冻干保护剂溶液低温退火特性的研究

利用差示扫描量热仪(DSC)研究了10%叔丁醇/10%蔗糖/水溶液的冻结特性, 退火温度及退火时间, 分析了溶液的退火行为. 实验结果表明, 溶液降温时, 蔗糖的存在阻碍了叔丁醇析出, 最大冻结浓缩溶液玻璃化转变温度Tg′由－32.5 ℃降低到－42.0 ℃, 升温时在－30 ℃叔丁醇发生反玻璃化. 在反玻璃化峰附近的温度进行退火可使叔丁醇充分析出, Tg′由－42.0 ℃上升到－34.9 ℃. 所需的退火时间与退火温度有关, 退火温度越接近Tg′, 所需的退火时间越长. 在－37 ℃时, 退火20 min可完全消除反玻璃化.     

Research on Ice Crystal Growth Inside the Vitrified Vs55 with Magnetic Nanoparticles During Devitrification by Cryomicroscopy

The effect of magnetic nanoparticles(mNPs) on the devitrification crystallization of typical vitrification solution Vs55 was systematically explored by differential scanning calorimetry(DSC) and cryomicroscope system. The results show tliat,(i) the mNPs coated by both carboxylic acid(CA) and polyethylene glycol(PEG) had little effect on the glass transition temperature(rg) of Vs55, but had significant effect on the devitrification transition temperature(7a) and devitrification enthalpy(Hrd),(ii) in the range of the devitrification area(-85- 0℃), the MNPs coated by CA can significantly accelerate the devitrification of Vs55 as the isothermal temperatures and the cooling rates increased, and the ice growth rate was 0.37 p.m/s at the isothermal temperature of-85 ℃, and was about 2.19 gm/s at -75℃. Also, the ice growth rates rose from 1.72 pm/s to 3.54 pm/s when the cooling rates were increased from 2 ℃/min to 100 ℃/min(at the isothennal temperature of -75℃),(iii) magnetic nanoparticles coated by both PEG and CA could promote the devitrification of Vs55, for instance, without any crystal growth inside Vs55 at the isothermal temperature of-80℃, but 1.04 and 2.31 gm/s for adding magnetic nanoparticles coated by CA and PEG, respectively. Compared with the samples coated by CA, PEG promoted the devitrification of Vs55 in a much more positive way, and the ice growth rates were 0.62 and 6.25 μm/s at the isothermal temperatures of -85 and -75 ℃, respectively. Tliese results indicate that the surface coating of MNPs could significantly affect tlie recrystallization of Vs55, and further work should be conducted in the future research.     

The non-isothermal devitrification of Li2O·TiO2·6GeO2 glass

The effect of a partial replacing of GeO₂ by TiO₂ structure and non-isothermal devitrification of lithium heptagermanate glass, examined by Fourier transform infrared spectra, differential thermal analysis and X-ray diffraction, is reported and discussed. The structure and the glass-transition temperature are not affected by the substitution of GeO₂ by TiO₂ but the investigated glass, unlike lithium heptagermanate glass, devitrifies only from the surface into a crystalline phase isomorphous with Li₂Ge₇O₁₅ crystals. The validity of the Arrhenius-type relationship between the rate constant of crystal growth and the absolute temperature is also discussed.     

The effect of changing the TiO2 content (0-6%) on the structure and thermal evolution of glasses obtained from porphyric sands and dolomite

Glasses have been obtained from mixtures of porphyric sands and dolomite. The influence of changes in the TiO₂ content (0-6%) on the glass structure and the formation of crystalline phases on reheating has been studied. The experimental results suggest that in the studied system TiO₂ promotes glass-in-glass phase separation and plays the role of a nucleating agent. The activation energy for crystal growth, E_C = 486 kJ mol⁻¹, and the Avrami parameter (m = 1) have been evaluated by means of thermoanalytical techniques in the case of the base glass (no TiO₂ added). The value of the Avrami parameter (m = 1) agrees well with SEM observations of dendritic crystal growth from surface nuclei. In the other glasses, lath-like crystals were observed, the microstructure being finer the greater the TiO₂%. The first addition of TiO₂ (2%) gives, on quenching, a partially devitrified product; subsequent additions of titania, surprisingly, allow glasses to be formed more easily. The experimental results suggest that Na₂O and K₂O, present in the porphyric sands and therefore in the glasses (to a total amount of ≈ 5.6%), segregate preferentially into the titania-rich phase with respect to MgO. Taking into account that Na₂O and K₂ are useful in lowering the liquidus temperature of glasses but are known to have a negative effect on the mechanical properties, this can be important in the production of glass ceramics.     

Thermodynamic properties of carbosilane dendrimers of the third to the sixth generations with terminal butyl groups in the range from T → 0 to 600 K

In the present work temperature dependences of heat capacity of carbosilane dendrimers with butyl terminal groups of the third and the fourth generations as well as of the fifth and the sixth generations have been determined first in the range from 6 to 340 K and between 6 and 600 K, respectively, by precision adiabatic vacuum and dynamic calorimetry. In the above temperature ranges the physical transformations have been detected and their thermodynamic characteristics have been estimated and analyzed. The experimental data were used to calculate standard thermodynamic functions, namely the heat capacity , enthalpy H^o(T) − H^o(0), entropy S^o(T) − S^o(0) and Gibbs function G^o(T) − H^o(T), for the range from T → 0 to (340–600) K. Linear dependences of changing the corresponding thermodynamic functions of the dendrimers on their molecular weight and the number of butyl groups on an outer sphere have been determined.     

纳米低温保护剂水合及玻璃化性质的DSC研究

利用差示扫描量热仪（DSC）研究了羟基磷灰石（HA）纳米微粒对丙三醇溶液冻结过程中水合性质及玻璃化性质的影响．实验结果表明在中高浓度HA纳米颗粒对溶液水合性质影响显著．与未加纳米颗粒的溶液相比,溶液结晶量减少,未冻水含量增大．在较低浓度溶液中,加入纳米颗粒后玻璃化温度变化不明显,但反玻璃化温度明显升高;当溶液浓度达到6...     

Devitrification behavior and structure of Li2O-B2O3-Al2O3 composite gels from metal alkoxides

(30 − x/2)Li₂O·(70 − x/2)B₂O₃·xAl₂O₃(x = 0, 5 and 10) composite gels have been fabricated by the sol-gel method. LiOCH₃, B(OC₄H₉)₃, and Al(OC₄H₉)₃ were used as precursor for Li₂O, B₂O₃, and Al₂O₃, respectively. B(OC₄H₉)₃ and Al(OC₄H₉)₃ were hydrolyzed separately and then mixed. The crystallization behavior and structure of the gels upon thermal treatment temperatures between 150 and 550 °C are characterized on the basis of SEM, XRD and IR analyses. Xerogel with x = 0 exhibits non-crystal features, whereas crystalline phases are found in the xerogels with x = 5 and 10. The crystalline phases are not found with increasing heat treatment temperatures from 150 to 450 °C, but crystalline phases appear present at 550 °C. The xerogel with x = 0, subject to thermal treatment below 450 °C, is found to be still amorphous, and a 550 °C heat treatment leads its structure changing from glassy to crystalline.     

Influence of superheat before quench on the structure and stability of NiP metallic glasses studied by neutron scattering techniques

The temperature dependent structure of Ni₈₁P₁₉ metallic glasses, rapidly quenched from melts which have undergone different heat treatments, has been investigated by small angle neutron scattering and neutron diffraction. All samples contain in the as-quenched state particles or clusters of a very wide range of sizes. These are amorphous regions of different compositions in a large composition range and/or crystallites of another Ni composition than the matrix, such as Ni₃P, Ni₅P₂ or Ni₁₂P₅, or even “voids”. The results can be interpreted within the concept of a heterogeneous structure existing in eutectic melts in a certain temperature range. Comparison is made with results from the literature on samples from the same ribbons investigated by calorimetry as well as by fractography and Weibull analysis of mechanical properties.