Curing, defects and mechanical performance of fiber-reinforced composites

Tradicionalmente, la fabricación de materiales compuestos de altas prestaciones se lleva a cabo en autoclave mediante la consolidación de preimpregnados a través de la aplicación simultánea de altas presiones y temperatura. Las elevadas presiones empleadas en autoclave reducen la porosidad de los componentes garantizando unas buenas propiedades mecánicas. Sin embargo, este sistema de fabricación conlleva tiempos de producción largos y grandes inversiones en equipamiento lo que restringe su aplicación a otros sectores alejados del sector aeronáutico. Este hecho ha generado una creciente demanda de sistemas de fabricación alternativos al autoclave. Aunque estos sistemas son capaces de reducir los tiempos de producción y el gasto energético, por lo general, dan lugar a materiales con menores prestaciones mecánicas debido a que se reduce la compactación del material al aplicar presiones mas bajas y, por tanto, la fracción volumétrica de fibras, y disminuye el control de la porosidad durante el proceso. Los modelos numéricos existentes permiten conocer los fundamentos de los mecanismos de crecimiento de poros durante la fabricación de materiales compuestos de matriz polimérica mediante autoclave. Dichos modelos analizan el comportamiento de pequeños poros esféricos embebidos en una resina viscosa. Su validez no ha sido probada, sin embargo, para la morfología típica observada en materiales compuestos fabricados fuera de autoclave, consistente en poros cilíndricos y alargados embebidos en resina y rodeados de fibras continuas. Por otro lado, aunque existe una clara evidencia experimental del efecto pernicioso de la porosidad en las prestaciones mecánicas de los materiales compuestos, no existe información detallada sobre la influencia de las condiciones de procesado en la forma, fracción volumétrica y distribución espacial de los poros en los materiales compuestos. Las técnicas de análisis convencionales para la caracterización microestructural de los materiales compuestos proporcionan información en dos dimensiones (2D) (microscopía óptica y electrónica, radiografía de rayos X, ultrasonidos, emisión acústica) y sólo algunas son adecuadas para el análisis de la porosidad. En esta tesis, se ha analizado el efecto de ciclo de curado en el desarrollo de los poros durante la consolidación de preimpregnados Hexply AS4/8552 a bajas presiones mediante moldeo por compresión, en paneles unidireccionales y multiaxiales utilizando tres ciclos de curado diferentes. Dichos ciclos fueron cuidadosamente diseñados de acuerdo a la caracterización térmica y reológica de los preimpregnados. La fracción volumétrica de poros, su forma y distribución espacial se analizaron en detalle mediante tomografía de rayos X. Esta técnica no destructiva ha demostrado su capacidad para analizar la microestructura de materiales compuestos. Se observó, que la porosidad depende en gran medida de la evolución de la viscosidad dinámica a lo largo del ciclo y que la mayoría de la porosidad inicial procedía del aire atrapado durante el apilamiento de las láminas de preimpregnado. En el caso de los laminados multiaxiales, la porosidad también se vio afectada por la secuencia de apilamiento. En general, los poros tenían forma cilíndrica y se estaban orientados en la dirección de las fibras. Además, la proyección de la población de poros a lo largo de la dirección de la fibra reveló la existencia de una estructura celular de un diámetro aproximado de 1 mm. Las paredes de las celdas correspondían con regiones con mayor densidad de fibra mientras que los poros se concentraban en el interior de las celdas. Esta distribución de la porosidad es el resultado de una consolidación no homogenea. Toda esta información es crítica a la hora de optimizar las condiciones de procesado y proporcionar datos de partida para desarrollar herramientas de simulación de los procesos de fabricación de materiales compuestos fuera de autoclave. Adicionalmente, se determinaron ciertas propiedades mecánicas dependientes de la matriz termoestable con objeto de establecer la relación entre condiciones de procesado y las prestaciones mecánicas. En el caso de los laminados unidireccionales, la resistencia interlaminar depende de la porosidad para fracciones volumétricas de poros superiores 1%. Las mismas tendencias se observaron en el caso de GIIc mientras GIc no se vio afectada por la porosidad. En el caso de los laminados multiaxiales se evaluó la influencia de la porosidad en la resistencia a compresión, la resistencia a impacto a baja velocidad y la resistencia a copresión después de impacto. La resistencia a compresión se redujo con el contenido en poros, pero éste no influyó significativamente en la resistencia a compresión despues de impacto ya que quedó enmascarada por otros factores como la secuencia de apilamiento o la magnitud del daño generado tras el impacto. Finalmente, el efecto de las condiciones de fabricación en el proceso de compactación mediante moldeo por compresión en laminados unidireccionales fue simulado mediante el método de los elementos finitos en una primera aproximación para simular la fabricación de materiales compuestos fuera de autoclave. Los parámetros del modelo se obtuvieron mediante experimentos térmicos y reológicos del preimpregnado Hexply AS4/8552. Los resultados obtenidos en la predicción de la reducción de espesor durante el proceso de consolidación concordaron razonablemente con los resultados experimentales. Manufacturing of high performance polymer-matrix composites is normally carried out by means of autoclave using prepreg tapes stacked and consolidated under the simultaneous application of pressure and temperature. High autoclave pressures reduce the porosity in the laminate and ensure excellent mechanical properties. However, this manufacturing route is expensive in terms of capital investment and processing time, hindering its application in many industrial sectors. This fact has driven the demand of alternative out-of-autoclave processing routes. These techniques claim to produce composite parts faster and at lower cost but the mechanical performance is also reduced due to the lower fiber content and to the higher porosity. Corrient numerical models are able to simulate the mechanisms of void growth in polymer-matrix composites processed in autoclave. However these models are restricted to small spherical voids surrounded by a viscous resin. Their validity is not proved for long cylindrical voids in a viscous matrix surrounded by aligned fibers, the standard morphology observed in out-of-autoclave composites. In addition, there is an experimental evidence of the detrimental effect of voids on the mechanical performance of composites but, there is detailed information regarding the influence of curing conditions on the actual volume fraction, shape and spatial distribution of voids within the laminate. The standard techniques of microstructural characterization of composites (optical or electron microscopy, X-ray radiography, ultrasonics) provide information in two dimensions and are not always suitable to determine the porosity or void population. Moreover, they can not provide 3D information. The effect of curing cycle on the development of voids during consolidation of AS4/8552 prepregs at low pressure by compression molding was studied in unidirectional and multiaxial panels. They were manufactured using three different curing cycles carefully designed following the rheological and thermal analysis of the raw prepregs. The void volume fraction, shape and spatial distribution were analyzed in detail by means of X-ray computed microtomography, which has demonstrated its potential for analyzing the microstructural features of composites. It was demonstrated that the final void volume fraction depended on the evolution of the dynamic viscosity throughout the cycle. Most of the initial voids were the result of air entrapment and wrinkles created during lay-up. Differences in the final void volume fraction depended on the processing conditions for unidirectional and multiaxial panels. Voids were rod-like shaped and were oriented parallel to the fibers and concentrated in channels along the fiber orientation. X-ray computer tomography analysis of voids along the fiber direction showed a cellular structure with an approximate cell diameter of 1 mm. The cell walls were fiber-rich regions and porosity was localized at the center of the cells. This porosity distribution within the laminate was the result of inhomogeneous consolidation. This information is critical to optimize processing parameters and to provide inputs for virtual testing and virtual processing tools. In addition, the matrix-controlled mechanical properties of the panels were measured in order to establish the relationship between processing conditions and mechanical performance. The interlaminar shear strength (ILSS) and the interlaminar toughness (GIc and GIIc) were selected to evaluate the effect of porosity on the mechanical performance of unidirectional panels. The ILSS was strongly affected by the porosity when the void contents was higher than 1%. The same trends were observed in the case of GIIc while GIc was insensitive to the void volume fraction. Additionally, the mechanical performance of multiaxial panels in compression, low velocity impact and compression after impact (CAI) was measured to address the effect of processing conditions. The compressive strength decreased with porosity and ply-clustering. However, the porosity did not influence the impact resistance and the coompression after impact strength because the effect of porosity was masked by other factors as the damage due to impact or the laminate lay-up. Finally, the effect of the processing conditions on the compaction behavior of unidirectional AS4/8552 panels manufactured by compression moulding was simulated using the finite element method, as a first approximation to more complex and accurate models for out-of autoclave curing and consolidation of composite laminates. The model parameters were obtained from rheological and thermo-mechanical experiments carried out in raw prepreg samples. The predictions of the thickness change during consolidation were in reasonable agreement with the experimental results.

MINLP Model for the Synthesis of Heat Exchanger Networks with Handling Pressure of Process Streams

This paper introduces a new mathematical model for the simultaneous synthesis of heat exchanger networks (HENs), wherein the handling pressure of process streams is used to enhance the heat integration. The proposed approach combines generalized disjunctive programming (GDP) and mixed-integer nonlinear programming (MINLP) formulation, in order to minimize the total annualized cost composed by operational and capital expenses. A multi-stage superstructure is developed for the HEN synthesis, assuming constant heat capacity flow rates and isothermal mixing, and allowing for streams splits. In this model, the pressure and temperature of streams must be treated as optimization variables, increasing further the complexity and difficulty to solve the problem. In addition, the model allows for coupling of compressors and turbines to save energy. A case study is performed to verify the accuracy of the proposed model. In this example, the optimal integration between the heat and work decreases the need for thermal utilities in the HEN design. As a result, the total annualized cost is also reduced due to the decrease in the operational expenses related to the heating and cooling of the streams.

Retrofit of heat exchanger networks with pressure recovery of process streams at sub-ambient conditions

This paper presents a new mathematical programming model for the retrofit of heat exchanger networks (HENs), wherein the pressure recovery of process streams is conducted to enhance heat integration. Particularly applied to cryogenic processes, HENs retrofit with combined heat and work integration is mainly aimed at reducing the use of expensive cold services. The proposed multi-stage superstructure allows the increment of the existing heat transfer area, as well as the use of new equipment for both heat exchange and pressure manipulation. The pressure recovery of streams is carried out simultaneously with the HEN design, such that the process conditions (streams pressure and temperature) are variables of optimization. The mathematical model is formulated using generalized disjunctive programming (GDP) and is optimized via mixed-integer nonlinear programming (MINLP), through the minimization of the retrofit total annualized cost, considering the turbine and compressor coupling with a helper motor. Three case studies are performed to assess the accuracy of the developed approach, including a real industrial example related to liquefied natural gas (LNG) production. The results show that the pressure recovery of streams is efficient for energy savings and, consequently, for decreasing the HEN retrofit total cost especially in sub-ambient processes.

Exploring Multi-Component Superconducting Compounds by a High-Pressure Method and Ceramic Combinatorial Chemistry

In this short review, we provide some new insights into the material synthesis and characterization of modern multi-component superconducting oxides. Two different approaches such as the high-pressure, high-temperature method and ceramic combinatorial chemistry will be reported with application to several typical examples. First, we highlight the key role of the extreme conditions in the growth of Fe-based superconductors, where a careful control of the composition-structure relation is vital for understanding the microscopic physics. The availability of high-quality LnFeAsO (Ln = lanthanide) single crystals with substitution of O by F, Sm by Th, Fe by Co, and As by P allowed us to measure intrinsic and anisotropic superconducting properties such as Hc2, Jc. Furthermore, we demonstrate that combinatorial ceramic chemistry is an efficient way to search for new superconducting compounds. A single-sample synthesis concept based on multi-element ceramic mixtures can produce a variety of local products. Such a system needs local probe analyses and separation techniques to identify compounds of interest. We present the results obtained from random mixtures of Ca, Sr, Ba, La, Zr, Pb, Tl, Y, Bi, and Cu oxides reacted at different conditions. By adding Zr but removing Tl, Y, and Bi, the bulk state superconductivity got enhanced up to about 122 K.

Sediment temperatures of the Håkon Mosby mud volcano measured continuously with a short temperature lance (LOOME)

The short sediment temperature probe were deployed and recovered with the LOOME observatory in 2009 and 2010, respectively. In addition to temperature, the loggers also recorded bottom water pressure at a sampling interval of 20 minutes. Even though the data obtained from the short temperature probe was strongly disturbed by leakage through a corroded connector, the data shows clearly that the probe was pulled out of the sediment on October 26, 2009, presumably by advancing mud flows.

OH concentration and temperature measurements by use of near-resonant holographic interferometry

Near-resonant holographic interferometry is demonstrated to measure temperature and species concentration in a two-dimensional steady premixed air-acetylene flame. A peak temperature of (2600 +/- 100) K and a peak OH number density of (9.6 +/- 0.3) X 10(22) m(-3) are obtained, consistent with the expected values for such a flame. These values are determined by recording interferograms with a laser assumed sufficiently detuned from line center so that pressure and temperature broadening can be ignored. The results are thus obtained without making prior assumptions on the temperature or pressure of the flame beyond the existence of thermal equilibrium. (C) 2004 Optical Society of America.

Analysis of the intraocular pressure pulse

This thesis was concerned with investigating methods of improving the IOP pulse’s potential as a measure of clinical utility. There were three principal sections to the work. 1. Optimisation of measurement and analysis of the IOP pulse. A literature review, covering the years 1960 – 2002 and other relevant scientific publications, provided a knowledge base on the IOP pulse. Initial studies investigated suitable instrumentation and measurement techniques. Fourier transformation was identified as a promising method of analysing the IOP pulse and this technique was developed. 2. Investigation of ocular and systemic variables that affect IOP pulse measurements In order to recognise clinically important changes in IOP pulse measurement, studies were performed to identify influencing factors. Fourier analysis was tested against traditional parameters in order to assess its ability to detect differences in IOP pulse. In addition, it had been speculated that the waveform components of the IOP pulse contained vascular characteristic analogous to those components found in arterial pulse waves. Validation studies to test this hypothesis were attempted. 3. The nature of the intraocular pressure pulse in health and disease and its relation to systemic cardiovascular variables. Fourier analysis and traditional parameters were applied to the IOP pulse measurements taken on diseased and healthy eyes. Only the derived parameter, pulsatile ocular blood flow (POBF) detected differences in diseased groups. The use of an ocular pressure-volume relationship may have improved the POBF measure’s variance in comparison to the measurement of the pulse’s amplitude or Fourier components. Finally, the importance of the driving force of pulsatile blood flow, the arterial pressure pulse, is highlighted. A method of combining the measurements of pulsatile blood flow and pulsatile blood pressure to create a measure of ocular vascular impedance is described along with its advantages for future studies.

Thermodynamic description and phase transformation of highly symmetrical monoatomic structures

Based on theoretical considerations an explanation for the temperature dependence of the thermal expansion and the bulk modulus is proposed. A new equation state is also derived. Additionally a physical explanation for the latent heat of fusion is presented. These theoretical predictions are tested against experiments on highly symmetrical monatomic structures. ^ The volume is not an independent variable and must be broken down into its fundamental components when the relationships to the pressure and temperature are defined. Using zero pressure and temperature reference frame, the initial parameters, volume at zero pressure and temperature[V°], bulk modulus at zero temperature [K°] and volume coefficient of thermal expansion at zero pressure[α°] are defined. ^ The new derived EoS is tested against the experiments on perovskite and epsilon iron. The Root-mean-square-deviations (RMSD) of the residuals of the molar volume, pressure, and temperature are in the range of the uncertainty of the experiments. ^ Separating the experiments into 200 K ranges, the new EoS was compared to the most widely used finite strain, interatomic potential, and empirical isothermal EoSs such as the Burch-Murnaghan, the Vinet, and the Roy-Roy respectively. Correlation coefficients, RMSD's of the residuals, and Akaike Information Criteria were used for evaluating the fitting. Based on these fitting parameters, the new p-V-T EoS is superior in every temperature range relative to the investigated conventional isothermal EoS. ^ The new EoS for epsilon iron reproduces the preliminary-reference earth-model (PREM) densities at 6100-7400 K indicating that the presence of light elements might not be necessary to explain the Earth's inner core densities. ^ It is suggested that the latent heat of fusion supplies the energy required for overcoming on the viscous drag resistance of the atoms. The calculated energies for melts formed from highly symmetrical packing arrangements correlate very well with experimentally determined latent heat values. ^ The optical investigation of carhonado-diamond is also part of the dissertation. The collected first complete infrared FTIR absorption spectra for carhonado-diamond confirm the interstellar origin for the most enigmatic diamonds known as carbonado. ^

Petrology and geochemistry of some high pressure rocks from northern part of Rio San Juan complex, Dominican Republic

The Rio San Juan Complex is an important occurrence of high pressure/low temperature rocks in the circum-Caribbean region which contains both coherent blueschist units and two varieties of melange in the same area. The melanges contain a diverse assemblage of blocks of various sizes, different degrees of metamorphism, and mineral assemblages. Some high pressure blocks show two stages of metamorphism. The earliest stage is characterized by high pressure-low temperature conditions and the second stage is characterized by high pressure-lower temperature conditions. The geochemistry of thirteen samples from the Rio San Juan Complex has been studied and data have been compared with rocks of adjacent regions. Geochemical evidence indicates that rocks from the Rio San Juan Complex have predominant calc-alkaline affinities with subordinate tholeiitic affinities. This suggests that they have a multiple tectonic provenance.

Data compilation on the biological response to ocean acidification: environmental and experimental context of data sets and related literature

The exponential growth of studies on the biological response to ocean acidification over the last few decades has generated a large amount of data. To facilitate data comparison, a data compilation hosted at the data publisher PANGAEA was initiated in 2008 and is updated on a regular basis (doi:10.1594/PANGAEA.149999). By January 2015, a total of 581 data sets (over 4 000 000 data points) from 539 papers had been archived. Here we present the developments of this data compilation five years since its first description by Nisumaa et al. (2010). Most of study sites from which data archived are still in the Northern Hemisphere and the number of archived data from studies from the Southern Hemisphere and polar oceans are still relatively low. Data from 60 studies that investigated the response of a mix of organisms or natural communities were all added after 2010, indicating a welcomed shift from the study of individual organisms to communities and ecosystems. The initial imbalance of considerably more data archived on calcification and primary production than on other processes has improved. There is also a clear tendency towards more data archived from multifactorial studies after 2010. For easier and more effective access to ocean acidification data, the ocean acidification community is strongly encouraged to contribute to the data archiving effort, and help develop standard vocabularies describing the variables and define best practices for archiving ocean acidification data.

Time series of air chemistry measurements at Georg-von-Neumayer station, Dronning Maud Land, Antarctica in the years 1982 to 1991

The first Air Chemistry Observatory at the German Antarctic station Georg von Neumayer (GvN) was operated for 10 years from 1982 to 1991. The focus of the established observational programme was on characterizing the physical properties and chemical composition of the aerosol, as well as on monitoring the changing trace gas composition of the background atmosphere, especially concerning greenhouse gases. The observatory was designed by the Institut für Umweltphysik, University of Heidelberg (UHEIIUP). The experiments were installed inside the bivouac lodge, mounted on a sledge and put upon a snow hill to prevent snow accumulation during blizzards. All experiments were under daily control and daily performance protocols were documented. A ventilated stainless steel inlet stack (total height about 3-4 m above the snow surface) with a 50% aerodynamic cut-off diameter around 7-10 µm at wind velocities between 4-10 m/s supplied all experiments with ambient air. Contamination free sampling was realized by several means: (i) The Air Chemistry Observatory was situated in a clean air area about 1500 m south of GvN. Due to the fact that northern wind directions are very rare, contamination from the base can be excluded for most of the time. (ii) The power supply (20 kW) is provided by a cable from the main station, thus no fuel-driven generator is operated in the very vicinity. (iii) Contamination-free sampling is controlled by the permanently recorded wind velocity, wind direction and by condensation particle concentration. Contamination was indicated if one of the following criteria were given: Wind direction within a 330°-30° sector, wind velocity <2.2 m/s or >17.5 m/s, or condensation particle concentrations >2500/cm**3 during summer, >800/cm**3 during spring/autumn and >400/cm**3 during winter. If one or a definable combination of these criteria were given, high volume aerosol sampling and part of the trace gas sampling were interrupted. Starting at 1982 through 1991-01-14 surface ozone was measured with an electrochemical concentration cell (ECC). Surface ozone mixing ratio are given in ppbv = parts per 10**9 by volume. The averaging time corresponds to the given time intervals in the data sheet. The accuracy of the values are better than ±1 ppbv and the detection limit is around 1.0 ppbv. Aerosols were sampled on two Whatman 541 cellulose filters in series and analyzed by ion chromatography at the UHEI-IUP. Generally, the sampling period was seven days but could be up to two weeks on occasion. The air flow was around 100 m**3/h and typically 10000-20000 m**3 of ambient air was forced through the filters for one sample. Concentration values are given in nanogram (ng) per 1 m**3 air at standard pressure and temperature (1013 mbar, 273.16 K). Uncertainties of the values were approximately ±10% to ±15% for the main components MSA, chloride, nitrate, sulfate and sodium, and between ±20% and ±30% for the minor species bromide, ammonium, potassium, magnesium and calcium.

High-pressure experiments on a natural olivine gabbro from ODP Hole 176-735B

We have conducted high-pressure experiments on a natural oceanic gabbro composition (Gb108). Our aim was to test recent proposals that Sr-enrichment in rare primitive melt inclusions from Mauna Loa, Hawaii, may have resulted from melting of garnet pyroxenite formed in the magma source regions by reaction of peridotite with siliceous, Sr-enriched partial melts of eclogite of gabbroic composition. Gb108 is a natural, Sr-enriched olivine gabbro, which has a strong positive Sr anomaly superimposed on an overall depleted incompatible trace element pattern, reflecting its origin as a plagioclase-rich cumulate. At high pressures it crystallises as a coesite eclogite assemblage, with the solidus between 1,300 and 1,350°C at 3.5 GPa and 1,450 and 1,500°C at 4.5 GPa. Clinopyroxenes contain 4-9% Ca-eskolaite component, which varies systematically with pressure and temperature. Garnets are almandine and grossular-rich. Low degree partial melts are highly siliceous in composition, resembling dacites. Coesite is eliminated between 50 and 100°C above the solidus. The whole-rock Sr-enrichment is primarily hosted by clinopyroxene. This phase dominates the mode (>75 wt%) at all investigated PT conditions, and is the major contributor to partial melts of this eclogite composition. Hence the partial melts have trace element patterns sub-parallel to those of clinopyroxene with ~10* greater overall abundances and with strong positive Sr anomalies. Recent studies of primitive Hawaiian volcanics have suggested the incorporation into their source regions of eclogite, formerly gabbroic material recycled through the mantle at subduction zones. The models suggest that formerly gabbroic material, present as eclogite in the Hawaiian plume, partially melted earlier than surrounding peridotite (i.e. at higher pressure) because of the lower solidus temperature of eclogite compared with peridotite. This produced highly siliceous melts which reacted with surrounding peridotite producing hybrid pyroxene + garnet lithologies. The Sr-enriched nature of the formerly plagioclase-rich gabbro was present in the siliceous partial melts, as demonstrated by these experiments, and was transferred to the reactive pyroxenite. These in turn partially melted, producing Sr-enriched picritic liquids which mixed with normal picritic partial melts of peridotite before eruption. On rare occasions these mixed, relatively Sr-rich melts were trapped as melt inclusions in primitive olivine phenocrysts.Yaxley-Sobolev