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Special Review

August 2007

The forty years of vermicular graphite


cast iron development in China ( Part  )
QIU han-quan1 and CHEN Zheng-de2
(1. Shandong institute of mechanical design and research; 2. Shanghai office of UK Vantage Co.)
CIC numbers: TG143.5/-1

Document Code: A

Article ID: 1672-6421 (2007) 03-175-07

2 Manufacturing methods and vermicularisers


2.1 Manufacturing methods
From the long period of practical experiences of VGCI
production, the following four points are very important for
the successful production of VGCI:
 Consistently control sulphur at the correct, low level
(consistency is the key point);
 Choose a suitable vermiculariser;
 Accurately control the weight of liquid metal to be treated;
 Control the iron melt temperature to obtain a consistent
treatment temperature;
If any of the above operations are ignored, then quality
fluctuations will occur.
The production of VGCI needs even more strict control than
that of SG iron and if it is well controlled, stable production of
VGCI can be obtained directly from cupola and blast furnace
iron. This has been confirmed by several VGCI manufacturers.
QIU Han-quan et al[42] have studied the control system for
VGCI production, which enabled the improvement of VGCI
production.
Several methods have been used for the production of VGCI
in China.

2.1.1 Sprinkling vermicularising alloy in the iron stream at


the spout
In this method, RE-FeSi or RE-Ca-FeSi alloy is sprinkled into
the iron stream at the spout of the cupola or electric furnace.
After mixing with treatment alloy, the iron is transferred into
the ladle, the molten iron is stirred; slag is removed, and then
poured. This was an early used method in China and is still
been used. This method is suitable for medium or heavy section
castings[5, 28, 43, 44].
PENG Ti-yuan et al[45] described a method in which an
intermediate vessel is used between the spout and the pouring
ladle (this is known as the double vessel swirling method).

Treatment alloy is well mixed with molten iron before entering


a pouring ladle. A double swirling method described in
reference [46] is similar to the intermediate vessel method.

2.1.2 Dam-ladle treatment


There are three variations of this method.
(1) Stirring by low boiling point alloy: RE-FeSi (or RE-CaFeSi alloy) and RE-Mg alloy are placed inside the dam in the
bottom of the ladle, either mixed together or in alternate layers.
Part of the molten iron (1/2 to 2/3) is tapped into the ladle for
VG treatment; the remainder of the iron is subsequently tapped
with the addition of inoculant on the furnace spout. The treated
iron is de-slagged, and then poured. This method is suitable
for medium size and large castings [47, 48].
Other vermicularisers such as RE-Mg-FeSi [49], RE-Mg-Sn-FeSi [50],
RE-Mg-Ti-FeSi [51], and low RE-Mg-Ti-FeSi [52, 53] alloys are also
used with the dam-ladle method.
(2) RE-Zn-FeSi alloy treatment: the vermiculariser is placed
insides the dam in the bottom of ladle, all the molton iron is
tapped into ladle. Stirring and inoculation are not necessary. This
treatment is suitable for medium and thick section castings [54, 55].
(3) RE-Mg-Ca-FeSi alloy treatment: RE-Mg-Ca-FeSi alloy,
together with common salt are placed inside the dam in the
bottom of ladle; the alloy is consolidated and covered with
plant ash. Two-third of the molten iron is tapped into the
ladle for VG treatment; the remaining one-third iron is tapped
later with the addition of inoculant. The treated iron is slagged
off, and then poured. This method is suitable for castings with
medium section sizes [56].

2.1.3 Addition of treatment alloy to the induction furnace


This method is suitable only for induction furnace melting.
RE-FeSi alloy is added on the top of the melt in the furnace
before tapping. Inoculant is then added on the top of the bath
after the vermiculariser has nearly melted. No manual stirring

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1 Mr. QIU Han-quan, born in 1937 in Xiamen city, is an outstanding expert with special government allowance, retired; he graduated from
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Shangdong University in 1960, and then taught in the university. From 1963 he worked in the Shandong Institute of Mechanical Design and
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Research and engaged in the research on VGCI for long time, particularly did practical research in many foundries. E-mail: qiuhanquan88@hotmail.
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com.
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2 Mr. CHEN Zheng-de, senior engineer, was born in 1946 in Shanghai. He graduated from Shanghai University of Science and Technology in
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1970, and worked in foundry for some years. From the early of 1980 worked in Shandong Academy of Science, and participated in the
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experiment, production and application of VGCI since 1970. Now he is the manager of he Shanghai office of UK Vantage Co. E-mail:
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chenkevin@126.com
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175

CHINA FOUNDRY
is necessary for this method as the induction power applied to
the furnace bath provides sufficient stirring action. This method
is suitable for medium section VGCI castings [57].

2.1.4 Two-step treatment


RE-Mg-FeSi alloy is placed inside the dam in the bottom of the
treatment ladle. Molten iron is tapped into the ladle and treated
into SG iron; more molten iron is tapped into the treatment
ladle with addition of the inoculant; the SG iron then is changed
to VGCI by reducing the magnesium and RE content. The
treated iron is slagged off, and then poured. This method is
suitable for the small and thin section castings [58].

2.1.5 Wire feeding method


The feasibility of using the wire feeding method was studied
by several investigators [59-61]. The composition and addition
rate of the wire were analysed and processing parameters were
determined. Wire feeding and ladle treatment were compared
and it has been shown that the wire feeding method has its
own advantages in the production of VGCI: the percentage of
VG is stable and consistent, and cost is reduced. Since 1991,
using wire feeding and induction furnace melting, the German
Foundry, Halberg has been producing VGCI V8 cylinder blocks
for an Austrian company. The cylinder block has 3.0 litre swept
volume and produces 150 kW; it weighs only 74 kg and its
main wall thickness of the cylinder is only 3.5 mm. The alloy
in the core of the wire is 5% Mg-FeSi and each treatment
weight is 1 200 kg. For the cylinder wall section, where specified
properties are necessary, the percentage of VG needs to be
greater than 90% [41].

2.1.6 Other methods


In addition, other methods are also used in production including
double ladle [62], tundish ladle [63], nitrogen blowing [64], powder
injection [65] and in-mould treatment [66] etc. These methods are
used very rarely now.
At present the most used methods are sprinkling
vermiculariser in the iron stream at the furnace spout and
dam-ladle treatment. With the requirement for more accurate
control of the production process and the percentage of VG,
the wire feeding method is being adopted by more and more
foundries.

2.2 Inoculation
Normally, inoculation results in an increase in eutectic cells in
VGCI [68-70], this was recognised in the production of SG iron as
early as in 1960 [67]. Therefore, for the requirement of a high
percentage of VG, large eutectic cells are desireable and no
inoculation is necessary for VGCI [54, 64, 71].
Some people thought that Ca is beneficial for forming VG
because of its inoculation or deoxidation and desulphuration.
ZHANG Zhi-shan [72] doubted the opinion above, since it is
difficult to explain some experimental results. The author
considered that in crystallisation, Ca may locally remelt the
austenite shell, or weaken the strength of the austenite shell,
making it easy to be broken and create beneficial conditions
for growth of vermicular graphite; maybe because Ca is
absorbed on the surface of graphite crystals, the surface tension
between the prismatic plane and the liquid iron is increased
to a level necessary for vermicular graphite to grow.
176

Vol.4 No.3
ZHANG Fu-quan et al [73] introduced a process of RE
vermicularisation and post inoculation. This process is cheap
and simple; with measures of control and testing in front of
the furnace, even for high sulphur (0.05%J0.07%) cupola
molten iron, VGCI can also be produced successfully.

2.3 Vermicularisers
The characteristics and quality of vermicularisers is one of the
essentials for stable and consistent production of VGCI. The
early vermicularisers used in China were all RE-FeSi alloy; the
problems with the RE-FeSi are:
1). The addition range for producing VG is narrow
2). Lots of dross is formed on the iron surface which is difficult
to remove
3). The resulting iron has a high chilling tendency
Intensive investigations have been carried out to try and solve
these problems and following results have been obtained [21, 74, 75].

2.3.1 The difference between upper and lower limits for the
suitable range of addition
For producing VG, the range of vermiculariser addition, (i.e.
the difference between under and over addition), is actually
the ability to modify graphite morphology. A vermiculariser
having strong modification ability will produce SG more easily;
whilst a vermiculariser having weak modification ability will
produce VG more easily. The addition range of vermiculariser
is Ca-FeSi alloy > RE-FeSi alloy > Mg-FeSi alloy. When using a
RE-high Ca-FeSi vermicularisor, after the addition of flux, its
strong dross forming ability is significantly reduced and its
absorption is greatly improved; the addition range is then REFeSi alloy > RE-high Ca-FeSi alloy > RE-Mg FeSi alloy. From
analysing the residual element content in the VGCI, the range
for VGCI is RE > Mg > Ca. Therefore, for the same vermiculariser
the range is very different depending on its absorption into
the molten iron. In the early days, a Ca vermiculariser was
considered to have the widest range for producing VG; actually,
this wide range resulted from poor absorption. Relatively
speaking, RE-FeSi alloy is the vermiculariser with which it is
the easiest to obtain VG, but was considered as the alloy having
the narrowest range. This is due to the poor melting condition
and poor iron quality (mainly high and variable sulphur content,
especially for cupola melting) in the early days in China. These
poor conditions should not be considered as suitable conditions
for the production of VGCI. Actually in China with the least
improved metling condition using cupola iron, many foundries
have produced VGCI successfully with RE-FeSi alloy. This
confirms the advantage of RE alloy.
Research work showed that a vermiculariser containing
mainly RE is more suitable for VGCI production [76]. SHEN Zeji et al [77] considered further that the increased La in RE
vermiculariser is beneficial for stable and consistent production
of VGCI and considered that a RE vermiculariser should contain
mainly La as the RE content.
The addition of other minor elements for widening the
addition range has been studied.
Ti and Sb: in the two elements, Ti is used more than Sb in
the production of VGCI. Until now, however, using these two
elements in vermiculaisers mainly containing RE, significant
and stable results have not been found yet [21, 74, 14, 78-80]. SU

Special Review

August 2007
Ying-long et al [81] found that when RE in a vermiculariser is
high, the addition range for producing VGCI is too narrow,
thus the anti-spheroidal element content needs to be
increased. The author considered that this fact is because RE
neutralises the deleterious effect of the subversive element
Ti on Mg; conversely it can be said that Ti consumes the RE.
Research has been carried out on low, medium and high Ti
irons and the results showed that the limits of suitable addition
range for a vermiculariser are moved up or down with Ti
content, but the range is not widened. This indicates that
when RE is high, the addition of Ti does not show a
corresponding effect for low RE. The addition of other
subversive elements will have a similar result. For example,
Sb is normally considered to be a strong subversive element
for SG iron; but when the author added 0.1% Sb into RE
VGCI, the nodularity was significantly increased. QI Mengdiao et al [46] studied the stability of VGCI production and
found that when using RE-FeSi with a trace of Sb, for
production of VGCI, using local pig iron having traces of
vanadium and titanium, and the sulphur in the base iron is
allowed to vary about 0.025%, satisfactory results were
obtained. Actually the research by QI Meng-diao et al [46]
confirmed that a trace of Sb has a significant effect on
increasing nodularity; when Sb is increased to certain content
it is beneficial for obtaining VG. The author considers that
this is because subversive elements Sb and Ti consume RE.
LI Qiu-shu et al [82, 83] considered that Ti exists as a precipitated,
blocky compound in VGCI, which changes the distribution
of spheroidsing elements in the iron and promotes VG; they
came to the conclusion that Ti expands the range of RE-MgFeSi alloy for producing VG.
Mg-Ti FeSi vermiculariser with trace RE (similar to Foote
alloy) can significantly expand the range for Mg because of
the existence of Ti. It is clear that this is due to the very small
amount of RE, therefore the neutralisation of subversive
element Ti is very little. HOU Yan-hong et al [84] considered
that the inherent Ti content in many local pig irons in China
is similar to the Ti content of the patent Foote alloy and
suggested using a vermiculariser without Ti. Using this alloy
for local pig irons containing Ti, good results could be
obtained in the laboratory. If industrial production of VGCI
can be realised using this alloy, certainly it will be a very
significant development.
Al: Shandong University studied the production of VGCI
using RE-FeSi and RE-Al-FeSi. The results showed that RE
VGCI with Al has a much larger range than the RE VGCI [85].
YU Hua-shun et al [86] studied the fading of VG containing
0.87%J4.20% Al and compared this with other VGCI. Using
the same amount of vermicularising element, the fading of
VGCI with Al can be delayed by 5 minutes. YU Hua-shun et
al [87] showed that with 0.87%J4.20%Al, the percentage of VG
is increased, ferrite is enhanced, strength and elasticity are
improved and the hardness is reduced, with less variation.
The anti-oxidation properties are improved with the increase
of Al content. Using optical microscope and computer
analysing YANG Xiang-shou et al [88] studied and analysed
the thin section Fe-C-Si alloy samples treated with RE-MgFeSi alloy and the patent alloy SG plus RE-Mg-FeSi; and

found that the SG plus RE-Mg-FeSi is good vermiculariser for


thin wall VG iron castings.
The effects of trace elements Ca, Zn, Bi, Cu, Al, Ti, Sn, As,
Pb and Sb on the addition range for VGCI were studied [89-97].
Based on the results, vermicularisers suitable for thin and thick
wall section castings were suggested.
With the exception of these trace elements, carbon, the most
important element in cast iron, has an important effect on the
addition range (or residual range) for VGCI. Study showed
that low carbon (2.58%J3.22%) iron has a wider addition range
than high carbon iron. This is in agreement with the results
obtained by QIU Han-quan and JIANG Yi-jian [7]. In low carbon
equivalent cast iron, due to its large austenite dendrites, carbon
is not easy to change to spheroidal and similar to SGCI; its
shrinkage tendency is high.
At present the vermicularisers used in production in China
are listed in Table 3 [75, 99]. Many foundries in China have
produced their own vermicularisers and since the 1980s, many
alloy companies have produced commercial vermicularisers; some
typical vermicularisers and their application are listed in Table 4

2.3.2 The formation mechanism of dross


When a vermiculariser, especially RE-FeSi or RE-Ca-FeSi, is
added to molten iron, a large amount of dross will be formed.
The author considered the cause of formation from chemical
dynamics and concluded that when the alloy is added to molten
iron, high melting point oxides, sulphides of RE and Ca, and
silicates are formed on the surface of vermiculariser particles.
These compounds do not move away from the vermiculaiser
particle surface immediately, but cover the particles and hinder
further de-oxidation, de-sulphuration and vermicularsation of
the alloy particles underneath the compounds. The compounds
covering alloy particles will float up to metal surface, with
other compounds and form dross. Therefore the key measures
for solving the dross problem are to eliminate or reduce these
covering compounds in the first place, then reduce the melting
point of the vermiculariser and increase the density of the
vermiculariser. Adding flux during treatment, using low melting
point alloys and adding a small amount of Zn and Al in
vermicularisers are all measures for reducing dross.

2.3.3 Chilling tendency of VGCI


RE has the strongest chilling tendency on cast iron in
vermicularisers. Therefore, if the vermiculariser has a high RE
content, graphitisation needs to be increased; for example,
strengthening inoculation or increasing graphitisation elements
in the vermiculariser. Thus from a technological point of view
the ideal composition of a vermiculariser should be beneficial
for forming VG, have a low dross forming tendency, easily
absorbed by molten iron and have a low chilling tendency.
Up to now more than thirty different vermicularisers, among
nine types, have been studied and corresponding technical standards
and treatment procedures have been set up; these vermicularisers
can satisfy the production of VGCI castings of varying section sizes,
under different conditions. However for those vermicularisers used
to produce thin section castings (as references 88, 90, 94, 96
recommended), more experiments need to be carried out to verify
whether they can obtain high percentages of VG.

177

CHINA FOUNDRY

Vol.4 No.3

Table 3 Typical vermicularisers and their application


Vermiculariser

Characteristics

Suitable for

Application

Easy to obtain VG with this alloy; addition


range is wide, chilling tendency is high,
cost is low; it is not as good as RE-Si-Ca
without flux for obtaining VGCI, but has
less critical addition and dross formation
is less than RE-Ca-FeSi.

Low sulphur iron from


induction furnace for medium
or heavy section castings or
cupola iron with stirring after
treatment

Used successfully with induction furnace


melting for producing high-power engine
cylinder heads in a rolling stock plant. Used
successfully with cupola melting for defence
application in a foundry in Shandong
province. Both of these irons have
inoculation after alloy treatment

Without flux, the addition range for VG


is wider than for RE-FeSi; chilling
tendency is less than for RE-FeSi; more
dross is formed and the addition rate and
cost are higher than for RE-FeSi alloy; with
adding flux, dross is reduced but chilling
tendency is increased and the range is
narrowed.

Low sulphur iron from


induction furnace for small to
medium castings

Used with CaF2 and FeSi inoculation to treat


induction furnace iron for hydraulic castings
by a research institute in Zhengzhou and a
hydraulic elements factory. Used for cupola
iron for steel ingot moulds by a metallurgical
plant. Used 70% RE-Ca-FeSi and 30% REMg-FeSi (used as a stiring alloy due to its
low boiling point) to treat cupola iron for
sliding plate, sliding block, medium and
heavy section castings in oil press in a heavy
machinery plant

The addition range is larger than for REMg-FeSi and similar to RE(24%)-FeSi; the
chilling tendency is in between that of
RE-FeSi and RE-Mg-FeSi alloy; less dross
is formed, no necessity for stirring and
no necessity for inoculation for medium
and thick section castings.

Suitable for not very thin


section castings; RE-Zn2%Mg2% is used for high
treatment temperature and low
sulphur iron; RE-Zn4%-Mg4% is
used for high temperature and
low sulphur iron.

Used for cupola iron for 350 kg medium


casting, the universal testing machine bed,
with a section difference of 12 folds by a
material test machinery company. Used for
blast furnace iron for ingot and glass mould
in an iron and steel plant. Used for cupola
iron for metallurgical castings, glass moulds
VGCI etc. in Shandong Zibo VGCI foundry.

Compared with the above alloys the


addition range is less; no much dross is
formed; chilling tendency is the lowest
and the critical addition is larger

Suitable for cupola and


induction furnace iron for small
and high chilling tendency
castings

Used for induction furnace iron for EQ140


engine manifold and gear housing in an
automobile factory. Used to treat cupola
iron for gears in textile machine in a textile
machinery in Beijing

The addition range and chilling tendency


are similar to that of RE-Zn-Mg- Al alloy;
dross is less than for RE-FeSi, but more
than for RE-Mg-FeSi; more fume is formed

Suitable for cupola iron for


small to medium VG castings

Used with salt in dam-ladle for cupola iron


for cylinder liner in a diesel engine company
in Jiangsu

RE-Mg-FeSi alloy

Compared with above five alloys the Suitable for cupola iron for
addition range is less; the dross is less medium and thick section VG
than for RE-Ca-Mg-FeSi alloy and more castings
for RE-Ca-Mg-Al-FeSi alloy; chilling
tendency is low. Has high nodularising
ability therefore the critical addition for
VG is less

Used for cupola iron with double ladles for


steel ingot moulds in an iron and steel plant
in Shanghai. Used for cupola iron with damladle for steel ingot moulds in a iron and
steel plant in Hangzhou

RE-FeSi alloy plus


RE-Mg-FeSi alloy

The addition range is slightly more than Suitable for cupola iron for
for RE-FeSi; the dross is more than for medium to large and thick
RE-Mg and RE-Zn-Mg-Al alloy; need two section VG castings
kinds of the alloys; it may be convenient
for the foundries having the two alloys,
otherwise may not convinient

Used for cupola iron with dam-ladle for


engine cylinder liners in a diesel engine
plant in Jiangsu. Used for cupola iron with
dam-ladle for glass moulds in a medical glass
plant in Gansu province.

RE-FeSi alloy
(RE21or RE24)

RE-Ca-FeSi alloy
(RECa13-3)

RE-Zn-FeSi alloy
(REZn2Mg2 or
REZn4Mg4)

Low RE-Mg-Ti
alloy

RE-Ca-Mg-FeSi
alloy

Note: the basic characteristics of vermicularisers indicate that for a similar kind of treatment alloy, the alloy with high RE will have a high
chilling tendency; the alloy with high Ca will produce more dross; the alloy with high Mg will have a small addition range and it will be easier
to produce spheroidal graphite.

3 Relationship between microstructure and properties


3.1 Study from two-dimensional morphology
In 1960 the relationship among properties, two-dimensional
microstructure, composition and alloy addition were studied [5, 8-13]
178

and a handbook, Metallography of Rare Earth Grey Iron, was


edited and published [101]. In the last ten years systematic
research work was carried out and further understanding of

Special Review

August 2007

Table 4 The range of vermiculariser products within a company


Vermiculariser
RE-FeSi-1
RE-FeSi-2
RE-Mg-1
RE-Mg-2
ER-Zn-1
RE-Zn-2
RE-Mg-Ca-1
RE-Mg-Ca-2
RE-Mg-Ti-1
RE-Mg-Ti-2
RE-Mg-Cu-1
RE-Mg-Cu-2

No.
RT-1
RT-2
RT-3
RT-4
RT-5
RT-6
RT-7
RT-8
RT-9
RT-10
RT-11
RT-12

RE
29J32
24J27
6J8
6J8
13J15
13J15
11J14
14J16
8J10
0.25J0.35
6J8
7J12

Mg
<1.0
<1.0
6J8
3J4
*
*
4J6
2J4
6J8
4J5
7J9
7J9

Ca
<2
<2
<3
<3
<5
<5
8J10
2J4
<3
4J5
<3
<3

the relationships among properties, two-dimensional


microstructure, composition and alloy addition have been
obtained [68, 72, 101-103]. These results indicated that the mechanical,
physical and casting properties of VGCI are mainly dependent
on graphite morphology, and that graphite morphology is
dependent on the vermicularising treatment process and the
treatment results. The graphite in VGCI is mainly a mixture of
vermicular and spheriodal particles with a different ratio;
therefore the properties of VGCI are in between those of SGCI
and GCI. When the two-dimensional microstructure contains
flake graphite the properties are in between those of GCI and
VGCI. The graphite morphology of VGCI affects all properties
and the effect varies gradually. When the graphite is mainly
VG the casting properties are close to those of GCI; with
graphite containing more spheroids, the casting properties
gradually approach those of SGCI. HE Zuo-zhi et al [102] showed
that when the VG percentage is less than 70%, the thermal
conductivity is decreased significantly; when the VG percentage is
less than 50%, the shrinkage and internal stress are all increased
considerably; at 700 high temperature plasticity is significantly
increased and may cause increasing the deformation of casting.
It should be pointed out that not all the properties of VGCI
are in between those of SGCI and GCI. Under certain conditions
the properties can be better than those of SGCI or worse than

Chemical composition, wt.%


Si
Cu
Zn
< 50
< 50
40J45
40J45
40J46
40J46
40J46
40J46
40J46
40J46
38J42
38J42

Ti

Al

Fe

<0.5
<0.5
<0.5
<0.5

<1.0
<1.0
<1.0
<1.0
0.6J1.2
0.6J1.2
<1.8
<1.8
1.2

Bal.
Bal.
Bal.
Bal.
Bal.
Bal.
Bal.
Bal.
Bal.
Bal.
Bal.
Bal.

6J8
3J4
<0.5
<0.5
4J6
8J10
7J9
17J23

<1.8
<1.8

those of GCI. For example, ZHU Shi-zhen et al [62] compared


the service life of GCI, VGCI and SGCI in small to medium
sized ingot moulds and showed that under water spray cooling
conditions the ingot mould with 10%J50% VG had the best
service life; under water immersion cooling conditions it was
not as good as a GCI mould; under air cooling conditions it
was not as good as an SGCI mould. Under the same cooling
conditions the VGCI ingot moulds with different amounts of
VG showed different service lives. In the laboratory, HU Zhongcheng [105] and HUANG Hui-song et al [106] carried out
experiments on the resistance to thermal shock under heating/
water quenching conditions. The results showed that the
resistance to thermal fatigue (thermal shock or the resistance
to cracking) of VGCI is superior to that of SGCI and GCI, (see
Table 5). DING Sen [107] compared national and international
research results and pointed out that the thermal fatigue
property of cast iron is strongly related to the thermal alternating
condition; for material selection except the thermal fatigue
property, the complexity of casting structure and casting process
also need to be considered. In addition the soundness and
anti-permeability (liquid tightness) of VGCI is superior to that
of SGCI and high grade GCI as well. This is due to the inherent
solidification characteristics of VGCI, which makes it suitable
for castings like hydraulics and valves etc.

Table 5 Resistance to thermal shock of GI, VGCI and SGI (cycles when first crack appears)* [105]
Test temperature
o
C
Room temperature _ 300
Room temperature _ 600
Room temperature _ 900

Grey iron
Cycles
590
65
10

Pearlitic-ferritic VGCI
Cycles

Pearlitic SG iron
Cycles

>1000 (no crack)


190
43

>1000 (no crack)


100
28

* The number of thermal shock cycles (heating/cooling) before the first crack appears on the sample surface

3.2 Study on three-dimensional morphology


What is vermicular graphite? There were dif fer ent
understandings on it in the past. With the development and
application of the Scanning Electron Microscope (SEM) it is
clear now that the observed isolated vermicular graphite flakes
and some spheroids observed using conventional optical
microscopy are actually connected to each other in space within
the eutectic cell. Some nodules are not really isolated nodules,

but are part of the vermicular graphite. Normally under


conventional 2-D microscopy inspection, the small isolated
nodules are not included as VG. Therefore the VG percentage
(not including the isolated nodules) is only a nominal
percentage, which is lower than the actual VG percentage. It
is reported that the 85% VG actually is 100% VG [116].
Using TEM (Transmission Electron Microscope) and SAED
(Selective Area Electro Diffraction) techniques it was found
179

CHINA FOUNDRY
that there are two kinds of VG: VG connected by many nodules
and VG connected by prism type graphite. An SAED study
also showed that the base face of prism graphite (0001) is
partially coherent with ferrite (111) face; the mismatch is 5% [117].
ZHANG Guo-zhi et al [118] showed that under a pulse electromagnetic field, the amount of branches of austenite is reduced
significantly and graphite becomes coarse, but after
spheriodisation the amount of spheriodal graphite is reduced
and the percentage of VG is increased significantly. It was
considered that the stirring action by pulse electro-magnetic
field and the thermal effect from an induced current destroy
the stability of the austenite shell and promote branching of
graphite, SG is easy to change to VG and VG is easy to change
to flake graphite. The author considered that this may be a
solution for over vermicularisation.
WANG Liang-yang et al [119] pointed out that VGCI containing
oxygen has less heteromophic graphite, graphite consists of
small blocky units; the edge of graphite is round and the ratio
of length over width is smaller. Using pig iron rich in Sn, As
and Pb elements for the production of VGCI will promote
more heteromorphic graphite [120].
Using unidirectional solidification research, the results showed
that the main structure of VG is combined prism type of graphite
with flower or star type of graphite around the prism [121].

3.3 Eutectic cells of VGCI


Due to the low sulphur and phosphorous content it is difficult
to clearly show and calculate the eutectic cell count of VGCI.
After many experiments and using alternate polishing and
etching techniques, a method has been found to detect the
eutectic cells in VGCI. The eutectic cells model of VGCI has
been developed and photos of VGCI eutectic cells have been
published [122-124]. Similarly with grey iron the vermicular graphite
flakes in VGCI are interconnected and the cell sizes are similar
to those in grey iron. However, unlike in grey iron, the
vermicular flakes are not mesh with the vermicular flakes in
the neighbouring cells; VG in neighbouring eutectic cells is
segregated by a layer of metal matrix. Normally there are some
graphite nodules in VGCI; within the eutectic cell the spheroidal
graphite nodules are not a real nodules, but the ends of
vermiculars; the nodules at the eutectic cell boundary are bigger
than those within the eutectic cell and they are the real isolated
nodules. The boundary of VGCI eutectic cells is not shown as
clearly as those in GCI, this because the impurity elements in
VGCI are much lower and not uniformly distributed as in GCI.

Vol.4 No.3
FAN Rui-xin et al [125] showed that the solidification of VGCI
consist of two stages. The continuous redistribution of
vermicularising elements in molten iron is the important factor
affecting graphite modification.
LI Ke-guan et al [126] considered that from the cooling curve
two transformation stages could be observed. Firstly, graphite
nodules form before eutectic transformation and the nodules
grow with the growth of the austenite shell. Secondly, VG
forms. This is because part of the austenite shell remelted and
VG grows with the contacting melt. Thus the nodules formed
at the eutectic stage become the start of VG growth.
ZHU Zhen-hua et al [127] showed that there are three types of
eutectic cells: VG without branching within the cell; VG
originating from larger graphite nodules within the cell and
VG with many branches within the cell.

3.4 Matrix structure


The properties of VGCI are mainly dependent on graphite
morphology, which has been concentrated on by great research
work; but the properties are also affected significantly by the
matrix structure.
Some literature abroad considered that a pearlitic structure
is very difficult to obtain in as cast VGCI. However in China,
as early as in the late 1960s, pearlitic VGCI (ferrite <5%) machine
tool castings were produced using cupola melted high sulphur
iron without any alloying addition [24]. By adjusting molten
iron composition, adding alloying elements and using different
treatment methods high pearlite content VGCI cylinder liners
and steel ball grinding plates were produced, using centrifugal
and sand casting techniques [128-131]. The effects of Si, Mn, Cr,
Mo, V, Sb, Cu, Sn and B on graphite morphology and matrix
structure of VGCI were studied in detail [132]. The results showed
that by properly adjusting carbon equivalent and adding a
certain amount of Mn and other alloying elements, VGCI with
more than 90% pearlite could be obtained consistently. The
tensile strength reached 430J470 MPa, transverse strength 900 MPa,
deflection 4J6 mm and hardness 249 HB ( 30 mm test bar).
In the early 1980s, VGCI microstructures were studied and
understood more thoroughly in China. Based on these results
some companies have compiled metallography of vermicular
graphite and VG metallography standard. In 1984, The
Metallography Standard for Vermicular Graphite Cast Iron,
(JB/T 3829-1984) [116,133-139] was issued by the former Machinery
Ministry of China; and it has been used in teaching, research
and production as an inspection standard since then.

4 The primary crystallisation of VGCI


In China, the research work on the primary crystallisation of
VGCI has been carried out and it has been concluded that the
crystallisation characteristics of VGCI are in between that of
GCI and SGCI. Nevertheless there still exists different
understandings and opinions about nucleation and growth;
and the study measures were also different.
Using improved liquid quenching and thermal analysis, it
was suggested that the growth of vermicular graphite is started
from distorted spheroidal graphite; VG grows alternately along
the c-direction and the a-direction, the main reason for the
180

alternating growth is the variation of spheroidising element


concentration in the growth front. Austenite has certain
influence on growth as well [140].
Through liquid quenching and scanning microscopy analysis,
DENG Xi-jun et al [141] confirmed two VG growth models: flake
graphite changes to vermicular graphite and spheroidal graphite
distorts into vermicular graphite.
It was suggested that modification element causes an inclined
twin. Inclined twins play an important role in the formation of
vermicular graphite. With less modification element the

August 2007

Special Review

inclination direction of a twin face changes continuously and


the beginning, VG is not formed from the distortion of
graphite forms a vermicular shape due to distortion. With more
spheroidal graphite and grows into various VG. ZHOU Qingmodification element the direction of a twin face inclines along
de and SU Jun-yi [16] and HONG Zhong-cheng et al [105] thought
one direction and graphite forms a spheroidal crystal [142].
that the growth crystallisation of VG is similar to that of SG
Using a scanning microscope, the observation of liquid
and grows with spiral dislocation steps.
PAN Zhen-hua [148] considered that the formation of VG is
quenched VGCI samples showed that at the early solidification
stage eutectic cells are enveloped entirely by austenite; part of
realised by many different ways. Using liquid quenching it
vermicular graphite branch still directly contacts with liquid
was suggested that virtually the vermicularisation is kind of an
iron. The spacing morphology of the VG eutectic cell is
un-completed even distorted spheroidisation. The formation
dissimilar to that of grey cast iron; some growth ends of
of liquid channels within the austenite shell indicates the
ver micular graphite have spiral dislocation growth
completion of SG distortion and the beginning of
characteristics [143]. Further study showed that during the entire
vermicularisation. The distortion of VG front condition and
crystallisation of VG there exist liquid channels contacting the
formation of secondary liquid channels are the indicators of
ends of VG and remaining liquid; these liquid channels result
re-branching. Spheroidal graphite at the interface between
from enrichment of alloying elements, which reduce the
austenite and liquid is the origin of a VG unit. The eutectic
solidification temperature of the liquid. These liquid channels
cells of VGCI consist of several VG units and these units are
not only supply a source of carbon but affect the branching
not connected to each other; but their eutectic austenite
[144]
and morphology of VG as well
.
dendrites are continuously connected. However, WANG GuiUsing optical and scanning microscopes ZHOU Qing-de and
sen [104] suggested that the vermicular flakes are from the same
[16]
SU Jun-yi observed the graphite growth morphology of the
origin and connected to each other within one cell.
GAN Yu and Loper [149] considered that the graphite
liquid-solid regions in the samples made from unidirectional
solidification. It was found that starting from SG distortion;
morphology is not dependent on the structure of nuclei but
depended on the local growth condition of the graphite particles.
VG grows in branching and finishes in the form of mushroom
type ends. Starting from flake graphite, VG grows along the aBecause of the variation of local growth condition, very different
and complicated graphite morphology can be developed.
direction as facet crystal, contacts with liquid cooperating with
Using simulation and decomposition/combination methods
the growing of austenite. Towards the ends VG grows as facet
along c-direction with spiral dislocation, forms mushroom type
FAN Zhi-kang et al [150] studied the orientation relationship of
ends and gradually enveloped by austenite. Small graphite
the base face of graphite in two-dimensional intercept and threenodules can also gather together, distorted, branch and grow
dimensional space. It is important to understand the relationship
to VG. LIU Bai-cheng et al [143] observed gathered small nodules
between the growth model and spatial morphology.
With the LMV unidirectional solidification technique YAO
under scanning microscope with magnification of 100. The
author considers that this may lead to a mistake thinking the
Xin et al [151] showed the whole continuous process of VG
origin of VG is gathering of small nodules. Using deep etching
growth: from crystallite to complete vermicular gaphite. It was
technique and scanning microscope with high magnification
found that vermicular crystallites precipitating between
the author found these small nodules are the some section of
austenite dendrites are quite normal in hypoeutectic VGCI.
branches of VG within eutectic cells.
Using liquid quenching ZHOU Bing et al [152,153] observed
Simulating the solidification of 250J300 mm castings with
and analysed VGCI samples with different cooling rates. It
was found that with increased cooling rate more spheriodal
the same composition as the VGCI and by quenching and
taking samples during different cooling stages of the VGCI
growth characteristics appeared in the graphite; the increased
cooling rate will make the iron crystallise under large
liquid, NIU Yin-yi et al [145] studied the growth of VG using
optical and electron microscopes. The results showed that at
undercooling and increase nuclei, inclined twins are formed,
the early stage of eutectic growth, the major growth is the
the tendency of spiral dislocation is increased, branching and
growth velocity are increased, the tendency of eutectic growth
graphite front branching growing along (10T0) with the front
directly contacting liquid; the minor growth is the side face
of graphite and austenite is reduced. Therefore the percentage
growing spirally along (0001). At the late stage of eutectic
of VG is reduced, eutectic cell size becomes small and the
growth, graphite grows within the austenite envelope; graphite
formed morphology of VG becomes more distorted and
fronts mainly grow spirally along (0001). Some people thought
rounder.
Using liquid quenching LI Xiu-zhen et al [154] revealed that
that at the very beginning VG grows like a graphite nodule; more
recently, it was realised that due to the breaking of the austenite
the frequent bending of VG is the result of interaction between
graphite and austenite, and not due to the modification
shell and the existing channels along the shell, graphite grows
[146, 70]
.
preferentially and locally and forms a vermicular shape
elements; through the direct effect on the growing interface,
Using the deep-etching method, SUN Guo-xiong and Loper [147]
modification elements change the growth of graphite and
took all the VG from a sample and observed it under a SEM. It
crystallized morphology.
was shown that many kinds of VG grow along the a-direction,
Extensive research work has been performed on the primary
indicating that VG is closer to flake graphite in growth
crystallisation of VGCI and it seems that more work needs to
characteristics; branching of VG happens at the late stage and
be carried out to obtain a deep and common understanding
the
graphite
ends
can
form
a
spheroidal
shape.
Normally
at
of the primary crystallisation of VGCI.
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181

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