Thermal characterization of portland cement-magnesia blends

Summary Due to growing environmental concerns and the need to use less energy-intensive building products, alternatives and improvements to Portland cement (PC) are being actively researched worldwide. Use of supplementary materials is now a common practice where PC is the predominant component of inorganic building products. This study aims to investigate the potential of magnesia (MgO), derived from a naturally occurring raw material magnesite, as a supplementary material. Results from mortar samples prepared with 10 and 20% replacements of ordinary Portland cement (OPC) by MgO are presented. DTA-TG was used to study and characterise the hydration behaviour of MgO in OPC environment after 3, 7, 14, 28, 56 and 90 days of moist curing. Microstructural and compressive strength determinations providing additional information on the influence of hydrated phases are also reported.     

Thermal characterization of polycarbonate/polycaprolactone blends

In this work, we prepared blends of bisphenol A polycarbonate (PC) and poly(ϵ‐caprolactone) (PCL) in a wide composition range by melt mixing and solution mixing. Two different molecular weights of PCL were used (nominally, 10.000 g/mol, PCL10, and 80.000 g/mol, PCL80). The thermal behavior of both systems was studied via differential scanning calorimetry under dynamic and isothermal conditions. The blends were miscible in the entire composition range in the liquid and amorphous states, as indicated by the single glass‐transition temperature (T_g) exhibited by both the PC/PCL10 and PC/PCL80 blends. The compositional variation of the T_g was accurately described by the Fox equation for the PC/PCL80 blends, whereas slight deviations from this equation were exhibited by the PC/PCL10 blends. For blend compositions containing 40% or more PCL, either one or both blend components crystallized. Crystallization occurred during cooling from the melt or during subsequent heating in the form of cold crystallization. Although PCL crystallization was reduced and its crystallization rate decreased with the addition of PC, PCL was a very effective macromolecular plasticizer for PC, to the extent that crystallization during the scan was detected for some blend compositions. Isothermal crystallization experiments allowed the determination of equilibrium melting points (T) by the Hoffman–Weeks extrapolation method. A T depression was found for both PCL and PC components as the content of the other blend component was increased. The Avrami equation was closely obeyed by both blend components during the isothermal overall crystallization kinetics up to crystalline conversion degrees of 60–70% and with values of Avrami indices ranging from 3 to 4, depending on the crystallization temperature employed. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 771–785, 2001     

Thermal behavior of bismaleimide resin

The cure of a bismaleimide (BMI) neat resin modified with an aromatic diamine and a siloxane elastomer, has been studied by ¹³C solid state nuclear magnetic resonance. Two chemical reactions occur during the cure cycle; at a low temperature, Michael's reaction predominates, while at a high temperature the polymerization of the double bond maleimide creates the network. The degradation of this BMI material was characterized with isothermal and dynamic thermogravimetric analyses in air and in nitrogen. The BMI thermal stability is lower in nitrogen than in air. This behavior is an indication of oxygen participating in reactions at high temperatures. The activation energy (E_a) of thermal degradation was determined from isothermal data using an Arrhenius equation (In V vs. 1/T). The global E_a for the weight loss in air was found to be 91 kJ/mol. The nature and the evolution of the thermal degradation products were the combined analyzed by techniques of pyrolysis, gas chromatography and mass spectrometry. The major thermal decomposition products obtained in the temperature range of 300–700°C are identified as benzene, methyl formamide, aniline, toluene and isocyanate-derived products.     

Thermal characterization of nitrile butadiene rubber (NBR)/PVC blends

Summary Nitrile butadiene rubber (NBR) and NBR/PVC blends were produced using 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ) or not as antioxidant. Controlled ozone degradation was performed in several samples. Thermal, compositional and morphological analysis was performed by means of differential scanning calorimetry, thermogravimetry, chemical analysis and scanning electron microscopy. Thermogravimetry analysis shows four mass loss processes related to plastizicer, complex rubber degradation and metallic oxides and other additives. In NBR (NBR/PVC blends) the onset temperature of the first degradation process varies between 227-231°C (259-262°C) and the apparent activation energy between 26 and 36 kJ mol^-1 (36-57 kJ mol^-1), the NBR/PVC samples non degraded presents the higher thermal stability.     

Rheological characterization and analysis of a bismaleimide matrix

Bismaleimide resins are becoming increasingly attractive as matrix materials for high-temperature applications in continuous fiber reinforced composites. Their relative low viscosity as well as the low processing temperature makes them attractive candidates as matrices in high-temperature applications while retaining the processing ease associated with epoxies. Traditional prepregging as well as autoclaving processes, especially for solvent free (hot melt) systems, are a viable way to proceed. However, the recent interest in toughened matrices makes these processing techniques difficult to specify and control. Specifically, during prepregging and autoclaving, the viscosity of the system must be specified from the initial stages of resin mixing through B-staging and gelation all the way to the viscoelastic “solid” region. In this work, based on a series of well-characterized bismaleimide resins, a generalized model for viscosity capable of describing matrix changes as it goes through the processing steps was developed. Measurements of viscosity by the different techniques were related through the model to provide a characterization scheme that may be applicable to both prepregging and lamination steps.     

Triphenylphosphine oxide-based bismaleimide and poly(bismaleimide): Synthesis,characterization, and properties

A novel phosphorus-containing bismaleimide, 3,3′-bis(maleimidophenyl)phenylphosphine oxide (BMPPPO), was synthesized from triphenylphosphine oxide. This bismaleimide exhibited good solubility in common organic solvents, such as methylethylketone, methylisobutylketone, dichloromethane, chloroform, tetrahydrofuran, acetone, methanol, ethanol, and hot toluene. A low melting point (T_m = 148 °C), a relatively low polymerization temperature (T_p = 214 °C), and a wide processing window (T_p − T_m = 66 °C) were also obtained for BMPPPO. This implies better processing capability. In contrast to most known phosphorus-containing polymers, the incorporation of BMPPPO into poly(bismaleimide) enhanced the polymer glass-transition temperature. Thermal stability at temperatures over 550 °C and char yields in the high-temperature region over 700 °C were also improved. As a result, the flame-retardant properties of the poly(bismaleimide)s were improved. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1716–1725, 2001     

Thermal treatment of pitch-polymer blends

Coal-tar pitch was modified by addition of polystyrene, poly(ethylene terephthalate), unsaturated polyester and coumarone-indene resin. The optimum conditions for production of homogeneous binary pitch-polymer blends containing 10% w/w of the polymer were established. Softening points, contents of toluene and quinoline-insoluble matters and rheological properties of the blends were determined. The yield of solid fraction in semi-coking the blends was also found. The effect of polymers on the coal-tar pitch blend properties was evaluated. Some pitch-polymer blends were then carbonized to carbon sorbents used for purification of water and wastewater.     

Thermal properties of binary polyolefin blends

The thermal properties of binary polyolefin blends (LDPE/HDPE, LDPE/PP, HDPE/PP) were examined by differential scanning calorimetry. The additon of a second polymer lowers the melting temperature although the melting temperature depression is not a defined function of the blend composition. DSC curves show two melting and two crystallization temperatures. The difference between crystallization temperatures for blends containing PP is smaller than the difference between melting temperatures. The enthalpies of fusion are nearly monotonic functions of blend composition.

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Zusammenfassung Die thermischen Eigenschaften binärer Polyolefinmischungen (LDPE/HDPE, LDPE/PP, HDPE/PP) wurden mittels DSC untersucht. Durch Zugabe eines zweiten Polymers wird die Schmelztemperatur erniedrigt, obwohl die Erniedrigung der Schmelztemperatur keine Funktion der Mischungszusammensetzung ist. Die DSC-Kurven zeigen zwei Schmelz- und zwei Kristallisationspeaks. Bei PP enthaltenden Mischungen ist der Unterschied zwischen den Kristallisationstemperaturen geringer als zwischen den Schmelztemperaturen. Die Schmelzenthalpie ist eine nahezu monotone Funktion der Mischungszusammensetzung.

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Thermal behaviour of polyetherimide peek blends

PEEK is characterised by high impact and fatigue resistance andT _g of 145C. Blends of PEEK and PEI have been made and scanning electron micro-graphs of the broken specimen show that the two polymers are completely miscible in all proportions. The study also shows that PEEKPEI 5050 blend, can be used as matrix for composite applications with appreciable enhancement ofT _g to 177C.     

Cure behavior and thermal stability of an epoxy: new bismaleimide blends for composite matrices

A new bismaleimide (BMI) resin was synthesized to formulate epoxy(tetraglycidyl diaminodiphenyl methane; TGDDM) – bismaleimide thermoset blends for composite matrix applications. 4,4′-diaminodiphenyl methane (DDM) was used as an amine curing agent for the TGDDM. A Fourier transform infrared (FTIR) spectroscopy was employed to characterize the new BMI resin. Cure behavior of the epoxy–BMI blends was studied using a differential scanning calorimeter (DSC). DSC thermograms of the thermoset blends indicated two exothermic peaks. The glass transition temperature of the thermoset blends decreased with BMI content. Thermogravimetric analysis (TGA) was carried out to investigate thermal degradation behavior of the cured epoxy–BMI thermoset blends. The new BMI resin reacted partially with the DDM and weak intercrosslinking polymer networks were formed during cure of the thermoset blends.     

Thermal properties of anhydride-cured bio-based epoxy blends

Epoxidized palm oil (EPO) (0–12 wt%) was added into petrochemical-based epoxy blends (diglycidyl ether of bisphenol-A (DGEBA)/cycloaliphatic epoxide resin/epoxy novolac resin) to develop a thermal curable bio-based epoxy system. The thermal behaviors of the EPO, epoxy blends (EB), and bio-based epoxy blends (EB/EPO) were characterized using differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMT) and thermo-mechanical analysis (TM). The glass transition temperature (T _g) and storage modulus (E′) of the EB/EPO system was reduced with the increasing of the EPO loading. This is attributed to the plasticizing effect of the EPO. It was found that epoxy blends with higher loading of EPO possessed higher coefficient of thermal expansion (CTE) and tanδ value. This is due to the increase of the free volume and chain flexibility in the three-dimensional network of the epoxy blends. The internal thermal stresses of the EB/EPO were decreased as the increasing loading of EPO, owing to the reduction of crosslink density, modulus of elasticity, and T _g in the epoxy blends.     

Thermal properties of bisitaconimide and bisbenzoxazine blends

Blends of cardanol-based bisbenzoxazine (BZc) and 4,4′-bisitaconimidodiphenyl ether (BIM) having nine different mass ratios (i.e. 100:0, 90:10, 75:25, 60:40, 50:50, 40:60, 25:75, 10:90 and 0:100) were prepared and their curing behaviour was studied by differential scanning calorimetry (DSC) and fourier transform infrared spectroscopy. A curing mechanism comprising two-steps: (1) homopolymerization and co-curing reaction of itaconimide with alkyl side chain double bonds of cardanol BZc at lower temperature (~443 K) and (2) ring-opening polymerization of oxazine at higher temperature (~453–483 K) has been proposed. The T _g of the cured resin blends was determined by DSC and the increase in BIM content in the blend resulted in an increase in T _g from 408 K BZc to 474 K BIM. Increase in bisitaconimide content resulted in improvement of char yield at 1,073 K as well as an increase in mass loss temperatures (5 and 10 %). Compared to BZc, the blends showed a higher thermal stability. The lap shear strength of these blends in metal–metal joints was investigated at 323, 523 and 573 K.     

Thermal properties of EPDM/NR blends

The thermal behaviour of EPDM/NR blends was studied by differential scanning calorimetry over the temperature range 335–435 K. O'Neill's method (O'Neill MG. Anal Chem 1964;36:1238) was used for calculating the specific heat capacity with aluminia as standard. The presence of natural rubber induces a marked thermal instability because of the high content of double bonds. The contribution of each component to the C_p of the tested polymer systems is discussed. The law of reciprocal affinity, the linear contribution of components to the specific heat capacity is followed by EPDM/NR blends. The influence of natural rubber on the thermal behaviour of tested mixtures was assessed by oxygen uptake method and the first derivative procedure reveals the sequence in thermal stability of ethylene-propylene-diene/natural rubber compounds.     

Preparation and characterization of bismaleimide/1,3-dicyanatobenzene modified epoxy intercrosslinked matrices

An intercrosslinked network of cyanate ester (CE)-bismaleimide (BMI) modified epoxy matrix system was made by using epoxy resin, 1,3-dicyanatobenzene and bismaleimide (N,N^′-bismaleimido-4,4^′-diphenyl methane) with diaminodiphenylmethane as curing agent. BMI-CE-epoxy matrices were characterised using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and heat deflection temperature (HDT) analysis. The matrices, in the form of castings, were characterised for their mechanical properties such as tensile strength, flexural strength and unnotched Izod impact test as per ASTM methods. Mechanical studies indicated that the introduction of cyanate ester into epoxy resin improves the toughness and flexural strength with reduction in tensile strength and glass transition temperature, whereas the incorporation of bismaleimide into epoxy resin influences the mechanical and thermal properties according to its percentage content. DSC thermograms of cyanate ester as well as BMI modified epoxy resin show an unimodal reaction exotherm. Electrical properties were studied as per ASTM method and the morphology of the BMI modified epoxy and CE-epoxy systems were studied by scanning electron microscope.     

Thermal decomposition characteristics of Alder-ene adduct of diallyl bisphenol A novolac with bismaleimide: effect of stoichiometry, novolac molar mass and bismaleimide structure

The addition-cured blends of diallyl bisphenol A formaldehyde resin (ABPF) with various bismaleimides (BMIs) were evaluated for thermal stability and degradation behavior by thermogravimetric analysis (TGA). TGA of the blend of ABPF and 2,2-bis 4-[(4-maleimido phenoxy) phenyl] propane (BMIP) with varying maleimide to allylphenol stoichiometry indicated that the thermal stability of the system was only marginally improved by the increase in BMI stoichiometry in the blend. The effect of BMI structure on thermal stability was studied using four different BMIs, viz. bis (4-maleimido phenyl) methane (BMIM), bis (4-maleimido phenyl) ether (BMIE), bis (4-maleimido phenyl) sulfone (BMIS) and BMIP. TGA showed a two stage decomposition pattern for BMIS system and a single stage for all the other three. The thermograms of BMIM and BMIE were identical and superior to that of BMIS; the latter showing a relatively poor performance at lower temperatures. Compared to the BMI-adduct of monomeric diallyl bisphenol A (DABA), the polymeric analog viz. ABPF system exhibited better thermal stability. Non-isothermal kinetic analyses of the different systems showed the decomposition occurring in at least two kinetic steps. The computed activation energy exhibited a direct correlation to the relative thermal stability of the systems.     

Thermal behaviour of bisitaconimide and reactive diluent blends

Thermal behaviour of blends based on N,N'-bis(4-itaconimidophenyl) ether (IE) and 4,4'-bis(4-allyl-2-methoxyphenoxy) benzophenone (R₁) or 4,4'-bis(2-allylphenoxy) benzophenone (R₂) are described in this paper. The reactive diluent content was varied from 5-50% (mass/mass) in these blends. A decrease in the melting point and exothermic peak temperature was observed with increasing mass percent of reactive diluent. Thermal stability of blends was affected at high mass percentage of reactive diluents. This revised version was published online in August 2006 with corrections to the Cover Date.     

Thermal analysis of soil-buried oxo-biodegradable polyethylene based blends

Low-density polyethylene (LDPE) blended with poly(3-hydroxybutyrate) (PHB) and additivated with pro-oxidant were soil buried for 180 days and characterized using thermogravimetry (TG) and differential scanning calorimetry (DSC). TG data showed that both onset and maximum rate degradation temperatures decreased as a function of biodegradation time. Apparent activation energies (E _a) using the Broido integral method decreased with the burial time increasing. PE crystallinity degree values increased in general up to 2 months of biodegradation. At the end of the soil burial (SB) test these values decreased principally for samples that were previously thermo-oxidized in an oven.     

Thermal properties of polyamide 6/polyurethane blends

Equilibrium melting temperatures and crystallization parameters of polyamide 6/polyurethane blends were investigated. Thermal properties of the crystalline phase of blends obtained from polyamide 6 and polyurethane containing 40 wt% of hard segments, are only limited influenced by the overall blend compositon. Because from separate measurements single glass transitions for all samples were estimated, so in the investigated case the blending process may occur mainly between amorphous fraction of polyamide 6 and the polyurethane or, what is more probable, the polyurethane phase is dispersed in the continuous polyamide matrix, although some interactions exist.     

Thermal and mechanical evaluation of cyanate ester resin modified with bismaleimide and diallyl phthalate

Cyanate ester resins have excellent dielectric, mechanical, and thermal properties; however, their major drawback is their brittleness. A high performance matrix blend was developed using bisphenol A dicyanate (BADCy), bismaleimide (BMI) and diallyl phthalate (DAP), and Cobalt (III) acetylacetonate dissolved in nonyl phenol (NP) as a complex catalyst system for BADCy. The properties of the BADCy/BMI/DAP blends, such as thermal and mechanical properties, were investigated in detail by dynamic mechanical analysis (DMA), thermogravimetric analysis (TGA), and mechanical measurement. The results show that the addition of the appropriate amount of DAP and BMI can improve the impact strength and the flexural strength and this possibly comes from forming an interpenetrating polymer network in the systems. However, the thermal stability of the blends was found to be lower than that of the unmodified BADCy resin. Copyright © 2009 John Wiley & Sons, Ltd.