Young׳s modulus,Vickers hardness and indentation fracture toughness of alumino silicate glasses

A wide range of alumino silicate glasses with different network modifier ions (Li, Mg, Na, Ca, Zn, La, Ba, Sr, and Pb) was prepared. The glasses were studied with respect to their mechanical properties: Poisson׳s ratio, Young׳s modulus, Vickers hardness and indentation fracture toughness. These properties were mostly affected by the field strength of network modifier ions. All determined properties increase with increasing field strength of the network modifier ions. The mixed modifier alumino silicate glasses with zinc and magnesium show a positive deviation from linearity with two maxima. Lanthanum containing glasses show larger values of mechanical properties for higher lanthanum concentrations. For magnesium alumino silicate glasses the mechanical properties get smaller with increasing SiO₂ concentration; an effect of the magnesium concentration is not observed. Furthermore, if up to 9 mol% MgO is replaced by MgF₂ the mechanical properties are not significantly affected. Compared to models predicting Young׳s moduli of all studied glass compositions, significant deviations are found.     

The critical organic modifier aliphatic tail length for the formation of poly(methyl methacrylate)-montmorillonite nanocomposites

In this article, we report the influence of organic modifier structure (alkyl chain length C8-C20, single vs ditallow) and thereby, the effect of hydrophobicity on the structure, thermal and mechanical properties of poly(methyl methacrylate) (PMMA)-clay hybrids. Melt processed PMMA-clay hybrids were characterized using wide-angle X-ray diffraction, transmission electron microscopy, and differential scanning calorimetry. The organoclays having an alkyl chain length of more than 12 CH₂ groups resulted in the formation of nanocomposites. The glass transition temperature (T_g) of PMMA increased in the presence of clay. The mean-field lattice model was used to predict the free energy for nanocomposite formation, which showed a reasonable match with the experimental results and provided a general guideline for the proper selection of polymer and organoclay (ie, organic modifier) to obtain nanocomposite. Tensile modulus showed maximum improvement of 58% for the nanocomposites compared to 9% improvement for the composites. Tensile modulus increased with increases in the alkyl chain length of the organic modifier and clay loading. The level of improvement for the tensile properties of nanocomposites prepared from primary and secondary ammonium-modified clay is the same as that obtained with the commercial organoclays.     

Structural and emission properties of Eu3+‐doped alkaline earth zinc‐phosphate glasses for white LED applications

Quaternary alkaline earth zinc‐phosphate glasses in molar composition (40 ? x)ZnO – 35P₂O₅ – 20RO – 5TiO₂ – xEu₂O₃ (where x=1 and R=Mg, Ca, Sr, and Ba) were prepared by melt quenching technique. These glasses were studied with respect to their thermal, structural, and photoluminescent properties. The maximum value of the glass transition temperature (T_g) was observed for BaO network modifier mixed glass and minimum was observed for MgO network modifier glass. All the glasses were found to be amorphous in nature. The FT‐IR suggested the glasses to be in pyrophosphate structure, which matches with the theoretical estimation of O/P atomic ratio and the maximum depolymerization was observed for glass mixed with BaO network modifier. The intense emission peak was observed at 613 nm (⁵D₀→⁷F₂) under excitation of 392 nm, which matches well with excitation of commercial n‐UV LED chips. The highest emission intensity and quantum efficiency was observed for the glass mixed with BaO network modifier. Based on these results, another set of glass samples was prepared with molar composition (40 ? x)ZnO – 35P₂O₅ – 20BaO – 5TiO₂ – xEu₂O₃ (x=3, 5, 7, and 9) to investigate the optimized emission intensity in these glasses. The glasses exhibited crystalline features along with amorphous nature and a drastic variation in asymmetric ratio at higher concentration (7 and 9 mol%) of Eu₂O₃. The color of emission also shifted from red to reddish orange with increase in the concentration of Eu₂O₃. These glasses are potential candidates to use as a red photoluminsecent component in the field of solid‐state lighting devices.     

Mixed modifier effect in Na2O·K2O·CaO aluminosilicate glasses: Pairwise and ternary interactions

The mixed modifier effect (MME) is one of the most challenging puzzles in the field of oxide glasses, as there exists no universal quantitative theoretical model for accurately describing and predicting the nonlinear deviation of property values. In this paper, pairwise and ternary interactions are examined experimentally to understand the MME in a series of aluminosilicate glasses. By keeping the glass network former concentration constant and adjusting the molar ratios of three network modifiers (Na₂O, K₂O, and CaO), the MMEs in glass transition temperature (T_g), Vickers hardness (H_v), and activation energy (E_a) for aqueous dissolution for each modifier cation are investigated. We examine whether a pairwise interaction model is sufficient, or if ternary interactions also need to be included to predict the MME in these aluminosilicate glass systems. This work reveals that the pairwise model can be used to predict the MME for T_g in complex multiple-modifier glass systems using only two-body interaction factors. However, ternary mixed-modifier interactions are present in other properties such as H_v and E_a.     

Field strength effect on elastoplastic behavior of aluminoborosilicate glass: I. Elastic moduli and indentation size effect

The modifier field strength (FS) is believed to play an important role in determining the elastic–plastic responses of aluminoborosilicate (ABS) glasses, but its effect is not well understood. Three novel alkali and three alkaline earth (AE) ABS compositions were created for this study which is the first part of two studies that explored the elastoplastic responses of these glasses. Six compositions were designed using different network modifiers (NWMs) to cover a range of cation FS. The glasses were also designed such that the concentrations of NWM and Al₂O₃ were similar, which maximized the three-coordinated boron fraction in the network. It is well known that modifier FS can affect the coordination number (CN) of Al and B in an ABS glass structure, for example, a higher FS modifier can promote B³ → B⁴ and higher [Al^5,6], but the degree of this depends on network former (NWF) ratios. Previous work used solid-state NMR spectroscopic analysis on the current glasses to find that there was variation between [B⁴] and [Al⁴] between the two glass series (alkali vs. AE) but that was attributed to synthesis factors and no trend with FS was associated with the varying NWF CN. Further, ²⁹Si ssNMR showed no evidence of NBOs which made sense based on composition. The conclusion, therefore, was that there was a far greater correlation with modifier FS for the increased mechanical and physical properties rather than the CN of Al and B. Part I of the current work focused on the elastic moduli, Poisson's ratio, the indentation size effect (ISE), and the bow-in parameter. This part laid out the foundation to investigate the intersection of these elastoplastic properties with hardness and crack resistance as a function of NWM FS. Results showed that: (i) the Young's, bulk, and shear moduli increased with modifier FS, whereas Poisson's ratio did not trend with FS; (ii) the alkali glasses had a significantly higher magnitudes of ISE compared to the AE glasses; and (iii) the bow-in parameter was load dependent and decreased with modifier FS at the highest indentation load.     

Compositional effects on the crosslink density of Ca–(Mg)–(Y)–Si–Al–oxyfluoronitride glasses

The effects of fluorine and nitrogen substitution for oxygen in aluminosilicate glasses, effectively oxyfluoronitride (OFN) glasses, modified by calcium, calcium–yttrium or calcium–magnesium on thermal and physical/mechanical properties have been compared. Thus, 42 glasses in the Ca–(Mg)–(Y)–Si–Al–O–(N)–(F) system have been prepared and characterized with respect to density (ρ), molar volume (MV), compactness (C), free volume (FV), glass transition temperatures measured by DTA (T_g,DTA) and dilatometry (T_g,dil), dilatometric softening point (T_DS), microhardness (μHv) and Young's modulus (E). Gradients of property variation with nitrogen or fluorine substitutions for oxygen are similar for all three different oxyfluoronitride glass systems and are comparable with those reported for other OFN glasses, again indicating independent and additive effects of nitrogen and fluorine. In attempting to further understand how fluorine affects the cross‐link density (CLD) in OFN glasses, it becomes apparent that it is necessary to allow for a greater contribution by aluminum in a modifier role as fluorine content is increased. This modified calculation of CLD values results in good linear fits between T_g and CLD values. This analysis clearly demonstrates and endorses the concepts that thermal properties are related to CLD while physical/mechanical properties are dependent on glass compactness.     

Polymer/clay nanocomposite plasticization: Elucidating the influence of quaternary alkylammonium organic modifiers

The potential of nanoclay organic modifiers to induce plasticizing effects in resin and coatings systems was studied. In previous work, it was found that while low amounts of incorporation of organomodified clays significantly improved the physical and mechanical properties of a ultraviolet (UV)‐curable nanocomposite, further increasing the organomodified clay content could result in the reduction of properties. To investigate the potential impact of the organic modifier composition and concentration on polymer properties, a series of experiments were carried out using only the organic modifier. Methyl, tallow, bis‐2‐hydroxyethyl ammonium (MTEtOH), the organic modifier used in montmorillonite clay Cloisite® 30B, was dispersed with precursor polyester oligomers at 1–10 wt % through an in situ synthesis process and via sonication, and UV‐curable coatings were prepared from these MTEtOH‐containing resins. The organic modifier cetyltrimethylammonium bromide (CTAB) was also studied to examine the impact of the organic modifier structure. According to differential scanning calorimetry, small decreases in the glass transition temperatures (T_g) of the MTEtOH‐containing polyesters were observed, but CTAB‐containing polyesters had small T_g increases. Polyester molecular weight and viscosity were also affected by both the structure of the organic modifier as well as its concentration. The mechanical performance of the UV‐curable coatings diminished with increased MTEtOH concentration for the films containing the organic modifier compared to a control film. Furthermore, the crosslink density was found to reduce ～ 50% with increased MTEtOH loading into the UV‐curable films. The cure characteristics, thermal stability, and optical clarity were also studied. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Tuning the thermal and insulation properties of bismuth borate glass for SiC power electronics packaging

Silicon carbide (SiC) power devices are attracting significant attention due to their outstanding stability in high-voltage, high-temperature, and high-frequency environments. To replace toxic Pb-based glass, there is an urgent need to develop Pb-free glass for SiC power device encapsulation, considering its superior electrical insulation properties and processing capabilities. Here, we developed a Bi-based glass for effective encapsulation practical of SiC power devices. By increasing the content of glass modifier BaO, the structure of bismuth borate glass can be tuned to reduce glass network density, leading to the transition of structural units from [BO₄] to [BO₃]. The softened temperature is reduced to 363.4°C with the BaO content increasing to 15 mol%. After encapsulating the SiC power devices using Bi-based glass, the glass demonstrated a reverse breakdown voltage of 650 V and an extremely low leakage current. Therefore, our work provided a route for adapting Pb-free-based low-melting glass for encapsulating SiC devices and offered potential for advanced semiconductor packaging.     

Cation Field Strength Effects on Boron Coordination in Binary Borate Glasses

The field strength of modifier cations in boron‐containing oxide glasses has important but complex effects on boron coordination, and has long been known to have major effects on glass and liquid properties. With well‐constrained compositional and fictive temperature information in three binary borate glass series, we report how different modifier cations (Na⁺, Ba²⁺, Ca²⁺) affect boron coordination (¹¹B MAS NMR), as well as glass transition temperatures and configurational heat capacities (DSC). Using estimated reaction enthalpies for converting a ^[4]B to a ^[3]B with an NBO from previous studies, we compare boron coordinations in glasses with different modifier cations on an isothermal basis. Temperature and modifier cation effects can thus be isolated. At low modifier contents [R = (Na₂,Ca,Ba)O/B₂O₃<0.45], N₄ is systematically higher in the order Na>Ba>Ca, suggesting the enhanced stabilization of NBO for the divalent cations, especially for the smaller Ca²⁺. At higher R values, N₄ for Na borates drops below values for Ca and Ba borates. The trend in N₄ with modifier field strength reverses at high R values (~ R > 0.7), with Ca > Ba > Na. The transition may be related to the enhanced stabilization of ^[4]B‐O‐^[4]B groups by higher field strength cations in NBO‐rich glasses in which boron is the primary network component.     

Morphological and optical behavior of thermoset matrix composites varying both polystyrene-block-poly(ethylene oxide) and TiO2 nanoparticle content

Novel inorganic/organic epoxy based materials were fabricated using both poly(styrene-b-ethylene oxide) (SEO) block copolymer and synthesized TiO₂ nanoparticles as modifier. The influence of the ratio between modifiers on the final morphology generated in the investigated epoxy systems was studied by atomic force microscopy (AFM) and transmission electron microscopy (TEM). Results indicated that even for high nanoparticle content, TiO₂ nanoparticles synthesized via sol-gel were homogenously dispersed in the epoxy-rich phase. The morphology of the inorganic/organic epoxy based composites consisted of both well-dispersed TiO₂ nanoparticles and microphase separated PS block in the continuous PEO block/epoxy-rich phase since block copolymer acted as templating agent for selective location of TiO₂ nanoparticles. Differential scanning calorimetry (DSC) was used to study the curing behavior and the influence of the type and quantity of modifier on the glass transition temperature of epoxy matrix. Additionally, optical properties, transparency and UV-shielding efficiency of these new multiphase advanced thermosetting materials were also investigated.     

Mechanical,Structural and Thermal Properties of Transparent Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–ZnO–TeO<Subscript>2</Subscript> Glass System

Oxide based optical glass materials has important potential material in many applications from fiber optic to sensor due to the high transparency and amourphous structures. The objective of this study is to synthesize the novel optical glass materials based on the bismuth and aluminum contents to be able to determine the physical, chemical and mechanical properties by considering the systematic experimental steps. In this study, Bi₂O₃–Al₂O₃ based tellurite optical glasses have been prepared by using conventional melt quenching method as a function of the both Bi₂O₃ and Al₂O₃ compositions. There is a strong interactions between the glass former and modifier ions that might effect on the structure and mechanical properties. During the experimental steps, thermal, structural and mechanical properties of the prepared glass materials have been determined considering the DTA/DSC, FT-IR spectroscopy, SEM and Vicker’s hardness techniques, respectively. Thermal parameters, like glass transition, T_g, onset, T_x, crystallization, T_p, and melting, T_m, temperatures were obtained by using DTA scan.     

Field strength effect on structure,hardness, and crack resistance in single modifier aluminoborosilicate glasses

Although the interactions among glass formers and modifiers, for example, connectivity and charge distribution, have been studied extensively in oxide glasses, the impact of a particular modifier species on the mechanical performance of aluminoborosilicate (ABS) glasses is not well understood. This work compares the indentation properties of six ABS glasses, each of which contains a different network modifier (NWM) with varying field strength (FS). Three alkali and three alkaline earth ABS glasses were designed with low NWM content and [NWM] ≈ [Al₂O₃], to test the modifier FS effect at low concentrations and to maximize three-coordinated boron. It has been found that both hardness and crack resistance increase with increasing FS in these ABS systems, which is surprising in the context of historical reports. Using ¹¹B, ²⁷Al, and ²⁹Si solid-state nuclear magnetic resonance, this work provides evidence of how charge distributions differ as a function of NWM species, and how this relates to the observed indentation behaviors.     

Factors Controlling Properties of Ca‐Mg,Ca‐Er,Ca‐Nd,or Ca‐Y‐Modified Aluminosilicate Glasses Containing Nitrogen and Fluorine

Glasses with composition (in eq.%) (30 ? x)Ca:xM:55Si:15Al:80O:15N:5F have been prepared with different levels of substitution of Ca²⁺ cations by Mg²⁺, Y³⁺, Er³⁺, or Nd³⁺. The properties of these glasses are examined in detail and changes observed in molar volume (MV), free volume, fractional glass compactness, Young's modulus, microhardness, glass transition temperature, and thermal expansion as a function of M content are presented. Using linear regression analysis, evidence is presented which clearly shows that these glass properties are either solely dependent on the effective cation field strength, if modifier cation valency is the same (e.g., Mg substitution for Ca), or dependent on the effective cation field strength and the number of (Si, Al) (O, N, F) tetrahedra associated with each modifier when Ca is replaced by the trivalent modifiers. Combining these correlations with those observed previously relating glass properties to N and F substitution for O, it becomes apparent that glass properties for Ca–M–Si–Al–O–N–F glasses can be described by correlations which involve independent, but additive contributions by N and F substitution levels, effective cation field strength, and the number of tetrahedra associated with each modifier ion.     

Modification of Glass Fiber-Reinforced Epoxy with Amine Functional Aniline Formaldehyde Condensate (AFAFC)

Unmodified epoxy glass fiber laminates are brittle by nature. In this study, an improvement of the mechanical properties, such as impact, tensile and flexural strengths of the reinforced glass fiber diglycidyl ether of bisphenol-A based epoxy laminate, was carried out by incorporating an amine functional aniline formaldehyde condensate (AFAFC) modifier. AFAFC was synthesized by reacting aniline and formaldehyde in an acid medium (pH 4) and was characterized by FT-IR and 1-H NMR spectroscopy, viscosity measurements, elemental analysis and potentiometric titration. The fracture energies of the modified glass fiber composite were vastly improved and the improvement depended on the concentration of the modifier. The optimum properties were obtained by adding 10 phr (parts per hundred parts of epoxy resin) of the modifier. Furthermore, the fracture energies of the modified glass fiber composite increased with increasing the number of glass fiber layers. Scanning electron microscopy showed that round shaped AFAFC oligomer domains were formed in the matrix. These oligomer domains led to improved strength and toughness due mainly to the 'rubber toughening' effect in the brittle epoxy matrix. The thermal stability of the modified epoxy composites by thermogravimetric analysis was also reported.     

Characterisation of glasses in the TeO2–WO3–PbO system

As potential candidates for photonic devices, non-linear materials and coatings, 22 glasses in the TeO₂–WO₃–PbO system have been formulated and prepared by conventional melting at temperatures ranging between 710 and 750 °C. The glass forming area has been determined for a wide region of the corresponding ternary diagram. Structural characterisation of the glasses was conducted through FTIR spectrometry and the variation of density values, which allowed calculation of the glass molar volume and the oxygen molar volume. UV–VIS spectra were recorded to determine optical absorption/transmission and energy gap values. Likewise, such results were correlated with the glasses composition and their ability for optical materials. DTA curves yielded data of transition temperature (T_g), onset crystallisation temperature (T_c) and the thermal stability range of glasses. Crystalline phases formed in devitrified and partially devitrified glasses were detected by X-ray diffraction. The properties and structural features of glasses were discussed in terms of their relative proportion of former/modifier oxides. The main glass former oxide is TeO₂, which arranges [TeO₄] groups with tetrahedral coordination, while PbO plays as glass modifier oxide. Tungsten oxide is incorporated as network former, alternating with TeO₂ and forming mixed linkages Te–O–W and W–O–W. WO₃ is the component that contributes most to increase the glass transition temperature, and to decrease both the oxygen molar volume and the thermal expansion coefficient.     

Glass forming,crystallization, and physical properties of MgO-Al2O3-SiO2-B2O3 glass-ceramics modified by ZnO replacing MgO

This study focused on the glass forming, crystallization, and physical properties of ZnO doped MgO-Al₂O₃-SiO₂-B₂O₃ glass-ceramics. The results show that the glass forming ability enhances first with ZnO increasing from 0 to 0.5 mol%, and then weakens with further addition of ZnO which acted as network modifier. No nucleating agent was used and the crystallization of studied glasses is controlled by a surface crystallization mechanism. The predominant phase in glass-ceramics changed from α-cordierite to spinel/gahnite as ZnO gradually replaced MgO. The phase type did not change; however, the crystallinity and grain size in glass-ceramics increased when the glasses were treated from 1030 °C to 1100 °C. The introduction of ZnO can improve the thermal, mechanical, and dielectric properties of the glass-ceramics. The results reveal a rational mechanism of glass formation, crystal precipitation, and evolution between structure and performance in the xZnO-(20-x)MgO-20Al₂O₃-57SiO₂-3B₂O₃ (0 ≤ x ≤ 20 mol%) system.     

Synthesis of a difunctional organolithium compound as initiator for the polymerization of styrene‐butadiene/isoprene‐styrene triblock copolymer

A difunctional organolithium compound was prepared by the addition of butyllithium (BuLi) to 1,4‐bis(4‐methyl‐1‐phenylethenyl)benzene (MPEB). The effects of the solvent, polar modifier (THF), butyl lithium structure, and reaction time on the formation of the difunctional organolithium compound were studied. Results showed that toluene as solvent was in favor of the addition reaction over cycohexane, in the absence of the polar modifier. However, cycohexane was a better option as solvent for the addition reaction, when polar modifier was employed. A small amount of polar modifier could efficiently accelerate the reaction rate and have no significant effect on the structure of the polydiene, which was initiated by the polar modifier containing organolithium compound. Results also showed that isobutyl lithium was more active in the addition reaction than n‐butyl lithium, because of inductive effect. The optimum molar ratio of THF/Li+ was determined as 4. The THF containing difunctional organolithium cyclohexane solution was sequentially used in the step‐wise polymerization of triblock thermoplastic copolymer SIBS. The so‐prepared SIBS shared the similar phase separation structure with SBS and exhibited excellent mechanic properties. As the content of the central polyisoprene block increases, the tensile strength of the copolymer is decreased, and the elongation at break is increased. The glass transition temperature T_g of the central block was correlated with its content as T_g = 0.33 × ?62.81, where × is the wt % of the central block, based on the triblock copolymer. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1395–1402, 2006     

Dependence of the Hydrogen Permeability Coefficient in Glasses of the Sodium-Silicate System on the Silica Modulus

The system Na₂O – SiO₂ used in designing compositions for producing gas microcontainers (microspheres) is investigated. Based on a known equation, an expression is obtained for the dependence of the hydrogen permeability coefficient of glass on its silica modulus. It is established that the alkaline modifier even in the form of an impurity can influence gas permeability. A conclusion is made on the need to apply criterial valuations in designing glasses. A nomogram is obtained for determining the silica modulus, hydrogen permeability coefficient, phase composition, and probability of glass formation in the Na₂O – SiO₂ system.     

Revealing structural role of ZrO2 in silicate glasses from macroscale property by rigid-unit packing fraction method

The structural role of an oxide as a former and modifier can have significant effects on the chemical durability and mechanical properties of the glass. Some oxides with high-field strength cations, for example, MgO and ZrO₂, are often labeled as a third group—intermediate, due to their either undetermined or dual structural roles dependent on the glass compositions. Based on our recent modification of the Makishima–Mackenzie (MM) model using the rigid-unit Packing Fraction (RUPF), we analyzed a series of novel zirconia-containing bioactive glasses. The RUPF-based MM-model provides better prediction of the elastic moduli of these new glasses in comparison to experimental measurements. At the same time, the structural role of zirconia can be determined by comparison with calculations by assuming various structural roles and those from experiments. We reveal that ZrO₂ acts as the network former in phosphosilicate glasses, which leading to significant increase in packing fraction and consequent increase in Young's modulus. The recent experimental and atomistic simulation results support the glass former role of zirconia in silicate glasses. This method is general and applicable to other oxides in glasses.     

Thermal aging of impact-modified polycarbonate

Glassy polymers undergo relatively rapid physical aging just below their glass transition temperatures that can lead to embrittlement of normally tough materials like polycarbonate (PC). One approach for solving the embrittlement problem is to incorporate an impact modifier that can cause toughening when the matrix loses its inherent ductility due to physical aging. The effects of thermal aging below the glass transition temperature of polycarbonate on selected properties of blends of PC with various core-shell impact modifiers have been studied. Observed changes in mechanical properties are related to rubber content, free volume, fracture morphology, discoloration, enthalpy relaxation, glass transition temperature, intrinsic viscosity, and dynamic mechanical behavior. Blend mechanical properties are affected by chemical changes in the impact modifier that occur simultaneous with the physical aging of the PC matrix. The degradation mechanisms involved reduce the effectiveness of the modifier for toughening and also lead to a loss of molecular weight of the PC matrix. Blends containing 10% methacrylated butadiene-styrene (MBS) core-shell impact modifiers give the maximum extension of time to embrittlement at 135°C in air. More thermally stable modifiers are required for further extending the ductile mode of failure for physically aged PC blends.