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== | The strength of '''metal oxide adhesion''' effectively determines the [[wetting]] of the metal-oxide interface. The strength of this adhesion is important, for instance, in production of light bulbs and [[Composite material|fiber-matrix composites]] that depend on the optimization of wetting to create metal-ceramic interfaces<ref name=peden>{{cite journal|last=Peden|first=C|coauthors=K.B. Kidd, N. D. Shinn|title=Metal/Metal-Oxide Interfaces: A surface science approach to the study of adhesion|journal= [[Journal of Vacuum Science and Technology]] |year=1991|issue=9|pages=1518–1524}}</ref> The strength of adhesion also determines the extent of dispersion on [[Catalysis|catalytically]] active metal.<ref name=peden/> | ||
Metal oxide adhesion is important for applications like complementary metal oxide [[semiconductor]] devices. These devices make possible the high packing densities of modern [[integrated circuit]]s. | |||
==Oxide Thermodynamics== | |||
The majority of the [[entropy]] of metal oxidation reactions is in the O<sub>2</sub>(g) because the [[gas]]eous oxygen molecules have translation entropy which is not present in the [[solid]] phase. For this reason, the change in entropy (ΔS) for oxidation is almost always negative because this reaction generates less disorder by creating a solid oxide layer from the solid metal and gaseous oxygen. The standard state change of enthalpy is relatively independent and thus the gradient of the change in [[Gibbs free energy]] as a function of temperature is linear. This dictates that an oxide becomes less [[Thermodynamics|thermodynamically]] stable with increasing temperature. | |||
An important distinction between equilibrium wetting and non-equilibrium wetting is that the non-equilibrium condition occurs when a chemical reaction is taking place. This non-equilibrium wetting is an irreversible thermodynamic process that accounts for the changes of the [[chemical potential]] when forming a new boundary phase, such as an oxide. | |||
===Work of Adhesion=== | |||
The ideal work of separation W<sub>sep</sub> is the [[Reversible process (thermodynamics)|reversible]] [[Work (physics)|work]] needed to separate the interface into two free surfaces.<ref name=finnis/> Important as a state function depending on the mechanical properties.<ref name=finnis>{{cite journal|last=Finnis|first=M W|title=The theory of metal-ceramic interfaces|journal= Journal of Physics, Condensed Matter |year=1996|issue=8|pages=5811–5836}}</ref> It is referred to as ideal because when the two free surfaces create an [[Interface (chemistry)|interface]], the concentration of the interface will only be identical to the bulk at the instant the surface is created. In order to reach chemical equilibrium, the process of [[diffusion]] will take place which will increase any measurement of the work of separation.<ref name=finnis/> The work of adhesion is the reversible [[Thermodynamic free energy|free energy]] change for making free surfaces from interfaces.<ref name=finnis/> It is represented by the equation: | |||
= | ::<big><math>W_{ad} = \gamma_m + \gamma_o - \gamma_{mo} </math></big> | ||
where: | |||
W<sub>ad</sub> is the work of adhesion | |||
γ<sub>m</sub> and γ<sub>o</sub> are the respective surface energies of the metal and oxide | |||
γ<sub>mo</sub> is the surface energy between the two materials in contact | |||
The following table gives some common metals and their corresponding surface energies. All the metals are [[Cubic crystal system|face-centered cubic]] crystal structure and these surface energies correspond to the (100) surface plane. | |||
{|class="wikitable" style= "text-align:center" | |||
|- | |||
! Material !! Surface Energy <math>J/{m^{-2}}</math> | |||
|- | |||
| Al|| 1.347 | |||
|- | |||
| Pb||0.377 | |||
|- | |||
| Yb|| 0.478 | |||
|- | |||
| Cu|| 2.166 | |||
|- | |||
| Pd||2.326 | |||
|- | |||
| Ag|| 1.200 | |||
|- | |||
| Pt|| 2.734 | |||
|- | |||
| Au||1.627 | |||
|} | |||
===Oxide Stability=== | |||
[[Ellingham diagram]]s are generated according to the [[second law of thermodynamics]] and are a graphical representation of the change in the Gibbs free energy with respect to changing temperature for the formation of oxides. | |||
==Solid-Gas Interface== | |||
===Structure=== | |||
Real surfaces may be [[Macroscopic scale|macroscopically]] [[Homogeneity and heterogeneity|homogeneous]], but their microscopic [[Homogeneity and heterogeneity|heterogeneity]] plays a crucial role in the relationship between the metal and its oxide. | |||
====Transition Metal Oxides==== | |||
[[File:Transition oxide.JPG|thumb|left|A diagram showing different layers of transition metal oxides formed on the surface of a metal.]] Certain [[transition metals]] form multiple oxide layers that have different stoichiometric compositions. This is due to the metal having different valency states that have fewer or greater electrons in the valence shell. These different [[Electron shell|valency states]] allow for multiple oxides to be formed from the same two [[Chemical element|elements]]. As the composition of the materials changes through diffusion, different oxides are able to stack up on one another. The adhesion in this situation involves the metal-oxide and oxide-oxide interfaces which add increasing complexity to the mechanics.<ref name=cox>{{cite book|last=Henrich|first=Victor|coauthors = Cox P A| title=The Surface Science of Metal Oxides|year=1996|publisher=Cambridge University Pre|isbn=0-521-56687-8}}</ref> | |||
====Roughness==== | |||
Increasing [[surface roughness]] increases the number of dangling bonds at the metal-oxide interface. The surface free energy of a crystal face is: | |||
::<big><math> \gamma = E - TS </math></big> | |||
<br /> | |||
where:<br /> | |||
E is the binding energy of the material | |||
T is the temperature of the system | |||
S is the surface entropy of the material | |||
The binding energy favors a smoother surface that minimizes the number of dangling bonds, while the surface entropy term favors a rougher surface with increasing dangling bonds as the temperature is increased.<ref name=libb>{{cite journal|last=Libbrecht|first=Kenneth|title=The physics of snow crystals|journal= Reports on Progress in Physics |year=2005|volume=68|pages=855–895 | doi = 10.1088/0034-4885/68/4/R03 }}</ref> | |||
====Heterogeneity==== | |||
[[File:Defect Energy.png|thumb|right|A graph depicting the presence of thermodynamic defects, specifically lattice vacancies, as determined by the lowest potential free energy. As the temperature increases, the equilibrium concentration of lattice vacancies grows.]] Solid adsorption of an oxygen molecule depends on the heterogeneity of the substrate. Crystalline solid adsorption is dependent on the exposed crystal faces, grain orientations, and inherent defects because these factors provide adsorption sites with different steric configurations. Adsorption is largely determined by the reduction of gibbs free energy associated with the exposed substrate. | |||
====Crystallographic Orientation==== | |||
A material's charge remains neutral when a surface is created by the law of [[charge conservation]], but individual [[Bravais lattice]] planes, defined by their [[Miller indices]], may be non-polar or polar based on their symmetry. A dipole moment increases the surface gibbs free energy, but the greater [[polarizability]] of oxygen ions as compared to metals allows polarization to decrease the surface energy and thus increase the ability of metals to form oxides. Consequently, different exposed metal faces may adhere weakly to non-polar oxide faces, but be able to perfectly wet a polar face. | |||
====Defects==== | |||
Surface [[Crystallographic defect|defects]] are the localized fluctuations of surface electronic states and binding energies. Surface reactions, adsorption, and nucleation can be drastically affected by the presence of these defects.<ref name=butt>{{cite book|last=Butt|first=Hans-Jurgen|coauthors= Karlheinz Graf, Michael Kappl| title=Physics and Chemistry of Interfaces|publisher= WILEY-VCH|year=2006|pages=167–169}}</ref> | |||
=====Vacancies===== | |||
[[File:Metal Oxide Reactions.png|thumb|right|x300px|A figure demonstrating the surface adsorption of O<sub>2</sub> based on surface reactions with the environment and the diffusion of the metal reactant to the reactive interface.]] | |||
Oxide growth is dependent upon the flux ([[diffusion]]) of either coupled or independent [[anions]] and [[cations]] through the oxide layer.<ref name=kasap>{{cite book|last=Kasap|first=S.O.| title=Principle of Electron Materials and Devices|year=2006|publisher=McGraw-Hill|isbn=978-0-07-295791-4| pages= 73–75}}</ref><ref name=malte>{{cite web|last=Behrens|first=Malte|title=Solid State Kinetics|url =http://www.fhi-berlin.mpg.de/acnew/groups/nanostructures/pages/teaching/pages/teaching__malte_behrens__solid_state_kinetics.pdf|work=Lecture Series|publisher=Fritz Haber Institute of the Max Planck Society Department of Inorganic Chemistry|accessdate=1 June 2011}}</ref> [[Stoichiometric]] oxides have an integer ratio of atoms can only support coupled diffusion of anions and cations through the lattice migration of [[Schottky defect]]s (paired anion/cation vacancies) or [[Frenkel defect]]s (complete anion lattice with cation [[vacancy defect|vacancies]] and [[interstitial defect|intersticials]]).<ref name=kasap/><ref name=malte/> Non-stoichiometric oxide films support independent ion diffusion and are either [[N-type semiconductor|n-type]] (extra electrons) or [[P-type semiconductor|p-type]] (extra electron holes). Although there are only two valence states, there are three types:<ref name=kasap/><ref name=malte/> | |||
* cation excess (n-type) | |||
* anion deficit (n-type) | |||
* cation deficit (p-type) | |||
Non-stoichiometric oxides most commonly have excess metal cations as a result of insufficient oxygen during the creation of the oxide layer. Excess metal atoms with a smaller radius than O<sup>2-</sup> anions are ionized within the crystal lattice as interstitial defects and their lost electrons remain free within the crystal, not taken by the oxygen atoms. The presence of mobile electrons within the crystal lattice significantly contributes to the conduction of electricity and the mobility of ions.<ref name=kasap/> | |||
=====Impurities===== | |||
[[Impurity]] elements in the material can have a large effect on the adhesion of oxide films. When the impurity element increases the adherence of the oxide to the metal it is known as the reactive element effect or RE effect. Many mechanics theories exist on this topic. The majority of them attribute the increase in adhesion strength to the greater thermodynamic stability of the impurity element bonded with oxygen than the metal bonded to the oxygen.<ref name=finnis/><ref name=pint>{{cite journal|last=Pint|first=B A|title=Progress in Understanding the Reactive Element Effect Since the Whittle and Stringer Literature Review|journal= Metals and Ceramics Division|year=2010|volume=18| issue=18|pages=2159–2168}}</ref> Inserting yttrium into nickel alloys to strengthen the oxide adhesion is an example of the reactive element effect. | |||
=====Dislocations===== | |||
[[Dislocation]]s are thermodynamically unstable, kinetically trapped defects. Surface dislocations often create a screw dislocation when stress is applied. In certain cases, screw dislocations can negate the [[nucleation]] energy barrier for crystal growth.<ref name=butt/> | |||
====Oxide-Support Relationship==== | |||
The adsorption of a [[monolayer]] of gas atoms is either commensurate or incommensurate. Commensurate adsorption is defined by having a crystal structure relationship between substrate-adsorbate layer that produces a coherent interface. Wood's notation is a description of the relationship between the simplest repeating unit area of the solid and adsorbate. The difference between the resulting commensurate interfaces can be described as an effect of misfit. The interfacial interaction can be modeled as the <math>\scriptstyle\gamma</math><sub>sg</sub> plus the stored elastic displacement energy due to lattice misfit. A large misfit corresponds to an incoherent interface where there is no coherency strain and the interface energy can be taken as simply the <math>\scriptstyle\gamma</math><sub>sg</sub>. In contrast, a small misfit corresponds with a coherent interface and coherency strain that results in the interfacial energy equivalent to the minimum <math>\scriptstyle\gamma</math><sub>sg</sub>.<ref name=johan>{{cite journal|last=Johansson|first=Sven|coauthors= Mikael Christensen, Goran Wahmstrom |title=Interface energy of semicoherent metal-ceramic interfaces|journal= Physics Review Letters |year=2005|volume=95 |issue=22|pages=226108|doi=10.1103/PhysRevLett.95.226108}}</ref> | |||
===Strength of Bond=== | |||
[[File:Force diagram1.JPG|thumb|right|x275px|A graph depicting the strength of forces as the stress required to debond materials increases. The positive trend seen shows as bonding increases, the force and stress required to debond the material does as well.]]The strength of the bond between the oxide and metal for the same nominal contact area can range from [[Pascal (unit)|Pa]] to [[gigapascal|GPa]] stresses. The cause of this huge range stems from multiple phenomena dealing with at least four different types of [[adhesion]]. The main types of bonding that form adhesion are electrostatic, dispersive ([[Van der Waals force|van der Waals]] or London forces), chemical and diffusive bonding. As the adhesive forces increase, separation in crystalline materials can go from elastic debonding to elasic-plastic debonding. This is due to a larger number of bonds being formed or an increase in strength of the bonds between the two materials. Elastic-plastic debonding is when local stresses are high enough to move dislocations or make new ones.<ref name=gerb>{{cite journal|last=Gerberich|first=W W| coauthors= M J Cordill |title=Physics of Adhesion|journal= Reports on Progress in Physics |year=2006|volume=69|pages=2157–2204|doi=10.1088/0034-4885/69/7/R03}}</ref> | |||
==Solid-Gas Kinetics== | |||
When a gas molecule strikes a solid surface the molecule may either rebound or be adsorbed. The rate at which gas molecules strike the surface is a large factor in the overall [[Chemical kinetics|kinetics]] of oxide growth. If there molecule is absorbed there are three potential outcomes. The surface interaction can be strong enough to dissociate the gas molecule into separate atoms or constituents. The molecule may also react with surface atoms to change its chemical properties. The third possibility is solid surface catalysis, a binary chemical reaction with a previously adsorbed molecule on the surface. | |||
===Dispersion=== | |||
Most often it is kinetically favorable for the growth of a single oxide monolayer to be completed before the growth of subsequent layers. [[Dispersion (chemistry)|Dispersion]] in general can be modeled by: | |||
::<big><math>D={N_s \over N_t}</math></big> | |||
where: | |||
N<sub>s</sub> is the number of atoms on the surface | |||
N<sub>t</sub> is the total number of atoms in the material | |||
Dispersion is crucial to the growth of oxides because only atoms that are exposed to the interface can react to form oxides. | |||
===Diffusion=== | |||
After the initial oxide monolayer is formed, new layers begin to build and the ions must be able to diffuse through the oxide in order to increase thickness of the oxide. The rate of oxidation is controlled by how fast these ions are able to diffuse through the material. As the thickness of the oxide increases, the rate of oxidation decreases because it requires the atoms to travel a further distance. This rate can quantified by calculating the rate of diffusion of vacancies or ions using [[Fick's laws of diffusion|Fick’s first law of diffusion]].<ref name=rutter>{{cite web|last=Rutter|first=N A|title=Environmental Stability of Materials|url =http://www.msm.cam.ac.uk/teaching/partIB/courseB.php|work=Lecture Series|publisher=University of Cambridge|accessdate=6 June 2011}}</ref> | |||
::<big><math>J= -D {\delta C \over \delta x} </math></big> | |||
where: | |||
<br /> | |||
J is the [[flux]] and has units of mol·m<sup>−2</sup>·s<sup>−1</sup><br /> | |||
D is the diffusivity of the ions in the material | |||
δC is the change in concentration of the material | |||
<br /> | |||
δx is the thickness of the oxide layer | |||
===Solid Surface Catalysis=== | |||
In 2007 the [[Nobel Prize]] in chemistry was awarded to [[Gerhard Ertl]] for the study of solid-gas interface molecular processes. One such process is the oscillatory kinetic catalysis. Oscillatory kinetic catalysis can be explained by different crystal surfaces favoring unmodified faces and reconstruction to reduce surface strain. The presence of CO can cause the reversal of surface reconstruction past a certain percent coverage. Once the reversal occurs, oxygen can be chemisorbed on the reverted surfaces. This produces an adsorption pattern with areas of surface coverage rich in CO and others O<sub>2</sub>.<ref name=prize>{{cite web|last=Ertl|first=Gerhard|title=Chemical Processes on Solid Surfaces|url =http://nobelprize.org/nobel_prizes/chemistry/laureates/2007/chemadv07.pdf|work=Nobel Prize|publisher=The Royal Swedish Academy of Sciences |accessdate=6 June 2011}}</ref> | |||
====Driving Force==== | |||
The driving force of [[catalysis]] is determined by the difference between the unprimed equilibrium and the instantaneous interfacial free energies.<ref name=finnis/> | |||
==See also== | |||
* [[Oxide]] | |||
* [[Crystallographic defect]] | |||
* [[Corrosion]] | |||
* [[Oxidation potential]] | |||
* [[Reduction potential]] | |||
* [[Pourbaix diagram]] | |||
* [[Ellingham diagram]] | |||
* [[MOSFET]] | |||
* [[Metal oxide varistor]] | |||
* [[Surface Properties of Transition Metal Oxides]] | |||
==References== | |||
{{reflist}} | |||
[[Category:Oxides]] | |||
Latest revision as of 19:34, 24 December 2012
The strength of metal oxide adhesion effectively determines the wetting of the metal-oxide interface. The strength of this adhesion is important, for instance, in production of light bulbs and fiber-matrix composites that depend on the optimization of wetting to create metal-ceramic interfaces[1] The strength of adhesion also determines the extent of dispersion on catalytically active metal.[1] Metal oxide adhesion is important for applications like complementary metal oxide semiconductor devices. These devices make possible the high packing densities of modern integrated circuits.
Oxide Thermodynamics
The majority of the entropy of metal oxidation reactions is in the O2(g) because the gaseous oxygen molecules have translation entropy which is not present in the solid phase. For this reason, the change in entropy (ΔS) for oxidation is almost always negative because this reaction generates less disorder by creating a solid oxide layer from the solid metal and gaseous oxygen. The standard state change of enthalpy is relatively independent and thus the gradient of the change in Gibbs free energy as a function of temperature is linear. This dictates that an oxide becomes less thermodynamically stable with increasing temperature.
An important distinction between equilibrium wetting and non-equilibrium wetting is that the non-equilibrium condition occurs when a chemical reaction is taking place. This non-equilibrium wetting is an irreversible thermodynamic process that accounts for the changes of the chemical potential when forming a new boundary phase, such as an oxide.
Work of Adhesion
The ideal work of separation Wsep is the reversible work needed to separate the interface into two free surfaces.[2] Important as a state function depending on the mechanical properties.[2] It is referred to as ideal because when the two free surfaces create an interface, the concentration of the interface will only be identical to the bulk at the instant the surface is created. In order to reach chemical equilibrium, the process of diffusion will take place which will increase any measurement of the work of separation.[2] The work of adhesion is the reversible free energy change for making free surfaces from interfaces.[2] It is represented by the equation:
where:
Wad is the work of adhesion
γm and γo are the respective surface energies of the metal and oxide
γmo is the surface energy between the two materials in contact
The following table gives some common metals and their corresponding surface energies. All the metals are face-centered cubic crystal structure and these surface energies correspond to the (100) surface plane.
| Material | Surface Energy |
|---|---|
| Al | 1.347 |
| Pb | 0.377 |
| Yb | 0.478 |
| Cu | 2.166 |
| Pd | 2.326 |
| Ag | 1.200 |
| Pt | 2.734 |
| Au | 1.627 |
Oxide Stability
Ellingham diagrams are generated according to the second law of thermodynamics and are a graphical representation of the change in the Gibbs free energy with respect to changing temperature for the formation of oxides.
Solid-Gas Interface
Structure
Real surfaces may be macroscopically homogeneous, but their microscopic heterogeneity plays a crucial role in the relationship between the metal and its oxide.
Transition Metal Oxides
Certain transition metals form multiple oxide layers that have different stoichiometric compositions. This is due to the metal having different valency states that have fewer or greater electrons in the valence shell. These different valency states allow for multiple oxides to be formed from the same two elements. As the composition of the materials changes through diffusion, different oxides are able to stack up on one another. The adhesion in this situation involves the metal-oxide and oxide-oxide interfaces which add increasing complexity to the mechanics.[3]
Roughness
Increasing surface roughness increases the number of dangling bonds at the metal-oxide interface. The surface free energy of a crystal face is:
where:
E is the binding energy of the material
T is the temperature of the system
S is the surface entropy of the material
The binding energy favors a smoother surface that minimizes the number of dangling bonds, while the surface entropy term favors a rougher surface with increasing dangling bonds as the temperature is increased.[4]
Heterogeneity
Solid adsorption of an oxygen molecule depends on the heterogeneity of the substrate. Crystalline solid adsorption is dependent on the exposed crystal faces, grain orientations, and inherent defects because these factors provide adsorption sites with different steric configurations. Adsorption is largely determined by the reduction of gibbs free energy associated with the exposed substrate.
Crystallographic Orientation
A material's charge remains neutral when a surface is created by the law of charge conservation, but individual Bravais lattice planes, defined by their Miller indices, may be non-polar or polar based on their symmetry. A dipole moment increases the surface gibbs free energy, but the greater polarizability of oxygen ions as compared to metals allows polarization to decrease the surface energy and thus increase the ability of metals to form oxides. Consequently, different exposed metal faces may adhere weakly to non-polar oxide faces, but be able to perfectly wet a polar face.
Defects
Surface defects are the localized fluctuations of surface electronic states and binding energies. Surface reactions, adsorption, and nucleation can be drastically affected by the presence of these defects.[5]
Vacancies
Oxide growth is dependent upon the flux (diffusion) of either coupled or independent anions and cations through the oxide layer.[6][7] Stoichiometric oxides have an integer ratio of atoms can only support coupled diffusion of anions and cations through the lattice migration of Schottky defects (paired anion/cation vacancies) or Frenkel defects (complete anion lattice with cation vacancies and intersticials).[6][7] Non-stoichiometric oxide films support independent ion diffusion and are either n-type (extra electrons) or p-type (extra electron holes). Although there are only two valence states, there are three types:[6][7]
- cation excess (n-type)
- anion deficit (n-type)
- cation deficit (p-type)
Non-stoichiometric oxides most commonly have excess metal cations as a result of insufficient oxygen during the creation of the oxide layer. Excess metal atoms with a smaller radius than O2- anions are ionized within the crystal lattice as interstitial defects and their lost electrons remain free within the crystal, not taken by the oxygen atoms. The presence of mobile electrons within the crystal lattice significantly contributes to the conduction of electricity and the mobility of ions.[6]
Impurities
Impurity elements in the material can have a large effect on the adhesion of oxide films. When the impurity element increases the adherence of the oxide to the metal it is known as the reactive element effect or RE effect. Many mechanics theories exist on this topic. The majority of them attribute the increase in adhesion strength to the greater thermodynamic stability of the impurity element bonded with oxygen than the metal bonded to the oxygen.[2][8] Inserting yttrium into nickel alloys to strengthen the oxide adhesion is an example of the reactive element effect.
Dislocations
Dislocations are thermodynamically unstable, kinetically trapped defects. Surface dislocations often create a screw dislocation when stress is applied. In certain cases, screw dislocations can negate the nucleation energy barrier for crystal growth.[5]
Oxide-Support Relationship
The adsorption of a monolayer of gas atoms is either commensurate or incommensurate. Commensurate adsorption is defined by having a crystal structure relationship between substrate-adsorbate layer that produces a coherent interface. Wood's notation is a description of the relationship between the simplest repeating unit area of the solid and adsorbate. The difference between the resulting commensurate interfaces can be described as an effect of misfit. The interfacial interaction can be modeled as the sg plus the stored elastic displacement energy due to lattice misfit. A large misfit corresponds to an incoherent interface where there is no coherency strain and the interface energy can be taken as simply the sg. In contrast, a small misfit corresponds with a coherent interface and coherency strain that results in the interfacial energy equivalent to the minimum sg.[9]
Strength of Bond
The strength of the bond between the oxide and metal for the same nominal contact area can range from Pa to GPa stresses. The cause of this huge range stems from multiple phenomena dealing with at least four different types of adhesion. The main types of bonding that form adhesion are electrostatic, dispersive (van der Waals or London forces), chemical and diffusive bonding. As the adhesive forces increase, separation in crystalline materials can go from elastic debonding to elasic-plastic debonding. This is due to a larger number of bonds being formed or an increase in strength of the bonds between the two materials. Elastic-plastic debonding is when local stresses are high enough to move dislocations or make new ones.[10]
Solid-Gas Kinetics
When a gas molecule strikes a solid surface the molecule may either rebound or be adsorbed. The rate at which gas molecules strike the surface is a large factor in the overall kinetics of oxide growth. If there molecule is absorbed there are three potential outcomes. The surface interaction can be strong enough to dissociate the gas molecule into separate atoms or constituents. The molecule may also react with surface atoms to change its chemical properties. The third possibility is solid surface catalysis, a binary chemical reaction with a previously adsorbed molecule on the surface.
Dispersion
Most often it is kinetically favorable for the growth of a single oxide monolayer to be completed before the growth of subsequent layers. Dispersion in general can be modeled by:
where:
Ns is the number of atoms on the surface
Nt is the total number of atoms in the material
Dispersion is crucial to the growth of oxides because only atoms that are exposed to the interface can react to form oxides.
Diffusion
After the initial oxide monolayer is formed, new layers begin to build and the ions must be able to diffuse through the oxide in order to increase thickness of the oxide. The rate of oxidation is controlled by how fast these ions are able to diffuse through the material. As the thickness of the oxide increases, the rate of oxidation decreases because it requires the atoms to travel a further distance. This rate can quantified by calculating the rate of diffusion of vacancies or ions using Fick’s first law of diffusion.[11]
where:
J is the flux and has units of mol·m−2·s−1
D is the diffusivity of the ions in the material
δC is the change in concentration of the material
δx is the thickness of the oxide layer
Solid Surface Catalysis
In 2007 the Nobel Prize in chemistry was awarded to Gerhard Ertl for the study of solid-gas interface molecular processes. One such process is the oscillatory kinetic catalysis. Oscillatory kinetic catalysis can be explained by different crystal surfaces favoring unmodified faces and reconstruction to reduce surface strain. The presence of CO can cause the reversal of surface reconstruction past a certain percent coverage. Once the reversal occurs, oxygen can be chemisorbed on the reverted surfaces. This produces an adsorption pattern with areas of surface coverage rich in CO and others O2.[12]
Driving Force
The driving force of catalysis is determined by the difference between the unprimed equilibrium and the instantaneous interfacial free energies.[2]
See also
- Oxide
- Crystallographic defect
- Corrosion
- Oxidation potential
- Reduction potential
- Pourbaix diagram
- Ellingham diagram
- MOSFET
- Metal oxide varistor
- Surface Properties of Transition Metal Oxides
References
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A vendor's stamp duty has been launched on industrial property for the primary time, at rates ranging from 5 per cent to 15 per cent. The Authorities might be trying to reassure the market that they aren't in opposition to foreigners and PRs investing in Singapore's property market. They imposed these measures because of extenuating components available in the market." The sale of new dual-key EC models will even be restricted to multi-generational households only. The models have two separate entrances, permitting grandparents, for example, to dwell separately. The vendor's stamp obligation takes effect right this moment and applies to industrial property and plots which might be offered inside three years of the date of buy. JLL named Best Performing Property Brand for second year running
The data offered is for normal info purposes only and isn't supposed to be personalised investment or monetary advice. Motley Fool Singapore contributor Stanley Lim would not personal shares in any corporations talked about. Singapore private home costs increased by 1.eight% within the fourth quarter of 2012, up from 0.6% within the earlier quarter. Resale prices of government-built HDB residences which are usually bought by Singaporeans, elevated by 2.5%, quarter on quarter, the quickest acquire in five quarters. And industrial property, prices are actually double the levels of three years ago. No withholding tax in the event you sell your property. All your local information regarding vital HDB policies, condominium launches, land growth, commercial property and more
There are various methods to go about discovering the precise property. Some local newspapers (together with the Straits Instances ) have categorised property sections and many local property brokers have websites. Now there are some specifics to consider when buying a 'new launch' rental. Intended use of the unit Every sale begins with 10 p.c low cost for finish of season sale; changes to 20 % discount storewide; follows by additional reduction of fiftyand ends with last discount of 70 % or extra. Typically there is even a warehouse sale or transferring out sale with huge mark-down of costs for stock clearance. Deborah Regulation from Expat Realtor shares her property market update, plus prime rental residences and houses at the moment available to lease Esparina EC @ Sengkang - ↑ 2.0 2.1 2.2 2.3 2.4 2.5 One of the biggest reasons investing in a Singapore new launch is an effective things is as a result of it is doable to be lent massive quantities of money at very low interest rates that you should utilize to purchase it. Then, if property values continue to go up, then you'll get a really high return on funding (ROI). Simply make sure you purchase one of the higher properties, reminiscent of the ones at Fernvale the Riverbank or any Singapore landed property Get Earnings by means of Renting
In its statement, the singapore property listing - website link, government claimed that the majority citizens buying their first residence won't be hurt by the new measures. Some concessions can even be prolonged to chose teams of consumers, similar to married couples with a minimum of one Singaporean partner who are purchasing their second property so long as they intend to promote their first residential property. Lower the LTV limit on housing loans granted by monetary establishments regulated by MAS from 70% to 60% for property purchasers who are individuals with a number of outstanding housing loans on the time of the brand new housing purchase. Singapore Property Measures - 30 August 2010 The most popular seek for the number of bedrooms in Singapore is 4, followed by 2 and three. Lush Acres EC @ Sengkang
Discover out more about real estate funding in the area, together with info on international funding incentives and property possession. Many Singaporeans have been investing in property across the causeway in recent years, attracted by comparatively low prices. However, those who need to exit their investments quickly are likely to face significant challenges when trying to sell their property – and could finally be stuck with a property they can't sell. Career improvement programmes, in-house valuation, auctions and administrative help, venture advertising and marketing, skilled talks and traisning are continuously planned for the sales associates to help them obtain better outcomes for his or her shoppers while at Knight Frank Singapore. No change Present Rules
Extending the tax exemption would help. The exemption, which may be as a lot as $2 million per family, covers individuals who negotiate a principal reduction on their existing mortgage, sell their house short (i.e., for lower than the excellent loans), or take part in a foreclosure course of. An extension of theexemption would seem like a common-sense means to assist stabilize the housing market, but the political turmoil around the fiscal-cliff negotiations means widespread sense could not win out. Home Minority Chief Nancy Pelosi (D-Calif.) believes that the mortgage relief provision will be on the table during the grand-cut price talks, in response to communications director Nadeam Elshami. Buying or promoting of blue mild bulbs is unlawful.
A vendor's stamp duty has been launched on industrial property for the primary time, at rates ranging from 5 per cent to 15 per cent. The Authorities might be trying to reassure the market that they aren't in opposition to foreigners and PRs investing in Singapore's property market. They imposed these measures because of extenuating components available in the market." The sale of new dual-key EC models will even be restricted to multi-generational households only. The models have two separate entrances, permitting grandparents, for example, to dwell separately. The vendor's stamp obligation takes effect right this moment and applies to industrial property and plots which might be offered inside three years of the date of buy. JLL named Best Performing Property Brand for second year running
The data offered is for normal info purposes only and isn't supposed to be personalised investment or monetary advice. Motley Fool Singapore contributor Stanley Lim would not personal shares in any corporations talked about. Singapore private home costs increased by 1.eight% within the fourth quarter of 2012, up from 0.6% within the earlier quarter. Resale prices of government-built HDB residences which are usually bought by Singaporeans, elevated by 2.5%, quarter on quarter, the quickest acquire in five quarters. And industrial property, prices are actually double the levels of three years ago. No withholding tax in the event you sell your property. All your local information regarding vital HDB policies, condominium launches, land growth, commercial property and more
There are various methods to go about discovering the precise property. Some local newspapers (together with the Straits Instances ) have categorised property sections and many local property brokers have websites. Now there are some specifics to consider when buying a 'new launch' rental. Intended use of the unit Every sale begins with 10 p.c low cost for finish of season sale; changes to 20 % discount storewide; follows by additional reduction of fiftyand ends with last discount of 70 % or extra. Typically there is even a warehouse sale or transferring out sale with huge mark-down of costs for stock clearance. Deborah Regulation from Expat Realtor shares her property market update, plus prime rental residences and houses at the moment available to lease Esparina EC @ Sengkang - ↑ 20 year-old Real Estate Agent Rusty from Saint-Paul, has hobbies and interests which includes monopoly, property developers in singapore and poker. Will soon undertake a contiki trip that may include going to the Lower Valley of the Omo.
My blog: http://www.primaboinca.com/view_profile.php?userid=5889534 - ↑ One of the biggest reasons investing in a Singapore new launch is an effective things is as a result of it is doable to be lent massive quantities of money at very low interest rates that you should utilize to purchase it. Then, if property values continue to go up, then you'll get a really high return on funding (ROI). Simply make sure you purchase one of the higher properties, reminiscent of the ones at Fernvale the Riverbank or any Singapore landed property Get Earnings by means of Renting
In its statement, the singapore property listing - website link, government claimed that the majority citizens buying their first residence won't be hurt by the new measures. Some concessions can even be prolonged to chose teams of consumers, similar to married couples with a minimum of one Singaporean partner who are purchasing their second property so long as they intend to promote their first residential property. Lower the LTV limit on housing loans granted by monetary establishments regulated by MAS from 70% to 60% for property purchasers who are individuals with a number of outstanding housing loans on the time of the brand new housing purchase. Singapore Property Measures - 30 August 2010 The most popular seek for the number of bedrooms in Singapore is 4, followed by 2 and three. Lush Acres EC @ Sengkang
Discover out more about real estate funding in the area, together with info on international funding incentives and property possession. Many Singaporeans have been investing in property across the causeway in recent years, attracted by comparatively low prices. However, those who need to exit their investments quickly are likely to face significant challenges when trying to sell their property – and could finally be stuck with a property they can't sell. Career improvement programmes, in-house valuation, auctions and administrative help, venture advertising and marketing, skilled talks and traisning are continuously planned for the sales associates to help them obtain better outcomes for his or her shoppers while at Knight Frank Singapore. No change Present Rules
Extending the tax exemption would help. The exemption, which may be as a lot as $2 million per family, covers individuals who negotiate a principal reduction on their existing mortgage, sell their house short (i.e., for lower than the excellent loans), or take part in a foreclosure course of. An extension of theexemption would seem like a common-sense means to assist stabilize the housing market, but the political turmoil around the fiscal-cliff negotiations means widespread sense could not win out. Home Minority Chief Nancy Pelosi (D-Calif.) believes that the mortgage relief provision will be on the table during the grand-cut price talks, in response to communications director Nadeam Elshami. Buying or promoting of blue mild bulbs is unlawful.
A vendor's stamp duty has been launched on industrial property for the primary time, at rates ranging from 5 per cent to 15 per cent. The Authorities might be trying to reassure the market that they aren't in opposition to foreigners and PRs investing in Singapore's property market. They imposed these measures because of extenuating components available in the market." The sale of new dual-key EC models will even be restricted to multi-generational households only. The models have two separate entrances, permitting grandparents, for example, to dwell separately. The vendor's stamp obligation takes effect right this moment and applies to industrial property and plots which might be offered inside three years of the date of buy. JLL named Best Performing Property Brand for second year running
The data offered is for normal info purposes only and isn't supposed to be personalised investment or monetary advice. Motley Fool Singapore contributor Stanley Lim would not personal shares in any corporations talked about. Singapore private home costs increased by 1.eight% within the fourth quarter of 2012, up from 0.6% within the earlier quarter. Resale prices of government-built HDB residences which are usually bought by Singaporeans, elevated by 2.5%, quarter on quarter, the quickest acquire in five quarters. And industrial property, prices are actually double the levels of three years ago. No withholding tax in the event you sell your property. All your local information regarding vital HDB policies, condominium launches, land growth, commercial property and more
There are various methods to go about discovering the precise property. Some local newspapers (together with the Straits Instances ) have categorised property sections and many local property brokers have websites. Now there are some specifics to consider when buying a 'new launch' rental. Intended use of the unit Every sale begins with 10 p.c low cost for finish of season sale; changes to 20 % discount storewide; follows by additional reduction of fiftyand ends with last discount of 70 % or extra. Typically there is even a warehouse sale or transferring out sale with huge mark-down of costs for stock clearance. Deborah Regulation from Expat Realtor shares her property market update, plus prime rental residences and houses at the moment available to lease Esparina EC @ Sengkang - ↑ 5.0 5.1 20 year-old Real Estate Agent Rusty from Saint-Paul, has hobbies and interests which includes monopoly, property developers in singapore and poker. Will soon undertake a contiki trip that may include going to the Lower Valley of the Omo.
My blog: http://www.primaboinca.com/view_profile.php?userid=5889534 - ↑ 6.0 6.1 6.2 6.3 20 year-old Real Estate Agent Rusty from Saint-Paul, has hobbies and interests which includes monopoly, property developers in singapore and poker. Will soon undertake a contiki trip that may include going to the Lower Valley of the Omo.
My blog: http://www.primaboinca.com/view_profile.php?userid=5889534 - ↑ 7.0 7.1 7.2 Template:Cite web
- ↑ One of the biggest reasons investing in a Singapore new launch is an effective things is as a result of it is doable to be lent massive quantities of money at very low interest rates that you should utilize to purchase it. Then, if property values continue to go up, then you'll get a really high return on funding (ROI). Simply make sure you purchase one of the higher properties, reminiscent of the ones at Fernvale the Riverbank or any Singapore landed property Get Earnings by means of Renting
In its statement, the singapore property listing - website link, government claimed that the majority citizens buying their first residence won't be hurt by the new measures. Some concessions can even be prolonged to chose teams of consumers, similar to married couples with a minimum of one Singaporean partner who are purchasing their second property so long as they intend to promote their first residential property. Lower the LTV limit on housing loans granted by monetary establishments regulated by MAS from 70% to 60% for property purchasers who are individuals with a number of outstanding housing loans on the time of the brand new housing purchase. Singapore Property Measures - 30 August 2010 The most popular seek for the number of bedrooms in Singapore is 4, followed by 2 and three. Lush Acres EC @ Sengkang
Discover out more about real estate funding in the area, together with info on international funding incentives and property possession. Many Singaporeans have been investing in property across the causeway in recent years, attracted by comparatively low prices. However, those who need to exit their investments quickly are likely to face significant challenges when trying to sell their property – and could finally be stuck with a property they can't sell. Career improvement programmes, in-house valuation, auctions and administrative help, venture advertising and marketing, skilled talks and traisning are continuously planned for the sales associates to help them obtain better outcomes for his or her shoppers while at Knight Frank Singapore. No change Present Rules
Extending the tax exemption would help. The exemption, which may be as a lot as $2 million per family, covers individuals who negotiate a principal reduction on their existing mortgage, sell their house short (i.e., for lower than the excellent loans), or take part in a foreclosure course of. An extension of theexemption would seem like a common-sense means to assist stabilize the housing market, but the political turmoil around the fiscal-cliff negotiations means widespread sense could not win out. Home Minority Chief Nancy Pelosi (D-Calif.) believes that the mortgage relief provision will be on the table during the grand-cut price talks, in response to communications director Nadeam Elshami. Buying or promoting of blue mild bulbs is unlawful.
A vendor's stamp duty has been launched on industrial property for the primary time, at rates ranging from 5 per cent to 15 per cent. The Authorities might be trying to reassure the market that they aren't in opposition to foreigners and PRs investing in Singapore's property market. They imposed these measures because of extenuating components available in the market." The sale of new dual-key EC models will even be restricted to multi-generational households only. The models have two separate entrances, permitting grandparents, for example, to dwell separately. The vendor's stamp obligation takes effect right this moment and applies to industrial property and plots which might be offered inside three years of the date of buy. JLL named Best Performing Property Brand for second year running
The data offered is for normal info purposes only and isn't supposed to be personalised investment or monetary advice. Motley Fool Singapore contributor Stanley Lim would not personal shares in any corporations talked about. Singapore private home costs increased by 1.eight% within the fourth quarter of 2012, up from 0.6% within the earlier quarter. Resale prices of government-built HDB residences which are usually bought by Singaporeans, elevated by 2.5%, quarter on quarter, the quickest acquire in five quarters. And industrial property, prices are actually double the levels of three years ago. No withholding tax in the event you sell your property. All your local information regarding vital HDB policies, condominium launches, land growth, commercial property and more
There are various methods to go about discovering the precise property. Some local newspapers (together with the Straits Instances ) have categorised property sections and many local property brokers have websites. Now there are some specifics to consider when buying a 'new launch' rental. Intended use of the unit Every sale begins with 10 p.c low cost for finish of season sale; changes to 20 % discount storewide; follows by additional reduction of fiftyand ends with last discount of 70 % or extra. Typically there is even a warehouse sale or transferring out sale with huge mark-down of costs for stock clearance. Deborah Regulation from Expat Realtor shares her property market update, plus prime rental residences and houses at the moment available to lease Esparina EC @ Sengkang - ↑ One of the biggest reasons investing in a Singapore new launch is an effective things is as a result of it is doable to be lent massive quantities of money at very low interest rates that you should utilize to purchase it. Then, if property values continue to go up, then you'll get a really high return on funding (ROI). Simply make sure you purchase one of the higher properties, reminiscent of the ones at Fernvale the Riverbank or any Singapore landed property Get Earnings by means of Renting
In its statement, the singapore property listing - website link, government claimed that the majority citizens buying their first residence won't be hurt by the new measures. Some concessions can even be prolonged to chose teams of consumers, similar to married couples with a minimum of one Singaporean partner who are purchasing their second property so long as they intend to promote their first residential property. Lower the LTV limit on housing loans granted by monetary establishments regulated by MAS from 70% to 60% for property purchasers who are individuals with a number of outstanding housing loans on the time of the brand new housing purchase. Singapore Property Measures - 30 August 2010 The most popular seek for the number of bedrooms in Singapore is 4, followed by 2 and three. Lush Acres EC @ Sengkang
Discover out more about real estate funding in the area, together with info on international funding incentives and property possession. Many Singaporeans have been investing in property across the causeway in recent years, attracted by comparatively low prices. However, those who need to exit their investments quickly are likely to face significant challenges when trying to sell their property – and could finally be stuck with a property they can't sell. Career improvement programmes, in-house valuation, auctions and administrative help, venture advertising and marketing, skilled talks and traisning are continuously planned for the sales associates to help them obtain better outcomes for his or her shoppers while at Knight Frank Singapore. No change Present Rules
Extending the tax exemption would help. The exemption, which may be as a lot as $2 million per family, covers individuals who negotiate a principal reduction on their existing mortgage, sell their house short (i.e., for lower than the excellent loans), or take part in a foreclosure course of. An extension of theexemption would seem like a common-sense means to assist stabilize the housing market, but the political turmoil around the fiscal-cliff negotiations means widespread sense could not win out. Home Minority Chief Nancy Pelosi (D-Calif.) believes that the mortgage relief provision will be on the table during the grand-cut price talks, in response to communications director Nadeam Elshami. Buying or promoting of blue mild bulbs is unlawful.
A vendor's stamp duty has been launched on industrial property for the primary time, at rates ranging from 5 per cent to 15 per cent. The Authorities might be trying to reassure the market that they aren't in opposition to foreigners and PRs investing in Singapore's property market. They imposed these measures because of extenuating components available in the market." The sale of new dual-key EC models will even be restricted to multi-generational households only. The models have two separate entrances, permitting grandparents, for example, to dwell separately. The vendor's stamp obligation takes effect right this moment and applies to industrial property and plots which might be offered inside three years of the date of buy. JLL named Best Performing Property Brand for second year running
The data offered is for normal info purposes only and isn't supposed to be personalised investment or monetary advice. Motley Fool Singapore contributor Stanley Lim would not personal shares in any corporations talked about. Singapore private home costs increased by 1.eight% within the fourth quarter of 2012, up from 0.6% within the earlier quarter. Resale prices of government-built HDB residences which are usually bought by Singaporeans, elevated by 2.5%, quarter on quarter, the quickest acquire in five quarters. And industrial property, prices are actually double the levels of three years ago. No withholding tax in the event you sell your property. All your local information regarding vital HDB policies, condominium launches, land growth, commercial property and more
There are various methods to go about discovering the precise property. Some local newspapers (together with the Straits Instances ) have categorised property sections and many local property brokers have websites. Now there are some specifics to consider when buying a 'new launch' rental. Intended use of the unit Every sale begins with 10 p.c low cost for finish of season sale; changes to 20 % discount storewide; follows by additional reduction of fiftyand ends with last discount of 70 % or extra. Typically there is even a warehouse sale or transferring out sale with huge mark-down of costs for stock clearance. Deborah Regulation from Expat Realtor shares her property market update, plus prime rental residences and houses at the moment available to lease Esparina EC @ Sengkang - ↑ One of the biggest reasons investing in a Singapore new launch is an effective things is as a result of it is doable to be lent massive quantities of money at very low interest rates that you should utilize to purchase it. Then, if property values continue to go up, then you'll get a really high return on funding (ROI). Simply make sure you purchase one of the higher properties, reminiscent of the ones at Fernvale the Riverbank or any Singapore landed property Get Earnings by means of Renting
In its statement, the singapore property listing - website link, government claimed that the majority citizens buying their first residence won't be hurt by the new measures. Some concessions can even be prolonged to chose teams of consumers, similar to married couples with a minimum of one Singaporean partner who are purchasing their second property so long as they intend to promote their first residential property. Lower the LTV limit on housing loans granted by monetary establishments regulated by MAS from 70% to 60% for property purchasers who are individuals with a number of outstanding housing loans on the time of the brand new housing purchase. Singapore Property Measures - 30 August 2010 The most popular seek for the number of bedrooms in Singapore is 4, followed by 2 and three. Lush Acres EC @ Sengkang
Discover out more about real estate funding in the area, together with info on international funding incentives and property possession. Many Singaporeans have been investing in property across the causeway in recent years, attracted by comparatively low prices. However, those who need to exit their investments quickly are likely to face significant challenges when trying to sell their property – and could finally be stuck with a property they can't sell. Career improvement programmes, in-house valuation, auctions and administrative help, venture advertising and marketing, skilled talks and traisning are continuously planned for the sales associates to help them obtain better outcomes for his or her shoppers while at Knight Frank Singapore. No change Present Rules
Extending the tax exemption would help. The exemption, which may be as a lot as $2 million per family, covers individuals who negotiate a principal reduction on their existing mortgage, sell their house short (i.e., for lower than the excellent loans), or take part in a foreclosure course of. An extension of theexemption would seem like a common-sense means to assist stabilize the housing market, but the political turmoil around the fiscal-cliff negotiations means widespread sense could not win out. Home Minority Chief Nancy Pelosi (D-Calif.) believes that the mortgage relief provision will be on the table during the grand-cut price talks, in response to communications director Nadeam Elshami. Buying or promoting of blue mild bulbs is unlawful.
A vendor's stamp duty has been launched on industrial property for the primary time, at rates ranging from 5 per cent to 15 per cent. The Authorities might be trying to reassure the market that they aren't in opposition to foreigners and PRs investing in Singapore's property market. They imposed these measures because of extenuating components available in the market." The sale of new dual-key EC models will even be restricted to multi-generational households only. The models have two separate entrances, permitting grandparents, for example, to dwell separately. The vendor's stamp obligation takes effect right this moment and applies to industrial property and plots which might be offered inside three years of the date of buy. JLL named Best Performing Property Brand for second year running
The data offered is for normal info purposes only and isn't supposed to be personalised investment or monetary advice. Motley Fool Singapore contributor Stanley Lim would not personal shares in any corporations talked about. Singapore private home costs increased by 1.eight% within the fourth quarter of 2012, up from 0.6% within the earlier quarter. Resale prices of government-built HDB residences which are usually bought by Singaporeans, elevated by 2.5%, quarter on quarter, the quickest acquire in five quarters. And industrial property, prices are actually double the levels of three years ago. No withholding tax in the event you sell your property. All your local information regarding vital HDB policies, condominium launches, land growth, commercial property and more
There are various methods to go about discovering the precise property. Some local newspapers (together with the Straits Instances ) have categorised property sections and many local property brokers have websites. Now there are some specifics to consider when buying a 'new launch' rental. Intended use of the unit Every sale begins with 10 p.c low cost for finish of season sale; changes to 20 % discount storewide; follows by additional reduction of fiftyand ends with last discount of 70 % or extra. Typically there is even a warehouse sale or transferring out sale with huge mark-down of costs for stock clearance. Deborah Regulation from Expat Realtor shares her property market update, plus prime rental residences and houses at the moment available to lease Esparina EC @ Sengkang - ↑ Template:Cite web
- ↑ Template:Cite web