Materials of Chemical Equipments

CHAPTER 2

Raw material into material :

What is Materials Technology? Materials technology is a relatively comprehensive discipline that begins with the production of goods from raw materials to processing of materials into the shapes and forms needed for specific applications.

State changing Raw material Energy, Additives

Processing/Manufacturing Equipment Energy, Additives

Material

Material Engineering : Material Science Material Technology Science : Material Structure Material Propeties Relationship between Internal Structure & Propeties Technology : Processing from Raw Material into Material Application Design and new development.

2.1 Metal and Alloy Metal

Iron and Steel Steel structure Carbon Steel & Cast Iron Crystal Structure Mixture & Impurities

Iron and steel

Applications: Cutting tools, pressure vessels, bolts, hammers, gears, cutlery, jet engine parts, car bodies, screws, concrete reinforcement, tin cans, bridges... Why? Ore is cheap and abundant

Processing techniques are economical (extraction, refining, alloying, fabrication) High strength Very versatile metallurgy - a wide range of mechanical and physical properties can be achieved, and these can be tailored to the application

Disadvantages:

Iron and steel

Low corrosion resistance (use e.g. titanium, brass instead)

High density: 7.9 g cm-3 (use e.g. aluminium, magnesium instead) High temperature strength could be better (use nickel instead) Basic distinction between ferrous and non-ferrous alloys: Ferrous metals are all-purpose alloys

Non-ferrous metals used for niche applications, where properties of ferrous metals are inadequate

Steel structure
Ferrite : (Ferrum), soft, easy to be processed at low temperature Austenite ( Roberts Austen), easy to be processed, non magnetic Zementite Fe3C : hard Ledeburite ( A. Ledebur): Structure at Eutectic point, hard to be processed Pearlite : Layer structure like pearl layers
9

Carbon Steel and Cast Iron

The Classification of Carbon Steel and Cast Iron
A. According to their Chemical Components : Iron Carbon Alloy: (>95%)Fe +(0.05% ~ 4%)C +(~1%)(impure steel and cast iron) B. According to the Carbon Content: Steel C%=0.02~2% Cast Iron C%>2% Engineering Pure Iron C%<0.02%

Pure Iron 0 0.02

Steel 2

Cast Iron 4

C%

Isomeric Transformation of Pure Iron

Inhomogeneous
is the phenomenon that the crystal configuration changes with the temperature in the state of solid.

Classification
t < 910 Cubic Lattice in Bulk Center, called -Fe t > 910 Cubic Lattice in Face Center, called -Fe

The transformation accomplishes in 910 without temperatur changing.

The structure of iron-carbon alloy steel

The structure of metal
The micro-structure of metal

Grain Boundary Grain

micrograph

Different structure cause different performance of materials.

Steel metallurgy
Iron is allotropic / polymorphic i.e. exhibits different crystal structures at different temperatures Most importantly: bcc <-> fcc transformation at 912C (for pure iron)

Solubility of carbon in ferrite (-iron, bcc): 0.02 wt% austenite (-iron, fcc): 2.1 wt% What happens to carbon when crystal structure transforms from fcc to bcc? Fundamental issue in metallurgy of low alloy steels

Pearlite
NB Pearlite is a MIXTURE of phases (on a very fine scale) Alternating layers of ferrite and cementite formed simultaneously from the remaining austenite when temperature reaches 723qC

Fe 1.3 wt% C: Cementite precipitates at austenite grain boundaries, remaining austenite is transformed into pearlite

High mechanic performance if structure of grain are homogeneous and tight

24

Crystal of Ferrite Steel ( -Fe)

Atom Carbon in the structure Ferrite

25

Crystal of Ferrite Steel (-Fe)

Atom chrom in the structure Ferrite

26

Crystal of Ferrite Steel (-Fe)

Atom silicium in the structure Ferrite

27

Crystal of Austenite Steel (-Fe)

Atom Carbon in the structure Austenite

28

Structure of different metal crystal under microscope

Ferrit, low mechanic endurance

Ferrit+ Perlit : 0,35% C, temper steel

Perlit : 0,8% C, mold steel, by cooling of Austenite

29

Structure of different metal crystal under microscope

Micrograph of Perlite & Zementite 1,3%C , tool steel

Micrograph of Austenite steel X10CrNi18.9

30

The transformation

-Fe

910

-Fe

Iron-iron carbide equilibrium diagram

Iron-iron carbide equilibrium diagram

908 Austenite Ferrite A3 + Austenite 722 A1 Ferrite + Pearlite 0 0.2 0.4 0.6 0.8 Percent carbon of weight

er u are p m T t e

 The lattice structure of steel varies from one form to another as the temperature changes. This is illustrated in the above diagram. Between room temperature and 722C, the steel consists of what is known as ferrite and pearlite. Ferrite is a solid solution of a small amount of carbon dissolved in iron. Pearlite, which is shown in the diagram, is a mixture of ferrite and iron carbide. The carbide is very hard and brittle. In the previous diagram between line A1 (lower critical temperature) and A3 (upper critical temperature) the carbide dissolves more readily into the lattice that is now called Ferrite and austenite. Austenite is a solid solution of carbon and iron that is denser than ferrite.

Above line A3 the lattice is uniform in property with the austenite the main structure. The actual temperature for this austenite range is a function of the carbon content of the steel as shown in the figure.

Carbon and its existing form in steel

The basic types of C existing in iron-carbon alloy:

Dissolution Chemical Combination Blending

Dissolution

C dissolute in the lattice of Fe to form Solid Solution Fe-C Solid Solution. Solvent the element without changing in lattice Fe is the solvent Solute the element dissolving in solvent C is the solute

Two kinds of common-used Solid Solution

Ferrite(F): The solid solution formed by C dissolving in -Fe is called Ferrite. Characteristics: Because the gap between atoms is small, the capacity to dissolve C is weak. Solubility of C At room temperature 723 0.006 % 0.02 %(maximum)

Properties
Low strength b = 200 ~ 280 MPa , s = 90 ~ 170 MPa Low hardness HB = 5.5 ~ 8.0 MPa Good plasticity

= 30 ~ 40%

Good toughness

ak = 1.8 ~ 2.5MJ / m

Austenite(A)
The solid solution formed by C dissolving in -Fe is called Austenite, it is denser than Ferrite. The lattice of C keeps in that of -Fe, i.e. Cubic Lattice in Face Center. Characteristics: Because the gap between atoms is large, the capacity to dissolve C is strong. Solubility of C 723 1147 0.8 % 2.06 %(maximum)

Properties
High strength High hardness Good plasticity Good toughness No ironic magnetism

The transformation between F and A: The irons that dissolve C will take the transformation between -Fe and -Fe in different temperature. Ferrite (F) 723 ~ 910 Austenite (A)

Both F and A have good plasticity and they are the structural basis of steels characteristic of excellent plasticity.

Cementite
Chemical Combination: C and Fe form the metallic compound Iron Carbide (Fe3C) whose crystal structure is called Cementite indicated by C.

C + 3Fe

Fe3C

Characteristics:
a)The carbon content of Cementite is high, the mass proportion is 6.67%. b)Hard and brittle (HB=78.4MPa) c)Almost no plasticity and toughness

Cementite
a) Low break-down strength (b35 MPa ) b) The Cementite is semi-stable compound, it will decompose into Fe and C at certain conditions, the extricated C exists in the form of graphite.

Fe3C

C + 3Fe

Mechanical Blending (Mixture)

The alloy whose components are blending together in the state of liquid can solidify into two types of mechanical mixtures: a) Mixture formed by two solid solutions; b) Mixture formed by a solid solution and metallic compound. For example: Pearlite (P),Ledeburite (L) is a kind of Mechanical Mixture. Pearlite (P) = Ferrite (F) + Cementite (C) Ledeburite (L) = Austenite (A) + Cementite (C)

Damascus sword: which Westerners first encountered during the Crusades against the Muslim nations

46

What Is Real Damascus Steel?

Genuine Damascus blades are known to have been made in that city and later elsewhere in the Muslim Middle East and Orientfrom small ingots made of steel (a mix of iron and carbon) shipped from India; those starting materials have been called wootz ingots or wootz cakes since around 1800. The steel contains around 1.5 percent carbon by weight, plus low levels of other impurities such as silicon, manganese, phosphorus and sulfur. DAMASCUS STEEL SWORD from the 17th century shows a classic damascene pattern of swirling light and dark bands. The inscription tells us that this excellent blade was made in 1691 or 1692 by Assad Allah, the most renowned Persian sword smith of his time.

Assemble the ingredients to load into the crucible, including high-purity iron, Sorel iron, charcoal, glass chips and green leaves. The quantity of carbon and impurity elements that end up in the ingot is controlled by the proportions of iron, Sorel iron and charcoal added to the mix.

Heat the crucible. During this process, the glass melts, forming a slag that protects the ingot from oxidizing. The leaves generate hydrogen, which is known to accelerate carburization of iron. The carbon content of the iron is raised to 1.5 percent, a good proportion for forming the hard iron carbide particles whose accretion into bands gives Damascus blades their characteristic wavy surface pattern. The leaves and glass can be left out, but ingots made without them are more prone to cracking during hammering.

When the crucible has cooled, remove the ingot, which bears a resemblance to the wootz cakes used by the ancients.

Heat the ingot to a precise temperature. Pendray is using a gas-fired furnace with the propane-to-air ratio adjusted to minimize the formation of oxide scale during forging. Typically, a surface oxide layer of about half a millimeter in thickness forms, and the final grinding operation must be sufficient to remove it.

Forge the ingot (deform it slightly with hammer blows while it is still hot). When the ingot gets too cold to deform without cracking, heat it up and forge again. Four separate stages of the ingot are shown here; each stage is the result of several cycles of heating and forging. A total of about 50 cycles may be needed to bang out the blade shape from the ingota highly labor-intensive process. Pendray uses a modern air hammer. A handheld hammer works, too, but it takes longer.

Cut the blade to final shape and hand-forge to add finer details.

Remove the excess steel and the decarburized surface metal. Pendray is using an electric belt grinder for this step.

Cut grooves and drill holes into the surface of the blade to create Mohammed's ladder and rose patterns, if desired. Forge the blade flat again and polish the surface to give the blade its near final form.

Etch blade surface with an acid to bring out the pattern; the softer steel darkens, and the harder steel appears as brighter lines.

The main impure elements are:

Mn is useful element. Si is useful element. S is harmful element. P is harmful element. O is harmful element. N is harmful element. H is harmful element.

The impure elements

Manganese (Mn):

Mn < 0.8% (the common existing impure element)

Coming from the deoxidizing and desulfurizing agent in the process of smelting. Function: eliminating S and O2.

They wont effect the properties of steels if the content of both are little. Mn > 0.8% ( the alloy element intentionally)

Function: Mn can disolve in the ferrite to form the solid solution strengthening the effect of ferrite.

Silicon (Si):
Si < 0.5% (common existing impure element)

Coming from the deoxidizing agent and ore. Function: 2FeO + Si 2 Fe + SiO2

Ability of deoxidation is stronger than Mn. Si can dissolve in the Ferrite and improve the strength and hardness of steels.

The existing form: Forming solid solution with Ferrite.

or Remaining in the steels in the form of deoxidation product (SiO2)

Sulphur (S):
Originating in the fuels in ore or which are used in the process of smelting (Coke). The existing form: FeS (S doesnt dissolve in Fe) Function: The low-melting-pointed compound (985C) formed by FeS and Fe makes the steel unit crack in the process of hot-working, this phenomenon is called Hot Brittle.

Controlling of the content of S: Common Steel : High Grade Steel : S 0.055 0.07% S 0.03 0.045% S 0.02 0.03%

Super High Grade Steel :

Phosphorus (P):
Originating in the ore. Function: P in steels can dissolves in -Fe and improves the strength of steels in normal atmospheric temperature & brittleness, but dramatically reduces their plasticity and toughness, this phenomenon is called Cold Brittle. When the content of P in the steel is P=0.3%, the impact toughness ak = 0. Controlling of the content of P: P 0.06%

Oxygen (O2)
Originating in the air. Existing form: O2 always exists in the steels in the form of non-metallic inclusion, such as FeO, SiO2 , MnO, MgO, Al2O3, etc. Function: These oxidations is in the steels as solid grains which are hard but brittle and damage the continuity of basic structure of steels sharply reducing the mechanical property of steels. Eliminating the O2 in the process of smelting.

Nitrogen (N)
Originating in the air. Function: Low Carbon Steels with high-content of N2 are particularly lack of resistance to corrosion. Easy to form the air bubble to be loose. Cause the phenomenon of Age-hardening. Methods: Adding Al and Ti to form AlN and TiN as if making the N fix in the steels (called N-fixed Treatment), this will eliminate the age-hardening.

Hydrogen (H2)
Originating in moist feed in steel-melting stove, pouring system and the moist air, etc. Function: Making the steels to be brittle (H-Brittle) Making the steels to be seriously defective (Fish-eye) Methods: Improve the environment of smelting. Clear up the moisture content in the feed. Purify the steel liquid.

2.2 Properties of Materials

Mechanical Properties Physical Properties Chemical Properties Manufacturing Properties

61

Mechanical Properties:
Definition: The capability of materials to resist external forces, but does not deformation beyond allowance or wreck. Main Performance Index: Five Index: Elasticity, Plasticity, Strength, Hardness, Toughness

62

Mechanical properties
Ferrite: soft and ductile Cementite: hard and brittle

Mechanical Properties:
Elastic State(curve o-b) 1.proportional limit:

Elasticity

2.elastic limit:

b a

64

Tensile curve of Low Carbon steel

Mechanical Properties:

Elasticity

Strength

ultimate tensile stress b yielding point s, creep limit n creep rupture strength D fatigue limit (strength) -1 shrinkage do Ao= do 4
2

Stress=

P Ao

(MPa)

lo

Strain= ll o
66

Mechanical Properties:
When it is stretched to a certain degree, there will be shrinkage ,and then break.
1. Yielding State (near point c) Conditional Yielding

Ps = Fo

0. 2

P0.2 = Fo

2. Intensification State (curve c-d) T. S. (Tensile Strength)

P = b Fo

3. Shrink Neck State (after d)

Mechanical Properties:
Yielding Point (MPa)
s

- minimum value in yielding state - plastic deformation appears.

Yielding point

0.2

have no apparent yielding phenomena and :

0.2 = stress in 0.2% of residue elongation

The stress of any point in the pressure vessel caused by pressure from medium should be below the elastic limit and cannot happen the plastic deformation.

Mechanical Properties: Ultimate Tensile Stress b (MPa)

The maximum value of stress from the beginning of being stressed to the end of fracture.

Ultimate Tensile Stress b (MPa)

Normal or low temperature: considering: yield [yield/tensile] ratio: s / b

b s Yielding point Generally speaking, s <b s/ b , Plasticity , Deformation s/ b , Plasticity, Deformation Strength Usage
Elastic Plastic

Mechanical Properties: Creep Rate

Elevated temperature:
considering: n and D as well as the previous

Temperature( C) 1Cr18Ni9Ti Creep Rate mm/mm*h(P con.) 425 176 475 91 520 33 550 6

10-6

Mechanical Properties:
Creep Limit
n

Creep phenomena: When the materials is in high temperature and in certain stress, the stress increases as the time is going. The temperature in which metals creep Carbon steel Alloy steel Light metal and alloy Pt, Sn > 420 0C > 450 0C 0 > 50-150 C Normal Temperature

Mechanical Properties:

Creep Curve

Mechanical Properties:
Creep limit (MPa)
n

Definition: The ability of materials to resist the slowly plastic deformation under high temperature.
Under certain temperature, the creep speed does not excess the stress stipulated.

Stipulated creep speed:

10-7 mm / mm . H 10-6 mm / mm . H

1% straining within 105 hours 1% straining within 104 hours

Mechanical Properties:
Creep Rupture Strength D (MPa)
Definition: Rupture strength under certain temperature, the material cracks in a stress after a period of stipulated time. This stress is called creep rupture strength.
Stipulated time: 105 hours Because the designed life time of chemical equipments is commonly 10 5 hours, the stress under which material cracks is said to be rupture strength. Creep rupture strength is the ability to resist cracking under certain temperature and load. The stronger the ability is, the longer it will endure under the same conditions.

Mechanical Properties:
Fatigue limit (Strength) -1(MPa)
Fatigue

phenomenon: the constructional elements destruct under the alternate load action.
Fatigue

strength: the maximum stress, under which the materials do not happen fatigue destruction or failure after infinite times of alternate load action.
Times

of Fatigue Test: 106 ~ 108

Mechanical Properties: Plastic Deformation

1)Definition: the ability of plastic deformation but not destructing under external force. 2)Commonly used Index: Percentage Elongation Shrinkage of Sectional Area Cold Bending Property

Elongation

After the unit of structure is cracked by tensile force, the ratio of the total stretched length and the origin length is called Percentage Elongation, described by %

Mechanical Properties: Plastic Deformation

Mechanical Properties:
l k l0 lk = 100% = 100% l0 l0

lk the gauge length after cracking, mm l0 the origin gauge length, mm lkthe absolute length after cracking, mm

Mechanical Properties:
The meaning of Percentage Elongation: i) The value of reflects the degree of the plastic deformation before the material cracks. ii) The larger , the better the plasticity of material. iii) Plastic material > 5%; Low carbon steel = 20~30% iv) Hard brittle material < 5%; Cast iron = 1%

Mechanical Properties:
SHRINKAGE SECTION After the unit of structure is cracked, the ratio of the reduced area of the cross-section and the original (cross) sectional area is called Shrinkage of Sectional Area which is described by %.

F Fk = 100% F
Fkthe minimum As after cracking mm2 F0original sectional area As mm2

Mechanical Properties:
The larger the , the better the plasticity
Cold Bending Property
Welding joint

of the material. The of Low Carbon Steel is about 60%.

With R increasing, the plasticity of materials will be better and better.

The real meaning of the Plastic Index: i) Forming handling(process) and welding ease, such as bending and rolling forging press cold impacting welding and etc. ii) Make the unit of structure to avoid cracking for deformation after bearing load. iii) The Pressure Vessels and their spare parts should have the characteristic.

Mechanical Properties:

Mechanical Properties: Hardness

I. Definition: when something which is harder than material itself is pressed on the surface of it, it will resist the pressure by deformation or be damaged, such abilities are called Hardness. I. The Hardness Index: Brinell Hardness (HB) Rochwell Hardness (HR) Vickers Hardness (HV)

Mechanical Properties:
The test of HB:
P p Pressure, N DThe diameter of the rigid ball, mm d The diameter of the indent, mm F The area of the Indent, mm2

p 2p HB = = F D( D D 2 d 2 )

( MPa )

Mechanical Properties:
The relationship of Hardness and Strength:
Generally, good Hardness leads to good Strength and good resistance to wear and tear. Experimental Value (MPa): Low Carbon Steel b 36 HB High Carbon Steel b 34 HB Gray Cast Iron b 10 HB

I.Application of Hardness in Engineering

Mechanical Properties: Impact toughness ak

Definition: The ability of materials to resist the impact load, i.e., the ability of materials that will make plastic deformation immediately and rapidly when suddenly attacked by dynamic loading.

88

Mechanical Properties:
Impact Toughness

Mechanical Properties:
The larger is a k , the better is the ability of materials to resist the impact load.

The relationship between Toughness and Plasticity: Generally, stronger toughness makes stronger plasticity; but strong plasticity may not make strong toughness . For Mediate and Low Pressure Vessels, a k30 35J/cm2 , commonly a k 60 J/cm2.

Hard Brittle Materials a k Plastic Materials a k

PLASTIC (PERMANENT) DEFORMATION

(at lower temperatures: T < T /3)

91

Physical Properties:
a. Modulus of elasticity (E)
E

(M Pa)

Nature of E: 1) Its the index of materials ability to resist elastic deformation. E , ability to resist deformation. E of steel is about 2.105 M Pa . 2) For the same material, T , E .

Physical Properties:
b. Poissons Ratio

' =
(For steel: 0.3) transverse stress longitudinal stress

Physical Properties:
c. Thermal Expansion Coefficient () l = l

lt

lt

(1 / C

Physical Meaning of :

When T increases by 1, the increasing length per unit length is called Thermal Expansion Coefficient. Application of in Engineering.

Chemical Properties:
Definition: Its the chemical stability of materials in medium, i.e. , its the nature that whether the materials react with medium chemically or electro-chemically leading to corrosion. Two index: Corrosion Resistance Resistance to Oxidation

Chemical Properties:
a. Corrosion resistance the ability of metal materials to resist the corrosion caused by the medium (such as atmosphere, water vapor, electrolyte). b. Oxidation resistance 1 Resist to high temperature oxidation; 2 Resist to oxide etch by other gaseous medium, such as water vapor, CO2 , SO2 , etc.

Manufacturing Properties
A. Definition: Proterties ( mechanical, physical & chemical) are technical / processing properties of material. B.Classification: Casting Forging Welding Machining Heat treatment Cold Warm forming

Manufacturing Properties
Casting Property : Fluidity, Congealing Shrinkage Rate Forging Property : Resistance to Thermal Fragment, Resistance to Oxidation, Thermo-plasticity. Welding Property : Fluidity of parent material and welding flux in the melting state, Congealing, Shrinkage Rate, Thermo-plasticity. Machining Property : Hardness, Brittleness. Heat Treatment Property : Heat Treatment Feasibility. Cold & Warm forming Property: Plasticity, Toughness.

1. According to the content of carbon (C%): Low Carbon Steel Medium Carbon Steel High Carbon Steel 2.According to the smelting methods: Full Killed Steel Rimmed Steel Semi-killed Steel 3.According to the quality: Common Steel High Grade Steel Super High Grade Steel

Classification and designation of the equipments

According to the content of carbon (C%)

1. Low-carbon steel (C<0.25%) : Low strength and good plasticity, used in chemical vessels in welding and mechanical units with low loads. 2. Medium Carbon Steel (C=0.25%~0.6%) : Medium strength and plasticity, used as the important units of shaft, gear, top cap of high pressure equipments and so on . 3. High Carbon Steel (C>0.6%) : High strength and hardness, poor plasticity, used as string, wire line and so on.

According to the smelting methods

Full Killed Steel: deoxidized with a strong deoxidizing agent(silicon or aluminum) to reduce the oxygen content during solidification of the molten steel in the ingot. Rimmed Steel ( boiled steel): A low-carbon steel containing sufficient iron oxide to give a continuous evolution of carbon monoxide while the ingot is solidifying, resulting in a case or rim of metal virtually free of voids. Sheet and strip products made from rimmed steel ingots have very good surface quality. Semi-killed Steel: A commonly used grade of steel manufactured for low carbon bars and structural. A steel is considered semi killed so that it is incompletely deoxidized and it contains sufficient dissolved oxygen to react with the carbon to form carbon monoxide to offset st in the ingot.

According to the quality

Common Steel High Grade Steel Super High Grade Steel

What happens during rapid cooling?

Phase diagrams only show stable phases that are formed during slow cooling If cooling is rapid, the phase diagram becomes invalid and metastable phases may form In the case of steel, the formation of ferrite and cementite requires the diffusion of carbon out of the ferrite phase. What happens if cooling is too rapid to allow this? The crystal lattice tries to switch from fcc (austenite) to bcc (ferrite). Excess carbon -> distorted body-centred lattice MARTENSITE

Martensite ()
Distorted bcc lattice Non-equilibrium carbon content Forms plate-like or needle-shaped

grains

Fe, C 2, Mn 0.7 (wt%)

Martensite
Hard and brittle Applications: crankshafts, spanners, high-tension bolts

In general too brittle to be useful, BUT if tempered can be used to produce optimum steel microstructure

Tempering
Heat treatment of martensite carried out at 200-600 C -> allows C atoms to diffuse out of martensite +Fe3C Result: Fe3C present as uniform distribution of fine, round precipitates high strength and toughness Qquenched & tempered steels

Producing quenched and tempered steels

Critical cooling rate for martensite formation depends on concentration of alloying elements (e.g. C, Mn, Cr, Ni). Alloying elements delay the formation of ferrite and pearlite -> increase chances for martensite formation Critical cooling rate defines concept of HARDENABILITY (i.e. ease of martensite formation) Component thickness is an important parameter

Medium carbon steels generally used in quenched and tempered condition, high-carbon steels almost always. Applications: chisels, hammers, drills, cutting tools, springs... Quenching and tempering not possible for low carbon steels -> microstructure = ferrite + pearlite Applications: car panels, bridges, pipes.

Corrosion

2.3. Corrosion & Protection of Chemical Equipments

Harm of corrosion Chemical Corrosion Electrochemical Corrosion Inter-crystalline corrosion Stress corrosion

Harm of corrosion 1.weight changing:

p0 p1 K= Ft g /m 2 h

K Corrosion Rate g/cm2h p0 WT before corrosion g p1 WT after corrosion g

Contact Area of corrosive F media and test piece

m2
h

t Time of corrosion action

Harm of corrosion 2.corrosion degree:

Metallic density

KaThickness variation per year g/cm3

mm/year

V = F h _ and _ V =
h = p F

P
F

Harm of corrosion 3.Three Grades Standard of Metallic Resistance to Corrosion: Grade I: Ka < 0.1 mm/year (corrosion resistant) Grade II: Ka = 0.1 ~ 1.0 mm/year (available) Grade III: Ka > 1.0 mm/year (unavailable)

Types of metallic corrosion

1.Uniform (General) Corrosion:
i. Corrosion is over the whole metallic surface ii. Effect and danger are small iii. Remaining enough corrosion allowance in designation can still assure the strength and expected life of equipments

2.Local Corrosion:
i. Corrosion is at the local region in metals ii. Very dangerous iii. Remaining the corrosion allowance in designation has no effect.

2.Local Corrosion:
iv. Categories of Local Corrosion (1)Seam Corrosion (2)Pitting Corrosion For example: the pitting corrosion of Cr-Ni stainless steel in the media containing [Cl- ]

2.Local Corrosion:
(3)Stress Corrosion (4)Inter-crystalline Corrosion For example: the inter-crystalline corrosion of Cr-Ni stainless steel under certain conditions

Chemical Corrosion
1.Definition:
The corrosion caused by chemical reactions between metals and drying gas or non-electrolyte solution is called Chemical Corrosion.

Chemical Corrosion
2.Characteristics:
i. Corrosion products are on the metallic surface ii. No electric current in the cause of corrosion iii. The two natures of the products from chemical reactions: (1)Stability Passivation (2)Unstability Activation

Chemical Corrosion
i. Metallic high temperature oxidation (1)Oxidation resistance: oxidized rapidly at high T

forming oxidation film stopping oxidation

Chemical Corrosion
(2)High temperature oxidation of carbon steel and cast iron:
T > 300 oxidation surface appears T < 570 oxidation layer forms inner layer Fe3O4 outer layer Fe2O3

Stable

T > 570 oxidation layer forms

layer I: Fe2O3 layer II: Fe3O4 layer III: FeO

Stable Unstable

Fe2O3 Fe3O4 FeO Fe

T < 570

T > 570

Composition of ironic oxidation layer

Chemical Corrosion
(3)Solutions: Adding some Cr Si Al to form stable oxidation film of Cr2O3 SiO2 Al2O3 which can prohibit the oxidation reaction from proceeding.

Chemical Corrosion
ii. High temperature decarburization (1) T > 700 oxidation and decarburization both exist Fe3C + O2 3Fe + CO2 Fe3C + CO2 3Fe + 2CO Fe3C + H2O 3Fe + CO + H2

Chemical Corrosion
(2)Result *Cementite Ferrite with Strength, hardness and Fatigue Strength all decreasing. *Forming the air bubble which is the crack initiation point. (3)Prevention Adding Al or W

Chemical Corrosion
iii. Hydrogen corrosion (hydrogen brittleness) At relevant low temperature and pressure (T200 , P 5MPa), H2 wont corrode the carbon and alloy steels apparently. At high T and P, the corrosion actions of H2 to steels are obvious.

Chemical Corrosion
Mechanism of hydrogen corrosion:
Stage I Hydrogen brittleness stage H disperses inward and dissolves. Stage II Hydrogen attack stage Chemical reaction vary the structure of steels: Fe3C + 2H2 3Fe + CH4

Electrochemical Corrosion

1.Definition:

The corrosion caused by electrochemical reactions between metals and electrolytes is called Chemical Corrosion.

Electrochemical Corrosion
2.Mechanism:
Anode reaction Me Me+ + e Electron movement eanode

ecathode Cathode reaction D + ecathode [D e]

Electrochemical Corrosion
3.Conditions of electrochemical corrosion: There is potential difference on the parts of metallic surface or between different metals. The parts which have potential difference are connected with each other or the anode is connected with cathode. The metal with potential difference is in the electrolyte or the electrolyte where the anode and cathode are connected with each other.

Inter-crystalline corrosion
Definition It is the phenomenon that the corrosion occurs between two crystalline surfaces and causes the grain boundary continuously damaged. Nature Its a kind of local and selective corrosive damage.

Inter-crystalline corrosion
Occurring in Austenitic stainless steels Reason Lack of Cr element in the grain boundary Austenitic stainless steels (C<0.14%) *At high temperature (1050C) C distributes completely in whole alloy.

*Between 400~850 C + Cr + Fe

(Cr . Fe)23C6 Cr%

Separate out along the grain boundary

Grain boundary Grain (Cr . Fe)23C6

Cr 12.5% Cr lacking

Cr lacking region

Corroding minicell

Cr lacking region Anode

Grain Cathode

Inter-crystalline Corrosion occurs

Stress corrosion
i. Definition The destruction is caused by both corrosive media and the tensile stress action, this kind of damage is called Stress Corrosion.

Stress corrosion
ii. Initiation Circumstances Carbon steel and various kinds of Alloy steel (such as austenitic stainless steel) are in the media listed as following: (1)High concentrated chloride solution above 80 (2)High temperature and pressure water at 150~300 (3)High temperature and concentrated caustic solution

Stress corrosion
iii. Mechanism

Stage I: Breeding stage

The primary destruction (mechanical crack) is formed in metallic surface under the co-action of corrosion and tensile stress.

Stress corrosion Stage II: Corrosion cracks extension stage

Corrosive media dissolve the passivation film in the cracks to form anode with the film becoming cathode, the electrochemical corrosion therefore occurs. The crack extents rapidly under the co-action of this corrosion and tensile stress.

Stress corrosion Stage III: Breaking stage

Stress corrosion
iv. Prevention measure
(1)Decrease or clear up the stress concentration (2)Select the stress corrosion resistant materials: Two-phase stainless steel austenite + small amount (about 5%) of Ferrite such as: 1Cr18Mn10Ni5Mo3N 0Cr17Mn13Mo2N 0Cr21Ni5Ti

Mechanism of cathodic protection:

The protected metallic devises are polarized into cathodes by the direct current (DC) from outer electrical power supply taking the auxiliary electrode as the anode. When the potential of cathode < that of anode, the corrosion will be prohibited.

Improving features of the materials

Corrosion Resistant Measures in Metallic Equipments

1.Selecting materials reasonably 2.Adding the lined protection

Adding the lined protection

i. Metallic lining: stainless steel, other metals(Cu Al Ti Cr Ni) ii. Nonmetallic lining: plastics, rubbers, enamelware, etc.

- + iii. Coating iv. Adding corrosion buffering agents v. Electrochemical protection such as: cathodic protection Cathodic Protection Apparatuses

1.Definition of heat treatment

Heat Treatment

Heat treatment is the technical process or treatments to steels in solid state according to the scheduled requirements like heating, keeping warm and cooling, their aims are to vary the internal structure and gain the desired properties. 2.Basic Theories of heat treatment: When the basic components of steels (Fe) is heated to a certain degree, its lattice structure of steel will vary from one form to another as the temperature. Ferrite (F) and Austenite (A) are both the solid solution of Fe, so they have the lattice structure of iron.

Heat Treatment
3.Bring forward the problem: Find out the method and path of altering the properties of steels 4.Purpose of heat treatment Eliminating some shortages of steels Improving some properties of steels 5.Advantages of heat treatment Intensifying the metallic materials, fully developing the potential of materials, lightening the mass of equipments and guaranteeing the security and expected life of equipments.

Processing steps of heat treatment: Heating

Temperature/C

Keeping warm

Cooling

Keeping warm Heating Cooling Time

Cooling media and way of cooling

Cooling in furnace Cooling in still air Cooling in oil Cooling in water Cooling in brine

Cooling Capacity Cooling Speed

Heat Treating Process of steels:

Annealing Normalizing Quenching Tempering

i. Annealing & Normalizing *Lowering hardness, improving plasticity,

making steels apt to the cold-work. *Homogenizing the steel structure, refining the grain, developing the mechanical properties. *Clearing up the internal stress, resisting the deformation of workpieces.

Quench
(1)Process :
Heating the steel pieces to the quenching temperature, cool them quickly in the quenching agents after the warm-keeping treatment, then the Austenite changes into the Matensite.

(2)Quenching Temperature
*Hypo-eutectoid Steel (C<0.8%) heating above the A3 line 30~50C *Hyper-eutectoid Steel (C>0.8%) heating above the A1 line 30~50C

(3)Quenching Agent
*Mineral Oil, Water, and Brine. *Generally speaking: Carbon Steel, cooling in water and brine. Alloy Steel, cooling in oil.

Quench
(4)Quenching Function
developing the hardness, strength and wear (abrasion) resistance. *The emergency cooling in quenching is apt to make flaw in the steel pieces, so the tempering is commonly needed to clear up the stress after quenching. *Quenching and Tempering are always combined to the technical process.

iii. Tempering
(1)Process
Heat the steel pieces which are already quenched to the certain temperature (T<Tcritical), cool them quickly in still air after the warm-keeping treatment.

(2)Purpose
Reduce or clear up the internal stress of workpieces after quenching, stabilize the internal structure and gain the different mechanical properties.

(3)Types of Tempering *Tempering at low temperature

after quenching, tempering between 150~250C. Functionreduces the internal stress and brittleness of quenching steels, and at the same time keeps the high hardness and high wear resistance. Usage in spares of various tools and ball bearing after carburation.

*Tempering at medium temperature

after quenching, tempering between 300~450C. Functionreduce the internal stress, reach the limit of high strength and high elasticity. Usagein the treatment of various spring.

*Tempering at high temperature

after quenching, tempering between 500~680C. Functiongain the certain strength, have higher plasticity and impact toughness, i.e. excellent overall mechanical properties.

Quenching + Tempering Thermal Refining

Usageimportant spares, such as gear, rod, crank shaft, etc.

Common used materials

Common carbon steel

Vietnamese Standard
Code
TCVN 3600-81 TCVN3601-81 TCVN 3779-83 TCVN 3780-83 TCVN 3781-83 TCVN 6525-99 TCVN 471:2004 TCVN 470:2005 TCVN 1765:75

Items

Roofing steel sheet. Galvanized, acid-pickled. Roofing steel sheet Thin acid-pickled sheet steels Tinplate. Size, dimensions Zincplate steel sheet. Technical requirements Hot-dip zinc-coated carbon steel sheet Coated metal products, used in internal and external construction works. Technical properties Aluminium coated and hot dip galvanised steel strip and sheets Carbon steel

Common carbon steel

- TCVN 1765-75 : 3 groups A, B, C. Group A : according to mechanical property Symbol : CTXX CT : means carbon steel XX : ultimate tensile stress b (N/mm2) example : CT38 Group A Gii hn bn (b = 380N/mm2)

Common carbon steel

G ad r
CT31 CT33 s CT33 n CT34 s CT34 n CT38 s CT38 n CT42 s CT42 n CT51 n CT61 n CT42 CT34 CT33

(N /mm 2 )
<310 310- 400 320- 420 330-420 340- 440 370-470

CT38

380- 490 410- 520 420- 540 510- 640 <610

CT51
CT61

Symbols of different Standards

TCVN GOCT GB C45 45 45 40Cr 40X 40Cr OL100Cr2 X15 GCr15 20Cr13 20X13 2X13 08Cr18Ni10 08X18H90 0Cr18Ni9 CD100 Y10 T10 210Cr12 X12 Cr12 8018Cr4V P18 W18Cr4V ----------ASTM ----------CT34 CT2 A2 GX28-48 C130 HT300 GC50-2 B150 QT500-7 UNS G10450 G51400 G52986 S42000 AISI/SAE JIS AFNOR DIN BS 1045 S45C X45 C45 06A45 5140 SCr440 42C4 42C4 530A40 42100 SUJ2 100C6 100C6 535A99 420 SUS420J1 Z20C13 X20Cr13 420S29 SUS304 SK4 SKD1 SKH2 Z7CN18.09 X15Cr-Ni18 304S31 Y1-90 10 Z200C12 C105W1 BD3 Z80WCV X210C12 BT1 18-04-01 S 18-0-1 F3360 FGL300 FGS500-7 Fe360 GG30 GGG50 Fe360 260 B500/7

S30200 304 T72301 T30403 T12001 W109 D3 T1

36 F12803 No40 F33800 8055-06

SS330 FC300 FCD500

Common carbon steel

The content of the harmful elements S & P can be a little more : (S0.055%, P0.045%)
Carbon steel Standard Designations France: AFNORXC 68 Germany: DIN 1.1231 Sweden: SS 1770 , SS 1778 United States: AMS 5115 , AMS 5115C , ASTM A29 , ASTM A510 , ASTM A576 , ASTM A682 , MIL SPEC MIL-S-11713 (2) , SAE J403 , SAE J412 , SAE J414 , UNS G10700

Element
c

Weight % 0.65-0.75 0.60-0.90 0.04 (max) 0.05 (max)

Mn p
s

Rimmed Carbon Steel

Suitable under the condition of P0.6MPa, t=0~250C, S12mm. a clean surface low in carbon content. known as drawing quality steel. the steel is partially deoxidized. Carbon content is less than 0.25% and manganese content is less than 0.6%. do not retain any significant percentage of highly oxidizable elements such as Aluminum, silicon or titanium. especially where ease of forming and surface finish are major considerations. ideal for rolling, large number of applications, and is adapted to cold-bending, cold-forming and cold header applications.

High-quality carbon steel

Content of S & P to be (S & P0.04%) Uniform texture, good surface quality, superior properties than Common Steels. The number in designation indicates the percentage of the average content of C=0.08% & C=0.2% Steels that commonly contain Mn (without indicating Mn), if Mn < 0,7% Steels that contain Mn=0.7~1.2% (indicating Mn)

Super high-quality carbon steel

S & P0.03% Both the texture and properties of this kind of steels are superior to that of High Grade Steel.

Stainless steels
Definition: > 11 wt% Cr. Ni, Mn may also be present Cr -> adherent Cr2O3 film -> protection against corrosion and oxidation Most stainless steels are austenitic (alloying elements stabilise phase down to room T) Austenitic stainless steel is non-magnetic -> useful as quick test Ferritic and martensitic stainless steels also available -> increases range of mechanical properties available for specific applications (Corrosion resistance not as good as for austenitic stainless steel)

Cast Iron
1.The chemical components of commonly used cast iron:
95% Fe + (2.5% ~ 4%) C + ( ~1%) Purities

2.Structure:
Pealite + Cementite + Ladeburite + Graphite

Cast Iron
High carbon content low melting point

Cast Iron
Cheap can produce complex parts quickly and easily through sand casting BUT brittle Two types: Grey iron: Fe + C (graphite)

Formation of graphite rather than cementite promoted through high C and Si content, slow solidification rate White iron: Fe + Fe3C

Properties and Characteristics

Excellent casting property Good machinability Good wear resistance Excellent property to reduce vibration Low plasticity and brittleness Low tensile strength and high (ultimate) compression strength

i. Gray cast iron

(1)Properties and characteristics

*C exists in the form of plate-like graphite *Gray fracture *Low mechanical properties *Excellent corrosion resistance in H2SO4 and NaOH

Grey cast iron

Among least expensive metallic materials High fluidity -> can cast complex shapes

Graphite flakes -> high damping capacity and good machineability -> used e.g. as base structure for machines and heavy equipment BUT brittle due to shape of graphite flakes -> nodular iron better

Fe, C 3.52, Si 3.26, Mn 0.47 (wt%)

Spherical graphite cast iron (1)Properties and characteristics *C exists in the form of spherical graphite *Have better strength and a certain plasticity and toughness, its overall mechanical properties are close to that of steels. *Better corrosion resistance than that of Gray Cast Iron except when it is in the acid solution.

Ductile / Nodular cast iron

Addition of Mg / Ce to grey iron -> graphite forms as spheres rather than flakes -> improved toughness Applications: valves, pump bodies, gears, crankshafts

Fe, C 3.2, Si 2.5, Mg 0.05 (wt%)

iii. High-silicon cast iron (G) (1)Properties and characteristics

*Adding amount of Si (14.5~18%) to improve the corrosion resistance of the cast iron.

White cast iron

Exceptionally hard, but brittle and almost impossible to machine used in very few applications e.g. rollers in rolling mills Used as intermediary in production of malleable iron: heat treatment at 800-900C causes decomposition of cementite -> graphite clusters. Resulting microstructure and properties similar to nodular iron. Typical applications: connecting rods, transmission gears, pipe fittings, flanges

High-silicon cast iron (G) Highly corrosion resistant media: nitric acid, sulfuric acid, phosphorus acid, acetic acid Medium corrosion resistant media: hydrochloric acid, Oxalic acid , formic acid Corrosive media: caustic soda, hydrofluoric acid

4.Properties and Designation of commonly used cast iron:

Gray cast iron :

Spherical graphite cast iron:

High-silicon cast iron

Common Material used in Chemical Equipments

Objectives Select suitable material of construction Specify design temperature and pressure Calculate wall thickness

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Material of Construction

Mechanical and physical properties Corrosion resistance Ease of fabrication Availability in standard sizes Cost
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Material of Construction
Preliminary Selection

Selection Charts
Literature Previous experience Advise from materials supplier Advise from equipment manufacturer Advise from consultants

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Material of Construction
Final Selection Based on economic analysis which would include Material cost Maintenance cost
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Commonly Used Materials

Metals Polymers or Plastics Ceramic Materials

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Metals

Carbon steels Stainless steels Specialty alloys

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Carbon Steels
Most common engineering material Advantages Inexpensive Good tensile strength and ductility Available in a wide range of standard forms and sizes Easily worked and welded
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Carbon Steels Limitations

Corrosion resistance not good External surface need painting to prevent atmospheric corrosion Suitable for use with: Most organic solvents Steam, air, cooling water, boiler feed water Concentrated sulfuric acid and caustic alkalies

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Stainless Steels
Most frequently used corrosion resistant materials in the chemical industry High chromium or high nickel-chromium alloys of iron chromium content must be > 12% Nickel added to improve weldability and corrosion resistance in non-oxidizing env.

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Stainless Steels
Main Types of Stainless Steel Type 304 18% Cr & 8% Ni Type 304L low carbon version to improve welding of thick plates Type 316 Mo added to improve corrosion resistance in reducing conditions and at high temperature.
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Stainless Steels Limitations

Intergranular corrosion or weld decay possible in reducing environment Stress cracking can be caused by a few ppm of chloride ions
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Special Alloys

Monel 67% Ni, 33% Cu

Better corrosion resistance than SS No stress-corrosion cracking in chloride solutions Temp. up to 500oC

Inconel - 76% Ni, 15% Cr, 7% Fe

High temperature acidic service Temp. up to 900oC

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Plastics
Provide corrosion resistance at low cost. Main advantages: Excellent resistance to weak mineral acids Tolerate small changes in pH, minor impurities or oxygen content Light weight, easy to fabricate and install
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Plastics
Major Limitations: Moderate tempeature and pressure applications (T < 100oC; P < 5 atm.) Low mechanical strength Only fair resistance to solvents
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Plastics
Main Classes: 1. Thermoplastic can be reshaped 2. Thermosetting cannot be remoulded Thermoplastic Polyethylenes (low cost; T < 50oC) Polypropylene ( T up to 120oC) Polyvinyl chloride ( T 60oC)
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Plastics
Thermosetting - good mechanical properties (T 95oC) - good chemical resistance (except strong alkalies) Examples: Phenolic resins filled with carbon, graphite, silica Polyester resins reinforced with glass or carbon fibre to improve strength

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Plastics
Polytetrafloroethylene (PTFE) Known under the trade names of Teflon and Fluon Can be used up to 250oC highest for all plastics Resistant to all chemicals except fluorine and molten alkalies
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Rubber Lining
Metal surface lined with rubber to provide;
Cost effective solution for corrosion control and abrasion resistance e.g. acid storage, steel pickling Why rubber?

Able to bond strongly to various surfaces Good combination of elasticity and tensile strength

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Ceramic Materials Provide high temperature corrosion resistance and/or thermal protection (up to 2000oC) Ceramic or refractory materials metal oxides, carbides and nitrides Used as either solid bodies or coatings Glass mostly used in glass lining

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1.4.2 Effect of Alloy Elements to the properties of steels

1.Alloy elements:
i. Definition The elements that are added on purpose to develop the structure and characteristics of steels. ii. Main alloy elements Cr Ni Mn Si Al Mo V Ti Cu B Nb W Re

2.Alloy Steel
Definition Alloy steels are those steels that contain the alloy elements which develop the properties of steels.

Characteristics of the main alloy elements:

i. Cr (1)Cr>13%, corrosion resistance dramatically (2)Strength, hardness, wear resistance, oxidation resistance and hardenability all (3)Plasticity and toughness (4)Adds strength at high temperature

ii. Ni (1)Enlarge the range of corrosion resistance of stainless steel, especially improve the resistance to base. (2)Broad the -phase region as to be the element that form the austenite. (3)Develop the strength as well as keep excellent properties of plasticity and toughness. (4)Improves strength at high T

iii. Mn

(1)Develop the strength and impact toughness at low temperature. (2)Broad the -phase region. (3) Counteracts sulfur brittleness. (4)Increases hardenability.

iv. Si (1)Develops strength and fatigue durability at high temperature. (2)Improve heat resistance (3)Resistant to the corrosion of such media as H2S and so on. (4)If amount of Si is too much, plasticity and impact toughness both (5)Strengthens steel (6)Increases hardenability

v. Mo (1)Develop the resistance of stainless steels to the chloride anion Cl-. (2)Enhances H corrosion resistance. (3)Improve the heat resistance. (4)Raises grain-coarsening temperature. (5)Mo<0.6%, plasticity . (6)Counteracts tendency toward temper brittleness.

vi. Al (1)Restricts grain growth. (2)Develops the impact toughness. (3)Resistant to the corrosion caused by H2S. (4)Improves the oxidation and heat resistance. (5)Cheap, common substitute for Cr among heat-resistant steels.

vii. Ti (1)Restricts grain growth. (2)Develops strength and toughness. (3)Improves the oxidation and heat resistance. (4)Stablizes C to prevent the inter-crystalline corrosion. (5)Prevents formation of austenite in high chromium steels; prevents localized depletion of chromium in stainless steel during long heating.

viii. V (1)Developes high-temperature strength. (2)Increases hardenability. (3)Restricts grain growth. (4)Keeps the strength and improve the plasticity. (5)Resists tempering

AE Cr Ni Mn Si Mo Al Ti V Re

H/WR IT

CR

OR

HR

FD

GR

P H2S Mo<0.6% HCl H2S in-c

Interpretation: AEalloy element S strength P plasticity H/WR hardness and wear resistance IT impact toughness CR corrosion resistance OR oxidation resistance HR heat resistance FD fatigue durability GR grain refining H hardability in-c inter-crystalline

Common Low Alloy Steel

1.Definition:
They are the steels that are formed by adding a few alloy elements at the basis of Common Low Carbon Steel.

2.Composition:
(1)C<0.2% (2)Alloy elements *Mn 1~1.5% *Si Cr Ti V Nb Ni Al 0.015 ~ 0.6%

3.Structure:
Ferrite + Pearlite

4.Properties and characteristics:

i. High strength and large yield ratio ii. Excellent welding property iii. Good resistance to the corrosion of atmosphere iv. Perfect properties at low temperature

5.Designation (GB1591-88) (New Designation GB/T1591-94)

16Mn 16MnR 16Mng 15MnV 15MnVR 15MnVg 09Mn2V 18MnMoNbR The number ahead is the percentage of the C content, such as 16Mn (C = 0.16%).

Indicate the main alloy elements, the number thereafter is the percentage of that element. If it is less than 1.5%, it can be omitted. Content of alloy elements: 1.5 ~ 2.49% Sign as 2 Sign as 3 3.5 ~ 4.49% 2.5 ~ 3.49% Sign as 4

Boiler Steel & Vessel Steel

1.Steels specially used in the manufacture of boilers and vessels. 2.There are some special requirements for boiler steel and vessel steel.

Commonly-used Designation:
i. Boiler Steel 20g 22g 12Mng 16Mng 15MnVg 14MnMoVg 18MnMoNbg ii. Vessel Steel Q235-AR 20R 16MnR 15MnVR 09MnVR 18MnMoNbR

Stainless Steel and Corrosion (Acid) Resistant Steel

Stainless Steels are the kind of alloy steels which are resistant to the corrosion caused by atmosphere, water or other soft caustic media.

Stainless Steel and Corrosion (Acid) Resistant Steel

Acid Resistant steels are the kind of alloy steels which are resistant to the corrosion caused by acid or strong caustic media. As a rule, we called them both Stainless Steel. Examples: *Chromium Stainless Steel *Chromium-nickel Stainless Steel

1.Chromium Stainless Steel:

i. Component < 0.2% C + (13 ~ 28%) Cr + Fe ii. Construction Ferrite or Martensite (no Austenite even at high temperature)

iii. Theories of corrosion resistance (1)In the oxidizing medium, a oxide skin Cr2O3 which is stable and tight will be formed, it has an effect on passivation, i.e. there is a passivation layer on the surface of the steels. (2)The degree of corrosion resistance depends on the content of C and Cr. The more Cr, the better the resistance The less C, the better the resistance

iv. Commonly-used Chromium Stainless Steel 1Cr13 2Cr13 0Cr13 0Cr17 0Cr17Ti v. Designation (1)The first number: Average C content Average with C amount of 1000 points 0 C < 0.1% 1: C0.15% 2: C0.2% (2)The second number: percentage of the average content of Cr

2.Chromium-nickel Stainless Steel:

i. Component 0.14% C + ( 17~19% ) Cr + ( 8 ~11%) Ni + Fe Briefly called 18 8 Steel Typical Designation: 1Cr18Ni9Ti ii. Construction Single austenite structure at normal temperature

iii. Characteristics (1)High strength and good plasticity & toughness (2)Large range of suitable temperature -196 ~ 800 (3)Excellent technical properties (4)Good corrosion resistance

Non-corrosive media: cold phosphorus acid, nitric acid, acetic acid, hydrogen sulfide, sulfate, nitride, base liquid, petroleum chemicals, etc. Corrosive media: hydrochloric acid, dilute sulfuric acid (<10%), hot phosphorus acid, oxalic acid , melting caustic potassium, melting caustic alkali, Cl-, bromine (Br), iodine (I), etc.

(5)Inter-crystalline corrosion easily occurs between 400~800 Definition of inter-crystalline corrosion: It is the phenomenon that the corrosion occurs between two crystalline surfaces and causes the grain boundary continuously damaged. Nature: Its a kind of local and selective corrosive damage.

Occurring in: Austenitic stainless steels Reason: Lack of Cr element in the grain boundary Austenitic stainless steels (C<0.14%): *At high temperature (1050C) C distributes completely in whole alloy.

*Between 400~800 C + Cr + Fe

(Cr . Fe)23C6 Cr%

Separate out along the grain boundary

Grain boundary Grain (Cr . Fe)23C6

Cr 12.5% Cr lacking

Cr lacking region

Corroding minicell

Cr lacking region Anode

Grain Cathode

Inter-crystalline Corrosion occurs

Damage: To be brittle, even softly beating can makes it break into dust. Have very low strength. Preventive measures: *Solution heat treatment quenching again (1100~1150C) to dissolve C and Cr into the austenite. *Reduce the content of C preventing C to combine with Cr, then less Cr will be separated out. For example: 0Cr18Ni9 (C 0.08%) 00Cr18Ni9 (C 0.03%)

*C stabilization treatment adding Ti or Nb to form TiC or NbC to stabilize C. For example: 1Cr18Ni9Ti 1Cr19Ni11Nb *Add microelement adding B can vary the nature of grain boundary to prevent (Cr . Fe)23C6 to be separated out.

(6) Pitting corrosion occurs in the media containing [Cl-] Mechanism: [Cl-] intrudes into the flaw of passivation film (Cr2 O3) and reacts with metallic ion to form strong acidic salts ([M+] + [Cl-] MCl) which can dissolve the passivation film the locally corroded film becomes a passiveactive minicell with corrosion taking place.

Damage: Fast corrosion speed easily perforates the thin (only several mini-meter thick) stainless steel by corrosion. Preventive measures: *Adding some alloy elements The most effective elements to improve the pitting corrosion resistance: Cr, Mo Secondarily effective elements: Ni, Si, N, Re

*Cr25%, pitting corrosion wont occur. 2%Mo improve pitting corrosion resistance dramatically, Mo and [Cl-] form the protective film (MoOCl2) which can prevent the passivation film being perforated. *Materials resistant to the corrosion of [Cl -]: high Cr-Ni stainless steel containing Mo such as: 1Cr18Ni12Mo2Ti 00Cr20Ni30Mo2Nb 000Cr30Mo2

Heat-resisting Steel and Lowtemperature Steel

1.Heat-resisting Steel:
i. Characteristics (1)Excellent high-temperature oxidation resistance (excellent high-T chemical stability) (2)Good high-T mechanical properties (strength at high T)

ii. Elements added Cr Mo V Ti W Si Ni Al iii. Commonly-used heat-resisting steel (a)Oxidation resistant steel *mainly resistant to oxidation, but has low strength. *used in the parts that are heated directly (800~1000) but small loaded. such as: heating tube support, nozzle, etc. *commonly used steels designation: Cr13SiAl Cr25Ti Cr17Ti Cr25Ni12

(b)Refractory steel *mainly resistant to creep but also resistant to oxidation. *used in the parts that are loaded at high T. such as: heating tube, reactor, etc. *commonly used steels designation: 12CrMo Cr5Mo 1Cr18Ni9Ti Cr25Ni20

2.Low-temperature Steel:
i. Working temperature < -20 Low temperature -20 ~-40 Non-cryogenic temperature < -40 Cryogenic temperature ii. Characteristics (1)Excellent low-temperature toughness (2)Excellent processing workability and weldability

iii. Requirements of structure (1)Low content of C (0.08~0.18%) form homogeneous ferritic structure. (2)Homogeneous austenitic structure is desirable at cryogenic temperature. iv. Elements added Mn Al Ti Nb Cu V N