Review of biomaterial thermal property measurements in the cryogenic regime and their use for prediction of equilibrium and non-equilibrium freezing applications in cryobiology

It is well accepted in cryobiology that the temperature history and cooling rates experienced in biomaterials during freezing procedures correlate strongly with biological outcome. Therefore, heat transfer measurement and prediction in the cryogenic regime is central to the field. Although direct measurement of temperature history (i.e. heat transfer) can be performed, accuracy is usually achieved only for local measurements within a given system and cannot be readily generalized to another system without the aid of predictive models. The accuracy of these models rely upon thermal properties which are known to be highly dependent on temperature, and in the case of significant cryoprotectant loading, also on crystallized fraction. In this work, we review the available thermal properties of biomaterials in the cryogenic regime. The review shows a lack of properties for many biomaterials in the subzero temperature domain, and especially for systems with cryoprotective agents. Unfortunately, use of values from the limited data available (usually only down to −40 °C) lead to an underestimation of thermal property change (i.e. conductivity rise and specific heat drop due to ice crystallization) with lower temperatures. Conversely, use of surrogate values based solely on ice thermal properties lead to an overestimation of thermal property change for most biomaterials. Additionally, recent work extending the range of available thermal properties to −150 °C has shown that the thermal conductivity will drop in both PBS and tissue (liver) due to amorphous/glassy phases (versus crystalline) of biomaterials with the addition of cryoprotective additives such as glycerol. Thus, we investigated the implications of using approximated or constant property values versus measured temperature-dependent values for predicting temperature history during freezing in PBS (phosphate-buffered saline) and porcine liver with and without cryoprotectants (glycerol). Using measured property values (thermal conductivity, specific heat, and latent heat of phase change) of porcine liver, a standard was created which showed that values based on surrogate ice properties under-predicted cooling times, while constant properties (i.e. based on limited data reported near the freezing point) over-predicted cooling times. Additionally, a new iterative numerical method that accommodates non-equilibrium cooling effects as a function of time and position (i.e. crystallization versus amorphous phase) was used to predict temperature history during freezing in glycerol loaded systems. Results indicate that in addition to the increase in cooling times due to the lowering of thermal diffusivity with more glycerol, non-equilibrium effects such as the prevention of maximal crystallization (i.e. amorphous phases) will further increase required cooling times. It was also found that the amplified effect of non-equilibrium cooling and crystallization with system size prevents the thermal history to be described with non-dimensional lengths, such as was possible under equilibrium cooling. These results affirm the need to use accurate thermal properties that incorporate temperature dependence and crystallized fraction. Further studies are needed to extract thermal properties of other important biomaterials in the subzero temperature domain and to develop accurate numerical methods which take into account non-equilibrium cooling events encountered in cryobiology when partial or total vitrification occurs.     

A quantitative analysis of the thermal properties of porcine liver with glycerol at subzero and cryogenic temperatures

There is a lack of information on the effect of cryoprotective agents (CPAs) on the thermal properties of biomaterials at cryobiologically relevant temperatures (i.e. <233.15 K, −40 °C). Thermal properties that are of most interest include: thermal conductivity, density, specific heat, and latent heat resulting from phase change in tissue systems. Availability of such information would be beneficial for accurate mathematical modeling of cryobiological applications. Recently, we reported these thermal properties in phosphate buffered saline (PBS) with varying concentrations of glycerol, a widely used cryoprotective agent. In this study we extend these results by assessing the effects of glycerol on the thermal properties of porcine liver at subzero temperatures. Differential scanning calorimeter (DSC) was used to measure the specific heat and the latent heat release of porcine liver immersed in PBS and varying concentrations of glycerol. The specific heat data obtained from the DSC experiments were also used to predict the bulk thermal conductivity. This was done using a transient heat transfer model with a thermistor probe technique. Results show that the introduction of glycerol significantly alters thermal properties from known values for H₂O and non-treated liver. Therefore, inaccuracies in thermal predictions can be expected due to the application of measured vs. predicted thermal properties such as from weight averaging. This supports the need for these and other measurements of biomaterial thermal properties, with and without CPA addition, in the cryogenic regime.     

Recommended gas transport properties of argon at low density using ab initio potential

The most important transport properties of argon have been calculated using classical kinetic theory expressions in conjunction with high-quality ab initio potential energy values computed by Patkowski and Szalewicz. Dilute gas transport properties have been calculated for the viscosity, thermal conductivity, self-diffusion coefficient and thermal diffusion factor from 83 to 10,000 K. Comparisons between experimental transport property data and values presently calculated indicate that the present theoretical predictions may be employed as recommended values for this set of transport properties over a wide temperature range.     

Changes in thermal and electrical properties of bone as a result of 1 MGy-dose gamma-irradiation

Determination of temperature dependencies of electric conductivity and thermal properties by differential scanning calorimetry (DSC) allow to analyse the processes of charge and heat transport in the bone being a complex collagen-hydroxyapatite (HAP)-water system. Modification of the bone structure by high doses of gamma-radiation changes the electrical and thermal properties of the bone. Electrical conductivity (sigma) of the bone decreases with consecutive heating runs. The decrease in sigma observed for irradiated samples was explained by the scission of the main chain of collagen macromolecule. Irradiation decreased the hydration level in the bone, its denaturation temperature and increased both enthalpy and entropy of the denaturation process.     

Properties of polylactic acid composites reinforced with oil palm biomass microcrystalline cellulose

In this work, polylactic acid (PLA) composites filled with microcrystalline cellulose (MCC) from oil palm biomass were successfully prepared through solution casting. Fourier transform infrared (FT-IR) spectroscopy indicates that there are no significant changes in the peak positions, suggesting that incorporation of MCC in PLA did not result in any significant change in chemical structure of PLA. Thermogravimetric analysis was conducted on the samples. The T₅₀ decomposition temperature improved with addition of MCC, showing increase in thermal stability of the composites. The synthesized composites were characterized in terms of tensile properties. The Young's modulus increased by about 30%, while the tensile strength and elongation at break for composites decreased with addition of MCC. Scanning electron microscopy (SEM) of the composites fractured surface shows that the MCC remained as aggregates of crystalline cellulose. Atomic force microscopy (AFM) topographic image of the composite surfaces show clustering of MCC with uneven distribution.     

A novel method for measuring the thermal conductivity of organisms

Based on the theories of tissue optics and artificial neural network, the relationship between the optical properties and biological parameters was studied, and a new experimental method was derived. The properties of the organism were obtained indirectly by a black-box model derived by self-study of the artificial neural network between optical parameters and thermo-physical properties without using the heat transfer equation. In this method, the energy of light in diffuse radiation, diffuse transmission and collimated transmission was absorbed by a dual-integrating sphere experimental system of a spectrometer, and the spectrogram of the energy was obtained. Combining these spectral data of the energy, the diffuse-reflecting power, the diffuse transmissivity and the collimated transmissivity were calculated. The calculated results were taken as the input parameters of a black-box model. The experimental results show that there are apparent differences between the spectrogram of the energy on the diffuse radiation, the diffuse transmission and the collimated transmission of different matters, while there is a little difference in the same matter. Each spectrogram has its own characteristic. The values of the four thermal properties including the density, the constant pressure specific heat, the thermal diffusivity and the viscosity were calculated using the black-box model. Compared with the real values the calculated one has an average relative error between −5% and 5%. The conductivity of the tongue is 0.68 W/(m K) that calculated from the value of the density, the constant pressure specific heat and the thermal diffusivity. The results also show that there is a little difference on the conductivities in the longitudinal cross-section and the transverse section, but the effect of temperature on the conductivity of the tongue is not apparent. The difference implies the anisotropy of the properties of the organism, which cannot be easily obtained by a conventional experimental method.     

Characterization of lignocellulose particles during lignocellulose solubilization by Clostridium thermocellum

Clostridium thermocellum is a candidate bacterium for lignocellulose utilization due to its efficient lignocellulose solubilization ability. It has been reported that C. thermocellum efficiently degrades purified cellulose substrates, but cannot completely degrade milled lignocellulose powders. Evaluation of cellulose and hemicellulose contents in a lignocellulose residue after the cultivation of C. thermocellum indicated that C. thermocellum degraded cellulose and hemicellulose equally. Microscopic observations demonstrated that C. thermocellum significantly degraded small-sized lignocellulose particles, but it only partially degraded the larger sized particles. The lignin content of the large-sized particles was higher than that of the small particles. The remained large-sized particles included vascular tissues. These results suggest that the lignified structures such as vascular tissues in milled lignocellulose were less susceptible to bacterial lignocellulose solubilization.     

The effect of alumina nanoparticles on the thermal properties of PMMA: a molecular dynamics simulation

Metal oxides, as one of the most promising flame retardant additives, improve the fire retardant and the thermal stability properties of polymers. In the present study, molecular dynamics (MD) simulations based on the united atom model were applied to study the effect of alumina nanoparticles on the density, thermal conductivity, heat capacity, and thermal diffusivity of isotactic poly(methyl methacrylate) (is-PMMA). Thermal diffusivity of PMMA and PMMA/alumina nanocomposite were investigated through calculating thermal conductivity, density and heat capacity in the range of 300–700?K. Heat capacity can be calculated using fluctuations properties of energy. Thermal conductivity was calculated through the nonequilibrium molecular dynamics (NEMD) simulation by Fourier’s law approach. Our results show that the addition of alumina nanoparticles decreases the heat capacity and increases the glass transition temperature (T_g), thermal conductivity and thermal diffusivity of the PMMA. Therefore, the addition of alumina nanoparticles to PMMA improves the fire retardancy of the polymer. In addition, we illustrate the links between the intermolecular and bulk properties of PMMA in the presence of the alumina nanoparticles.     

Gamma-radiation induced changes in the physical and chemical properties of lignocellulose

gamma-radiation induced effects on the physical and chemical properties of natural lignocellulose (jute) polymer were investigated. Samples were irradiated to required total doses at a particular dose rate. The changes in the parameters such as the tensile strength, elongation at break, and work done at rupture for the lignocellulose samples on irradiation with the gamma-rays from a cobalt-60 source were measured. The mechanical properties were found to have nonlinear relations with the radiation doses. The chemical stability of irradiated fibers was found to degrade progressively with the increase of radiation dose. Additionally, other chemical changes of the samples due to exposure to high-energy radiation were also investigated using fluorescence and infrared spectroscopic analysis. Differential scanning calorimetry and thermogravimetric studies showed a significant reduction in thermal stability. The wide-angle X-ray diffraction study showed that structural changes of cellulose appeared due to the radiation-induced chemical reaction of lignocellulose.     

Adsorption of cellulase fromTrichoderma viride on microcrystalline cellulose

Summary The adsorption behaviour of cellulase fromTrichoderma viride on microcrystalline celluloses with different specific surface areas was studied. The adsorption was found to fit a Langmuir isotherm. There was an increase in the maximum adsorption amount (A_max) as the specific surface area of microcrystalline cellulose increased. The values of A_max and adsorption equilibrium constant (K) decreased with increasing temperature. Thermodynamic parameters in adsorption were calculated from K. It was found from the enthalpy of adsorption, that van der Waals-Type interaction was responsible for adsorption of cellulase on microcrystalline cellulose. The adsorption process was exothermic and an adsorption enthalpy-controlled reaction.     

纤维素酶的糖基化

木质纤维素价格低廉,供应充足,且未得到充分开发利用。把纤维素降解成葡萄糖,进而生产纤维素乙醇的技术已经进入商业应用阶段。提高纤维素酶的活性,有利于充分利用自然界中大量存在的木质纤维素,开发生物质资源,以缓解能源危机。糖基化修饰对纤维素酶的活性、稳定性以及其他性质有着重要的影响。因此,对纤维素酶糖基化的了解,以及合理地改善糖基化修饰,可以极大地提高木质纤维素降解速率,有利于工业上液体燃料的生产。     

Relaxation of a thermal perturbation in a collisional plasma

The relationship between the nonlocal and nonstationary effects in electron heat transport processes in a weakly collisional plasma is investigated by considering the problem of the relaxation of a thermal perturbation as an example. It is shown that, for small-scale perturbations, the electron thermal conductivity depends not only on the temperature scale length but also on time. The consequence is that there exist two qualitatively different characteristic relaxation regimes of thermal perturbations on small and large scale lengths. As a result, the evolution of hot spots in laser plasmas should be described with allowance for the nonstationary nature of electron heat transport. In the course of this evolution, relaxation on the collisional kinetic time scale is clearly seen to change into relaxation on the collisional hydrodynamic time scale.     

Synergistically Optimizing Electrical and Thermal Transport Properties of BiCuSeO via a Dual‐Doping Approach

The layered oxyselenide BiCuSeO system is known as one of the high‐performance thermoelectric materials with intrinsically low thermal conductivity. By employing atomic, nano‐ to mesoscale structural optimizations, low thermal conductivity coupled with enhanced electrical transport properties can be readily achieved. Upon partial substitution of Bi³⁺ by Ca²⁺ and Pb²⁺, the thermal conductivity can be reduced to as low as 0.5 W m^?1 K^?1 at 873 K through dual‐atomic point‐defect scattering, while a high power factor of ≈1 × 10^?3 W cm^?1 K^?2 is realized over a broad temperature range from 300 to 873 K. The synergistically optimized power factor and intrinsically low thermal conductivity result in a high ZT value of ≈1.5 at 873 K for Bi_0.88Ca_0.06Pb_0.06CuSeO, a promising candidate for high‐temperature thermoelectric applications. It is envisioned that the all‐scale structural optimization is critical for optimizing the thermoelectricity of quaternary compounds.     

Enhancement of Thermoelectric Figure of Merit by the Insertion of MgTe Nanostructures in p‐type PbTe Doped with Na2Te

The thermoelectric properties of crystalline melt‐grown ingots of p‐type PbTe–xMgTe (x = 1–3 mol%) doped with Na₂Te (1–2 mol%) were investigated over the temperature range of 300 K to 810 K. While the powder X‐ray diffraction patterns show that all samples crystallize in the NaCl‐type structure with no MgTe or other phases present, transmission electron microscopy reveals ubiquitous MgTe nanoprecipitates in the PbTe. The very small amounts of MgTe in PbTe have only a small effect on the electrical transport properties of the system, while they have a large effect on thermal transport significantly reducing the lattice thermal conductivity. A ZT of 1.6 at 780 K is achieved for the PbTe containing 2% MgTe doped with 2% Na₂Te.     

A molecular dynamics simulation on the effect of different parameters on thermal resistance of graphene-argon interface

Molecular dynamics simulations of argon molecules confined between two parallel graphene sheets are carried out to investigate the parameters affecting heat transfer and thermal properties. These parameters include wall–fluid interaction strength, fluid density and wall temperature. For constant wall temperature simulations, we show that the first two parameters have influence on near-wall fluid density. As a result, the heat transfer at wall–fluid interfaces and thus through argon molecules across the domain will change. Also, we demonstrate that variations in wall temperature rarely affects the density profiles of argon molecules next to the walls. Therefore, in these cases, the variations in thermal resistance at the interface is most dominantly due to wall temperature itself. To analyse the results, the density and temperature profiles and also other parameters including heat flux and temperature gradient of bulk of argon molecules, Kapitza length and argon thermal conductivity are considered. The Kapitza length describes thermal resistance at liquid–solid interface. According to the results, increasing wall–fluid interaction strength leads to greater molecular aggregation of argon molecules near the walls and, consequently, decreasing the Kapitza length. Furthermore, higher fluid density leads to greater thermal resistance at wall–fluid interactions and therefore greater temperature jumps are observed in temperature profiles.     

Decreasing the Effective Thermal Conductivity in Glass Supported Thermoelectric Layers

As thermoelectric devices begin to make their way into commercial applications, the emphasis is put on decreasing the thermal conductivity. In this purely theoretical study, finite element analysis is used to determine the effect of a supporting material on the thermal conductivity of a thermoelectric module. The simulations illustrate the heat transfer along a sample, consisting from Cu, Cu₂O and PbTe thermoelectric layers on a 1 mm thick Pyrex glass substrate. The influence of two different types of heating, at a constant temperature and at a constant heat flux, is also investigated. It is revealed that the presence of a supporting material plays an important role on lowering the effective thermal conductivity of the layer-substrate ensemble. By using thinner thermoelectric layers the effective thermal conductivity is further reduced, almost down to the value of the glass substrate. As a result, the temperature gradient becomes steeper for a fixed heating temperature, which allows the production of devices with improved performance under certain conditions. Based on the simulation results, we also propose a model for a robust thin film thermoelectric device. With this suggestion, we invite the thermoelectric community to prove the applicability of the presented concept for practical purposes.     

Preparation of poly(l-lactide) blends and biodegradation by Lentzea waywayandensis

As a biodegradable polyester, polylactide (PLA) has applications as a packaging material, in biomedical fields and tissue engineering. With the dual aim of improving its properties and biodegradability, PLA was blended with other polymers such as gum arabic, thermoplastic starch, microcrystalline cellulose, polyethylene glycol and polyhydroxy butyrate in 1:1 (w/w) by melt-blending technique. The thermal properties of the blends were compared with that of unblended PLA by thermo-gravimetric analysis. Biodegradation using Lentzea waywayandensis was in the order of PLA–gum arabic?>?PLA–thermoplastic starch?>?PLA(virgin)?>?PLA–microcrystalline cellulose?>?PLA–polyethylene glycol?>?PLA–polyhydroxy butyrate. Weight loss of 99?% (w/w) was noted within 4?days for PLA–thermoplastic starch and PLA-gum arabic blends.     

Mixed Convective Peristaltic Flow of Water Based Nanofluids with Joule Heating and Convective Boundary Conditions

Main objective of present study is to analyze the mixed convective peristaltic transport of water based nanofluids using five different nanoparticles i.e. (Al₂O_3, CuO, Cu, Ag and TiO₂). Two thermal conductivity models namely the Maxwell''s and Hamilton-Crosser''s are used in this study. Hall and Joule heating effects are also given consideration. Convection boundary conditions are employed. Furthermore, viscous dissipation and heat generation/absorption are used to model the energy equation. Problem is simplified by employing lubrication approach. System of equations are solved numerically. Influence of pertinent parameters on the velocity and temperature are discussed. Also the heat transfer rate at the wall is observed for considered five nanofluids using the two phase models via graphs.     

Progressive Regulation of Electrical and Thermal Transport Properties to High‐Performance CuInTe2 Thermoelectric Materials

p‐type CuInTe₂ thermoelectric (TE) materials are of great interest for applications in the middle temperature range because of their environmentally benign chemical component and stable phase under operating temperatures. In order to enhance their TE performance to compete with the Pb based TE materials, a progressive regulation of electrical and thermal transport properties has been employed in this work. Anion P and Sb substitution is used to tune the electrical transport properties of CuInTe₂ for the first time, leading to a sharp enhancement in power factor due to the reduction of electrical resistivity by acceptor doping and the increase of the Seebeck coefficient resulted from the improvement of density of states. Concurrently, In₂O₃ nanoinclusions are introduced through an in situ oxidation between CuInTe₂ and ZnO additives, rendering a great reduction in the thermal conductivity of CuInTe₂ by the extra phonon scattering. Then, by integrating the anion substitution and nanoinclusions, a high power factor of 1445 μW m^?1 K^?2 and enhanced ZT of 1.61 at 823 K are achieved in the CuInTe₂ based TE material. This implies that the synergistic regulation of electrical and thermal transport properties by anion substitution and in situ nanostructure is a very effective approach to improve the TE performance of CuInTe₂ compounds.     

Rational Design of Advanced Thermoelectric Materials

Advanced thermoelectric technologies can drastically improve energy efficiencies of industrial infrastructures, solar cells, automobiles, aircrafts, etc. When a thermoelectric device is used as a solid‐state heat pump and/or as a power generator, its efficiency depends pivotally on three fundamental transport properties of materials, namely, the thermal conductivity, electrical conductivity, and thermopower. The development of advanced thermoelectric materials is very challenging because these transport properties are interrelated. This paper reviews the physical mechanisms that have led to recent material advances. Progresses in both inorganic and organic materials are summarized. While the majority of the contemporary effort has been focused on lowering the lattice thermal conductivity, the latest development in nanocomposites suggests that properly engineered interfaces are crucial for realizing the energy filtering effect and improving the power factor. We expect that the nanocomposite approach could be the focus of future materials breakthroughs.