New Technology and Materials PDF

New Technologies and Materials
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Rheology
Rheology is the study of flow and deformation of materials under applied forces. The measurement of rheological properties is applicable to all materials from fluids such as dilute solutions of polymers and surfactants through to concentrated protein formulations, to semi-solids such as pastes and creams, to molten or solid polymers. Rheological properties can be measured from bulk sample deformation using a mechanical rheometer, or on a micro-scale by using a microcapillary viscometer or an optical technique such as Microrheology. Many commonly-used materials and formulations exhibit complex rheological properties, whose viscosity and viscoelasticity can vary depending upon the external conditions applied, such as stress, strain, timescale and temperature. Internal sample variations such as protein concentration and stability, and formulation type for biopharmaceuticals, are also key factors that determine rheological properties. Rheological properties impact at all stages of material use across multiple industries from formulation development and stability to processing to product performance. Examples of rheological measurements include: Viscosity profiling for non-Newtonian shear-dependent behavior to simulate processing or use conditions. Viscoelastic fingerprinting for material classification to determine extent of solid-like or liquidlike behavior. Optimising dispersion stability. Determination of thixotropy of paints and coatings for product application and final finish quality. Impact of molecular architecture of polymers on viscoelasticity for processing and end-use performance. Benchmarking Food and Personal Care products for ability to pump or spread. Full cure profiling for bonding or gelling systems. Preformulation screening for therapeutics, particularly biopharmaceuticals. Concrete's and mortar's workability is related to the rheological properties of the fresh cement paste. The mechanical properties of hardened concrete increase if less water is used in the concrete mix design, however reducing the water-to-cement ratio may decrease the ease of mixing and application. To avoid these undesired effects, superplasticizers are typically added to decrease the apparent yield stress and the viscosity of the fresh paste. Their addition highly improves concrete and mortar properties.
Surface Properties
A materials property is an intensive, often quantitative, property of a solid or quasi-solid. Quantitative properties may be used as a metric by which the benefits of one material versus another can be assessed, thereby aiding in materials selection. Page 1 of 38
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A property may be a constant or may be a function of one or more independent variables, such as temperature. Materials properties often vary to some degree according to the direction in the material in which they are measured, a condition referred to as anisotropy. Materials properties that relate two different physical phenomena often behave linearly (or approximately so) in a given operating range, and may then be modeled as a constant for that range. This linearization can significantly simplify the differential constitutive equations that the property describes. Some materials properties are used in relevant equations to predict the attributes of a system a priori. For example, if a material of a known specific heat gains or loses a known amount of heat, the temperature change of that material can be determined. Materials properties are most reliably measured by standardized test methods. Many such test methods have been documented by their respective user communities and published through ASTM International. 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. Acoustical properties Atomic properties Chemical properties Electrical properties Environmental properties Magnetic properties Manufacturing properties Mechanical properties Optical properties Radiological properties Thermal properties
Acoustical properties
Acoustical absorption Speed of sound Atomic properties Atomic mass Atomic number - applies to pure elements only Atomic weight - applies to individual isotopes or specific mixtures of isotopes of a given element.
Chemical properties
Corrosion resistance Hygroscopy pH Reactivity Specific internal surface area Surface energy Surface tension
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Electrical properties
Dielectric constant Dielectric strength Electrical conductivity Permeability Permittivity Piezoelectric constants Seebeck coefficient
Environmental properties
Embodied energy Embodied water
Magnetic properties
Curie Point Diamagnetism Hysteresis Permeability
Manufacturing properties
Castability Extruding temperature and pressure Hardness Machinability rating Machining speeds and feeds
Mechanical properties
Compressive strength : Maximum stress a material can withstand before compressive failure (MPa) Ductility : Ability of a material to deform under tensile load (% elongation) Fatigue limit : Maximum stress a material can withstand under repeated loading (MPa) Flexural modulus Flexural strength Fracture toughness : Energy absorbed by unit area before the fracture of material (J/m^2) Hardness : Ability to withstand surface indentation (e.g. Brinell hardness number) Plasticity (physics) : Ability of a material to undergo irreversible deformations (-) Poisson's ratio : Ratio of lateral strain to axial strain (no units) Shear modulus : Ratio of shear stress to shear strain (MPa) Shear strain : Change in the angle between two perpendicular lines in a plane Shear strength : Maximum shear stress a material can withstand Page 3 of 38
New Technologies and Materials Specific modulus : Modulus per unit volume (MPa/ m^3) Specific strength : Strength per unit density (Nm/kg) Specific weight : Weight per unit volume (N/m^3) Tensile strength : Maximum tensile stress a material can withstand before failure (MPa) Yield strength : The stress at which a material starts to yield (MPa) Young's modulus : Ratio of linear stress to linear strain (MPa) Coefficient of friction (also depends on surface finish) Coefficient of restitution Roughness
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Optical properties
Absorptivity Color Luminosity Photosensitivity Reflectivity Refractive index Scattering Transmittance
Radiological properties
Neutron cross-section Specific activity
Thermal properties
Autoignition temperature Binary phase diagram Boiling point Coefficient of thermal expansion Critical temperature Curie point Emissivity Eutectic point Flammability Flash point Glass transition temperature Heat of fusion Heat of vaporization Inversion temperature Melting point Phase diagram Page 4 of 38
New Technologies and Materials Pyrophoricity Solidus Specific heat Thermal conductivity Thermal diffusivity Thermal expansion Seebeck coefficient Triple point Vapor pressure Vicat softening point
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Surfactants
Surfactants are compounds that lower the surface tension between two liquids or between a liquid and a solid. Surfactants may act as detergents, wetting agents, emulsifiers, foaming agents, and dispersants.
Etymology and definition

The term surfactant/surfactants is a blend of surface active agents. In Index Medicus and the United States National Library of Medicine, surfactant/surfactants is reserved for the meaning pulmonary surfactant. For the more general meaning, surface active agent/s is the heading.
Composition and structure

Surfactants are usually organic compounds that are amphiphilic, meaning they contain both hydrophobic groups (their tails) and hydrophilic groups (their heads). Therefore, a surfactant contains both a water insoluble (or oil soluble) component and a water soluble component. Surfactants will diffuse in water and adsorb at interfaces between air and water or at the interface between oil and water, in the case where water is mixed with oil. The insoluble hydrophobic group may extend out of the bulk water phase, into the air or into the oil phase, while the water soluble head group remains in the water phase. This alignment of surfactants at the surface modifies the surface properties of water at the water/air or water/oil interface. World production of surfactants is estimated at 15 Mton/y, of which about half are soaps. Other surfactants produced on a particularly large scale are linear alkylbenzenesulfonates (1700 kton/y), lignin sulfonates (600 kton/y), fatty alcohol ethoxylates (700 ktons/y), and alkylphenol ethoxylates (500 kton/y).
Structure of surfactant phases in water

In the bulk aqueous phase, surfactants form aggregates, such as micelles, where the hydrophobic tails form the core of the aggregate and the hydrophilic heads are in contact with the surrounding liquid. Other types of aggregates such as spherical or cylindrical micelles or bilayers can be formed. The shape of the aggregates depends on the chemical structure of the surfactants, depending on the balance of the Page 5 of 38
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sizes of the hydrophobic tail and hydrophilic head. This is known as the HLB, Hydrophilic-lipophilic balance. Surfactants reduce the surface tension of water by adsorbing at the liquid-gas interface. The relation that links the surface tension and the surface excess is known as the Gibbs isotherm.
Dynamics of surfactants at interfaces

The dynamics of adsorption of surfactants is of great importance for practical applications such as foaming, emulsifying or coating processes, where bubbles or drops are rapidly generated and need to be stabilized. The dynamics of adsorption depends on the diffusion coefficient of the surfactants. Indeed, as the interface is created, the adsorption is limited by the diffusion of the surfactants to the interface. In some cases, there exists a barrier of energy for the adsorption or the desorption of the surfactants, then the adsorption dynamics is known as kinetically limited'. Such energy barrier can be due to steric or electrostatic repulsions. The surface rheology of surfactant layers, including the elasticity and viscosity of the surfactant layers plays a very important role in foam or emulsion stability.
Characterization of interfaces and surfactant layers

Interfacial and surface tension can be characterized by classical methods such as the -pendant or spinning drop method. Dynamic surface tensions, i.e. surface tension as a function of time, can be obtained by the Maximum Bubble Pressure apparatus The structure of surfactant layers can be studied by ellipsometry or X-Ray reflectivity. Surface rheology can be characterized by the oscillating drop method or shear surface rheometers such as double-cone, double-ring or magnetic rod shear surface rheometer.
Detergents in biochemistry and biotechnology

In solution, detergents help solubilize a variety of chemical species by dissociating aggregates and unfolding proteins. Popular surfactants in the biochemistry laboratory are SDS and CTAB. Detergents are key reagents to extract protein by lysis of the cells and tissues: They disorganize the membrane's lipidic bilayer (SDS, Triton X-100, X-114, CHAPS, DOC, and NP-40), and solubilize proteins. Milder detergents such as (OctylThioGlucosides) are used to solubilize sensible proteins (enzymes, receptors). Nonsolubilized material is harvested by centrifugation or other means. For electrophoresis, for example, proteins are classically treated with SDS to denature the native tertiary and quaternary structures, allowing the separation of proteins according to their molecular weight. Detergents have also been used to decellularise organs. This process maintains a matrix of proteins that preserves the structure of the organ and often the microvascular network. The process has been successfully used to prepare organs such as the liver and heart for transplant in rats. Pulmonary surfactants are also naturally secreted by type II cells of the lung alveoli in mammals.
Classification of surfactants
The "tail" of most surfactants are fairly similar, consisting of a hydrocarbon chain, which can be branch, linear, or aromatic. Fluorosurfactants have fluorocarbon chains. Siloxane surfactants have siloxane chains. Page 6 of 38
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Many important surfactants include a polyether chain terminating in a highly polar anionic group. The polyether groups often comprise ethoxylated (polyethylene oxide-like) sequences inserted to increase the hydrophilic character of a surfactant. Polypropylene oxides conversely, may be inserted to increase the lipophilic character of a surfactant. Surfactant molecules have either one tail or two; those with two tails are said to be double-chained. Most commonly, surfactants are classified according to polar head group. A non-ionic surfactant has no charge groups in its head. The head of an ionic surfactant carries a net charge. If the charge is negative, the surfactant is more specifically called anionic; if the charge is positive, it is called cationic. If a surfactant contains a head with two oppositely charged groups, it is termed zwitterionic. Commonly encountered surfactants of each type include:
Anionic Sulfate, sulfonate, and phosphate esters

Anionic surfactants contain anionic functional groups at their head, such as sulfate, sulfonate, phosphate, and carboxylates. Prominent alkyl sulfates include ammonium lauryl sulfate, sodium lauryl sulfate (SDS, sodium dodecyl sulfate, another name for the compound) and the related alkyl-ether sulfates sodium laureth sulfate, also known as sodium lauryl ether sulfate (SLES), and sodium myreth sulfate. Docusates: dioctyl sodium sulfosuccinate, perfluorooctanesulfonate (PFOS), perfluorobutanesulfonate, linear alkylbenzene sulfonates (LABs). These include alkyl-aryl ether phosphates and the alkyl ether phosphate
Carboxylates
These are the most common surfactants and comprise the alkyl carboxylates (soaps), such as sodium stearate. More specialized species include sodium lauroyl sarcosinate and carboxylate-based fluorosurfactants such as perfluorononanoate, perfluorooctanoate (PFOA or PFO).
Cationic head groups

pH-dependent primary, secondary, or tertiary amines: Primary and secondary amines become positively charged at pH < 10: Octenidine dihydrochloride;
Permanently charged quaternary ammonium cation: Alkyltrimethylammonium salts: cetyl trimethylammonium bromide (CTAB) a.k.a. hexadecyl trimethyl ammonium bromide, cetyl trimethylammonium chloride (CTAC) Cetylpyridinium chloride (CPC) Benzalkonium chloride (BAC) Benzethonium chloride (BZT) Page 7 of 38
New Technologies and Materials 5-Bromo-5-nitro-1,3-dioxane Dimethyldioctadecylammonium chloride Cetrimonium bromide Dioctadecyldimethylammonium bromide (DODAB)
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Zwitterionic surfactants
Zwitterionic (amphoteric) surfactants have both cationic and anionic centers attached to the same molecule. The cationic part is based on primary, secondary, or tertiary amines or quaternary ammonium cations. The anionic part can be more variable and include sulfonates, as in CHAPS (3-[(3Cholamidopropyl)dimethylammonio]-1-propanesulfonate). Other anionic groups are sultaines illustrated by cocamidopropyl hydroxysultaine. Betaines, e.g., cocamidopropyl betaine. Phosphates: lecithin
Nonionic surfactant
Many long chain alcohols exhibit some surfactant properties. Prominent among these are the fatty alcohols cetyl alcohol, stearyl alcohol, and cetostearyl alcohol (consisting predominantly of cetyl and stearyl alcohols), and oleyl alcohol. Polyoxyethylene glycol alkyl ethers (Brij): CH3(CH2)1016(O-C2H4)125OH: o Octaethylene glycol monododecyl ether o Pentaethylene glycol monododecyl ether Polyoxypropylene glycol alkyl ethers: CH3(CH2)1016(O-C3H6)125O Glucoside alkyl ethers: CH3(CH2)1016(O-Glucoside)13OH: o Decyl glucoside, o Lauryl glucoside o Octyl glucoside Polyoxyethylene glycol octylphenol ethers: C8H17(C6H4)(O-C2H4)125OH: o Triton X-100 Polyoxyethylene glycol alkylphenol ethers: C9H19(C6H4)(O-C2H4)125OH: o Nonoxynol-9 Glycerol alkyl esters: o Glyceryl laurate Polyoxyethylene glycol sorbitan alkyl esters: Polysorbate Sorbitan alkyl esters: Spans Cocamide MEA, cocamide DEA Dodecyldimethylamine oxide Block copolymers of polyethylene glycol and polypropylene glycol: Poloxamers Polyethoxylated tallow amine (POEA).
According to the composition of their counter-ion

In the case of ionic surfactants, the counter-ion can be: Monoatomic / Inorganic: o Cations: metals : alkali metal, alkaline earth metal, transition metal Page 8 of 38
New Technologies and Materials o Anions: halides: chloride (Cl), bromide (Br), iodide (I) Polyatomic / Organic: o Cations: ammonium, pyridinium, triethanolamine (TEA) o Anions: tosyls, trifluoromethanesulfonates, methylsulfate
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Current market and forecast

The annual global production of surfactants was 13 million metric tons in 2008, and the annual turnover reached US$24.33 billion in 2009, nearly 2% up from the previous year. The market is expected to experience quite healthy growth by 2.8% annually to 2012 and by 3.54% thereafter. Specialists expect the global surfactant market to generate revenues of more than US$41 billion in 2018 translating to an average annual growth of 4.5%
Health and environmental controversy

Surfactants are routinely deposited in numerous ways on land and into water systems, whether as part of an intended process or as industrial and household waste. Some of them are known to be toxic to animals, ecosystems, and humans, and can increase the diffusion of other environmental contaminants. As a result, there are proposed or voluntary restrictions on the use of some surfactants. For example, PFOS is a persistent organic pollutant as judged by the Stockholm Convention. Additionally, PFOA has been subject to a voluntary agreement by the U.S. Environmental Protection Agency and eight chemical companies to reduce and eliminate emissions of the chemical and its precursors. The two major surfactants used in the year 2000 were linear alkylbenzene sulfonates (LAS) and the alkyl phenol ethoxylates (APE). They break down in the aerobic conditions found in sewage treatment plants and in soil. Ordinary dishwashing detergent, for example, will promote water penetration in soil, but the effect would last only a few days (many standard laundry detergent powders contain levels of chemicals such as alkali and chelating agents that can be damaging to plants and should not be applied to soils). Commercial soil wetting agents will continue to work for a considerable period, but they will eventually be degraded by soil micro-organisms. Some can, however, interfere with the life-cycles of some aquatic organisms, so care should be taken to prevent run-off of these products into streams, and excess product should not be washed down. Anionic surfactants can be found in soils as the result of sludge application, wastewater irrigation, and remediation processes. Relatively high concentrations of surfactants together with multimetals can represent an environmental risk. At low concentrations, surfactant application is unlikely to have a significant effect on trace metal mobility.
Biosurfactants
Biosurfactants are surface-active substances synthesised by living cells. Interest in microbial surfactants has been steadily increasing in recent years due to their diversity, environmentally friendly nature, possibility of large-scale production, selectivity, performance under extreme conditions, and potential applications in environmental protection. Few of the popular examples of microbial biosurfactants Page 9 of 38
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includes Emulsan produced by Acinetobacter calcoaceticus, Sophorolipids produced by several yeasts belonging to candida and starmerella clade, and Rhamnolipid produced by Pseudomonas aeruginosa etc. Biosurfactants enhance the emulsification of hydrocarbons, have the potential to solubilise hydrocarbon contaminants and increase their availability for microbial degradation. The use of chemicals for the treatment of a hydrocarbon polluted site may contaminate the environment with their by-products, whereas biological treatment may efficiently destroy pollutants, while being biodegradable themselves. Hence, biosurfactant-producing microorganisms may play an important role in the accelerated bioremediation of hydrocarbon-contaminated sites. These compounds can also be used in enhanced oil recovery and may be considered for other potential applications in environmental protection. Other applications include herbicides and pesticides formulations, detergents, healthcare and cosmetics, pulp and paper, coal, textiles, ceramic processing and food industries, uranium ore-processing, and mechanical dewatering of peat. Several microorganisms are known to synthesise surface-active agents; most of them are bacteria and yeasts. When grown on hydrocarbon substrate as the carbon source, these microorganisms synthesise a wide range of chemicals with surface activity, such as glycolipid, phospholipid, and others. These chemicals are synthesised to emulsify the hydrocarbon substrate and facilitate its transport into the cells. In some bacterial species such as Pseudomonas aeruginosa, biosurfactants are also involved in a group motility behavior called swarming motility.
Safety and environmental risks

Most anionic and nonionic surfactants are nontoxic, having LD50 comparable to sodium chloride. The situation for cationic surfactants is more diverse. Dialkyldimethylammonium chlorides have very low LD50's (5 g/kg) but alkylbenzyldimethylammonium chloride has an LD50 of 0.35 g/kg. Prolonged exposure of skin to surfactants can cause chaffing because surfactants (e.g., soap) disrupts the lipid coating that protects skin (and other) cells.
Biosurfactants and Deepwater Horizon

The use of biosurfactants as a way to remove petroleum from contaminated sites has been studied and found to be safe and effective in the removal petroleum products from soil. Biosurfactants were not used by BP after the Deepwater Horizon oil spill. However, unprecedented amounts of Corexit (active ingredient: Tween-80), were sprayed directly into the ocean at the leak and on the sea-water's surface, the theory being that the surfactants isolate droplets of oil, making it easier for petroleum-consuming microbes to digest the oil.
Applications
Surfactants play an important role as cleaning, wetting, dispersing, emulsifying, foaming and antifoaming agents in many practical applications and products, including: Detergents Fabric softeners Page 10 of 38
New Technologies and Materials Emulsions Paints Adhesives Inks Anti-fogs Ski waxes, snowboard wax Deinking of recycled papers, in flotation, washing and enzymatic processes Laxatives Agrochemical formulations o Herbicides (some) o Insecticides Quantum dot coatings Biocides (sanitizers) Cosmetics: o Shampoos o Hair conditioners (after shampoo) o Toothpastes Spermicides (nonoxynol-9) Firefighting Pipelines, liquid drag reducing agent Alkali Surfactant Polymers (used to mobilize oil in oil wells) Ferrofluids Leak Detectors
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Thermal conduction
In heat transfer, conduction (or heat conduction) is the transfer of heat energy by microscopic diffusion and collisions of particles or quasi-particles within a body due to a temperature gradient. The microscopically diffusing and colliding objects include molecules, electrons, atoms, and phonons. They transfer microscopically disorganized kinetic and potential energy, which are jointly known as internal energy. Conduction can only take place within an object or material, or between two objects that are in direct or indirect contact with each other. Conduction takes place in all forms of ponderable matter, such as solids, liquids, gases and plasmas. Whether by conduction or by thermal radiation, heat spontaneously flows from a body at a higher temperature to a body at a lower temperature. In the absence of external drivers, temperature differences decay over time, and the bodies approach thermal equilibrium. In conduction, heat flows within and through the body itself. In contrast, in heat transfer by thermal radiation, the transfer is often between bodies. Also possible is transfer of heat by a combination of conduction and thermal radiation. In convection, internal energy is carried between bodies by a material carrier. In solids, conduction is mediated by the combination of vibrations and collisions of molecules, of propagation and collisions of phonons, and of diffusion and collisions of free electrons. In gases and Page 11 of 38
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liquids, conduction is due to the collisions and diffusion of molecules during their random motion. Photons in this context do not collide with one another, and so heat transport by electromagnetic radiation is conceptually distinct from heat conduction by microscopic diffusion and collisions of material particles and phonons. In condensed matter, such as a solid or liquid, the distinction between conduction and radiative transfer of heat is clear in physical concept, but it is often not phenomenologically clear, unless the material is semi-transparent. In a gas the distinction is both conceptually and phenomenologically clear. In the engineering sciences, heat transfer includes the processes of thermal radiation, convection, and sometimes mass transfer. Usually more than one of these processes occurs in a given situation. The conventional symbol for the material property, thermal conductivity, is .
Overview
On a microscopic scale, conduction occurs within a body considered as being stationary; this means that the kinetic and potential energies of the bulk motion of the body are separately accounted for. Internal energy diffuses as rapidly moving or vibrating atoms and molecules interact with neighboring particles, transferring some of their microscopic kinetic and potential energies, these quantities being defined relative to the bulk of the body considered as being stationary. Heat is transferred by conduction when adjacent atoms or molecules collide, or as several electrons move backwards and forwards from atom to atom in a disorganized way so as not to form a macroscopic electric current, or as phonons collide and scatter. Conduction is the most significant means of heat transfer within a solid or between solid objects in thermal contact. Conduction is greater in solids because the network of relatively close fixed spatial relationships between atoms helps to transfer energy between them by vibration. Fluids (and especially gases) are less conductive. This is due to the large distance between atoms in a gas: fewer collisions between atoms means less conduction. Conductivity of gases increases with temperature. Conductivity increases with increasing pressure from vacuum up to a critical point that the density of the gas is such that molecules of the gas may be expected to collide with each other before they transfer heat from one surface to another. After this point conductivity increases only slightly with increasing pressure and density. Thermal contact conductance is the study of heat conduction between solid bodies in contact. A temperature drop is often observed at the interface between the two surfaces in contact. This phenomenon is said to be a result of a thermal contact resistance existing between the contacting surfaces. Interfacial thermal resistance is a measure of an interface's resistance to thermal flow. This thermal resistance differs from contact resistance, as it exists even at atomically perfect interfaces. Understanding the thermal resistance at the interface between two materials is of primary significance in the study of its thermal properties. Interfaces often contribute significantly to the observed properties of the materials. The inter-molecular transfer of energy could be primarily by elastic impact as in fluids or by free electron diffusion as in metals or phonon vibration as in insulators. In insulators the heat flux is carried almost entirely by phonon vibrations.
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Metals (e.g. copper, platinum, gold,etc.) are usually good conductors of thermal energy. This is due to the way that metals are chemically bonded: metallic bonds (as opposed to covalent or ionic bonds) have free-moving electrons which are able to transfer thermal energy rapidly through the metal. The "electron fluid" of a conductive metallic solid conducts most of the heat flux through the solid. Phonon flux is still present, but carries less of the energy. Electrons also conduct electric current through conductive solids, and the thermal and electrical conductivities of most metals have about the same ratio. A good electrical conductor, such as copper, also conducts heat well. Thermoelectricity is caused by the interaction of heat flux and electrical current. Heat conduction within a solid is directly analogous to diffusion of particles within a fluid, in the situation where there are no fluid currents. To quantify the ease with which a particular medium conducts, engineers employ the thermal conductivity, also known as the conductivity constant or conduction coefficient, k. In thermal conductivity k is defined as "the quantity of heat, Q, transmitted in time (t) through a thickness (L), in a direction normal to a surface of area (A), due to a temperature difference (T) *...+." Thermal conductivity is a material property that is primarily dependent on the medium's phase, temperature, density, and molecular bonding. Thermal effusivity is a quantity derived from conductivity which is a measure of its ability to exchange thermal energy with its surroundings.
Steady-state conduction
Steady state conduction is the form of conduction that happens when the temperature difference(s) driving the conduction are constant, so that (after an equilibration time), the spatial distribution of temperatures (temperature field) in the conducting object does not change any further. Thus, all partial derivatives of temperature with respect to space may either be zero or have nonzero values, but all derivatives of temperature at any point with respect to time are uniformly zero. In steady state conduction, the amount of heat entering any region of an object is equal to amount of heat coming out (if this were not so, the temperature would be rising or falling, as thermal energy was tapped or trapped in a region). For example, a bar may be cold at one end and hot at the other, but after a state of steady state conduction is reached, the spatial gradient of temperatures along the bar does not change any further, as time proceeds. Instead, the temperature at any given section of the rod remains constant, and this temperature varies linearly in space, along the direction of heat transfer. In steady state conduction, all the laws of direct current electrical conduction can be applied to "heat currents". In such cases, it is possible to take "thermal resistances" as the analog to electrical resistances. In such cases, temperature plays the role of voltage, and heat transferred per unit time (heat power) is the analog of electrical current. Steady state systems can be modelled by networks of such thermal resistances in series and in parallel, in exact analogy to electrical networks of resistors. See purely resistive thermal circuits for an example of such a network.
Transient conduction
In general, during any period in which temperatures are changing in time at any place within an object, the mode of thermal energy flow is termed transient conduction. Another term is "non steady-state" conduction, referring to time-dependence of temperature fields in an object. Non-steady-state Page 13 of 38
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situations appear after an imposed change in temperature at a boundary of an object. They may also occur with temperature changes inside an object, as a result of a new source or sink of heat suddenly introduced within an object, causing temperatures near the source or sink to change in time. When a new perturbation of temperature of this type happens, temperatures within the system will change in time toward a new equilibrium with the new conditions, provided that these do not change. After equilibrium, heat flow into the system will once again equal the heat flow out, and temperatures at each point inside the system no longer change. Once this happens, transient conduction is ended, although steady-state conduction may continue if there continues to be heat flow. If changes in external temperatures or internal heat generation changes are too rapid for equilibrium of temperatures in space to take place, then the system never reaches a state of unchanging temperature distribution in time, and the system remains in a transient state. An example of a new source of heat "turning on" within an object which causes transient conduction, is an engine starting in an automobile. In this case the transient thermal conduction phase for the entire machine would be over, and the steady state phase would appear, as soon as the engine had reached steady-state operating temperature. In this state of steady-state equilibrium, temperatures would vary greatly from the engine cylinders to other parts of the automobile, but at no point in space within the automobile would temperature be increasing or decreasing. After establishment of this state, the transient conduction phase of heat transfer would be over. New external conditions also cause this process: for example the copper bar in the example steady-state conduction would experience transient conduction as soon as one end was subjected to a different temperature from the other. Over time, the field of temperatures inside the bar would reach a new steady-state, in which a constant temperature gradient along the bar will finally be set up, and this gradient would then stay constant in space. Typically, such a new steady state gradient is approached exponentially with time after a new temperature-or-heat source or sink, has been introduced. When a "transient conduction" phase is over, heat flow may still continue at high power, so long as temperatures do not change. An example of transient conduction which does not end with steady-state conduction, but rather no conduction, occurs when a hot copper ball is dropped into oil at a low temperature. Here the temperature field within the object begins to change as a function of time, as the heat is removed from the metal, and the interest lies in analyzing this spatial change of temperature within the object over time, until all gradients disappear entirely (the ball has reached the same temperature as the oil). Mathematically, this condition is also approached exponentially; in theory it takes infinite time, but in practice it is over, for all intents and purposes, in a much shorter period. At the end of this process with no heat sink but the internal parts of the ball (which are finite), there is no steady state heat conduction to be reached. Such a state never occurs in this situation, but rather the end of the process is when there is no heat conduction at all. Analysis of non steady-state conduction systems is more complex than steady-state systems, and (except for simple shapes) calls for the application of approximation theories, and/or numerical analysis by computer. One popular graphical method involves the use of Heisler Charts. Page 14 of 38
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Occasionally transient conduction problems may be considerably simplified if regions of the object being heated or cooled can be identified, in which thermal conductivity is very much greater than that for heat paths leading into the region. In this case, the region with high conductivity can often be treated in the lumped capacitance model, as a "lump" of material with a simple thermal capacitance consisting of its aggregate heat capacity. Such regions show no temperature variation across their extent during warming or cooling (as compared to the rest of the system) due to their far higher conductance. During transient conduction, therefore, their temperature changes uniformly in space, and as a simple exponential in time. An example of such systems are those which follow "Newton's law of cooling" during transient cooling (or the reverse during heating). The equivalent thermal circuit consists of a simple capacitor in series with a resistor. In such cases, the remainder of the system with high thermal resistance (comparatively low conductivity) plays the role of the resistor in the circuit.
Relativistic conduction
The theory of relativistic heat conduction is a model that is compatible with the theory of special relativity. For most of the last century, it was recognized that Fourier equation is in contradiction with the theory of relativity because it admits an infinite speed of propagation of heat signals. For example, according to Fourier equation, a pulse of heat at the origin would be felt at infinity instantaneously. The speed of information propagation is faster than the speed of light in vacuum, which is physically inadmissible within the framework of relativity. Alterations to the Fourier model provided for a relativistic model of heat conduction, avoiding this problem.
Quantum conduction
Second sound is a quantum mechanical phenomenon in which heat transfer occurs by wave-like motion, rather than by the more usual mechanism of diffusion. Heat takes the place of pressure in normal sound waves. This leads to a very high thermal conductivity. It is known as "second sound" because the wave motion of heat is similar to the propagation of sound in air.
Fourier's law
The law of heat conduction, also known as Fourier's law, states that the time rate of heat transfer through a material is proportional to the negative gradient in the temperature and to the area, at right angles to that gradient, through which the heat is flowing. We can state this law in two equivalent forms: the integral form, in which we look at the amount of energy flowing into or out of a body as a whole, and the differential form, in which we look at the flow rates or fluxes of energy locally. Newton's law of cooling is a discrete analog of Fourier's law, while Ohm's law is the electrical analogue of Fourier's law.
Differential form
The differential form of Fourier's Law of thermal conduction shows that the local heat flux density, is equal to the product of thermal conductivity, , and the negative local temperature gradient, . The heat flux density is the amount of energy that flows through a unit area per unit time. ,
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where (including the SI units) is the local heat flux, Wm2 is the material's conductivity, Wm1K1, is the temperature gradient, Km1. The thermal conductivity, , is often treated as a constant, though this is not always true. While the thermal conductivity of a material generally varies with temperature, the variation can be small over a significant range of temperatures for some common materials. In anisotropic materials, the thermal conductivity typically varies with orientation; in this case is represented by a second-order tensor. In non-uniform materials, varies with spatial location. For many simple applications, Fourier's law is used in its one-dimensional form. In the x-direction,
Integral form
By integrating the differential form over the material's total surface Fourier's law: , we arrive at the integral form of
where (including the SI units)
: :
is the amount of heat transferred per unit time (in W) and is an oriented surface area element (in m2)
The above differential equation, when integrated for a homogeneous material of 1-D geometry between two endpoints at constant temperature, gives the heat flow rate as:
Where A is the cross-sectional surface area, is the temperature difference between the ends, is the distance between the ends. Page 16 of 38
New Technologies and Materials This law forms the basis for the derivation of the heat equation.
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Conductance
Writing
where U is the conductance, in W/(m2 K). Fourier's law can also be stated as:
The reciprocal of conductance is resistance, R, given by:
and it is resistance which is additive when several conducting layers lie between the hot and cool regions, because A and Q are the same for all layers. In a multilayer partition, the total conductance is related to the conductance of its layers by:
So, when dealing with a multilayer partition, the following formula is usually used:
When heat is being conducted from one fluid to another through a barrier, it is sometimes important to consider the conductance of the thin film of fluid which remains stationary next to the barrier. This thin film of fluid is difficult to quantify, its characteristics depending upon complex conditions of turbulence and viscosity, but when dealing with thin high-conductance barriers it can sometimes be quite significant.
Intensive-property representation
The previous conductance equations, written in terms of extensive properties, can be reformulated in terms of intensive properties. Ideally, the formulae for conductance should produce a quantity with dimensions independent of distance, like Ohm's Law for electrical resistance: , and conductance: .
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New Technologies and Materials From the electrical formula: area, we have sectional area. For Heat,
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, where G is conductance, k is conductivity, x is length, and A is cross-
where U is the conductance. Fourier's law can also be stated as:
analogous to Ohm's law:
or
The reciprocal of conductance is resistance, R, given by:
analogous to Ohm's law: The rules for combining resistances and conductances (in series and in parallel) are the same for both heat flow and electric current.
Cylindrical shells
Conduction through cylindrical shells (e.g. pipes) can be calculated from the internal radius, , the external radius, , the length, , and the temperature difference between the inner and outer wall, .
The surface area of the cylinder is When Fouriers equation is applied:
and rearranged:
then the rate of heat transfer is: Page 18 of 38
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the thermal resistance is:
and log-mean radius.
, where
. It is important to note that this is the
Spherical
The conduction through a spherical shell with internal radius, calculated in a similar manner as for a cylindrical shell. The surface area of the sphere is: Solving in a similar manner as for a cylindrical shell (see above) , and external radius, , can be
produces:
Transient Thermal Conduction

Interface Heat Transfer
The heat transfer at an interface is considered a transient heat flow. To analyze this problem, the Biot number is important to understand how the system will behave. The Biot number is determined by: The heat transfer coefficient, h, is introduced in this formula, and is measured
in . If the system has a Biot number of less than 0.1, the material behaves according to Newtonian cooling, i.e. with negligible temperature gradient within the body. If the Biot number is greater than 0.1, the system will behave as a series solution. The temperature profile in terms of time can be determined by the function can be derived from the equation:
Which will become:
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The heat transfer coefficient, h, is measured in , and represents the transfer of heat at an interface between two materials. This value is different at every interface, and is an important concept in understanding heat flow at an interface. The Series Solution can be analyzed with a nomogram. A nomogram has relative temperature as the y coordinate and the Fourier number, which is calculated by: The Biot number increases as the Fourier number decreases. There are 5 steps to determine a temperature profile in terms of time. Step 1. Step 2. Step 3. Step 4. Step 5. Calculate the Biot number Determine which relative depth matters, either x or L. Convert time to the Fourier number. Convert to relative temperature with the boundary conditions. Compared required point to trace specified Biot number on the nomogram.
Thermal Conduction Applications

Splat Cooling
Splat cooling is a method for quenching small droplets of molten materials by rapid contact with a cold surface. The particles undergo a characteristic cooling process, with the heat profile at for initial temperature as the maximum at and at and , and the heat profile at for as the boundary conditions. Splat cooling rapidly ends in a steady state temperature, and is similar in form to the Gaussian diffusion equation. The temperature profile, with respect to the position and time of this type of cooling, varies with:
Splat cooling is a fundamental concept that has been adapted for practical use in the form of thermal
spraying. The thermal diffusivity coefficient, represented as alpha, can be written as varies according to the material.
. This
Colloids
A colloid is one of the three main types of mixtures, with the other two being a solution or suspension. A colloid is a solution that has particles ranging between 1 and 1000 nanometers in diameter, yet is still able to remain evenly distributed throughout the solution. These are also known as colloidal dispersions because the substances remain dispersed and don't settle to the bottom. In a colloid one substance is evenly dispersed in another. The substance being dispersed is referred to as being in the dispersed phase, while the substance in which it is dispersed is in the continuous phase.
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New Technologies and Materials 1. 2. 3. 4. 5. 6. 7. 8. Properties of Colloids Types of Colloids Classifying Colloids References Outside Links Practice Problems Answers Contributors
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Properties of Colloids
In order to be classified as a colloid, the substance in the dispersed phase must be larger than the size of a molecule but smaller than what can be seen with the naked eye. This can be more precisely quantified as one or more of the substance's dimensions must be between 1 and 1000 nanometers. If the dimensions are smaller than this the substance is considered a solution and if they are larger than the substance is a suspension.
Types of Colloids
A common method of classifying colloids is based on the phase of the dispersed substance and what phase it is dispersed in. They types of colloids includes sol, emulsion, foam, and aerosol. Sol is a colloidal suspension with solid particles in a liquid. Emulsion is between two liquids. Foam is formed when many gas particles are trapped in a liquid or solid. Aerosol contains small particles of liquid or solid dispersed in a gas.
When the dispersion medium is water, the colloidal system is referred to as a hydrocolloid. The particles in the dispersed phase can take place in different phases depending on how much water is available. For example, Jello powder mixed in with water creates a hydrocolloid. A common use for hydrocolloids is in the creation of medical dressings. Dispersion Medium Solid Solid Solid Liquid Liquid Liquid Gas Gas Dispersed Phase Solid Liquid Gas Solid Liquid Gas Solid Liquid Type of Colloid Solid sol Solid emulsion/gel Solid foam Sol Emulsion Foam Aerosol Aerosol Page 21 of 38 Example Ruby glass Pearl, cheese Lava, pumice Paints, cell fluids Milk, oil in water Soap suds, cream Smoke Fog, mist whipped
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Classifying Colloids
An easy way of determining whether a mixture is colloidal or not is through use of the Tyndall Effect. When light is shined through a true solution, the light passes cleanly through the solution, however when light is passed through a colloidal solution, the substance in the dispersed phases scatters the light in all directions, making it readily seen. An example of this is shining a flashlight into fog. The beam of light can be easily seen because the fog is a colloid. Light being shined through water and milk. The light is not reflected when passing through the water because it is not a colloid. It is however reflected in all directions when it passes through the milk, which is colloidal. Another method of determining whether a mixture is a colloid is by passing it through a semipermeable membrane. The dispersed particles in a colloid would be unable to pass through the membrane. Dialysis takes advantage of the fact that colloids cannot diffuse through semipermeable membranes to filter them out of a
Practice Problems
Q 1) Is dust a colloid? If so, what type is it? Q 2) Is whipped cream a colloid? if so, what type is it? Q 3) What does Sol mean? Q 4) When hit by light what happens to a colloidal mixture? Q 5) What is the mixture considered if the particles are larger than the particles of a colloidal substance
Answers
A 1) A 2) A 3) A 4) A 5) Dust is a colloid. It consists of a solid in a gas, so it is a aerosol. Whipped cream is a colloid. It consists of a gas in a liquid, so it is a foam. Sol is a colloidal suspension with solid particles in a liquid. The light is reflected off the large particles and spread out. It's considered a suspension if the particles are larger than 1000 nanometers.
Work Hardening or Strain Hardening

Work hardening, also known as strain hardening or cold working, is the strengthening of a metal by plastic deformation. This strengthening occurs because of dislocation movements and dislocation generation within the crystal structure of the material. Many non-brittle metals with a reasonably high melting point as well as several polymers can be strengthened in this fashion. Alloys not amenable to heat treatment, including low-carbon steel, are often work-hardened. Some materials cannot be workhardened at normal ambient temperatures, such as indium,however others can only be strengthened via work hardening, such as pure copper and aluminum.
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Theory
Before work hardening, the lattice of the material exhibits a regular, nearly defect-free pattern (almost no dislocations). The defect-free lattice can be created or restored at any time by annealing. As the material is work hardened it becomes increasingly saturated with new dislocations, and more dislocations are prevented from nucleating (a resistance to dislocation-formation develops). This resistance to dislocation-formation manifests itself as a resistance to plastic deformation; hence, the observed strengthening. In metallic crystals, irreversible deformation is usually carried out on a microscopic scale by defects called dislocations, which are created by fluctuations in local stress fields within the material culminating in a lattice rearrangement as the dislocations propagate through the lattice. At normal temperatures the dislocations are not annihilated by annealing. Instead, the dislocations accumulate, interact with one another, and serve as pinning points or obstacles that significantly impede their motion. This leads to an increase in the yield strength of the material and a subsequent decrease in ductility. Such deformation increases the concentration of dislocations which may subsequently form low-angle grain boundaries surrounding sub-grains. Cold working generally results in a higher yield strength as a result of the increased number of dislocations and the Hall-Petch effect of the sub-grains, and a decrease in ductility. The effects of cold working may be reversed by annealing the material at high temperatures where recovery and recrystallization reduce the dislocation density. A material's work hardenability can be predicted by analyzing a stress-strain curve, or studied in context by performing hardness tests before and after a process Hollomon's equation is a power law relationship between the stress and the amount of plastic strain: where is the stress, K is the strength index, p is the plastic strain and n is the strain hardening exponent.
Advantages and Disadvantages

Advantages
No heating required Better surface finish Superior dimensional control Better reproducibility and interchangeability Directional properties can be imparted into the metal Contamination problems are minimized
Disadvantages
Greater forces are required Heavier and more powerful equipment and stronger tooling are required Metal is less ductile Metal surfaces must be clean and scale-free Page 23 of 38
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Intermediate anneals may be required to compensate for loss of ductility that accompanies strain hardening The imparted directional properties may be detrimental Undesirable residual stress may be produced
Capillarity
The phenomenon in which water rises above the ground water table against the pull of gravity, but is in contact with the water table as its source, is referred to as Capillary rise with reference to soils. The water associated with capillary rise is called capillary moisture. The phenomenon by virtue of w hich a liquid rises in capillary tubes is, in general, called Capillarity. Capillary action can be defined as the ascension of liquids through slim tube, cylinder or permeable substance due to adhesive and cohesive forces interacting between the liquid and the surface. When intermolecular bonding of a liquid itself is substantially inferior to a substances surface it is interacting, capillarity occurs. Also, the diameter of the container as well as the gravitational forces will determine amount of liquid raised. While, water possesses this unique property, a liquid like mercury will not display the same attributes due to the fact that it has higher cohesive force than adhesive force.
Forces in Capillary Action

Three main variables that determine whether a liquid possesses capillary action are: Cohesive force: It is the intermolecular bonding of a substance where its mutual attractiveness forces them to maintain a certain shape of the liquid. Surface tension: This occurs as a result of like molecules, cohesive forces, banding together to form a somewhat impenetrable surface on the body of water. The surface tension is measured in Newton/meter. Adhesive force: When forces of attraction between unlike molecules occur, it is called adhesive forces. Capillary action only occurs when the adhesive forces are stronger than the cohesive forces, which invariably becomes surface tension, in the liquid. A good way to remember the difference between adhesive and cohesive forces is that with adhesive forces you add another set of molecules, the molecules of the surface, for the liquid to bond with. With cohesive forces, the molecules of the liquid will only cooperate with their own kind. Decreased surface tension also increases capillary action. This is because decreased surface tension means that the intermolecular forces are decreased, thus decreasing cohesive forces. As a result, capillary action will be even greater.
Applications:
Practical use of capillary action is evident in all forms of our daily lives. It makes performing our tasks efficiently and effectively. Some applications of this unique property include:
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The fundamental properties are used to absorb water by using paper towels. The cohesive and adhesive properties draw the fluid into the paper towel. The liquid flows into the paper towel at a certain rate. A technique called thin layer chromatography uses capillary action in which a layer of liquid is used to separate mixtures from substances. Capillary action helps us naturally by pumping out tear fluid in the eye. This process cleanses the eye and clears all of the dust and particles that are around the ducts of the eye. To generate energy: A possible use for capillary action is as a source of renewable energy. By allowing water to climb through capillaries, evaporate once it reaches the top, the condensate and drop back down to the bottom spinning a turbine on its way to create the energy, capillary action can make electricity! Although this idea is still in the works, it goes to show the potential that capillary action holds and how important it is.
Formula and Mathematics

Formula for the Height of a Meniscus
When measuring the level of liquid of a test tube or buret, it is imperative to measure at the meniscus line for an accurate reading. It is possible to measure the height (represented by h) of a test tube, buret, or other liquid column using the formula:
In this formula, represents the surface tension in a liquid-air environment, is the angle of contact or the degree of contact, is the density of the liquid in the representative column, g is the acceleration due to the force of gravity and r is the radius of the tube in which the liquid is presented in. At optimum level, in which a glass tube filled with water is present in air, this formula can determine the height of a specific column of water in meters (m):
However, the following conditions must be met for this formula to occur. = 0.0728 N/m (when water is at a temperature of 20C) = 20 is 1000 kg/m3 g= 9.8 m/s2
Formula for Volume of Liquid Transport in Medium:

When certain objects that are porous encounter a liquid medium, it will begin to absorb the liquid at a rate which actually decreases over a period of time. This formula is written as:
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In this specific formula, A is the wet area (cross-section), S is the sorptivity (capacity of medium to absorb using the process of capillary action), V is the volume of liquid absorbed in time, t.
Rise of Water in Capillary Tubes
This equation helps one in computing the capillary rise of water in a glass capillary tube.
Conceptual and Mathematical Quiz

Q 1) Name one way to increase capillary action, and one way to decrease it. Q 2) If cohesion is greater than adhesion, will the meniscus be convex or concave? Q 3) What would be the height of a liquid in a column, on earth, with a liquid-air surface tension 0f .0973 N/m, contact angle of 30 degrees, density of 1200 kg/m3? Note that the radius of the tube is 0.2 meters. Q 4) What would be the height of water in a glass tube with a radius of .6mm?
Answers to Quiz
A 1)Increase capillary action: Increase temperature, decrease capillary tube diameter, perform any number of actions to decrease surface tension, etc! Decrease capillary action: The opposite of the steps you would take to increase, also, increasing the density of the liquid you're working with. A 2)The meniscus will result in a convex formation. A 3)Using the formula above, the height of the liquid will be 7.165* 10-5m high. A 4)Using the formula above, the height of the water in the glass tube would be .014m high.
Workout in Capillarity
Q 1) To what height would water rise in a glass capillary tube of 0.01 mm diameter? What is the water pressure just under the meniscus in the capillary tube? Q 2) The D10 size of a soil is 0.01 mm. Assuming (1/5) D10 as the pore size, estimate the height of capillary rise assuming surface tension of water as 75 dynes/cm. Q 3) The effective sizes of two soils are 0.05 mm and 0.10 mm, the void ratio being the same for both. If the capillary rise in the first soil is 72 cm, what would be the capillary rise in the second soil?
Atomic Bonding
Atomic bonding is chemical bonding. Chemical bonding is the physical process that is responsible for the interactions between atoms and molecules. Bonds vary widely. There are covalent, ionic, hydrogen, metallic, as well as many other types of bonds, and all have a working connection in all living things. Page 26 of 38
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There are two different types of atomic bonds: primary and secondary. The primary bonds produce chemical bonds that hold atoms together. A chemical bond is an attraction between atoms that allows the formation of chemical substances that contain two or more atoms. The bond is caused by the electrostatic force of attraction between opposite charges, either between electrons and nuclei, or as the result of a dipole attraction. The strength of chemical bonds varies considerably; there are "strong bonds" such as covalent or ionic bonds and "weak bonds" such as dipoledipole interactions, the London dispersion force and hydrogen bonding. Since opposite charges attract via a simple electromagnetic force, the negatively charged electrons that are orbiting the nucleus and the positively charged protons in the nucleus attract each other. An electron positioned between two nuclei will be attracted to both of them and the nuclei will be attracted toward electrons in this position. This attraction constitutes the chemical bond. Due to the matter wave nature of electrons and their smaller mass, they must occupy a much larger amount of volume compared with the nuclei, and this volume occupied by the electrons keeps the atomic nuclei relatively far apart, as compared with the size of the nuclei themselves. This phenomenon limits the distance between nuclei and atoms in a bond. In general, strong chemical bonding is associated with the sharing or transfer of electrons between the participating atoms. The atoms in molecules, crystals, metals and diatomic gases indeed most of the physical environment around us are held together by chemical bonds, which dictate the structure and the bulk properties of matter.
Types of Atomic Bonds

Atomic bonds have two types of bonds: primary and secondary bonds. The primary bonds have three types of bonds: metallic, covalent and ionic. The secondary bonds also subsections of bonds, and are considered the weaker elements.
Overview of main types of chemical bonds

A chemical bond is an attraction between atoms. This attraction may be seen as the result of different behaviors of the outermost electrons of atoms. Although all of these behaviors merge into each other seamlessly in various bonding situations so that there is no clear line to be drawn between them, nevertheless behaviors of atoms become so qualitatively different as the character of the bond changes quantitatively, that it remains useful and customary to differentiate between the bonds that cause these different properties of condensed matter.
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In the simplest view of a so called 'covalent' bond, one or more electrons (often a pair of electrons) are drawn into the space between the two atomic nuclei. Here the negatively charged electrons are attracted to the positive charges of both nuclei, instead of just their own. This overcomes the repulsion between the two positively charged nuclei of the two atoms, and so this overwhelming attraction holds the two nuclei in a fixed configuration of equilibrium, even though they will still vibrate at equilibrium position. Thus, covalent bonding involves sharing of electrons in which the positively charged nuclei of two or more atoms simultaneously attract the negatively charged electrons that are being shared between them. These bonds exist between two particular identifiable atoms, and have a direction in space, allowing them to be shown as single connecting lines between atoms in drawings, or modeled as sticks between spheres in models. In a polar covalent bond, one or more electrons are unequally shared between two nuclei. Covalent bonds often result in the formation of small collections of better connected atoms called molecules, which in solids and liquids are bound to other molecules by forces that are often much weaker than the covalent bonds that hold the molecules internally together. Such weak intermolecular bonds give organic molecular substances, such as waxes and oils, their soft bulk character, and their low melting points (in liquids, molecules must cease most structured or oriented contact with each other). When covalent bonds link long chains of atoms in large molecules, however (as in polymers such as nylon), or when covalent bonds extend in networks though solids that are not composed of discrete molecules (such as diamond or quartz or the silicate minerals in many types of rock) then the structures that result may be both strong and tough, at least in the direction oriented correctly with networks of covalent bonds. Also, the melting points of such covalent polymers and networks increase greatly. In a simplified view of an ionic bond, the bonding electron is not shared at all, but transferred. In this type of bond, the outer atomic orbital of one atom has a vacancy which allows addition of one or more electrons. These newly added electrons potentially occupy a lower energy-state (effectively closer to more nuclear charge) than they experience in a different atom. Thus, one nucleus offers a more tightly bound position to an electron than does another nucleus, with the result that one atom may transfer an electron to the other. This transfer causes one atom to assume a net positive charge, and the other to assume a net negative charge. The bond then results from electrostatic attraction between atoms, and the atoms become positive or negatively charged ions. Ionic bonds may be seen as extreme examples of polarization in covalent bonds. Often, such bonds have no particular orientation in space, since they result from equal electrostatic attraction of each ion to all ions around them. Ionic bonds are strong (and thus ionic substances require high temperatures to melt) but also brittle, since the forces between ions are short-range, and do not easily bridge cracks and fractures. This type of bond gives rise to the physical characteristics of crystals of classic mineral salts, such as table salt. A less often mentioned type of bonding is the metallic bond. In this type of bonding, each atom in a metal donates one or more electrons to a "sea" of electrons that reside between many metal atoms. In this sea, each electron is free (by virtue of its wave nature) to be associated with a great many atoms at once. The bond results because the metal atoms become somewhat positively charged due to loss of their electrons, while the electrons remain attracted to many atoms, without being part of any given atom. Metallic bonding may be seen as an extreme example of de-localization of electrons over a large system of covalent bonds, in which every atom participates. This type of bonding is often very strong Page 28 of 38
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(resulting in the tensile strength of metals). However, metallic bonds are more collective in nature than other types, and so they allow metal crystals to more easily deform, because they are composed of atoms attracted to each other, but not in any particularly-oriented ways. This results in the malleability of metals. The sea of electrons in metallic bonds causes the characteristically good electrical and thermal conductivity of metals, and also their "shiny" reflection of most frequencies of white light. All bonds can be explained by quantum theory, but, in practice, simplification rules allow chemists to predict the strength, directionality, and polarity of bonds. The octet rule and VSEPR theory are two examples. More sophisticated theories are valence bond theory which includes orbital hybridization and resonance, and the linear combination of atomic orbitals molecular orbital method which includes ligand field theory. Electrostatics is used to describe bond polarities and the effects they have on chemical substances.
Valence bond theory

In 1927, valence bond theory was formulated and it argues that a chemical bond forms when two valence electrons, in their respective atomic orbitals, work or function to hold two nuclei together, by virtue of effects of lowering system energies. Building on this theory, the chemist Linus Pauling published in 1931 what some consider one of the most important papers in the history of chemistry: "On the Nature of the Chemical Bond". In this paper, elaborating on the works of Lewis, and the valence bond theory (VB) of Heitler and London, and his own earlier works, Pauling presented six rules for the shared electron bond, the first three of which were already generally known: 1. The electron-pair bond forms through the interaction of an unpaired electron on each of two atoms. 2. The spins of the electrons have to be opposed. 3. Once paired, the two electrons cannot take part in additional bonds. His last three rules were new: 4. The electron-exchange term for the bond involves only one wave function from each atom. 5. The available electrons in the lowest energy level form the strongest bonds. 6. Of two orbitals in an atom, the one that can overlap the most with an orbital from another atom will form the strongest bond, and this bond will tend to lie in the direction of the concentrated orbital. Building on this article, Pauling's 1939 textbook: On the Nature of the Chemical Bond would become what some have called the "Bible" of modern chemistry. This book helped experimental chemists to understand the impact of quantum theory on chemistry. However, the later edition in 1959 failed to adequately address the problems that appeared to be better understood by molecular orbital theory. The impact of valence theory declined during the 1960s and 1970s as molecular orbital theory grew in usefulness as it was implemented in large digital computer programs. Since the 1980s, the more difficult problems of implementing valence bond theory into computer programs have been solved largely, and valence bond theory has seen resurgence.
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Comparison of valence bond and molecular orbital theory

In some respects valence bond theory is superior to molecular orbital theory. When applied to the simplest two-electron molecule, H2, valence bond theory, even at the simplest Heitler-London approach, gives a much closer approximation to the bond energy, and it provides a much more accurate representation of the behavior of the electrons as chemical bonds are formed and broken. In contrast simple molecular orbital theory predicts that the hydrogen molecule dissociates into a linear superposition of hydrogen atoms and positive and negative hydrogen ions, a completely unphysical result. This explains in part why the curve of total energy against interatomic distance for the valence bond method lies below the curve for the molecular orbital method at all distances and most particularly so for large distances. This situation arises for all homonuclear diatomic molecules and is particularly a problem for F2, where the minimum energy of the curve with molecular orbital theory is still higher in energy than the energy of two F atoms. The concepts of hybridization are so versatile, and the variability in bonding in most organic compounds is so modest, that valence bond theory remains an integral part of the vocabulary of organic chemistry. However, the work of Friedrich Hund, Robert Mulliken, and Gerhard Herzberg showed that molecular orbital theory provided a more appropriate description of the spectroscopic, ionization and magnetic properties of molecules. The deficiencies of valence bond theory became apparent when hypervalent molecules (e.g. PF5) were explained without the use of d orbitals that were crucial to the bonding hybridisation scheme proposed for such molecules by Pauling. Metal complexes and electron deficient compounds (e.g. diborane) also appeared to be well described by molecular orbital theory, although valence bond descriptions have been made. In the 1930s the two methods strongly competed until it was realised that they are both approximations to a better theory. If we take the simple valence bond structure and mix in all possible covalent and ionic structures arising from a particular set of atomic orbitals, we reach what is called the full configuration interaction wave function. If we take the simple molecular orbital description of the ground state and combine that function with the functions describing all possible excited states using unoccupied orbitals arising from the same set of atomic orbitals, we also reach the full configuration interaction wavefunction. It can be then seen that the simple molecular orbital approach gives too much weight to the ionic structures, while the simple valence bond approach gives too little. This can also be described as saying that the molecular orbital approach is too delocalised, while the valence bond approach is too localised. The two approaches are now regarded as complementary, each providing its own insights into the problem of chemical bonding. Modern calculations in quantum chemistry usually start from (but ultimately go far beyond) a molecular orbital rather than a valence bond approach, not because of any intrinsic superiority in the former but rather because the MO approach is more readily adapted to numerical computations. However better valence bond programs are now available.
Bonds in chemical formulas

The fact that atoms and molecules are three-dimensional makes it difficult to use a single technique for indicating orbitals and bonds. In molecular formulas the chemical bonds (binding orbitals) between Page 30 of 38
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atoms are indicated by various methods according to the type of discussion. Sometimes, they are completely neglected. For example, in organic chemistry chemists are sometimes concerned only with the functional groups of the molecule. Thus, the molecular formula of ethanol may be written in a paper in conformational, three-dimensional, full two-dimensional (indicating every bond with no threedimensional directions), compressed two-dimensional (CH3CH2OH), separating the functional group from another part of the molecule (C2H5OH), or by its atomic constituents (C2H6O), according to what is discussed. Sometimes, even the non-bonding valence shell electrons (with the two-dimensional approximate directions) are marked, i.e. for elemental carbon .'C'. Some chemists may also mark the respective orbitals, i.e. the hypothetical ethene4 anion (\/C=C/\ 4) indicating the possibility of bond formation.
Strong chemical bonds

Strong chemical bonds are the intramolecular forces which hold atoms together in molecules. A strong chemical bond is formed from the transfer or sharing of electrons between atomic centers and relies on the electrostatic attraction between the protons in nuclei and the electrons in the orbitals. Although these bonds typically involve the transfer of integer numbers of electrons (this is the bond order, which represents one transferred electron or two shared electrons), some systems can have intermediate numbers of bonds. An example of this is the organic molecule benzene, where the bond order is 1.5 for each carbon atom, meaning that it has 1.5 bonds (shares three electrons) with each one of its two neighbors. The types of strong bond differ due to the difference in electro negativity of the constituent elements. A large difference in electro negativity leads to more polar (ionic) character in the bond.
Metallic Bond
Metallic bonds are a metal, and share outer bonds with atoms in a solid. Each atom gives off a positive charge by shedding its outer electrons, and the negatively charges electrons hold the metal atoms together. In a metallic bond, bonding electrons are delocalized over a lattice of atoms. By contrast, in ionic compounds, the locations of the binding electrons and their charges are static. The freely-moving or delocalization of bonding electrons leads to classical metallic properties such as luster (surface light reflectivity), electrical and thermal conductivity, ductility, and high tensile strength.
Ionic Bond
Atoms are filled with an outer shell of electrons. Electron shells are filled by transferring electrons from one atom to the next. Donor atoms will take on a positive charge, and the acceptors will have a negative charge. They will attract each other by being positive and negative, and bonding will then occur. Ionic bonding is a type of electrostatic interaction between atoms which have a large electronegativity difference. There is no precise value that distinguishes ionic from covalent bonding, but a difference of electronegativity of over 1.7 is likely to be ionic, and a difference of less than 1.7 is likely to be covalent. Ionic bonding leads to separate positive and negative ions. Ionic charges are commonly between 3e to +3e. Ionic bonding commonly occurs in metal salts such as sodium chloride (table salt). A typical feature Page 31 of 38
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of ionic bonds is that the species form into ionic crystals, in which no ion is specifically paired with any single other ion, in a specific directional bond. Rather, each species of ion is surrounded by ions of the opposite charge, and the spacing between it and each of the oppositely charged ions near it, is the same for all surrounding atoms of the same type. It is thus no longer possible to associate an ion with any specific other single ionized atom near it. This is a situation unlike that in covalent crystals, where covalent bonds between specific atoms are still discernible from the shorter distances between them, as measured by with such techniques as X-ray diffraction. Ionic crystals may contain a mixture of covalent and ionic species, as for example salts of complex acids, such as sodium cyanide, NaCN. Many minerals are of this type. X-ray diffration shows that in NaCN, for example, the bonds between sodium cations (Na+) and the cyanide anions (CN-) are ionic, with no sodium ion associated with any particular cyanide. However, the bonds between C and N atoms in cyanide are of the covalent type, making each of the carbon and nitrogen associated with just one of its opposite type, to which it is physically much closer than it is to other carbons or nitrogens in a sodium cyanide crystal. When such crystals are melted into liquids, the ionic bonds are broken first because they are nondirectional and allow the charged species to move freely. Similarly, when such salts dissolve into water, the ionic bonds are typically broken by the interaction with water, but the covalent bonds continue to hold. For example, in solution, the cyanide ions, still bound together as single CN- ions, move independently through the solution, as do sodium ions, as Na+. In water, charged ions move apart because each of them are more strongly attracted to a number of water molecules, than to each other. The attraction between ions and water molecules in such solutions is due to a type of weak dipoledipole type chemical bond. In melted ionic compounds, the ions continue to be attracted to each other, but not in any ordered or crystalline way.
Covalent Bonds
Atoms like to share their electrons and this causes their outer shell to be complete. A covalent bond is produced by the sharing of atoms and electrons. This produces a strong covalent bond. Covalent bonding is a common type of bonding, in which the electronegativity difference between the bonded atoms is small or nonexistent. Bonds within most organic compounds are described as covalent. See sigma bonds and pi bonds for LCAO-description of such bonding. A polar covalent bond is a covalent bond with a significant ionic character. This means that the electrons are closer to one of the atoms than the other, creating an imbalance of charge. They occur as a bond between two atoms with moderately different electronegativities, and give rise to dipole-dipole interactions. The electronegativity of these bonds is 0.3 to 1.7 . A coordinate covalent bond is one where both bonding electrons are from one of the atoms involved in the bond. These bonds give rise to Lewis acids and bases. The electrons are shared roughly equally between the atoms in contrast to ionic bonding. Such bonding occurs in molecules such as the ammonium ion (NH4+) and are shown by an arrow pointing to the Lewis acid. Also known as non-polar covalent bond, the electronegativity of these bonds range from 0 to 0.3.
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Molecules which are formed primarily from non polar covalent bonds are often immiscible in water or other polar solvents, but much more soluble in non-polar solvents such as hexane.
One- and three-electron bonds

Bonds with one or three electrons can be found in radical species, which have an odd number of electrons. The simplest example of a 1-electron bond is found in the dihydrogen cation, H2+. Oneelectron bonds often have about half the bond energy of a 2-electron bond, and are therefore called "half bonds". However, there are exceptions: in the case of dilithium, the bond is actually stronger for the 1-electron Li2+ than for the 2-electron Li2. This exception can be explained in terms of hybridization and inner-shell effects. The simplest example of three-electron bonding can be found in the helium dimer cation, He2+. It is considered a "half bond" because it consists of only one shared electron (rather than two) in addition to one lone electron on each atom; in molecular orbital terms, the third electron is in an anti -bonding orbital which cancels out half of the bond formed by the other two electrons. Another example of a molecule containing a 3-electron bond, in addition to two 2-electron bonds, is nitric oxide, NO. The oxygen molecule, O2 can also be regarded as having two 3-electron bonds and one 2-electron bond, which accounts for its paramagnetism and its formal bond order of 2. Chlorine dioxide and its heavier analogues bromine dioxide and iodine dioxide also contain three-electron bonds. Molecules with odd-electron bonds are usually highly reactive. These types of bond are only stable between atoms with similar electronegativities.
Electron-deficient bonding
In three-center two-electron bonds ("3c2e") three atoms share two electrons in bonding. This type of bonding occurs in electron deficient compounds like diborane. Each such bond (2 per molecule in diborane) contains a pair of electrons which connect the boron atoms to each other in a banana shape, with a proton (nucleus of a hydrogen atom) in the middle of the bond, sharing electrons with both boron atoms. In certain cluster compounds, so-called four-center two-electron bonds also have been postulated. In certain conjugated (pi) systems, such as benzene and other aromatic compounds (see below), and in conjugated network solids such as graphite, the electrons in the conjugated system of -bonds are spread over as many nuclear centers as exist in the molecule, or the network.
Aromatic bonding
In organic chemistry, certain configurations of electrons and orbitals infer extra stability to a molecule. This occurs when orbitals overlap and combine with others on different atomic centres, forming a long range bond. For a molecule to be aromatic, it must obey Hckel's rule, where the number of electrons fit the formula 4n + 2, where n is an integer. The bonds involved in the aromaticity are all planar.
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In benzene, the prototypical aromatic compound, 18 (n = 4) bonding electrons bind 6 carbon atoms together to form a planar ring structure. The bond "order" (average number of bonds) between the different carbon atoms may be said to be (18/6)/2=1.5, but in this case the bonds are all identical from the chemical point of view. They may sometimes be written as single bonds alternating with double bonds, but the view of all ring bonds as being equivalently about 1.5 bonds in strength, is much closer to truth. In the case of heterocyclic aromatics and substituted benzenes, the electronegativity differences between different parts of the ring may dominate the chemical behaviour of aromatic ring bonds, which otherwise are equivalent.
Hypervalent bonding
In hypervalent molecules, there exist bonds which have significant non-bonding ionic quality to them. This manifests as non-bonding orbital levels in molecular orbital theory, while in valence bond theory it is analyzed as a form of resonant bonding.
Resonant bonding
Secondary Bonds
Secondary bonds are significantly weaker than primary bonds in that they often produce weak links, and create deformations in the bond. Secondary bonds include hydrogen and van der waals bonds.
Hydrogen Bonds
A common bond is a hydrogen bond. They are most common in covalently bonded molecules that contain hydrogen. Hydrogen bonds share between covalent and oxygenated atoms. This leads to very small electrical charges around the hydrogen bond, and negative charges around the oxygenated bonds.
Van der Waals Bonds

Van der waals bonds are the weakest bond, but are incredibly important gases, that are cooled at low temperatures. These bonds are created by small charges of positive and negative electron that produce a weak bond. Van der waals bonds are overwhelmed by thermal energy, causing them to malfunction.
Intermolecular bonding
There are four basic types of bonds that can be formed between two or more (otherwise nonassociated) molecules, ions or atoms. Intermolecular forces cause molecules to be attracted or repulsed by each other. Often, these define some of the physical characteristics (such as the melting point) of a substance. A large difference in electronegativity between two bonded atoms will cause a permanent charge separation, or dipole, in a molecule or ion. Two or more molecules or ions with permanent dipoles can interact within dipole-dipole interactions. The bonding electrons in a molecule or ion will, on average, be closer to the more electronegative atom more frequently than the less electronegative one, giving rise to partial charges on each atom, and causing electrostatic forces between molecules or ions.
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A hydrogen bond is effectively a strong example of an interaction between two permanent dipoles. The large difference in electronegativities between hydrogen and any of fluorine, nitrogen and oxygen, coupled with their lone pairs of electrons cause strong electrostatic forces between molecules. Hydrogen bonds are responsible for the high boiling points of water and ammonia with respect to their heavier analogues. The London dispersion force arises due to instantaneous dipoles in neighbouring atoms. As the negative charge of the electron is not uniform around the whole atom, there is always a charge imbalance. This small charge will induce a corresponding dipole in a nearby molecule; causing an attraction between the two. The electron then moves to another part of the electron cloud and the attraction is broken. A cationpi interaction occurs between a pi bond and a cation.
Electrons in chemical bonds

In the (unrealistic) limit of "pure" ionic bonding, electrons are perfectly localized on one of the two atoms in the bond. Such bonds can be understood by classical physics. The forces between the atoms are characterized by isotropic continuum electrostatic potentials. Their magnitude is in simple proportion to the charge difference. Covalent bonds are better understood by valence bond theory or molecular orbital theory. The properties of the atoms involved can be understood using concepts such as oxidation number. The electron density within a bond is not assigned to individual atoms, but is instead delocalized between atoms. In valence bond theory, the two electrons on the two atoms are coupled together with the bond strength depending on the overlap between them. In molecular orbital theory, the linear combination of atomic orbitals (LCAO) helps describe the delocalized molecular orbital structures and energies based on the atomic orbitals of the atoms they came from. Unlike pure ionic bonds, covalent bonds may have directed anisotropic properties. These may have their own names, such as sigma bond and pi bond. In the general case, atoms form bonds that are intermediates between ionic and covalent, depending on the relative electronegativity of the atoms involved. This type of bond is sometimes called polar covalent.
Bond Energy
In chemistry, bond energy (E) is the measure of bond strength in a chemical bond. It is the heat required to break one Mole (unit) of molecules into their individual atoms. For example, the carbon-hydrogen bond energy in methane E(CH) is the enthalpy change involved with breaking up one molecule of methane into a carbon atom and 4 hydrogen radicals divided by 4. Chemical bonds that form do so at differing strengths (or, bond energies) based on the electronegativity of the atoms involved. Atoms like carbon (C), hydrogen (H), nitrogen (N) and oxygen (O) consistently form bonds and break to form new compounds. The carbon-oxygen double bond, as seen in carbon dioxide (CO2), has the highest bond energy (hardest to break) of these atoms. The carbon-nitrogen single bond has the lowest bond energy (easiest to break).
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Bond energy (E) should not be confused with bond-dissociation energy. It is a roughly transferable property, and enthalpy of formation can typically be roughly approximated by simply adding tabulated values for bond energies for all bonds in a molecule, with an error of sometimes just a few percent. However, to get a better approximation is much more difficult.
Bond energy/distance correlation

Bond strength (energy) can be directly related to the bond length/bond distance. Therefore, we can use the metallic radius, ionic radius, or covalent radius of each atom in the molecule to determine the bond strength. For example, the covalent radius of boron is estimated at 83.0 pm, but the bond length of BB in B2Cl4 is 175 pm, a significantly larger value. This would indicate that the bond between the two boron atoms is a rather weak single bond. In another example, the metallic radius of rhenium is 137.5 pm, with a ReRe bond length of 224 pm in the compound Re2Cl8. From this data, we can conclude that the bond is a very strong bond or a quadruple bond. This method of determination is most useful for covalently bonded compounds.
Factors affecting ionic bond energy

There are several contributing factors but usually the most important is the difference in the electronegativity of the two atoms bonding together.
Crystal structure
In mineralogy and crystallography, crystal structure is a unique arrangement of atoms or molecules in a crystalline liquid or solid. A crystal structure is composed of a pattern, a set of atoms arranged in a particular way, and a lattice exhibiting long-range order and symmetry. Patterns are located upon the points of a lattice, which is an array of points repeating periodically in three dimensions. The points can be thought of as forming identical tiny boxes, called unit cells, that fill the space of the lattice. The lengths of the edges of a unit cell and the angles between them are called the lattice parameters. The symmetry properties of the crystal are embodied in its space group. A crystal's structure and symmetry play a role in determining many of its physical properties, such as cleavage, electronic band structure, and optical transparency.
Unit cell
The crystal structure of a material (the arrangement of atoms within a given type of crystal) can be described in terms of its unit cell. The unit cell is a small box containing one or more atoms arranged in 3-dimension. The unit cells stacked in three-dimensional space describe the bulk arrangement of atoms of the crystal. The unit cell is given by its lattice parameters, which are the length of the cell edges and the angles between them, while the positions of the atoms inside the unit cell are described by the set of atomic positions (xi , yi , zi) measured from a lattice point.
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Within the unit cell is the asymmetric unit, smallest unit the crystal can be divided into using the crystallographic symmetry operations of the space group. The asymmetric unit is also what is generally solved when solving a structure of a molecule or protein by X-ray crystallography.
Miller indices
Vectors and atomic planes in a crystal lattice can be described by a three-value Miller index notation (mn). The , m, and n directional indices are separated by 90, and are thus orthogonal. In fact, the component is mutually perpendicular to the m and n indices. By definition, (mn) denotes a plane that intercepts the three points a1/, a2/m, and a3/n, or some multiple thereof. That is, the Miller indices are proportional to the inverses of the intercepts of the plane with the unit cell (in the basis of the lattice vectors). If one or more of the indices is zero, it means that the planes do not intersect that axis (i.e., the intercept is "at infinity"). A plane containing a co-ordinate axis is translated so that it no longer contains that axis before its Miller indices are determined. The Miller indices for a plane are integers with no common factors. Negative indices are indicated with horizontal bars, as in (123). In an orthogonal co-ordinate system, the Miller indices of a plane are the Cartesian components of a vector normal to the plane. Considering only (mn) planes intersecting one or more lattice points (the lattice planes), the perpendicular distance d between adjacent lattice planes is related to the (shortest) reciprocal lattice vector orthogonal to the planes by the formula:
Planes and directions

The crystallographic directions are geometric lines linking nodes (atoms, ions or molecules) of a crystal. Likewise, the crystallographic planes are geometric planes linking nodes. Some directions and planes have a higher density of nodes. These high density planes have an influence on the behavior of the crystal as follows: Optical properties: Refractive index is directly related to density (or periodic density fluctuations). Adsorption and reactivity: Physical adsorption and chemical reactions occur at or near surface atoms or molecules. These phenomena are thus sensitive to the density of nodes. Page 37 of 38
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Surface tension: The condensation of a material means that the atoms, ions or molecules are more stable if they are surrounded by other similar species. The surface tension of an interface thus varies according to the density on the surface. Microstructural defects: Pores and crystallites tend to have straight grain boundaries following higher density planes. Cleavage: This typically occurs preferentially parallel to higher density planes. Plastic deformation: Dislocation glide occurs preferentially parallel to higher density planes. The perturbation carried by the dislocation (Burgers vector) is along a dense direction. The shift of one node in a more dense direction requires a lesser distortion of the crystal lattice.
Some directions and planes are defined by symmetry of the crystal system. In monoclinic, rombohedral, tetragonal, and trigonal/hexagonal systems there is one unique axis (sometimes called the principal axis) which has higher rotational symmetry than the other two axes. The basal plane is the plane perpendicular to the principal axis in these crystal systems. For triclinic, orthorhombic, and cubic crystal systems the axis designation is arbitrary and there is no principal axis.
Cubic structures
For the special case of simple cubic crystals, the lattice vectors are orthogonal and of equal length (usually denoted a); similarly for the reciprocal lattice. So, in this common case, the Miller indices (mn) and *mn+ both simply denote normals/directions in Cartesian coordinates. For cubic crystals with lattice constant a, the spacing d between adjacent (mn) lattice planes is (from above):
Because of the symmetry of cubic crystals, it is possible to change the place and sign of the integers and have equivalent directions and planes: Coordinates in angle brackets such as <100> denote a family of directions that are equivalent due to symmetry operations, such as [100], [010], [001] or the negative of any of those directions. Coordinates in curly brackets or braces such as {100} denote a family of plane normals that are equivalent due to symmetry operations, much the way angle brackets denote a family of directions. For face-centered cubic (fcc) and body-centered cubic (bcc) lattices, the primitive lattice vectors are not orthogonal. However, in these cases the Miller indices are conventionally defined relative to the lattice vectors of the cubic supercell and hence are again simply the Cartesian directions.
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