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The selection of mortar for conservation of historic and heritage buildings can be challenging. Achieving compatibility with the historic fabric, durability and efficient use of materials within a practical timeframe often requires the use of hydraulic lime-based mortars which set more rapidly than the more traditional air lime mortars. These are considered to be more compatible with historic fabric than cement-based mortars, although, due to the modern production techniques and their natural variability, a deeper knowledge of their chemical and physical properties is needed to minimise damage due to incompatibility and make the decision process easier and safer. Natural hydraulic lime (NHL) binders are currently classified under EN 459-1:2015 in three designations, NHL 2, NHL 3.5 and NHL5, with the suffix representing the minimum compressive strength (in MPa) of a standard mortar mix at 28 days. The performance of NHL binders, manufactured by burning a naturally impure limestone, can be difficult to predict due to the inherent variability of both their physical and chemical characteristics. At the same time, the tolerance values for each classification allow for binders with significantly compressive strength differences to be classified by the same designation. The main aim of this research was to study a range of NHL binders, understand and quantify the variability of their characteristics and to establish how these properties influence the performance of mortars cured under standard and simulated weather conditions. In the first stage of the project, a selection of NHL binders from different origins and distinct designation were rigorously examined through physical, chemical and mineralogical characterisation to elucidate surface area, particle size distribution, oxide composition and crystalline phase composition. The characteristics of the binders were found to vary greatly, particularly amongst binders from the same classification and distinct origins, and in one particular case even from the same origin. A change of properties over time was also identified, binders manufactured in different years could have very different properties, even though, as far as could be ascertained from the packaging, it was the same product. Starting from a selection of 11 NHLs and 1 hydrated lime, the next step involved the manufacture of mortar samples using a sand aggregate appropriate for a conservation mortar with 1:2 ratio (binder:aggregate by volume). Sufficient water was added to produce a spread by flow table of 165 ± 10 mm. These mortars were cured under standard conditions and for a smaller group of binders under simulated weather conditions. For the standard cure conditions, the properties of the binders were compared to the physical properties in terms of strength (from 7 to 1080 days), porosity, capillary water absorption, water vapour permeability and freeze-thaw resistance of mortars made with the binders. The carbonation was also studied by phenolphthalein stain after all the flexural strength tests and after 2 years by XRD. The mortars under climate simulation were studied in terms of mechanical properties (up to 360 days) and carbonation. For comparison purposes, cement-lime (1:1:6 and 1:2:9 cement:lime:aggregate volumetric ratio), lime-metakaolin (MK) (with MK addition of 5, 10 and 20% of the lime mass) and lime putty mortars were manufactured to the same workability as the NHL mortars. These were studied in terms of strength up to 360 days, porosity and water absorption by capillarity action. The strength of the studied mortars does not follow the classification of the binders, with one binder, specified as NHL 2, resulting in a stronger mortar than another binder specified as NHL 5, and one NHL 3.5 mortar surpassing all the other mortars in terms of mechanical strength. The mechanical strength was found to correlate with the hydraulic phases, alite and belite, identified within the binders. The relative long-term performance of the mortars manufactured with the different binders can therefore be predicted based on the mineral properties rather than the standard classification. Pore related properties, such as water vapour permeability and water absorption by capillarity, were found to be related to the water/binder ratio of the NHL mortars. Later in the project, using the standard cured mortars data, a model was developed to predict compressive strength based on the proportion of crystalline phases present in the mortars, the surface area and the water/binder ratio. This model, applied to the studied mortars, was found to predict, with low error, the measured performance of the mortars, meaning that the model can be used as tool to predict mortar strength. The outcomes of this thesis demonstrated that with sufficient knowledge of the underlying chemistry of NHL binders, it is possible to establish the relative performance of mortars, thus making the decision on which binder to use easier and safer for the historic fabric.

NR 20140805

<p>Diffusion of liquids into and through polymers is an important factor that negatively may influence the durability or lifetime of a polymer structure used in industrial applications. In this work two types of polymers, a liquid crystalline polymer (LCP, Vectra A950) and various thermoset resins as used in fibre reinforced plastics (FRP) process equipment were studied with regard to barrier properties, chemical resistance and long-term performance. LCP are known for their outstanding chemical resistance and barrier properties. FRP used in process equipment may be a cost-efficient solution in chemically aggressive environments where standard carbon or stainless steel cannot be used due to its limited corrosion resistance. Transport properties of typical industrial environments were determined for the LCP and the influence of annealing and orientation was investigated to study whether the barrier properties can be improved. The possibility to use LCP as cost-effective lining for FRP was explored. Special focus was put on the diffusion of water and its effect on long-term transport properties and stability of thermoset resins as the performance of FRP is strongly related to the diffusion of water. </p><p>The results showed that Vectra A950 was suitable for organic solvent and non-oxidising acid environments. Its transport properties were gravimetrically determined and found to be 10 to 102 times lower than that of a high barrier fluoropolymer of type FEP. The degree of molecular packing increased with annealing time both below and above the melting point. Below the melting point this was – at least – partly due to crystal formation whereas above the melting point other mechanisms were involved. The effects of annealing and orientation on the transport properties in LCP were, however, very small or not significant and probably significantly longer annealing times are required. LCP has potential to be used as lining material for FRP as the use of an LCP-lining substantially reduced the permeability of and the solute sorption in a bisphenol A epoxy-based vinyl ester resin. The bonding strength was improved significantly by a combined abrasive and oxygen plasma treatment.</p><p>The long-term sorption of water in thermoset resins including bisphenol A epoxy-based vinyl ester, novolac-based vinyl ester, urethane modified vinyl ester and bisphenol A polyester resins was found to increase with exposure time whereas the diffusion coefficient was not significantly affected. It was shown that the presence of water induced relaxation processes that were considered to be the primarily reason for the increase in sorption coefficient in comparison to degradation processes, such as hydrolysis, causing osmotic processes. A general relationship for the estimation of the sorption coefficient at 80ºC in dependence of the water activity and the sorption coefficient at unit activity independent of the resin type was established.</p>

Diffusion of liquids into and through polymers is an important factor that negatively may influence the durability or lifetime of a polymer structure used in industrial applications. In this work two types of polymers, a liquid crystalline polymer (LCP, Vectra A950) and various thermoset resins as used in fibre reinforced plastics (FRP) process equipment were studied with regard to barrier properties, chemical resistance and long-term performance. LCP are known for their outstanding chemical resistance and barrier properties. FRP used in process equipment may be a cost-efficient solution in chemically aggressive environments where standard carbon or stainless steel cannot be used due to its limited corrosion resistance. Transport properties of typical industrial environments were determined for the LCP and the influence of annealing and orientation was investigated to study whether the barrier properties can be improved. The possibility to use LCP as cost-effective lining for FRP was explored. Special focus was put on the diffusion of water and its effect on long-term transport properties and stability of thermoset resins as the performance of FRP is strongly related to the diffusion of water. The results showed that Vectra A950 was suitable for organic solvent and non-oxidising acid environments. Its transport properties were gravimetrically determined and found to be 10 to 102 times lower than that of a high barrier fluoropolymer of type FEP. The degree of molecular packing increased with annealing time both below and above the melting point. Below the melting point this was – at least – partly due to crystal formation whereas above the melting point other mechanisms were involved. The effects of annealing and orientation on the transport properties in LCP were, however, very small or not significant and probably significantly longer annealing times are required. LCP has potential to be used as lining material for FRP as the use of an LCP-lining substantially reduced the permeability of and the solute sorption in a bisphenol A epoxy-based vinyl ester resin. The bonding strength was improved significantly by a combined abrasive and oxygen plasma treatment. The long-term sorption of water in thermoset resins including bisphenol A epoxy-based vinyl ester, novolac-based vinyl ester, urethane modified vinyl ester and bisphenol A polyester resins was found to increase with exposure time whereas the diffusion coefficient was not significantly affected. It was shown that the presence of water induced relaxation processes that were considered to be the primarily reason for the increase in sorption coefficient in comparison to degradation processes, such as hydrolysis, causing osmotic processes. A general relationship for the estimation of the sorption coefficient at 80ºC in dependence of the water activity and the sorption coefficient at unit activity independent of the resin type was established.

Theoretical-methodology part: properties-assessing, characteristics of long-term properties, financial statements and international financial reporting standards. Application part: problems of the Madeta Inc. long-term properties, properties-assessing possibilities in the company and their influence on the probative qualities of data contained in the financial statements, the concrete example of a properties-depreciation calculation and impacts of the particular ways of depreciation on the probative qualities of the financial statements of the company.

This thesis focuses on transport properties and durability of liquid crystalline polymers (LCP)and fibre reinforced plastics (FRP) with regard to application in industrial process equipment.In the first part of the study the possibility of using a thermotropic LCP of type Vectra A950as lining material for FRP process equipment was investigated. Its performance wascompared to that of a fluorinated ethylene propylene copolymer (FEP) with respect tochemical and permeation resistance. Transport property and chemical resistance data wereestablished for different types of LCP film (compression molded, uniaxially and biaxiallyoriented film) exposed to selected chemicals chosen to represent typical industrial processenvironments. Annealing of the LCP, which may reduce the disclination density and henceimprove the barrier properties, induced a crystallinity increase, but did not significantlyimprove the barrier and chemical resistance properties. Different surface treatments toincrease the bonding between the LCP and FRP were explored. The conclusion was that LCPhas potential to serve as lining material for FRP in contact with water, organic solvents andnon-oxidizing acid environments, although certain issues, such as jointing techniques, stillhave to be evaluated. The second part of the study focused on transport and long-termproperties of commercial thermoset and FRP materials for industrial process equipment inaqueous environments (50 – 95 °C, water activity 0.78 – 1, exposure time ≤ 1000 days). Thewater transport properties in different thermosets were related to their chemical structureusing the solubility parameter concept. The transport of water in the thermosets with differentchemical structures could be predicted from the water activity, regardless of the actual type ofionic or non-ionic solute in the solution. An empirical relationship, independent of boththermoset chemistry and temperature, was established to describe the water concentration inthe thermoset as a function of water activity and the water concentration in pure water. Inlong-term, the water concentration in the thermosets increased with exposure time. Thisseemed to be primarily related to stress relaxation processes induced by water absorption andcertain leaching effects. The effects of hydrolysis seemed to be small. The glass fibrereinforcement may to various extents affect the water transport properties by capillarydiffusion and additional absorption around fibre bundles. The extent of such processesseemed to depend on temperature, water activity and the type of thermoset and reinforcement.The present work may be a useful contribution to an increased understanding of water effectsand durability of FRP process equipment. However, open questions still remain for a morecomprehensive durability analysis. / QC20100629