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Calcium alkali phosphates Ca(Na,K)PO4 are main constituents of bioceramics and thermochemically produced phosphorus fertilizers because of their bioavailability. Sparse thermodynamic data are available for the endmembers CaNaPO4 and CaKPO4. In this work, the missing data were determined for the low-temperature phase modifications of the endmembers CaNaPO4 and CaKPO4 and three intermediate Ca(Na,K)PO4 compositions. Standard enthalpy of formation ranges from - 2018.3 ± 2.2 kJ mol-1 to - 2030.5 ± 2.1 kJ mol-1 and standard entropy from 137.2 ± 1.0 J mol-1 K-1 to 148.6 ± 1.0 J mol-1 K-1 from sodium endmember b-CaNaPO4 to potassium endmember b0-CaKPO4.
Thermodynamic functions are calculated up to 1400 K for endmembers and the sodium-rich intermediate phase b-Ca(Na0.93K0.07)PO4. Functions above 640 K are extrapolated because of the phase transition from low- to high-temperature phase. Impurities in the synthesized intermediate phases c-Ca(Na0.4K0.6)PO4 and c-Ca Na0.35K0.65)PO4 and one additional phase transition around 500 K impeded the determination of high-temperature thermodynamic functions. In general, data for phase transition temperatures agree with the previously reported phase diagrams.
Speed of sound is one of the thermodynamic properties that can be measured with least uncertainty and is of great interest in developing equations of state. Moreover, accurate models are needed by the H2 industry to design the transport and storage stages of hydrogen blends in the natural gas network. This research aims to provide accurate data for (CH4 + H2) mixtures of nominal (5, 10, and 50) mol-% of hydrogen, in the p = (0.5 up to 20) MPa pressure range and with temperatures T = (273.16, 300, 325, 350, and 375) K. Using an acoustic spherical resonator, speed of sound was determined with an overall relative expanded (k = 2) uncertainty of 220 parts in 10^6 (0.022%). Data were compared to reference equations of state for natural gas-like mixtures, such as AGA8-DC92 and GERG-2008.
Average absolute deviations below 0.095% and percentage deviations between 0.029% and up to 0.30%, respectively, were obtained. Additionally, results were fitted to the acoustic virial equation of state and adiabatic coefficients, molar isochoric heat capacities and molar isobaric heat capacities as perfect-gas, together with second and third acoustic virial coefficients were estimated. Density second virial coefficients were also obtained.
Understanding the evolution of the cooperative molecular mobility as a function of time and temperature remains an unsolved question in condensed matter physics. Many recent works concern the question of the molecular dynamic slowdown in a temperature domain ranging from the crossover temperature T c (beginning of cooperative relaxation) down to the calorimetric glass transition temperature T g. Recent studies have shown that the estimation of cooperativity length based on calorimetric investigations using Donth's approach can be extended to a wider temperature range from T g to T c. To describe the relaxation time evolution and the characteristic length evolution of cooperative motions, besides the Donth's fluctuation approach other models exist in the literature such as '4 points correlation function' model. Whatever the model used, calorimetric investigations are needed to estimate the heat capacity as a function of the temperature. In this work, we have focused our attention on the modulated temperature differential scanning calorimetry (MT-DSC) experiments and we have tested different MT-DSC protocols allowing the heat capacity determination. For this goal we decided to work on different amorphous glass formers in order to cover a large range of glass transition temperature. The influence of the protocol used on the cooperativity length calculation is discussed in detail. Lissajous figures were constructed to verify whether the steady state is reached.
Some of the properties intrinsically present in the backbone of polyalkylene glycols (PAGs), which have nowadays attracted the automotive original equipment manufacturers (OEMs), are presented, such as bio-no-tox properties, heat capacity, extended drains, low friction, low AlSi-liner wear, fuel economy, and very high viscosity indices, and are achieved with metal-, ash-, and polymer-free formulations, which guarantee no adverse contamination of the lambda sensor and the active centers of the catalyzer as well as not to increase the exhaust back pressure of the particulate filter through ash deposits. This paper illuminates the latest results from OEM's engine bench and road testing supporting the following functional benefits: (a) bio-no-tox, (b) improvements of fuel economy, even when compared with latest hydrocarbon-based prototype oils, (c) reduced wear, (d) reduced engine friction, (e) extended drains, (f) suited for bio-fuels, (g) no adverse effects on after-treatment devices through ash-, metal-, and polymer-free formulations, etc.
The use of alternative base oils, like esters or polyglycols, with more intrinsic properties for the lubrication of automobile engines has a potential for ecological and technical advantages. Being in competition with hydrocarbon-based formulations, detailed knowledge of several thermophysical and viscometric properties as well as tribological properties over a large temperature range are required (mapping). The tested polymer-free polyglycols and ester-based formulations displayed no visible tribological weaknesses regarding wear resistance and EP-behavior as well as offering significant advantages in order to meet metal- and ash-free and bio-no-tox criteria. Especially the formulated polyglycols without friction modifiers also showed an intrinsic retention of low coefficients of friction and a hydrodynamic film forming behavior comparable to hydrocarbon-based factory-fill oils. The wear resistance and EP-behavior of low-additivated polyglycols, but also of esters, can be enhanced by means of triboactive materials. Lubricious oxides or triboactive materials and polar base oils, or a combination thereof, may substitute the EP and AW properties realized by the additives, thus enabling long drains and responding to eco-tox or bio-no-tox requirements as well as restrictions from the chemical box.
The use of alternative oils for the lubrication of automobile engines has a potential of ecological and technical advantages. It requires the detailed knowledge of several thermophysical and viscometric properties in a large temperature range (mapping). Therefore, the following properties of up to twenty-eight different oils have been measured in the temperature range from 22 °C to 150 °C: density, heat capacity, thermal conductivity, viscosity at ambient pressure, viscosity under shear rates above 10 6 s-1, and the viscosity at elevated pressures (maximum 100 MPa). The last two have been measured with a substantially improved and a newly developed apparatus, respectively. The pressure- viscosity coefficient has been measured on four hydrocarbon-based, factory-fill oils, a paraffin oil and twenty-three alternative oils. Nine of the alternative oils are based partly or completely on esters, the other fourteen on polyglycols, two of them additionally on water.