CORROSION INVESTIGATIONS IN PULPING AND

BLEACHING MEDIA

A THESIS

Submitted in fulfilment of the

requirements for the award of the degree
of
DOCTOR OF PHILOSOPHY

By
AWANISH KUMAR SHARMA

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13Olis
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DEPARTMENT OF PAPER TECHNOLOGY

INDIAN INSTITUTE OF TECHNOLOGY ROORKEE
SAHARANPUR CAMPUS, P.B. 83
SAHARANPUR-247 001 (INDIA).
JULY, 2006
0 INDIAN INSTITUTE OF TECHNOLOGY, ROORKEE, 2006
ALL RIGHTS RESERVED

6th Annual Convocation- 2006

Degree conferred on 11.1t2006

Sidt.-(1:(0-§FCR)
 INDIAN INSTITUTE OF TECHNOLOGY ROORKEE
ROORKEE

CANDIDATE'S DECLARATION

I hereby certify that the work which is being presented in the thesis entitled
Corrosion Investigations in Pulping and Bleaching Media in fulfilment of the
requirements for the award of the Degree of Doctor of Philosophy and submitted
in the Department of Paper Technology of the Indian Institute of Technology
Roorkee, Roorkee is an authentic record of my own work carried out during a
period from July 2000 to July 2006 under the supervision of Dr. A. K. Singh.

The matter presented in this thesis has not been submitted by me for the
award of any other degree of this or any other University/Institute.

(AWANISH KUMAR SHARMA)

This is to certify that the above statement made by the candidate is correct
to the best of my knowledge.

Dr. A. K.SINGH
Professor
Date : 10.7. (istr6 Department of Paper Technology
Indian Institute of Technology-Roorkee
(Saharanpur Campus)
SAHARANPUR-247001

The Ph.D. Viva-Voce. Examination of Mr. AWANISH KUMAR SHARMA,

Research Scholar has been held on al. 10. 2-oat

Sqlt\A
Signature of Supervisor Signature of H.O.D. Signature of External Examiner
 ABSTRACT

The thesis starts with introducing the process and conditions of paper making with a

view to have an idea about the corrosivity of the liquors and possible candidate

materials of construction. Since pulping and bleaching sections are among the more

corrosion prone sections, the investigations were performed related to these sections.

Accordingly, emphasis has been given on the description of pulping and bleaching

section. A review of the literature has been presented in the first chapter dealing with

corrosion aspects and materials performance in pulping and bleach plant and related

liquors. The second chapter deals with the experimental aspects of the various

laboratory and in-plant tests conducted. The next three chapters discuss and analyze

the results of various tests done as a part of the present dissertation. Attempt has also

been made to suggest possible materials of construction. The last chapter deals with

the conclusion on the work and recommendations about the work that needs to be done

in future. A brief idea of the above has been given in following paragraphs.

Chapter -1 : Introduction

This chapter introduces about paper making process and gives an account of corrosion

prevailing in pulping and bleaching sections, being the more corrosive sections of a paper

mill. A survey of the literature has been done to show various attempts made in past for

controlling corrosion in pulping and bleaching sections by appropriate material selection or

otherwise. The prevailing process conditions in pulping section indicate to be corrosive due
to various sulphur compounds. In bleaching section it is mainly due to the application of

oxidizing bleaching chemicals. Consequently following was proposed for investigation:

1. Construction of E-pH diagram for S-H20 and Fe-S-H20 system for the electrolyte

having sulfide and thiosulfate in the amount as observed in pulping liquor. Long

term immersion test in laboratory prepared pulping liquor at room temperature on

mild steel, austenitic stainless steel 304L, 316L and duplex stainless steel 2205.

This had to be followed by quantitative estimation of uniform and localized

corrosion attack and the analyses of the result on the basis of liquor composition

and E-pH diagram, wherever possible.( Chapter 3 )

2. In-plant corrosion test in Kraft digester on newly developed grade of duplex

stainless steels LDX, SAF 2304, 2205 including conventional materials as mild

steel, 304L, 316L, to investigate the extent of corrosion attack, its correlation with

the process parameters and to compare the suitability of the test materials.(

Chapter 4 )

3. Electrochemical polarization tests and long term immersion tests on mild steel

and stainless steel 304L, 316L, 254SM0 and 2205 in peracid solutions

simulating to those likely to be observed in peracid bleaching of pulp with the

aim of understanding the corrosivity of peracid solutions, suitability of the test

materials and mechanism of corrosion in these solutions ( Chapter 5 ).

ii
Chapter - 2 : Experimental Procedure

Various experimental techniques, brief technical discussion of experimental equipments

and formulae used have been described in this chapter. For long term immersion tests

and in-plant test, the coupons from plates of different steels namely mild steel, 304L,

316L, 2205, SAF2304, LDX were selected. The surface preparation was done as per

ASTM specification. For immersion test, the coupons fitted with serrated washer were

immersed in the test solution. For in-plant test, the coupons were mounted on the rack

and fitted in digester near strainer. After exposure the corroded coupons were analyzed

for uniform corrosion and localized type attack.

In the electrochemical polarization tests, E vs time curve, potentiodynamic polarization,

potentiostatic and cyclic polarization curve were performed on cylindrical samples

obtained from rods of SS304L, 316L, 2205 and 254SM0. Electrochemical polarization

techniques were used to investigate the corrosion mechanism and effect of process

variables on corrosion behavior of steels. Chemical compositions of plate and rod

samples used in corrosion study are given in this chapter.

Chapter - 3 : Corrosion in Solutions having Sulfur Compounds

In this chapter E-pH diagrams for S-H20, Fe-S-H20 systems have been drawn for

concentration of various sulphur species as observed in pulping liquor. For S-H20

systems following sulfur species were considered H2S, HS", S2", S2032", S, S4062", S032"

H2S03 and HS03. The diagrams show that within the pH range likely to be observed for

iii
the cooking liquor, sulfur species present in the solution could be HS" and to some

extent S2", S2032" and S032" depending upon the potential, which will in turn be

governed by the nature of material exposed e.g. mild steels or stainless steels. Fe-S-

H20 diagrams were constructed considering above sulfur species and concentrations.

Thus if the liquor consists of S2032", different corrosion products likely to form in the pH

range of interest (pH — 12-14) are mackinawite, troilite, pyrrhotite and pyrite. Of these,

the first two products are non-protective type while other two are protective type.

However, the region of protection also indicates the possibility of localized corrosion if

the protective layer breaks. This usually happens at higher potentials which one can

observe, if the amount of S2032' increases. It indicates that if the amount of S2032" is

higher, the steel is likely to experience localized corrosion.

Long term immersion test in sulfide solutions having varying 52032" in the

presence/absence of Cl" (pH -13.6) and —20% sulfidity was performed on test materials

mild steel, stainless steel 304L, 316L and 2205. The test solutions covered with a layer

of paraffin oil to avoid contact of atmospheric oxygen with the solution. The later was

found to change the solutions' composition by oxidizing Na2S to Na2S2O3. The exposure

duration of test was 6 months. After exposure the corroded test materials analyzed for

uniform and localized type attack. The results of this test showed no significant

corrosion on the tested stainless steels. Mild steel experiences uniform corrosion and

crevice corrosion. Corrosion rates increased with the increased amount of S2032"

content in the solution. This behavior becomes more pronounced in the presence of Cl"

ions.

iv
Measurement of redox potential of 304L and 2205 in pH = 14 solution having sulfidity,

as considered in drawing E-pH diagram, shows that sulphur species near 304L

electrode will be mainly S032" and S2032" while those near the 2205 electrode will be

mainly HS". Accordingly, E-pH diagram Of Fe-S-H20 shows that corrosion products

forming on 304L will be pyrite or iron oxide and on 2205 it could be

pyrrhotite/troilite/mackinawite depending upon the potential. Except mackinawite and

troilite, other sulfides /oxide provide protection. This could be the reason for observing

lesser corrosion rates in these stainless steels.

Chapter - 4 : In-Plant Corrosion test of Steels in Digester of Paper Mill

This chapter discusses the results of in-plant test done in digester of an Indian paper

mill. This mill used 80% poplar and 20% eucalyptus as raw material for making

printing/writing and packaging grade paper. The capacity of digester was 85 m3 and it

was constructed of mild steel. Liquor to wood ratio was kept as 1:2.8. Volume of

cooking liquor inside the digester was kept between 37- 42 m3. The cooking liquor

consists of mainly NaOH (92 gpl as NaOH) and Na2S (22.4 gpl as NaOH) having pH

—13.2. Maximum temperature attained during the pulping process was 162 °C and it

operates at a pressure of 6.2 Kg/Cm2.

The selection of materials for the in-plant test was done on the basis of their utilization

presently and their possible applications in future for constructing the digester and

related allied machinery in pulp and paper industry. Consequently, autogenously welded

coupons of austenitic stainless steels 304L and 316L, duplex stainless steels 2205,
SAF2304 and LDX and mild steel were considered for the in-plant test. After exposure

of six month duration the corroded coupons were analyzed for uniform and localized

type attack. The results of in-plant test show varying degree of uniform corrosion and

pitting was observed on different steels. Crevice corrosion was observed but was non

measurable while no weld related attack has been observed on these coupons. Mild

steel experienced maximum uniform corrosion. Pitting was maximum in case of 304L

whereas duplex stainless steel did not show any pitting attack. The attack can be

correlated with the amount of Cr and N present in steels. At these pH (-14), Mo content

of stainless steel does not provide protection as it gets dissolved as Mo042" . The extent

of attack shows that, for lower sulfidity levels, mild steel may be suitable for cylindrical

section of the batch digester. However, for cooking liquors with increased sulfidity and

/or for parts of the digester which are affected by the erosive action of the liquors (e.g

bottom cone, liquor heater tubes etc.), one may have to opt for duplex stainless steels

with Cr and N as preferable alloying elements. The performance of materials was

compared with other in-plant tests, conducted elsewhere.

Chapter - 5 : Corrosion Study of Steels in Peracid Bleach Solutions

In this chapter, the results of the electrochemical and weight loss test conducted on

steels in peracid solutions have been discussed. The electrochemical polarization tests

E vs time curve, potentiodynamic polarization, potentiostatic and cyclic polarization

curve were performed on stainless steels 304L, 3161, 2205 and 254SM0 in solutions of

peracetic acid (Pa), caro's acid (Pr) and mixture of Pa and Px (Pxa) simulating to those

observed for peracid bleaching. The pHs of these solutions for electrochemical test

vi
were kept 6 and 9 with chloride and without chloride. Chloride content varied from 0 to

1000ppm. Weight loss test was also conducted on mild steel, stainless steels 304L,

316L and 2205 in above peracid solutions with chloride content of 1000 ppm. After the

exposure of six months, corroded coupons were analyzed for uniform and localized type

attack.

Electrochemical results of tested steels in per acid solutions with Cr, show high degree

of localized corrosion whereas it is less severe in case of solutions without CI'. In

general, corrosivity of the solutions is observed to increases in following order : P Pxa

• x <•

<Pa. Higher degree of corrosivity of peracetic acid as compared to that of Caro's acid

can be attributed to the former's higher electrophilic character. Mild steel is found to

observe very high degree of uniform corrosion hence can not be suggested for handling

these media. Stainless steels therefore have to be used. For this reason their resistance

against localized corrosion has to be checked as they are observed to experience very

less uniform corrosion. In CI' containing solutions, very high degree of localized

corrosion is observed on the tested stainless steels except on 254 SMO. Both

electrochemical and weight loss tests on stainless steel showed increased resistance

against corrosion in order of : 304L<316L<2205<254SM0.

Chapter - 6 : Conclusion and Recommendations

In this chapter, conclusions drawn on the basis of work done are discussed. The E-pH

diagrams for S-H20 system show that HS- and S2- are the species depending on the pH

of the sulfide solution and S2032- and S032- are the species depending upon the nature

vii
of material exposed in it. Fe-S-H20 diagrams show that around pH — 12-14, products

mackinawite, troilite, pyrrhotite and pyrite are formed. Of these, the first two are non-

protective type while other two are protective type .The laboratory test in sulphide

solutions showed that none of the tested stainless steels experienced significant

corrosion attack. Mild steel experiences uniform corrosion and crevice corrosion.

Corrosion rates increased with the increased amount of S2032" content in the solution.

This behavior becomes more pronounced in the presence of CI" ions. The nature of

variation has been hypothesized on the basis of mixed potential theory. This needs to

be verified by electrochemical polarization experiments in sulfides solutions.

The in-plant test conducted in batch digester showed varying degree of uniform

corrosion and pitting on different steels. Crevice corrosion is observed but is non

measurable while no weld related attack has been observed on these coupons. Mild

steel experienced maximum uniform corrosion and pitting was maximum in case of

304L. Duplex stainless steel did not show any pitting attack. For the lower sulfidity

levels, mild steel may be suitable for cylindrical section of the batch digester. However,

for cooking liquors with increased sulfidity and /or for parts of the digester which are

affected by stress corrosion cracking (top part of digester) and the erosive action of the

liquors (e.g. bottom cone, liquor heater tubes etc.), mild steel may not be suitable. For

such cases, in-plant test needs to be done in which coupons should be fixed either at

top or in the bottom cone of the digester.

Corrosion investigation in peracids, reported in present thesis concludes that peracetic

acid is most corrosive whereas caro's acid is least corrosive. The comparison of

viii
performance of different test materials showed Avesta254SMO to be most resistant

while 304L least resistant against corrosion attack. It is concluded that Avesta254SMO

is appropriate for handling Cr containing peracid solutions and duplex stainless steel

2205 for handling these solutions without CI- on the basis of degree of attack alongside

comparison of cost vis-a-vis strength of different stainless steels. It is recommended

that, to suggest guidelines for fabricating machinery for handling peracid bleach

solutions, in-plant corrosion tests should be conducted in peracid bleach media. Weight

loss and electrochemical tests for varying % of active oxygen, with and without fibrous

raw materials, in the presence and absence of chloride at room and at high temperature

should also be conducted in these solutions.

ix
 ACKNOWLEDGEMENT

I wish to express my sincere and heartfelt thanks to my supervisor Dr. A. K. Singh,

Professor, Department of Paper Technology Saharanpur Campus. I am highly indebted

to Dr. A. K. Singh whose astute research methodology and profound knowledge of the

subject have greatly benefited me in easy grasping of this interdisciplinary subject. I

reaffirm my sincere thanks to him for his painstaking efforts in helping me complete this

work.

I express my sincere thanks to present Head, Professor A. K. Ray and past Head,

Professor J. S. Upadhyay, Department of Paper Technology for providing me all kinds

of laboratory facilities and administrative help during my research work.

I would like to express my sincere thanks to Dr. N. J. Rao, Professor, and

Dr. M. C. Bansal, Professor Department of Paper Technology Saharanpur for giving

valuable suggestion regarding my research work.

I would like to express my sincere thanks to Dr. Satish Kumar, Professor,

Dr. V. P. Singh, Professor and Dr. S. P. Singh, Associate Professors, Department of

Paper Technology Saharanpur for giving valuable suggestions and help regarding my

research work.

I am highly obligated to Dr. Satya Parkash, Professor, and Dr. S. K. Nath, Associate

Professor, Department of Materials and Metallurgical engineering, IIT-Roorkee for

providing laboratory facilities for microstructure studies of the steels and giving valuable

suggestions about microstructure.

The author thankfully acknowledges the Star Paper Mills Ltd. Saharanpur for permitting

me to conduct In-Plant studies. Free supply of stainless steel coupons from Avaesta

Polarit, Sweden and rod samples from Metal samples CO. 152 metal Samples Road

Munford, AL 36268, USA is gratefully acknowledged.

I am highly obligated to Mrs. Rama Singh, wife of Dr. A. K. Singh for encouraging and

giving me moral support throughout the course of this work.

I am highly obligated to Dr. N. P. Gupta and Dr. Vakul Bansal, J.V. Jain Degree College

Saharanpur for encouraging and giving moral support throughout the course of this

work.

I am highly obligated to my family specially wife of my brother Renu Sharma for

encouraging and giving moral support throughout the course of this work.

My sincere thanks are also due to my senior fellow Dr. G. Singh and Dr. Mrs. Saini

Jacob and my contemporaries Mr. Mohan Lal, Mr. Puneet Kumar Agnihotri, Mr Sudheer

Kumar Shukla, Mr. Alok Tyagi, Mr. Deepak Kumar, Mrs. Alka Jain, Ms. 'Rachna

Malohtra, Ms Shalini Singh, Ms. Swarnima Agnihotri and Mr. Vipin Choudhary for their

co-operation and encouraging company during the research work. I am highly obligated

xi
to Mr. Vinod Gaur, Mr. Lakhpat Singh and Mr. Khilanand for providing different facilities

during my research work.

Timely financial assistance received from IIT-Roorkee is gratefully acknowledged.

This dissertation is dedicated to Lord Shiva Parvati and My Parents whose love

remained with me at every stage during the research work.

AWANISH KUMAR SHARMA

xii
 RESEARCH PAPERS

1. Investigation on digester corrosion

International Conference On Corrosion, GORGON 2003, Mumbai.

2. In-Plant test in Kraft digester for evaluating performance of steels against

corrosion.

12th National Congress On Corrosion Control, Vishakhapatnam

Sept. 20-22, 2004.

3. Corrosion due to extractives from paper making raw material -An aspect

of digester corrosion in paper industry.

International Conference On Corrosion, Chennai, 28-30 Nov., 2005.

4. In-Plant test of steels in Kraft batch digester for evaluating corrosion

Performance.

Tappi Journal, USA, (Communicated).

5. Corrosion study of steels in peracid bleach solutions.

Appita Journal, Australia, (Communicated).

 LIST OF CONTENTS :

Chapter : Page No.

1.Introduction 2

2. Experimental Procedure 28

3. Corrosion in Solutions having Sulfur Compounds 64

4. In-Plant Corrosion test of Steels in Digester of Paper Mill 101

5. Corrosion Study of Steels in Peracid Bleach Solutions 118

6. Conclusion and Recommendations 134

Bibliography : 143
 Chapter :1

Introduction

Contents : Page No.

1.1. The Paper making process 6

1.2. Corrosion in Paper Industry 7

1.2.1. Pulping Section 8

1.2.2. Bleach Plant Section 12

1.2.2.1. Chlorination (C) Stage 13

1.2.2.2. Chlorine-Dioxide (D) Stage 14

1.2.2.3. Hypochlorite (H) Stage 16

1.2.2.4. Peroxide (P) Stage 17

1.2.2.5. Oxygen (0) Stage 18

1.2.3. Recovery Section 18

1.2.4. Paper Machine Section 19

1.3. Recent Developments in Pulping and Bleaching 20

1.3.1. Higher degree of delignification in pulping 20

1.3.2. Oxygen delignification 21

1.3.3. Decreasing use of chlorine or use of

non-chlorine bleach chemicals 21

1.3.4. Water reuse or closure of mills 23

1.3.5. Closure in case of non-chlorine bleach plants 23

1.4. Statement of the Problem 24

2
'Corrosion' is probably the commonest electrochemical phenomenon whose effects on

metal bodies are observable in our day to day life. Common examples of corrosion

include rusting/staining of iron and steel utensils/railings/other structural items, the

blistering of chromium plating and paint work on cars, discharge of colored water from

domestic taps, tarnishing of silver and copper wares, seizure of nuts and bolts etc. From

indtistrial application point, the term 'Corrosion' is used to describe an unintentional

electrochemical reaction between a metal and its environment e.g. air, marine, steam,

high temperatures and chemicals etc., which results in degradation of the former. This

happens due to the conversion of metal into metal oxide or some other compound

which are weak and brittle. This causes overall reduction in the load bearing capability

of the metal. Thus, corrosion adversely affects those very properties of metal e.g.

strength, ductility, stability etc., that are to be preserved in order for the metals to be

used as material for constructing process equipment/machinery, Bolton (24).

In industry, corrosion is responsible not only for weakening of metal structures and

consequent premature failure of plant but also for pollution of process liquors and

contamination/discoloration of products. The losses due to purely mechanical forces are

known as wear, fretting etc. However, in some cases, chemical or electrochemical

attack may be accompanied by the mechanical forces leading to stress corrosion

cracking, corrosion-erosion, corrosion fatigue or fretting corrosion. Such shortcoming of

metal affects the production through unwanted shutdowns due to sudden failures,

excessive leakage of chemicals/steam etc., Ravindranath et al (104), which escalate

maintenance and operating costs. In some industries e.g. food, pulp and paper etc,

contamination of product due to corrosion is another disadvantage. All this enhances

3
the production cost hence affects the economy. Also it makes the working environment

less safe. These negative aspects of a natural phenomenon 'corrosion' forced the

scientists and technologists to develop necessary preventive measures against

corrosion and thereby reduce the revenue loss.

Corrosion in chemical industries requires more attention which otherwise will reduce the

production efficiency, quality of products and at the same time making it costlier. Paper

industry, being chemical industry, is no exception to corrosion problems. Corrosion

problems in this industry are quite serious, as it is using wide variety of corrosive

chemicals like chlorine, chlorine dioxide, sodium sulfide, caustic soda, etc. and

generating other similar corrosive substances as reaction products at various stages.

The liquid media in this industry range from highly alkaline type (pH-14) to highly acidic

(pH-1-2). Additionally, the process involves high pressure as well as high temperatures

in some stages, Garner (45), Yaske (149), In fact the paper industry was first to utilize

molybdenum bearing stainless steels more than seventy years ago and also it has

shown enthusiastic acceptance of FRP construction. An idea about severity of corrosion

in pulp and paper industry can be had from the estimate of huge losses in terms of

repair and replacement. Unexpected failures, due to corrosion, of pressure vessels

have resulted in to loss of life thus making the working environment less safe.

Consequently, industry looses considerable amount of money on account of corrosion.

Several studies/ surveys (Table -1.1) have been reported which try to estimate the

losses due to corrosion and the amount of wealth that can be saved by adopting

suitable corrosion protecti6n measure, Aroma et al (7), Bhaskaran et al (22), Chandler

et al (26), Chakrapani et al (28), Raman (102), Singh, A. K. (111), Singh, D. D. N. (112),

4
As per the report of Battelle and the Specialty Steel Industry of North America, Aroma et

at (7), about one-third of the cost of corrosion is. avoidable and could be saved by

broader application of corrosion resistant materials and application- of proper anti-

corrosive methods. Moreover, human costs associated with the catastrophic failure of

corrosion damaged equipments are beyond measure.

In recent years, the Paper industry is undergoing rapid changes in the process to meet

the demands of market keeping in view the depleting resources of fiber raw material

and government regulations with regard to specially the pollution control and

abatement. Developments in the industry are aimed at improvement in paper quality,

reduction in manufacturing costs, adoption of environment friendly and energy efficient

paper technology and introduction of new and modified paper' produc*Accordingly, the

changes coming up in the paper making process include reduction and elimination of

chlorine and its compounds etc., decrease in overall water use, recycle of as much of

the bleaching effluents as possible, higher degree of delignification during pulping stage

etc. These changes have brought drastic effect on process conditions of the working

environment. Since the corrosion phenomenon is closely related with the proceis

parameters, the above mentioned changes in the process are likely to alter corrosion in

industry. It is, therefore, important to investigate the effects of these changes on

corrosion performance of materials of construction. As such, the thesis deals with

studies carried on corrosion and its control by suitable measures in changed scenario of

pulping and bleaching process. To introduce the reader with subject of thesis, a brief is

given about paper making process and then a review of corrosion in pulp and paper

5
industry has been given. Finally, justification of the problem dealt in the present work

and being presented in the thesis with objectives has been outlined.

1.1. The Paper Making process :

Paper is used by the world community to satisfy various needs. It is an essential

component in the process of business and communication through newspapers,

•

periodicals, magazines, books etc. It contributes to industrial development with

improved packaging for protection and conservation in transport and storage of goods.

In fact, it is important material in the economic development of a country and the extent

of paper usage is a parameter of the standard of living in a country. Paper is a fiber

network formed on the fine screen from water suspension. These fibers are extracted

from various wood/non-wood species. Paper making process essentially involves the

pulping of wood species to draw fibers from wood. In pulping process, individual or

small agglomerate fibers are withdrawn from wood by mechanical, thermal, chemical or

by a combination of these treatments. The Kraft process (chemical pulping) is most

popular among the pulping process. In this process, pulping is carried out in a pressure

vessel called 'digester', by chemical reaction between constituents of wood chips

namely lignin and cooking liquor at a pressure around 6.5-7 Kg/cm2 and temperature

165 -170°C.The cooking liquor is composed of sodium hydroxide and sodium sulfide in

the approximate proportion of 5 parts of NaOH and 2 parts of Na2S. Alongside,

Na2S2O3, Na2SO3, polysulfides etc. are also present as by products. The liquor has a

pH of 13.5 to14.0.The resulting pulp is send in brown stock washer for removal of all the

traces of liquor and unwanted foreign particle e.g. sand, metal etc. The filtrate from
brown stock washer, known as black liquor, is processed in the recovery system to

recover unused NaOH and Na2S, which is used as cooking liquor for pulping after

making up for the lost chemicals. Organic constituents from black liquor are burnt in

recovery boiler to recover energy. Washed pulp from brown stock washers is sent to

bleaching section for brightening the fibers. Bleaching is generally carried out in a

multistage process with bleaching stages e.g. chlorination (C), alkali extraction (E),

hypochlorite (H), chlorine dioxide (D), peroxide oxygen (0), ozone (Z), per acetic acid

(Pa) or caro acid (Pr) or mixture of per acetic acid and caro's acid named (Pn) etc. The

pulp after bleaching is then subjected to beating and refining by mechanical action to

develop good bonding between fibers. Afterwards various chemicals like alum, talcum,

rosin etc. are added for getting special properties in the pulp. This mixture called stock

is passed over paper machine comprising of head box, fourdrinier, couch roll, suction

rolls, press rolls and lastly dryers and Calendars for making the final product paper,

McDonald (82), Smook (118).

1.2. Corrosion in Paper Industry :

The corrosion problem in pulp and paper industry is more serious as compared to any

other industry because paper industry uses wide variety of very corrosive chemicals and

environment, Garner (45), Yaske (149). Further, paper making technology is

experiencing continuous changes due to shortage of fibrous raw material, ecological

restriction, demand of quality paper, efforts for increasing output to meet growing

demand of paper. These continuous changes along with the rising cost of equipment's

replacement make problem due to corrosion as a matter of growing concern. As such,

7
various forms of corrosion are experienced in different sections of a paper mill. Various

factors affecting corrosion are type of raw material, cooking liquor concentration,

digester operation, bleaching chemicals and sequence of bleaching, dissolved gases

differential aeration, bacteria, existence of stresses etc. From the standpoint of

corrosion, a typical paper mill can be divided in the following four sections: Pulping

section, Bleaching plant, recovery section and paper machine. Out of these, pulping and

bleaching are the sections where corrosion is a major problem in the industry. Since the

thesis deals with corrosion aspects related to pulping and bleaching section, a brief idea

about corrosion and related investigations in these sections is given in the following

paragraphs.

1.2.1. Pulping Section :

In this section, corrosion problems are more serious in digester house which consists of

digester, preheaters, circulation pump, white liquor storage tanks, cooking liquor feed

lines, digester blow line and blow tanks as various units. Generally two types of

digesters are in use in paper industry (a) continuous digester and (b) batch digester. In

Indian mills; mostly batch digesters are used. A typical batch digester consists of a

vertical cylindrical vessel with a hemispherical or ellipsoidal top head and conical

bottom. Batch digesters are typically 8 to 13 ft (2.4 to 4.0m) in diameter and about 60-ft

(18.3m) high. In most cases, these are used to cook the wood chips with Kraft cooking

liquor. The Kraft cooking liquor contains inorganic chemicals like sodium hydroxide,

sodium sulfide, sodium sulfite, sodium carbonate, sodium chloride, sodium thiosulfate,

polysulfides, sodium sulfate etc. Cooking is usually performed at pH — 13.5 -14 and

8
temperature of 170°C. Until the 1950s, only batch digesters were used to produce kraft

pulp, Gullicbsen et al (56), in conventional batch cooking. In the early 1960s, continuous

cooking systems, due to better energy economy, began to compete seriously with batch

plants. In the early 1980s, energy efficient Kraft batch processes using various

displacement technologies became available (RDH method). In addition, increased

pressure to minimize environmental impact and effluent volumes during the 1970s

contributed to the development of batch cooking using modified cooking chemistry and

extended cooking. In the early 1980s, trials of combined modified cooking chemistry

with energy efficient liquor displacement were undertaken (cold blow cooking). In the

late 80s, the development of liquor displacement batch cooking systems continued with

the aim of providing greater optimization of pulp quality, resulting in super batch

concept. The RDH, Superbatch, Enerbatch cooking techniques find use today. Later as

development in the technology of continuous digesters, the implementation of extended

modified cooking (EMCC),isothermal cooking (ITC),black liquor impregnation (BLI),

diamondback pre —steaming, the Lo-level feed system, and solids cooking system have

resulted in improved performance, decreased capital costs, and lower maintenance

costs.

The efforts have been, Maspers (81), to search for optimal cooking conditions that allow

cooking to very low kappa numbers so that after oxygen delignification, final bleaching

to full brightness can now take place in ECF/TCF sequence. Further, additional steps

towards closing up the bleaching systems will in the near future result in totally closed

pulp mill TEF, totally effluent free. All recent research and development, though

important from the economical and environmental point of view, have introduced

9
accelerating influence on the corrosion conditions in the digester. Some digesters

already show clear signs of shell corrosion, and as the intensive inspection goes on the

list of corroded digesters will most probably increase.

Many reports related to digester corrosion have been published/ presented in

conferences in past years. Most serious corrosion problem with carbon steel continuous

digesters has been caustic stress corrosion cracking (SCC) of un-stress-relieved seam

welds in the impregnation zone or in the impregnation vessel for two vessel systems,

Crowe (35). In one study, Olsson et al (88), reported the corrosion rate of digester

approximately 5 mils after three years of service, where selective phase corrosion

occurred. Various factors responsible for wide spread of corrosion, are type of raw

materials, cooking liquor composition, concentration, sulfidity, hot plate boiling on

digester surface during liquor charging, circulation and impingement and direct

steaming, temperature galvanic effect, violent agitation of pulp and blowing causing

erosion of passivation film, Presence of thiosulfate in white liquor, presence of lignin

compounds, chlorides etc., Banks et al (13), Mall et al (80).The acids for cleaning such

as sulfamic acid and formic acid are less corrosive to digesters, Crowe (33). Cooking

liquor and numerous organic species arising from dissolution of cellulosic raw material,

many of them are responsible for corrosion in digester. Sulfur is used in pulp mill for

improving the sulfidity which is converted to polysulfide and causes severe corrosion.

Sodium sulfide and sodium thiosulfate activate corrosion and act to impair passivation.

The corrosion is dependent on the equilibrium of reaction, Kiessling (68),

S2'+S2032"---> 5032 +522'

10
The S2032' I S032- molar ratio can be used as a corrosion factor of the liquor, Kiessling

(68). Mueller (84) indicated that the corrosion rate of mild steel could vary from 1-100

mpy. The increased amount of silicon in the batch digester steel result in the increasing

rate of corrosion. Many mills have therefore insisted that the rimmed steel rather than

killed steel should be used for digester. The corrosion in digester is basically uniform in

nature but chip loading, liquor circulation, and scale can cause localized attack e.g.

pitting, crevice or cracking. Stress corrosion cracking of continuous digester became a

serious problem in 1980's following a catastrophic failure of a pressure vessel

weakened by extensive stress corrosion of a girth weld. Corrosion rates are generally,

higher in batch digester than continuous one. The application of stainless steel cladding

or weld overlay to in-service digesters has been effective in reducing the internal

corrosion of the batch digester and prolonging their service lives, Tuthill (128). Digesters

blow bends and blow tank at the top also get corroded very rapidly and their rates have

increased substantially with the use of more and more hard wood and higher

percentage of oversized chips and knots. The zone of most severe corrosion varies

from mill to mill, and perhaps from digester to digester. In most digesters the corrosion

is most pronounced in the cylindrical section. In other digesters it is worst in the bottom

cone, in yet others, it is the top dome. Corrosion of stainless steels (both in wrought

form and overlays) is primarily a function of the chromium content of the overlay.

Austenitic stainless steel grades such as type 316L (16-18% Cr, Mo — 2%) and Type

304L (18-20% Cr) can experience rapid corrosion up to 40 mpy. Digesters usually, are

constructed of mild steel plate with stainless steel linings; however carbon steels are

susceptible to stress corrosion cracking in the caustic environment and temperature

prevailing in the alkaline digester, Bennet (20). Study by Wensley (138), corrosion has

11
been observed to increase with the concentration of thiosulfate in the digester. Lignin

has no passivating effect in shell and increases corrosion. Work by Audouard (8-12), to

investigate corrosion during "hot plat boiling" has revealed that duplex stainless steel

with even higher chromium content (22-27% Cr) resists corrosion better than

conventional austenitic grades. In another study, Delblanc et at (37), the use of SS to

reduce the corrosion risk due to the Kraft process, a new cooking process for

continuous digesters, in the paper industry is discussed. The corrosion rates for 304L

and 316L have been measured at -0.02 mm/year. The corrosion damages are

prevented by regulating the processes and by selecting the appropriate material.

1.2.2. Bleach Plant Section :

Bleach plant in a paper mill is meant for brightening the pulp which otherwise is brown

in colour. The brightening of pulp is achieved by bleaching through a multistage

process. Thus bleaching sequences e.g. CEH, CH1H2, CEDED etc. (C-chlorination, E-

alkali extraction, H-hypochlorite, D-chlorine dioxide) are among the more commonly

used sequences. In addition some sequences use or may start using peroxide (P),

oxygen (0), ozone (z), peracids (PA) etc. Due to severe objections on usage of chlorine

and chlorine 'compounds because of their tendency of forming compounds with lignin

having carcinogenic character, the trend now-a-days is to use more and more non-

chlorine bleach chemicals. Each bleach stage consists of mainly three parts - reaction

tower, washer, pumps and pipe line. Due to process conditions existing in bleach plant,

corrosion is the most serious problem in bleach plant and accounts for nearly 50% of

total mill corrosion. The corrosivity of this section has been found to increase on

12
adoption of filtrate recycling to reduce water consumption as well as water pollution.

Such aggressive corrosivity is due to strong oxidants along with several corrosion

promoting factors like pH, chloride etc. in bleach plant. Average process conditions

prevailing in bleach plant are shown in Singh (113). Corrosion damage in bleach plant

usually appears in the form of pitting, crevice corrosion, stress corrosion cracking

(SCC), and inter granular corrosion (IGC) or weld decay. Reaction tower, where the

pulp is combined with various bleaching chemicals are generally constructed of brick

and tiles or other non-metallic materials and hence face comparatively much lesser

corrosion problem. It is mainly the pulp washing and conveying machinery that is

affected badly. This has led to increasing application of higher grade of stainless steel,

titanium and non-metals as construction material of bleach plant machinery and

structure. 'Electrochemical protection' has also been applied effectively by Femina (42),

Quraishi (101), Roy et al. (105) and Wallinder et al (137), to minimize the localized

corrosion in this area. Now a brief idea about corrosion in different stages of bleach

plant is given.

1.2.2.1 Chlorination (C) Stage :

Highly' acidic and oxidizing (residual chlorine) environment prevails in chlorination

section. Washer in this stage experiences maximum corrosion. Presence of CI' in the

process liquor, due to reduction of chlorine and also because of their presence in water,

facilitate the propagation of localized attack .Corrosion in the gaseous phase has

generally more serious than that of liquid or wet/dry phase existing in the washer,

Garner (48,49,50,51), Gaur et al (53), Henrikson et al (60,62) and report (120).The

13
SS under wet deposits in atmosphere containing C102 can be investigated

quantitatively. Feng et at (41), indicated the diffusion coefficient of C102 in resin 199 and

life of resin coating when the consistency was 10g/I. One study, Laliberte (75), showed

that the austenitic SS with more than 6% Mo like 254SMO, 654SM0 cronifer 1925HM0,

AL-6X and ferrite with 4% Mo appears to provide resistance in all of C, D and H stage

liquid phase even in welded condition. One In- plant study, Singh et al (115), showed

the duplex SS 2205 as the appropriate material for C, D, and H liquid media. Laliberte et

at (76), reveals that the installation and running cost of electrochemical protection

system are small as compared to the resulting cost savings.

1.2.2.3. Hypochlorite (H) Stage :

The corrosion problem in this washer is less serious, than observed in C and D

washers, primarily due to presence of alkaline environment, Ahlers (1). Pitting and

crevice are the dominant forms of corrosion, usually, found in this washer. Degree of

corrosivity mainly depends upon pH and available residual chlorine. Maximum corrosion

rate is observed near neutral pH, it is probably because of conversion of hypochlorite

ion to hypochlorous acid (1) which is more corrosive than C12. With fall in pH (i.e. below

7) HOCI increasingly converts into less corrosive chlorine while at higher pH (above 7),

hydroxyl ions act as an inhibitor and hence reduces the corrosion rate. The liquid phase,

Garner (49), corrosion is more severe than in gaseous phase generally higher rate is

observed when residual chlorine concentration is higher at pH. A significant reduction of

corrosion rate may be obtained by maintaining pH in the range of 10.0 - 11.0.,

Henrickson (60). SS 316L and 317L are the principal construction material of washer

16
drum, piping and mixing equipments. In-plant study by Gaur et at (53), for different

phases in washers, the degree of corrosivity is in the order of gas> liquid> wet/dry.

Exceptions are the hypochlorite washers of mill A, where the degree of crevice /general

corrosion is more in the wet/dry phase, in the H1 stage and in the liquid phase in the H2

stage. In yet another laboratory study by Gaur et al (54), study corrosion on mild steel in

hypochlorite solutions indicate that corrosion rates increase with free available chlorine

concentration and are independent of chloride ions. Polarization curves indicate that

reactions can be understood in terms of three redox systems.

1.2.2.4. Peroxide (P) Stage :

Peroxide is a strong oxiaizer and can create an aggressive condition to candidate

material in presence of equivalent chloride concentration. H202 is degradable by some

metal ions ferric, cupric, manganese etc., which might enter in the solution through

corrosion reaction with washer materials, Yau (150), and thereby reducing bleaching

efficiency. Though the corrosion reactions due to peroxide appear less severe as

compared to those due to 012 and C102 yet zirconium and titanium have been suggested

for the construction materials of peroxide washer. Application of these metals may also

reduce degradation of peroxide. Yang (151), studied the corrosivity of m-benzol

unsaturated polyester resin containing filler in H202. Results show that (i) anticorrosion

of m-benzol unsaturated polyester resin in H202 is relatively good; (ii) the environmental

temperature should be controlled below 180 degrees. Been et at (18), studied the

corrosion of grade 2 titanium in alkaline hydrogen peroxide environments and found

calcium and pulp was as corrosion inhibitors. Been et at (19), showed that in hydrogen

17
peroxide stage, calcium and pulp acts as corrosion inhibitors. Presently stainless steel

316L is generally used for construct of washer equipments. In another study by Singh et

al (116), it was found that in peroxide media of TCF bleaching, one may use SS 304 or

316 without localized corrosion while SS316 is suitable for peroxide media of ECF

bleaching. Chelant addition increases the upper limit of CI" content in liquors.

1.2.2.5. Oxygen (0) Stage :

High pH (-11), significant amount of chloride along with high temperature (130°C), in

this washer, increase the possibilities of stress corrosion cracking. One study by

Laliberte (73), has shown that at pH = 13 and 10 gpl NaCI, cracking occurs in both liquid

as well as in gaseous phase. It also has concluded that the invariable presence of

monoxide in oxygen bleaching process reduces the risk of SCC of austenitic stainless

steel containing molybdenum at sodium chloride concentration of 10 gpl. Most of the

equipments are made of Mo containing stainless steel for this washer, but oxygen

reactors are often made of high nickel containing steel such as 20cb3 to guard against

chloride cracking. Wensley (144), studied about external stress cracking of stainless

steel vessels (oxygen reactor, concentrators, evaporators steaming vessels and tanks).

1.2.3. Recovery Section :

Various corrosive environments which are responsible for corrosion in various sections

of recovery plants are chloride, thiosulfate, sulfide, polysulfide, CO2, high temperature,

dissolved oxygen etc. Corrosion in evaporator occurs when hot black liquor

18
inadvertently comes in contact with carbon steel surfaces because of foaming excessive

liquor through-put and other operative misadventures. SS304 or 316 are frequently as

evaporator tube. To avoid SCC SAF2205 are suitable alternatives.

Carbon steel tubes in recovery boiler experiences extensive corrosion in certain areas

as a result of reaction by the furnace gases. Type SS-304 clad carbon steel tubes

appears to provide a solution to these problems, Klarin (71). In recausticizing plant,

plain carbon steel storage tanks, clarifiers, piping, lime and slurry pumps suffer severe

corrosion. The corrosion rate as high as 20-30 mpy are experienced on the walls and

trays of storage tanks and clarifiers where liquors relatively stagnant, Yaske (149).

1.2.4. Paper Machine Section :

The paper machine section of paper industry also is very corrosive. Different parts of

paper machine section suffering serious corrosion include machines head boxes,

suction and cough rolls etc. paper machine environment is acidic pH (-4-6),

temperature 40 - 55°C, very high humidity and contain 300 to 2000ppm dissolved

solids. Sulfate and chloride anions have also been identified for promoting pitting and

crevice corrosion of stainless steel component, Yoshitake et al (153). In yet another

study by Perdomo et al (94), investigated corrosion fatigue of heat treated duplex

stainless steel in paper machine white water. Cracking of suction rolls is favored by

corrosion fatigue included by fluctuating stresses that are imposed during routine

operations. Corrosion of paper machine becomes, further, a matter of great concern

with introduction of system closure, either directly or after treatment.

19
1.3. Recent Developments in Pulping and Bleaching :

In recent past, paper making practice has observed several changes, because of

reasons outlined above. Important among these changes are : higher degree of

delignification in pulping, oxygen delignification, partial replacement of chlorine by

chlorine dioxide thereby decreasing use of chlorine or use of non-chlorine bleach

chemicals and water reuse or closure of mills

1.3.1. Higher degree of delignification in pulping :

Global demand for paper is rising every year and current market conditions require

papermakers to increase quantity of paper with improved product quality at lower cost

without increasing pollution load. An effective way to meet these conflicting

requirements is to use high yield pulp, with its superior bulk and other desirable

characteristics. High yield of pulp could be obtained by higher degree of delignification

of fibrous raw material in pulping section and this also reduces the bleach plant

discharge. In higher degree of delignification wood chips are cooked more selectively to

increase the pulp yield without degradation of pulp. The higher degree of delignification

is achieved by cooking wood chips in higher sulfidity liquor which is being practiced in

the normal kraft process compared to an aspect of RDH or super batch cooking. One

survey, Clarke (32), shows that mills with higher sulfidity experiences more corrosion

with than mills with lower sullfidity.

20
1.3.2. Oxygen delignification :

Use of Oxygen in alkaline delignification process and to assist the delignification in

extraction bleaching stages has the primary effect of making these hot, alkaline

environments more strongly oxidizing in nature. In some cases, this may result in

increased localized corrosion. Although limited data exist so far on corrosion

performance of stainless steels in oxygen delignification service. Such environment

causes pitting of stainless 304 and 316 where chloride level is high. Although the

oxygen delignification before chlorination reduces the chlorine consumption in

chlorination stage and hence tends to be less corrosive, Garner (50).

1.3.3. Decreasing use of chlorine or use of non-chlorine bleach chemicals :

It has now become a common practice in pulp bleaching to substitute some Cl2 with

C102 to keep control on pulp quality and pollution due to effluent discharge from

chlorination washer. The use of C102 in chlorination stage reduces the amount of

chloride produced. Consequently the aggressiveness of environment should also

reduce. Whereas experimental report, Ahlers (2), has shown the opposite, concluding

that the addition of C102 or chlorite, even in small amount to chlorine containing solution

activate the chlorine almost equally corrosive as chlorine dioxide for stainless steels.

While, under some conditions it was more corrosive than D—stage environment. In

recent years, Hatch (58), developments are being directed towards the use of ozone,

per acids, enzymes and biological treatments for delignification and bleaching of pulps.

Per acids such as per acetic acid (Pa), caro's acid (Px) and mixed per acids (Pxa)

21
containing both Pa and Px have been evaluated as delignification agents or bleaching

agents for chemical pulp and textile since the early 1950's. In other studies, Bennett

(21), Kirk-Othmer (69), Panda et at (91), Thierry et al (123), Zhu et at (154), it is found

that per acids act both as delignification and brightening of chemical pulp. According to

Pehkonen et at (92), on corrosion in ozone and per acetic acid bleaching solution, the

results indicate that higher alloy content steels, 254SM0, 654SM0 and duplex 27, are

resistant to pitting corrosion in 1g/L PM solution having lgpl CI" at 80°C. In another

laboratory study by Sing et at (114), corrosive effect of per acids with acidic pH studied

at room and also at high temperature. The results of this study show that Pa is most

corrosive while Px is least corrosive. Tested materials show order of increasing

corrosion resistance 3041<3161<3171<2205. Alloy 2205 could be handled in all the

solutions. Bio-bleaching is another good option from environmental point of view,

requires longer reaction time and yet to be recognized. Baily et al (17), published a

research paper describing the use of per acetic acid for both delignification and

brightening of chemical pulp. This initial work found that minimum pulp degradation

occurred in the pH range of 5.0 to 9.0, temperature and consistency did not have an

effect in this pH range.

Ozone and enzymes are also attractive candidates for replacement of chlorine-based

bleaching agents due to their good brightening ability at around pH = 3.5-6.0.

22
1.3.4. Water reuse or closure of mills :

Of late, paper industry is increasingly adopting bleach plant closure with a view of

pollution abatement as well as energy saving measure. However, this strategy changes

the parameters of washer vat which are of great concern from the standpoint of

corrosion mechanism. Laliberte (74), shows the significant increase in the residual

C12/C102 concentration, dissolved solids (e.g. co and temperature followed by lowering

of pH to more acidic range. All these parameters enhance the corrosivity of liquors to

the bleach plant washer materials. This indicates that the more resistant alloys are

needed to withstand the bleach plant environment according to degree of closure made.

1.3.5. Closure in case of non-chlorine bleach plants :

The liquors of the new bleaching stages, having non-chlorine bleach chemicals, may not

have Cr and therefore expected to be less corrosive than chlorine and chlorine

containing bleaching stages, Nutt et al (87), Turner et al (127). Also the closure of

bleach plant to the zero discharge level may be exercised with much lesser corrosion

hazards. However, extensive corrosion study in the solutions of these bleaching

chemicals is required. Higher consistency bleaching practice may result into the more

corrosive bleaching environment because of increased concentration of residual

oxidants, dissolved salts (especially chloride) and high temperature associated with

lower pulp dilution levels.

23
The displacement bleaching practiced to meet the demand of energy conservation and

environmental control reduces effluents from pulp mill. The corrosion conditions here

are more severe than its conventional counterpart. High temperature bleaching is

practiced for pulp at high consistency. The latter is desired for reducing fresh water

demand while need of shortening the reaction time requires the temperature to be

raised. Thus the material's susceptibility to localized corrosion, in case of high

consistency bleaching, is expected to increase.

1.4. Statement of the Problem :

The process modifications have been necessary due to the clear market demand and

the mills that have converted to modern process systems have achieved positive effects

both economically and environmentally. Pulping now is being done at higher sulfidity, so

as to achieve better delignification, which increases the concentration of other sulfur

compounds present in cooking liquor. A negative side effect of this, however, is the

influence on the corrosion condition in the digester area and shell thinning has been

registered in some digesters all over the world. This aspect therefore needs to be

investigated further. Starting in mid 1960's, pollution control measures and reduced

supply of fresh waters led to recycling of filtrate in the bleach plant and thereby

concomitant increase in the corrosivity in bleach washers. The bleaching section of the

paper industry provides one of the most corrosive environments for machinery materials

as obvious from previous section. A number of modifications introduced in the bleaching

practices in the last few years have contributed to the changed corrosivity of chemical

environment thereby affecting the performance of materials of construction. Today is the

24
era of closed bleach plant, D and CID bleaching, total chlorine free bleaching, high

temperature bleaching and displacement bleaching. Some countries, averse to the idea

of using Cl2 or chlorine based bleach chemicals, started adopting new technology for its

bleaching stage. Consequently, the elemental chlorine free (ECF) or total chlorine free

bleaching (TCF) came into existence, Kinstrey et al (70), Yang et al (152). As such,

C102 in ECF and much lesser toxic bleach chemicals e.g. per acids, hydrogen peroxide,

ozone, enzyme etc. in TCF process are likely to play an important role in bleaching.

Alongside the above scenario on the changes in bleaching, it is also worthwhile to take

a stock of the situation as regards the material performance in present day bleach

plants and that expected in plants of the future. Per acids have not been adopted by

Indian paper industry up to now but these are the futuristic bleach chemicals. Further,

there are very few studies related to corrosivity in per acids solutions, Pehkonen et al

(92) and Sing et al (114). It is with this background that, the author planned to do the

following investigations and address the related problems:

1. Construction of E-pH diagram for S-H20 and Fe-S-H20 system for the

electrolyte having sulfide and thiosulfate in the amount as observed in

pulping liquor and long term immersion test in laboratory prepared pulping

liquor at room temperature on mild steel, austenitic stainless steel 304L, 316L

and duplex stainless steel 2205. This had to be followed by quantitative

estimation of uniform and localized corrosion attack and the analyses of the

result on the basis of liquor composition and E-pH diagram, wherever

possible. ( Chapter 3 )

25
2. In-plant corrosion test in Kraft digester on newly developed grade of duplex

stainless steels LDX, SAF 2304, 2205 including conventional materials as

mild steel, 304L, 316L, to investigate the extent of corrosion attack, its

correlation with the process parameters and to compare the suitability of the

test materials (Chapter 4).

3. Electrochemical polarization tests and long term immersion tests on mild steel

and stainless steel 304L, 316L, 254SM0 and 2205 in peracid solutions

simulating to those likely to be observed in peracid bleaching of pulp with the

aim of understanding the corrosivity of peracid solutions, suitability of the test

materials and mechanism of corrosion in these solutions (Chapter 5).

26
 Table -1.1

Estimated Annual Corrosion Cost

S.No. Country Industry Year of Survey Annual Loss

1. U.K. General 1971 3.5% of GNPr
2. USA General 1996 $ 300 billion'
Paper & Pulp 1984 $ 525 -1170 millionill
3. Canada Paper & Pulp 1989 $ 300 millionni
4. India Paper & Pulp 1985 Rs. 160 millionsi°2
2005 $ 130,00022

27
 Chapter : 2

Experimental Procedure

Contents : Page No.

2.1. Material Selection 30

2.2. Specimen Preparations 31

2.2.1. Shape and Size of Specimen 31

2.2.2. Surface Preparation 32

2.3. Exposure Details 33

2.3.1. In-plant test 33

2.3.2. Laboratory Tests 34

2.4. Solution preparation for Laboratory Tests 35

2.4.1. Sulfide Solutions 35

2.4.2. Peracids solutions 35

2.5. Analysis of Kraft white Liquors of Lab and mill 36

Tests and peracid solutions

2.5.1. Chloride Ion Determination 36

2.5.2. pH Determination 37

2.5.3. Analysis of white liquor 37

2.5.4. Analysis of Per acid Solutions 42

2.6. Weight-Loss Determination 43

2.7. Nature and Degree of Localized Corrosion 44

2.8. Electrochemical Measurements 45

2.9. Experimental Equipments 50

2.10. Microstructure Examination 56

28
Corrosion testing provides the basis for the practical control of corrosion by selecting

appropriate material of construction or lining material, monitoring the corrosiveness of

process streams and thereby controlling the excess amount of chemicals or by opting

an electrochemical protection system, Rai et al (103), Shrier et al (110). Thus in order to

select a corrosion resistant material or opt for suitable protective measures for pulping

and bleaching sections, the present study was carried out through (i) In-plant test in

digester and (ii) long term immersion test in laboratory in liquors simulating to digester

white liquor at room temperature.(iii) long term immersion and electrochemical tests, in

laboratory, in futuristic bleach plant solutions e.g. per acids . The in-plant tests are the

best and often only way to monitor the effect of process variables on the material

performance in "real life" conditions, since it may not be possible to replicate plant

conditions in the laboratory or it may be very difficult because of intricacies involved in

sustaining the temperature, pressure, flows, contaminant etc. as prevailed in the actual

mill conditions. It is, therefore, possible to predict on the basis of mill tests about the life

of material for any given environment. However, there are pitfalls in the field-testing.

The test may not faithfully reproduce such factors as crevices, stresses or weld-related

phenomenon. Sometimes, this testing takes a long time and for this reason it is

impractical in many circumstances. On the other hand, laboratory corrosion testing are

useful when service history is lacking time and budget constraints prohibit simulated

field testing. They can also be used as screening tests prior to simulated service testing.

Laboratory tests are particularly useful for quality control, material selection, material

and environmental comparison and the study of corrosion mechanism. These tests

cover a spectrum ranging from simple immersion test to sophisticated electrochemical

tests. Standardized tests methods, especially electrochemical tests are very useful for

29
specifications and for routine use to compare experimental alloys and such products as

inhibitors, coating and insulation materials. These are accelerated tests and can give

material's life only in relative sense. In the following paragraphs are given the details of

the procedures adopted in the proposed work.

2.1. Material Selection :

Recent Survey shows that Carbon steel has been the principal material of construction

for kraft batch/continuous digesters since last many decades. Change in processing

conditions during last several years has seen increase in corrosion rates of digesters up

to 100 mpy in new steel digesters. Accordingly digesters are provided with corrosion

allowance. Alternatively they have been formed of corrosion resistant materials e.g. low

alloy steel (Cr 0.8%,Mo 0.5%,Si 0.25%), SS304L, 316L, 317L, 321, 347, duplex 2205,

superduplex (higher Cr than duplex SS), Inconel 625, ferritic SS. Carbon steel digesters

have been provided with protective layer of the above mentioned resistant materials by

cladding /weld overlaying/thermal spraying. In very few cases, low alloy steel, ferritic SS

and Inconel have been used. Duplex SS is a recent addition due to its better resistance

against cracking in digester liquor and chloride stress cracking, Davison (36), in addition

to better strength/weight ratio. It has been documented that the austenite stainless

steels possess a wide spectrum of corrosion resistance making them suitabile for the

bleach plant service, Krisher (72). Newer generation ferritic stainless steel (low

interstitial) grades e.g. 29-4-2, 29-4C, Crucible SC-1 etc. provide satisfactory

performance in many bleach plant environment but have limited availability in the

product forms needed for wide spread applications, Bennett et al (21). Also these steels

30
are not easy to weld and are prone to embrittlment when thick sections are welded. The

austenitic stainless steels generally have good and high ductility alongside corrosion

resistance. An elevated nickel amount in them increases their resistance to stress

cracking and higher molybdenum content imparts better resistance against crevice and

stress corrosion cracking, Avesta Bulletin (65, 66). Accordingly, for In-plant test in

digester, mild steel, austenitic grade steels 304L, 316L and three duplex grades 2205,

LDX, SAF2304 stainless steels were selected as the test materials. For weight loss

tests in sulfide solutions mild steel, austenitic stainless steel 304L, 316L, and a duplex

stainless steel 2205 were selected. For weight loss and electrochemical tests in per acid

solutions mild steel, austenitic stainless steel 304L, 316L, and 254SM0 and duplex

stainless steel 2205 were selected.

2.2. Specimen Preparations :

2.2.1. Shape and Size of Specimen :

To get a meaningful data on corrosion performance, test specimens are selected in

specific size and shape. These are influenced by several factors. Sufficient thickness of

specimens is required to minimize the possibility of perforation of coupon during the test

exposure. Their size should be so large that they can be conveniently handled, the

limitation being imposed by the problem of effective entry into the operating equipment.

The most common shape of coupons, for the test purpose, is rectangular. Circular and

disk type shapes are also used but rectangular is common because most alloys are

available in plate or sheet form. Also materials are exposed such that their major

31
exposed area to corrosive media is their surface. As such their thickness is much

smaller as compared to surface area hence they are tested in plate or sheet form. For

the mill test and weight loss test in sulfide and per acid solutions, coupons orthe size 6

cm x 6cm with thickness varying between 2 — 4 mm with a hole of diameter 0.375" at its

center were used in case of all steels except mild steel whose coupons were of

4cmx4cm and thickness 5 mm. The chemical composition of samples is given in Table -

2.1.

For electrochemical tests, the corrosion cell used employs cylindrical shaped samples.

Accordingly the test materials were obtained from rods of the test materials. Size of the

test specimen was 1.0cm in diameter and 1.31cm in length. The chemical composition

of samples is given in Table -2.2.

2.2.2. Surface Preparation :

The condition of the surface of test sample can markedly affect the corrosion test

results. An unprepared surface may facilitate the corrosion because of scratches and

unevenness. Accordingly, the general and localized corrosion e.g. pitting and crevice

closely depend upon the surface of test specimen and, therefore, a clean surface is

required. Standard surface conditions are therefore desirable and necessary in order to

compare thp corrosion resistance of different materials and also the effect of process

variables on the corrosion of metal specimen. It is necessary to remove any extra soil or

greases from finished surface so as to allow free access of corrodants, Carter et al (25),

other (67). For the present work, polishing machine with two different speeds of rotation

32
i.e. 300 and 600 rev. /min. was used for grinding and polishing the surface. The surface

finishing was done by abrading the specimens on emery or silicon carbide paper with

grit sequence starting from coarser towards fine i.e. 120, 240, 320, 600 and 800 fitted of

motor driven polishing wheels. The coupons were held by hand and water stream was

made to fall continuously during the grinding process. This was done to avoid any heat

generated metallurgical damages. Moderate to heavy pressure was applied evenly. It

was ensured that the surface was completely scratch free and also sharp corners were

machined to avoid preferential attack. The specimens were then subjected to polishing

by using self adhesive cloth sprinkled with fine polishing alumina (prepared by adding 1

part of alumina slurry to ten parts of water) at a speed varying up to 600 rev/min. Finally

the coupons were degreased ultrasonically in 50% acetone solution in distilled water

and then dried. The dried coupons were weighed on semi micro balance and

dimensions were measured by vernier calipers. These coupons were exposed for in-

plant study and weight loss study. Similarly surface preparations were done on

cylindrical samples for electrochemical tests.

2.3. Exposure Details :

2.3.1. In-plant test :

The In-plant test was conducted on mild steel and stainless steel coupons in the

digester of nearby paper mill. The duplicate coupons of each test material were fitted in

a rack formed of five SS-316 rods and nuts so as to support the coupons rigidly

(photograph 2.1) the coupons were separated from each other by serrated washers of

33
teflon with the aim to (i) avoid bimetallic corrosion (ii) form crevices to investigate

corrosion. The test rack was fitted somewhere near strainer in digester and it was

removed after six months exposure for analyzing the corroded coupons.

2.3.2. Laboratory Tests :

(i)Weight Loss tests :

In this test, various steel and stainless steel coupons were exposed in sulfide and per

acid solutions simulating those in digester and bleach plant. Duplicate coupons of each

test samples, with serrated washer, were hanged in the test solution using nylon thread.

The test duration of these tests was six months. After the exposure the above coupons

were analyzed for degree of uniform and localized corrosion.

(ii) Electrochemical tests :

These tests were performed at room temperature on cylindrical specimens of steel and

stainless steel in per acid bleach solutions namely paeracetic acid, caro's acid and

mixture of paeracetic and caro's acid. Cylindrical shape of the specimen is desired as

per the geometry of polarization cell (Green's cell) (Fig. 2.1), used in the

electrochemical testing. More details about this test are discussed later.

34
2.4. Solution preparation for Laboratory Tests :

2.4.1. Sulfide Solutions :

For sulfide solutions, first stock solutions of known amount of sodium hydroxide, sodium

sulfide and sodium thiosulfate separately were prepared in deoxygenenated distilled

water and analyzed. After analysis these stock solutions were mixed so that a required

level of concentration of solution could be obtained. Desired chloride level was obtained

by adding A.R. grade sodium chloride. All chemicals were analyzed after the

preparation of the solution so as to ensure required composition. The solutions were

covered rapidly by half inch paraffin oil layer so that oxidation of the liquor could be

prevented.

2.4.2. Peracids solutions :

The per acids (Pa - Peracitic acid, Px - Caro's acid, Pxa - mixture of Pa and Px) were

prepared by H202, CH3COOH and H2SO4, Bijan (23). Peracitic acid was prepared by

adding glacial acetic acid to hydrogen peroxide containing about 1 ml of sulfuric acid as

catalyst. The mixture was then warmed to 45°C, held at this temperature for two hours,

stored overnight in a refrigerator to allow the mixture to come to equilibrium. Caro's acid

was prepared by adding sulfuric acid to hydrogen peroxide, while maintaining the

reaction temperature at 30-35°C. P xa solutions were prepared by adding the required

amount of glacial acetic acid to the cold solution of Px. Then these solutions were

analyzed to determine their active oxygen content prior to use and diluted to a required

35
level. The pH was increased by adding diluted NaOH. Desired chloride level was

maintained by A.R. grade sodium chloride (NaCI) crystals.

2.5. Analysis of Kraft white Liquors of Lab and mill Tests and peracid solutions :

2.5.1. Chloride Ion Determination :

Two procedures were used for the estimatetion of CI" in these solutions.

(i) In white liquors, sodium chloride was estimated by Scan (108) methods (Chloride

determination in white liquor). The reagents used were hydrogen peroxide, H202

=30%,0.1 N silver nitrate solution, 10% acetic acid and 0.1% in ethanol Phenolphthalein

indicator and 10% Potassium chromate solution in distilled water. Pipette 10 nil liquor

into a 250 ml conical flask and dilute with about 25 ml of distilled water. add several ml

portions of H202 while heating until the oxidation is complete and the solution becomes

colorless and then boil for 5 min. after cooling add three drops of Phenolphthalein

indicator and neutralize with acetic acid until the red color disappears. Add 10 drops of

Potassium chromate solution and titrate with silver nitrate solution until the precipitate

remains faintly red .denote the consumption as A ml. to obtain a blank, titrate the same

volume of distilled water with 10 drops of Potassium chromate solution added until the

solution is of the same color as when titrating the sample. Denote the consumption as B

ml. Content of sodium chloride, gram of NaCl/1 as X.

X=5.85(A-B) n where n= normality of silver nitrate solution

36
(ii) This procedure was used for peracid solutions. The chloride containing per acid

solution is treated with an excess of standard silver nitrate solution. Thus precipitated

silver chloride is separated by filtration and silver nitrate is determined by titrating the

filtrate. against thiosulfate solution using ferric ion indicator observe end point,

Chlorination Washer (30), Henrikson (62), Laliberte (73).

2.5.2. pH Determination :

This was determined by a pH meter. The pH meter was calibrated by 0.05M potassium

hydrogen phthalate and 0.01M sodium tetra borate (borax) for pH= 4.0 and 9.0

respectively at room temperature.

2.5.3. Analysis of white liquor :

For Analysis of white liquor Scandivian methods (109) were used.

Reagents : Hydrochloric acid 1.0N, standardized., Barium chloride solution, 200g of

BaCl2.2H20 per lit., Formaldehyde HCH0,40% neutralize with 1.0N sodium hydroxide

solution to a faint red colour with phenolphthalein as the indicator. Thymolphthalein

indicator, 0.1%.dissolve 0.1g in 100m1 of ethanol (equivalent point pH 9.5).,

Phenolphthalein indicator, 0.1%. Dissolve 0.1 g in 100 ml of ethanol (equivalent point

pH 8.0). Bromophenol-blue indicator 0.1%. Dissolve 0.1 g in 100 ml of distilled water

(equivalent point pH 4.0).

37
2.5.3.1. Determination of total alkali and active alkali :

Pipette 5.0 ml of liquor into a 200 ml conical flask, dilute with about 30.0 ml of distilled

water and add 20 ml of barium chloride solution. Titrate in a hood immediately with the

hydrochloric acid using 0.5 ml of the thymolphthalein solution as the indicator the

consumption, a ml is equivalent to Na0H+0.5Na2S in a 5.0 ml sample. Add immediately

5.0 ml of neutralized formaldehyde solution wait 0.5 min. and titrate to a very faint blue

colour .add 0.5 ml of phenolphthalein solution and titrate to a faint blue colour. The acid

consumption, b ml, is equivalent to NaOH+Na2S in 5.0 ml sample. Add 0.5 ml of

bromophenol- blue solution and continue the titration to the end point the total

consumption of acid, c ml is equivalent to the NaOH+Na2S+Na2CO3 in a 5.0 ml sample.

Total alkali, calculated as g of NaOH per lit= 8.0 c.n

Active alkali, calculated as g of NaOH per lit. = 8.0 b.n

Sodium carbonate calculated as g NaOH per lit. =TA - AA,

Where TA= Total Alkali, AA= Active Alkali

a= consumption of acid to the thymolphthalein end point, ml

b=consumption of acid to the phenolphthalein end point, ml

c=consumption of acid to the bromophenol-blue end point, ml

n= normality of the hydrochloric acid.

and then converted all chemicals as gpl as chemicals.

38
2.5.3.2. Determination of Na2S, Na2S2O3 and NaOH :

Pipette 25.0 ml of liquor into a 500.0 ml of volumetric flask, dilute with distilled water to

the mark and mix thoroughly.

A: Determination of a and b :

Preliminary testi: pipette 10.0 ml of diluted liquor into a conical flask, add 3 drops of

phenolphthalein solution and titrate slowly with the acetic acid. Note the consumption.

Preliminary test 2: acidify 10.0 ml of the diluted liquor with about 2.0 ml of acetic acid

and titrate with 0.1N iodine solution using starch solution as the indicator. Note the

amount of solution consumed in the titration.

Measure from a buret into a conical flask 5 times the amount of 0.1N iodine solution

consumed in preliminary test 2, measured to the nearest milliliter plus an excess of 7.0

ml add 5 times the amount of acetic acid consumed in preliminary testi plus an excess

of about 4.0 ml pipette 50.0m1 of the diluted liquor into the acidified iodine solution and

titrate with 0.1N sodium thiosulphate solution using starch solution as the indicator. Note

the consumption of sodium thiosulphate solution, a ml, and the volume of iodine solution

added, b ml.

39
B: Determination of c :

Prepare a zinc carbonate suspension by mixing equal volumes (200.0m1) of the zinc

sulphate and sodium carbonate solution .pipette 100.0 ml of liquor in to a 1000.0m1

volumetric flask and add 50.0m1glycerol. Precipitate the sulphide with about 300.0 ml of

the freshly prepared zinc carbonate suspension, added in portions .shake the flask after

each addition when the precipitate has settled, transfer one drop of the clear solution to

a lead acetate paper. If the paper blackens, indicating the presence of residual sulfide,

add more of the zinc carbonates suspension to the liquor. When all the sulphide is

precipitated, dilute with distilled water to the mark and shake the flask. Filter the solution

through a dry, pleated filter paper or a sintered glass filter.

Preliminary test 3: determine the consumption of acetic acid by 10.0m1 of filtrate as

described under preliminary testi . Pipette 100.0 ml of the filtrate into a conical flask and

acidify with 10 times of the amount of acetic acid consumed in preliminary test 3 plus an

excess of 4.0 ml. titrate immediately with 0.1N iodine solution with starch solution as the

indicator. Determine the consumption as c ml.

X=3.9(4b.n1 - 4a.n2 - c.n1) where

X=content of sodium sulfide, g of Na2S/l.

a= 0.1N sodium thiosulphate consumed in titration A, ml.

b= 0.1N iodine solution added in titration A. ml

c= 0.1N iodine solution consumed in titration C, ml.

ni=normality of the iodine solution.

n2 =normality of the sodium thiosulphate solution.

40
C: Determination of d :

Now pipette100.0 ml from the filtrate obtained under B into a conical flask and adds 5.0

ml of formaldehyde. Mix and acidifies with 10 times the amount of acetic acid consumed

in preliminary test 3 plus an excess of 4.0 ml .titrate after 1 min. with 0.1N iodine

solution using starch solution as the indicator. Denote the consumption as d ml.

Z=15.8 d.n1 where

Z=content of sodium thiosulphate, g of Na2S203/I.

ni=normality of the iodine solution.

d= consumption of iodine used in above titration.

Sodium hydroxide is calculated by Subtracting sodium sulfide as sodium hydroxide from

AA (active alkali) as sodium hydroxide.

2.5.3.3.. Determination of Polysulfide as free sulfur :

A gravimetric method for measuring polysulfide sulphur concentration in unoxidized and

oxidized samples of white liquor is described, Dorris et al (38). A 25.0 ml volume of

clear liquor was transferred by pipette into 100.0 ml of distilled water in a 250.0 ml

beaker equipped with a magnetic stirrer. The beaker was then placed in a fume hood

and a combination glass pH electrode inserted in the beaker. Using a Pasteur pipet, the

liquor was rapidly acidified to a pH of 8 with HCI (3 mol/l) and constant agitation .the pH

was then adjusted to 5.0-5.5 with HCI (1 mo1/1).the solution then had a milky white

appearance as a result of the finely divided elemental sulpher. A 4.7 cm diameter

Millipoi-e —type GS filter with a pore size of 0.22pm, weighed on an analytical balance

41
without drying, was fitted on a 4.7 cm Millipore filter holder to filter the fine precipitate

.the filter assembly was mounted on a 250 ml filtering flask which contained a solution

of NaOH (0.1 mo1/1, 100.0m1) to reduce H2S emission. The whole slurry was filtered

under vacuum .small aliquot of distilled water (a total 50.0 ml) were used to transfer the

precipitate quantitively to the filter. After dewatering, the precipitate was washed with an

additional 25.0 ml of distilled water and dewatered again under vaccum. At this stage

the wet precipitate have a yellow color .using a pair of tweezers, the membrane filter

was transferred to watch glass for drying results were obtained by placing the samples

in a desiccator for 2.0 hours. During the filtration, washing and drying steps, the filter

membrane lost between 0.4 and 0.6 mg an average negative correction of 0.5 mg was

therefore applied to the original weight of the filter .The concentration of polysulfide

sulpher in gpl. was then calculated from the difference between the dry weight of the

membrane filter with the precipitated sulpher and the weight of the filter, divided by the

volume of liquor acidified.

2.5.4. Analysis of Per acid Solutions (23) :

These solutions were analyzed for active oxygen content. For this purpose about 0.3-

0.4 g of the Caro's acid was added to a 500.0 ml Erlenmeyer flask containing 100.0 ml

of distilled water and 10.0 ml of 20% sulfuric acid. One to three drops of ferroin indicator

was then added to the flask (solution turns reddish-orange in color) and it was titrated

immediately with 0.1 ceric ammonium sulfate to a pale blue end point. Approximately

10.0 ml of 25% potassium iodide was then added to the Erlenmeyer flask and the

mixture was titrated with 0.1 N sodium thiosulfate until the dark reddish color of iodine

42
began to fade. A starch indicator, 2.0-3.0 ml, was added at this point and the titration

was continued until the dark blue color disappeared to a pale reddish-orange color end

point. The concentration of per acids in terms of active oxygen was determined by using

the following formula:

A.O. = (V thiosulphate x 0.1x0.8)

Sample weight

Where A.O. = Active oxygen.

2.6. Weight-Loss Determination :

In this test, the weight of the metal is lost uniformly with time from exposed to corrosive

media. Change in the weight or thickness of the material should therefore give a good

estimation of the severity of corrosion. This is denoted by a parameter called 'corrosion

rate,' defined in two ways. Firstly, it is weight loss per unit exposed surface area of

metal per unit exposure time in corrosive environment. Secondly, it has been defined

from engineering point of view. In this case rate of metal penetration (due to corrosion)

or rate of thinning of material per unit time is considered. Corrosion rate is represented

as mils per year 'mpy' (1000 mil=1.0 inch). In the estimation of weight loss and corrosion

rate determination, a cleaned metal coupon, of measured size and weight, is allowed to

corrode for a specific duration. The corroded coupons then are cleaned off the rust

mechanically by light brushing of the specimen to remove lose bulky corrosion products.

Later they are cleaned by chemical cleaning procedures, Ailor et al (3), in which

coupons were treated with cold solution of concentrated HCI acid + 50.0gpl SnCl2

43
20.0gpl SbCI3 which has been specifically suggested for cleaning corroded steel

surfaces Ailor et al (3). Cleaned coupons thus obtained are weighed to know weight

loss. Following formula was used for corrosion rate calculations, Fontana et al (44).

Corrosion Rate (mpy) = 3.45 x 106 x w

DAT

W = weight loss in grams, D = density of metal in gm/cm3, A = area in cm2 and

T = exposure time in hours

2.7. Nature and Degree of Localized Corrosion :

Weight loss is not a realistic indicator of material performance if the material

experiences pitting/crevice corrosion in a given environment. As such, separate

determination of degree of pitting and crevice corrosion was made in present case.

Crevice on the coupons is formed around the holes due to its covering by serrated

washers. Preferential attack on the covered surface is a good representation of crevice

corrosion. For this purpose, the pit and crevice depth measurements were done to know

the extent of localized corrosion. Thus on the basis of maximum depth under pit /crevice

corrosion resistance against pitting/ crevice corrosion of various alloys can be

categorized by Singh (113), Tuthill et al (131).

In present study pit depth measurement was done by examining the cleaned coupons

under optical metallurgical microscope (Reichert Jung, USA make). A single pit was

located on the surface under the microscope at low magnification. This was followed by

44
increasing magnification until the pit area covered most of the field under view.

Microscope was then focused at the top of pit by fine focusing knob and initial reading

was recorded. Microscope was refocused at bottom of the same pit and final reading

was noted down. The difference of initial and final reading was obtained as a pit depth,

ASTM. (40).

2.8. Electrochemical Measurements :

2.8.1. Basics :

Metals undergo corrosion when it comes in contact with liquid (mostly aqueous

solutions). In this state, the metal and liquid both undergo several redox reactions which

are chemical and electrochemical in nature, because of which metal is corroded.

Consequently, the phenomenon of metal corrosion is termed as electrochemical

corrosion. Test methods depending upon study of these redox reactions are known as

electrochemical methods. These methods provide useful tool for studying the corrosion

phenomenon. Thus the electrochemical kinetics (corrosion rate) in specific

environments can be investigated and also these methods help to measure and control

the oxidizing power i.e. the potential of the environment. Moreover, these techniques

may also be used to predict about resistance of metal to localized corrosion e.g. pitting,

crevice, etc. The earliest applications of these techniques were attractive because they

offered direct method of accelerating a corrosion process without changing the

environment namely by adding strong oxidizer or increasing temperature as in other

non-electrochemical laboratory testing. In this technique, the corrosion rate can be

45
measured without removing the specimen from the environment or altering the sample

itself. This capability offers distinct advantages over weight-loss and visual observation

testing procedures in the sense that kinetics of corrosion process can be studied

quantitatively. In Electrochemical tests, the material to be studied is put in (Corrosion

Cell Fig. 2.1) the test solution as one of the three electrodes of an electrical cell. The

other two electrodes are a counter electrode and a reference electrode. Connections

from these electrodes are sent to equipment named potentiostat which does several

jobs. Using potentiostat, one measures for the test material (i) electrode potential (ii)

current-potential relationship where potential is changed in predetermined manner

(potentiostatic, potentiodynamic/cyclic polarization tests) (iii) potentiostatic (current vs.

time behavior) etc. In present investigations, corrosion potential measurement,

potentiodynamic/cyclic polarization and Potentiostatic (current vs. time plot)

measurements were recorded in order to understand the electrochemical kinetic of

stainless steels in different media. These are now discussed briefly.

2.8.2. Corrosion Potential Measurement :

On dipping a metal in solution, the metal oxidizes thereby relieving metal ions in solution

with the electronic charge remaining on the metal sample itself. On attaining equilibrium,

the metal is surrounded by metal ions and therefore develops electrical potential known

as corrosion potential (E,„(r) or open circuit potential (OCP). Time taken to achieve this

potential depends upon material- solution system and could vary from a few hours to

even days. For corrosion potential measurements, the test sample is immersed in the

test solution and potentiostat records a potential versus time curve until a reasonable

46
steady state value is achieved. This potential indicates about the tendency of metal to

corrode and also whether the material is in passive state or is in transpassive region.

(i) Potentiodynamic / Cyclic Polarization :

These are the polarization characteristics measured as a function of applied potential by

gradually polarizing the specimen anodically, at a preselected scan rate, by several 100

my with respect to corrosion potential (Fig.2.2). It can yield the impaitant information

such as (i) the ability of material to spontaneously passivate in the particular medium (ii)

the potential region over which the specimen remains passive (iii) materials tendency to

experience localized corrosion i.e. pitting, crevice corrosion and (iv) the corrosion rate.

This plot can be described in following way. Region A in (Fig.2.2) is the active region in

which the metal specimen corrodes as applied potential is made more positive; At B,

further increase in the current ceases due to passivation which is typical of iron,

stainless steels, Ni and Cr alloys. This point is characterized by the primary passive

potential (Epp) and critical current density (la). In the region C, termed as passivation

region termed as passivation region, the current, hence corrosion rate, decreases

rapidly to minimum value as the passivating film is formed over the surface of specimen.

As one proceeds to potential beyond passivation region, the current again increases

(region D). This high current behavior is referred to as transpassive region, and results

from breakdown of passive film. The metal in this region experiences pitting. The

potential at which protective passive film breaks is know as critical pitting or breakdown

potential. A slight modification of the potentiodynamic polarization plot, called as 'cyclic

polarization', is if external applied potential of metal is made to decrease after reaching

47
some value in the transpassive region, a part of polarization curve termed as 'reverse

scan'. The polarization curve then crosses the passive region somewhere or it does not

cut at all (Fig. 2.2), the former is a case where pits get passivated. The corresponding

potential is termed as repassivation potential and is an indication that at potential higher

than repassivation potential only, metal experiences crevice corrosion. If during reverse

scan, polarization curve does not cut the passivation curve then either pits do not

passivate indicating that metal is not resistant to crevice corrosion or probably reverse

scan was initiated even before the onset of pitting. The more noble the repassivation

potential, obtained at fixed scan rate, the less susceptible is the alloy to initiate crevice

corrosion. To record polarization curves, clean polished specimen was immersed in test

solution for an hour so as to reach the steady state before initiating polarization.

Potential was scanned at the rate of 0.166 mV / sec. The change of current with the

potential was recorded in computer loaded with corrosion software supplied with the

potentiostat. The scanning direction was reversed when current reaches corresponding

to vertex potential (100 my above the pitting potential) or current reaches 1 mA/cm2

,Wilde et al (146).The scanning is continued until reverse scan curve crosses the

forward scan curve or until the corrosion potential is reached (Fig. 2.2).

(ii) Potentiostatic :

Although the tendency of pitting/ crevice corrosion can be measured by potentio-

dynamic test, the technique can not measure the critical pitting potential (Er) and

repassivation potential (Es), accurately, since these vary with scan rate. In case of

48
higher scan rates, these values are observed to have higher magnitude, Bennett et al

(21) and Wilde et al (147).

Therefore, for determining tendency of pitting and crevice corrosion, potentiostatic test

method is used. In this method, ASTM (96), active pits are initiated at the potential more

noble than pitting potential (En) (obtained from potentiodynamic polarization curves).

This is confirmed by recording current vs. time plot indicating continuous increase in

current density with time or current density exceeds 50uA/cm2. After stimulation of

localized corrosion, the potential is returned as rapidly as possible to preselected value

e.g. El (El.? Ecorr.) to determine if the specimen will repassivate or localized corrosion

will continue to propagate at the preselected potential. If the pitted or creviced local

regions repassivate at the preselected potential, the polarizing current drops quickly to

zero or to low values consistent with a passive conditions and monitor the current for 15

minutes (Fig. 2.3a), After ensuring repassivation at El, by observing decreasing trend of

current for 15 minutes, stimulation step is repeated and changed the. potential to the

second preselected value which is 0.05 V more noble than El. The current vs. time plot

is again recorded this potential (E1+50) my. If current immediately starts rising and

continue to rise (Fig.2.3b), test is stopped after 20 sec. If current first drops, the test is

continued until 15 minutes. It is quite possible that at later stage, the current rises as

shown in curve III of (Fig.2.3b), at this stage the test is stopped. The pitting potential is

considered to be between E1 and (E1 + 50 my). To ascertain that this is really pitting

potential, the sample is checked under microscope for pitting attack. For determining

repassivation potential (Es), the specimen is fixed in a collar of PTFE which forms

crevices. Rest of the procedure is same as for determining Ep.

49
2.9. Experimental Equipments :

The equipments used in present study, to perform different type of electrochemical

measurements is computer controlled Electrochemical Measurement System Voltalab

40 model PGZ301 of Radiometer France supplied with compatible corrosion

measurement software and a corrosion cell, (Photograph 2.2). Different parts of this

system are summarized below:

2.9.1. Corrosion Cell :

The corrosion cell selected for the present study is versatile, contaminant free e.g.

rubber, etc, temperature resistant and can provide reproducible conditions from one to

another experiment. The most important components of the cell are the working

electrode, reference electrode and auxiliary electrode (counter electrode). Working

electrode is internally threaded cylinder of the alloy being tested. It is fixed against the

tubular glass holder using a threaded metal rod and a Teflon gasket to avoid crevices.

The reference electrode, saturated calomel electrode (SC) rests in a luggin capillary

which is adjusted so that the tip is close to the test electrode. This reduces error in the

measurement of electrode potential which is attributed to l-R drop. During polarization

and potentiostatic tests, current flows between the test and auxiliary electrodes. These

electrodes are graphite rods. Auxiliary electrodes are arranged symmetrically around

the test electrode to provide an even distribution of current. The cell atmosphere is

controlled by the gas inlet and outlet continuously through the inlet tubes. The desired
epouta. um).44.

Age.
ftg
Dog
c
gas is admitted continuously through the inlet tubes and dispersed throughout the

solution by means of fritted glass tube

2.9.2. Saturated Calomel Electrode (SCE) :

The saturated calomel electrode was used as a reference electrode in present study. It

does not poison easily or contaminate because of its design. Another advantage of SCE

over the others is that its potential is fairly constant with temperature (dE/dT =7.6 x 104

V/ °C). The electrode consist of pool covered with a layer of mercurous chloride, Hg2Cl2

(calomel) and immersed in a solution of saturated KCI, electrolyte. Electric contact on to

mercury is made with a platinum wire which is often fused through the glass wall of the

container. The half cell reactions are :

Hg2Cl2 —> Hg" • + 2Cr

Hg' + 2e- —> Hg

Hg2Cl2 + 2e" —> 2Hg + 2CI'

Its corresponding Nernst equation at 25°C is

Ecalomal = Eclig2C1 2/Hg - 0.0592 log (a co

Ecaiomal (for saturated KCI solutions) = +0.242 V. The value of E° at 25°C for the calomel

half cell has been found to be 0.2677V. Consequently, above equation becomes

Ecaiomai = 0.2677 - 0.0592 log (a CI')

The values of potentials given in this thesis are with respect to SCE.

51
2.9.3. Potentiostat I Galvanostat :

The electrochemical measurement system measures polarization curves through

potentiostat/galvanostat. It is a device which controls and measures the potential of the

test electrode vs. a reference electrode. When it works as a current controlling device, it

is called as a galvanostat. Potentiostat supplies a current of a needed magnitude and

polarity to the test electrode using an auxiliary electrode in the cell. Therefore, the

potential measurement is done between test and reference electrode while potential

adjustment is achieved by passing the current between the test and auxiliary electrodes.

The potentiostat is, generally, used for conducting potentiostatic (constant potential) and

potentiodynamic (variable potential) polarization experiments. The potentiostat used in

present work implements analog and microcomputer design advances to provide high

performance and unlimited versatility in electrochemical measurements. This extends

the range from -10 to +10 V with constraints that the difference.

2.9.4. Electrometer :

It is an electronic voltmeter with extremely high input impedance (108 ohms).it can be

used to measure the electrode potential directly or in conjunction with a potentiometer

as a null point indicator. For present study, it was in association of potentiostat. The

electrometer should have very high input impedance i.e. order of 108 ohms or greater

for electrochemical measurements. This ensures that only negligible current will be

drawn from the system during the potential measurements.

52
2.9.5. Metallurgical Microscope :

The metallurgical microscope Reichert Jung, USA make Epi Star model, has been used

to examine the pit I crevice depth and area has also been measured by metallurgical

microscope. The light microscope has been designed by combining various lenses to

resolve and reveal the fine details of microstructure of the sample being examined. It

illuminates the specimen with incident (reflected) light. There are two basic types of

microscope: upright and inverted type, the term upright and inverted refers to orientation

of the face of the polished sample that is examined. The microscope used in present

study is upright type (Photograph 2.3) having single illuminator (incident light only). In

this microscope, the specimen is placed on a slide on the stage so that the polished

surface may be perpendicular to the light beam. Various components of microscope are

described below:

(i)Illuminating System :

Tungsten-halogen filament lamps are used in the microscope (Epi Star model) procured

for present study. The incident light illuminator using a long life high intensity 6V (20W)

quartz lamp. The 4.5 V setting is recommended for the most bright field work, the red

5V and 6V settings are usually required for microphotography, phase contrast and dark

field application. These are widely used for their high intensity and high color

temperature. Light intensity can be control by varying the current or by use of neutral

density filter.

53
(ii) Condenser :

An adjustable lens, free of spherical aberration and coma, is placed in front of the light

source to focus the light at the desired point in optical path. A field diaphragm is

adjusted for best image contrast. A second adjustable diaphragm, the aperture

diaphragm, is placed in the light path before the vertical illuminator. Opening or closing

of this diaphragm alters the amount of light and the angle of cone of the light entering

the object. The optimum setting for this aperture varies with each objective lens and

compromise among the image contrast, sharpness and depth of the field. Opening this

aperture increases the image sharpness but reduces contrast while closing the aperture

increases contrast but impairs image sharpness. The aperture diaphragm should not be

used for reducing light intensity. It should be adjusted for contrast and sharpness.

(iii)Light Filters :

These are used to modify the light for ease of observation, for improved

photomicroscopy, or to alter contrast. Neutral density filters are used to reduce the light

intensity uniformly across the visible spectrum. Thus they are useful for safe

comfortable viewing and reducing the light intensity without reducing the numerical

aperture the system.

54
(iv)Objective Lens :

The objective lens forms the image of the specimen and is the most important

component of the optical microscope. The numerical aperture (NA) is a measure of light

collection capability of the objectives and is define as NA = n Sin a

where -n is minimum refraction index of various materials between the specimen and

the objective lens and a is half angle of the most oblique rays the front lens of the

objective. Objective lenses have been mounted on a nosepiece turret that can accept

four to six objectives. The vertical illuminator contains a reflector or prism that deflects

tile light down the objectives on to the specimen surface. it usually holds the aperture,

field diaphragms and filters as well. This illuminator provides only one or two type of

illumination, such as bright field and dark field and polarized light illumination. The tube

length is the length of the body tube from the eye line of the eye piece to the objective

thread. This length is not standardized and can vary. The objectives are designed for

use with tube length of 170 mm and can not be interchanged.

The microscope used for present study have Plano chromatic objective which are

corrected for chromatic aberration and flatness of the field. This provides relatively long

working distance, that is the working distance from front lens o f the specimen surface.

Working distance decreases as magnification of the objective increases. All the

objectives in this microscope are per focal, indicating that the specimen is essentially in

focus when nosepiece is rotated to change from one magnification to another.

Perfocality does not adversely affected by any random selection or arrangement of

objectives on the nosepieces. This series of objectives is also par centered i.e. when a

55
is selected in the centre of the field for a given magnification, it remains well within field

of view for the next highest magnification.

(v) Eyepieces (Ocular) :

The major function of eyepiece is to magnify the primary image produced by the

objective so that the eye can use the full resolution of the objectives. Microscope

produces a virtual image of the specimen at the point of most distinct generally, 250

mm (10 inch) from the eye. The eyepiece magnifies this image permitting achievement

of useful magnification. Epi Star Industrial Microscope is equipped four 10x wide field

eyepieces of different field of view. In the compound microscope image produced by

the objective lens system is further magnified by the eyepiece. Total magnification is

therefore, the product of the magnification of the objective lens and the eyepiece Me

Magnification total = Mo X Me

2.10. Microstructure Examination :

The stainless steel samples were mounted on plastic base for polishing and etched for

microscopically examination. Before etching, the samples were cleaned off scale by

grinding them from 120 to 1200 grit on polishing machine without excessive heating.

Then they were polished by emery papers no. 0 to 4/0 grade followed by final finish on

adhesive cloth paper sprinkled with alumina slurry. All the microstructures were taken

by Axiovert 200 Mat. The materials, their respective time of etching and etchant

chemicals are given in Table 2.3.

56
 Table - 2.1

Composition of Stainless Steels Plate Samples

Alloy C Si Mn P S Cr Ni Mo N Cu Ti
MS 0.18 0.04 1.66 - - - - - - - -
304L 0.036. 0.44 1.84 0.024 0.001 18.11 8.01 0.26 0.058 0.46 0.002
316L 0.019 0.5 1.11 0.027 0.002 17.43 11.26 2.03 0.048 0.40 0.001
2205 r 0.022 0.35 1.47 0.02 0.001 22.13 5.55 3.16 0.188 0.21 0.004
2304 0.019 0.42 1.45 0.026 0.0005 22.94 4.73 0.33 0.104 0.25 0.004
LDX 0.024 0.69 5.07 0.017 0.0 21.36 1.49 0.30 0.232 0.32 0.0

Table - 2.2

Composition of Stainless Steels Cylindrical Samples

Alloy C Fe Ni Co Mn P Cr Mo S Cu N Si
304L 0.02 - 11.52 - 1.92 - 18.1 - - - - 0.59
316L 0.02 BAL* 10.87 0.18 1.69 0.03 17.44 2.16 0.03 0.31 0.04 0.69
2205 0.02 BAL* 5.48 - 1.45 0.026 22.25 3.08 0.002 - 0.15 0.52
254SM0 0.009 BAL* 18.00 - 0.44 0.028 20.10 6.15 0.001 0.74 0.20 0.31

* BALANCE

Table - 2.3

Materials, Their Respective Time of Etching and Etchant Chemicals

Materials Time of Etching Etchants

Mild Steel 10 seconds HNO3 (1-5 ml) mixing in

100 ml methanol
Austenitic Stainless Steels 10-15 seconds Solution of 100 gm of oxalic
304L,316L acid(A.R grade) crystals in
900 ml of distilled water
Duplex Stainless Steels 45 seconds Solution of 20 ml
2205, LDX, SAF2304 glycerin,20 ml HCI, 10 ml.
HNO3 and 10 ml H202

57
Photo. 2.1. : TEST RACK USED IN DIGESTER

58
Photo. 2.2.: ELECTROCHEMICAL EXPERIMENTAL SET- UP FOR CORROSION
MEASUREMENTS

59
Photo. 2.3. : METALLURGICAL MICROSCOPE USED FOR MICROSCOPICAL
OBSERVATIONS

60
 j--- GAS OUTLET

THERMOMETER

GAS INLET
SALT BRIDGE
CONNECTION
AUXILIARY
ELECTRODE
HOLDER

PROBE

WORKING
ELECTRODE

Fig. 2.1. : SCHEMATIC DIAGRAM OF POLARIZATION CELL

61
 BREAKDOWN
POTENTIAL

PITTING

CREVICE CORROSION

POTENT' A L, E
REPASSIVATION
POTENTIAL

PASSIVATION

LOG I

Fig. 2.2.: ACTIVE PASSIVE TRANSITION CURVE

62
 15 Min
0 Time -->

(a )

1Smin
Tim% --IP-

Fig. 2.3.: POTENTIOSTATIC CURVES (I Vs TIME)

63
 Chapter : 3

Corrosion in Solutions having Sulfur Compounds

Contents : Page No.

3.1. Introduction 65

3.2. Pourbaix (E-pH) diagrams for S-H20 and Fe- S-H20 system 67

3.2.1. Thermodynamic data and activites of various sulfur species. 68

3.2.2. Redox Reactions and Equations for S-H20 System 69

3.2.3. Redox Reactions Equations for Fe-S-H20 system 73

3.3. Corrosion test in alkaline sulfide solutions 84

3.3.1. Material Selection 84

3.3.2. Test Liquor 85

3.3.3. Long term immersion test 86

3.3.4. Evaluation of Corrosion Attack 87

3.4. Results and Discussion 87

3.4.1. S-H20 System 87

3.4.2. Fe-S-H20 system 88

3.4.3. Long Term Immersion test 89

64
3.1. Introduction

Due to the prevailing practice of making paper by kraft pulping process, - 84% of

chemical pulping and - 64% of all pulping processes, it is obvious that most work

related to corrosion in pulping section has considered the composition of test liquor and

test conditions as those observed in case of kraft pulping. Kraft process uses alkaline

sulfide solution for the purpose of delignification of wood/nonwood species in order to

draw cellulose fibers from them, which in turn are made into paper. This alkaline sulfide

liquor (pH -14) consists of NaOH and Na2S mainly, but due to recycling of unused

chemicals of pulping process after the liquor containing unused chemicals has been

treated in recovery and recausticizing sections, the cooking liquor also contains various

other sulfur compounds and chemicals. In addition the liquor may also have CI' ions as

contaminants from wood, fresh water or filtrates in the case of mill closure etc. A typical

composition of cooking liquor in Indian mills is given in Table - 3.1.

Since last few years, paper making is experiencing significant changes because of

several reasons. These are pressures to reduce effluent discharge and air pollution,

dwindling papermaking fiber resources, goals to reduce energy/water/chemical

consumption with a view to make the product more competitive etc. Important one

among them being the pollution control measures and efforts to increase fiber yield.

One option is to cook the wood chips more selectively so as to increase pulp yield. This

in turn also reduces chemical demand in the succeeding bleaching stages which help in

reducing the concentration of effluents in the bleach plant discharge. The selective

delignification of wood chips is achieved by cooking them in liquor of higher sulfidity

65
which is being practiced in the normal kraft process and is also an aspect of Rapid

Displacement Heating (RDH) or superbatch cooking, Christofer et al (31) and

Superbatch (122). Adoption of this change is observed in the difference of sulfidity

levels in Indian (- 20%) and American mills (- 38%) (Table - 3.1).

Out of these ions, S2', S2032- , S.2" and Cr affect, Metals Handbook (83) and Wensley

(145), corrosivity of liquor significantly. Cooking liquor with higher sulfidity will obviously

have higher concentration of these sulfur ions which is expected to result in increased

corrosivity of liquor. This is evident from several cases reported of increased corrosion

in digesters, after the mills opted for liquor of higher sulfidity. It seems the corrosion in

digesters depends very strongly on the relative amount of the different sulfur species in

cooking liquor, which is likely to be different in different mills, rather than simply on

temperature, pH and sulfide content only. In the past, several cases have been reported

by Maspers (81), Pvt. Discussion (100), Report (121), Udayshankar (135), Wensley

(138) of increased corrosion, in digesters where not only increased general corrosion

associated with erosion corrosion but also localized corrosion e.g. pitting, grooving,

cracks etc. have been observed. To address these issues of enhanced corrosion,

corrosion experiments were planned in solutions having sulfur containing compounds

with their composition matching with those observed in paper mills. In order to analyze

the corrosion attack and corrosivity of the solutions, it was planned to use E-pH

(Pourbaix) diagram for S-H20 and Fe-S-H20 system. Since these diagrams were not

available for the conditions corresponding to the pulping process, they were constructed

accordingly. This chapter therefore describes first the construction of E-pH diagram for

S-H20 and Fe-S-H20 system for the solutions simulating to the composition of pulping

66
liquor. This is followed by the description of the corrosion test done in the solutions

having sulfur compounds (similar to those observed in pulping liquor) and the analysis

of the test result on the basis of the constructed E-pH diagram.

3.2. Pourbaix (E-pH) diagrams for S-H20 and Fe-S-H20 system :

The introduction of potential— pH (E-pH) diagrams, popularly called as Pourbaix

diagrams, into electrochemistry created a new era in the study of electrochemical

reactions occurring in an aqueous medium near an electrode. These diagrams are

based on the dependence of equilibrium potential on pH and composition of the

aqueous solution at a given temperature. With the help of these diagrams, it is possible

to predict, on a thermodynamic basis, for a given element, the equilibrium states of all

the possible reactions between this element, its ions and its solid and gaseous phases

in the presence of water and other aqueous solutions at different temperatures.

Application of the data contained in these diagrams is limited by the reactions which

have been considered in establishing them as well as by the values assumed for the

standard chemical potentials of the substances taking part in these reactions. The

diagrams are based on the activities of ions and not on their real concentrations.

Presently, the potential - pH diagrams concern only pure metals and non-metals, these

diagrams therefore cannot give us information about the behavior of alloys, which often

differs from that of pure metals. However, even with these restrictions, it is evident that

in many cases the diagrams provide information which lead to important conclusions

concerning the possible reactions. Some of these conclusions are particularly important

in the study of corrosion in aqueous media e.g. whether in given aqueous media, a

67
given material will be corroding or immune to corrosion or will be under passivation. The

later also indicates the possibility of experiencing localized corrosion. Also it helps in

predicting the protective nature of various corrosion products and hence is useful in

estimating the conditions for electrochemical protection thermodynamically. Potential —

pH diagrams for the systems S-H20 and Fe-S-H20 are useful for the study and the

understanding of corrosion of iron and carbon steel in the presence of sulfides and of

sulphur compounds as aqueous solution.

3.2.1. Thermodynamic data and activities of various sulfur species :

To construct these diagrams for the systems S-H20 and Fe-S-H20, composition and

pH, as observed for pulping liquors, were considered for forming the equations showing

E—pH dependence for various thermo dynamical equilibrium reactions. Since these

diagrams were used for analyzing the results of the corrosion tests at room

temperature, different equations were formed at 25°C using activity of various sulphur

species corresponding to the chemical concentrations found in the pulping liquors.

(Table - 3.2).

Thus except one case, total activity of sulfur species was found on the basis of

concentration of Na2S and Na2S203 in different solutions meant for immersion test.

Values of the activity are given in Table -3.2. This activity was considered for drawing E-

pH diagram, irrespective of the form of sulphur species. Different iron and sulfur species

considered, in the present study, to draw E-pH diagrams, are given in Table -3.3 along

with their chemical potential at 25°C, Pourbaix et al (97) and Singh et al (117).

68
3.2.2. Redox Reactions and Equations for S-H20 System :

To construct the E-pH diagrams for S-H20 system (Fig- 3.1, 3.2), following sulfur

species were considered : H2S, HS-, S2-, S2032 , S, S4062-, S032- H2S03 and HS03.

Various thermodynamic reactions and their corresponding equations along with the

thermodynamic data e.g. chemical potential for different species were taken from

Pourbaix et al (97) and Singh et al (117).These equations were modified for

concentration of total sulfur corresponding to total amount of various sulfur species

considered in the pulping liquors. Thus activity of total sulfur was considered to be a s =

0.2, 0.3, 0.44 and 0.7 gram mole/liter on the basis of total amount of S2- and S2032"

found in the pulping liquors.

Following are given different equations used in constructing the E-pH diagram:

1. H2S 4-4 + H+ (Reaction and Equation 1 ref 97)

log (HS7H2S) = -6.992 + pH

2. HS" 4-4 S- + H+ (Reaction and Equation 2 ref 97)

log (S-/HS") = -14.01 + pH

9. H2S034-+ HS03" + H+ (Reaction and Equation 9 ref 97)

log (HS03-/H2S03) = -1.861 + pH

10. HS034-4 S03- + H+ (Reaction and Equation 10 ref 97)

log (S03-1HS03) = -7.210 + pH

Above equations are Irrespective of the value of activity of sulpher species, as,

69
20. S203- + 6H+ +8e•i- + 3H20 (Reaction and Equation 20 ref 97)

E =0.007 - 0.0443pH - 0.0074 log (as)

E =0.011 - 0.04pH (as=0.2gram mol/lit)

E =0.0109 - 0.044pH (as=0.3grammol/lit)

E =0.009 - 0.044pH (as=0.44gram mol/lit)

E =0.0078 - 0.044pH (as=0.7gram mol/lit)

21. S203- + 8H+ +8e- 4-9 2HS" + 3H20(Reaction and Equation 21 ref 97)

E =0.214 - 0.0591pH - 0.0074 log (as)

E =0.22 - 0.0591pH (as=0.2gram mol/lit)

E =0.219 - 0.059pH (as =0.3gram mol/lit)

E =0.217 - 0.059pH (a, =0.44gram mol/lit)

E =0.215 - 0.059pH (as =0.7gram mol/lit)

22. S203- + 10H+ +8e- 4-4 2H2S + 3H20 Reaction and Equation 22 ref 97)

E =0.317 - 0.0739pH - 0.0074 log (as)

E =0.318 - 0.0739pH (as =0.2gram mol/lit)

E =0.318 - 0.0739pH (as =0.3gram mol/lit)

E=0.317 - 0.0739pH (as =0.44gram mol/lit)

E=0.317 - 0.074pH (as =0.7gram mol/lit)

25. S406- + 20H+ + 18e- 4-+ 4H2S + 6H20 (Reaction and Equation 25 ref 97)

E =0.285 - 0.0657pH - 0.0098 log (as)

E =0.285 - 0.066pH (as =0.2gram mol/lit)

E =0.287 - 0.066pH (as =0.3gram mol/lit)

E =0.288 - 0.066pH (a, =0.44gram mol/lit)

E =0.29 - 0.066pH (as=0.7grammol/lit)

70
29a. SO3-- + 7H+ +6e- 4-4 HS- + 3H20 (Reaction and Equation 29a ref 97)

E = 0.368 - 0.069pH (as =0.2gram mol/lit).

E = 0.368 - 0.069pH (as =0.3gram mol/lit)

E = 0.368 - 0.069pH (as =0.44gram mol/li)

E = 0.368 - 0.069pH (as =0.7gram mol/lit)

40. S406-- +2e- 4-> 2S203-- (Reaction and Equation 40 ref 97)

E = 0.033 - 0.0295 log (as)

E= 0.053 (as =0.2gram mol/lit)

E= 0.050 (as =0.3gram mol/lit)

E = 0.0436 (as =0.44gram mol/lit)

E = 0.0375 (as =0.7gram mol/lit)

41. 2S03" + 6H+ +4e- 4-+ S203" + 3H20 (Reaction and Equation 41 ref 97)

E =0.676 - 0.0887pH + 0.0148 log (as)

E =0.665 - 0.0887pH (as =0.2gram mol/lit)

E =0.666 - 0.0887pH (as =0.3gram mol/lit)

E =0.668 - 0.0887pH (as =0.44gram mol/lit)

E =0.670- 0.0887pH (as =0.7gram mol/lit)

42. 2HS03" + 4H+ + 4e - H S203- + 3H20(Reaction and Equation 42 ref 97)

E =0.463 - 0.0591pH + 0.0148 log (as)

E =0.453 - 0.0591pH (a, =0.3gram mol/lit)

E =0.455 - 0.0591pH (as =0.3gram mol/lit)

E =0.46 - 0.0591pH (as =0.3gram mol/lit)

E =0.461 - 0.0591pH (as =0.3gram mol/lit)

71
43. 4HS03- + 8H+ + 6e S406-- + 6H20 (Reaction and Equation 43 ref 97)

E =0.606 - 0.0788pH + 0.0295 log (as)

E =0.58 - 0.0788pH (a, =0.2gram mol/lit)

E =0.59 - 0.0788pH (as =0.3gram mol/lit)

E =0.595 - 0.0788pH (as =0.44gram mol/lit)

E =0.601 - 0.0788pH (as =0.7gram mol/lit)

44. 4H2S03 + 4H+ + 6e - 4-4 S406- + 6H20(Reaction and Equation 44 ref 97)

E =0.533 - 0.039pH + 0.0295 log (as)

E =0.51 - 0.039pH (as =0.2gram mol/lit)

E =0.52 - 0.039pH (as =0.3gram mol/lit)

E =0.523 - 0.039pH (as =0.44gram mol/lit)

E =0.528 - 0.039pH (as =0.7gram mol/lit)

60. S + H++2e- 4-4 HS- (Reaction and Equation 60 ref 97)

E = -0.062-0.0295 pH -0.0295 log (as)

E = -0.041-0.0295 pH (as =0.2gram mol/lit)

E = -0.05 -0.029 pH (as=0.3gram mol/lit)

E = -0.051-0.0295 pH (as=0.44gram mol/lit)

E = -0.057-0.0295 pH (as =0.7gram mol/lit)

61. S + 2H+ +2e"4-4 H2S (Reaction and Equation 61 ref 97)

E =0.144 -0.0591 pH -0.0295 log (as)

E =0.16 -0.0591 pH (as =0.2gram mol/lit)

E =0.16 -0.0591 pH (as =0.3gram mol/lit)

E =0.154 -0.0591 pH (as=0.44gram mol/lit)

E =0.154 -0.0591 pH (as =0.7gram mol/lit)

72
 63. S203- + 6H+ +4e• +4 2S + 3H20 (Reaction and Equation 63 ref 97)

E =0.494 - 0.0887pH + 0.0148 log (as)

E =0.48 - 0.089pH (as =0.2gram mol/lit)

E =0.483 - 0.089pH (as =0.3gram mol/lit)

E =0.488 - 0.089pH (as =0.44gram mol/lit)

E =0.492 - 0.089pH (as =0.7gram mol/lit)

64. S406- + 12H+ +10e- 4-- 4S + 6H20 (Reaction and Equation 64 ref 97)

E =0.401 - 0.0709pH + 0.0059 log (as)

E =0.395 - 0.071pH (as =0.2gram mol/lit)

E =0.397 - 0.071pH (as =0.3gram mol/lit)

E =0.398 - 0.071pH (as =0.44gram mol/lit)

E =0.40 - 0.071pH (as =0.7gram mol/lit)

Using above equations, the E-pH diagram constructed for S-H20 system having pH

14 and as= 0.2 and 0.7 gram mol per lit. Corresponding to Na2S =20 gpl and Na2S2O3 =

0 and 35 gpl, is shown in (Fig -3.1, 3.2).

3.2.3. Redox Reactions Equations for Fe-S-H20 system :

E-pH diagrams for this system shows which corrosion products are likely to form when

steel is exposed to liquors having various sulfur species. Since some of these corrosion

products will be protective type, therefore, under the circumstances when such

corrosion products form, the steel will show corrosion resistance. Accordingly, one can

predict from these diagrams as to for which conditions of cooking liquor, steel will resist

73
the corrosion attack or it will be attacked through general corrosion or localized

corrosion. In other words, one can predict the corrosivity of the cooking liquor

depending upon its composition and temperature. Activity of sulpher species is

considered as in S-H20 system and for Fe', Fe' is considered 10'6 gram ion per lit.

Activity of iron compounds is considered 1. Following equations formed on above

considered activities.

1.Fe' + 2e- 4-, Fe (Reaction and Equation 1 ref 117)

E = -0.474 +0.029 log (Fe++)

E = -0.65

Irrespective of activity of sulpher specie

2. FeS2 + 4H+ + 2e - 4-+ Fe++ +2H2S (Reaction and Equation 2 ref 117)

E = -0.066 - 0.118pH - 0.029 log (Fe++) - 0.059 log (H2S)

E = 0.149 - 0.118pH (as =0.2gram mol/lit)

E = 0.14 - 0.118pH (as =0.3gram mol/lit)

E = 0.13 - 0.118pH (as =0.44gram mol/lit)

E = 0.117 - 0.118pH (as =0.7gram mol/lit)

3. FeS1.14 + 2.280H++0.280e Fe++ +1.14H2S (Reaction and Equation 3 ref 117)

E = -0.056 - 0.481pH - 0.221 log (Fe++) - 0.241log (H2S)

E= 1.38 - 0.481pH (a5 =0.2gram mol/lit)

E = 1.34 - 0.481pH (as =0.3gram mol/lit)

E = 1.3 - 0.481pH (a5=0.44gram mol/lit)

E = 1.25 - 0.481pH (as =0.7gram mol/lit)

74
4. FeS1.14 + 2.280H+ + 2.280e - 4-4 Fe+ 1.14H2S (Reaction and Equation 4ref 117)

E = -0.409 - 0.059pH - 0.029 log (H2S)

E = -0.389 - 0.059pH (as =0.2gram mol/lit)

E = -0.39 - 0.059pH (a, =0.3gram mol/lit)

E = -0.398 - 0.059pH (as=0.44gram mol/lit)

E = -0.404 - 0.059pH (as =0.7gram mol/lit)

5. FeStia + 1.140H+ + 2.280e - Fe +1.14HS- (Reaction and Equation5ref 117)

E = -0.616 - 0.029pH - 0.029 log (HS")

E = -0.595 - 0.029pH (as =0.2gram mol/lit)

E = -0.6 - 0.029pH (as =0.3gram mol/lit)

E = -0.605 - 0.029pH (as=0.44gram mol/lit)

E = -0.611 - 0.029pH (as=0.7gram mol/lit)

6. FeS2 +1.720H++1.720e- 4-4 FeS, 14 0.860H2 S (ReactionandEquation6 ref117)

E = -0.085 - 0.059pH - 0.029 log (H2S)

E = -0.065 - 0.059pH (as=0.2gram mol/lit)

E = -0.07 - 0.059pH (as=0.3gram mol/lit)

E = -0.0745 - 0.059pH (as=0.44gram mol/lit)

E = -0.08 - 0.059pH (as=0.7gram mol/lit)

7. FeS2 + 0.860H+ + 1.720e-4-4 FeS1.14 + 0.860HS"(ReactionandEquation7 ref117)

E = -0.292 - 0.029pH - 0.029 log (HS")

E = -0.271 - 0.029pH (as=0.2gram mol/lit)

E = -0.28 - 0.029pH (as=0.3gram mol/lit)

E = -0.28 - 0.029pH (as=0.44gram mol/lit)

E = -0.287 - 0.029pH (as=0.7gram mol/lit)

75
8. Fe++ +2S +2e - 4- FeS2 (Reaction and Equation 8 ref117)

E = 0.355 + 0.029 log (Fe++)

E = 0.335 (as=0.2gram mol/lit)

E = 0.33 (as=0.3gram mol/lit)

E = 0.181 (as=0.44gram mol/lit)

E = 0.180 (as=0.7gram mol/lit)

9.2Fe++ + S406- + 12H+ + 14e - -- 2FeS2 + 6H20 (Reaction and Equation 9 ref117)

E = 0.384 - 0.051pH + 0.008 log (Fe++) +0.004 log (S406-)

E = 0.333 - 0.051pH (as=0.2gram mol/lit)

E = 0.333 - 0.051pH (as=0.3gram mol/lit)

E = 0.335 - 0.051pH (as=0.44gram mol/lit)

E = 0.335 - 0.051pH (a, =0.7gram mol/lit)

10. yFe203+ S405- +18H+ +16e- 4-4 2FeS2+ 9H20(Reaction andEquation10 ref117)

E = 0.44 - 0.066pH + 0.0037 log (S406-)

E = 0.437 - 0.066pH (a, =0.2gram mol/lit)

E = 0.438 - 0.066pH (as =0.3gram mol/lit)

E = 0.44 - 0.066pH (as=0.44gram mol/lit)

E = 0.44 - 0.066pH (as =0.7gram mol/lit)

11.Fe304+3S203-+26H++20e"4-3FeS2+13H20(ReactionandEquation11ref117)

E = 0.506 - 0.077pH + 0.0088 log (S203-)

E = 0.499 - 0.077pH (as=0.2gram mol/lit)

E = 0.499 - 0.077pH (as=0.3gram mol/lit)

E = 0.503 - 0.077pH (as=0.44gram mol/lit)

E = 0.504 - 0.077pH (as=0.7gram mol/lit)

76
12.yFe203+ 2S203-- +18H+ + 14e- 4-42FeS2+9H20(Reaction and Equation12ref117)

E = 0.5 - 0.076pH + 0.008 log (S203-)

E = 0.494 - 0.076pH (as=0.2gram mol/lit)

E = 0.49 - 0.076pH (as=0.3gram mol/lit)

E = 0.497 - 0.076pH (as=0.44gram mol/lit)

E = 0.498 - 0.076pH (as=0.7gram mol/lit)

13. y Fe203 +6H+ +2e- 4-4 2Fe++ + 3H20 (Reaction andEquation13ref117)

E = 0.83 - 0.177pH - 0.059 log (Fe++)

E = 1.184 - 0.177pH (as=0.2gram mol/lit)

E = 1.18 - 0.177pH (as=0.3gram mol/lit)

E =1.18 - 0.177pH (as=0.44gram mol/lit)

. E = 1.18 - 0.177pH (as=0.7gram malt)

14.FeS0,943 +1.886H+ +1.886e- 4-- Fe + 0.943H2S (ReactionandEquation14ref117)

E = -0.368 - 0.059pH - 0.029 log (H2S)

E = -0.347 - 0.059pH (as=0.2gram mol/lit)

E = -0.353 - 0.059pH (as=0.3gram mol/lit)

E = -0.36 - 0.059pH (as=0.44gram mol/lit)

E = -0.363 - 0.059pH (as=0.7gram mol/lit)

15. FeS0943 + 0.943H+ +1.886e-4-4 Fe+0.943HS- (Reaction andEquation15ref117)

E = -0.575 - 0.029pH - 0.029 log (HS-)

E = -0.554 - 0.029pH (as =0.2gram mol/lit)

E = -0.556 - 0.029pH (as =0.3gram mol/lit)

E = -0.56 - 0.029pH (as=0.44gram mol/lit)

E = -0.57 - 0.029pH (as =0.7gram mol/lit)

77
16.Fe+++0.943H2S + 0.114e" H FeSo 943+1.886W(ReactionandEquationl6ref117)

E = -2.234 + 0.978pH +0.5181og (Fe++) + 0.489 log (H2S)

E = -5.68 + 0.978pH (as =0.2gram mol/lit)

E = -5.6 + 0.978pH (as =0.3gram mol/lit)

E = -5.52 + 0.978pH (as=0.44gram mol/lit)

E = -5.42 + 0.978pH (as =0.7gram mol/lit)

17. FeS2+ 2.114H+ +2.114e+-FeSo 9431-1.06H2S (ReactionandEquation17ref117)

E = -0.183 - 0.059pH - 0.029 log (H2S)

E = -0.163 - 0.059pH (as =0.2gram mol/lit)

E = -0.17 - 0.059pH (as =0.3gram mol/lit)

E = -0.172 - 0.059pH (as =0.44gram mol/lit)

E = -0.178 - 0.059pH (as =0.7gram mol/lit)

18. FeS2+1.057H++2.114e- FeSo.943+1.057HS (ReactionandEquation18ref117)

E = -0.389 - 0.029pH - 0.029 log (HS")

E = -0.368 - 0.029pH (as=0.2gram mol/lit)

E = -0.374 - 0.029pH (as=0.3gram mol/lit)

E = -0.38 - 0.029pH (as=0.44gram mol/lit)

E = -0.384 - 0.029pH (as=0.7gram mol/lit)

19. 3y Fe2O3 +2H+ +2e- 4-4 2Fe3O4 + H2O (Reaction and Equationl9 ref117)

E = 0.359 - 0.059pH (as =0.2gram mol/lit)

E = 0.359 - 0.059pH (as =0.3gram mol/lit)

E = 0.359 - 0.059pH (as =0.44gram mol/lit)

E = 0.359 - 0.059pH (as =0.7gram mol/lit)

78
20.2Fe304+3S406-+52H++46e-i-,6FeS2+26H20 (Reaction and Equation20 ref117)

E = 0.444 - 0.067pH + 0.0038 log (S406-)

E = 0.441 - 0.067pH (as =0.2gram mol/lit)

E = 0.442 - 0.067pH (as =0.3gram mol/lit)

E = 0.442 - 0.067pH (as =0.44gram mol/lit)

E = 0.443 - 0.067pH (as =0.7gram mol/lit)

21. Fe++ +S203- +6H+ + 6e - 4-FeS2 +3H20 (Reaction and Equation2l ref117)

E = 0.445 - 0.059pH + 0.0098 log (Fe++) +0.0098 log (S203-)

E = 0.379 - 0.059pH (a, =0.7gram mol/lit)

E = 0.38 - 0.059pH (a5 =0.7gram mol/lit)

E = 0.381 - 0.059pH (as =0.7gram mol/lit)

E = 0.384 - 0.059pH (as =0.7gram mol/lit)

22. FeS + 2H+ + 2e - H Fe + H2S (Reaction and Equation 22 ref117)

E = -0.364 - 0.059pH (as =0.2gram mol/lit)

E = -0.37 - 0.059pH (as =0.3gram mol/lit)

E = -0.373 - 0.059pH (as =0.44gram mol/lit)

E = -0.379 - 0.059pH (as =0.7gram mol/lit)

23. FeS + H+ + 2e - 4-4 Fe +HS' (Reaction and Equation23 ref117)

E = -0.59 - 0.029pH - 0.029 log (HS-)

E = -0.569 - 0.029pH (as =0.2gram mol/lit)

E = -0.574 - 0.029pH (as =0.3gram mol/lit)

E = -0.58 - 0.029pH (as =0.44gram mol/lit)

E = -0.585 - 0.029pH (as =0.7gram mol/lit)

79
24. FeS + 2H+ 4-+ Fe++ +H2S (Reaction and Equation 24 ref117)

log (Fe++) = 3.071 - 2pH - log (H2S)

pH = 4.88 (as =0.2gram mol/lit)

pH = 4.86 (as =0.3gram mol/lit)

pH = 4.71 (a, =0.44gram mol/lit)

pH = 4.61 (a, =0.7gram mol/lit)

25. FeS2 + 2H+ + 2e - H FeS +H2S (Reaction and Equation 25 ref117)

E = -0.156 - 0.059pH - 0.029 log (H2S)

E = -0.135 - 0.059pH (a, =0.2gram mol/lit)

E = -0.141 - 0.059pH (as =0.3gram mol/lit)

E = -0.145 - 0.059pH (as =0.44gram mol/lit)

E = -0.151 - 0.059pH (as =0.7gram mol/lit)

26. FeS2 + H+ + 2e - H FeS +HS" (Reaction and Equation 26 ref117)

E = -0.363 - 0.029pH 0.029 log (HS")

E = -0.343 - 0.029pH (as =0.2gram mol/lit)

E = -0.35 - 0.029pH (as =0.3gram mol/lit)

E = -0.352 - 0.029pH (as =0.44gram mol/lit)

E = -0.358 - 0.029pH (a, =0.7gram mol/lit)

27. Fe304 +8H+ +2e- 4- 3Fe++ + 4H20 (Reaction and Equation 27 ref117)

E = 1.066 - 0.236pH -0.089 log (Fe')

E = 1.6 - 0.236pH (a, =0.2gram mol/lit)

E = 1.6 - 0.236pH (as =0.3gram mol/lit)

E = 1.6 - 0.236pH (as =0.44gram mol/lit)

E = 1.6 - 0.236pH (as =0.7gram mol/lit)

80
28. Fe+++ +e - 4-+ Fe++ (Reaction and Equation 28 ref117)

E = 0.769 +0.059 log (Fe+++) - 0.059 log (Fe++)

E = 0.769 (as =0.2gram mol/lit)

E = 0.769 (a, =0.3gram mol/lit)

E = 0.769 (as =0.44gram mol/lit)

E = 0.769 (as =0.7gram mol/lit)

29. yFe2O3 +6H+ 4-0 2Fe+++ + 3H20 (Reaction and Equation 29 ref117)

pH = 2.3 (as =0.2gram mol/lit)

pH = 2.3 (as =0.3gram mol/lit)

pH = 2.3 (as =0.44gram mol/lit)

pH = 2.3 (as =0.7gram mol/lit)

30. HFe02+ 3H++ 2e" H Fe + 2H20 (Reaction and Equation 30 ref117)

E =0.396-0.088 pH +0.029 log (HFeO2)

E =0.22 -0.088 pH (as =0.2gram mol/lit)

E =0.22 -0.088 pH (a, =0.3gram mol/lit)

E =0.22 -0.088 pH (as =0.44gram mol/lit)

E =0.22 -0.088 pH (as =0.7gram mol/lit)

31. HFe02+ HS-+ 2H+ 4- FeS + H2O (Reaction and Equation 31 ref117)

log (HFe02) = -33.367 + 2pH - log (HS")

pH = 13.3 (as =0.2gram mol/lit)

pH = 13.42 (a, =0.3gram mol/lit)

pH = 13.5 (as =0.44gram mol/lit)

pH = 13.6 (as =0.7gram mol/lit)

81
32. Fe304 + 3HS" +5H+ +2e- 4-4 3FeS + 4H20 (Reaction and Equation 32 ref117)

E = 1.114 - 0.147pH + 0.088 log (HS-)

E = 1.052 - 0.147pH (as =0.2gram mol/lit)

E = 1.07 - 0.147pH (as =0.3gram mol/lit)

E = 1.08 - 0.147pH (as =0.44gram mol/lit)

E = 1.1 - 0.147pH (as =0.7gram mol/lit)

33.FeS1.14+2H20 +0.28e - -+HFe02" + 1.14HS" (Reaction and Equation 33ref117)

E = -0.575 - 0.029pH - 0.029 log (HS") + 1.86H+

E = -6.41 +0.391pH (as=0.2gram mol/lit)

E = -6.46 +0.391pH (as=0.3gram mol/lit)

E = -6.5 +0.391pH (as=0.44grammol/lit)

E = -6.54 +0.391pH (as=0.2gram mol/lit)

34Fe304+3.42HS-+4.58H++1.163FeS1 14+4H20 (ReactionandEquation34ref117)

E = 2.498 - 0.232pH + 0.1741og (HS")

E = 2.376 - 0.232pH (as=0.2grammol/lit)

E = 2.4- 0.232pH (as=0.3gram mol/lit)

E = 2.43- 0.232pH (as=0.44gram mol/lit)

E = 2.47- 0.232pH (as=0.7gram mol/lit)

35. Fe304 + 2H20+2e- 4-4 3 HFe02" + H+ (Reaction and Equation 35 ref117)

E = -1.846 +0.029pH 0.088 log (HFe02-)

E = -1.32 +0.029pH (as=0.2grammol/lit)

E = -1.32 +0.029pH (as=0.3grammol/lit)

E = -1.32 +0.029pH (as=0.44grammol/lit)

E = -1.32 +0.029pH (as=0.7grammol/lit

82
 36. yFe203 +H20 +e- 4-42.HFe02- (Reaction and Equation 36 ref117)

E = -0.556- 0.059 log (HFe02)

E = -0.556 (as=0.2grammol/lit)

E = -0.556 (as=0.3grammol/lit)

E = -0.556 (as=0.44grammol/lit)

E = -0.556 (as=0.7grammol/lit)

37. FeS2 + 4H20 + 4e- 4-Fe304+6HS" +2H+ (Reaction and Equation 37 ref117)

E = -1.101 + 0.029 pH - 0.088 log (HS)

E = -1.039 + 0.029 pH (as=0.2grammol/lit)

E = -1.05 + 0.029 pH (as=0.3grammol/lit)

E = -1.07 + 0.029 pH (as=0.44grammol/lit)

E = -1.08 + 0.029 pH (as=0.7grammol/lit)

38. FeS2 + 2H20 + 2e• HFe02" +2HS- +H+ (Reaction and Equation 38 ref117)

E = -1.349 + 0.029 pH - 0.029 log (HFe02) -0.059 log (HS-)

E = -1.349 + 0.029 pH (as=0.2grammol/lit)

E = -1.145 + 0.029 pH (as=0.3grammol/lit)

E = -1.15 + 0.029 pH (as=0.44grammol/lit)

E = -1.166 + 0.029 pH (as=0.7grammol/lit)

39. Fe++ +2HS03" +10H+ + 10e - = FeS2 + 6H20 (Reaction and Equation 39 ref117)

E = 0.452-0.059pH + 0.0059 log (Fe++) +0.012 log HS03)

E = 0.408 - 0.059pH (as=0.2grammol/lit)

E = 0.408 - 0.059pH (as=0.3grammol/lit)

E =0.410 - 0.059pH (as=0.44grammol/lit)

E = 0.414 - 0.059pH (as=0.7grammol/lit)

83
Using above equations, the E-pH diagram constructed for Fe-S-H20 system having pH

up to -14 and as= 0.2 and 0.7 gram mol per lit corresponding to Na2S= 20 gpl,

Na2S203= 0 and 35gp1, is shown in (Fig - 3.3, 3.4)

3.3. Corrosion test in alkaline sulfide solution :

Long term immersion corrosion test was conducted for duration of six months in alkaline

sulphide solutions under anaerobic conditions having 20% sulfidity. The materials

considered for this test were: ms (mild steel), austenitic stainless steels 304L, 316L and

duplex stainless steel 2205.

3.3.1. Material Selection :

Carbon steel has been the principal material of construction for kraft batch/ continuous

digesters since last many decades. Change in processing conditions during last several

years has seen increase in corrosion rates of digesters up to - 100 mpy in new steel

digesters. Accordingly digesters are provided with corrosion allowance. Alternatively

they have been formed of corrosion resistant solid materials/steel e.g. low alloy steel

(Cr-0.8%, Mo-0.5%, Si-0.25%), SS-304L, 316L, 317L, 321, 347, duplex 2205,

superduplex (higher Cr than duplex SS), Inconel 625, ferritic stainless etc. or C-steel

digesters have been provided with protective layer of the above mentioned resistant

materials by cladding/ weld overlaying/ thermal spraying. In very few cases, low alloy

steel, ferritic SS and Inconel have been used while duplex SS is a recent addition.

Accordingly mild steel, austenitic grade 304L, 316L and duplex grade 2205 stainless

84
steels have been selected as the test materials. Composition of these tested steels has

been given in, Table -2.1.

3.3.2. Test Liquor :

Since cooking liquors in different mills are likely to differ in terms of the relative amount

of S2", S2032- , Sx2" and CI" , even though having same pH and sulfidity, it was decided to

prepare test liquors having varying amount of these species. Accordingly, following

composition of liquors were planned on the basis of amount of different species

observed in different mills

NaOH 80 gpl

Na2S 20 — 34 gpl (considering 20% - 30% sulfidity level)

Na2S2O3 5 - 35 gpl

Sx2. 2 — 20 gpl

Cr 1.21 gpl (corresponding to 2 gpl NaCI)

The preparation of liquor with varying Sx2- content has posed biggest problem. Several

methods, referred from literature, Barker(16), Dorris et al (38) , Greene et al (55),

Hassler (59), Sanyer et al (107), have been attempted but it has not been possible to

obtain amount of Sx2" by more than 2.5 gpl (as free sulfur) although amount of sulfur

added was — 10 gpl. It seems that requirement for efficient conversion of free sulfur into

polysulfide are not being met, and most of sulfur is getting converted mainly into S2032".

Efforts are being made to improve the equipment for generating polysulfide. Meanwhile,

85
the solutions having 80 gpl NaOH, 20 gpl Na2S and varying amount of S2032" (5 to 35

gpl) and Cr (up to 1.2 gpl) were prepared for the long term immersion test. Composition

and variation of various test solutions is given in Table -3.4

3.3.3. Long term immersion test :

Long term immersion test in sulfide solutions was undertaken to understand the effect of

varying S2032" in the presence/absence of Cr in sulfide solutions (pH - 14), having

-20% sulfidity, on corrosion attack on test materials. The test materials, including

autogenously welded part, of stainless steels 304L, 316L and 2205 of size 6cmx6cm

and thickness varying between 2-4 mm along with mild steel of 4cmx4cm and thickness

5mm were used. The test materials were cleaned using emery paper from coarse to fine

up to 800 grit on a polishing machine. The coupons were fitted with cerrated washers

(photo. 3.1a) to know the affect of crevice corrosion. This assembly was immersed in

the test solution for the weight loss test (photo3.1 b). The test solutions had to be

covered with a layer of paraffin oil to avoid contact of atmospheric oxygen with the

solution. The later was found to change the solutions' composition by oxidizing Na2S to

Na2S2O3. Hence these solutions are prepared in nitrogenous atmosphere and the tests

are being carried under anaerobic conditions. This test was carried for duration of 6

months. Since the beginning of the test, parameters e.g. pH, sulfidity, S2032" and CI"

were monitored weekly by Scan methods (108,109).

86
3.3.4. Evaluation of Corrosion Attack :

The corroded coupons, after taking out from the test solutions were cleaned initially

mechanically and later chemically using solution of 50 gpl SnCl2 +20 gpl SbCI3 in

concentrated HCI, as per ASTM guidelines (98). The corroded cleaned test samples

were also analyzed for any localized attack namely pitting, crevice corrosion and weld

related attacks using metallurgical microscope (Reichert Jung, USA). The results of the

analysis are given in Table -3.5

3.4. Results and Discussion :

On the basis of E-pH diagrams and long term immersion corrosion test following results

and discussion are given.

3.4.1. S-H20 System :

For S-H20 System (Fig-3.1,3.2), the diagrams show that within the pH range likely to be

observed for the cooking liquor, indicates that sulfur species present in the solution

could be HS-, to some extent S2", S2032- and 5032" depending upon the potential, which

will in turn be governed by the nature of material exposed, mild steels or stainless

steels. Measurement of redox potential of 304L and 2205 in pH — 14 solution having

sulfidity, as considered in drawing E-pH diagram, shows that sulphur species near 304L

electrode will be mainly S032- and S2032- while those near the 2205 electrode will be

mainly HS".

87
3.4.2. Fe-S-H20 system

Fe-S-H20 diagrams (Fig-3.3, 3.4) were constructed considering above sulfur species

and activities. Thus if the liquor consists of S2032", different corrosion products likely to

form in the pH range of interest (pH - 12-14) are mackinawite, troilite, pyrrhotite and

pyrite. Of these, the first two products are non-protective type while other two are

protective type. However, the region of protection also indicates the possibility of

localized corrosion if the protective layer breaks. This usually happens at higher

potentials which one can observe, if the amount of S2032- increases. It indicates that if

the amount of S2032' is higher, the steel is likely to experience localized corrosion.

Accordingly, E-pH diagram Of Fe-S-H20 shows that corrosion products forming on 304L

will be pyrite or iron oxide and on 2205 it could be pyrrhotite/troilite/mackinawite

depending upon the potential. Except mackinawite and troilite, other sulfides /oxide

provide protection. This could be the reason for observing lesser corrosion rates in

these stainless steels.

Since these aspects are dependent on the amount of sulfur species and the

temperature, it is necessary to draw these diagrams at higher sulfidity values and higher

temperature. Further, one also has to consider polysulfides Sx2" as one of the sulfur

species while drawing these E-pH diagrams. This will be useful for digester operation

because the digester material experiences temperature varying from room temperature

to about 180°C. Further, above 120°C, polysulfides are not stable; one has to consider

this aspect also while drawing these diagrams for temperatures > 120°C.

88
3.4.3. Long Term Immersion test

A visual examination of the corroded specimens, after cleaning, shows no observable

pitting attack but crevice attack is visible in case of mild steel samples only but not

measurable. The extent of uniform attack, assessed from corrosion rate, was obtained

on the basis of weight loss observed by the samples during the six months test.

Corrosion rates experienced by different steels are given in Table- 3.5 One observes

that mild steel experiences maximum corrosion. Corrosion rates on stainless steels are

negligible. Only mild steel shows crevice attack. A visual examination show the crevice

attack to be higher in case of steel samples immersed in solutions having chloride in

comparison to those without chloride.

Comparison of corrosion rate on ms shows (a) increase in S2032- concentration

increases corrosion rate (Table -3.5). (b) There appears a sudden increase in corrosion

rate when concentration of S2032" increases from 25 to 35 gpl. (c) Inclusion of CI' in the

solution also increases corrosion rate in the solution having corresponding amount of

S2032- . Corrosion rates on stainless steels are negligibly small and the variation

between their values basically reflects the experimental error, hence there does not

appear any definite correlation between corrosion rate experienced by stainless steels

and the composition of the solutions.

Corrosion of steel in these solutions is the consequence of following oxidation and

reduction reactions:

Fe H Fe2+ + 2e" (oxidation reaction) - (eq.1 of Fe-S-H20)

89
S2032" + 8 H4 + 8 e" 4-* 2 HS' + 3 H2O (reduction reaction)- (eq.2lof S-H20)

Fe24 + 0.943 HS" + 0.114 e" FeSo.943 + 0.943 H4 ( reduction reaction) - (iii)

Since the conditions are anaerobic, reduction of 02 can not be considered here. Thus

as the steel is brought in contact with test solutions, the pH of the solution should

change to less acidic values because of the reduction reaction (eq.2lof S-H20) while

pH will change to more acidic values due to reduction reaction (iii), as the corrosion of

steel proceeds. The monitoring of pH, during the test, although does not show much

change but it is definitely decreased of pH in all the cases. This indicates the rate of

reaction (iii) to be more than that of reaction (eq.21 of S-H20) which thereby results into

net decrease in pH of the solution. At this stage, one should look at the possibility of

other reduction reactions also, so as to get a better qualitative idea on the rates of the

different reactions. Reaction (iii) results into formation of iron sulfide (mackinawite)

which is highly soluble type, is non-protective type and is dark in colour. This is

corroborated by the findings of the test that (a) the solutions turns dark in colour after

steel samples have been put in them for some time (b) on cleaning the corroded

samples by acidic solution, one feels the smell of H2S (c) corrosion rates are high in

case of mild steel samples.

The dependence of corrosion rate on the amount of 52032' can be understood by

considering the variation of redox potential for reduction reaction (eq.21 of S-H20) given

below

E = E0 - 0.059 pH + 0.007 log (S2032") - 0.014 log (HS") (eq.21 S-H20)

90
E becomes more anodic on increasing the amount of S2032-. On the basis of mixed

potential theory, as the value of E increases, the cathodic polarization line showing

S2032' / HS" cuts the anodic polarization curve of steel through activation polarization

part, then the passivation region and lastly the transpassive region. This results into

observation of first increase of corrosion current, followed by its decrease and lastly a

sudden increase in its value. On introducing the CI" in the solution, the anodic

polarization curve seems to shift towards higher currents and decreased value of

transpassive potential (Fig.-3.5), thereby showing the increase in corrosion rates in the

case of solutions having C. These suggestions need to be checked by recording

electrochemical polarization curves for this system, which forms part of the future work.

91
 Table — 3.1

Composition of Cooking Liquor (gpl)

Chemicals U. S. Mills Indian Mills

NaOH 44.7 65
Na2S 28 15
2-
S 1.8 2.4
Na2S2O3 6 2.3
Na2CO3 25 25.33
Na2SO4 9.79 13.5
Na2SO3 1 1.79

Table - 3.2

Activity (in gram mol per liter) of Different Chemicals

Chemicals Concentration gram per liter)

Na2S 20 20 20 20
Na2S2O3 0 5 15 35
Total activity (gram mol per liter)
0.2 0.3 0.44 I 0.7

92
 Table - 3.3

Standard Chemical Potentials (p°) (Cal/mole) at 25°C

Chemical Species (p°) Cal/mole

H2O -56687
Fe+ -21880
Fe0H+ -65847
Fe (OH)2aq -107154
HFe03 -95089
+++
Fe -4130
Fe304 -243191
yFe203 -175500
H2Saq -6674
HS" 2860
S406 -248701
S203- -124899
S- 21958
H2S03 -128668
HS03 -126130
S03- -116299
FeS2 -38256
FeS -24368
FeS1.14 -29123
FeS0.943 -22300
Amorphous FeS -571258

93
 Table - 3.4

Variation of Chemicals (gpl) during Long Term Immersion Test

Solutions NaOH Na2S Na2S2O3 NaCI pH

1 80±0.3 19.8±0.25 5±0.3 0
2 80±0.21 19.8±0.2 15±0.21 0
3 80±0.42 19.8±0.22 25±0.21 0
4 80±0.46 19.8±0.2 35±0.3 0 13.6±0.21
5 80±0.27 19.7±0.23 5±0.23 2±0.01
6 80±0.51 19.7±0.3 15±0.22 2±0.01
7 80±0.44 19.8±0.2 . 25±0.3 2±0.01
8 80±0.34 19.8±0.3 35±0.3 2±0.01

Table- 3.5

Corrosion Rates (mils per year) of Steels in Alkaline Sulfide Liquor

Materials Soln.1 Soln.2 Soln.3 Soln.4 SoIn.5 Soln.6 Soln.7 Soln.8

ms 0.601 0.981 0.771 3.26 1.112 1.213 1.012 3.256
SS304L 0.003 0.003 0.004 N 0.001 0.001 0.008 N
SS316L N 0.002 0.002 N N 0.002 N N
2205 N 0.001 0.001 0.001 0.001 N 0.001 0.009

94
 (a)

(b)

Photo. 3.1.: LONG TERM IMMERSION TEST SPECIMEN

95
2.0 System at 26CC
activity of Sulpher=0.2 gram mole per lit

1_54

10
9

]-12S03 11S0-
3
SO
0.5 ----.44, 3

- .43

I 40
0- 63
61 41
E
VS
3 SS-304 L
NHB - 60
21 ... i 44.3riv
.., mv

-658mv (s2-sol)

-8/5mvj
HS - SS-2205

j 2

-1

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
pH

Fig. 3.1. E-pH diagram for S-H20 system, 4=0.2 gram mol per lit
96
2.0 Oc
S-I-120 System at 25
activity of sulpher=0.7 gram mol per lit.

1.5

1.0-

H2SC, H SO-
10

0.5 -
64
1_ 43
SOi
61
LL
41
SS 3041
60
s. -423mv
21 "- --1 .=533mv
HS -658mv
-825mv
(
SS 2205
S."
1
2

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 pH
pH

Fig. 3.2. E-pH diagram for S-H20 system, as=0.7gram mol per lit.
97
2.0- o
Fe-S-H20 system at 25
activity of Sulpher=0.2 grm mole per lit

1.5

29
S ++
1.0 Fe
IE
28

y-Fe20 3
0.5

0 FeiO4 /y--Fe,O3 •
pyrite
-2 3mv
I9
pyrrhotite 'Ai& -423mv
-----, ------- 583041
4.5- , 7 3mv
16 l7- - - --,--:- -.=--- -65Efiliv
7. :-. -- - -
----.
--,.._ .._ ------- .-------
1--- ,t4-...mackinawite -- -------:::
18 7 ::=7-7-- -----, SS2205
--=.
tCOI lit e -825mv
4 ----

-1.0- 5
Fe

4 5 6 7 10 11 12 13 lttaBed livop•c
0 1 2 pH

Fig. 3.3. E-pH diagram for Fe- S-H20 system, as=0.2 gram mol per lit.
98
 1
off

Fe-S-H20 system at 25° C

activity or suipher = 0.7 gram mol per lit.

Fe+ ++ 29
1.0
28

3.5
+ -I- 13 y-Fe20 3
Fe
\ •

0
Pyrite 19
Fer,0A / -FP003
t), =7, 40
Pyrrhotite jmv
0.5- e
Fe
17 -658my
4 mackinawite
-82 my
23
1.0-

.1.5-

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
pH

Fig. 3.4. E-pH diagram for Fe-S-H20 system, a$=0.7 gram mol per lit.

99
 Anodic polarization of iron

Log i

Fig.3.5. ANODIC/CATHODIC POLARIZATION CURVE

100
 Chapter : 4

In-Plant Corrosion test of Steels in Digester of Paper Mill

Contents : Page No.

4.1. Introduction 102

4.2 Details of in-plant test 104

4.2.1. Paper Mill and conditions in Digester 104

4.2.2. Materials 105

4.2.3 Exposure of Coupons 105

4.2.4. Evaluation of Corrosion Attack 106

4.3. Results and Analysis 106

4.4. Comparison with Other In-Plant Test 109

4.5. Material Performance 110

101
4.1. Introduction :

Extensive corrosion is experienced by the process equipment and machinery items in

different sections of paper mill. Digester house is one such section which is severely

affected by corrosion. Carbon steel kraft digesters generally gave good service life up to

1935. Since then some undetermined changes have been found to cut the life to as little

as 1-2 years. An extensive review by Wensley (141), about different aspects related to

corrosion in digesters and its control has appeared in 1996. Two cases of sudden failure

of digesters due to corrosion have been reported in past, Bennet et al (20), Pulp and

paper week (99). Interest about corrosion of digester can be gauged from reporting of

large number of articles dealing with mill survey, in - plant tests, in-situ corrosion

monitoring, inspection for digester etc. In the first ever reported mill survey, Essen (39),

on corrosion problems in sulfate pulp mills, increased corrosion was observed due to

presence of (i) sulfide in liquor and (ii) Si in digester steel. A mill questionnaire by

Peoples et al (95), found the corrosivity in kraft operations to have increased

considerably between 40's and 50's. Another survey by Clarke (32), observed that

-75% of the digesters were 28-48 years old. Approximately 73% of the digesters had

SS weld overlay at at-least some part of the digester. Mills with. higher sulfidity were

found to have higher corrosion. An inspection on corrosion in digester house, Flynn et al

(43), revealed uneven corrosion in digesters formed of 405 stainless alloys as lining

material in approximate 5 years. The cause of this type of attack was related to hot plate

boiling action. In yet another inspection, Hopper (63), corrosion in kraft digester was

observed to due to (i) high C and Si in killed steel (ii) circulation of gases and liquor

impinging on the walls of digester (iii) change in chemical concentration. Similarly, in —

102
plant tests have been conducted to investigate corrosion performance of the candidate

materials. Thus in first ever reported in-plant test by Huseby et al (64), done on mild

steel (ms) and ms-welds in sulfate mills showed (i) corrosion rate of ms varying from 28

to 138 mpy linearly with Si content, (ii) surface preparation and heat treatment affecting

the degree of attack (iii) galvanic coupling, for the purpose of protective lining, of SS 347

or inconel with ms does increase corrosion of ms significantly. In another in-plant test by

Troselious (126), C-steel and SS coupons were exposed to 6 kraft digesters. Corrosion

rate of C-steel was very high while that of SS was very low in all cases with no sign of

localized corrosion. Duplex SS showed least corrosion. Cause of increased corrosion

was found to be higher concentration of oxidizing chemicals e.g. thiosulfate and

polysulfide etc. Similar conclusion has been drawn in test reports (78,121), with regard

to the dependence of the corrosivity of liquor on its composition. It has been argued that

a higher concentration of polysulfides may show passivating effect. Addition of sulfur

was suggested as means of reducing corrosion. In yet another in-plant test, Delblanc et

al (37), corrosion rate for 304L and 316L have been measured at —0.02 mm/year.

With a view to enhance production of paper with better pulp quality and reduce

pollutants in their stream, the process of cooking of wood chips has undergone marked

changes. Thus digesters now operate at increasingly higher temperature and use

cooking liquors having higher sulfidity. These liquors also have higher concentration of

other sulfur compounds namely thiosulfate, polysulfide which along with increased

amount of CI" enhance corrosion attack on digester material. Accordingly, instance of

severe corrosion attack in the form of caustic cracking and higher metal loss assisted

with water, pitting and crevice corrosion have been reported inrecent years by Clarke

103
(32), Heikki (61), Pvt. Discussion (100), Rooks (106), Report (121), Tuthill (132),

Udayshankar (135), Wensely (142,143). In this changed scenario, it was thought

appropriate, to conduct an in-plant corrosion test for investigating the performance of

materials normally used in kraft digesters. Based on a report, Thorpe (124), on the

experiences of digesters fabricated of duplex Stainless steel, coupons of several newly

developed duplex steels were also considered for the present test. Incidentally, the

present reported test appears to be the first ever in-plant test performed in the digester

of mills in South/South East Asia,

4.2. Details of in-Plant test :

4.2.1. Paper Mill and conditions in Digester :

The in-plant test was done in the batch digester of a paper mill which uses 80% poplar

and 20% eucalyptus as raw material for making printing/writing and packaging grade

paper. The digester used in the in—plant study has a capacity of 85 m3 and it is

constructed of mild steel. The wood chips are filled in the digester and cooking liquor is

then charged keeping liquor to wood ratio as 1:2.8. Volume of cooking liquor inside the

digester is kept between 37 to 42 m 3. The cooking liquor consists of mainly NaOH (92

gpl as NaOH) and Na2S (22.4 gpl as NaOH) having pH —13.1. Maximum temperature

attained during the pulping process is 162°C and it operates at a pressure of 6.2

Kg/Cm2.

104
4.2.2. Materials :

The selection of materials for the in-plant test was done on the basis of their current

utilization and their possible applications in future for constructing the digester and

related allied machinery in pulp and paper industry. While mild steel have been used as

the basic material of construction, SS304L and 316L have been suggested for cladding

or weld overlaying the digester requiring refurbishment as a result of enhanced

corrosion attack. Of late, newly developed duplex Stainless steels have been suggested

to be the prospective material of construction for digesters by Thorpe (124), Tuthill

(132), Wensley (142) because of their better corrosion resistance not only against

localized attack but also against caustic stress corrosion cracking (an important factor in

digester corrosion). Consequently, following materials were considered for the in-plant

test : mild steel, austenitic SS 304L and 316L, duplex Stainless Steels 2205, SAF2304

and LDX. The stainless steel samples were supplied courtesy M/S Avesta AB, Sweden

along with their chemical analysis (Table -2.1) and mechanical properties (Table - 4.1).

Coupons of these materials were selected for the present test.

4.2.3. Exposure of Coupons :

For exposure in digester, duplicate coupons, including autogenously welded part, of

stainless steel of size 6cmx6cm and thickness varying between 2-4mm along with mild

steel coupon of 4cmx4cm and thickness 5mm were fixed in a rack formed of SS-316

rods and plates .The coupons were cleaned using emery paper from coarse to fine up

to 800 grit on a polishing machine .These cleaned and acetone degreased coupons

105
were weighed and their surface area was measured prior to putting for the test. The

coupons were mounted in the rack having spacers between them which also acted as

sites for initiating crevice corrosion (photograph 2.1) after this the test rack was welded

in digester near strainer (Fig.4.1). The rack was kept in this position for duration of six

months after which coupons were removed for the analysis of corrosion attack. During

this period, the pulping liquor was analyzed weekly for its chemical constituents

following SCAN procedure (108,109) and Dorris et al (38). The chemical analysis of

various chemicals found in pulping white liquor, on the basis of average values, is given

in Table - 4.2.

4.2.4. Evaluation of Corrosion Attack :

The corroded coupons (photograph 4.1), after removing them from the rack, were

cleaned initially mechanically and later chemically using solution of 50 gpl SnCl2 +20 gpl

SbCI3 in concentrated HCI, as per ASTM guidelines (98). The cleaned coupons were

also analyzed for any localized attack namely pitting, crevice corrosion and weld related

attacks using metallurgical microscope (Reichert Jung, USA) (photo graph 2.3).The

results of the analysis are given in Table - 4.3.

4.3. Results and Analysis :

Microstructures of the tested steels of base metal as well as welded part are shown in

(Fig. 4.2, 4.3). Microstructure of base metal of LDX, duplex stainless steel, shows that it

is a rolled structure. Rolling direction is in the horizontal direction. It shows two phases'

106
ferrite and austenite. Lighter part is probably ferrite whereas darker part is austenite.

Microstructure of SAF2304, base metal structure shows two phases' ferrite and

austenite. The welded part of this steel shows absence of any rolling direction. It shows

two phases and a typical weld metal. Most of the area has acicular structure. Some

areas are free from acicular ties. Acicular plates are in the direction of heat flow. This is

a cast metal structure. The microstructure of 2205, base metal structure shows that it is

a rolled structure and have elongated grains. It consist ferrite and austenite phase.

Welded part structure of 2205 shows that directionality is gone due to rolling. Long

needle like ferrite is visible in austenite phase. This is typical cast structure. In middle

portion equiaxed ferrite is also visible. The base metal structure of 316L, austenite

stainless steel shows that it consist of single phase. At grain boundaries carbide is

precipitated, thick boundary grains are elongated in the rolling direction. Rolling

direction is horizontal. Welded structure of 316L shows that it has acicular, coarse

structure. The microstructure of 304L, base metal structure shows that it is a single

phase structure. It shows austenite grains. Twins are also visible. Welded part of this

steel shows that it is a cast structure. Structure is refined. Absence of twins across the

grains and some carbide are visible in the grains. Cast structure is aligned in one heat

flow direction. The microstructure of mild steel shows that it is a two phase structure

black portion is pearlite whereas white part is ferrite. Grains are not visible clearly.

Chemically analyzed pulping liquor of the mill has a sulfidity of -19%. This is the sulfidity

usually observed in Indian mills. However, it is much lesser than that observed in mills

of USA, Canada and Scandinavia etc. (-40% or so). Polysulfide and thiosulfate content

is also lesser in the mill under report. Higher sulfidity, polysulfides and thiosulfates have

107
been indicated to be the factors responsible for higher corrosivity of the cooking liquor.

The corroded coupons show uniform corrosion. Pitting is observed significantly in some

cases while in others no visible attack is observed .Crevice corrosion is also observed

on the coupons. A comparison of corrosion attack on different materials indicates

uniform corrosion of lesser degree even in case of mild steel Table - 4.3. The degree of

pitting attack in case of 304L and 316L is within the limit of acceptability, Singh (113),

for a material of construction.

Maximum corrosion rate is experienced by mild steel followed by 304L, 316L and

duplex stainless steels. Thus mild steel show least resistance from the standpoint of

uniform corrosion. Duplex stainless steels show lesser corrosion rate in comparison to

the austenitic stainless steels, in accordance with earlier observation by Troselious et at

(126). Their better resistance, in digester liquor, can be attributed to the higher amount

of Cr and N in all the three of them 2205, SAF2304, LDX as compared to 304L and

316L. Whereas Cr provides protection against corrosion by forming stable Cr(OH)3 layer

at higher pH, Mo has not been considered for imparting corrosion resistance since it

dissolves as Mo042- at these pH, Andreasson (4), Normally resistance against corrosion

attack (including pitting), in acidic chloride environments is estimated on the basis of

pitting resistance equivalent number (PRE), Garner (46). It is, however, not applicable

and may give misleading result if applied to alkaline environments of the digesters,

Tuthill (133).

No non uniform corrosion is observable on mild steel samples. Pitting is observed in

case of 304L and 316L whereas the duplex stainless steels do not show any visible

attack. 304L is observed to be lesser resistant against pitting in comparison to 316L. As

108
indicated in above paragraph, for alkaline pH as in digester, Cr and N in SS appear to

be more important than Mo in providing the corrosion resistance. Probably this may

result into development of duplex stainless steels, without Mo, having equivalent

mechanical properties and resistance against localized corrosion. Such steels are also

likely to be cost effective. It may be noted here that higher proof strength, comparable

ductility and better resistance against localized corrosion and cracking (due to lesser Ni

content) of duplex Stainless steels in comparison to 316L is slowly but surely turning

duplex stainless steels as the preferable material in comparison to the conventional

316L in case of digesters, Thorpe (124).

4.4. Comparison with Other In-Plant Test :

Findings of the present in-plant test could be compared with those of Swedish test,

Troselious et al (126), only because the other test relate to different aspects of material

performance, Huseby et al (64), and third test by Delblanc et al (37), is related to

continuous digester. Comparisons of the results reveal the following. In general, the

Swedish mills (having a sulfidity of -40%) show a higher corrosion rate of mild steels

(1.7-5.9 gm/m2 .cook with an average of 3.3 gm/m2 cook). The amount of silicon in the

tested mild steel varies between 0.06 - 0.1 %. In the present test, mild steel shows

lesser corrosion rate (-0.74 gm/m2.cook, considering - 500 cooks in the test duration of

6 months). This could be due to lesser Si content (-0.4%) in the mild steel and less

(-19%) sulfidity in the digester liquor. Both these factors have been suggested to affect

corrosion rate in the manner as observed here, Troselious et al (126). Lesser sulfidity

probably is also responsible for lower corrosion rates in case of stainless steels as

109
compared to those in Swedish mill. Unlike the case of Swedish mill, mild steel does not

show non uniform attack. Pitting is observed on SS-304L (max. pit depth - 95 pm and

average pit depth - 55 pm) and 316L (max. - 60 pm and average 52 pm) coupons

while other coupons showed no visible pitting. The steel coupons do not show any

crevice attack. Non- observance of crevice attack could be due to highly alkaline nature

of the digester liquor.

4.5. Material Performance :

An overall view of the corrosion attack indicates that all the materials, including mild

steel, tested have sufficient corrosion resistance in the tested media. However, since

the liquor composition is likely to change in future so as to have higher sulfidity,

thiosulfate and polysulfide content because of advantages associated with high sulfide

pulping, it is likely that mild steel will no more be considered suitable and one may have

to opt for duplex stainless steels. This aspect needs to be checked in laboratory

prepared solutions using long term immersion and electrochemical tests on various

steels. Secondly, the part of digester that is affected most by corrosion reactions is due

to erosion assisted corrosion and this part is the bottom cone of digester. The present

in-plant test seems to support this hypothesis as near strainer (where the rack of

coupons was fixed) the materials experience only corrosion and practically no erosion.

This test, therefore, also seems to indicate that with the present liquor and the process

conditions, the middle cylindrical part of the digester (near strainer) can be constructed

of mild steel without severe risk of corrosion. However, to look for the alternate material

for the bottom part of the cone, another in-plant test needs to be conducted where the

110
metal coupons are fixed in the bottom cone of the digester so that they experience

corrosion as well as erosion in successive batches of pulping cycle.

111
 Table- 4.1

Mechanical Properties of Stainless Steels

Grade Proof Strength Tensile Strength Elongation

(NImm2) (N/mm2) (%)
304L 276 616 62
316L 276 575 61
2205 636 712 40
SAF2304 538 749 33
LDX - - -

Table- 4.2

Chemical Composition of White Pulping Liquor

pH 13.1
Sulfidity 19.1%
NaOH (Sodium hydroxide) 91.5±0.3 gpl
Na2S (sodium Sulfide) 21.1±0.4 gpl
Sx2" (Poly Sulfides) 0.056±0.016 gpl
Na2S203 (Sodium thiosufate) 2.3±0.9 gpl
Na2CO3 (Sodium Carbonate) 16.7±3.0 gpl
CI" (Chloride) 1.29±0.24 gpl

Table- 4.3

Corrosion Attack on the Tested Coupons

Corrosion Rate Max. Pit Depth Crevice Corrosion

Grade (mils per year) (mm)
MS 3.74 NVA No
304L 0.01 0.095
316L 0.006 0.060 Measurable
2205 0.003 NVA
SAF 2304 0.001 NVA Attack
LDX 0.005 NVA

112
 (a) Front Face

(b) Opposite Face

Photo. 4.1. : CORRODED COUPONS AFTER SIX MONTH EXPOSURE IN

DIGESTER
113
 (c) Front Face

(d) Opposite Face

Photo. 4.1.: CORRODED COUPONS AFTER SIX MONTH EXPOSURE IN

DIGESTER

114
 LIQUOR
TOP
DISTRIBUTOR

4' ... ....

.■ II '.4.
4. '1

1
, 0 .:); f 4 ;"1.'0 •
I 0 0 .4 4 .
. d ' jI 1 1 ' 7

HEAT
EXCHANGER

LOCA
TION
OF
TEST
RACK

PUMP

Fig. 4.1. : KRAFT BATCH DIGESTER WITH LOCATION OF TEST RACK

115
 (a) MS (X200) (b) 304L (X500)

(c) 316L (X200) (d) 2205 (X500)

(e) SAF 2304 (X200) (f) LDX (X200)

Fig. 4.2. : MICROSTRUCTURE OF MILD STEEL AND STAINLESS STEELS

(BASE METAL)
116
(a) 304L (X500) (b) 316L (X200)

(c) 2205 (X500) (d) SAF 2304 (X200)

Fig. 4.3. : MICROSTRUCTURE OF STAINLESS STEELS

(WELD METAL)

117
 Chapter : 5

Corrosion Study of Steels in Peracid Bleach Solutions

Contents : Page No

5.1. Introduction 119

5.2. Experimental 120

5.2.1. Material 120

5.2.2. Solutions 120

5.2.3. Tests 121

5.3. Results 121

5.4. Discussion 122

5.4.1. Corrosivity of solutions 122

5.4.2. Material Performance 125

5.4.3. Material Selection 127

5.1. Introduction :

Paper industry is adopting non-chlorine chemicals e.g. hydrogen peroxide, peracids,

oxygen, ozone etc. for bleaching with the aim of reducing pollution. The peracids

namely per acetic acid (Pa), Caro's acid (Pr) and (Pxa) mixture of Pa and Px, have been

used as brightening agent and as activating agents for lignin. Chemically, Pa is

CH3C000H with molecular weight of 76.05 and active oxygen as 21% whereas, Px is

peroxymonosulfuric acid (H2S05) having molecular weight of 114.08 gram and 14%

active oxygen content. Peracids are considered as effective for bleaching as peroxide

and ozone but they are preferred over the latter two alternatives on account of their

superiority with regard to associated safety hazards, ingredient costs and effluent loads,

Bijan et at (23) and Liebergott (77). With the use of newer chemicals, their corrosive

effect has also been studied. Thus Varjonen et at (136) while studying corrosion of Ti in

peroxide found that MgSO4 was not an effective inhibitor, in contradiction to Macdiarmid

et at (79). In a similar study, Wyllie (148), sodium silicate and calcium nitrate were found

to be effective inhibitor for pH —12 but not EDTA. Been et at (19), doubts the

effectiveness of calcium as inhibitor for Ti in peroxide media. Singh et at (116) studied

the effect of chelants on the corrosivity of peroxide solutions. Pehkonen et al (92)

studied corrosion of stainless steel in ozone and per acetic acid without Cl.
" Sodium

sulfate was found to inhibit the corrosive effect of CI" in ozonated solutions. Singh et al

(114) recently studied corrosive effect of per acids with acidic pH. Present work reports

about the investigations performed on corrosion of mild steel and stainless steels in per

acids of acidic as well as alkaline pH. The corroded samples were evaluated for

localized and uniform corrosion for their possible use in per acid bleach plant.
119
5.2. Experimental :

5.2.1. Material :

Corrosion test coupons from plate samples of mild steel, austenitic stainless steel 304L,

316L and duplex stainless steel 2205 were selected for the weight loss test. Cylindrical

samples from the rods of the above steels including 254SM0 (except mild steel) were

used for electrochemical tests. The compositions of the stainless steels are given in

Table -2.1 and Table -2.2. All the test samples were solution annealed as per ASTM

specification A240. Before exposure, they were polished up to 600 grit, then degreased

using acetone solution and weighed in case of weight loss test.

5.2.2. Solutions :

Samples were exposed to peracid solutions namely Pa, Px and Pxa, prepared as

described earlier, Bijan (23). Accordingly, Pa was prepared by adding glacial acetic acid

to hydrogen peroxide (1 molar ratio) containing 1 ml. of concentrated sulfuric acid as

catalyst. The mixture was then warmed to 45°C, held at this temperature for two hours,

and stored overnight in a refrigerator to allow the mixture to come to equilibrium. Px was

prepared by adding sulfuric acid to hydrogen peroxide (one molar ratio) while

maintaining the reaction temperature at 30-35°C. Pxa solutions were prepared by adding

equal amount of Pa and Px. NaCI was added in the solutions to get desired level of Cr.

The pH of these solutions was kept 6.0, 7.5 and 9.0 by adding required amount of

NaOH. Table -5.1 gives the test conditions and composition of the solutions.

120
5.2.3. Tests :

Immersion test and electrochemical polarization tests were conducted in the present

study. In the immersion test, the steel coupons were exposed for duration of six months

at room temperature. Each coupon was immersed in the solutions (Table-5.1) with the

serrated washers for initiating crevice corrosion. During the test, % active oxygen (A.O.)

and pH of the solutions were monitored and maintained each day. While pH did not

change much (±0.1), decrease in %A.O. was compensated, to keep it within limit as per

table-5.1, by adding requisite amount of peracetic acid, Caro's acid and mixture of both

(Pxa). After the exposure, the corroded coupons were cleaned mechanically and by

treating with cold solution of concentrated HCI with 50 gpl SnCl2 and 20gpl

SbCl3(98).The coupons were then weighed for determining weight loss and corrosion

rate and viewed under the microscope for estimating the extent of localized attack. The

electrochemical tests E versus time, potentiodynamic, cyclic polarization and

potentiostatic tests were conducted in Pa , Px and Pxa solutions having pH=6.0 and 9.0,

using potentiostat and polarization cell having five necks meant for a working electrode,

two counter electrodes, a reference electrode (saturated calomel electrode in present

case) and for gas purging. Open circuit potential (OCP), Corrosion (Emu), pitting (Er)

and repassivation potential (Es) were evaluated from these tests.

5.3. Results :

Corrosion rate was calculated from weight loss, determined by subtracting the weight of

the corroded and cleaned coupons from its original weight. The extent of pitting was

121
evaluated by measuring the maximum depth of pits formed on freely exposed surface

and crevice corrosion was estimated by measuring the maximum depth of attack on

occluded surface formed by serrated washers. Values of these parameters are given in

Table -5.2. The OCP values for different cases was determined from E vs. time curves

(Fig. 5.1 shows some E vs. time curves for SS 304L in pH = 9 solutions). The

potentiostatic test (current versus time behavior at a pre-selected potential applied to

metal electrode) (Fig. 5.2 shows some representative curves) was conducted to

evaluate Ep which decides the vortex potential/current required for recording the cyclic

polarization curves. The closed loop (Fig. 5.3) indicates that the localized corrosion has

begun and that the downward curve therefore shows a weighted average of the alloys

behavior in the base solution and the localized corrosion environment. Various

parameters e.g. Emu, Ep and Ec obtained from the electrochemical polarization tests are

given in Table -5.3.

5.4. Discussion :

5.4.1. Corrosivity of solutions :

Table -5.3 shows that the OCP's of different steels are higher than their respective Ecorr.

Eton/OCP of steels is higher for pH=6.0 solutions than pH=9.0. Also increase in Cr and

decrease in pH decrease passivation range.

In all solutions without CI", no pitting was observed, under microscope (6.5X), in

samples after having undergone the potentiostatic test up to —1300-1400 my, indicating

122
Ep for such cases to be higher than this range. Exceptions were 304L and 316L in Pa

solutions. However, in case of all steel samples, the anodic polarization curves in these

solutions show a kink indicating onset of pitting around 1000-1050 my in most cases.

Cyclic polarization curves, in these cases, also show hysteresis behavior (Fig. 5.4)

when polarization scan reverses to cathodic direction on reaching vortex potential. This

is an indication that pits were formed and now have started passvating. Probably the

pits formed were not observable under the microscope, due to their small size, but their

effect is clear in polarization curves. P. although overall seems less corrosive, yet the

tested steels show lesser in this solution as compared to that in pa and Pxa solutions, as

appears from low expected values of Ec, in former solutions. This observation needs

further investigation.

In all the three solutions with Cr =1000ppm, all test samples except 254SM0 showed

significant amount of metal dissolution after the potential reaches near Ep or crosses Ep,

while performing polarization test. In them, one observes non —passivating pits (Fig.

5.5), except for 2205 in P. , pH=9.0 solution which is a case of material, more resistant

than 3041 and 316L, exposed to least corrosive solution. Even in this case, (Ec — Ecorr)

does not appear to be very high (< 190 my), representing 2205 not very dependable

material for handling these media. One observes higher degree of pitting attack on all

samples, except 254SM0, exposed to these solutions in potentiostatic test at pre-

selected potential Ep. In one such case, maximum pit depth of 40 pm was observed

on 2205 in Pa solution of pH=9.0. Maximum resistance against localized corrosion of

254SM0 is exhibited by the observance of passivating pits in all the tested solutions

(Fig. 5.3 and 5.6). However, (Ec — Ecorr) for this material, was measured to be < 172 my

123
when exposed to Pa solution (pH=6.0) with CI- , exhibiting its limited performance in

handling most corrosive of the test solutions.

Thus in general, Pa solutions are most corrosive followed by Pxa and Px solutions. This

can be understood on the basis of (i) the prevailing reduction reactions which in turn

affect the corrosion of materials and (ii) the nature of peracetic acid and

peroxomonosulfuric acid. Following reduction reactions can be considered to be

responsible for corrosion in these solutions :

CH3C000 + 3H+ + CH3COOH + H2O - (i)

2HS08" + 2H+ + 1--* S2082- + 21120 - (ii)

From the reduction reactions (i) and (ii), 2 ions of CH3C000" are responsible for

consumption of 6 e" whereas 3 ions of HS08" are required for the same purpose. Thus

corrosion of steel should be higher when exposed to peracetic acid as compared to the

steel exposed to same amount of caro's acid.

Peracids (peracetic acid, CH3C000H, and peroxomonosulfuric acid, H2S08) are

considered to be more oxidizing than hydrogen peroxide due to the capability of former

showing electrophilic/ nucleophilic character which is not shown by the peroxide, Thierry

et al (123). Further a comparision of kinetics of several peroxyacids, Chang et al (29),

shows that electrophilicity of CH3C000H is greater than that of H2S08. Accordingly,

peracetic acid, at a given pH, is likely to show higher corrosivity than Caro's acid.

124
5.4.2. Material Performance :

In Px solutions with/without chloride, degree of corrosion resistance varies as 2205>

316L> 304L. This is due to (i) higher Ep in Px solutions (except in case of pH=9.0

solution without Cl") (ii) passivation range for 2205 is maximum while that of 304L is

lowest. (Except in case of pH= 6.0 solution without Cl").

In P. and Pxa solutions without CI', passivation range and Ep is highest for 304L and

lowest for 316L/ 2205 (In contrast to observed higher resistance of 22051316L than

304L against pitting). This has been predicted in an earlier report by Pehkonen et at

(92). However, resistance against crevice corrosion is observed to be higher in case of

22051316L than 304L. This aspect of corrosion behavior needs to be further

investigated.

" 304L and 316L show a very low value Ep

For Pa solution of pH=9.0 having Cl,

(potentiostatic test) and their Ec is likely to be around Ecorr. For 2205, Ep and passivation

range is slightly higher. Cyclic polarization curves show non passivating pits (Ec< Ecorr)

in all cases, thereby showing practically no resistance against crevice corrosion, except

in case of 2205 exposed to Px solution of pH=9.0. Only in case of 254SM0, exposed to

peracid solution, one observes passivating pits hence Ec> Ecorr. This, stainless steel

also shows maximum passivation range among the tested metals. The above

observations lead to conclude that stainless steels 304L and 316L show practically no

resistance against either pitting or crevice corrosion, 2205 shows to some extent

resistance against pitting only. Only 254SM0 shows resistance against both pitting and

125
crevice corrosion. In case of pH=6.0 solution, the performance is still poorer with none

of the steels, except 254SM0, showing resistance against localized corrosion.

For Pxa solutions, resistance of 304L and 316L against pitting was checked only through

potentiostatic tests. No cyclic polarization tests were performed on them since they

were expected to show non passivating pits, like in the case of lesser corrosive Px

solutions. Since the performance of 2205 against localized corrosion in Px solutions is

observed to be unsatisfactory, this steel was not tested in case of more corrosive Pxa

solutions. However, more resistant stainless steel 254SM0 was tested in these

solutions through potentiostatic and cyclic polarization test. Thus in Pxa solutions also,

304L and 316L are expected to experience localized corrosion while only 254SM0 is

expected to show satisfactory performance against both pitting and crevice corrosion.

Performance of different tested materials, as compared to that in respective Pa

solutions, indicates Pxa solutions to be, in general lesser corrosive than Pa.

Thus, in solutions with Cr = 1000ppm, in general resistance against localized corrosion

is maximum for 254SM0 followed by 2205, 316L and 304L. In solutions without Cr

however 304L appears more resistant than 316L and 2205 on the basis of Ep but lesser

resistant on the basis of Ec.

Corrosion rates of mild steel and stainless steels, determined on the basis of long term

immersion tests, in general, show Pa to be most corrosive followed by Pxa and Px. Extent

of localized corrosion, as observed in these tests, also in most cases show similar

grading on the comparative corrosivity of liquors.

126
The results of these tests show high degree of uniform corrosion on mild steel as is

evident from corrosion rates (Table -5.2).So mild steel has to be ruled out as a material

of construction for handling these media even at alkaline pH. In case of stainless steels,

uniform corrosion is very low hence suitability of these materials has to be checked on

the basis of localized corrosion .On the basis of degree of pitting and crevice corrosion,

304L and 316L show similar resistance while 2205 exhibit maximum resistance against

corrosion attack. Site of welded joint does not show significant attack basically

indicating the absence of stress related corrosion effects especially in view of the fact

that the coupons were autogenously welded.

5.4.3. Material Selection :

A proposition is now given about the appropriate material for handling peracid solutions

with Cr considering the results and analysis of immersion and electrochemical

polarization tests. Thus on the basis of immersion test and criterion by Tuthill (134),

304L and 316L are not appropriate for Pa and Pxa solutions with pH=6.0 and 7.5. In case

of pH=9.0 solution also, their use is doubtful in view of the electrochemical

measurements. Immersion test show better performance of 2205, however,

electrochemical tests indicate its vulnerability to localized corrosion in these solutions.

Exhibition of resistance of Avesta 254SM0 against localized corrosion in these

solutions indicate this steel to be more appropriate. Further, 254SM0 for Px solutions

with pH=6.0 and 2205 for solutions with pH=9.0 appear suitable on the basis of two

tests. In case of peracids without chloride, considering the result of electrochemical

127
tests alone, even where 316L could be an appropriate material, application of 2205 is

more cost effective on the basis of its improved cost/strength ratio in addition to better

corrosion resistance. Accordingly, a list of proposed suitable materials for handling

peracids is given in Table -5.4.

128
 Table - 5.1

Chemical Composition of the Peracid Solutions

Solutions Chemical Charge pH Chloride (ppm)

(as % A. 0.)*
0 1000ppm
6.0±0.1 Px 1 Pxci 1
Caro's Acid 7.5±0.1 Px 2 Px ci 2
9.0±0.1 Px 3 Px ci 3
Mixture of 6.0±0.1 Pxa 1 Pxa CI 1
Caro's Acid + 0.47 ± 0.05 7.5±0.1 Pxa 2 Pxa CI 2
Peracetic acid 9.0±0.1 Pxa 3 Pxa CI 3
6.0±0.1 Pa 1 Pa Ci 1
Peracetic Acid 7.5±0.1 Pa 2 Pa C12
9.0±0.1 Pa 3 Pa CI 3

* A . 0. - Active Oxygen

Table - 5.2

Corrosion Parameters in Peracid Solutions (IMMERSION TEST)

Metal Mild Steel SS - 304L SS - 316L 2205

Corrosion rate(mpy )
Corrosion rate(mpy)

Corrosion rate(mpy)
Corrosion rate(mpy)

Crevice attack((pm)

Welded attack((pm)
Welded attack((pm)

Welded attack((pm)

Crev ice attack((pm)

Crevice attack((pm)

Welded attack((pm)

Crevice attack((pm)

Pit depth(pm)

Pitdepth(pm)
"Pit depth(pm)
Pit depth(pm)

a
0
.4.j
13 I
cn a
Pa 6.0 34.7 145 80 - 0.43 80 70 nva 0.49 110 60 nva 0.09 nva nva nva
7.5 27.1 60 60 - 0.53 120 60 nva 0.41 80 70 nva 0.04 nva nva nva
9.0 22.8 nm 85 - 0.21 60 50 nva 0.21 70 55 nva .002 nva nva nva
Pxa 6.0 32.5 205 180 - 0.32 60 55 nva 0.43 100 80 nva 0.08 nva nva nva
7.5 26.9 110 110 - 0.16 100 60 nva 0.23 55 45 nva 0.02 nva nva nva
9.0 22.1 60 60 - 0.37 55 50 nva 0.41 70 65 nva 0.03 nva nva nva
Px 6.0 21.9 nm 60 - 0.22 105 70 nva 0.26 100 65 nva 0.08 nva nva nva
7.5 18.9 80 85 - 0.21 60 nva nva 0.19 50 50 nva 0.03 nva nva nva
9.0 18.0 nm nm - 0.16 60 50 nva 0.17 50 50 nva 0.02 nva nva nva

All solutions having chloride1000ppm,

nm - Not measurable attack, nva -No visible attac

129
 Table - 5.3

Electrochemical Polarization Test Results

pH 6.0
Solution Caro's Acid Pxa Peracetic Acid
CI' Metal 304L 316L 2205 254 304L 316L 2205 254 304L 316L 2205 254
SMO SMO SMO
OCP - 292.5 266 197.4 263.7 - - 222.4 224.8 . 250.6 -
Err 195 179.5 228.5 151 , 145 - - 130.8 161.5 154 -
Pass. 820 851.5 807.5 985 779 - - 879.2 747.5 712.4 -
Ep* 1015 1031 1036 1136 923 - - 1010 909 866.4 -
... Ep** >1300 >1400 >1400 1300 -1325 - - 1350 1350 >1300 -
Not Tested

Ec <665 - <254 849 - - <491 814.6 865.3 -

OCP 280.6 241.1 - 208.9 213.1 - 296.6 213.3 232.7 231.5 301.3
Epp, 199.3 130 - 165.5 - - - 175
1000 ppm

Pass. 737.5 801.5 - - - 633.8 - - - 597

Ep* 936.8 931.5 - - - - 799.3 - - - 771.5
Ep** 875 875 - - - - 1050 <250 <250 375 1025
Ep npp npp - - - - 556.8 - - - <347
pH .9.0
Solution Caro's Acid Pxa Peracetic Ac'cl
OCP 129.4 154.2 - 82.2 80.2 - - 102.7 114 139.1 -
Ecorr 74.8 56.9 - 32.7 59.9 - - 75.9 53.1 92.4 -
Pass. 953.2 960.1 - 982.3 818.9 - - 942.1 932.9 731.6 -
Ep* 1028 1017 - 1015 878.8 - - 1018 986 824 -
EP ** >1400 >1300 >1400 1325 1325 - - 1400 1400 >1350 -
Not Tested

=
° Ec 309 263.7 - 864.6 914.2 - - 931.4 870.2 ? -
OCP 88.7 102.7 96.8 77.1 80.6 - 113.6 130.1 122 167.8 112.3
Ecar 48.1 60.8 61.9 33.5 - - 90.3 68.1 - 61,.9 90.8
1000 ppm

Pass. >869 951.2 963.1 . 146.2 - - 930.7 323.8 - 338 739

Ep* >917 1012 1025 179.7 - 1021 391.9 - 400 829.7
0
E ** 875 875 1325 <100 175 - 1075 175 175 375 1075
Ec - npp <253 - - - 761.8 - - npp 782.6

Table- 5.4

Materials for Handling Peracid Solutions

Chloride=Oppm Chloride=1000ppm
Solution pH pH
6.0 9.0 6.0 9.0
Pa 2205 2205 2548m0 254SM0
Pxa 2205 2205 254SM0 254SM0
Px 2205 2205 254SM0 2205

130
Fig. 5.1 : E vs. time curve for calculating OCP for stainless steel 304L in pH=9
Peracid solutions (1) Px (w/o co, (2) Pxa (w/o Cr) (3) Px (Cr -1000 ppm),
(4) Pxa (CI" -1000 ppm) (5) Pa (C1- —1000 ppm ) solutions.

Fig. 5.2 : Potentiostatic Test ( Current density vs. time curves ) for SS-304L in Pa
solution with pH=9 and CE = 1000 ppm. Applied potential for Curve 1 = 300 mV, Curve 2
= 200 mV and Curve 3 = 150 mV (w.r.to SCE)

131
Fig. 5.3 : Cyclic polarization curve of Avesta 254SM0 in Pa solution having pH = 6 and
cr = 1000 ppm.

Fig. 5.4 : Cyclic polarization curve of SS 304L in Px solution, without CI', having pH = 6

132
Fig. 5.5 : Cyclic Polarization Curves exhibiting non-passive nature of pits. Curve 1 and 2
: SS 304L and 316L in Px solution having pH = 6, and Cr = 1000 ppm, Curve 3 : Duplex
stainless steel 2205 in Pa solution having pH = 9 and Cr = 1000 ppm.

Fig. 5.6 : Cyclic Polarization Curve of Avesta 254SM0 in Pa solution having pH = 9 and
CI' = 1000 ppm.

133
 Chapter : 6

Conclusion and Recommendations

Contents Page No.

6.1 Corrosion in Solutions having Sulfur Compounds 135

6.2 In-Plant Corrosion test of Steels in Digester of Paper Mill 137

6.3 Corrosion Study of Steels in Peracid Bleach Solutions 139

6.4 Recommendations for Future Work 140

134
This chapter describes the conclusions drawn on the basis of laboratory and in-plant

corrosion tests performed on steels in different corrosive media/conditions. The

description has been given in the same order as the investigations described in

chapters 3, 4 and 5. This is followed by the recommendations about the future work that

should be done related to corrosion in pulping and bleaching section.

6.1 Corrosion in Solutions having Sulfur Compounds :

Corrosion test and their investigations in alkaline solutions having sulfur compounds (as

described in Chapter 3) were undertaken in order to mitigate the corrosion problems

faced by the digesters in the paper mills. To understand the problems from the basics of

corrosion phenomenon, to begin with, E-pH diagrams for S-H20 and Fe-S-H20 systems

were constructed and long term immersion test was performed in the alkaline solutions

having sulfur compounds in proportion as normally observed in pulping liquor. Following

conclusion can be drawn on the basis of analysis of above results:

1. The E-pH diagrams for S-H20 system show that within the pH range likely to be

observed for the pulping liquor, sulfur species present in the solution could be

HS' and to some extent 82-, S2032' and S032- depending upon the potential,

which will in turn be governed by the nature of material exposed e.g. mild steels

or stainless steels

2. Fe-S-H20 diagrams constructed for considering above sulfur species and

concentrations. Thus if the liquor consists of S2032-, different corrosion products

135
 likely to form in the pH range of interest (pH — 12-14) are mackinawite, troilite,

pyrrhotite and pyrite. Of these, the first two products are non-protective type

while other two are protective type. However, the region of protection also

indicates the possibility of localized corrosion if the protective layer breaks. This

usually happens at higher potentials which one can observe, if the amount of

52032" increases. It indicates that if the amount of 52032" is higher, the steel is

likely to experience localized corrosion.

3. In long term immersion test, the metallic samples were exposed for six months in

sulfide solutions. After the exposure, the corroded test materials were analyzed

for uniform and localized type attack. The results of this test showed no

significant corrosion on the tested stainless steels. Mild steel experiences

uniform corrosion and crevice corrosion. Corrosion rates increased with the

increased amount of S2032' content in the solution. This behavior becomes more

pronounced in the presence of CI' ions.

4. Measurement of redox potential of 304L and 2205 in pH —14 solution having

sulfidity, as considered in E-pH diagram, shows that sulphur species near 304L

electrode will be mainly S032" and S2032" while those near the 2205 electrode will

be mainly HS". Accordingly, E-pH diagram of Fe-S-H20 shows that corrosion

products forming on 304L will be pyrite or iron oxide and on 2205 it could be

pyrrhotite/ troilite/ mackinawite depending upon the potential. Except

mackinawite and troilite, other sulfides /oxide provide protection. This could be

the reason for observing lesser corrosion rates in these stainless steels.

136
6.2 In-Plant Corrosion test of Steels in Digester of Paper Mill :

In - plant corrosion test was conducted by exposing different steels near the middle part

in kraft digester of a nearby paper mill. The aim was to observe their performance

against corrosion attack and to correlate same with conditions inside digester. After the

six month exposure, the corroded coupons were analyzed for uniform corrosion, pitting,

crevice corrosion and weld related attack. Following conclusions can be drawn on the

basis of this analysis:

1. Varying degree of uniform corrosion and pitting is observed on different steels.

Crevice corrosion is observed but is non measurable while no weld related attack

has been observed on these coupons.

2. Mild steel is observed to experience maximum uniform corrosion. While pitting is

maximum in case of 304L whereas duplex stainless steel do not show any pitting

attack. The attack can be correlated with the amount of Cr and N present in

steels. At these pH (-14), Mo content of stainless steel does not provide

protection as it gets dissolved as Mo042- .

3. For the lower sulfidity levels, mild steel may be suitable for cylindrical section of

the batch digester. However, for cooking liquors with increased sulfidity and /or

for parts of the digester which are affected by the erosive action of the liquors

(e.g. bottom cone, liquor heater tubes etc.), one may have to opt for duplex

stainless steels with Cr and N as preferable alloying elements.

137
4. An overall view of the corrosion attack indicates that all the materials, including

mild steel, tested have sufficient corrosion resistance in the tested media.

However, since the liquor composition is likely to change in future so as to have

higher sulfidity, thiosulfate and polysulfide content because of advantages

associated with high sulfide pulping, it is likely that mild steel will no more be

considered suitable and one may have to opt for duplex stainless steels.

5. Findings of the present in-plant test could be compared with those of Swedish

test. Comparisons of the results reveal the following. In general, the Swedish

mills (having a sulfidity of -40%) show a higher corrosion rate of mild steels (1.7-

5.9 gm/m2.cook with an average of 3.3 gm/m2 cook). The amount of silicon in the

tested mild steel varies between 0.06 - 0.1 %. In the present test, mild steel

shows lesser corrosion rate (-0.74 gm/m2.cook, considering - 500 cooks in the

test duration of 6 months). This could be due to lesser Si content (-0.4%) in the

mild steel and less (-19%) sulfidity in the digester liquor. Both these factors have

been suggested to affect corrosion rate. Lesser sulfidity probably is also

responsible for lower corrosion rates in case of stainless steels as compared to

those in Swedish mill. Unlike the case of Swedish mill, mild steel does not show

non uniform attack. Pitting is observed on SS-304L and 316Lcoupons while other

coupons showed no visible pitting. The steel coupons do not show any crevice

attack. Non- observance of crevice attack could be due to highly alkaline nature

of the digester liquor.

138
6.3 Corrosion Study of Steels in Peracid Bleach Solutions :

Peracid bleach solutions may be potential non-chlorine chemicals for future bleach

plants. It is therefore necessary to check as to how the metallurgy of bleach plant

machinery will behave in the presence of peracids. Accordingly, electrochemical and

weight loss test were conducted on steels in peracid solutions to investigate the

corrosivity of the chemicals and performance of test materials against corrosion attack

in the test solutions. Conclusion were drawn on the basis of results obtained from the

electrochemical polarization tests and weight loss tests performed on mild steel and

stainless steels 304L, 3161, 2205 and 254SM0 in solutions of peracetic acid (Pa),

caro's acid (Pr) and mixture of P. and Px (Pxa) having Cl upto 1000 ppm and pH

between 6 — 9. These conclusions are given below :

1. OCP's of different steels are higher than their respective Ecorr. Ecorr/OCP of steels

is higher for pH=6.0 solutions than pH=9.0. Also increase in Cl and decrease in

pH decrease passivation range

2. Electrochemical measurements on stainless steels in per acid solutions with Cr,

show high degree of localized corrosion whereas it is less severe in case of

solutions without Cr. In general, corrosivity of the solutions increases in following

order : Px<Pxa <Pa. *

3. Performance of mild steel is observed very poor against corrosion attack in these

solutions. Stainless steel, tested in the present investigations, can be put in

139
 following order of increased resistance against corrosion:

304L<316L<2205<254SM0.

4. Corrosion investigation in peracids, reported in chapter 5, concludes that

peracetic acid is most corrosive whereas caro's acid is least corrosive. The

comparison of performance of different test materials showed Avesta254SMO to

be most resistant while 304L least resistant against corrosion attack.

5. It is concluded that Avesta254SMO is appropriate for handling CI" containing

peracid solutions and duplex stainless steel 2205 for handling these solutions

without CI" on the basis of degree of attack alongside comparison of cost vis-à-

vis strength of different stainless steels.

6.4 Recommendations for future work :

The work carried on the corrosivity of sulfur containing solutions included immersion test

at room temperature only while E-pH diagrams were constructed without considering

polysulfides and for room temperature only. In order that the analysis of corrosion test

results is complete and laboratory tests and E-pH diagram can correlate with the actual

conditions faced by the material of construction of digester, following needs to be done

further as an extension of this work:

- Electrochemical polarization (AC/DC) and Immersion tests of different steels in

alkaline solutions having different sulfur compounds including polysulfides and

140
 with varying sulfidity. The test should be done at room temperature and at high

temperatures upto 160°C, as observed in digesters globally.

Construction of E-pH diagrams for S-H20 and Fe-S-H20 systems considering

varying sulfidity and polysulfides as one of the sulfur containing compounds at

temperatures varying up to 120°C and 160°C, because polysulfides are unstable

beyond 120°C.

In the in-plant test, described in Chapter 4, coupons of different steels were fixed in

digester nearby strainer, where the effect of erosion due to flow of pulp slurry at the end

of the batch is not significant. Consequently, one of the reasons for not observing high

corrosion even on mild steel coupon was assigned to almost absence of the effect of

erosion. However, bottom cone of the digesters in the mills, where erosive effects are

maximum, have been found to show excessive corrosion, hence a better idea about the

suitable material of construction can be obtained if an in-plant corrosion test is

conducted where the coupons of the steels are fixed in bottom cone. Similarly, for top

part of the digester and other parts which are affected by caustic cracking, an in-plant

test needs to be conducted where coupons are fixed in top and other parts of the

digester that are prone caustic cracking.

Corrosion investigations in peracids, reported in the present thesis, are related to fixed

amount of active oxygen and Cr content. Further, in the present tests only synthetically

prepared solutions were considered for the test. In comparison to these conditions of

the laboratory tests, the mill conditions will have varying amount of active oxygen and

Cl" content, also the corrosive media will be pulp slurry instead of just solution of

141
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