Beruflich Dokumente
Kultur Dokumente
August 2007
Document Code: A
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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].
2.2 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
177
CHINA FOUNDRY
Vol.4 No.3
Characteristics
Suitable for
Application
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.
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
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
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.
Special Review
August 2007
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
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
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
* The number of thermal shock cycles (heating/cooling) before the first crack appears on the sample surface
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].
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.
August 2007
Special Review
181