Materials Science and Engineering Commons^™

Effects Of Niobium On The Mechanical And Oxidation Properties Of Additively Manufactured Tungsten, Alexander Lesieur, Cayla Eckley, Ryan A. Kemnitz

Faculty Publications

Although additive manufacturing presents a novel and customizable approach to fabricating tungsten (W) alloys, the layer-by-layer production technique presents a unique set of processing challenges which are further exacerbated by the metal’s refractory properties. In this study, additions of niobium (Nb) were found to improve the mechanical properties and oxidation resistance of additively manufactured W. Microstructural investigation revealed the effect of Nb on the cracking, grain size, and texture in the as-built material. Mechanical compression testing showed significant improvement in ductility with increasing Nb content. The low concentrations of Nb used did not induce large changes in the yield strength …

Influence Of Temperature, Oxygen Partial Pressure, And Microstructure On The High-Temperature Oxidation Behavior Of The Sic Layer Of Triso Particles, Visharad Jalan, Adam Bratten, Meng Shi, Tyler Gerczak, Haiyan Zhao, Jonathan D. Poplawsky, Xiaoqing He, Grant Helmreich, Haiming Wen

Materials Science and Engineering Faculty Research & Creative Works

Tri structural isotropic (TRISO)-coated fuel particles are designed for use in high-temperature gas-cooled nuclear reactors, featuring a structural SiC layer that may be exposed to oxygen-rich environments over 1000 °C. Surrogate TRISO particles were tested in 0.2–20 kPa O2 atmospheres to observe the differences in oxidation behavior. Oxide growth mechanisms remained consistent from 1200–1600 °C for each PO2, with activation energies of 228 ± 7 kJ/mol for 20 kPa O2 and 188 ± 8 kJ/mol for 0.2 kPa O2. At 1600 °C, kinetic analysis revealed a change in oxide growth mechanisms between 0.2 and 6 kPa O2. In 0.2 kPa …

Nanomaterial-Enabled Enhancements In Thylakoid-Based Biofuel Cells, Amit Sarode, Gymama Slaughter

Center for Bioelectronics Publications

Thylakoid-based photosynthetic biofuel cells (TBFCs) harness the inherent light-driven electron transfer pathways of photosynthesis to enable sustainable solar-to-electrical energy conversion. While TBFCs offer a unique route toward biohybrid energy systems, their practical deployment is hindered by sluggish electron transfer kinetics, unstable redox mediators, and inefficient interfacing between biological and electrode components. This review critically examines recent advances in TBFCs, with a focus on three key surface engineering strategies: (i) incorporation of nanostructured materials to enhance electrode conductivity and surface area; (ii) application of redox mediators to facilitate charge transfer between photosynthetic proteins and electrodes; and (iii) functional exploitation of individual …

Linking Molecular Structure Evolution To Mechanical Degradation During Environmental Aging In Conventional And Recyclable Epoxy Systems, Ben T. Jewell

Dissertations, Master's Theses and Master's Reports

The long-term performance of polymeric materials in extreme environments is governed by complex chemical and physical aging processes that alter their molecular structure and mechanical integrity. Conventional thermoset epoxies, while widely used in structural applications, are particularly susceptible to oxidative degradation at elevated temperatures, leading to embrittlement and loss of structural integrity. In the first part of this work, diffusion-limited oxidation (DLO) in a bulk structural epoxy was systematically investigated to establish the link between heterogeneous microstructural evolution and macroscopic mechanical degradation. High-temperature oxidation experiments were conducted in a controlled environmental chamber, and the resulting chemical, thermal, and mechanical changes …

Oxidation Behavior Of Silicon Carbide, Matrix Graphite, And Refractory Multi-Principal Element Alloy, Visharad Jalan

Doctoral Dissertations

"The present study focuses on the investigation of the oxidation behavior of silicon carbide, matrix graphite in a water vapor environment. It also examines the oxidation behavior of refractory multi-principal element alloys when exposed to air. The oxidation behavior of silicon carbide and matrix graphite were investigated in conditions pertaining to off-normal incidents in high-temperature gas-cooled nuclear reactors. Understanding this is crucial for the prediction of their performance in such accidents and ensuring that the nuclear reactor is accident tolerant. Upon exposure to water vapor, the two A3-based matrix graphite exhibited different behaviors. The A3-27 type showed oxidation in all …

Oxidation Of Additively Manufactured Zrb2–Sic In Air And In Co2 At 700–1000 °C, Marharyta Lakusta, Nicholas M. Timme, Abid H. Rafi, Jeremy Lee Watts, M. (Ming) C. (Chuan) Leu, Gregory E. Hilmas, William G. Fahrenholtz, David W. Lipke

Materials Science and Engineering Faculty Research & Creative Works

Oxidation behavior of additively manufactured zrb2–sic in air and in co2 is reported in the temperature range of 700–1000 °c. Observed scale morphologies in air and in co2 were similar, featuring an outer borosilicate layer and an inner porous zirconia layer containing partially oxidized silicon carbide particles and remnant borosilicate products. Oxide scale thicknesses and parabolic scaling constants in air were approximately twice those observed in co2 across all studied temperatures. Activation energies for oxidation of 140 ± 20 kj/mol in air and 110 ± 20 kj/mol in co2 were determined, indicating similar diffusion processes that appear to be rate-limiting. …

In-Depth Characterization Of The Selective Oxidation Products Of Hafnium Carbide, Jonathan Allen Scott

Doctoral Dissertations

"Materials capable of withstanding oxidative environments at temperatures >2000°C are necessary for hypersonic applications. Hafnium carbide (HfC) shows a combination of properties that lends itself toward these applications; however, its oxidation behavior is poorly understood. At 1300°C, HfC was found to oxidize via the following mechanism: 1) Initial oxidation of both C and Hf present in the system, 2) Formation of an interconnected pore network, whose size is related to the volume of gases being generated during the oxidation process, 3) Growth of the oxide scale to become sufficiently protective, 4) Formation of an initially amorphous “HfO₂C” at …

Water Vapor Oxidation Of Sic Layer Of Tristructural Isotropic Particles, Visharad Jalan, Adam Bratten, Matthew Luebbe, Haiming Wen

Materials Science and Engineering Faculty Research & Creative Works

Tri structural isotropic (TRISO) fuel particles, developed for use in high-temperature gas-cooled nuclear reactors, can be subjected to oxidizing environments in off-normal accident scenarios. In this study, surrogate TRISO fuel particles were oxidized at 1000–1350°C for 4 h in 20 kPa water vapor atmosphere balanced with ultrahigh-purity helium gas. The oxide scale morphology and thickness were studied via scanning electron microscopy, focused ion beam, and transmission electron microscopy. The oxide thickness increased as the oxidation temperature was increased. Although the oxide scale at 1000°C was completely amorphous, pockets of crystalline oxide were observed on particles oxidized at 1200 and 1300°C. …

High Temperature Oxidation Regime Transitions In Hafnium Carbide, Jonathan A. Scott, Xiaoqing He, David W. Lipke

Materials Science and Engineering Faculty Research & Creative Works

Understanding the oxidation behavior of hafnium carbide is crucial to its application in extreme environments. In this work, the transition in high-temperature oxidation kinetics regimes in hafnium carbide is explained based on phase equilibria considerations supported by observed changes in oxide scale microstructure evolution associated with different transformation pathways. Below, a composition-dependent critical temperature and oxygen pressure, hafnium carbide first transforms to an amorphous material with nominal composition HfO2C followed by phase separation into carbon and hafnia domains. Subsequently, gaseous transport through a nanometric pore network formed by oxidative removal of phase-separated carbon becomes rate-limiting. Above this critical point, the …

Processing-Microstructure-Properties Relationships In Additively Manufactured Zrb2-Sic Ceramics, Marharyta Lakusta

Doctoral Dissertations

"The study explores the pressure less sintering (PS) and chemical compatibility of ZrB₂-30 vol.%SiC produced by additive manufacturing (AM) with CO₂. The oxidation kinetics and scale microstructures were compared for ZrB₂-SiC made by hot pressing (HP) and by AM coupled with PS. All specimens exhibited parabolic oxidation kinetics. The difference in oxidation behavior becomes evident at temperatures of 1100-1400°C (200-900h). Oxidation rates increased as grain size increased. Similar oxide scale morphologies were observed in both CO₂ and air, with an outer borosilicate layer and an inner porous ZrO₂ layer containing partially oxidized …

Processing, Stability, And High-Temperature Properties Of Doped Lacro3-Based Refractory Ceramics And Composites For Harsh Environments Sensing Applications, Javier A. Mena

Graduate Theses, Dissertations, and Problem Reports (ETD)

In order to test and monitor the operational stability and conditions of various energy, transportation, and manufacturing systems and their components, accurate sensors capable of operating at temperatures over 1000 °C in various environments for long durations are required. In addition, many of these harsh environmental systems do not permit sensors to be directly inserted into the environment, so the sensors need to be embedded into the surrounding support or thermal protective materials. Some technological and industrial applications that require the use of harsh environment conditions sensing include nuclear and chemical reactors, jet engines, heavyduty gas turbines, rotating bearings in …

Oxidation Of Hafnium Diboride—Silicon Carbide At 1500 °C In Air; Effect Of Compressive Stress, Anthony J. Degregoria, Marina B. Ruggles-Wrenn, Glen E. Pry

Faculty Publications

The long-term oxidation behavior of HfB₂ and of HfB₂-20 vol.% SiC was studied. Test samples of each material were oxidized at 1500 °C in air using a box furnace. The exposure times were 0, 0.5, 1, 2, 3, 6, 9, 12, 15, 30, 45 and 90 h. Weight gain, oxide scale composition and oxide scale thickness were characterized for both materials. Crystal structure of the surface scales was analyzed using x-ray diffraction. Oxide scales were further characterized via scanning electron microscopy with energy dispersive spectroscopy analysis. For HfB₂ the oxide scale consists predominantly of porous HfO …

Effect Of Cr And Ni Concentrations On Resilience Of Cast Nb-Alloyed Heat Resistant Austenitic Steels At Extreme High Temperatures, Simon N. Lekakh, Mario F. Buchely, Mei Li, Larry Godlewski

Materials Science and Engineering Faculty Research & Creative Works

Austenitic Cr–Ni Alloyed Heat Resistant Steels with Nb Additions Are Used for Intensively Thermo-Mechanically Loaded Cast Components Working in Extreme High Temperature Oxidizing Environment. their Performance during Static Oxidation and Transient Thermo-Mechanical Loading Was Investigated to Recommend an Optimal Cost-Effective Cr/Ni Composition of Nb-Alloyed Austenitic Class Steels. the Static Oxidation and Transient Thermo-Mechanical Behavior of Three Austenitic Steels with Different Cr/Ni Alloying Levels Were Investigated and Compared for Variety of Working Conditions. Static Oxidation Was Performed between 900 °C and 1000 °C in Air for 400 H. the Critical Temperature Which Increases Spallation during Static Oxidation Was Determined for Each …

The Oxidation Of The Hisimo Cast Irons Alloyed With Cr/Al At 800 °C, Wenhui Zhu, Bruce A. Pint, Yang Huo, Larry Godlewski, Bita Ghaffari, Simon Lekakh, Carlos Engler-Pinto, Mei Li

Materials Science and Engineering Faculty Research & Creative Works

To improve the oxidation resistance of cast iron containing Si and Mo (HiSiMo), 1wt.% Cr and 3wt.% Al were added into the base alloy to improve high temperature oxidation resistance for exhaust manifold applications. Oxidation tests were performed in both dry and wet air (air + 10% H2O) at 800 °C for 1, 10, 24, and 50 h. The mass change and oxide thickness were measured to evaluate the oxidation resistance. Scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDS) and transmission electron microscopy (TEM) were employed to characterize the oxidized samples. The results showed that the additions of Al …

The Role Of Microstructure On High-Temperature Oxidation Behavior Of Hafnium Carbide, Jonathan A. Scott, Xiaoqing He, David W. Lipke

Materials Science and Engineering Faculty Research & Creative Works

Microstructure development of the products formed upon oxidation of hafnium carbide (HfCx, x = 0.65, 0.81, or 0.94) at 1300°C and 0.8 mbar oxygen pressure was investigated using Raman spectroscopy, X-ray diffraction, electron microscopy, and electron energy-loss spectroscopy. For all specimens a multilayered oxide scale was observed featuring an outermost porous hafnia layer and an interlayer adjacent to the parent carbide containing hafnia interspersed with carbon. The outermost hafnia features coarse pores presumably formed during initial stages of oxidation to allow rapidly evolving gaseous products to escape from the oxidation front. As the oxidation scale thickens, diffusional resistance results in …

Effect Of Spallation On Oxidation Kinetics Of Heat-Resistant Cr–Ni Austenitic Steels On Air And Combustion Atmosphere, Simon N. Lekakh, Oleg Neroslavsky, Mei Li, Larry Godlewski, Wenhui Zhu

Materials Science and Engineering Faculty Research & Creative Works

Thin-walled castings made from Cr–Ni austenitic steels offer a combination of light weight of a near-net component with significant high temperature corrosion protection by forming a surface oxide layer. However, above critical service conditions (temperature, atmosphere, thermal cycling), oxidized surface can result in intensive surface degradation due to scale spallation. Scale spallation can decrease the wall thickness which could be detrimental to the in-service life of thin-walled castings. Experiments and stochastic simulations of spallation assisted oxidation were performed with three cast austenitic heat-resistant steels having different Cr–Ni concentrations at temperatures between 900 and 1000 ℃ on air and water vapor …

Minimizing Cr-Evaporation From Balance Of Plant Components By Utilizing Cost-Effective Alumina-Forming Austenitic Steels, Lingfeng Zhou

Graduate Theses, Dissertations, and Problem Reports (ETD)

A solid oxide fuel cell (SOFC) is a clean and efficient energy conversion device. The development of intermediate-temperature SOFCs has made it preferable to use metallic interconnects (MICs) to greatly reduce the cost and significantly increase the efficiency compared to ceramic interconnect materials. However, gaseous chromium species will evaporate from the chromium-containing layer formed on the surface of commonly used MICs and balance of plant (BoP) components. Volatile chromium species have been shown to form solid deposits which poison the cathodes of SOFCs, causing drastic cell performance degradation and thereby limiting commercialization. In order to alleviate the Cr poisoning and …

Steam Oxidation Of Ytterbium Disilicate Environmental Barrier Coatings With And Without A Silicon Bond Coat, Ken A. Kane, Eugenio Garcia, Sharon Uwanyuze, Michael Lance, Kinga A. Unocic, Sanjay Sampath, Bruce A. Pint

Materials Science and Engineering Faculty Research & Creative Works

The current generation of multilayer Si/Yb₂Si₂O₇ environmental barrier coatings (EBCs) are temperature limited by the melting point of Si, 1414°C. To investigate higher temperature EBCs, the cyclic steam oxidation of EBCs comprised of a single layer of ytterbium disilicate (YbDS) was compared to multilayered Si/YbDS EBCs, both deposited on SiC substrates using atmospheric plasma spray. After 500 1-h cycles at 1300°C in 90 vol%H₂O-10 vol%air with a gas velocity of 1.5 cm/s, both multilayer Si/YbDS and single layer YbDS grew thinner silica scales than bare SiC, with the single layer YbDS forming the …

Continuous Preparation And Application Of Novel Heterogeneous Catalysis, Michael B. Burkholder

Theses and Dissertations

Transition metal heterogeneous catalysts are widely used across many chemical industries to reduce waste and emissions and reduce production time while increasing rate. The prevalence of these materials results from the complex relationship between metal nanoparticles and supports affecting final catalytic performance. Rational catalyst synthesis describes the ability to precisely engineer structures through controlled preparation. Novel materials and continuous processing represent a promising approach for rational catalyst synthesis.

The application of these catalysts in continuous, multiphase processes, such as cross-coupling reactions, oxidation chemistry, and nitroreduction processes, are paramount to developing new commercial routes for high-value products. Pd/G catalysts synthesized by …

A Computational Investigation Of The Interstitial Oxidation Thermodynamics Of A Mo-Nb-Ta-W High Entropy Alloy Beyond The Dilute Regime, Adib J. Samin

Faculty Publications

High entropy alloys (HEAs) are promising candidates for high-temperature structural material applications. Oxidation is a major factor that must be accounted for when designing such materials and it is thus important to study the oxidation behavior of HEAs to enable the optimum design of next generation materials. In this study, the thermodynamic behavior of interstitial oxygen in a Mo-Nb-Ta-W high entropy alloy was explored beyond the dilute limit. This was accomplished by sampling configurations of the HEA and HEA-oxygen systems from an isothermal–isobaric ensemble using a series of first-principle-based Monte Carlo simulations. It was found that the interstitial oxygen had …

A Novel Method For Making Titanium Dioxide For Photocatalytic Applications, Gary Wilson

Graduate Theses & Non-Theses

Titanium dioxide possesses near-ideal properties for large-scale application as a photocatalyst. It is cheap and abundant, nontoxic, and environmentally safe. However, it still suffers from logistical problems preventing its application in industry: namely, rapid electron-hole recombination and inability to utilize visible light. For nearly five decades researchers in this booming field have made numerous attempts to address these problems, doping and combining titanium dioxide with a wide range of materials. A novel ambient-temperature approach to synthesis and doping/modification of anatase-form titanium dioxide was attempted using both oxygen-rich and oxygen deprived synthetic routes. Reactants were exposed to various wavelengths of ultraviolet …

Carbon Oxidation At The Atomic Level: A Computational Study On Oxidative Graphene Etching And Pitting Of Graphitic Carbon Surfaces, Simon Schmitt

Theses and Dissertations--Mechanical and Aerospace Engineering

In order to understand the oxidation of solid carbon materials by oxygen-containing gases, carbon oxidation has to be studied on the atomic level where the surface reactions occur. Graphene and graphite are etched by oxygen to form characteristic pits that are scattered across the material surface, and pitting in turn leads to microstructural changes that determine the macroscopic oxidation behavior. While this is a well-documented phenomenon, it is heretofore poorly understood due to the notorious difficulty of experiments and a lack of comprehensive computational studies. The main objective of the present work is the development of a computational framework from …

Electron Tunneling And X-Ray Photoelectron Spectoscopy Studies Of The Superconductiong Properties Of Nitrogen-Doped Niobium Resonator Cavities, Eric M. Lechner, Basu Dev Oli, Junki Makita, Gianluigi Ciovati, Alex Gurevich, Maria Iavarone

Physics Faculty Publications

We use scanning tunneling microscopy (STM) and spectroscopy (STS), and x-ray photoelectron spectroscopy (XPS) to investigate the effect of nitrogen doping on the surface electronic and chemical structures of cutouts from superconducting Nb radio-frequency cavities. The goal of this work is to get insights into the fundamental physics and materials mechanisms behind the striking decrease of the surface resistance with the radio-frequency magnetic field, which has been observed on N-doped Nb cavities. Our XPS measurements reveal significantly more oxidized Nb 3d states and a thinner metallic suboxide layer on the N-doped Nb surfaces, which is also confirmed by tunneling spectroscopy …

Characterization Of Zirconium Oxides Part I: Raman Mapping And Spectral Feature Analysis, Corey M. Efaw, Jordan L. Vandegrift, Michael Reynolds, Samuel Mcmurdie, Brian J. Jaques, Hui Xiong, Michael F. Hurley

Materials Science and Engineering Faculty Publications and Presentations

Raman mapping of sectioned zirconium cladding oxides was performed to analyze different spectral features before and after breakaway, as well as between zirconium and its alloys Zr-2.65Nb, Zry-3, and Zry-4. Oxide phase composition, or percent tetragonality, was defined to compare tetragonal to monoclinic zirconia. Percent tetragonality was spatially mapped to support distinction of zirconia phase distribution. A tetragonal-rich layer was seen at the metal/oxide interface, while post-breakaway samples exhibited increased amount of tetragonal phase in the bulk of their oxides. Spatial mapping of spectral peak location and half-width at half-maximum was accomplished to distinguish differences in stability mechanisms of tetragonal-rich …

Oxidation Behavior Of Welded Zry-3, Zry-4, And Zr–1nb Tubes, Jordan Vandegrift, Clemente J. Parga, Ben Coryell, Darryl P. Butt, Brian J. Jaques

Materials Science and Engineering Faculty Publications and Presentations

The Transient Reactor Test (TREAT) facility is a research reactor designed to simulate rapid transients to test new fuel designs. TREAT's cladding is exposed to unique conditions compared to normal water reactors. These conditions include: exposure to air at high temperatures (≥600 °C), rapid heating (≈700 °^C/_s), and cladding geometry that includes chamfers and welds. This work investigates the effects of chamfering and welding on the oxidation behavior of zirconium alloys (Zircaloy-3, Zircaloy-4, and Zr–1Nb). Tube specimens were examined under isothermal and transient conditions in dry and humid air. The effect of weld type (tungsten inert …

Improving Boron For Combustion Applications, Kerri-Lee Annique Chintersingh

Dissertations

Boron has received much attention as a potential additive to explosives and propellants due to its high theoretical gravimetric and volumetric heating values. The challenge, however, is that boron particles tend to agglomerate, have lengthy ignition delays and very low combustion rates. Prior research indicates that boron’s long ignition delays are due to its inhibiting naturally occurring oxide layer, impeding the diffusion of reactants for oxidation. For combustion, current studies report that boron particles have two consecutive stages, but the actual reaction mechanism is poorly understood. Despite many years of relevant research, quantitative combustion data on micron-sized boron particles are …

Oxidation Behavior Of Zirconium, Zircaloy-3, Zircaloy-4, Zr-1nb, And Zr- 2.5nb In Air And Oxygen, Jordan L. Vandegrift, Patrick M. Price, John-Paul Stroud, Clemente J. Parga, Isabella J. Van Rooyen, Brian J. Jaques, Darryl P. Butt

Materials Science and Engineering Faculty Publications and Presentations

The Transient Reactor Test (TREAT) facility at the Idaho National Laboratory currently utilizes a legacy Zircaloy- 3 cladding, which is no longer commercially available. TREAT is air cooled and routinely operates at temperatures well above that of traditional reactor designs. This study investigates the oxidation behavior of pure zirconium and its alloys (Zircaloy-3, Zircaloy-4, Zr-1Nb, Zr-2.5Nb) in Ar+20%O₂ and N₂+20%O₂ atmospheres at temperatures ranging from 400–800 °C to determine which alloy should be implemented as TREAT's cladding. While the oxidation behavior of zirconium based cladding materials has been extensively documented, this study focuses on direct comparison …

No2- And No3- Enhance Cold Atmospheric Plasma Induced Cancer Cell Death By Generation Of Onoo-, Dehui Xu, Qingjie Cui, Yujing Xu, Zhijie Liu, Zeyu Chen, Wenjie Xia, Hao Zhang, Dingxin Liu, Hailan Chen, Michael G. Kong

Bioelectrics Publications

Cold atmospheric plasma (CAP) is a rapidly developed technology that has been widely applied in biomedicine especially in cancer treatment. Due to the generation of various active species in plasma, CAP could induce various tumor cells death and showed a promising potential in cancer therapy. To enhance the biological effects of gas plasma, changing the discharging parameters is the most commonly used method, yet increasing discharging power will lead to a higher possibility of simultaneously damage surrounding tissues. In this study, by adding nontoxic concentration of additional nitrite and nitrate in the medium, we found that anti-tumor effect of CAP …

Numerical Study Of Oxidation In Stainless Steel Alloy Ep-823 By Liquid Lead-Bismuth Eutectic, Rajyalakshmi Palaparty

UNLV Theses, Dissertations, Professional Papers, and Capstones

The oxidation of stainless steel is influenced by the presence of oxygen in the surrounding medium; the oxygen reacts with the alloy to form an oxide. In certain environments, such as nuclear reactor coolant systems, minimal oxidation of the stainless steel containment functions as a protective shield from corrosive coolants such as liquid lead-bismuth eutectic.

In the current study, this minimal oxidation is evaluated for a system in which corrosion-resistant stainless steel alloy EP-823 is subject to an environment of flowing oxygenated liquid lead-bismuth eutectic at a temperature of 743 K, whereby the thickness of the forming oxide layer is …

Creep Of Hi-Nicalon™ S Ceramic Fiber Tows At 1000°C In Air And In Silicic Acid-Saturated Steam, Brian G. Kroeger

Theses and Dissertations

Advanced SiC/SiC ceramic matrix composites (CMCs) are being considered for a variety of applications. Of interest is their ability to withstand exposure to high temperature in an aggressive oxidizing environment. The presence of steam creates such an environment. As steam traverses across a SiC/SiC composite and through cracks in the SiC matrix, it becomes saturated with silicic acid, Si(OH)₄. It is essential to understand the long-term impacts and durability of SiC/SiC CMCs that have been exposed to such a demanding environment. The present research investigated creep of Hi-Nicalon™ S SiC fibers at 1000°C in air and in silicic …