Quantifying the free energy landscape between polymers and minerals

Higher organisms as well as medical and technological materials exploit mineral-polymer interactions, however, mechanistic understanding of these interactions is poorly constrained. Dynamic force spectroscopy can probe the free energy landscape of interacting bonds, but interpretations are challenged by the complex mechanical behavior of polymers. Here we restate the difficulties inherent to applying DFS to polymer-linked adhesion and present an approach to gain quantitative insight into polymer-mineral bindingpublishersversionPeer reviewe

Carboniferous metamorphism on the north (upper) side of the Sebago Batholith

Guidebook for field trips in southwestern Maine: New England Intercollegiate Geological Conference, 78th annual meeting, Bates College, Lewiston, Maine, October 17, 18, and 19, 1986: Trip C-

Growth from Solutions: Kink dynamics, Stoichiometry, Face Kinetics and stability in turbulent flow

1. Kink dynamics. The first segment of a polygomized dislocation spiral step measured by AFM demonstrates up to 60% scattering in the critical length l*- the length when the segment starts to propagate. On orthorhombic lysozyme, this length is shorter than that the observed interkink distance. Step energy from the critical segment length based on the Gibbs-Thomson law (GTL), l* = 20(omega)alpha/(Delta)mu is several times larger than the energy from 2D nucleation rate. Here o is tine building block specific voiume, a is the step riser specific free energy, Delta(mu) is the crystallization driving force. These new data support our earlier assumption that the classical Frenkel, Burton -Cabrera-Frank concept of the abundant kink supply by fluctuations is not applicable for strongly polygonized steps. Step rate measurements on brushite confirms that statement. This is the1D nucleation of kinks that control step propagation. The GTL is valid only if l* <Dk/vk, the diffusion path of a kink that has diffusivity Dk and average growth velocity vk. This is equivalent to supersaturations sigma less than approx. alpha/2l*, where alpha is the building block size. For lysozyme, sigma much less than (1%). Conventionally used interstep distance generated by screw dislocation, 19(omega)alpha/Delta(mu) should be replaced by the very different real one, approx.4l*. 2. Stoichiometry. Kink, and thus step and face rates of a non-Kossel complex molecular monocomponent or any binary, AB, lattice was found theoretically to be proportional to 1/(zeta(sup 1/2) + zeta(sup - 1/2)), where zeta = [B]/[A] is the stoichiometry ratio in solution. The velocities reach maxima at zeta = 1. AFM studies of step rates on CaOxalate monohydrate (kidney stones) from aqueous solution was found to obey the law mentioned above. Generalization for more complex lattice will be discussed. 3. Turbulence. In agreement with theory, high precision in-situ laser interferometry of the (101) KDP crystal face shows step bunching if solution flows parallel to the step flow. The bunch height increases with the distance the bunch travels, i.e. with the face size. However, when the flow rate, u, increases, at u greater than approx. 1 m / s , the average step bunch height decreases as 1/u. The pheonomenon is attributed to the turbulent rather than laminar viscous boundary layer where diffusivity Dt = 0.5u(sub tau),y, i.e. increases linearly with the distance y from the solid face. Friction velocity, u(sub tau) approx. u(sup 7/8). Dramatically larger rate of the mass/heat transport within the turbulent, as compared to the laminar, viscous layer will be discussed

Laser conditioning study of KDP on the optical sciences laser using large area beams

Considerable attention has been paid over the years to the problem of growing high purity KDP and KD*P to meet threshold requirements on succeeding generations of inertial confinement fusion lasers at LLNL. While damage thresholds for these materials have increased over time, the current National Ignition Facility (NIF) maximum fluence requirement (redline) for KD*P frequency triplers of 14.3 J/cm{sup 2} at 351 nm, 3 ns has not been reached without laser (pre)conditioning. It is reasonable to assume that, despite the rapid increase in damage thresholds for rapidly grown crystals, -a program of large scale conditioning of the 192 NIF triplers will be required. Small area ramp (R/1) tests on single sites indicate that KDP damage thresholds can be raised on average up to 1.5X the unconditioned values. Unpublished LLNL 3{omega} raster conditioning studies on KDP, however, have not conclusively shown that off-line conditioning is feasible for KD*P. Consequently, investigating the feasibility of on-line conditioning of NIF triplers at 3{omega} has become a high priority for the KDP damage group at LLNL. To investigate the feasibility of on-line conditioning we performed a series of experiments using the Optical Sciences Laser (OSL) on numerous samples of conventional and rapid growth KDP and KD*P. The experiment entailed exposing sites on each sample to a range of ramped shot (N/l) sequences starting at average fluences of -2 J/cm{sup 2} (in a 7 mm ``top hat`` beam @ 351 nm, 3 ns) up to peak fluences of approximately 13 J/cm{sup 2}. Test results indicated that the most effective conditioning procedure entailed a 7-8 shot ramp starting at 2 J/cm{sup 2} and ending at 12-13 J/cm{sup 2}. The pinpoint onset fluence for the 8/1 tests was 1.4 times that of the unconditioned site. Damage evolution appears to be exponential as a function of increasing fluence. When damage occurs after conditioning however, pinpoint density evolution exhibits a greater slope than less conditioned sites. The overall reduction in the total pinpoint number can be as high as 30OX. Despite laser conditioning , the pinpoint onset for the samples considered is below the NIF redline fluence of 14.3 J/cm{sup 2}. In addition, the exponential pinpoint evolution curves indicate that damage levels at NIF redline fluences will be on the order of 10{sup 4} pinpoints/mm{sup 2}. This suggests that there will be significant damage in NIP triplers, however, substantial damage has not been observed in the large Beamlet tripler (conventionally grown KD*P) under similar exposure conditions. By applying the OSL damage evolution curves to model NIF THG output spatial profiles it is possible to show damage in NIF triplers will be slight, consisting of isolated clusters with a few pinpoints at high fluence portions of the beam. This prediction has been verified by scatter mapping the 37 cm Beamlet tripler crystal. These results will be discussed in a future memo. These results indicate the feasibility of on-line conditioning for the NIF laser

Mechanistic insight into biopolymer induced iron oxide mineralization through quantification of molecular bonding

Microbial production of iron (oxyhydr)oxides on polysaccharide rich biopolymers occurs on such a vast scale that it impacts the global iron cycle and has been responsible for major biogeochemical events. Yet the physiochemical controls these biopolymers exert on iron (oxyhydr)oxide formation are poorly understood. Here we used dynamic force spectroscopy to directly probe binding between complex, model and natural microbial polysaccharides and common iron (oxyhydr)oxides. Applying nucleation theory to our results demonstrates that if there is a strong attractive interaction between biopolymers and iron (oxyhydr)oxides, the biopolymers decrease the nucleation barriers, thus promoting mineral nucleation. These results are also supported by nucleation studies and density functional theory. Spectroscopic and thermogravimetric data provide insight into the subsequent growth dynamics and show that the degree and strength of water association with the polymers can explain the influence on iron (oxyhydr)oxide transformation rates. Combined, our results provide a mechanistic basis for understanding how polymer-mineral-water interactions alter iron (oxyhydr)oxides nucleation and growth dynamics and pave the way for an improved understanding of the consequences of polymer induced mineralization in natural systems

Impurity and laser-induced damage in the growth sectors of rapidly grown DKP crystals

We report the experimental results of impurity contamination and laser-induced damage investigations on rapidly grown potassium dihydrogen phosphate (KDP) crystals. Using absorption spectroscopy and chemical analysis, we determined the impurity distribution in the different growing sectors of KDP single crystals. The level of impurity was dependent on starting materials and growth rate. We also studied influence of impurities on laser-induced damage in fast grown KDP. The laser damage threshold (LDT) in the impurity-rich prismatic sector is same as in the high purity pyramidal sector within experimental error. Meanwhile, the LDT at the boundary of the prismatic and pyramidal sectors is less than half of that in the bulk. Furthermore, we found that the thermal annealing of the crystal eliminated the weakness of this sector boundary and increased its LDT to the same level as in the bulk of the crystal. Result suggests that the laser damage occurred in the vicinity of a high; localized strain field

Rapid growth of large-scale (40-55 cm) KDP crystals

KDP (KH{sub 2}PO{sub 4}) single crystals up to 47 cm in size have been grown by the rapid growth technique on the point seed in glass recrystallizers of 1000 L in volume at growth rates of 10 to 25 mm/day in both the [001] and [100] directions. Measurements of the optical quality of 41 x 41 cm single crystal plates are presented

Lawson criterion for ignition exceeded in an inertial fusion experiment

For more than half a century, researchers around the world have been engaged in attempts to achieve fusion ignition as a proof of principle of various fusion concepts. Following the Lawson criterion, an ignited plasma is one where the fusion heating power is high enough to overcome all the physical processes that cool the fusion plasma, creating a positive thermodynamic feedback loop with rapidly increasing temperature. In inertially confined fusion, ignition is a state where the fusion plasma can begin "burn propagation" into surrounding cold fuel, enabling the possibility of high energy gain. While "scientific breakeven" (i.e., unity target gain) has not yet been achieved (here target gain is 0.72, 1.37 MJ of fusion for 1.92 MJ of laser energy), this Letter reports the first controlled fusion experiment, using laser indirect drive, on the National Ignition Facility to produce capsule gain (here 5.8) and reach ignition by nine different formulations of the Lawson criterion

Tuning calcite morphology and growth acceleration by a rational design of highly stable protein-mimetics

In nature, proteins play a significant role in biomineral formation. One of the ultimate goals of bioinspired materials science is to develop highly stable synthetic molecules that mimic the function of these natural proteins by controlling crystal formation. Here, we demonstrate that both the morphology and the degree of acceleration or inhibition observed during growth of calcite in the presence of peptoids can be rationally tuned by balancing the electrostatic and hydrophobic interactions, with hydrophobic interactions playing the dominant role. While either strong electrostatic or hydrophobic interactions inhibit growth and reduces expression of the {104} faces, correlations between peptoid-crystal binding energies and observed changes in calcite growth indicate moderate electrostatic interactions allow peptoids to weakly adsorb while moderate hydrophobic interactions cause disruption of surface-adsorbed water layers, leading to growth acceleration with retained expression of the {104} faces. This study provides fundamental principles for designing peptoids as crystallization promoters, and offers a straightforward screening method based on macroscopic crystal morphology. Because peptoids are sequence-specific, highly stable, and easily synthesized, peptoid-enhanced crystallization offers a broad range of potential applications