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KOROSI LOGAM

H. Kurnia, PhD Dosen FPMIPA , Universitas Pendidikan Indonesia, Bandung FAKULTAS PENDIDIKAN MATEMATIKA DAN ILMU PENGETAHUAN ALAM

UNIVERSITAS PENDIDIKAN INDONESIA 2011

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Pengertian Korosi Logam Korosi Besi dan Baja Macam-macam Korosi Logam Dampak Ekonomi Korosi Logam Upaya pencegahan Korosi Logam

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Mengetahui dan menyadari faktor-faktor lingkungan yang menyebabkan terjadinya korosi pada besi dan baja.

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Mengetahui dan menyadari masalah-masalah dan kerugiankerugian yang disebabkan oleh korosi besi dan baja yang terjadi di sekitarnya
Menunjukkan bagian logam/baja yang mudah terkorosi Menggambarkan proses korosi sebagai sel elektrokimia Mengetahui cara mengatasi dan melindungi besi dan baja dari korosi

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Mengetahui deret kereaktifan logam-logam

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Apakah yang anda ketahui tentang korosi logam ? Masalah-masalah dan kerugian-kerugian apakah yang dapat ditimbulkan karena korosi? Logam-logam manakah yang mudah terkorosi? Pada kondisi manakah korosi logam dapat terjadi ? Zat-zat apakah yang menyebabkan korosi ? Bagaimanakah reaksi kimia yang terjadi pada korosi logam ?

KASUS KOROSI LOGAM BIDANG ENGINERING

The collapsed Silver Bridge, as seen from the Ohio side

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Corrosion may be defined as the destruction of a metal or an alloy because of chemical or electrochemical reaction with its surrounding environment or medium Corrosion is defined as the deterioration of a material,usually a metal, because of a reaction with its environment and which requires the presence of an anode, a cathode, an electrolyte, and an electrical circuit. Metal Corrosion can be defined as the destructive attack of a metal through interaction with its environment.

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Definisi korosi di atas menunjukkan bahwa proses korosi logam (reaksi oksidasi-reduksi) dapat berlangsung dengan dua cara :
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Pemindahan elektron secara langsung dari zat pereduksi (besi) ke zat pengoksidasi (oksigen). Dalam keadaan ini, oksidasi dan reduksi terjadi pada tempat yang sama. Pemindahan elektron secara tidak langsung (melalui suatu konduktor logam) dari satu tempat di mana oksidasi terjadi ke tempat lainnya di mana reduksi terjadi. Sel elektrokimia atau sel galvani merupakan salah satu contohnya.

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Galvanic Cells
anode oxidation cathode reduction

spontaneous redox reaction

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TABEL I Potensial Elektroda Standar Pada 25oc

Unsur Litium Kalium

Sim bol Li K

Potensial Elektroda Standar (volt) -3,045 -2,920 -2,340 -1,700 -1,670 -1,050 -0,762 -0,744 -0,440 -0,402 -0,350 -0,325

Magnesium Berilium Aluminium Mangan Seng Khrom Besi Kadmium Yellow Brass 50-50 solder timahtimbal Nikel Timah Timbal Hidrogen (Elektroda pembanding) Titanium Tembaga Raksa Perak Karbon Platinum Emas Grafit

Mg Be Al Mn Zn Cr Fe Cd

Ni Sn Pb H Ti Cu Hg Ag C Pt Au C

-0,250 -0,136

-0,126 0,000 +0,055 +0,340 +0,789 +0,799 +0,810 +1,200 +1,420 +2,250

ANODIK (AKTIF) KATODIK (PASIF)

Natrium

Na

-2,712

FAKTOR-FAKTOR LINGKUNGAN YANG BERPENGARUH TERHADAP KOROSI LOGAM

1Sheir,

L.L., R.A. Jarman, and G.T. Burstein, eds. Corrosion. 3rd ed. Vol. 1. 2000, Butterworth-Heinemann: Oxford.
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2Fontana,

M.G., Corrosion Engineering. 3rd ed. 1986, New York: McGraw-Hill.


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4Uhlig,

H.H. and R.W. Revie, Corrosion and Corrosion Control. 3rd ed. 1985, New York: John Wiley & Sons.
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Materials are precious resources Engineering design is incomplete without knowledge of corrosion Applying knowledge of corrosion protection can minimize disasters Corrosion contaminate products such as pharmaceutical, food and dairy products or luxury items like soap Corrosion products threat to the environment Artificial implants for the human body!!!

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MACAM-MACAM KOROSI

Forms of Corrosion
1. General Corrosion (Uniform Corrosion), 2. Galvanic Corrosion (Bimetal Corrosion), 3. Concentration-cell (Crevice Corrosion Cracking) (Korosi Celah), 4. Pitting Corrosion (Korosi Sumuran), 5. Intergranular Corrosion, 6. Stress Corrosion Cracking, 7. Dealloying, 8. Erosion Corrosion 9. Microbiologically Induced Corrosion

Galvanic corrosion
Galvanic corrosion is an electrochemical oxidation-reduction (redox) process, which occurs when two dissimilar metals or alloys are brought into electrical contact and immersed into an electrolyte solution. Electrochemistry of galvanic corrosion The two metals immersed into an electrolyte forms a galvanic cell, in which the metal having lower value of electrode potential (higher position in the table of Electrochemical series) will oxidize (anodic reaction) and the metal having higher value of electrode potential (more noble) will provide cathodic reaction (reduction) on its surface. The algebraic difference between the electrode potentials of the two metals determines the driving force of galvanic corrosion. Two examples of galvanic corrosion are presented in the figure below.

system iron-zinc the standard electrode potentials of the metals: e0zn = -0.763 v, e0fe = -0.44 v. the difference: e0fe e0zn = 0.323 v. the potential of zn is lower therefore it dissolves in electrolyte according to anodic reaction: zn = zn2+ + 2e- (corrosion of zinc). the electrons given up by the anode flow to the cathode (iron) where they are discharged in the cathodic reaction: h+ + e- = h.

System iron-copper The standard electrode potentials: E0Fe = -0.44 V, E0Cu = +0.337 V. The difference: E0Cu - E0Fe = 0.777 V. Potential of iron is lower therefore it reacts anodically (dissolves) in this system: Fe = Fe2+ + 2e- (corrosion of iron). Cathodic reaction of the electrons with hydrogen ions occurs on the copper surface.

Factors of galvanic corrosion


The following factors determine thermodynamic and kinetic conditions of galvanic corrosion:
a.
b. c. d.

e. f.

Difference between the electrode potential of the two metals. The greater the difference the higher the driving electric force of corrosion. Contact resistance at the boundary between the two metals. High contact resistance limits the electrons transfer through the boundary and decrease the corrosion rate. Electric resistance of electrolyte solution. Dilute solutions having high electric resistance provide low corrosion rate. Anode-to-cathode areas ratio. Large anode connected to a small cathode result in low corrosion rate. Presence of passive film. Electrolyte solution properties (PH, oxygen content, temperature, flow rate).

Chemistry In Action: Dental Filling Discomfort

2+ Hg2 /Ag2Hg3 0.85 V


2+ Sn /Ag3Sn -0.05 V 2+ Sn /Ag3Sn -0.05 V

Pitting Corrosion
Subset of Crevice Corrosion
Formation of pits: local thickness reduction

Difficult to detect
O2 O2 OHClH+ M+ OHClH+ M+ H+ M+ O2 OH-

M+
H+

Cl-

ClM+

http://www.materialsengineer.com/dup%20image/corrosion%2005b.jpg

Pitting Corrosin

Anodic reactions inside the pit:

Fe = Fe2+ + 2e- (dissolution of iron)


The electrons given up by the anode flow to the cathode (passivated surface) where they are discharged in the cathodic reaction: 1/2O2 + H2O + 2e- = 2(OH-) As a result of these reactions the electrolyte enclosed in the pit gains positive electrical charge in contrast to the electrolyte surrounding the pit, which becomes negatively charged. The positively charged pit attracts negative ions of chlorine Cl- increasing acidity of the electrolyte according to the reaction: FeCl2 + 2H2O = Fe(OH)2 + 2HCl PH of the electrolyte inside the pit decreases (acidity increases) from 6 to 2-3, which causes further acceleration of corrosion process. Large ratio between the anode and cathode areas favors increase of the corrosion rate. Corrosion products (Fe(OH)3) form around the pit resulting in further separation of its electrolyte.

Pitting corrosion
Pitting corrosion is an electrochemical oxidationreduction (redox) process, which occurs within localized holes (cells) on the surface of metals coated with a passive film. Pitting corrosion is considered much more dangerous than uniform corrosion since its rate is 10-100 times higher. Pitting corrosion is highly accelerated if chloride, sulphate or bromide ions are present in the electrolyte solution. Stainless steels and other metals forming a passive oxide layers on their surfaces (Aluminum alloys, Copper alloys, chromium) in electrolytes and atmosphere are sensitive to pitting corrosion.

Mechanism of pitting corrosion is similar to that of Crevice corrosion: dissolution of the passivating film and gradual acidification of the electrolyte caused by its insufficient aeration (Oxygen penetration). Stages of pitting corrosion: Pit initiation. An initial pit may form on the surface covered by a passive oxide film as a result of the following:

Mechanical damage of the passive film caused by scratches. Anodic reaction starts on the metal surface exposed to the electrolyte. The passivated surrounding surface act as the cathode. Particles of a second phase (non-metallic inclusions, intermetallic inclusions, metallic particles, Microsegregation) emerging on the metal surface. These particles precipitating along the grains boundaries may function as local anodes causing localized galvanic corrosion and formation of initial pits. Localized stresses in form of dislocations emerging on the surface may become anodes and initiate pits. Non-homogeneous environment may dissolve the passive film at certain locations where initial pits form.

Pit growth. In presence of chloride ions pits are growing by autocatalytic mechanism. Pitting corrosion of a stainless steel is illustrated in the figure.

Passivation
Passivation is a formation of a thin film of oxidation products preventing further corrosion of the metal. The oxide passivation film may form either on exposure to air or in electrolyte with presence of oxygen. Conditions (electrode potential vs. PH) of formation of passive film are determined by the Pourbaix diagrams. Low carbon steel does not corrode in concentrated nitric acid due to protection effect of passive film however dilute nitric acid does not form stable passive film and therefore easily dissolves steel. Passive film is formed on the surface of aluminum, chromium, silicone and titanium in air, water and dilute acids.

Passivation
Good corrosion and oxidation resistance of Stainless steels is also a result of formation of chromium reach oxide passive layer. The passivation effect is achieved if the chromium content is not less than 10.5%. Other elements (nitrogen, titanium, nickel, molybdenum) enhance corrosion resistance of stainless steels. A stainless steel heated to 900-1400F (482-760C) during welding may lose its corrosion resistance because of depletion of chromium consumed for formation of chromium carbides. This effect is called sensitization.

A damage of the passive film may cause intensive localized corrosion (pitting corrosion). Passive oxide layers are dissolved in electrolytes containing sulfates and chlorides. Phosphate and chromate ions stabilize passive films promoting repair of its defects.

Erosion corrosion
is an acceleration in the rate of corrosion attack in metal due to the relative motion of a corrosive fluid and a metal surface. The increased turbulence caused by pitting on the internal surfaces of a tube can result in rapidly increasing erosion rates and eventually a leak. Erosion corrosion can also be aggravated by faulty workmanship.

Microbial corrosion
also called bacterial corrosion, bio-corrosion, microbiologically-influenced corrosion, or microbially-induced corrosion (MIC), is corrosion caused or promoted by microorganisms, usually chemoautotrophs. It can apply to both metals and non-metallic materials. There are several ways that bacterial action can cause corrosion: (1) by direct action, e.g., by the production of corrosive substances such as CO2, H2S, NH3, organic or inorganic acids; (2) by metabolic production of organic products that can act as depolarizers or catalysts of corrosion reactions; and (3) in cases similar to the anaerobic corrosion of iron, by the activities of the sulfate-reducing organisms where, under some conditions, the corrosion reaction is an integral part of the metabolic cycle

Microbial corrosion
The theory is that the acceleration of corrosion by bacteria is based on the fact that hydrogen acceptors and oxidation-reduction systems, set up during bacterial metabolism, are present at the surface of the metal. For the disulfide-mercaptan system, it was suggested that depolarization might well be the mechanism of corrosion. Under anaerobic conditions, sulfate-reducing bacteria (SRB) were found to have an adverse effect on copper and its alloys as a consequence of the hydrogen sulfide formed by the bacteria. Bacteriologically produced hydrogen sulfide has been identified in underground corrosion of copper pipes.

DAMPAK EKONOMI KOROSI

KERUGIAN KARENA KOROSI


Korosi menghabiskan ongkos yang tinggi antara lain : Biaya perbaikan konstruksi dan permesinan Biaya jasa untuk penggantian dan pemeliharaa Hilangnya produksi selama terhentinya pabrik Kerusakan produk oleh terhentinya pabrik Biaya produksi tambahan oleh terhentinya atau kebocoran 6. Biaya tambahan penggunaan bahan-bahan tahankorosi 7. Biaya pencegahan korosi 8. Biaya penelitian dalam menangani korosi, pencegahan dan pengembangan bahan-bahan tahan-korosi.
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BIAYA TAHUNAN LANGSUNG KOROSI


In light of the thermodynamic basis for corrosion it is not surprising that costs associated with corrosion are high. Several studies over the past 30 years have shown that the annual direct cost of corrosion to an industrial economy is approximately 3.1% of the country's Gross National Product (GNP). In the United States, this amounts to over $276 B per year. The Department of Defense alone has corrosion costs of $20 B. Because of the significant economic, safety, and historical impact of corrosion on society and because corrosion of metals is an electrochemical process, it is also not surprising that the Corrosion Division is one of the oldest divisions within ECS.

Cost of Corrosion(2004) in billion US$5


Country
USA Japan Former USSR Germany UK Australia Belgium India Poland Canada ..... .....

Direct Cost
303.76 59.02 55.01 49.26 8.51 7.32 6.75 3.78 3.53 3.38

Indirect Cost
200 (approximately)

.....
Global
5Bhaskaran, R.,

510.14

940 (approximately)

N. Palaniswamy, and N.S. Rengaswamy, Global Cost of CorrosionA Historical Review, in Corrosion: Materials, Vol 13B, ASM Handbook. 2005, ASM International.

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UPAYA PENCEGAHAN KOROSI

CORROSION PREVENTION
1. Electrically insulate the two metals from each

other.Unless they are in electrical contact, there can be no galvanic couple set up.
2. Coating the two materials or if it is not possible to

coat both, the coating shall be applied to the more noble, the material with higher potential.
3. Another way is to keep the metals dry and/or

shielded from ionic compounds (salts, acids, bases), for example by painting or encasing the protected metal in plastic or epoxy, and allowing them to dry.

CORROSION PREVENTION
1. Proper selection of materials with known

resistance to the service environment .


2. Control pH, chloride concentration and

temperature
3. Cathodic protection and/or Anodic Protection. 4. Regular mechanical cleaning if possible. 5. Chemical treatment with biocides to control

the population of bacteria.


6. Complete drainage and dry -storage.

Sacrificial pelapis

Cathodic Protection of an Iron Storage Tank

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Sacrificial anode in the hull of a ship

Perlindungan katodik

UPAYA PENGENDALIAN KOROSI

Pengendalian Korosi
Prinsip dasar pengendalian korosi sebenarnya sangat sederhana. Faktor-faktor yang mempengaruhi korosi dapat dibagi dalam dua kategori, yaitu faktor logam (faktor dalam) dan faktor lingkungan (faktor luar).Jumlah paduan logam maupun variasi lingkungan sangat banyak,sehingga dapat diperkirakan bahwa persoalan korosi tampaknya sangat kompleks. Dasar-dasar pengendaliannya dapat kita bagi kedalam 4 metode :
1. Membuat logam tahan korosi
2. Membuat lingkungan menjadi tidak korosif 3. Membalikkan arah arus korois 4. Memisahkan logam dari lingkungan.

THE FUTURE

Corrosion mechanism of steel

Corrosion Mechanisms Can be Minimized By Avoiding Microgalvanic Cell Formation Present in Conventional and Micro-Alloyed Steels

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