Jo urn al o f Scienti fic & Industri al Research

Vol. 62 , June 2003, pp 583-588

High-chromium (22-34 per cent) Cast Iron Alloys and Their Simulated Behaviour
at the Sugar Industry
E Zumelzu *, 0 Opitz and C Cabezas
Instituto de Materiales y Procesos Termomeca ni cos. Uni vers id ad Austral de C hil e, Casill a 567 , Valdivia, C hil c

and

A Parada and L Goyos

Facultad de Ingeni e rfa Mecani ca. ISPJAE. La Habana, C uba

Received: 17 Janu a ry 2003; rev ised received: 06 March 2003; accep ted: 25 Marc h 2003

The good result s ob tai ned by cast iron wi th C r a nd Cr- Ni investigated in th e maki ng of part for pumping equipmen t in
suga r cane industry are g iven. Cas t iron all oy co upo ns were prepared in o rd er to stu dy th eir ha rd ness, res ilience, co rrosio n
res istance. a nd wear-out behav io ur by means of simul ating the co ndition s found at th e suga r ind ustry processes.
Mi cros tru ctural characterisati on of all oys was mad e by scanning elec tron mi croscopy (SEM) . and th e electrochemica l tria ls in
o rde r to assess corrosion susceptibil ity were pe rformed with a specific sugar soluti o n. The behavio ur of all oys to wea r-o ut a nd
co rros io n de pe nd s mainl y o n the chemical co mposition and effect of the all oying ele me nt s the form ati on of ca rbid es during
so liditi cati o n, and the presence o f impuriti es and in clusions at a surface level. The res ult s ob tained in th is study mad e possib le
the selecti o n of better all oys, which can be e mpl oyed at the sugar ind ustry such as 0.78 C-33 , 5 Cr-7 .7 Ni which have a high-
chromium co nte nt. This mate ri al impli es a considerable economic saving for sugar indu stry.

Keywords : High chromium cas t iron , Simul ation , Sugar industry, Scanning Electron Mi croscopy

Introduction technological difficulties impli ed in the treat me nt of

It is necessary to improve material s
c harac teris tics suc h as res ili ence, wear and corrosion
2
res istance for severe service application s ' .
T he development of new method s and thermal
treatment for cast iron all oys all ow new mate rial s to
perform better mechanically and again st co rros ion
when unde r aggress ive industri al environments 3.4 .
White c hrome cast irons are curre ntly leading several
fi e ld s of applications, be ing mainl y emp loyed in
mechanical parts su bmitted to severe wearing-away.
In addition , they are used whe n hi gh corrosion
resistance is required . Therma l treatments app li ed to
these all oys are concerned with two large fields
which invo lve standard quench in g a nd annealing
treatme nts, and maintenance treatments' under c riti ca l
te mperature . The latter has been app li ed to dec rease
costs invo lved with stand ard treatments and overco me
*Co rrespo ndin g au thor
large parts. In the evaluati on of new all oys , des igned
to operate in aggress ive medi a, it becomes essential to
know the transformation s undergo ne durin g the rmal
treatments and the ir influ e nce on th e ex pected
mechanical and corros ion properties'.
For the preparation of sampl es, various factors
a nd aspects related to thi s type of all oys were
considered . Thus, e g, chrome addit ion strong ly
favours formation of carbides dur in g iron
so lidification and pearlite- like matrix formati on
during e utecto id trans formation 6 .
At 9.5- 15 per cent c hrome, carb ides of type
(Cr,Fe)7C3 appea r, and at a hi gh 30 pe r ce nt c hrome,
carbide type (C r,FebC(, so lidifi es . O n the oth e r
hand , an increase in th e c hrome co ntent durin g
casti ng, reduces the equilibrium te mperature of
eutec ti c tran sformation (TO> accordin g to th e stab le
Fe-C system a nd tn creases th e equilibrium
temperature of eutec ti c tra nsfo rmati on (T ill)
584 J SCI IND RES VOL 62 JU E 2003
acco rdin g to the un stab le system . Greater levels of
C r initiat e formation of an ox id e- impe ne trabl e laye r
o n th e surface of cas t p ieces, which adhere very well
to the metal. Due to thi s, chrome iro ns a re resistant
7
to th e action of hea t a nd various co rrodin g media .
Above 16 per cent Cr, an oxide la ye r ty pe FcO.Cr20 ,
for ms o n the iro n s urface, which stron g ly increases
th e resistance to hea t, makin g opera ti o ns poss ibl e at
0c:
tc mpe ratures of th e o rd e r of I , I 00 On th e other
hand, it is we ll known that c hro me in c reases
hardness and te ns il e strength of white a nd g rey
s
irons . Furthermore, lite rature shows that hi g h-
chrome alloys ex hibit good eros io n-co rro s ive a nd
eros ion-ab ras ive behaviours'> 10 . Also, no n- sta nd a rd
al loys of minut e scattered carbides a nd matrix alloys
(ex: ) present good res po nse to eros io n. For eros ion-
co rros io n res istant alloys, matrices are sugges ted to
be sta inl ess with limited parti c ipatio n of carbides,
and e rosio n-abras io n res istant alloys req uire hi g h
participation of carbides, makin g poss ible a greater
hard e nin g of th e st ructure; as a res ult of coo lin g and
the sca tte rin g of ca rbides th e structure is capable of
s ustainin g th e de te rioration mec hani sms as a
co nseq ue nce of defo rmation and c uttin g by abras ive
partlc
. Ies II . 12 .
Howeve r, addition of nicke l in hi gh-chrome
a ll oys faci I itates fo rmation of pea rl ite, increases
hardness and te ns il e strength of iron. Furthermore th e
presence of Ni reduces volume of carbides in the
a ll oy. Therefore the action of Ni is of a co mpl ex
nature, stabil is ing austenite which presents a greate r
ca pac ity of carbon disso luti on than ferrite, and
decreasing carbides precipitation. The prese nce of Ni
in c ry stal I ine matrix , du e to its smaller atomic
diamete r, ca n counterwe ig h effects of ch rome and
molibdene, obtaining, the re fore, a more uniform
stress fie ld. Thi s causes a reduction in the di stortion
e ffect of the lattice w hi c h favours th e ex it of
l
ca rbidin g e lements '. Th e prec ipitation of carbides is
also reduced in thi s situation.
The re fore the purpose of the present work was
the preparation and manufacture of high-chrome (23-
34 pe r cent) a ll oys by determining the adequate
combinations of chemical components through tests
invol vin g thermal treatme nts , in order to e valuate the
influ e nce on a ll oys so as to warrant th e best
mec hanical behav iour in wear-out co nd itions and
co rros ion res istance in s ugar media as th ose found in
indu strial processes.
Th e preparation of hi g h-c hrome iro n a ll oys that
co mbine res istance to wear-out and co rros ion allows
a greate r be ha vioural knowl e dge o f these materials,
mainly fo r their use in application s in suga r indu stry
where s uc h deterio ration s take place; and with a n
inc reased knowledge of th e practi a l and theoretical
a lloyin g e le me nt limitati o ns.
Materials and Methods
Several hi g h-c hro me alloys wcre prepa red in an
inductio n furnace of 1.2 kg capac ity. high-frequency,
with me lt in in ves tme nt casting, in flat coupons 70 x
70 x 5 mm represen tin g the ave rage thi ck ness of cast
Iro n walls III sugar process ing and handling
equipme nts .
The criteria used to select a part icu la r c hem ical
co mposition were based mainl y o n hi g h carbon
contents in order to obtain a good parti c ipati on of
carbides. Chrome was used in am oun ts above 18 per
cent (22-34 per ce nt), as it con tributes to th e
formation of stru ctures with hi g h parti c ipati o n of hard
chrome carbides thu s ach iev ing a good co rrosio n-
eros ion res istance. Ni c ke l was used at 0.5-7.7 pe r
cent, as it improves th e formation of a passivation
layer in corros ion processes; as up LO 8 pe r cent Ni is
reco mmend ed in alloys used in sugar appli ca tion s. On
th e other hand , ni cke l at about 2 pe r cent leve l
provides be tte r mec hanical propert ies a nd causes
auto-quenching in structures of hardened matri ces
most adequate for erosion wear-o ut. Additionally,
small propo rtion s of other a lloyi ng e le me nts we re
added to cast iron alloys as g iven in Table I.
Furthermore, standard control sa mpl es of
regul ar al loy were prepared , w hi ch conta in ed
different proportion of alloying e lements , in order to
eva lu ate cha nges In the properti es of these
ex perime ntal a ll oys. The resultin g tes ted alloy
sa mples were characterised by scanning elect ro n
mi croscopy (SEM) throu g h EDAX. Hardn ess of a ll oy
samples was mechani ca ll y measured th rough standard
procedures by means of a Roc kwell C T es ting Dev ice
so as to dete rmine res ilience, to kn ow the ca pac ity o f
the mate rial to absorb e ne rgy during e lasti c
defor mation .
All wear-out trials were pe rformed in situ at a
Su gar Processing Plant ; in that conn ec tion, a bypass
on the juice-mixing lin e wa s made . Th e medium
conditions we re as foll o ws : pH 5.2, co rrespondin g to
organic acids at 30 C; tangen tial acce le ration of 15-
 ZUMELZU el al.: HIGH CHROMIUM CAST IRO N ALLOYS 5 85

Tabl e 1- C hemical composi tion of all oys

Alloy C hemi cal Composit ion, per cen t by Illass

C Cr Ni Mo Mn Cu Si Ti V

0.50 35.80 0 .20 < 0.05 0 .56 < 0.05 0.72 0 .1 6 0.02

2 0 .80 23.50 1.50 0.083 0.29 0.04 1. 73 0. 12 0.01

3 0.78 24.15 7.00 0.12 0.30 0.05 1.74 0 . 15 0.03

4 0.78 33 .50 7.68 < 0.05 0.40 < 0.05 0.94 0 .1 8 0.03

5 1.48 2 1. 30 1.10 < 0.05 0 .35 < 0.05 1.96 0.12 0.03

Nb < 0 .3; and Co < 0. 1

20 mis, in th e presence o f hard solids .(Si0 2) at 0.6- Table 2-Solutio n simulating the indu strial suga r j ui ce
1.5 per cent by we ig ht. Th e tri a ls we re pe rfo rmed for
Component Concen trati o n
200 h in a 45-c m drum , in which all a ll oy sampl es
were pl aced s imul a ting blades spinning at 1,700 rpm . Phos phoric ac id 6.0 g

The wear-out was de te rmined by weight loss Sac harose 140.0 g

w he n a ll oy samples were co mpared with a control Sodium ch lo ride 400 ppm
alloy (85 Cu-5 Sn-5 Zn-5 Pb).
Sili co n I per cent
To study the poss ibl e improvements in the wear- Water 840 IllL
o ut res istance properties of cast alloy sampl es,
Citric acid 3.0 g
the rmal treatme nt was carri ed out which co ns isted of
the austenisation at 975C for 1 h, coo lin g by movin g
a ir d own to 300 C, a nd keeping a ll oy sampl es for
8 h. The results of cast alloys were compa red with
th ose of the rmal treatme nts to determine the ex iste nce 6
of a decrease in the wear-out prope rti es of hi gh-
c hrome alloys. N 5
b
,...
In o rde r to eva lu a te the corrosio n performance, N
~4
alloy lO x 10 mm sampl es were prepared . A E
standardi sed e lectroc he mi cal trial with pote nti osta ti c
1:.
-.. 3
Cl
measurements was carri ed out to determine the 'i::'2
C\)
CI)
corros ion c urre nt den s ity (ieorr), measured at a n ::: ----fr- WITH
overpotential of 10 mY (ESC) afte r a time spa n of 30
TREATMEN
min . In thi s the iron a ll oy sampl es were used as a +-----,----1
T
e lectrodes; a platinum counter e lectrode, and a 14.4
ca lo me l re fe rence e lectrode were also e mpl oyed . The CrlC
e lectro lyte used as a corrosive medium, which
s imulates the indu stri a l sugar juice, is desc ribed in
Fig ure I - Evaluation of wea r resistance versus CrlC rati o of
Tabl e 2 .
cast iron all oys
The set of trials carri ed out with hi g h-c hrome
iron alloys and the respective mi c rostructura l
c harac te ri sati ons, allowed de te rmination of sampl es Results and Discussion
which performed bes t and co rrelated these res ults Th e th e rmal treatme nt appl ied to the all oy
w ith a ppli cation s in suga r process in g under wear-o ut sampl es obtained from casting red uced th e average
and co rros ion conditi o ns. wear-out of the tested alloys , as s how n in Figure I .
586 J SC I IND RES VOL 62 JUNE 2003

A ll oy sample I, used as co nt ro l; was a low- 2.5

ca rbon and high-c hrome a ll oy w hic h rep resent s the ~

'"'E 2
standard compos iti on of c hro me a ll oys de ve lo ped fo r u
use In ex treme wear-out cond iti o ns. Wear-out E
res istan ce, un der tes ted cond iti o ns, decreased en 1.5
~
accord in g to th e CrlC ratio. T he C propo rti on ---CIl
U
influ e nced suc h dec rease th rough the fo rmati o n o f c:
,!!:!
c hrome ca rb ides a nd lead to th e co nseque nt c hrome '~ 0.5
loss fro m th e matrix whi c h caused the a ll oy stru cture a:
to be susceptibl e to corros io n. Ho we ve r, hi g he r o +------,------,------,-----,------,
c hrome pro porti ons a ll owed a hi g h-c hrome stainl ess 14.4 29.4 30. 9 42.9 71.6
matri x.
eriC
W he n a therm a l treatme nt was appli ed to a lloy
sa mp les 4 a nd 5, th ey sho wed be tte r wear-out Figure 3 -- Resi lience variation versus CrlC ratio of cast iron
res ista nce th a n th e co nt ro l sa mpl e I . Sa mpl es with a all oys
hi ghe r c hro me pro po rti o n in c reased the wea r-o ut
resistance, whi c h was ev ide nt with a hi ghe r Ni
con ten t; th e refo re, therma l treatme nt of a ll oys a nd 1cxxx)
~
in co rpo rati o n o f Ni at 2 pe r cent leve l pro ved '"E 1CXXl
benefic ia l in in c reas in g resis tance. u
100
Co ncernin g ha rdness, a decreas in g tre nd was <t
shown as the CrlC rati o inc reased (Fi gure 2) .
.s.
...
10
...0 1
Greate r hardness occ urred in sa mpl es 2 and 5, 0
0.1
whi c h were over 10 points in the a + (Cr, Fe)7C6
0.01
phase whe n co mpared to the contro l. T he inc reas ing
carbo n co nte nt favoured formation of a greate r Alloy sarrple t-k>.
num ber of c hro me carb ides at nic ke l concentrati o n of
1.5 pe r ce nt. Fi gure 4 -- Evalu ati on of co rros ion suscept ibili ty versus
cast iro n alloys
In the studi ed a ll oys, the mec hani ca l pro pe rty,
the res ili e nce first in c reased with CrlC ratio up to
CrlC 30 .9, and the n w ith furth e r inc rease in CrIC , All oy sampl es 3 a nd 4 exceeded the co ntro l
fro m 30. 9 to 71 .6, it dec reased in a lmost a linear sampl e I in res il ience. In these high-c hro me iron
manne r (F ig ure 3). alloy s, nicke l was sig nifi cant in su ch an in c rease,
s ince g reate r res ili ence va lu es were o bt ained at a Ni
4J conte nt of 7 per cent.
:Ii Th e results of the corros io n suscept ibility tri a ls
( 3) fo r hi g h chrome iron a ll oys tested in suga r med ia are
a: shown in Fi gure 4 .
:r: 2)
~ ;:o All oy sa mpl es 2 a nd 4 presented th e best
Q)

~ 15 corrosion res istance. Sampl e 5 was hi gh in carbo n

ell
:r: 1O
and low in ni c ke l, a nd during its manu fac turing a
passivati o n layer was achi eved w hi c h protected the
5
al loy surface aga in st th e sugar medi um . O n the o th e r
0 +------.-------.------,------,-------
hand , sa mp le 3 wi th propo rti o ns 24 C r-7 Ni , a lso
144 ::9.4 3)9 429 71.6
provi ded good corros io n res ista nce. A hi gh ch ro me
OC
conte nt, ma inta ini ng th e N i ra ti o, d id no t lead to good
Figure 2 -- Evaluation of hard ness as a function of the CrlC ra tio
results aga in st corros ion. The re fo re, ca re mu st be
of cast iron alloys ta ke n in the rati os of these alloy in g e lemen ts.
 ZUMELZU e/ al.: HI GH CHROMI UM CAST IRON ALLOY S 587

The sa mpl es show ing the lowest susceptibility

to corrosio n were sa mpl es 2 and 4, with ioni c
clisso lut io ns of Fe, Cr, and Ni under 0.05 mg/L. The
SEM of sa mpl e 4 showed no ev idence of surface
damage (Figure 5) on the all oy ca used by th e
elec trolyte used, and this exh ibited a homogeneous
morp hology, without defects. The sampl e 2 also did
not show any evidence of deterioration (Figure 6) ,
however, small and incipient pits could be
apprec iated (top upper and left corners).
On the co ntrary, the SEM of samp le 5 (Figure 7)
showed intergranular co rrosio n wit h ioni c dissolutioll
(b lack line) caused by chro me separati on from the
Figure 6 - Incipienl pits on the surfacc of sample 2 (SEM. X 500)
alloy. The Figure 8 with the hi ghes t magnifi cati on
showed the damage morphology by the sugar medium
betwee n the ferrite grains and corros ion products
(li ght areas) in sa mpless

Conclusions
Of the res ults obtained under the ex perimental
co nditions of thi s stud y the following co nc lu sions
cou ld be drawn :
The chemical compos iti on has a stro ng influence
on th e properties of all oys, i. e., the characteri stics
01 carb ides rega rdin g th eir proportion , size and
shape; and the type of matrix formed.
With rega rd to the structural characteri sti cs the
Fi gure 7 - Surface morphology of sample 5 with intcrgranular
amount of chrome ill the matri x of tested alloys
corros ion (SEM, X 500)
proved to be signifi cant and determinant of the
proporti on, size, and di stance of carb ides which
cluste r th emse lves formi ng small discontinuous
co lonies on grain edges, with distances that va ry
from 3 to 6 ~l1n .

Figure 8 - Effcct of corrosion on the micrnst ru clUre of

sample 5, damage morphology (SEM, 4, 26ll)

Three attack mechanisms of co rros ion on the

Figure 5-S urface morphol ogy of samp le 4 without attack alloys under study were obse rved; I' i~., ga lva ni c
(SEM. X 6,400) action , pitting mi crocorros ion aro und impurities,
588 J SCIIND RES VOL 62 JUNE 2003

and inte rgranular corrosion due to chrome 3 Kible A & Pearce J T H, Influence of heat treatment on the
detac hme nt from the matrix. microstructure and hardness of 19% high- chromium cast
irons. Cast Metals, 6 (I) ( 1993) 9-15.
All th e observations were carried out, to 4 Pattyn R L, Heat treatment of hi gh--Cr white irons, AFS
eval uate the potential perfomance of cast iron alloys Trans , 93 ( I ) ( 1998) 161-167.
under study, i.e., the corrosion resistance, electron 5 Goyos L, Castaneda R, Weltinck E, Va lera R & Moors M,
microscopy observations, microanalyses, and Behaviour nodul ar iron with austempering in corrosion and
wear, Proc Fourth Iberalll Congr Mech Eng (Univers idad de
mechanica l properties, comply with the requirements
Santiago), 1 (1999) 1-6.
for discrimination and adequate information to be 6 Fras E, Serrano J L & Bustos A, Casl iron (ILAFA , Saltillo,
incorporated into a total quality control, and also in Mexico) 1990.
this manner, to study necessary strategies for the 7 Durmann R W, Achievement or hi",h quality all oyed white
se lecti on of better alloys. iron castings , The FOllndryman , 83 ( 1990) 25-27.
8 Dupin P, Saverna J & Schissler J M, A structural study of
Acknowledgements chromiun wl}ite cast iron , A FS Tran s, 90 ( 19X3) 71 1-718.
The authors gratefu ll y acknowledge the 9 Perce J T H, Structure and wear pt'rfomance of abrasion
resistan t chromium white cast iron . AFS Trans , 92 (1984)
financial support provided by CONICYT
599 -622.
C hile/CITMA proj ec t W 1998 02 159; and the 10 Abrasion resistin g IVhite cast irons, Pa rI 3: High chromil/Ill
Laboratory for Iron and Stee lmarking, Universiteit grades (B riti sh Standards Institution, Lo ndon) 1986. BS
Gent, Belgium. 4844.
II Uetz H, Abrasioll and erosion (Grundlagen , betriebliche
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