Pure Hydrocarbons Research Articles

Effect of monovalent and divalent salts on the interfacial tension of pure hydrocarbon-brine systems relevant for low salinity water flooding

Interfacial tension between hydrocarbon liquids and salt water is a very important property for many industrial applications, especially in petroleum industry. Interfacial tension, in addition to other factors, has direct impact on displacement process in porous media so thus on oil recovery. Very recently, the salinity of injection brine has been regarded as a key factor in oil recovery using low salinity water flooding process. Decrease in the interfacial tension between crude oil and injection brine at low salinity condition might be a reason behind recovery improvement as suspected by some researchers; but there are also other effects associated with low salinity water flooding like wettability alteration, fine migration, mineral dissolution etc. It is suspected that the interaction of polar components at oil-water interface lead to the reduction of interfacial tension. However, the actual mechanism is not known and still under research. The main objective of this work is to determine the effect of salt concentration and type of ions present in an aqueous phase on the interfacial tension between pure hydrocarbon liquids and water. Different hydrocarbon liquids, such as aliphatic and aromatics, have been tested to understand the interaction of monovalent and divalent salts on the interfacial tension. The study reports the interfacial tension of five pure hydrocarbon liquids against solutions of three different salts (NaCl, MgCl2 and CaCl2) over a wide range of salinities. The interfacial tension measurements were done using Wilhelmy plate method by a dynamic contact angle tensiometer. All the experiments were conducted at room temperature and atmospheric pressure. The results lead us to the view that there is low a salinity concentration where the hydrocarbon/brine interfacial tension shows a minimum value. The type of salt also has a significant effect on interfacial tension of aliphatic and aromatic hydrocarbons. Monovalent salt found to be effective in reducing interfacial tension of aliphatic hydrocarbons while divalent salts were found to be effective for aromatic hydrocarbons. The possible mechanism for the reduction in IFT at low salt concentration has also been explained using Gibb's adsorption isotherm. In addition, the trend in IFT has been explained in the light of well-known Jones-Ray effect.

High performance direct absorption spectroscopy of pure and binary mixture hydrocarbon gases in the 6\u201311 upmum range

The availability of accurate and fast hydrocarbon analyzers, capable of real-time operation while enabling feedback-loops, would lead to a paradigm change in the petro-chemical industry. Primarily gas chromatographs measure the composition of hydrocarbon process streams. Due to sophisticated gas sampling, these analyzers are limited in response time. As hydrocarbons absorb in the mid-infrared spectral range, the employment of fast spectroscopic systems is highly attractive due to significantly reduced maintenance costs and the capability to setup real-time process control. New developments in mid-infrared laser systems pave the way for the development of high-performance analyzers provided that accurate spectral models are available for multi-species detection. In order to overcome current deficiencies in the availability of spectroscopic data, we developed a laser-based setup covering the 6–11 upmum wavelength range. The presented system is designated as laboratory reference system. Its spectral accuracy is at least 6.6times 10^{-3} cm^{-1} with a precision of 3times 10^{-3} cm^{-1}. With a “per point” minimum detectable absorption of 1.3times 10^{-3} cm^{-1} Hz^{{-}{1/2}} it allows us to perform systematic measurements of hydrocarbon spectra of the first 7 alkanes under conditions which are not tabulated in spectroscopic database. We exemplify the system performance with measured direct absorption spectra of methane, propane, iso-butane, and a mixture of methane and propane.

A novel model for predicting lower flammability limits using Quantitative Structure Activity Relationship approach

The lower flammability limit (LFL) is the minimum concentration of a combustible gas or vapor that is capable of propagating a flame through a homogeneous mixture with air, so knowledge of the LFL of a combustible gas is indispensable from a safety standpoint. However, it is often time-consuming and costly to measure the LFL of combustible gases by experiment, and is even precarious for toxic or explosive chemicals. Therefore, an effective predictive model is indispensable in this respect. In present work, a QSAR (quantitative structure activity relationships) model of four descriptors is proposed for predicting the LFL of organic compounds containing heteroatoms atoms such as S, N, Si, P and halogen. The proposed model is developed and evaluated based on a set of 458 experimental measurements of LFL. The performance of goodness-of-fit (R2) and predictive capability (Q2) are found to be 0.914 and 0.930, respectively. The average absolute errors (AAE) of training set (366 measurements) and test set (92 measurements) are 0.344 v % and 0.304 v %, respectively. According to the ASTM E 681 method, the experimental reproducibility in measuring LFL is of 0.1 v% for pure hydrocarbons, therefore AAEs of this model indicate that it could predict LFL with reasonable accuracy.

Enthalpy of Vaporization Measurements of Liquid Methane, Ethane, and Methane + Ethane by Differential Scanning Calorimetry at Low Temperatures and High Pressures

This paper presents measurements of the enthalpy of vaporization of pure and binary hydrocarbon fluid mixtures using a commercial differential scanning calorimeter (DSC). The DSC was modified to allow the direct measurement of enthalpies of vaporization, ΔvapH, at temperatures as low as 80 K and pressures as high as 10 MPa and was tested by measuring enthalpies of vaporization, both under vaporization and under condensation, for pure methane at T = (118, 123, 128, and 133) K and pure ethane at T = (208 and 213) K. The measured values had relative deviations of less than 3% from recommended literature values. Then ΔvapH was measured for mixtures of methane + ethane, methane + propane, and ethane + propane at various temperatures by both condensing and vaporizing samples. In contrast to the pure fluid measurements, the measurement pathway affected the value of ΔvapH obtained because the condensation occurred along a constant composition pathway whereas the composition varied during vaporization as a result ...

Excited-State Deactivation Pathways and the Photocyclization of BN-Doped Polyaromatics.

Boron-nitrogen doping of polyaromatic hydrocarbons (PAH), such as borazine-core hexabenzocoronene, presents possibilities for tuning the properties of organic electronics and nanographene materials while preserving structural characteristics of pure hydrocarbons. Previous photochemical studies have demonstrated extension of a borazine-core PAH network (1,2:3,4:5,6-tris(o,o'-biphenylylene)borazine, 1) by photoinduced cyclodehydrogenation. We present steady-state and femtosecond-to-microsecond resolved spectroscopic studies of the photophysics of 1 and a related borazine-core PAH in order to characterize competing excited-state relaxation pathways that determine the efficacy of bond formation by photocyclization. Transient spectra evolve on time scales consistent with S1 fluorescence lifetimes (1-3 ns) to features that persist onto microsecond time scales. Nanosecond-resolved oxygen-quenching measurements reveal that long-lived metastable states are triplets rather than cyclized products. Determination of fluorescence and triplet quantum yields reveal that photochemical bond formation is a minor channel in the relaxation of 1 (∼5% or less), whereas highly efficient fluorescence and intersystem crossing result in negligible photoinduced bond formation in more extended borazine-core networks. Results of computational investigations at the RICC2 level reveal sizable barriers to cyclization on the S1 potential energy surfaces consistent with quantum yields deduced from experiment. Together these barriers and competing photophysical pathways limit the efficiency of photochemical synthesis of BN-doped polyaromatics.

Third‐Order Nonlinear Optical Properties of One‐Dimensional Quinoidal Oligothiophene Derivatives Involving Phenoxyl Groups

The diradical characters (y) and third‐order nonlinear optical (NLO) properties of open‐shell quinoidal oligothiophene derivatives with phenoxyl groups, and the corresponding reduced (hydrogenated)‐state oligomers, are investigated by using the broken‐symmetry density functional theory method. The oxidized (dehydrogenated) states are predicted to have an open‐shell singlet ground state and their y values increase with the number of units. Static second hyperpolarizabilities (γ) of the open‐shell oligomers with intermediate y are shown to be enhanced significantly compared with those of the closed‐shell analogues. Furthermore, owing to the effective diradical distances, the γ values of open‐shell oligomers are found to exceed that of s‐indaceno[1,2,3‐cd;5,6,7‐c′d′]diphenalene, which is known as an organic molecule with the largest two‐photon absorption cross‐section in this size of the pure hydrocarbons. This feature extends the range of efficient open‐shell third‐order NLO materials to a novel class of one‐dimensional conjugated oligomers with redox‐based high tunability of third‐order NLO properties.

Pressure-Temperature-Induced Transformations of Hydrocarbon- Fluorocarbon Mixtures into Nano- and Micron-Size Diamonds

Studies of thermal transformations of naphthalene (С10Н8), fluorographite (CF1.1) and octafluoronaphthalene (С10F8) and their binary mixtures (С10Н8 – CF1.1, С10Н8 – C10F8) under pressure of 8 GPa have been undertaken as models for gaining understanding of processes of carbonization, graphitization and diamond formation in pure hydrocarbon, fluorocarbon and carbon-hydrogen-fluorine-containing systems under high pressures. The studies found a significant reduction in the initiation temperature thresholds for all major thermal transformation processes in case of binary mixtures with respect to thresholds for pure hydrocarbon and fluorocarbon compounds. Another distinctive feature of the transformations of binary mixtures with respect to diamond formation stage of the transformations of pure hydrocarbons, has been the presence of massive quantity of nanosize (10–60 nm) diamond fraction in the products from binary mixtures along with the micron-size (5–20 μm) diamond fraction, typically observed in the transformations of pure hydrocarbons. The origin of nanodiamond was related to the specifics of carbonization of fluorocarbon compounds under pressure, which at 800–1000 °С produces, along with submicron particles of graphite-like material, a significant amount of closed shell 2–5 layer carbon nanoparticles of 5–15 nm size. These onion-like carbon nanoparticles act as precursors for formation of nano size diamond fractions in the transformations of binary mixtures of hydrocarbon and fluorocarbon compounds. These results potentially open a new direction for metal catalyst-free synthesis of pure and doped diamonds for broad applications. The present article gives an overview of this emerging area of rese arch.

Identification of PAH Isomeric Structure in Cosmic Dust Analogues: the AROMA setup.

We developed a new analytical experimental setup called AROMA (Astrochemistry Research of Organics with Molecular Analyzer) that combines laser desorption/ionization techniques with ion trap mass spectrometry. We report here on the ability of the apparatus to detect aromatic species in complex materials of astrophysical interests and characterize their structures. A limit of detection of 100 femto-grams has been achieved using pure polycyclic aromatic hydrocarbon (PAH) samples, which corresponds to 2x108 molecules in the case of coronene (C24H12). We detected the PAH distribution in the Murchison meteorite, which is made of a complex mixture of extraterrestrial organic compounds. In addition, collision induced dissociation experiments were performed on selected species detected in Murchison, which led to the first firm identification of pyrene and its methylated derivatives in this sample.

A practical method to obtain kinetic data from TGA (thermogravimetric analysis) experiments to build an air injection model for enhanced oil recovery

To build an air injection model for enhanced oil recovery, it is necessary to obtain the kinetic data from thermal experiments. For TGA (thermogravimetry analysis) experiments, fitting the weight loss data using different forms of the Arrhenius Equation is practiced to obtain a single set of kinetic data which are used for the whole temperature range. The problem is that the kinetic data changes with the test temperature, oil composition, etc. Therefore, the obtained kinetic data do not represent the actual physics. This paper presents a detailed practical method to obtain kinetic data from TGA experiments to build an air injection model. The air injection model contains two parts. One part is to define fluid pseudo-components and their physical properties. The other part is to define oxidation reaction and the corresponding kinetic data. In order to validate the air injection model, both air purging TGA experiments and nitrogen purging TGA experiments are conducted. The fluid model (pseudo-components and their properties) is validated by matching model results with the nitrogen purging TGA experiments. Then, the kinetic data are obtained by matching the model results with the air purging TGA experiments.To verify the above approach to build an air injection model, TGA experiments using a pure hydrocarbon C20 and a Wolfcamp crude oil were conducted. The pure hydrocarbon C20 is used to verify the approach. Then seven oxidation reactions of seven pseudo components are utilized to define the air injection model for the Wolfcamp crude oil. The selection of the pseudo components was validated with the nitrogen purging TGA experiments and the oxidation reactions were validated with the air purging TGA experiments. The result shows that the combination of isomerization reactions and oxygen addition reactions can perfectly simulate a light oil air injection process in the low temperature region. This paper shows that an air injection model can be built using the kinetic data by analyzing TGA experiments.

Theoretical Study on the Open-Shell Singlet Nature and the Second Hyperpolarizabilities of Corannulene Derivatives with Two Phenoxyl Radicals.

Using the spin-unrestricted density functional theory method, we investigate the interplay between the diradical character y and second hyperpolarizabilities γ (the third-order nonlinear optical (NLO) properties at the molecular scale) of corannulene derivatives with two phenoxyl radicals. This molecule in the singlet state exhibits intermediate y and thus displays a significantly larger γ value than the triplet state and the closed-shell bis-phenol analogue. We also examine the planar molecules involving a coronene moiety in place of the curved corannulene. The intermediate y and large γ values of the corannulene systems are found to originate not from their curved skeleton but from the equilibrium between benzenoid/quinoid resonance forms due to delocalization of the radical electrons of the terminal phenoxyl rings. The longitudinal γ value of the singlet state is found to be comparable to that of s-indaceno[1,2,3-cd;5,6,7-c'd']diphenalene, which is known to be one of the organic molecules with the largest two-photon absorption cross section in this size of pure hydrocarbons. The present system is thus expected to be a promising candidate for highly efficient open-shell NLO molecules.

Evaluation of mineral oil saturated hydrocarbons (MOSH) and mineral oil aromatic hydrocarbons (MOAH) in pure mineral hydrocarbon-based cosmetics and cosmetic raw materials using 1H NMR spectroscopy.

Mineral hydrocarbons consist of two fractions, mineral oil saturated hydrocarbons (MOSH) and mineral oil aromatic hydrocarbons (MOAH). MOAH is a potential public health hazard because it may include carcinogenic polycyclic compounds. In the present study, 400 MHz nuclear magnetic resonance (NMR) spectroscopy was introduced, in the context of official controls, to measure MOSH and MOAH in raw materials or pure mineral hydrocarbon final products (cosmetics and medicinal products). Quantitative determination (qNMR) has been established using the ERETIC methodology (electronic reference to access in vivo concentrations) based on the PULCON principle (pulse length based concentration determination). Various mineral hydrocarbons (e.g., white oils, paraffins or petroleum jelly) were dissolved in deuterated chloroform. The ERETIC factor was established using a quantification reference sample containing ethylbenzene and tetrachloronitrobenzene. The following spectral regions were integrated: MOSH δ 3.0 - 0.2 ppm and MOAH δ 9.2 - 6.5, excluding solvent signals. Validation showed a sufficient precision of the method with a coefficient of variation <6% and a limit of detection <0.1 g/100 g. The applicability of the method was proven by analysing 27 authentic samples with MOSH and MOAH contents in the range of 90-109 g/100 g and 0.02-1.10 g/100g, respectively. It is important to distinguish this new NMR-approach from the hyphenated liquid chromatography-gas chromatography methodology previously used to characterize MOSH/MOAH amounts in cosmetic products. For mineral hydrocarbon raw materials or pure mineral hydrocarbon-based cosmetic products, NMR delivers higher specificity without any sample preparation besides dilution. Our sample survey shows that previous methods may have overestimated the MOAH amount in mineral oil products and opens new paths to characterize this fraction. Therefore, the developed method can be applied for routine monitoring of consumer products aiming to minimize public health risks.

A comparison between Peng-Robinson and Soave-Redlich-Kwong cubic equations of state from modification perspective

The Cubic Equations of State (CEOSs) are the most important tools in PVT calculations due to their simplicity in use and their extrapolative abilities to condition well outside their correlation ranges. Peng-Robinson (PR) and Soave-Redlich-Kwong (SRK) are most successful in the CEOSs which have repeatedly been modified in order to improve their accuracy in wider ranges of temperature and pressure. Unfortunately, most of modifications carried out on these EOSs have no adequate justification for selecting either of these as the basic starting point for the modifications. In this paper, PR and SRK EOSs were critically compared with each other using some new features of their subcritical and supercritical results. For this purpose, the CEOSs were assessed using comprehensive tests of the PVT calculations in the vapor-liquid equilibrium (for pure hydrocarbons over a wide range of acentric factor values: Methane, Ethane Propane, Butane, Heptane and Nonane) and Joule–Thomson Inversion Curves' (JTICs) predictions (for compounds which have reliable JTICs data: Methane, Ethane, Ethylene, Nitrogen, Oxygen, Argon and Carbon dioxide) in subcritical and supercritical regions, respectively. The results indicated that the PR EOS by using any of realistic α-function forms will never be able to accurately predict the JTICs in full span. On the other hand, the subcritical results revealed that the great success of the PR CEOS in predicting liquid phase density is only due to its function in shifting the results of the SRK CEOS to the lower values with the same curve trend. In addition, the Patel and Teja's (PT) EOS, has been reevaluated and the results showed that most of the defects of PR EOS still remain. This article suggests that in order to develop CEOSs, the original SRK EOS is a better candidate than original and alternative forms of PR EOS.

Modeling gas/vapor viscosity of hydrocarbon fluids using a hybrid GMDH-type neural network system

Estimation of natural gas viscosity is essential for accurate analysis of gas reserves, reservoir simulation and optimum gas consumption. The general method for calculation of gas viscosity is to conduct experimental tests, however, these tests are normally time consuming and expensive as well as sometimes even impossible at some specific pressure and temperature conditions. In this study, a group method of data handling (GMDH)-type neural network was utilized to predict the viscosity of pure hydrocarbon and gas mixtures containing heavy components and impurities such as carbon dioxide, helium and nitrogen by using more than 3800 data points. First, the data sets were divided into three parts based on their density. Next, a model was developed for each part as a function of molecular weight, pseudo reduced temperature, pseudo reduced pressure and density. The proposed models were compared to 13 well-known models by performing graphical and statistical error analyses. The results indicate that the average absolute percent relative error of the proposed GMDH models is 3.45% and the standard deviation from experimental data is 0.0566. Error distribution curves indicate that the proposed models are able to accurately estimate natural gas viscosity over a wide range of pressure and temperature conditions as no significant error trend is observed in the predictions. Finally, the results of relevancy factor analysis showed that the mixture density has the largest impact on viscosity compared to the other input parameters.

Characterization of Gas-Phase Organics Using Proton Transfer Reaction Time-of-Flight Mass Spectrometry: Aircraft Turbine Engines

Nonmethane organic gas emissions (NMOGs) from in-service aircraft turbine engines were investigated using a proton transfer reaction time-of-flight mass spectrometer (PTR-ToF-MS) at an engine test facility at Zurich Airport, Switzerland. Experiments consisted of 60 exhaust samples for seven engine types (used in commercial aviation) from two manufacturers at thrust levels ranging from idle to takeoff. Emission indices (EIs) for more than 200 NMOGs were quantified, and the functional group fractions (including acids, carbonyls, aromatics, and aliphatics) were calculated to characterize the exhaust chemical composition at different engine operation modes. Total NMOG emissions were highest at idling with an average EI of 7.8 g/kg fuel and were a factor of ∼40 lower at takeoff thrust. The relative contribution of pure hydrocarbons (particularly aromatics and aliphatics) of the engine exhaust decreased with increasing thrust while the fraction of oxidized compounds, for example, acids and carbonyls increased. Exhaust chemical composition at idle was also affected by engine technology. Older engines emitted a higher fraction of nonoxidized NMOGs compared to newer ones. Idling conditions dominated ground level organic gas emissions. Based on the EI determined here, we estimate that reducing idle emissions could substantially improve air quality near airports.

Flash Points of Hydrocarbons and Petroleum Products: Prediction and Evaluation of Methods

The flash point of hydrocarbons and petroleum mixtures is important safety-related data for processing and handling of these materials. In this paper, experimentally measured data on flash points of about 140 pure hydrocarbons and petroleum fractions were collected and used to evaluate existing methods for prediction of these data available in the literature. The errors for the available methods varied from 1.6 to 4.9% for pure hydrocarbons and from 3.7 to 11.1% for petroleum fractions. In these methods, parameters such as vapor pressure, boiling point, molecular weight, density, activity coefficient, and composition were used. On the basis of the available methods and simplified relations for vapor pressure prediction, it was found that the ratio of the flash point to the boiling point of hydrocarbon systems and their mixtures is a constant and a value of this constant is about 0.7 when both temperatures are expressed in absolute degrees. The average absolute deviation for this simplified method was 1.7%...

Determination of Volumetric Properties Using Refractive Index Measurements for Nonpolar Hydrocarbons and Crude Oils

A novel method to evaluate volumetric properties, namely the thermal expansivity (αP) and the isothermal compressibility (κT) for nonpolar hydrocarbon systems using refractive index measurements, is presented in this work. New expressions for αP and κT are derived from the Lorentz–Lorenz equation and the One-Third rule, respectively. A further simplified expression for αP is proposed requiring only refractive index data and molecular weight for calculation. Densities and refractive indices of 12 pure nonpolar hydrocarbons, 6 hydrocarbon mixtures, and 3 crude oils are measured at temperatures from 283.15 K up to 343.15 K and at 0.1 MPa. The measured refractive indices are used to calculate αP for a wide range of temperatures using the proposed method, and the measured densities are used to calculate αP for comparison. Reported densities and refractive indices of benzene at 298.15 K and at pressures up to 90 MPa are used for κT evaluations with the proposed method. Values of αP and κT calculated from refractive index measurements are in good agreement with experimental data and those determined from densities. This work aims to establish the foundation for experimental methods to determine volumetric properties of nonpolar hydrocarbon systems based on refractive index measurements. A high temperature and high pressure refractometer is expected to have multiple advantages over conventional techniques for density measurements, which include but are not limited to smaller amounts of sample needed, simpler calibration, faster measurement, and cells that are corrosion-resistant (i.e., sapphire glass).

New relation between viscosity and surface tension for pure hydrocarbon liquids

ABSTRACTA new relation between viscosity and surface tension is proposed and checked for 21 pure hydrocarbon liquids, and validated with the National Institute of Science and Technology data. The performance and accuracy of the proposed relation are compared with the reported empirical correlations in the form of absolute average deviation. The proposed relation remains valid for higher hydrocarbons (up to C25H52). A total of 418 data points for 21 pure hydrocarbon liquids were taken into consideration for checking the accuracy of the proposed relation. The proposed relation gives an absolute average deviation of 5.66%, indicating high accuracy of the proposed relation.

The Interplay between Surface Nanotopography and Chemistry Modulates Collagen I and III Deposition by Human Dermal Fibroblasts.

The events within the foreign body response are similar to, but ultimately different than, the wound healing cascade. Collagen production by fibroblasts is known to play a vital role in wound healing and device fibrous encapsulation. However, the influence of surface nanotopography on collagen deposition by these cells has not been reported so far. To address this gap, we have developed model substrata having surface nanotopography of controlled height of 16, 38, and 68 nm and tailored outermost surface chemistry of amines, carboxyl acid, and pure hydrocarbon. Fibroblast adhesion was reduced on nanotopographically modified surfaces compared to the smooth control. Furthermore, amine and acid functionalized surfaces showed increased cell proliferation over hydrophobic hydrocarbon surfaces. Collagen III production increased from day 3 to day 8 and then decreased from day 8 to day 16 on all surfaces, while collagen I deposition increased throughout the duration of 16 days. Our data show that the initial collagen I and III deposition can be modulated by selecting desired combinations of surface nanotopography and chemistry. This study provides useful knowledge that could help in tuning fibrous capsule formation and in turn govern the fate of implantable biomaterial devices.

Polyolefin Thermoplastics for Multiple Shape and Reversible Shape Memory.

This work reports the first pure hydrocarbon thermoplastic polyolefin material with reversible shape memory effect under stress-free or very small external loading condition. A thermoplastic ethylene/1-octene diblock copolymer with designed chain microstructure was synthesized. The polyolefin material performed not only the conventional one-way multishape memory effects, but also a two-way reversible shape memory effect (RSME). The elongation and contraction induced by oriented crystallization with heating was confirmed as the mechanism of RSME without chemical cross-linking. This work demonstrated that the thermoplastic reversible shape memory could be achieved through careful design of chain microstructure, based on sole hydrocarbon materials such as ethylene-1-octene copolymer.

Studies on the growth and characterization of an organic single crystal – 1,3,5- Triphenylbenzene

Single crystals of a pure hydrocarbon, 1,3,5-Triphenylbenzene (TPB) have been successfully grown using toluene as a solvent by controlled slow cooling solution growth technique. TPB crystallises in orthorhombic structure with the space group Pna21. High-resolution X-ray diffraction measurements were carried out to find the structural perfection of the grown TPB crystal. The functional groups of the grown crystal were identified using FTIR measurements. The range and percentage of the optical transmission are ascertained by recording the UV–Vis spectrum. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) were carried out to study its thermal properties. The initial screening of NLO properties of TPB crystal is identified using powder second-harmonic generation studies. Dielectric studies have been carried out on the grown crystals. The mechanical stability of TPB was studied from Vickers microhardness test. Laser damage threshold value was determined using Nd:YAG laser operating at 1064 nm.