Enthalpies of combustion of 2,2-trans-4,6- (1) and 4,4,6,6-tetramethyl- (2) and 2,4,4,6,6- (3) and 2,2,4,4,6-pentamethyl-1,3-dioxanes (4) were determined to estimate their enthalpies of formation in the gas phase. By comparing the latter with the corresponding enthalpies estimated based on the various bond–bond interactions allowed to determine the chair–2,5-twist energy difference (ΔHCT = 29.8 kJ mol–1) for 1 since C-13 shift correlations indicate that it escapes to the 2,5-twist form where the 2-methyl groups are isoclinal and 4- and 6-methyl groups pseudoequatorial to avoid syn-axial interactions. Compounds 2 and 3 in turn give the values 21.0 and 21.6 kJ mol–1 for the 4,6-diaxial Me,Me-interaction. Finally compound 4, which retains the chair conformation to avoid pseudoaxial interactions in the twist forms gives the value 19.5 kJ mol–1 for the 2,4-diaxial Me,Me-interaction indicating that its chair form appears to be somewhat deformed.

Loose abrasive grinding was performed on a wide range of optical workpiece materials [single crystals of Al2O3 (sapphire), SiC, Y3Al5O12 (YAG), CaF2, and LiB3O5 (LBO); a SiO2-Al2O3-P2O5-Li2O glass-ceramic (Zerodur); and glasses of SiO2: TiO2 (ULE), SiO2 (fused silica), and P2O5-Al2O3-K2O-BaO (phosphate)]. Using the magneto rheological finishing (MRF) taper wedge technique (where a wedge was polished on each of the ground workpieces and the resulting samples were appropriately chemically etched), the subsurface mechanical damage (SSD) characteristics were measured. The SSD depth for most of the workpiece materials was found to scale as E-1(1/2)/H-1, where E-1 is the elastic modulus and H-1 is the hardness of the workpiece. This material scaling is the same as that for the growth of lateral cracks, suggesting that lateral cracks are a dominant source for SSD rather than radial/median cracks, as previously proposed. Utilizing the SSD depth data from both this study and others, semiempirical relationships have been formulated, which allows for estimating the SSD depth as a function of workpiece material and important grinding parameters (such as abrasive size and applied pressure). (C) 2019 Society of Photo-Optical Instrumentation Engineers (SPIE)

Gold nanoparticles are important constituents in plasmonic arrays, lending themselves to electronic, optical, biomedical, sensing, and catalytic applications, among numerous others. Process variables that must be controlled when engineering plasmonic nanoparticle ensembles include nanoparticle size, shape, and spatial distribution on surfaces. The challenge in generating arrays of nanoparticles with control over these three parameters increases dramatically as spatial requirements for uniformity extend to larger processing areas. We present a procedure that exploits thermally driven solid-state diffusional dewetting to yield considerable flexibility in generating ensembles of gold nanoparticles. Such submelting dewetting introduces fine control over particle spatial features that are currently difficult to achieve through conventional methods of generating nanoparticle arrays. Because of the simplicity of the process and its area-scalability, solid-state diffusional dewetting is shown here to be a method that could be easily scaled up to apply to large-area plasmonic fabrication processes.

A key challenge for metasurface research is locally controlling at will the nanoscale geometric features on meter-scale apertures. Such a technology is expected to enable large aperture meta-optics and revolutionize fields such as long-range imaging, lasers, laser detection and ranging (LADAR), and optical communications. Furthermore, these applications are often more sensitive to light-induced and environmental degradation, which constrains the possible materials and fabrication process. Here, we present a relatively simple and scalable method to fabricate a substrate-engraved metasurface with locally printed index determined by induced illumination, which, therefore, addresses both the challenges of scalability and durability. In this process, a thin metal film is deposited onto a substrate and transformed into a mask via local laser-induced dewetting into nanoparticles. The substrate is then dry-etched through this mask, and selective mask removal finally reveals the metasurface. We show that masking by the local nanoparticle distribution, and, therefore, the local index, is dependent on the local light-induced dewetting temperature. We demonstrate printing of a free-form pattern engraved into a fused silica glass substrate using a laser raster scan. Large-scale spatially controlled engraving of metasurfaces has implications on other technological fields beyond optics, such as surface fluidics, acoustics, and thermomechanics.

The nanomechanical deformations on a broad range of optical material surfaces (single crystals of Al2O3 [sapphire], SiC, Y3Al5O12 [YAG], CaF2, and LiB3O5 [LBO]; a SiO2-Al2O3-P2O5-Li2O glass-ceramics [Zerodur]; and glasses of SiO2:TiO2 [ULE], SiO2 [fused silica], and P2O5-Al2O3-K2O-BaO [Phosphate]) near the elastic-plastic load boundary have been measured by nanoindentation and nanoscratching to mimic the nanoplastic removal caused by a single slurry particle during polishing. Nanoindenation in air was performed to determine the workpiece hardness at various loads using a commercial nanoindenter with a Berkovich tip. Similarly, an atomic force microscope (AFM) with a stiff diamond coated tip (150nm radius) was used to produce nanoplastic scratches in air and aqueous environments over a range of applied loads (20-170N). The resulting nanoplastic deformation of the nanoscratches were used to calculate the removal function (i.e., depth per pass) which ranged from 0.18 to 3.6nm per pass for these materials. A linear correlation between the nanoplastic removal function and the polishing rate (using a fixed polishing process with colloidal silica slurry on a polyurethane pad) of these materials was observed implying that: (a) the polishing mechanism using colloidal silica slurry can be dominated by mechanical rather than chemical interactions; and (b) the nanoplastic removal function, as opposed to interface particle interactions, is the controlling factor for the polishing material removal rate. Furthermore, this correlation is consistent with the Ensemble Hertzian Multi-Gap (EHMG) microscopic material removal rate model described previously. The nanoplastic removal depth was also found to correlate to the measured nanoindentation hardness (H-1) of the optical material, scaling as H-1(-3.5). Two-dimensional (2D) finite element analysis simulations of nanoindentation showed a similar nonlinear dependence of plastic deformation with the workpiece material hardness. The findings of this study are used to determine an effective Preston coefficient for the material removal rate expression and enhance the predictive nature of the nanoplastic polishing rate for various materials utilizing their material properties.

High-energy laser systems are limited by the onset and subsequent growth of damage on constituent optics. This has been extensively studied for optics comprised of fused silica, but less so for other common optical materials. There are very few materials as well characterized as fused silica and, in this work, we explore the growth characteristics of other widely used optical materials with a range of physical parameters, namely sapphire, potassium dihydrogen phosphate, calcium fluoride, and compare them to fused silica. Since current understanding is that material fracture must be present before the fluences used in ns laser systems might cause a surface flaw to grow, we have chosen to study flaws on the exit surfaces created with a Vickers indenter. A range of indenter forces were selected that would produce flaw sizes typical of those that have been seen in laser created damage. Samples with arrays of indents were tested in the in the Optical Science Laser (OSL), a master oscillator power amplifier system, with a front-end pulse shaping capability able to deliver relevant fluences with a large area beam. Samples were tested in vacuum at 351 nm and at atmosphere at 1053 nm with a single shot fired every 45 minutes exposing multiple sites simultaneously. High resolution images of each flaw were taken after every shot to document changes. Additional tests at 1064 nm were conducted of individual sites at a 60 Hz rep rate in the Gigashot Optical Laser Damage (GOLD) system. The probability of growth at 3ω at 5.5 J/cm2 is near 100% for both calcium fluoride and fused silica about 50% for the other materials. The growth rates at 3ω at from 5 to 8 J/cm2 are comparable for all but potassium dihydrogen phosphate which are better than five times lower. At 1ω all the materials had about a factor of five increase in the threshold for growth.

Additive manufacturing offers new routes to lightweight optics inaccessible by conventional methods by providing a broader range of reconciled functionality, form factor, and cost. Predictive lattice design combined with the ability to 3D print complex structures allows for the creation of low-density metamaterials with high global and local stiffness and tunable response to static and dynamic loading. This capacity provides a path to fabrication of lightweight optical supports with tuned geometries and mechanical properties. Our approach involves the simulation and optimization of lightweight lattices for anticipated stresses due to polishing and mounting loads via adaptive mesh refinement. The designed lattices are 3D printed using large area projection microstereolithography (LAPuSL), coated with a metallic plating to improve mechanical properties, and bonded to a thin (1.25 mm) fused silica substrate. We demonstrate that this lightweight assembly can be polished to a desired flatness using convergent polishing, and subsequently treated with a reflective coating. *This work performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344 within the LDRD program. LLNL-ABS-738806.

In article 1700323, Rebecca Dylla-Spears and co-workers form optical quality silica and silica-titania glasses by three-dimensional (3D) printing silica inks formulated directly from molecular precursors, followed by heat treatment and polishing. This method demonstrates the potential of sol-gel chemistry for creating alternate glass compositions for optical 3D printing applications, which may lead to chemical and structural tuning of optical components.

A method for fabricating optical quality silica and silica–titania glasses by three‐dimensional (3D) printing is reported. Key to this success is the combination of sol–gel derived silica and silica–titania colloidal feedstocks, direct ink writing (DIW) technology, and conventional glass thermal processing methods. Printable silica and silica–titania sol inks are prepared directly from molecular precursors by a simple one‐pot method, which is optimized to yield viscous, shear‐thinning colloidal suspensions with tuned rheology ideal for DIW. After printing, the parts are dried and sintered under optimized thermal conditions to ensure complete organic removal and uniform densification without crystallization. Characterizations of the 3D‐printed pure silica and silica–titania glasses show that they are equivalent to commercial optical fused silica and silica–titania glasses. More specifically, they exhibit comparable chemical composition, SiO2 network structure, refractive index, dispersion, optical transmission, and coefficient of thermal expansion. 3D‐printed silica and silica–titania glasses also exhibit comparable polished surface roughness and meet refractive index homogeneity standards within range of commercial optical grade glasses. This method establishes 3D printing as a viable tool to create optical glasses with compositional and geometric configurations that are inaccessible by conventional optical fabrication methods.

Particle adsorption was explored in a model optical polishing system, consisting of silica colloids and like-charged silica surfaces. The adsorption was monitored in situ under various suspension conditions, in the absence of surfactants or organic modifiers, using a quartz crystal microbalance with dissipation monitoring (QCM-D). Changes in surface coverage with particle concentration, particle size, pH, ionic strength and ionic composition were quantified by QCM-D and further characterized ex situ by atomic force microscopy (AFM). A Monte Carlo model was used to describe the kinetics of particle deposition and provide insights on scaling with particle concentration. Transitions from near-zero adsorption to measurable adsorption were compared with equilibrium predictions made using the Deraguin-Verwey-Landau-Overbeek (DLVO) theory. In addition, the impact of silica surface roughness on the propensity for particle adsorption was studied on various spatial scale lengths by intentionally roughening the QCM sensor surface using polishing methods. It was found that a change in silica surface roughness at the AFM scale from 1.3 nm root-mean-square (rms) to 2.7 nm rms resulted in an increase in silica particle adsorption of 3-fold for 50-nm diameter particles and 1.3-fold for 100-nm diameter particles far exceeding adsorption observed by altering suspension conditions alone, potentially because roughness at the proper scale reduces the total separation distance between particle and surface. (C) 2017 Elsevier B.V. All rights reserved.

During optical glass polishing, a number of interactions between the workpiece (i.e., glass), polishing slurry, and pad can influence the resulting workpiece roughness at different spatial scale lengths. In our previous studies, the particle size distribution of the slurry, the pad topography, and the amount of material removed by a single particle on the workpiece were shown to strongly correlate with roughness at AFM scale lengths (nm-m) and weakly at -roughness scale lengths (m-mm). In this study, the polishing slurry pH and the generation of glass removal products are shown to influence the slurry particle spatial and height distribution at the polishing interface and the resulting -roughness of the glass workpiece. A series of fused silica and phosphate glass samples were polished with various ceria and colloidal silica slurries over a range of slurry pH, and the resulting AFM roughness and -roughness were measured. The AFM roughness was largely invariant with pH, suggesting that the removal function of a single particle is unchanged with pH. However, the -roughness changed significantly, increasing linearly with pH for phosphate glass and having a maximum at an intermediate pH for fused silica. In addition, the spatial and height distribution of slurry particles on the pad (as measured by laser confocal microscopy) was determined to be distinctly different at low and high pH during phosphate glass polishing. Also, the zeta potential as a function of pH was measured for the workpiece, slurry, and pad with and without surrogate glass products (K3PO4 for phosphate glass and Si(OH)(4) for silica) to assess the role of interfacial charge during polishing. The addition of K3PO4 significantly raised the zeta potential, whereas addition of Si(OH)(4) had little effect on the zeta potential. An electrostatic DLVO three-body force model, using the measured zeta potentials, was used to calculate the particle-particle, particle-workpiece, and particle-pad attractive and repulsive forces as a function of pH and the incorporation of glass products at the interface. The model predicted an increase in particle-pad attraction with an increase in pH and phosphate glass products consistent with the measured slurry distribution on the pads during phosphate glass polishing. Finally, a slurry island distribution gap (IDG) model has been formulated which utilizes the measured interface slurry distributions and a load balance to determine the interface gap, the contact area fraction, and the load on each slurry island. The IDG model was then used to simulate the workpiece surface topography and -roughness; the results show an increase in roughness with pH similar to that observed experimentally.

The nanomechanical deformations on glass surfaces near the elastic–plastic load boundary have been measured on various glasses by nanoscratching using an atomic force microscope ( AFM ) to mimic the mechanical interactions of polishing particles during optical polishing. Nanoscratches were created in air and aqueous environments using a 150‐nm radius diamond‐coated tip on polished fused silica, borosilicate, and phosphate glass surfaces; the topology of the nanoscratches were then characterized by AFM . Using load ranges expected on slurry particles during glass polishing (0.05–200 μN), plastic‐type scratches were observed with depths in the nm range. Nanoscratching in air generally showed deeper & narrower scratches with more pileup compared to nanoscratching in water, especially on fused silica glass. The critical load needed to observe plastic deformation was determined to range from 0.2–1.2 μN for the three glasses. For phosphate glass, the load dependence of the removal depth was consistent with that expected from Hertzian mechanics. However, for fused silica and borosilicate glass in this load range, the deformation depth showed a weak dependence with load. Using a sub‐ T g annealing technique, material relaxation was observed on the nanoscratches, suggesting that a significant fraction of the deformation was due to densification on fused silica and borosilicate glass. Repeated nanoscratching at the same location was utilized for determining the effective incremental plastic removal depth. The incremental removal depth decreased with increase in number of passes, stabilizing after ~10 passes. In water, the removal depths were determined as 0.3–0.55 nm/pass for fused silica, 0.85 nm/pass for borosilicate glass, and 2.4 nm/pass for phosphate glass. The combined nanoscratching results were utilized to define the composite removal function (i.e., removal depth) for a single polishing particle as a function of load, spanning the chemical to the plastic removal regimes. This removal function serves as an important set of parameters in understanding material removal during polishing and the resulting workpiece surface roughness.

Measurements leading to the calculation of thermodynamic properties in the ideal-gas state for indan (Chemical Abstracts registry number [496-11-7], 2,3-dihydro-1H-indene) are reported. Experimental methods were adiabatic heat-capacity calorimetry, differential scanning calorimetry, comparative ebulliometry, and vibrating-tube densitometry. Molar thermodynamic functions (enthalpies, entropies, and Gibbs energies) for the condensed and ideal-gas states were derived from the experimental studies at selected temperatures. Statistical calculations were performed based on molecular geometry optimization and vibrational frequencies calculated at the B3LYP/6-31+G(d, p) level of theory. Computed ideal-gas properties derived with the rigid-rotor harmonic-oscillator approximation are shown to be in excellent accord with ideal-gas entropies derived from thermophysical property measurements of this research, as well as with experimental heat capacities for the ideal-gas state reported in the literature. Literature spectroscopic studies and ab initio calculations report a range of values for the barrier to ring puckering. Results of the present work are consistent with a large barrier that allows use of the rigid-rotor harmonic-oscillator approximation for ideal-gas entropy and heat-capacity calculations, even with the stringent uncertainty requirements imposed by the calorimetric and physical property measurements reported here. All experimental results are compared with property values reported in the literature. (C) 2016 Published by Elsevier Ltd.

Glass optics with ultra‐low roughness surfaces (<2 Å rms) are strongly desired for high‐end optical applications (e.g., lasers, spectroscopy, etc.). The complex microscopic interactions that occur between slurry particles and the glass workpiece during optical polishing ultimately determine the removal rate and resulting surface roughness of the workpiece. In this study, a comprehensive set of 100 mm diameter glass samples (fused silica, phosphate, and borosilicate) were polished using various slurry particle size distributions (PSD), slurry concentrations, and pad treatments. The removal rate and surface roughness of the glasses were characterized using white light interferometry and atomic force microscopy. The material removal mechanism for a given slurry particle is proposed to occur via nano‐plastic deformation (plastic removal) or via chemical reaction (molecular removal) depending on the slurry particle load on the glass surface. Using an expanded Hertzian contact model, called the Ensemble Hertzian Multi‐gap (EHMG) model, a platform has been developed to understand the microscopic interface interactions and to predict trends of the removal rate and surface roughness for a variety of polishing parameters. The EHMG model is based on multiple Hertzian contacts of slurry particles at the workpiece–pad interface in which the pad deflection and the effective interface gap at each pad asperity height are determined. Using this, the interface contact area and each particle's penetration, load, and contact zone are determined which are used to calculate the material removal rate and simulate the surface roughness. Each of the key polishing variables investigated is shown to affect the material removal rate, whose changes are dominated by very different microscopic interactions. Slurry PSD impacts the load per particle distribution and the fraction of particles removing material by plastic removal. The slurry concentration impacts the areal number density of particles and fraction of load on particles versus pad. The pad topography impacts the fraction of pad area making contact with the workpiece. The glass composition predominantly impacts the depth of plastic removal. Also, the results show that the dominant factor controlling surface roughness is the slurry PSD followed by the glass material's removal function and the pad topography. The model compares well with the experimental data over a variety of polishing conditions for both removal rate and roughness and can be extended to provide insights and strategies to develop practical, economic processes for obtaining ultra‐low roughness surfaces while simultaneously maintaining high material removal rates.

Thermodynamic properties for 1-naphthol (Chemical Abstracts registry number [90-15-3]) in the ideal-gas state are reported based on both experimental and computational methods. Measured properties included the triple-point temperature, enthalpy of fusion, and heat capacities for the crystal and liquid phases by adiabatic calorimetry; vapor pressures by inclined-piston manometry and comparative ebulliometry; and the enthalpy of combustion of the crystal phase by oxygen bomb calorimetry. Critical properties were estimated. Entropies for the ideal-gas state were derived from the experimental studies for the temperature range 298.15 <= T/K <= 600, and independent statistical calculations were performed based on molecular geometry optimization and vibrational frequencies calculated at the B3LYP/6-31+G(d,p) level of theory. The mutual validation of the independent experimental and computed results is achieved with a scaling factor of 0.975 applied to the calculated vibrational frequencies. This same scaling factor was successfully applied in the analysis of results for other polycyclic molecules, as described in a series of recent articles by this research group. This article reports the first extension of this approach to a hydroxy-aromatic compound. All experimental results are compared with property values reported in the literature. Thermodynamic consistency between properties is used to show that several studies in the literature are erroneous. The enthalpy of combustion for 1-naphthol was also measured in this research, and excellent agreement is seen with several values already reported in the literature. Published by Elsevier Ltd.

The chemical characteristics and the proposed formation mechanisms of the modified surface layer (called the Beilby layer) on polished fused silica glasses are described. Fused silica glass samples were polished using different slurries, polyurethane pads, and at different rotation rates. The concentration profiles of several key contaminants, such as Ce, K, and H, were measured in the near surface layer of the polished samples using Secondary Ion Mass Spectroscopy (SIMS). The penetration of K, originating from KOH used for pH control during polishing, decreased with increase in polishing material removal rate. In contrast, penetration of the Ce and H increased with increase in polishing removal rate. In addition, Ce penetration was largely independent of the other polishing parameters (e.g., particle size distribution and the properties of the polishing pad). The resulting K concentration depth profiles are described using a two‐step diffusion process: (1) steady‐state moving boundary diffusion (due to material removal during polishing) followed by (2) simple diffusion during ambient postpolishing storage. Using known alkali metal diffusion coefficients in fused silica glass, this diffusion model predicts concentration profiles that are consistent with the measured data at various polishing material removal rates. On the other hand, the observed Ce profiles are inconsistent with diffusion based transport. Rather we propose that Ce penetration is governed by the ratio of Ce–O–Si and Si–O–Si hydrolysis rates; where this ratio increases with interface temperature (which increases with polishing material removal rate) resulting in greater Ce penetration into the Beilby layer. Calculated Ce surface concentrations using this mechanism are in good agreement to the observed change in measured Ce surface concentrations with polishing material removal rate. These new insights into the chemistry of the Beilby layer, combined together with details of the single particle removal function during polishing, are used to develop a more detailed and quantitative picture of the polishing process and the formation of the Beilby layer.

Measurements leading to the calculation of thermodynamic properties in the ideal-gas state for 1- phenylnaphthalene (Chemical Abstracts registry number [605-02-7]) and 2-phenylnaphthalene (Chemical Abstracts registry number [612-94-2]) are reported. Experimental methods for 1- phenylnaphthalene were adiabatic heat-capacity calorimetry, differential scanning calorimetry, inclined-piston manometry, comparative ebulliometry, vibrating-tube densitometry, and combustion calorimetry. For 2-phenylnaphthalene, the experimental methods were adiabatic heat-capacity calorimetry, differential scanning calorimetry, and comparative ebulliometry. Critical properties were estimated for both compounds. Molar thermodynamic functions (enthalpies, entropies, and Gibbs free energies) for the condensed and ideal-gas states were derived from the experimental studies at selected temperatures. Statistical calculations were performed based on molecular geometry optimization and vibrational frequencies calculated at the B3LYP/6-31+G(d, p) and B3LYP/cc- pVTZ levels of theory. Ideal-gas entropies derived with two the independent methods are shown to be in good accord for 1-phenylnaphthalene, but significant differences are apparent for 2- phenylnaphthalene. These differences are likely due to a disorder of unknown type in the crystals of 2-phenylnaphthalene at low temperatures, as evidenced by the presence of a glass-like transition in the measured heat capacities for the solid state. All experimental results are compared with property values reported in the literature. Published by Elsevier Ltd.

Progress on understanding phenomena influencing surface figure and roughness during pad polishing are reviewed, followed by a description of a new Convergent Polishing process allowing single iteration, process variation-free finishing of optical flats & spheres.