arXiv subjects

P. Boolchand

Publications and source records attributed to P. Boolchand.

27 records · Page 2Linked to original sources

arXiv2006

Onset of rigidty in glasses: from random to self-organized networks

We review in this paper the signatures of a new elastic phase that is found in glasses with selected compositions. It is shown that in contrast with random networks, where rigidity percolates at a single threshold, networks that are able to self-organize to avoid stress will remain in an almost stress- free state during a compositional interval, an intermediate phase, that is bounded by a flexible phase and a stressed rigid phase. We report the experimental signatures and describe the theoretical efforts that have been accomplished to characterize the intermediate phase. We illustrate one of the methods used in more detail with the example of Group III chalcogenides and finally suggest further possible experimental signatures of self-organization.

cond-mat.mtrl-sci↗

arXiv2005

Pressure Raman Effects and Internal Stress in Network Glasses

Raman scattering from binary GexSe1-x glasses under hydrostatic pressure shows onset of a steady increase in the frequency of modes of corner-sharing GeSe4 tetrahedral units when the external pressure P exceeds a threshold value Pc. The threshold pressure Pc(x) decreases with x in the 0.15 < x < 0.20 range, nearly vanishes in the 0.20 < x < 0.25 range, and then increases in the 0.25 < x < 1/3 range. These Pc(x) trends closely track those in the non-reversing enthalpy, DeltaHnr(x), near glass transitions (Tgs), and in particular, both DeltaHnr(x) and Pc(x) vanish in the reversibility window (0.20 < x < 0.25). It is suggested that Pc provides a measure of stress at the Raman active units; and its vanishing in the reversibility window suggests that these units are part of an isostatically rigid backbone. Isostaticity also accounts for the non-aging behavior of glasses observed in the reversibility window.

cond-mat.dis-nn↗

arXiv2005

Self-Organization and the Physics of Glassy Networks

Network glasses are the physical prototype for many self-organized systems, ranging from proteins to computer science. Conventional theories of gases, liquids, and crystals do not account for the strongly material-selective character of the glass-forming tendency, the phase diagrams of glasses, or their optimizable properties. A new topological theory, only 25 years old, has succeeded where conventional theories have failed. It shows that (probably all slowly quenched) glasses, including network glasses, are the result of the combined effects of a few simple mechanisms. These glass-forming mechanisms are topological in nature, and have already been identified for several important glasses, including chalcogenide alloys, silicates (window glass, computer chips), and proteins.

cond-mat.dis-nn↗

arXiv2005

The Thermally Reversing Window in Ternary GexPxS1-2x glasses

GexPxS1-2x glasses in the compositional range 0.05 < x < 0.19 have been synthesized and examined in temperature modulated differential scanning calorimetry (MDSC) and Raman scattering experiments. Trends in the non-reversing enthalpy DHnr(x) near Tg show the term to almost vanish in the 0.090(5) < x < 0.135(5) range, and to increase by an order of magnitude at x < 0.09, and at x > 0.135. In analogy to previous results on chalcogenide glasses, we identify compositions at x < 0.09 to be elastically floppy, those in the 0.090 < x < 0.135 range to be in the intermediate phase, and those at x > 0.135 to be stressed rigid. MDSC results also show the DHnr term ages in the stressed-rigid and floppy phases but not in the intermediate phase. The intermediate phase is viewed to be a self-organized phase of a disordered network. It consists of at least four isostatically rigid local structures; corner-sharing GeS4, edge-sharing GeS2, pyramidal P(S1/2)3 and quasi-tetrahedral S=P(S1/2)3 units for which evidence comes from Raman scattering. The latter method also shows existence of P4S7 and P4S10 molecules in the glasses segregated from the backbone. These aspects of structure contribute to an intermediate phase that is significantly narrower in width than in corresponding selenide glasses.

cond-mat.dis-nn↗

arXiv2004

Direct evidence of rigidity loss and self-organisation in silicate glasses

The Brillouin elastic free energy change $DF$ between thermally annealed and quenched $(Na_2O)_x(SiO_2)_{1-x}$ glasses is found to decrease linearly at $x > 0.23$ (floppy phase), and to nearly vanish at $x < 0.18$ (stressed- rigid phase). The observed $D F(x)$ variation closely parallels the mean-field floppy mode fraction $f(x)$ in random networks, and fixes the two (floppy, stressed-rigid) elastic phases. In calorimetric measurements, the non-reversing enthalpy near $T_g$ is found to be large at $x < 0.18$ and at $x > 0.23$, but to nearly vanish in the $0.18 < x < 0.23$ range, suggesting existence of an intermediate phase between the floppy and stressed-rigid phases.

cond-mat.mtrl-sci↗

arXiv2003

Reversibility Window, Aging, and Nanoscale Phase Separation in GexAsxS1-2x Bulk Alloy Glasses

The non-reversing enthalpy near Tg, DHnr, in bulk GexAsxS1-2x glasses is found to display a global minimum (~0) in the 0.11 < x < 0.15 range, the reversibility window. Furthermore, the DHnr term is found to age for glass compositions both below (x < 0.11) and above (x > 0.15) the window but not in the window. Glass compositions in the window are rigid but stress-free, those below the window are floppy, and those above the window are stressed-rigid. Raman scattering shows floppy and stressed rigid networks to consist in part of monomers. The latter aspect of structure narrows the width of the reversibility window and suppresses in part aging effects observed outside the window in contrast to those in the fully polymerized selenide counterparts.

cond-mat.mtrl-sci↗

arXiv2003

Intrinsic Nanoscale Phase Seperation of bulk As2S3 Glass

Raman scattering on bulk AsxS1-x glasses showes that vibrational modes of As4S4 monomer first appear near x=0.38, and their concentration increases precipitously with increasing x, suggesting that the stoichiometric glass (x=0.40) is intrinsically phase seperated into small As-rich(As4S4) and large S-righ clusters. Support for the Raman-active vibrational modes of the orpiment-like and realgar-like nanophases is provided by ab-initio density functional theory calculations on appropriate clusters. Nanoscale phase seperation provides a basis for understanding the global maximum in the glass transition temperature Tg near x=0.40, and the departure from Arrhenius temperature activation of As2S3 melt viscosities.

cond-mat.mtrl-sci↗

arXiv2003

The Intermediate Phase in Ternary GexAsxSe1-2x Glasses

Melt-quenched AsxGexSe1-2x glasses over the composition range, 0 < x < 0.26, are examined in Raman scattering, T-modulated Differential Scanning Calorimetry (MDSC), and 119Sn Mossbauer spectroscopy measurements. The non-reversing enthalpy near Tg, DHnr(x), accessed from MDSC shows a global minimum (~ 0) in the xc(1) = 0.09 < x < xc(2) = 0.16 range, and increases by an order of magnitude both at x < xc(1) and at x > xc(2). Raman mode frequency of corner-sharing Ge(Se1/2)4 tetrahedra studied as a function of x, also shows three distinct regimes (or power-laws, p) that coincide with DHnr(x) trends. These regimes are identified with mechanically floppy (x < xc(1)), intermediate (xc(1) < x < xc(2)), and stressed-rigid (x > xc(2)) phases. The Raman elasticity power-law in the intermediate phase, p1 = 1.04(3), and in the stressed rigid phase, p2= 1.52(5), suggest effective dimensionalities of d = 2 and 3 respectively.

cond-mat.dis-nn↗

arXiv2003

Aging, Fragility and Reversibility Window in Bulk Alloy Glasses

Non-reversing relaxation enthalpies (DHnr) at glass transitions Tg(x) in the PxGexSe1-2x ternary display a wide, sharp and deep global minimum (~0) in the 0.09 < x < 0.145 range, within which Tg becomes thermally reversing. In the reversibility window these glasses are found not to age, in contrast to aging observed for fragile glass compositions outside the window. Thermal reversibility and lack of aging are paradigms that molecular glasses in the window share with proteins in transition states, which result from structural self-organization in both systems. In proteins the self-organized structures appear to be at places where life sustaining repeating foldings and unfoldings occur.

cond-mat.dis-nn↗