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Critical issues in Material Selection for Phosphoric Acid Plants Dr MP Sukumaran Nair FIE The Fertilizers And Chemicals

Travancore (FACT) Ltd Cochin, India


(Abstract) Techno-economic considerations are vital in selecting the material of construction for phosphoric acid plant equipment. This is mainly due to the vulnerability of commonly available materials to withstand the combined effects of corrosion and abrasive erosion accelerated by operating temperature and concentration of the medium. Even though pure phosphoric acid is less corrosive than other stronger mineral acids the impurities in the rock phosphate raw material that goes into solution upon acidiculation of the rock phosphates makes phosphoric acid highly corrosive. Rock phosphate is a mined product and its composition varies from mine to mine. Moreover good quality rock phosphate deposits are getting depleted and industry is increasingly exploring the use of lower grades of rock phosphate deposits. The increased presence of impurities in these varieties of rock adds on to the corrosive nature of the slurry. Extremes of operating conditions such as reaction temperature and velocity of movement of slurry particles also aggravate corrosion. Thus selection of material for construction of different equipment in the phosphoric acid plants and its reliability and economics of operation would depend on these factors. Over the years in its search for corrosion resistant and cost effective materials, the industry has witnessed a transition from austenitic to super austenitic to Duplex varieties of stainless steels and development of several proprietary alloys. Surface hardening of stainless steels by carburization, development of high chromium white cast irons, improved designs of equipment facilitated by techniques such as computational fluid dynamics (CFD), life cycle analysis and costing influence the material selector of the day in making his judgment prudent. This paper is an attempt to critically review the above issue of material selection in the light of problems encountered in actual operating environment of the plant.

Nature of corrosion in Phosphoric Acid Plants

Material selectors are worried not about the corrosive nature of pure phosphoric acid vis--vis stronger acids like sulphuric and hydrochloric acids, but on the nature of impurities in the raw material rock phosphate that goes into solution upon acidiculation and render phosphoric acid highly corrosive. Rock phosphate is a mined product and its composition varies from mine to mine. Moreover good quality rock phosphate deposits are getting depleted and industry is increasingly exploring the use of lower grades of rock phosphate deposits. Commonly available Phosphate Rock mineral deposits are Tri-calcium Phosphate Fluorapatite Carbonate apatite Hydroxyapatite Ca3(PO4)2 Ca10(PO4}6 F2 Ca10(PO4)6 CO3 Ca10(PO4)6 (OH)2 (46 % P2O5) (42 % P2O5) (41 % P2O5) and (42 % P2O5)

Around 60 grades of phosphate rock are available from the deposits in 24 countries world over. Typical analysis of high grade and low grade Rock phosphates are given below: Table 1: Analysis of Rock Phosphates Constituent CaO P2O5 Fe2O3 Al2O3 MgO SiO2 F Cl CO2 Na2O K2O Organics : : : : : : : : : : : : High Low ( wt % dry basis ) 53.2 44.25 37.35 26.7 1.71 0.15 2.3 0.1 1.65 traces 16 0.65 3.88 0.9 0.105 0.004 6.5 0.9 2.2 0.05 0.07 0.006 2.4 0.18

It can be seen that any source of rock phosphate essentially contains impurities like iron and aluminium, sodium and potassium, magnesium, fluorine, silica and chlorides etc. Besides other impurities such as Ba, Mn, Ni, Cu, Zn, As, Sr, V, Cr, Pb, Hg, Co, Cd, U, Th, Y, Ti, Se may also be present in very small quantities. From the corrosion point, the presence and

concentration of Fluorine and chlorine make selection of material of construction (MoC) of equipment difficult. Other impurities affect scaling tendency and excise interference in operation of the phosphoric and end product processes. The corrosive nature of the slurry in phosphoric acid production is also dependant on factors like the temperature of slurry (usually around 80 oC) and velocity of movement of slurry

particles (peripheral speed of impeller, agitator etc.) also. The reaction slurry contains around 40 per cent solids by weight and the abrasive nature of the gypsum crystals further aggravate the corrosion on materials of construction of the equipment. Thus selection of material for construction of different equipment in the phosphoric acid plants would depend on these considerations. In the past when good quality rock deposits were plenty, the level of impurities in rock phosphates was comparatively low and were within acceptable limits. With the depletion of major pioneering mines, use of low-grade phosphates with higher content of impurities has become necessary due to economic and practical considerations. The current practice is to blend of different grades of rock phosphate to keep the impurity content within acceptable limits, go for high quality material of construction or adopt life cycle costing as the basis of material selection for critical equipment.

Impurities in Rock Phosphates


Chlorine Chlorine in the rock exists as mineral chlorides and also come from water used in the beneficiation and other process. Chlorides upon acidiculation form hydrogen chloride which is highly corrosive and spoil the passive film on the metal surface. Chloride attack is severe in shallow pits on the surface of equipment parts leading to pitting corrosion. P.Baker has established that the exponential effect of chlorine corrosion with temperature. Fluorine Fluorine is present in all phosphate rocks to the tune of 10 to 14 per cent of P2O5. When acidulated, it forms hydrofluoric acid. If there is sufficient quantity of reactive silica in the rock, this may end up in production of hydroflurosilicic acid (H2SiF6) thus lowering the corrosive effect. To a lesser extent aluminium also help to fix fluorine as aluminium silico fluoride. Acceptable corrosion rates are achieved with a F/SiO2 ratio of 1.8. Other wise, the excess hydrogen fluoride (HF) will remain as free acid and cause excessive corrosion. Presence of Ca, Na and Mg though lead to scale formation do not contribute to corrosion. Ferric (Fe3+) ion promotes the formation of a passivation film inhibiting corrosion. Sulphuric acid The slurry in reaction tanks contains around 2040 mg /litre (mgl) sulphuric acid. The optimum level for each rock is different based on rock characteristics. It is reported that increasing sulfuric acid concentration in the attack slurry from 20 -40 mgl will enhance corrosion by a factor of 4 to 10.

Reaction conditions
Velocity of Slurry flow Due to presence of abrasive silica, erosion corrosion occur parts of equipment such as impellors and pipelines. Abrasion corrosion depends on the peripheral speed of equipment parts. Increase in peripheral speed will result in enhanced erosion corrosion rate exponentially by a factor of 2.4. Temperature. Increase in slurry temperature severely accelerates corrosion. The rate corrosion rate is doubled upon increase of temperature from 70oC to 85oC. Combination effect of corrosion factors In the normal operating environment of the plant, corrosive impurities, temperature of slurry and its velocity synergistically impact and the effect of corrosion is much higher. Calcined rocks show more corrosive tendency than uncalcined rocks due to its reductive nature. Use of mineral and organic oils for defoaming of slurry cause damage to rubber linings. Complexing Ratio It is well known that silica and aluminium readily form complexes with fluorine and thus fixation of fluorine and hydrogen fluoride will reduce its corrosive effect. The tendency to form such complexes is defined by a molar ratio as Complexing Ratio = ( % SiO2/60 + % Al2O3/102) / ( % F/114) If the rock contains an excess of silica and alumina with respect to fluorine, the ratio tends to be less than 1 and thus the corrosivity will be lower. Impurities such as Fe, Mg, Ca, and Na which under the reaction conditions of the attack tank form soluble or insoluble fluoro aluminates or silicates that settle on the metallic surface as scales also reduce the impact of corrosion. Development of metallurgy for Phosphoric acid application In the 1960s, stainless steels of 300 series grade were widely used in Phosphoric acid plant for slurry and acid services. AISI 316L and 317L were employed for years as material for pumps, piping and filters in phosphoric acid plants. Over the years, the developments in the metallurgy of alloy steels and improved heat treatment processes gave birth to special grade alloy steels with better corrosion and erosion resistance. These special grade alloy steels contains elements like chromium nickel and molybdenum in various proportions and also trace elements like tantalum, titanium niobium, copper etc in small quantities. Thus high nickel chromium alloys of the types N08020 (Carpenter 20-Cb), N10276 (Hastelloy C-276), N08825

(Incolly 825), N06985 (Hastelloy G-3), N 06030 (Hastelloy G-30) etc became well accepted as the material of construction for critical equipment in phosphoric acid plants. Table 2: Alloys for Phosphoric Acid plants : Chemical composition % wt Grade 316 L 317 L N08020 (Carpenter 20Cb-3) N 10276 (Hastelloy C-276) PR EN 26 31 C 0.020 max 0.030 max Si 0.50 max 1 max Mn 1.7 max 2 max P 0.015 max 0.045 max S 0.010 max 0.030 max Cr 17.5 1820 Ni 14.5 1115 Mo 2.5 3-4 Cu 3-4 Cb+Ta 1 max 2-3 W 3-4.5 V 0.35 Co 2.5 16 W 4 Al 0.2 Ti 0.6-1.2 Co 2 2.5- Cu 1.5-3 3.5 Cb + Ta 0.5 max W 1.5 max Cu 1.5-2.5 6-8 Co 5 max Cb + Ta 0.31.5 W 1.5 -4 Cu 1-2.4 4-6 Co 5 max Others

28

0.060 max

1 max 0.08 max

2 max 1 max

0.035 max 0.03 max

0.035 max 0.015 max

1921

32.5 -35

69

0.01 max

16

57

N 08825 (Incoloy 825)

31

0.05 max

0.5 max

1 max

0.03 max

0.030 max

19.5 23.5

3846

N 06985 (Hastelloy G-3)

45

0.015 max

1 max

1 max

0.04 max

0.030 max

2123.5

48

N 06030 (Hastelloy G-30)

46

0.03 max

0.8 max

1.5 max

0.04 max

0.02 max

2831.5

43

To withstand the service environment of the corrosive fluid nature, erosion and temperature tailor made alloys were developed under strictly controlled conditions and later their mechanical properties like strength, weldability, workability etc were improved by special treatment process. The higher the content of elements like chromium and nickel in the steel, greater the corrosion resistance and service life and cost of the material. During the 1970s Prayon Technologies, Belgium built several plants all over the world with HV series of material for most equipment. The supplier of this proprietary material alloys HV9 and HV-90A cast super-austenitic alloys produced by the Belgian casting shop Usines E. Henricot, a foundry which was closed. The compositions of alloys HV-9 , HV-9A, HV-93and

HV-90A though of similar types, were changed slightly but significantly in the past 30 years to adjust to increasingly more difficult corrosion conditions. Table 3: Chemical composition of HV grades % wt Grade HV 9 PRE N 35 C 0.04 max 0.04 max 0.03 max 0.03 max Si 1 max 1 max 1 max 1 max Mn 2 max 2 max 2 max 2 max P 0.030 max 0.030 max 0.030 max 0.030 max S 0.030 max 0.030 max 0.030 max 0.030 max Cr 2023 2023 1922 1922 Ni 2426 2426 2327 30 Mo 4 other Nb Cu 1-2, Nb Nb Nb

HV 9A HV 93 HV 90 A

36 37 37

4.5 4.85.5 4.85.5

Indeed these super-austenitic grades are difficult to produce particularly as thick cast parts. As these parts are used in very aggressive media (phosphoric acid slurries containing high enough contents in H2SO4, HCl, HF, H2SiF6 , Chlorides etc) the metallurgical condition must withstand the corrosive impact. Heat treatments must be carefully controlled, i.e. full solution annealing at 1050C-1150C for long enough time depending on the thickness, and then rapid quenching in order to prevent re-precipitation of intergranular intermetallic phases and chromium carbides. Any delivery must be carefully checked by metallographic examinations and well suited corrosion tests. Pitting resistance index Pitting resistance index -- a means of comparing corrosion resistance of stainless steel provide a useful guideline for material selection among different alloys for corrosive in environments. Pitting resistance equivalent number (PREN) or Pitting resistance index = % Cr + 3.3 X % Mo + l6 X % N

New Generation Alloys UNS N.08904 The super austenitic alloy 904 L is fully austenitic steel with low carbon content. It has superior corrosion resistance against pitting, crevice corrosion and stress corrosion cracking for the full range of concentrations and temperature up to 110 oC , than ordinary acid resistant stainless steels and classical stainless steel brands used for phosphoric acid plants It has a good weldability and formability and high mechanical strength. Due to a low carbon content chances for hot cracking and intergrannular corrosion after weld are minimal. It is well suited for attack tanks, agitators, heat exchangers , filters , centrifuges and pumps. Table 4: UNS N 08904 Chemical composition Grade Element C Si 1.00 max 600 45 240 155 35 Mn 2.0 max P 0.030 max S 0.020 max Cr 1921 Ni 2426 Mo 4.05.0 Cu 1.02.0

UNS.N 0.020 08904 % max Mechanical Properties Tensile Strength Elongation 0.2% Yield Point Hardness PREN

N/mm2 % min N/mm2 HB

These following proprietary steel grades are covered by the general equivalences UNS N.08904, Werkstoff nr. 1.4539, AFNOR Z.2.NCDU.25.20 or DIN X.1.NiCrMoCu.25.20.5. Trade Names URANUS.B-6 from Creusot-Loire (France) 2-RK-65 from Sandvik (Sweden), 904-L from Udelholm (Sweden) Jessop 700 (USA). UNS N.08028 This is a multipurpose austenitic stainless extra low carbon alloy for service in highly

corrosive conditions. It is characterized by very high corrosion resistance in strong acids, very good resistance to stress and intergrannular corrosion in various environments, resistance to pitting and crevice corrosion and also posses good weldability. It is used for pumps, piping, heat exchangers, evaporators and agitators. A proprietary alloy of this family viz; Sanicro 28

is in service in the phosphoric acid industry for the last three decades with excellent corrosion protection at temperatures in the 80-85 deg C rang and liquid velocities of 3.5 m/sec.

Table 5: UNS N 08028 Chemical composition Grade UNS.N 08028 Element % C 0.020 max Si 0.6 max Mn P S 0.015 max Cr 27 Ni 31 Mo 3. 5 Cu 1. 0

2.0 0.025 max max

Mechanical Properties Tensile Strength Elongation 0.2% Yield Point Hardness PREN Other general equivalences are 550-750 40 220 90 39 N/mm2 % min N/mm2 HB

ASTM: N08028, EN: 1.4563, EN Name: X 1 NiCrMoCu 31-27-4, W Nr.: 1.4563 DIN: X 1 NiCrMoCuN 31 27 4, SS: 2584 , AFNOR: Z1NCDU31-27-03 Trade Names Sanicro 28 (Sandvik, Sweden) UR B28 (Creusot-Loire, France) UNS S.31254 Another austenitic high Molybdenum grade alloy stainless steel which is coming up in phosphoric acid service is of the 904hMo type and is designated as UNS 31254 . Table 6: UNS S 31254 Chemical composition Grade UNS S31254 Composition Nominal % C 0.020 max Mn 1.00 max Si 0.80 max P 0.030 max S 0.010 max Cr 20 Mo 18 Ni 6.1 Cu 0.7 N 0.20

Mechanical Properties Tensile Strength Elongation 0.2% Yield Point Hardness PREN Other general equivalences are Werkstoff Nr. 1.4529, DIN X.1.NiCrMoCuN.25.20.6 (German) 650+ 35 300 96 83 N/mm2 % min N/mm2 HB

UNS S.31254 (US) Z1NCDU20.18.06AZ, AFNOR (French) Trade Names 254SMO Sandvik (Sweden) 19.25.HMo (USA) UR B 25 (Creusot-Loire , France) 654SMO Avesta Duplex Steels UNS S 31803 Duplex grade stainless steel grades containing 20-27 % Cr and 4-8 % Ni and 2.5 -3.5 % Mo are capable of withstanding high mechanical stress under severe corrosive condition as in phosphoric acid plants. Compared to austenitic grades Duplex type of steel have twice the yield strength and a high resistance against general corrosion, stress cracking and erosion. As these alloys contain lesser nickel than in austenitic high grade steels , they are less costly . Though the weldability is good, after heat treatment it has a strong tendency for embrittlement of the heat affected zones. This restrict its application in the processing industry. The erosion and corrosion resistance of this material to the hot slurry and cold phosphoric acid service essentially depends on the post treatment actions carried out during the manufacture of the same.To a certain extent the disadvantages caused by the heat treatment operation can be contained by carefully controlling the chemical composition. It has an extensive application in the phosphoric acid industry for pumps and agitators, slurry piping and vessels. Table 7: UNS S 31803 Chemical composition Grade UNS.S 31803 Element % C 0.030 max Si Mn P S 0.02 max Cr Ni Mo N

2.0 0.030 1.0max max max

21- 4.5- 2.5- 0.0823 6.5 3.5 0.20

Mechanical Properties Tensile Strength Elongation 0.2% Yield Point Hardness PREN Other general equivalences are American designation UNS S31803, European designation X2CrNiMoN 22-5-3 680-900 25 450 290 34 N/mm2 % min N/mm2 HB

Werkstoff nr 1.4462, J.93370 (USA). Trade Names URANUS-45.N, ( from Creusot-Loire France) SAF 2205 (Sandvik, Sweden)CD4MCu Duriron Co Lewmet 15 ( Chas A. Lewis & Co, USA) Industry operators admit that proprietary material procured from different suppliers have given prolonged service in some cases and at the same time failed very fast on other occasions. Instances of failure of this grade of material have been reported in the case of agitator blades and pumps. It is noticed that the material is very vulnerable to corrosion due to increased levels of chloride in the service medium. The sourcing of good quality material for a specific service in itself a big challenge for the material selector and the user. ASTM test procedures may be adopted as acceptance standards for chemical composition, mechanical properties, corrosion tests and post repair checks. UNS S32550 S32550 are a group of super duplex stainless steel with 25per cent Cr and excellent resistance to pitting and erosion . The molybdenum and nitrogen additions have been optimized in order to obtain the best corrosion resistance properties even for heavy plates. High nitrogen content improves the structural stability particularly in heat affected zones. Its corrosion resistance is much better than N08904 and roughly equivalent to 6 Mo super austenitic alloys. Copper addition increase the corrosion resistance properties, particularly in sulphuric acid media. It is a cost efficient grade for offshore, marine, phosphoric acid, sulphuric acid applications in presence of chlorides. The duplex microstructure provides high mechanical properties and thus the alloy is best suited for abrasion corrosions for pumps, agitators, rakes etc. Table 8: UNS S 32550 Chemical composition Grade UNS.S 32550 Element % C 0.030 max Si Mn P S 0.02 max Cr Ni Mo Cu 3-5 0.5-3 N 0.20.35

1.5 0.035 0.80max max max

24- 5.526 8

Mechanical Properties Tensile Strength 770 N/mm2

10

Elongation 0.2% Yield Point Hardness PREN Other general equivalences are

25 550 310 52

% min N/mm2 HB

EURONORM 1. 4507 - X2 Cr Ni Mo Cu N 25.6.3 AFNOR Z3 CNDU 25.07 AZ ASTM UNS S32550/S32520 Trade Names URANUS-52.N+ Ferralium 255 White Cast Irons ASTM Specification A532 covers the composition and hardness of abrasion-resistant white irons.. The high alloy white cast irons, which contain the alloying elements above 4 percent, with their predominant carbides in the microstructures, provide the high hardness that is necessary to withstand erosion without degradation. The supporting matrix structure is adjusted by alloy content and heat treatment to develop the most cost effective balance between resistance to abrasive wear and the toughness required. The high alloy white irons are readily cast to the shapes required for the handling of abrasive medium such as slurries. White irons offer considerable versatility in properties for a variety of abrasion-resistant applications. The composition of the white iron used to produce a given casting can be selected and heat treatments specified to develop the carbide distribution and the matrix microstructures that will give maximum service life and cost effectiveness. The alloyed irons all contain chromium to prevent the formation of graphite and to insure the stability of the carbides in the microstructure. Many of the alloy white irons also contain nickel, molybdenum, copper or combinations of these metals to prevent or to minimize the formation of pearlite in the microstructure. Alloyed martensitic white irons develop Brinell hardnesses in the range 500-700. For many abrasion-resistant applications, the more expensive alloyed white cast irons with martensitic matrix structures provide the most economical service. ( Creusot-Loire France) (Langley Alloys, UK)

The high alloy white irons are classified into three groups as:

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1. Nickel Chromium white irons, a low chromium group (1-4% chromium and 3-5% nickel, with one modification which contains 7-11% chromium) 2. Chromium Molybdenum irons, a high chromium group (14-28% chromium, 1-3% molybdenum, often alloyed further with additions of nickel or copper. 3. High chromium white irons, (25-28 % chromium with molybdenum and/or nickel up to 1.5%) The above categories of white irons though possess outstanding wear resistance their acid corrosion resistance are poor. Hence new varieties have been developed with very high chromium content up to 50 per cent and containing carbon up to 3 percent. Several pump manufacturers have developed proprietary versions of high chromium white irons containing 34-50 per cent of chromium, 2.5 per cent of carbon together with Ni, Mo, Mn, Si, Cu and other micro alloying elements for the phosphoric acid service. Table 9: High Chromium White Iron : Chemical composition Grade High chromium cast iron Element C 2.52.9 Si Mn 11.2 P 0.04 max S 0.04 max Cr 2123

0.6-0.8

Mechanical Properties Tensile Strength 410-690 N/mm2 Hardness 430 HB Trade Names Gastite T90G of GIW industries, USA 349 XL EnviroTech, USA

Table 10 : Materials for Phosphoric acid plant equipment


Equipment

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Commonly used Material of Construction

Attack tank reactor, Digestion vessel Agitator for hot slurry / filtrate service

CS or RCC with Rubber lining and Carbon brick lining at bottom and sides. CS / RCC with rubber lining at top. UNS No N08904 , N08825, N08020, S 32520 Impeller & Shaft UNS No N 06985, N 06030, S 31254, S 32520

Agitator for cold acid service Impeller & Shaft UNS No N08904 Filter Trays UNS No N08904

Cloth Polypropylene Impeller SS 316 L Casing cast steel rubber lined (CSRL) Impeller UNS No N8028 , S 31254 Casing - UNS No N8028 Impeller & casing UNS No N8028

Scrubber fan

Flash Cooler Pump

Slurry Circulator

Filter feed pump

Impeller and Casing UNS No N08904, S.31254, N08028 UNS S 31803 , S 32520

Scrubber tower Exhaust fan

CSRL with PVC coupling / PTFE spray nozzles. Impeller SS 316 L Casing CSRL

Wash acid pumps

Impeller UNS S 31803 Casing UNS No N08020

Mixing head Evaporator

UNS No N10276 UNS No N08028, S 31254, N 06985, N 06030

Scrubber Circulation Pump (Weak Fluorosilicic Acid ) Impeller and Casing UNS No N08020

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Sludge Pump

Impeller and Casing UNS No N08904, N 06030

Cold Phosphoric Acid Pump

Impeller and Casing UNS No N08904, S 31803

Vacuum Pump

Impeller Bronze 90%, Cu 10% Casing Cast Iron

Life Cycle Costing Traditionally the selection of a material for a given application has been on the basis of the lower purchase price. We may either go for cheaper low grade alloy steels with lesser service life and frequent replacements or costlier higher grade alloy steel with increased service life and lower frequency of replacements. It is now recognized that the cheapest purchase price may not be the most economic choice if we consider additional costs due to installation, regular maintenance and periodic replacement are also considered. In the case of critical plant equipment production loss on account of unscheduled down-time of the equipment are also to be seen. In many industries this lost time cost far outweighs all other costs, and must certainly be included in estimates of life cycle cost. Life Cycle Costing (LCC) in material selection quantifies the total costoperation, maintenance, replacement etc-- over the entire life of the equipment with the aim of selecting the most economic alternative. Thus the choice of the material for a specific service as for phosphoric acid ultimately is decided by the operation and maintenance philosophy adopted for running the plant. Often the material is selected for the worst corrosion scenario and with due consideration to economics. However safety, environmental consequences and unexpected loss of production due to plant outages remain prime considerations. This approach in material selection always help to improve the bottom line of operation.

References

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1. Phosphates and Phosphoric Acid, Raw Materials, Technology, and Economics of the Wet Process, Becker P., Marcel Dekker, Inc., New York, 1989. 2. Phosphoric Acid, Slack A.V., Ed., Marcel Dekker, Inc., New York, 1968. 3. Solving Corrosion Problems in Wet Process Phosphoric Acid Plants Mr. C.M. Schillmoller & Mr. P.K. Bhattacharjee, Fertiliser Industry Annual review , 1994. 4. Corrosion and wear resistant alloys in phosphoric acid service, Phosphorous and Potassium, No.208, British Sulphur Publishing, UK, 1997. 5. Corrosion Manual, Part 1, Wet Phosphoric Acid, IFDC, Muscle Shoals, USA, 1981. 6. Iron Casting Handbook, American Foundrymens Society, Des Plaines, Illinois, USA. www.sandvik.com, www.nidi.org, www.hayensintnl.com, 7. Websites: www.giwindustries.com, www.cartech.com,

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