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Is glass a state of matter? 玻璃是物质的一种状态吗?
IF 0.6 4区 材料科学 Q4 CHEMISTRY, PHYSICAL Pub Date : 2022-07-28 DOI: 10.13036/17533562.63.5.15
Benjamin Guiselin, G. Tarjus, L. Berthier
Glass is everywhere. We use and are surrounded by glass objects which make tangible the reality of glass as a distinct state of matter. Yet, glass as we know it is usually obtained by cooling a liquid sufficiently rapidly below its melting point to avoid crystallisation. The viscosity of this supercooled liquid increases by many orders of magnitude upon cooling, until the liquid becomes essentially arrested on experimental timescales below the ‘glass transition‘ temperature. From a structural viewpoint, the obtained glass still very much resembles the disordered liquid, but from a mechanical viewpoint, it is as rigid as an ordered crystal. Does glass qualify as a separate state of matter? We provide a pedagogical perspective on this question using basic statistical mechanical concepts. We recall the definitions of states of matter and of phase transitions between them. We review recent theoretical results suggesting why and how an ‘ideal glass’ can indeed be defined as a separate equilibrium state of matter. We discuss recent success of computer simulations trying to analyse this glass state. We close with some experimental perspectives.
玻璃无处不在。我们使用并被玻璃物体所包围,这些物体使玻璃作为一种独特的物质状态的现实变得有形。然而,我们所知道的玻璃通常是通过将液体迅速冷却到熔点以下以避免结晶而获得的。这种过冷液体的粘度在冷却时增加了许多数量级,直到液体在低于“玻璃化转变”温度的实验时间尺度上基本停止。从结构的观点来看,得到的玻璃仍然很像无序的液体,但从力学的观点来看,它和有序的晶体一样坚硬。玻璃有资格作为一种独立的物质状态吗?我们使用基本的统计力学概念来提供这个问题的教学视角。我们回顾物质状态和它们之间相变的定义。我们回顾了最近的理论结果,这些结果表明为什么以及如何将“理想玻璃”确实定义为物质的独立平衡状态。我们讨论了最近成功的计算机模拟,试图分析这种玻璃状态。我们以一些实验观点作为结束。
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引用次数: 7
Properties of lithium aluminoborate glasses 铝酸锂玻璃的性能
IF 0.6 4区 材料科学 Q4 CHEMISTRY, PHYSICAL Pub Date : 2022-01-01 DOI: 10.13036/17533562.63.2.15
Kathleen A. Siuzdak Weber, J. Shelby
The density, refractive index, thermal expansion coefficient, glass transformation temperature and d.c. conductivity have been determined for a number of lithium aluminoborate glasses. The glasses studied lie on lines of constant Al2O3 to Li2O concentration with values of 0 (binary lithium borate glasses), 1/2 and 1/1. The thermal expansion coefficient passes through a minimum for all three series of glasses, while the glass transformation temperature for each series passes through a maximum. This behaviour is characteristic of the borate anomaly for all three series of glasses. Replacement of B2O3 by Al2O3 in these glasses has only a slight effect on the density and refractive index. The d.c. electrical conductivity of these glasses is controlled by the Li2O concentration, with little change due to replacement of B2O3 by Al2O3.
测定了几种铝酸锂玻璃的密度、折射率、热膨胀系数、玻璃化温度和直流电导率。所研究的玻璃位于Al2O3 - Li2O恒定浓度线上,值分别为0(二元硼酸锂玻璃)、1/2和1/1。三个系列玻璃的热膨胀系数都经过一个最小值,而每个系列的玻璃转变温度都经过一个最大值。这种行为是所有三个系列玻璃的硼酸盐异常的特征。在这些玻璃中,用Al2O3取代B2O3对密度和折射率只有轻微的影响。这些玻璃的直流电导电性受Li2O浓度的控制,由于Al2O3取代B2O3而变化不大。
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引用次数: 0
Water diffusion and solubility in sodium aluminosilicate melts 水在铝硅酸钠熔体中的扩散和溶解度
IF 0.6 4区 材料科学 Q4 CHEMISTRY, PHYSICAL Pub Date : 2022-01-01 DOI: 10.13036/17533562.63.5.09
D. B. Rapp, J. Shelby
The diffusivity and solubility of water at 1200°C has been measured in a series of sodium aluminosilicate melts. Both the diffusivity and solubility of water in these melts decrease as Na2O is replaced by Al2O3. The partial molar solubilities of SiO2, Na2O and Al2O3 have been determined. The diffusivity of water in these melts exhibits an inverse relationship with the viscosity of the melt, which can be extended to include sodium silicate melts at the same temperature. The glass transformation temperature of these glasses decreases with increasing water concentration. The magnitude of this effect is shown to be similar to that for many other compositional systems.
在一系列铝硅酸钠熔体中测定了水在1200℃时的扩散率和溶解度。当Na2O被Al2O3取代时,水在这些熔体中的扩散率和溶解度都降低了。测定了SiO2、Na2O和Al2O3的偏摩尔溶解度。水在这些熔体中的扩散率与熔体的粘度呈反比关系,这可以扩展到包括相同温度下的硅酸钠熔体。这些玻璃的玻璃化温度随水浓度的增加而降低。这种影响的程度与许多其他成分系统相似。
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引用次数: 0
Optical and electron paramagnetic resonance studies of VO2+ doped mixed alkali–alkaline earth oxide borate glass system 掺VO2+混合碱-碱土氧化硼酸盐玻璃体系的光学和电子顺磁共振研究
IF 0.6 4区 材料科学 Q4 CHEMISTRY, PHYSICAL Pub Date : 2022-01-01 DOI: 10.13036/17533562.63.2.78
G. Srinivas, J. Shiva Kumar, M. Shareefuddin, M. Chary, R. Sayanna
Glasses with the composition xK2O–(25−x) Li2O–12·5BaO–12·5MgO–48B2O3–2V2O5 (0≤x≤20) were prepared by the melt quenching method. The mixed alkali effect (MAE) has been investigated in the glass system through density, molar volume, optical absorption and EPR studies. VO2+ ions were used as the spin probes. From the optical absorption studies the values of the optical band gap (Eopt) for indirect transitions and the Urbarch energy (∆E) were evaluated. The values of Eopt, ∆E and density exhibited nonlinear behaviour with the variation of Li2O content, which may be attributed to the mixed alkali effect. The EPR spectra have structures which are characteristic of a hyperfine interaction arising from an unpaired electron with the 51V nucleus and it builds up in intensity as x increases. The spin-Hamiltonian parameters were evaluated from the EPR spectra. For x=0 mol%, the EPR spectrum was found to be more intense and well resolved. The variation of g‖ versus A‖ and N versus 1/x as a function of Li2O content was found to be nonlinear, which may be due to the mixed alkali effect. The results obtained were explained.
采用熔体淬火法制备了xK2O -(25−x) Li2O-12·5BaO-12·5MgO-48B2O3-2V2O5(0≤x≤20)的玻璃。通过密度、摩尔体积、光吸收和EPR研究了玻璃体系中的混合碱效应。用VO2+离子作为自旋探针。通过光吸收研究,计算了间接跃迁的光学带隙(Eopt)和厄巴奇能(∆E)。Eopt、∆E和密度随Li2O含量的变化呈非线性变化,这可能与混合碱效应有关。EPR谱具有由未配对电子与51V核产生的超精细相互作用的特征,并且随着x的增加而增强。利用EPR谱计算了自旋哈密顿参数。当x=0 mol%时,EPR光谱更强,分辨率更高。g‖对A‖和N对1/x随Li2O含量的变化是非线性的,这可能是由于混合碱的影响。对所得结果进行了说明。
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引用次数: 0
The structure of CaO–SiO2 and PbO–SiO2 glasses CaO-SiO2和PbO-SiO2玻璃的结构
IF 0.6 4区 材料科学 Q4 CHEMISTRY, PHYSICAL Pub Date : 2022-01-01 DOI: 10.13036/17533562.63.1.02
A. Wright, N. Vedishcheva
Whereas the cybotactic theory and thermodynamic modelling have proved invaluable tools in understanding the structures and properties of alkali silicate glasses, questions have been raised as to their validity for alkaline earth and related glasses such as PbO–SiO2. The present paper discusses the specific cases of the CaO–SiO2 and PbO–SiO2 systems, and it is shown that the presence of Si[3] units (silicate tetrahedra with three bridging and one nonbridging oxygen atoms) can easily be explained in terms of the thermodynamic equilibria that underlie the model of associated solutions and the cybotactic theory. Similarly, the much more random distribution of silicate tetrahedral species in PbO–SiO2 glasses derives from the amphoteric nature of PbO. A related question concerns the relevance of atomistic structural modelling/simulation to the evaluation of structural theories of glasses, but to date all of the models of binary silicate glasses have been generated using periodic boundary conditions, which means that they are incapable of reproducing the long range disorder that characterises the vitreous state. Furthermore, it is demonstrated that, in their present form, the RMC and related computer codes, such as EPSR, are fundamentally flawed, in that they merely involve the fitting of an early crystallite model to experimental diffraction data, albeit one where the average internal structure of the crystallites is based on a large highly disordered unit cell, but the crystallites themselves have an entirely unphysical shape. It is also concluded that, to fully interpret the structure of binary and multicomponent glasses, it is essential to study the relevant phase diagram, together with the structures of the thermodynamically-stable and metastable crystalline phases that occur in that particular glass-forming system, and to understand that, since the supercooled liquid is only transiently metastable, the cybotactic/chemical grouping species present in the final glass may not necessarily be determined by equilibrium thermodynamics, but may be greatly influenced by the quench rate. The temperature range over which these crystalline phases/polymorphs are stable is also important, as is the temperature dependence of the glass transition temperature, Tg, and its relationship to the solidus temperature, Ts, at the same composition. Only in this way is it possible to derive the maximum information concerning the structure of a given glass and, much more importantly, to explain why this glass has its particular structure. It is therefore concluded that the key to developing a comprehensive theory of the formation and structure of the vitreous state lies not with ever more precise determinations of the short range order (i.e. diffraction studies), but rather in understanding the role of the thermodynamic equilibria that drive the characteristic long wavelength fluctuations in both number density and composition that distinguish the vitreous from the crystall
尽管细胞动力学理论和热力学模型已被证明是理解碱硅酸盐玻璃结构和性质的宝贵工具,但它们对碱土和相关玻璃(如PbO-SiO2)的有效性提出了疑问。本文讨论了CaO-SiO2和PbO-SiO2体系的具体情况,结果表明,Si[3]单元(具有三个桥接氧原子和一个非桥接氧原子的硅酸盐四面体)的存在可以很容易地用相关溶液模型和细胞动力学理论基础上的热力学平衡来解释。同样,PbO - sio2玻璃中硅酸盐四面体的随机分布源于PbO的两性性质。一个相关的问题涉及到原子结构建模/模拟与玻璃结构理论评估的相关性,但迄今为止,二元硅酸盐玻璃的所有模型都是使用周期性边界条件生成的,这意味着它们无法再现表征玻璃状态的远程无序。此外,还证明了RMC和相关的计算机代码(如EPSR)在目前的形式下存在根本缺陷,因为它们仅仅涉及早期晶体模型与实验衍射数据的拟合,尽管其中晶体的平均内部结构是基于一个大的高度无序的单元胞,但晶体本身具有完全非物理的形状。为了充分解释二元和多组分玻璃的结构,有必要研究相关的相图,以及在特定的玻璃形成体系中发生的热力学稳定和亚稳晶相的结构,并了解由于过冷液体只是瞬态亚稳,最终玻璃中存在的细胞活性/化学基团不一定由平衡热力学决定,但可能受到淬火速率的极大影响。这些晶相/多晶稳定的温度范围也很重要,同样重要的是玻璃化转变温度Tg的温度依赖性,以及它与固体温度Ts的关系。只有这样,才有可能得出关于给定玻璃杯结构的最大信息,更重要的是,才能解释为什么这个玻璃杯具有其特定的结构。因此,得出结论,发展玻璃体状态形成和结构的综合理论的关键不在于更精确地确定短程顺序(即衍射研究),而在于理解热力学平衡的作用,这种平衡驱动了数字密度和组成的特征长波波动,从而将玻璃体与晶体状态区分出来。
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引用次数: 0
Phase separation and the properties of lithium strontium silicate glasses 硅酸盐锶锂玻璃的相分离与性能研究
IF 0.6 4区 材料科学 Q4 CHEMISTRY, PHYSICAL Pub Date : 2022-01-01 DOI: 10.13036/17533562.63.1.11
J. Shelby
The immiscibility region covers most of the region of glass formation in the lithium strontium silicate system. Although the density, refractive index, and thermal expansion coefficient are insensitive to the presence of phase separation, the glass transformation temperature can be used to determine the limit of immiscibility in this system. The dilatometric softening temperature was used to determine the boundary the limit of connectivity of the silica-rich phase. The electrical conductivity and activation energy for conduction were used to determine the limit of connectivity of the lithium-rich phase.
非混相区覆盖了硅酸锶锂体系玻璃形成的大部分区域。虽然密度、折射率和热膨胀系数对相分离的存在不敏感,但玻璃化转变温度可以用来确定该体系的不混相极限。用膨胀软化温度确定了富硅相的连接边界和极限。利用电导率和传导活化能来确定富锂相的连接极限。
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引用次数: 0
Comparative studies of structural and optical properties of Nb2O5–Sb2O3–TeO2 glass and glass-ceramics Nb2O5-Sb2O3-TeO2玻璃与微晶玻璃结构及光学性能的比较研究
IF 0.6 4区 材料科学 Q4 CHEMISTRY, PHYSICAL Pub Date : 2022-01-01 DOI: 10.13036/17533562.63.3.02
Rajesh Siripuram, P. Satya Gopal Rao, S. Sripada
A new, transparent antimony-tellurite glass and glass-ceramic systems doped with Nb2O5 have been prepared by using the conventional melt quenching method and heat treatment process, respectively. Various physical, optical and structural studies were reported through XRD, TEM, SEM, ultraviolet-visible, Raman, infrared and ESR investigations. XRD analysis of glass and glass-ceramic samples revealed their amorphous and crystalline natures, respectively. The Williamson-Hall approach was used to determine the average crystallite size of synthesised glass-ceramics and the values were found to be in the range of 23 to 85 nm. The SEM result reveals that glass-ceramics contain perspicuous and haphazardly distributed nanoclusters possessing sizes in the range of 45 to 120 nm. TEM analysis shows the size of particles in the glass-ceramics is in the range of 10 to 90 nm. The Eopt of the glass system has decreased from 2·873 to 2·606 eV, whereas in the glass-ceramic system it is observed to increase from 1·340 to 1·748 eV. Raman and infrared spectral analysis confirm the existence of various structural units such as TeO4, TeO3+1, TeO3, NbO6, NbO4, SbO3 in the glass and glass ceramic systems.The ESR spectral analysis reveals that the (Δg‖/Δg^) parameter seems to decrease from 4·444 to 2·453 in glass sytem, whereas in glass-ceramics it is observed to increase from 2·357 to 4·188. Glass transition temperature and onset crystalline temperatures are influenced by the Nb2O5 in both glass and glass-ceramic samples.
采用传统的熔体淬火法和热处理工艺制备了新型透明碲酸锑玻璃和掺Nb2O5的玻璃陶瓷体系。通过x射线衍射(XRD)、透射电镜(TEM)、扫描电镜(SEM)、紫外可见光谱(uv)、拉曼光谱(Raman)、红外光谱(ir)和ESR等方法对其进行了物理、光学和结构研究。玻璃和玻璃陶瓷样品的XRD分析分别显示了它们的非晶和结晶性质。Williamson-Hall方法用于测定合成微晶玻璃的平均晶粒尺寸,其值在23至85 nm之间。扫描电镜结果表明,微晶玻璃含有明显的、随机分布的纳米团簇,其尺寸在45 ~ 120 nm之间。TEM分析表明,微晶玻璃的颗粒尺寸在10 ~ 90nm之间。玻璃体系的Eopt从2.873 eV下降到2.606 eV,而玻璃陶瓷体系的Eopt从1.340 eV增加到1.748 eV。拉曼光谱和红外光谱分析证实了玻璃和玻璃陶瓷体系中存在TeO4、TeO3+1、TeO3、NbO6、NbO4、SbO3等多种结构单元。ESR谱分析表明,(Δg‖/Δg^)参数在玻璃体系中从4.444减小到2.453,而在微晶玻璃体系中从2.357增大到4.188。Nb2O5对玻璃和玻璃陶瓷样品的玻璃化转变温度和起晶温度均有影响。
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引用次数: 1
ALD deposited amorphous alumina coatings can slow glass alteration ALD沉积的非晶氧化铝涂层可以减缓玻璃蚀变
IF 0.6 4区 材料科学 Q4 CHEMISTRY, PHYSICAL Pub Date : 2022-01-01 DOI: 10.13036/17533562.63.4.07
M. Hiebert, Jamie L. Weaver, T. Lam, N. Little, Ethan Hyde, E. Vicenzi, R. Phaneuf
Atomic layer deposited (ALD) amorphous aluminium oxide and titanium oxide coatings have been investigated for use in reducing the rate of silicate glass alteration. Mass spectrometric analysis of leachate from elevated temperature aqueous immersion alteration experiments showed a marked decrease in the concentration of released Na and Si from the glass when the vitrified material was ALD coated as compared to uncoated glass. This decrease is consistent with the proposed protective effect of the ALD coating. Additionally, visual observations indicate formation of significant amounts of amorphous, secondary phase sediment for immersed, uncoated glass. This sediment was not present in the solution of the ALD coated and altered glass samples. However, the ALD coating did delaminate after protracted immersion, a likely limiting factor of the efficacy of ALD coatings. This limitation may be mitigated through a proposed refinement of the ALD coating procedure.
研究了原子层沉积(ALD)非晶氧化铝和氧化钛涂层在降低硅酸盐玻璃蚀变率方面的应用。通过对高温浸泡蚀变实验所得渗滤液的质谱分析发现,与未涂覆玻璃相比,涂覆ALD后玻璃中Na和Si的释放浓度明显降低。这种减少与ALD涂层提出的保护作用是一致的。此外,视觉观察表明,浸入式未镀膜玻璃形成了大量无定形的二次相沉积物。这种沉积物不存在于ALD涂层和改变玻璃样品的溶液中。然而,ALD涂层在长时间浸泡后确实分层,这可能是ALD涂层效果的限制因素。这一限制可以通过改进ALD涂层工艺得到缓解。
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引用次数: 0
Intrinsic strength and the structure of glass 玻璃的内在强度和结构
IF 0.6 4区 材料科学 Q4 CHEMISTRY, PHYSICAL Pub Date : 2020-12-12 DOI: 10.13036/17533562.61.6.KURKJIAN
C. Kurkjian, P. Gupta
Intrinsic strength is the strength of a glass without extrinsic flaws. Knowledge of the composition dependence of the intrinsic strength is important both technologically for the development of high strength glass compositions and theoretically as it may provide important structural information. Intrinsic strength is easy to define but difficult to measure experimentally. In this paper we discuss intrinsic (σ*) strength measured in normal laboratory conditions as well as the inert intrinsic (σ0*) strength. We define these terms in a rigorous manner and indicate how to gauge if they have been measured by developing a set of criteria. Based on these criteria, we tabulate those values of intrinsic strengths that have been measured to date.
内在强度是指没有外在缺陷的玻璃的强度。了解成分对内在强度的依赖关系对于开发高强度玻璃成分在技术上和理论上都是重要的,因为它可以提供重要的结构信息。固有强度很容易定义,但很难通过实验测量。本文讨论了在正常实验室条件下测量的本征强度(σ*)和惰性本征强度(σ0*)。我们以严格的方式定义这些术语,并指出如何通过开发一组标准来衡量它们。基于这些标准,我们将迄今为止测量过的内在优势的值制成表格。
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引用次数: 2
Generalised kinetics of overall phase transition useful for glass crystallisation when assuming non-isothermal conditions 假定非等温条件时,对玻璃结晶有用的总体相变的广义动力学
IF 0.6 4区 材料科学 Q4 CHEMISTRY, PHYSICAL Pub Date : 2020-12-12 DOI: 10.13036/17533562.61.6.006
I. Avramov, J. Šesták
The modelling of reaction kinetics is a fashionable subject of publications. We developed an analogue of the KJMA equation under non-isothermal conditions α(T)=1−exp(−(T/θ)N) that describes the dependence of degree of transformation α(T) at a constant rate, q, of heating with characteristic temperature θ(q) and power N, proportional to the Avrami parameter, n. This equation is valid even when the activation energy of the process is not constant. We demonstrate that reliable information about the activation energy is obtained when the experimental data are plotted in coordinates: logq (heating rate) against logTp (peak temperature).
反应动力学的建模是出版物的时髦主题。我们建立了一个非等温条件下α(T)=1−exp(−(T/θ)N)的近似的KJMA方程,它描述了在恒定速率q下,特征温度θ(q)和功率N与Avrami参数N成正比的转变程度α(T)的依赖关系。该方程即使在过程的活化能不恒定时也是有效的。我们证明,当实验数据在坐标:logq(升温速率)和logTp(峰值温度)中绘制时,可以获得有关活化能的可靠信息。
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引用次数: 2
期刊
Physics and Chemistry of Glasses-European Journal of Glass Science and Technology Part B
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