Verpackung – Verpackungen zur Beförderung gefährlicher Güter – Vergleichende Werkstoffprüfung von Polyethylensorten ausgewählten Materialkennwerte Schmelze-Masse-Fließrate MFR, Dichte D, Kerbschlagzähigkeit acN bei -30 °C, Spannungsrissbeständigkeit FNCT (full notch creep test) und Beständigkeit gegen oxidativen Abbau Ox (bestimmt durch den prozentualen Anstieg der MFR in 55 %-iger Salpetersäure) stehen in einer systematischen Beziehung mit Baumusterprüfungen. So stehen die mit Prüfkörpern aus gepressten Platten bestimmte Kerbschlagzähigkeit acN bei -30 °C und die Beständigkeit gegen oxidativen Abbau der Polyethylenformstoffe in einem Zusammenhang mit den Fallprüfungen der Baumuster aus diesen Formstoffen bei -18 °C, wobei die Baumuster einer 21-tägigen Vorlagerung mit der Standardflüssigkeit 55 %-ige Salpetersäure bei 40 °C unterzogen werden. Untersuchungen in der Dissertation zum Thema: Vergleich der Materialkennwerte von Formstoffen aus Polyethylen hoher Dichte mit dem Baumusterverhalten von Gefahrgutverpackungen haben gezeigt, dass bei 21-tägiger Vorlagerung der Baumuster mit 55 %-iger Salpetersäure die Grenzfallhöhen ansteigen, anstatt zu sinken. Zur Bestätigung und Erweiterung dieser Untersuchungsergebnisse wurden die Abhängigkeit der Grenzfallhöhen in den Fallprüfungen bei -18 °C, der MFR sowie der Zugeigenschaften Zugfestigkeit, Bruchdehnung und E-Modul von der Dauer der Vorlagerung mit 55 %-iger Salpetersäure bei 40 °C und 23 °C untersucht. Verpackungsbaumuster aus drei Formstoffen verschiedener Hersteller wurden mit 55 %-iger Salpetersäure 21, 42 und 84 Tage bei 40 °C sowie 6 Monate bei 23 °C vorgelagert. Die MFR und die Zugeigenschaften wurden von Kanisterwandausschnitten bestimmt. In Fallprüfungen bei -18 °C wurden die Grenzfallhöhen der Baumuster ermittelt. Die Werte der Kerbschlagzähigkeit bei -30 °C der Formstoffe stehen nicht im Zusammenhang mit den in den Kältefallprüfungen ermittelten Grenzfallhöhen. Die Grenzfallhöhen der nicht vorgelagerten Kanister aus den Formstoffen mit niedrigerer Kerbschlagzähigkeit sind höher im Vergleich zum Formstoff mit höherer Kerbschlagzähigkeit. Der oxidativ schädigende Einfluss der Salpetersäure wirkt sich in höherem Maße bei dem Formstoff mit der niedrigeren Beständigkeit gegen oxidativen Abbau in einer stärkeren Reduzierung der Grenzfallhöhen mit zunehmender Vorlagerungsdauer aus. Die 21-tägige Vorlagerung mit 55 %-iger Salpetersäure bei 40 °C bewirkte bei den Kanistern aus Formstoffen mit höherer Beständigkeit gegen oxidativen Abbau eine Erhöhung der Grenzfallhöhe in den Kältefallprüfungen. Mit Erhöhung der Vorlagerungszeit der Kanister auf 42 und 84 Tage wurden auch die Grenzfallhöhen der Kanister aus diesen Formstoffen aufgrund der mit dem längeren Zeitraum der Einwirkung verbundenen stärkeren oxidativen Schädigung durch die Salpetersäure reduziert. Die Grenzfallhöhe der Kanister aus dem Formstoff mit der niedrigeren Beständigkeit gegen oxidativen Abbau wurde dagegen durch die 21-tägige Vorlagerung erniedrigt und stieg mit zunehmender Vorlagerungsdauer wieder an. Der Formstoff wurde durch die Einwirkung der Salpetersäure über einen längeren Zeitraum elastisch. Gemäß DIN EN ISO 16101 ist die oxidativ schädigende Wirkung der 55 %-igen Salpetersäure über einen Zeitraum von 21 Tagen bei 40 °C mit der oxidativ schädigenden Wirkung der 55 %-igen Salpetersäure innerhalb von 180 Tagen (6 Monaten) bei 23 °C zu vergleichen. Der Vergleich der Grenzfallhöhen der Kanister und der MFR von Wandausschnitten aus diesen Kanistern nach 21-tägiger Vorlagerung bei 40 °C und nach der sechsmonatigen Vorlagerung bei 23 °C zeigte, dass die oxidative Schädigung der Polyethylenformstoffe nach sechs Monaten Vorlagerung bei 23 °C stärker im Vergleich zur 21-tägigen Vorlagerung bei 40 °C ist. Die Messergebnisse zeigten deutlich, dass die sechsmonatige Vorlagerung der Kanister bei 23 °C einen höheren Anstieg der MFR und niedrigere Grenzfallhöhen der Kanister in den Kältefallprüfungen im Vergleich zur 21-tägigen Vorlagerung der Kanister bei 40 °C bewirkte. Als Folge der Diffusion von Salpetersäure in die Polyethylenformstoffe und ihrer Reaktion mit dem Polymeren verändern sich die mechanischen Eigenschaften. Die prozentualen Werte der Abnahme bzw. Zunahme der Zugfestigkeit und der Bruchdehnung von Probekörpern aus der Seitenwand der Baumuster nach unterschiedlichen Vorlagerungszeiten stehen nur teilweise mit den Grenzfallhöhen der Kanister in den Kältefallprüfungen im Zusammenhang. Bemerkenswert ist, dass beim Vergleich der Zugfestigkeit und der Bruchdehnung des Formstoffes mit einer hohen Beständigkeit gegen oxidativen Abbau mit den Grenzfallhöhen der Kanister aus diesem Formstoff diese Materialkennwerte mit zunehmender Vorlagerungsdauer ansteigen, aber die Grenzfallhöhe nur nach der 21-tägigen Vorlagerung ansteigt und anschließend mit zunehmender Vorlagerungsdauer abfällt. Zugfestigkeit und Bruchdehnung der Probekörper aus dem Formstoff mit der geringeren Beständigkeit gegen oxidativen Abbau sinken in Analogie zu den Grenzfallhöhen mit steigender Vorlagerungsdauer der Kanister mit der Säure. Der Vergleich der Werte des E-Moduls mit den Grenzfallhöhen zeigte, dass bei den Kanistern aus dem Formstoff mit der niedrigeren Beständigkeit gegen oxidativen Abbau sich E-Modul und Grenzfallhöhe analog verhalten. Mit zunehmender Vorlagerungsdauer der Kanister steigen der E-Modul und die Grenzfallhöhen in den Kältefallprüfungen an. Die, durch die Einwirkung der Salpetersäure, entstandenen Eigenspannungszustände sind die Ursache für den ansteigenden E- Modul der Probekörper aus diesen Formstoffen. Bei den Probekörpern von Kanistern aus dem Formstoff mit der höheren Beständigkeit gegen oxidativen Abbau wurde ein markanter Abfall des E-Moduls nach 21-tägiger Vorlagerung der Kanister gemessen. Der E-Modul sinkt noch geringfügig nach der 42-tägigen Vorlagerung und steigt mit zunehmender Vorlagerungsdauer dagegen wieder an. Die Grenzfallhöhen verhalten sich erwartungsgemäß gegenläufig.
Einleitung
Bei der Detektion von Mikrorissen und der Charakterisierung spezifischer Schädigungen von Polymer- und Kompositwerkstoffen kommt es neben quantitativen Bewertungen auch auf die Analyse von orientierungsabhängigen Struktureffekten an. Am Beispiel typischer Vertreter ausgewählter Materialien (PP/PE, CFK) wird dargestellt, inwieweit das Potential der Röntgen-Refraktions-Topographie vorteilhaft zur umfassenden Materialcharakterisierung genutzt werden kann. Die korrosiven Eigenschaften nichtmetallischer Werkstoffe werden maßgeblich vom mikrostrukturellen Aufbau der verwendeten Materialien bestimmt. Typische Versagens-mechanismen von Faser-Kompositen sind neben der Faserenthaftung vor allem durch Mikrorisse gekennzeichnet, die sich teils parallel, teils senkrecht zu den Fasern in der Matrix ausbreiten. Eine wichtige Anwendung der Röntgen-Refraktions-Topographie umfaßt die orientierungsselektive Detektion von Mikroriß-Oberflächen. Die Nachweisgrenze derartiger Schädigungen erstreckt sich bis zum Nanometerbereich. Definiert herbeigeführte Ermüdungsschäden an Kompositmaterialien lassen sich mit dieser Methode ausgezeichnet erfassen und gestatten eine quantitative Korrelation zu mechanischen Kenngrößen. Mittels schrittweiser Probenabtastung und der ortskorrelierten Speicherung von simultan erfassten Refraktions- bzw. Absorptionszählraten wird ein zweidimensionales Röntgen-Refraktions-Topogramm rekonstruiert, das u.a. die präzise Information der integralen Rissdichte enthält.
Studienziel: Zwei Nagelsysteme, zum einen der unaufgebohrte Tibianagel mit 3fach-Verriegelung in 2 Ebenen und großem Bolzenspiel (UTN® der Fa. Mathys®) mit der Möglichkeit von medial zweifach und von ventral einfach zu verriegeln und zum anderen der unaufgebohrte Tibianagel mit 3fach-Verriegelung in einer Ebene mit geringem Bolzenspiel (Targon®-Nagel der Fa. Aesculap®), der 3 mediale Verriegelungsmöglichkeiten besitzt, wurden im Biegeversuch statisch geprüft. Anatomisch besteht bei der ventralen Verriegelung immer die Verletzungsmöglichkeit von Sehnen, Nerven und Gefäßen. Andererseits besteht bei einem höheren Bolzenspiel immer ein höherer Instabilitätsgrad. Inwieweit ist die Verriegelung in zwei Ebenen notwendig?
Methode: Wir prüften statisch zwei intramedulläre Verriegelungssysteme an 8 Leichenknochen (matched pairs) in zwei Ebenen an einer Universalprüfmaschine der Firma Schenk-Trebel im Biegeversuch.
Ergebnisse: Die Untersuchungsergebnisse zeigen, dass nicht die Bolzenlage, sondern das so genannte Bolzenspiel für die Stabilität der distalen Fragmente entscheidend ist. Die Verriegelung sollte somit prinzipiell durch ein formschlüssiges winkelstabiles Bolzensystem möglich sein.
With a growing percentage of elderly people in the population and, correspondingly, an increasing rate of fractures of the proximal femur, the question how to stabilize medial femoral-neck fractures is gaining increasing importance. Especially in Hungary and Scandinavian countries, femoral-head-preserving surgery is advocated. However, the main problems of this procedure are re-dislocation and necrosis of the femoral head. Encouraged by two theoretical mathematical considerations, a biomechanical experiment was performed to investigate two different methods of screw fixation of medial femoral-neck fractures. The results showed that a head-preserving internal fixation with two cranial screws and a three-point supported screw at the bottom of the neck had distinct biomechanical advantages compared to conventional screw fixation. This has encouraged us to more frequently perform this minimally invasive and head-preserving surgery in Pauwels I and II medial fractures of the femoral head.
The material parameters melt flow rate (MFR), density (D), notched impact strength (NIS) at –30°C, stress crack resistance [determined with the Full Notch Creep Test (FNCT)] and resistance to oxidative degradation (Ox) have been selected for a comparison of polyethylene grades in the European standard EN 15507. These parameters have a relationship with design type tests of packagings for the transport of dangerous goods.
This paper presents the results of additional investigations to determine the impact of the pre-storage time of jerricans with 55% nitric acid at 40°C and 23°C on the marginal drop heights in drop tests at –18°C, on the MFR and on the tensile properties. Jerricans made of different polyethylene grades were pre-stored with 55% nitric acid for 21, 42 and 84 days at 40°C and for six months at 23°C.
The tests showed that the NIS values at –30°C of polyethylene grades were not comparable with marginal drop heights determined in drop tests at –18°C.
Pre-damage with 55% nitric acid for 21 days at 40°C led to an increase in the marginal drop heights of the jerricans. Altering the test regulations by increasing pre-storage time with 55% nitric acid to 42 days would be an alternative.
The test results demonstrated clearly that pre-storage of the jerricans for six months at 23°C caused a higher increase in the MFR and lower marginal drop heights for the jerricans when compared with pre-stored jerricans for 21 days at 40°C.
The material parameters melt flow rate MFR, density D, notched impact strength N.I.S. at -30 °C, stress crack resistance FNCT and resistance to oxidative degradation Ox (determined by the increase of MFR) have been selected for a comparison of polyethylene grades for one design type in the “European Standard EN 15507 - Transport packaging for dangerous goods - Comparative material testing of polyethylene grades”. The parameters have a systematic relationship with design type tests. The notched impact strength at -30 °C and the resistance to oxidative degradation of polyethylene grades determined with test specimens of compression moulded sheets are directly comparable with drop tests at -18 °C of design types produced of these grades after pre-storage with 55 % nitric acid for 21 days at 40 °C. The impact of the pre-storage time of jerricans with 55 % nitric acid at 40 °C and 23 °C on the marginal drop heights in drop tests at -18 °C, on the MFR and on the tensile properties tensile strength, breaking elongation and the elastic modulus were investigated. Packaging design types (jerricans) made of three polyethylene grades from different producers were pre-stored with 55 % nitric acid for 21,42 and 84 days at 40 °C as well as for six months at 23 °C. The MFR and tensile properties of test specimens taken from the design type side walls as well as the marginal drop heights of the jerricans in drop tests at -18 °C were determined.
The values of the notched impact strength at -30 °C of polyethylene grades are not comparable with the marginal drop heights determined in drop tests at -18 °C. The oxidative damaging impact of nitric acid has a greater effect on the grade with lower resistance to oxidative degradation by reducing more significantly the marginal drop heights with increasing pre-storage time.
Pre-damage with 55 % nitric acid for 21 days at 40 °C, as recommended in ISO 16101 and EN 15507 caused an increase in the marginal drop heights of most design types in drop tests when compared with design types without pre-damage. The test results demonstrated clearly that pre-storage of the jerricans for six months at 23 °C caused a higher increase in the MFR and lower marginal drop heights of the jerricans in drop tests at -18 °C compared with pre-storage of the jerricans for 21 days at40 °C.
The mechanical properties change as a result of diffusion of nitric acid into the polyethylene grades and the reaction of the nitric acid with the polymers. The percentage decrease and increase in the tensile strength, breaking elongation and elasticity modulus of test specimens taken from the design type side walls after different pre-storage times were only partly comparable with the marginal drop heights in drop tests at -18 °C.
Studienziel: Bei der zunehmenden Überalterung der Bevölkerung und der zunehmenden Inzidenz an hüftgelenknahen Oberschenkelfrakturen nimmt die Frage der Versorgung der medialen Schenkelhalsfraktur eine zunehmende Rolle ein. Vor allem aus Ungarn und den skandinavischen Ländern wird die kopferhaltende Therapie propagiert. Das Redislozieren dieser Frakturen und die Hüftkopfnekrose sind jedoch dagegenstehende Probleme. Methode: Ermutigt durch zwei theoretische mathematische Überlegungen wurden in einem biomechanischen Experiment zwei verschiedene Möglichkeiten der Verschraubung der medialen Schenkelhalsfraktur erprobt. Ergebnisse: Als Ergebnis zeigte sich, dass eine kopferhaltende Versorgung mit 2 kranial liegenden Schrauben und einer dreipunktabgestützten Schraube am Adam'schen Bogen deutliche biomechanische Vorteile hat gegenüber der herkömmlichen Verschraubung. Schlussfolgerung: Dies ermutigt uns, zunehmend die minimalinvasive und kopferhaltende Versorgung der medialen Schenkelhalsfraktur insbesondere bei Pauwels-I- und II-Verletzungen einzusetzen.
Schädigungsnachweis in kurzglasfaserverstärkten Thermoplasten mittels ortsauflösender ZfP-Methoden
(2001)
Resistance to stress cracking by wetting solution is one of the selected properties together with the corresponding test method FNCT and tolerances for a comparison of polyethylene grades of one design type in the procedural rule on suitability proof for alternative plastic resins used for packagings and intermediate bulk Containers (IBCs) for the transport of dangerous goods.
The environmental stress crack resistance determined by Full Notch Creep Test (FNCT) represents the impacts from the stacking tests at 40 °C performed with Standard liquid wetting solution (without pre-storage) and with normal butyl acetate saturated wetting solution (pre-storage with normal butyl acetate). Environmental stress crack resistance determined with FNCT for the polyethylene grades was related to the times to failure of different jerrican samples made of these grades in stacking tests with 5 % wetting solution and a n-butyl acetate saturated wetting solution (pre-storage with n-butyl acetate) at 40 °C. The FNCT is suitable for comparison of polyethylene grades in relation to environmental stress crack resistance independent of their use as drum, IBC or jerrican material. The stiffness of polyethylene grades should be taken into account to the comparison as jerricans are not only chemically but also mechanically stressed.
The time-dependent sorption of biodiesel in a typical polyethylene for container applications is investigated in comparison to conventional diesel fuel at three different temperatures. In this context, the desorption behavior is also addressed. Subsequently, the effects of both penetrants on mechanical properties are characterized in terms of impact strength and dynamic-mechanical analysis. The discussion of property changes is firstly based on the sorption kinetics of biodiesel and diesel, which is determined by immersion experiments allowing for the calculation of respective diffusion coefficients. Changes in impact strength as determined by the Charpy method are further characterised in more detail by analyzing the fracture surfaces, and correlated with results of dynamic-mechanical analysis.
The aim of this research is to study the influence of moisture absorption at low moisture contents on the creep behaviour of an epoxy adhesive in steel bonded joints. Single lap joints were manufactured using high strength steel adherends and a two-component epoxy adhesive. The single lap joints were tested at load Levels corresponding to average lap shear stresses of±5%, 15%, 30% and 45% of the dry lap shear strength in both 40 °C air and 40 °C distilled water. Specimens were not pre-aged to be able to analyse the coupled effect of moisture and loading. The test results show that an increase in the load level resulted in an increase in the instantaneous strain and in the creep strain rate. The creep strain of single lap joints loaded in water was generally larger than for the ones loaded in air. For joints loaded in water the creep behaviour was found to be dependent on the moisture concentration in the adhesive. At low moisture percentages creep was suppressed, resulting in a lower instantaneous strain. At higher moisture percentages creep was promoted, resulting in a larger strain rate. The suppression of creep at low moisture percentages is attributed to water molecules bonding to the epoxy macromolecules, resulting in a reduction in molecular mobility and a smaller creep strain. At higher moisture percentages the plasticizing effect of the water dominates, resulting in a larger creep strain. The Maxwell threeelement solid model and Kelvin-Voigt three-element solid model were used to simulate the creep behaviour of the single lap joints loaded in air and water. The models gave good representations of the creep Response across the different load levels in both water and air, they were however unable to give a correct representation of the instantaneous strain of the single lap joints loaded in water. This is attributed to the models being unable to account for the present short-term relaxation process that is dependent on the moisture concentration.
Relation of craze to crack length during slow crack growth phenomena in high‐density polyethylene
(2024)
The craze‐crack mechanism occurring in high‐density polyethylene (HDPE) causing slow crack growth and environmental stress cracking is investigated in detail with respect to the relation of crack length and the related craze zone. This is essential for the understanding of the resulting features of the formed fracture surface and their interpretation in the context of the transition from crack propagation to ductile shear deformation. It turns out that an already formed craze zone does not inevitably result in formation of a propagating crack, but could also undergo ductile failure. For the examination, the full notch creep test (FNCT) was employed with a subsequent advanced fracture surface analysis that was performed using various imaging techniques: light microscopy, laser scanning microscopy, scanning electron microscopy, and X‐ray micro computed tomography scan. FNCT specimens were progressively damaged for increasing durations under standard test conditions applying Arkopal, the standard surfactant solution, and biodiesel as test media were used to analyze the stepwise growth of cracks and crazes. From considerations based on well‐established fracture mechanics approaches, a theoretical correlation between the length of the actual crack and the length of the preceding craze zone was established that could be evidenced and affirmed by FNCT fracture surface analysis. Moreover, the yield strength of a HDPE material exposed to a certain medium as detected by a classic tensile test was found to be the crucial value of true stress to induce the transition from crack propagation due to the craze‐crack mechanism to shear deformation during FNCT measurements.
Highlights
- Progress of crack formation in high‐density polyethylene is analyzed by different imaging techniques
- Determined growth rates depend on distinction between craze zone and crack
- The ratio of the present crack to the anteceding craze zone is validated theoretically
- The transition from crack propagation to ductile shear deformation is identified
- An already formed craze zone may still fail by ductile mechanisms
In the present study, a simple approach was used to investigate the effect of UV-exposure on two high density Polyethylene materials (PE-HD), commonly used for storage tanks, on fuel sorption behavior and colonization by microorganisms. The aim was to investigate whether the sorption behavior of the fuels (diesel/biodiesel) and the colonization by microorganisms, frequently occurring in the fuel, is affected and may lead to undesirable or safety-relevant material changes. We showed that the UV-irradiation leads to significant changes of the sorption behavior due to chemi-crystallization and crosslinking. The fuel Sorption is affected by the UV-induced formation of polar carbonyl and hydroxyl groups predominantly occurring at the surface. With respect to microbial colonization behavior for Bacillus subtilis and Pseudomonas aeruginosa, isolated from a contaminated diesel sample, differences of the initial adhesion could be shown depending on the initial type of polyethylene as well as on the degree of UV-induced degradation.
Technically high-quality hollow articles made of polyethylene have proved many times their value as dangerous goods packagings. Design type tests according to the international regulations for the transport of dangerous goods - drop test, stacking test, hydraulic pressure test and leakproofness test must be performed for every design type and manufacturer. The properties melt flow rate (MFR), relative density (D), low temperature notched Impact strength (N.I.S.) at -30 °C, environmental stress crack resistance (FNCT) and resistance to oxidative degradation Ox by nitric acid (determined by the increase of MFR) have been selected together with the corresponding test methods and tolerances for a comparison of polyethylene grades of one design type in the procedural rule on suitability proof for alternative plastic resins used for dangerous goods packagings and intermediate bulk containers (IBCs) – EN 15507. We wanted to proof the practical relevance of this standard by comparing the relationship between the results of the FNCT and the times to failure of design types in stacking tests with wetting solution and normal butyl acetate saturated wetting solution.
In previous papers, we investigated the influence of biodiesel or diesel on mechanical properties of a high-density polyethylene (PE-HD) for tank applications using Charpy impact tests and dynamicmechanical analysis (DMA). In this work, covering two more PE-HD materials, we extend our study to addressing the tensile properties, especially changes of Young's modulus, after immersion in biodiesel or diesel at 60 °C. As we cover sorption and desorption behavior, during desorption, i.e. storage at 60 °C in a circulating air oven, ageing or degradation phenomena were also observed and characterized in some detail using spectral reflectance measurements and FT-IR spectroscopy. The results obtained here support the concept of co-oxidation, i.e. the faster oxidation of the PE-HD matrix if the samples were previously saturated with biodiesel, itself easily oxidizable.
In a previous paper we investigated the influence of sorbed biodiesel or diesel on mechanical properties of a typical polyethylene grade for tank applications. Besides the basic sorption and desorption behavior of these two fuels, the study addressed the concentration-dependent mechanical properties as revealed by a non-instrumented Charpy impact test and dynamic mechanical analysis (DMA). In the present paper we extend this investigation focusing on the temperature-dependent impact fracture behavior. Therefore, an instrumented Charpy impact test was employed, allowing a more detailed analysis of the fracture behavior. Furthermore, from the load-time-diagrams obtained from the instrumented impact test, corresponding fracture times can be calculated, allowing a clear correlation of the fuel sorption induced changes in fracture toughness with the enhanced ß-relaxation observed by DMA. As in the previous study, the fracture surfaces of the impact tested specimens were analyzed in order to confirm the brittle or ductile character of the fracture indicated by impact strength and the corresponding load-deflection diagrams.
Resistance to stress cracking by wetting solution is one of the selected properties together with the corresponding test method FNCT and tolerances for a comparison of polyethylene grades of one design type in the procedural rule on suitability proof for alternative plastic resins used for packagings and intermediate bulk containers (IBCs) for the transport of dangerous goods.
The environmental stress crack resistance determined by Full Notch Creep Test (FNCT) represents the impacts from the stacking tests at 40 °C performed with standard liquid wetting solution (without pre-storage) and with normal butyl acetate saturated wetting solution (pre-storage with normal butyl acetate).
Environmental stress crack resistance determined with FNCT for the polyethylene grades was related to the times to failure of different jerrican samples made of these grades in stacking tests with 5% wetting solution and a n-butyl acetate saturated wetting solution (pre-storage with n-butyl acetate) at 40 °C. The FNCT is suitable for comparison of polyethylene grades in relation to environmental stress crack resistance independent of their use as drum, IBC or jerrican material. The stiffness of polyethylene grades should be taken into account to the comparison as jerricans are not only chemically but also mechanically stressed.
Effect of different sulphur-based crosslink networks on the nitrile rubber resistance to biodiesel
(2017)
Biodiesel possesses some comparable physical properties to petroleum diesel in addition to its improved environmental benefits. Nonetheless, both fuels differ greatly with respect to their chemical compositions.
Therefore, the compatibility of the materials, which are commonly employed in contact with diesel, must also be assured for biodiesel. This paper assessed the influence of sulphur-based curing systems on the resistance of nitrile rubber to soybean biodiesel. Formulations were prepared using highacrylonitrile-content nitrile rubber by employing a two-level experimental design. The amounts of two different accelerators and sulphur were varied to achieve different types of vulcanisation systems.
Thermal analyses, mechanical tests and microscopy analyses were conducted to evaluate the behaviour of the material after contact with biodiesel. The results showed that the choice of the accelerator played an important role on the resistance of the rubber to the biofuel, and crosslink density was not a key factor with respect to the resistance.
Different imaging techniques were employed to monitor Full Notch Creep Test (FNCT) experiments addressing environmental stress cracking in more detail. The FNCT is a well-established test method to assess slow crack growth and environmental stress cracking of polymer materials, especially polyethylene. The standard test procedure, as specified in ISO 16770, provides a simple comparative measure of the resistance to crack growth of a certain material based on the overall time to failure when loaded with a well-defined mechanical stress and immersed in a liquid medium promoting crack propagation.
Destructive techniques which require a direct view on the free fracture surface, such as light microscopy and laser scanning microscopy, are compared to non-destructive techniques, i.e. scanning acoustic microscopy and xray micro computed tomography. All methods allow the determination of an effective crack length. Based on a series of FNCT specimens progressively damaged for varied Durations under standard test conditions, the estimation of crack propagation rates is also enabled. Despite systematic deviations related to the respective Imaging techniques, this nevertheless provides a valuable tool for the detailed evaluation of the FNCT and its further development.
The damage mechanisms slow crack growth (SCG) and environmental stress cracking (ESC), relevant for PE-HD materials are characterized based on improved full notch creep testing (FNCT) of two selected typical PE-HD materials for container applications. In this context, a distinction of the failure mechanisms as well as a categorization of involved media is suggested. Employing a novel FNCT device, elongation data were obtained in addition to conventional time-to-failure results of stress-dependent as well as temperature-dependent measurements. Changes in failure behavior, as determined by fracture surface analysis based on light microscopy (LM) and laser scanning microscopy (LSM), are correlated with FNCT results and used to introduce an additional possibility for the identification of brittle/ductile fracture behavior.
The full-notch creep test (FNCT) is widely used to characterize the slow crack growth (SCG) behavior of polyolefin materials in “inert” media as well as effects of environmental stress cracking (ESC) in which the medium has decisive influence on damage mechanism and time to failure. The test is of greatest importance for pipe and blow molding types of polyethylene, high density (PE-HD). Usually the full-notch creep test is applied as a standardized testing method (ISO 16770) using a few universal liquid media, such as solutions of Arkopal N 100. In our study, selected relevant polyethylene, high density materials are investigated also in real media – practical formulations as well as representative pure chemicals – and influences of temperature and geometry of specimen and notch are explicitly addressed. Furthermore, the investigations comprise also the environmental stress cracking behavior of polyethylene, high density in media that are sorbed to a significant extent – examples are diesel and biodiesel – based on comparison with samples previously saturated with those media. Thus, also the underlying diffusion controlled sorption process has to be assessed before. The investigations were performed using a full-notch creep testing device with 12 individual sub-stations, each equipped with individual electronic stress and temperature control and continuous online monitoring of the specimen elongation.
Packaging containers for dangerous goods that include aggressive liquids require that any packaging material that is based on high-density polyethylene has a high degree of stability and durability. This work is focused on testing the environmental stress cracking of the high-density polyethylenes used for such containers in contact with crop protection formulations, in particular, two model liquids established in Germany as standardized test media representatives for crop protection formulations containing the various admixtures typical for such products. One of the liquids is water-based and contains mostly surface-active ingredients, while the other is solvent-based and includes some emulsifiers. Originally established for pin impression tests, these model liquids and their individual components were here used for the first time as environmental media in the Full Notch Creep Test, which addresses the resistance against environmental stress cracking. The Full Notch Creep Test was carried out on five high-density polyethylene types with both model liquids, and also on one selected material with its components. The evaluation was focused on the fracture surface structures, which were visualized by a scanning electron microscope and by optical in situ imaging of the notch opening. While the water-based model liquid and its surface-active individual components induced environmental stress cracking with the characteristic pattern for a craze-crack mechanism and so-called brittle fracture on the surface, the solvent-based model liquid and its soluble ingredients exhibited rather ductile failure behavior, caused by the plasticizing effect on the polymer that reduced the yield stress of the high-density polyethylene.
For both cases, fracture surface analysis, together with side views of the crack opening, showed a clear relation between surface pattern, notch deformation (e.g., by blunting), or crack opening due to crack growth with time to failure and the solubility of the liquids in high-density polyethylene.
The crack propagation rate of environmental stress cracking was studied on high-density polyethylene compact tension specimens under static loading. Selected environmental liquids are distilled water, 2 wt% aqueous Arkopal N100 solution, and two model liquid mixtures, one based on solvents and one on detergents, representing stress cracking test liquids for commercial crop protection products. The different surface tensions and solubilities, which affect the energetic facilitation of void nucleation and craze development, are studied. Crack growth in surface-active media is strongly accelerated as the solvents induce plasticization, followed by strong blunting significantly retarding both crack initiation and crack propagation. The crack propagation rate for static load as a function of the stress intensity factor within all environments is found to follow the Paris–Erdogan law. Scanning electron micrographs of the fracture surface highlight more pronounced structures with both extensive degrees of plasticization and reduced crack propagation rate, addressing the distinct creep behavior of fibrils. Additionally, the limitations of linear elastic fracture mechanisms for visco-elastic polymers exposed to environmental liquids are discussed.
The dataset provided in this repository comprises data obtained from a series of full-notch creep tests (FNCT) performed on selected high-density polyethylene (PE-HD) materials (for further details, see section 1 Materials in this document) in accordance with the corresponding standard ISO 16770.
The FNCT is one of the mechanical testing procedures used to characterize polymer materials with respect to their environmental stress cracking (ESC) behavior. It is widely applied for PE-HD materials, that are predominantly used for pipe and container applications. It is based on the determination of the time to failure for a test specimen under constant mechanical load in a well-defined and temperature controlled liquid environment. The test device used here also allows for continuous monitoring of applied force, specimen elongation and temperature.
Four typical high-density polyethylene container materials were used to investigate damage or stress cracking behavior in contact with model liquids for crop protection products. These model liquids are established in German regulations for the approval of dangerous goods containers and consist of typical admixtures used for crop protection products but without biological active ingredients. This study is performed with the standardized method of Full Notch Creep Test, adapting the media temperature to 40 °C according to the usual conditions where these test liquids are applied. The two model liquids differ into a water-based solution and a composition based on different organic solvents which are absorbed by the material up to significant levels. Therefore, extensive sorption measurements are performed. The fracture surfaces obtained are analyzed in detail not only by light microscopy, but also by laser scanning microscopy as well as scanning electron microscopy. Influence of pre-saturation and applied stress are addressed by respective systematic series of experiments.
The impact fracture behavior of two common high-density polyethylene grades for container applications were intensively studied by the instrumented Charpy impact test after well-defined exposure to UV-irradiation. Individual stages of the impact event, such as crack initiation and crack propagation energy as well as maximum impact load, were investigated from the recorded load–deflection curves. UV-induced material property changes were further investigated by infrared spectroscopy, differential scanning calorimetry, and dynamic-mechanical analysis as well as density measurements. Based on the results of the Charpy impact test, three indicators were identified to describe the extend of photooxidation on high-density polyethylene: (a) a reduced Charpy impact strength—at least to half of its initial value for a distinctly brittle impact fracture, (b) a marked decrease in the crack propagation contribution to the impact strength, and (c) an increase of the brittle features of the fracture surface.
The phenomenon of environmental stress cracking is still a major issue in materials engineering as well as from a scientific perspective. Especially in the case of packaging materials made of high-density polyethylene, assessing the potential of premature damage due to environmental stress cracking is complex because of the large number of components in possible liquid filling goods. As a first guideline, the well-known effect of detergents and dispersants is usually considered, but the interplay with other components, such as organic solvents is often unknown. Particularly challenging in this respect are crop protection products, consisting of several different admixtures in addition to the biologically active ingredients. This study is based on two model liquids representing these admixtures that were established for testing in this context. The model liquids as well as their constituting components were used as liquid media in the Full Notch Creep Test to characterize the environmental stress cracking behavior of a typical high-density polyethylene. Complementary to the time-to failure of a notched specimen obtained from these tests, the crack opening was monitored optically, and the fracture surface was analyzed post-failure by laser scanning microscopy as well as scanning electron microscopy. Based on the results, the effect of various surfactants as well as the influence of organic solvents on environmental stress cracking are discussed.
The fracture surface of slow and continuous crack propagation during environmental stress cracking of a semicrystalline polyethylene exhibits isotropic roughness exponents at the local scale but resolved across the macroscopic fracture surface a clear position dependence is found. The spatially resolved roughness exponent admits values in the range between 0.1 and 0.4, demonstrating nontrivial exponents in the small length-scale regime. Instead, they vary across the fracture surface according to the stress-state distribution, which suggests that the exponents are intimately linked to the locally dominating dissipation processes during craze cracking.
A phenomenological criterion for an optical assessment of PE-HD fracture surfaces obtained from FNCT
(2021)
The full-notch creep test (FNCT) is a common test method to evaluate the environmental stress cracking (ESC) behavior of high-density polyethylene (PE-HD), e.g. for container materials. The test procedure as specified in ISO 16770 provides a comparative measure of the resistance against ESC using the time to failure of PE-HD specimens under constant mechanical load in a well-defined liquid test environment. Since the craze-crack damage mechanism underlying the ESC phenomenon is associated with brittle failure, the occurrence of a predominantly brittle fracture surface is a prerequisite to consider an FNCT measurement as representative for ESC, i.e. a time to failure dominated by craze-crack propagation.
The craze-crack propagation continuously reduces the effective residual cross-sectional area of the specimen during the test, which results in a corresponding increase of the effective mechanical stress. Thus, a transition to ductile shear deformation is inevitable at later stages of the test, leading usually to a pronounced central ligament.
Therefore, an optical evaluation of FNCT fracture surfaces concerning their brittleness is essential. An enhanced imaging analysis of FNCT fracture surfaces enables a detailed assessment of craze-crack Propagation during ESC. In this study, laser scanning microscopy (LSM) was employed to evaluate whether FNCT fracture surfaces are representative with respect to craze-crack propagation and ESC. Based on LSM height data, a phenomenological criterion is proposed to assess the validity of distinct FNCT measurements. This criterion is
supposed to facilitate a quick evaluation of FNCT results in practical routine testing. Its applicability is verified on a sample basis for seven different commercial PE-HD container materials.
High-density polyethylene becomes optically transparent during tensile drawing when previously saturated with diesel fuel. This unusual phenomenon is investigated as it might allow conclusions with respect to the material behavior. Microscopy, differential scanning calorimetry, density measurements are applied together with two scanning X-ray scattering techniques: wide angle X-ray scattering (WAXS) and X-ray refraction, able to extract the spatially resolved crystal orientation and internal surface, respectively. The sorbed diesel softens the material and significantly alters the yielding characteristics. Although the crystallinity among stretched regions is similar, a virgin reference sample exhibits strain whitening during stretching, while the diesel-saturated sample becomes transparent. The WAXS results reveal a pronounced fiber texture in the tensile direction in the stretched region and an isotropic orientation in the unstretched region. This texture implies the formation of fibrils in the stretched region, while spherulites remain intact in the unstretched parts of the specimens. X-ray refraction reveals a preferred orientation of internal surfaces along the tensile direction in the stretched region of virgin samples, while the sample stretched in the diesel-saturated state shows no internal surfaces at all. Besides from stretching saturated samples, optical transparency is also obtained from sorbing samples in diesel after stretching.
The physical and chemical effects of diesel and biodiesel fuels on two high-density polyethylene (PE-HD) types were investigated. Both semi-crystalline PE-HD are common thermoplastic materials for container and storage tank applications. Biodiesel, a composition of unsaturated fatty acid esters from renewable resources, was chosen as it is regarded a possible green alternative to fossil fuels. The study aims at identifying significant differences between biodiesel and conventional diesel fuels based on the differences in the chemical nature of the two. The physical effects of the fuels on the polymer at first comprises the sorption behavior, i.e. kinetics and final equilibrium concentration. Not only are both fuels absorbed by the amorphous phase of the semi-crystalline PE-HD, they also induce a plasticization effect that modifies the molecular mobility and therefore also the characteristic yielding properties, manifest in the obtained stress-strain curves. The chemical effects related to degradation phenomena is investigated by a long-term storage scenario using partially immersed tensile test specimens in diesel and biodiesel. We were able to confirm the proposed co-oxidation mechanism by Richaud et al. for polyethylene-unsaturated penetrant systems on a larger scale based on practical tensile tests. One of the investigated polyethylene grades subjected to tensile drawing showed a significant loss of plastic deformation and the onset of premature failure after 150 days of storage in biodiesel. Further biodiesel storage showed a systematically reduced elongation at break before necking. None of these effects were observed in diesel. Oxidation of fuels and polymer after progressing storage times were analyzed by the evolution of carbonyl species in FT-IR/ATR spectroscopy.