CHAPTER 3: Physical and Chemical Properties

Physical properties are those that can be observed without changing the identity of the substance. The general properties of matter such as color, density, hardness, are examples of physical properties. Properties that describe how a substance changes into a completely different substance are called chemical properties. Flammability and corrosion/oxidation resistance are examples of chemical properties. The difference between a physical and chemical property is straightforward until the phase of the material is considered. When a material changes from a solid to a liquid to a vapor it seems like them become a difference substance. However, when a material melts, solidifies, vaporizes, condenses or sublimes, only the state of the substance changes. Consider ice, liquid water, and water vapor, they are all simply H2O. Phase is a physical property of matter and matter can exist in four phases solid, liquid, gas and plasma. Some of the more important physical and chemical properties from an engineering material standpoint will be discussed in the following sections.

Phase Transformation Temperatures Density Specific Gravity Thermal Conductivity Linear Coefficient of Thermal Expansion Electrical Conductivity and Resistivity Magnetic Permeability Corrosion Resistance

3.1: Phase Transformation Temperatures

When temperature rises and pressure is held constant, a typical substance changes from solid to liquid and then to vapor. Transitions from solid to liquid, from liquid to vapor, from vapor to solid and visa versa are called phase transformations or transitions. Since some substances have several crystal forms, technically there can also be solid to another solid form phase transformation. Phase transitions from solid to liquid, and from liquid to vapor absorb heat. The phase transition temperature where a solid changes to a liquid is called the melting point. The temperature at which the vapor pressure of a liquid equals 1 atm (101.3 kPa) is called the boiling point. Some materials, such as many polymers, do not go simply from a solid to a liquid with increasing temperature. Instead, at some temperature below the melting point, they start to lose their crystalline structure but the molecules remain linked in chains, which results in a soft and pliable material. The temperature at which a solid, glassy material begins to soften and flow is called the glass transition temperature.

3.2: Density
Mass can be thinly distributed as in a pillow, or tightly packed as in a block of lead. The space the mass occupies is its volume, and the mass per unit of volume is its density. Mass (m) is a fundamental measure of the amount of matter. Weight (w) is a measure of the force exerted by a mass and this force is force is produced by the acceleration of gravity. Therefore, on the surface of the earth, the mass of an object is determined by dividing the weight of an object by 9.8 m/s2 (the acceleration of gravity on the surface of the earth). Since we are typically comparing things on the surface of the earth, the weight of an object is commonly used rather than calculating its mass. The density (r) of a material depends on the phase it is in and the temperature. (The density of liquids and gases is very temperature dependent.) Water in the liquid state has a density of 1 g/cm3 = 1000kg/m3 at 4o C. Ice has a density of 0.917 g/cm3 at 0oc, and it should be noted that this decrease in density for the solid phase is unusual. For almost all other substances, the density of the solid phase is greater than that of the liquid phase. Water vapor (vapor saturated air) has a density of 0.051 g/cm3. Some common units used for expressing density are grams/cubic centimeter, kilograms/cubic meter, grams/milliliter, grams/liter, pounds for cubic inch and pounds per cubic foot; but it should be obvious that any unit of mass per any unit of volume can be used. Substance Air Gasoline Wood Water (ice) Water (liquid) Aluminum Steel Silver Lead Mercury Gold Density (g/cm3) 0.0013 0.7 0.85 0.92 1.0 2.7 7.8 10.5 11.3 13.5 19.3

3.3: Specific Gravity

Specific gravity is the ratio of density of a substance compared to the density of fresh water at 4C (39 F). At this temperature the density of water is at its greatest value and equal 1 g/mL. Since specific gravity is a ratio, so it has no units. An object will float in water if its density is less than the density of water and sink if its density is greater that that of water. Similarly, an object with specific gravity less than 1 will float and those with a specific gravity greater than one will sink. Specific gravity values for a few common substances are: Au, 19.3; mercury, 13.6; alcohol, 0.7893; benzene, 0.8786. Note that since water has a density of 1 g/cm3, the specific gravity is the same as the density of the material measured in g/cm3. The Discovery of Specific Gravity The discovery of specific gravity makes for an interesting story. Sometime around 250 B.C., the Greek mathematician Archimedes was given the task of determining whether a craftsman had defrauded King Heiro II of Syracuse. The king had provided a metal smith with gold to make a crown. The king suspected that the metal smith had added less valuable silver to crown and kept some of the gold for himself. The crown weighed the same as other crowns but due to its intricate designs it was impossible to measure the exact volume of the crown so its density could be determined. The king challenged Archimedes to determine if the crown was pure gold. Archimedes had no immediate answer and pondered this question for sometime. One day while entering a bath, he noticed that water spilled over the sides of the pool, and realized that the amount of water that spilled out was equal in volume to the space that his body occupied. He realized that a given mass of silver would occupy more space than an equivalent mass of gold. Archimedes first weighed the crown and weighed out an equal mass of pure gold. Then he placed the crown in a full container of water and the pure gold in a container of water. He found that more water spilled over the sides of the tub when the craftsmans crown was submerged. It turned out that the craftsman had been defrauding the King! Legend has it that Archimedes was so excited about his discovery that he ran naked through the streets of Sicily shouting Eureka! Eureka! (Which is Greek for I have found it!).

3.4: Thermal Conductivity

Thermal conductivity () is the intrinsic property of a material which relates its ability to conduct heat. Heat transfer by conduction involves transfer of energy within a material without any motion of the material as a whole. Conduction takes place when a temperature gradient exists in a solid (or stationary fluid) medium. Conductive heat flow occurs in the direction of decreasing temperature because higher temperature equates to higher molecular energy or more molecular movement. Energy is transferred from the more energetic to the less energetic molecules when neighboring molecules collide. Thermal conductivity is defined as the quantity of heat (Q) transmitted through a unit thickness (L) in a direction normal to a surface of unit area (A) due to a unit temperature gradient (T) under steady state conditions and when the heat transfer is dependent only on the temperature gradient. In equation form this becomes the following: Thermal Conductivity = heat distance / (area temperature gradient) = Q L / (A T) Approximate values of thermal conductivity for some common materials are presented in the table below. Material Air at 0 C Aluminum Brass Concrete Copper Glass, ordinary Gold Ice Iron Lead Polyethylene HD Polystyrene expanded Silver Styrofoam Steel Water at 20 C Wood Thermal Conductivity W/m, oK 0.024 205.0 109.0 0.8 385.0 0.8 310 1.6 34.7 0.5 0.03 406.0 0.01 50.2 0.12-0.04 Thermal Conductivity (cal/sec)/(cm2, oC/cm) 0.000057 0.50 0.002 0.99 0.0025 0.005 0.163 0.083 1.01 0.0014 0.0001

3.5: Linear Coefficient of Thermal Expansion

When heat is added to most materials, the average amplitude of the atoms' vibrating within the material increases. This, in turn, increases the separation between the atoms causing the material to expand. If the material does not go through a phase change, the expansion can be easily related to the temperature change. The linear coefficient of thermal expansion ( a) describes the relative change in length of a material per degree temperature change. As shown in the following equation, a is the ratio of change in length ( Dl) to the total starting length (li) and change in temperature ( DT).

By rearranging this equation, it can be seen that if the linear coefficient of thermal expansion is known, the change in components length can be calculated for each degree of temperature change. This effect also works in reverse. That is to say, if energy is removed from a material then the object's temperature will decrease causing the object to contract. Thermal expansion (and contraction) must be taken into account when designing products with close tolerance fits as these tolerances will change as temperature changes if the materials used in the design have different coefficients of thermal expansion. It should also be understood that thermal expansion can cause significant stress in a component if the design does not allow for expansion and contraction of components. The phenomena of thermal expansion can be challenging when designing bridges, buildings, aircraft and spacecraft, but it can be put to beneficial uses. For example, thermostats and other heat-sensitive sensors make use of the property of linear expansion. Linear Coefficient of Thermal Expansion for a Few Common Materials Material Aluminum Concrete Copper Brass Steel Timber Quartz Glass Acrylic a (m/m/oK) 23.8 x 10-6 12.0 x 10 18.5 x 10 12.0 x 10 40.0 x 10 0.5 x 10
-6

a (mm/m/oK) 0.0238 0.011 0.0176 0.0185 0.0115 0.04 0.0005 0.040-0.200 0.075

17.6 x 10 -6
-6 -6 -6

-6

Polymeric Materials 40-200 x 10 -6 75.0 x 10

-6

3.6: Electrical Conductivity and Resistivity

It is well known that one of the subatomic particles of an atom is the electron. The electrons carry a negative electrostatic charge and under certain conditions can move from atom to atom. The direction of movement between atoms is random unless a force causes the electrons to move in one direction. This directional movement of electrons due to an electromotive force is what is known as electricity. Electrical Conductivity Electrical conductivity is a measure of how well a material accommodates the movement of an electric charge. It is the ratio of the current density to the electric field strength. Its SI derived unit is the Siemens per meter, but conductivity values are often reported as percent IACS. IACS is an acronym for International Annealed Copper Standard, which was established by the 1913 International Electrochemical Commission. (More Information on the IACS.) The conductivity of the annealed copper (5.8001 x 107S/m) is defined to be 100% IACS at 20C . All other conductivity values are related back to this conductivity of annealed copper. Therefore, iron with a conductivity value of 1.04 x 107 S/m, has a conductivity of approximately 18% of that of annealed copper and this is reported as 18% IACS. An interesting side note is that commercially pure copper products now often have IACS conductivity values greater than 100% IACS because processing techniques have improved since the adoption of the standard in 1913 and more impurities can now be removed from the metal. Conductivity values in Siemens/meter can be converted to % IACS by multiplying the conductivity value by 1.7241 x10-6. When conductivity values are reported in microSiemens/centimeter, the conductivity value is multiplied by 172.41 to convert to the % IACS value. Electrical conductivity is a very useful property since values are affected by such things as a substances chemical composition and the stress state of crystalline structures. Therefore, electrical conductivity information can be used for measuring the purity of water, sorting materials, checking for proper heat treatment of metals, and inspecting for heat damage in some materials. Electrical Resistivity Electrical resistivity is the reciprocal of conductivity. It is the is the opposition of a body or substance to the flow of electrical current through it, resulting in a change of electrical energy into heat, light, or other forms of energy. The amount of resistance depends on the type of material. Materials with low resistivity are good conductors of electricity and materials with high resistivity are good insulators. The SI unit for electrical resistivity is the ohm meter. Resistivity values are more commonly reported in micro ohm centimeters units. As mentioned above resistivity values are simply the reciprocal of conductivity so conversion between the two is straightforward. For example, a material with two micro ohm centimeter of resistivity will have microSiemens/centimeter of conductivity. Resistivity values in microhm centimeters units can be converted to % IACS conductivity values with the following formula: 172.41 / resistivity = % IACS Temperature Coefficient of Resistivity As noted above, electrical conductivity values (and resistivity values) are typically reported at 20 oC. This is done because the conductivity and resistivity of material is temperature dependant. The conductivity of most materials decreases as temperature increases. Alternately, the resistivity of most material increases with increasing temperature. The amount of change is material dependant but has been established for many elements and engineering materials.

The reason that resistivity increases with increasing temperature is that the number of imperfection in the atomic lattice structure increases with temperature and this hampers electron movement. These imperfections include dislocations, vacancies, interstitial defects and impurity atoms. Additionally, above absolute zero, even the lattice atoms participate in the interference of directional electron movement as they are not always found at their ideal lattice sites. Thermal energy causes the atoms to vibrate about their equilibrium positions. At any moment in time many individual lattice atoms will be away from their perfect lattice sites and this interferes with electron movement. When the temperature coefficient is known, an adjusted resistivity value can be computed using the following formula: R1 = R2 * [1 + a * (T1T2)] Where: R1 = resistivity value adjusted to T1 R2 = resistivity value known or measured at temperature T2 a = Temperature Coefficient T1 = Temperature at which resistivity value needs to be known T2 = Temperature at which known or measured value was obtained For example, suppose that resistivity measurements were being made on a hot piece of aluminum. Normally when measuring resistivity or conductivity, the instrument is calibrated using standards that are at the same temperature as the material being measured, and then no correction for temperature will be required. However, if the calibration standard and the test material are at different temperatures, a correction to the measured value must be made. Presume that the instrument was calibrated at 20oC (68oF) but the measurement was made at 25oC (77oF) and the resistivity value obtained was 2.706 x 108 ohm meters. Using the above equation and the following temperature coefficient value, the resistivity value corrected for temperature can be calculated. R1 = R2 * [1 + a * (T1T2)] Where: R1 = ? R2 = 2.706 x 10-8 ohm meters (measured resistivity at 25 oC) a = 0.0043/ oC T1 = 20 oC T2 = 25 oC R1 = 2.706 x 10-8ohm meters * [1 + 0.0043/ oC * (20 oC 25 oC)] R1 = 2.648 x 10-8ohm meters Note that the resistivity value was adjusted downward since this example involved calculating the resistivity for a lower temperature. Since conductivity is simply the inverse of resistivity, the temperature coefficient is the same for conductivity and the equation requires only slight modification. The equation becomes: s1 = s2 / [1 + a * (T1T2)] Where: s1 = conductivity value adjusted to T1 s2 = conductivity value known or measured at temperature T2

a = Temperature Coefficient T1 = Temperature at which conductivity value needs to be known T2 = Temperature at which known or measured value was obtained In this example lets consider the same aluminum alloy with a temperature coefficient of 0.0043 per degree centigrade and a conductivity of 63.6% IACS at 25 oC. What will the conductivity be when adjusted to 20 oC? s1= 63.6% IACS / [1 + 0.0043 * (20 oC 25 oC)] s1= 65.0% IASC The temperature coefficient for a few metallic elements is shown below. Material Nickel Iron Molybdenum Tungsten Aluminum Copper Silver Platinum Gold Zinc Temperature Coefficient (/ oC) 0.0059 0.0060 0.0046 0.0044 0.0043 0.0040 0.0038 0.0038 0.0037 0.0038

3.7: Magnetic Permeability

Magnetic permeability or simply permeability is the ease with which a material can be magnetized. It is a constant of proportionality that exists between magnetic induction and magnetic field intensity. This constant is equal to approximately 1.257 x 10-6 Henry per meter (H/m) in free space (a vacuum). In other materials it can be much different, often substantially greater than the free-space value, which is symbolized 0. Materials that cause the lines of flux to move farther apart, resulting in a decrease in magnetic flux density compared with a vacuum, are called diamagnetic. Materials that concentrate magnetic flux by a factor of more than one but less than or equal to ten are called paramagnetic; materials that concentrate the flux by a factor of more than ten are called ferromagnetic. The permeability factors of some substances change with rising or falling temperature, or with the intensity of the applied magnetic field. In engineering applications, permeability is often expressed in relative, rather than in absolute, terms. If o represents the permeability of free space (that is, 4p X10-7H/m or 1.257 x 10-6 H/m) and represents the permeability of the substance in question (also specified in henrys per meter), then the relative permeability, r, is given by: r = / 0 For non-ferrous metals such as copper, brass, aluminum etc., the permeability is the same as that of "free space", i.e. the relative permeability is one. For ferrous metals however the value of r may be several hundred. Certain ferromagnetic materials, especially powdered or laminated iron, steel, or nickel alloys, have r that can range up to about 1,000,000. Diamagnetic materials have r less than one, but no known substance has relative permeability much less than one. In addition, permeability can vary greatly within a metal part due to localized stresses, heating effects, etc. When a paramagnetic or ferromagnetic core is inserted into a coil, the inductance is multiplied by r compared with the inductance of the same coil with an air core. This effect is useful in the design of transformers and eddy current probes.

3.8: Oxidation and Corrosion

Corrosion involves the deterioration of a material as it reacts with its environment. Corrosion is the primary means by which metals deteriorate. Corrosion literally consumes the material reducing load carrying capability and causing stress concentrations. Corrosion is often a major part of maintenance cost and corrosion prevention is vital in many designs. Corrosion is not expressed in terms of a design property value like other properties but rather in more qualitative terms such as a material is immune, resistant, susceptible or very susceptible to corrosion. The corrosion process is usually electrochemical in nature, having the essential features of a battery. Corrosion is a natural process that commonly occurs because unstable materials, such as refined metals want to return to a more stable compound. For example, some metals, such as gold and silver, can be found in the earth in their natural, metallic state and they have little tendency to corrode. Iron is a moderately active metal and corrodes readily in the presence of water. The natural state of iron is iron oxide and the most common iron ore is Hematite with a chemical composition of Fe203. Rust, the most common corrosion product of iron, also has a chemical composition of Fe2O3. The difficulty in terms of energy required to extract metals from their ores is directly related to the ensuing tendency to corrode and release this energy. The electromotive force series (See table) is a ranking of metals with respect to their inherent reactivity. The most noble metal is at the top and has the highest positive electrochemical potential. The most active metal is at the bottom and has the most negative electrochemical potential.
Note that aluminum, as indicated by its position in the series, is a relatively reactive metal; among structural metals, only beryllium and magnesium are more reactive. Aluminum owes its excellent corrosion resistance to the barrier oxide film that is bonded strongly to the surface and if damaged reforms immediately in most environments. On a surface freshly abraded and exposed to air, the protective film is only 10 Angstroms thick but highly effective at protecting the metal from corrosion.
Partial Electromotive Force Series Standard Potential Au3+ + 3e- -> Au Pd2+ + 2e- -> Pd Hg + 2e -> Hg Ag+ + e- -> Au Cu+ + e- -> Cu Cu + 2e -> Cu 2H+ + 2e- -> H2 Pb2+ + 2e- -> Pb Sn2+ + 2e- -> Sn Ni + 2e -> Ni Co2+ + 2e- -> Co Cd + 2e -> Cd Fe2+ + 2e- -> Fe Cr + 3e -> Cr Cr2+ + 2e- -> Cr Zn2+ + 2e- -> Zn Mn + 2e -> Mn Ti2+ + 2e- -> Ti Al + 3e -> Al Be2+ + 2e- -> Be Mg + 2e -> Mg Li+ + e- -> Li
2+ 3+ 2+ 3+ 2+ 2+ 2+ 2+ -

Electrode Reaction (at 25oC), V-SHE 1.498 0.987 0.854 0.799 0.521 0.337 0.000 (Ref.) -0.126 -0.136 -0.250 -0.277 -0.403 -0.440 -0.744 -0.910 -0.763 -1.180 -1.630 -1.662 -1.850 -2.363 -3.050

Corrosion involve two chemical processesoxidation and reduction. Oxidation is the process of stripping electrons from an atom and reduction occurs when an electron is added to an atom. The oxidation process takes place at an area known as the anode. At the anode, positively charged atoms leave the solid surface and enter into an electrolyte as ions. The ions leave their corresponding negative charge in the form of electrons in the metal which travel to the location of the cathode through a conductive path. At the cathode, the corresponding reduction reaction takes place and consumes the free electrons. The electrical balance of the circuit is restored at the cathode when the electrons react with neutralizing positive ions, such as hydrogen ions, in the electrolyte. From this description, it can be seen that there are four essential components that are needed for a corrosion reaction to proceed. These components are an anode, a cathode, an electrolyte with oxidizing species, and some direct electrical connection between the anode and cathode. Although atmospheric air is the most common environmental electrolyte, natural waters, such as seawater rain, as well as man-made solutions, are the environments most frequently associated with corrosion problems.

A typical situation might involve a piece of metal that has anodic and cathodic regions on the same surface. If the surface becomes wet, corrosion may take place through ionic exchange in the surface water layer between the anode and cathode. Electron exchange will take place through the bulk metal. Corrosion will proceed at the anodic site according to a reaction such as M M++ + 2ewhere M is a metal atom. The resulting metal cations (M++) are available at the metal surface to become corrosion products such as oxides, hydroxides, etc. The liberated electrons travel through the bulk metal (or another low resistance electrical connection) to the cathode, where they are consumed by cathodic reactions such as 2H+ + 2e- H 2 The basic principles of corrosion that were just covered, generally apply to all corrosion situation except certain types of high temperature corrosion. However, the process of corrosion can be very straightforward but is often very complex due to variety of variable that can contribute to the process. A few of these variable are the composition of the material acting in the corrosion cell, the heat treatment and stress state of the materials, the composition of the electrolyte, the distance between the anode and the cathode, temperature, protective oxides and coating, etc. Types of Corrosion Corrosion is commonly classified based on the appearance of the corroded material. The classifications used vary slightly from reference to reference but there is generally considered to be eight different forms of corrosion. There forms are: Uniform or general corrosion that is distributed more or less uniformly over a surface. Localized corrosion that is confined to small area. Localized corrosion often occurs due to a concentrated cell. A concentrated cell is an electrolytic cell in which the electromotive force is caused by a concentration of some components in the electrolyte. This difference leads to the formation of distinct anode and cathode regions.

Pitting corrosion that is confined to small areas and take the form of cavities on a surface. Crevice corrosion occurring at locations where easy access to the bulk environment is prevented, such as the mating surfaces of two components. Filiform Corrosion that occurs under some coatings in the form of randomly distributed threadlike filaments.

Intergranular preferential corrosion at or along the grain boundaries of a metal.

Exfoliation a specific form of corrosion that travels along grain boundaries parallel to the surface of the part causing lifting and flaking at the surface. The corrosion products expand between the uncorroded layers of metal to produce a look that resembles pages of a book. Exfoliation corrosion is associated with sheet, plate and extruded products and usually initiates at unpainted or unsealed edges or holes of susceptible metals.

Galvanic corrosion associated primarily with the electrical coupling of materials with significantly different electrochemical potentials. Environmental Cracking brittle fracture of a normally ductile material that occurs partially due to the corrosive effect of an environment.

Corrosion fatigue fatigue cracking that is characterized by uncharacteristically short initiation time and/or growth rate due to the damage of corrosion or buildup of corrosion products. High temperature hydrogen attack the loss of strength and ductility of steel due to a high temperature reaction of absorbed hydrogen with carbides. The result of the reaction is decarburization and internal fissuring. Hydrogen Embrittlement the loss of ductility of a metal resulting from absorption of hydrogen. Liquid metal cracking cracking caused by contact with a liquid metal. Stress corrosion cracking of a metal due to the combined action of corrosion and a residual or applied tensile stress.

Erosion corrosion a corrosion reaction accelerated by the relative movement of a corrosive fluid and a metal surface. Fretting corrosion damage at the interface of two contacting surfaces under load but capable of some relative motion. The damage is accelerated by movement at the interface that mechanically abraded the surface and exposes fresh material to corrosive attack. Dealloying the selective corrosion of one or more components of a solid solution alloy.

Dezincification corrosion resulting in the selective removal of zinc from copper-zinc alloys.