The ClayScienceSociety

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Japan
Japan

Cdy Science 9, 169-179 (1994)

OF PHENOLIC
RESIN ON RESINDECOMPOSITION
COATED
SAND MIXED WITH SEPIOLITE

CATALYTIC

YVJI SAKAKIBARA, MAsAH!Ro SumuRA, YAsuo TAKADA, HiRoAKI HAyAsHi

TAKATOSHI SUZUKI
Res, and Develop. Labs. Inc.,
7byota Central
48e-11, Jupan
41-1 Ybkomichi, Ndgakute-cho, Aichi-gun,
Dec. 1, 1994)
(Accepted

and

ABSTRACT
molding process,
catalytic decomposition of phenolic resin on resinin the presence of scpiolite was investigated,Phenolic resin-coatcd
of smokc
and irritating
sand
mixed
with sepiolite libcratedlessamounts
gascs than
but also in the casting. The results
that without
$epiolite
not only in the molding,
indicatcthat the sepiolite has promoted therrnaldeeompositien of the irritating
gases as catalyst. The bendingstrength of the mold dccreased withthe increasing

In the

coated

sepiolitc

Kcy

shell

sand

contents.

words:

sand,
Sepiolite,Mold, Resin-coated
Phenols,Foundry, Phenolic resin.

Smoke, Ammonia,

Aldehydcs,

INTRODUCTION
of
Shell molding process has been utilized forthe production
casting. The mo]ding
material used consists of finesjlica sand coated
resin

molds
with

and

cores

for

thermosetting

likephenolicresin.

However, the resin-coated sand givesoff smoke and irritating

gases such as ammonia,
as well as casting. Studies on
formaldehyde and phenol, in the process of molding
Bates and James,
emissions
from
foundry
molds
and
Bates,
1976;Scott,
chemical
(Scott
1977) have clarified in detailthe liberatedgasesformed by thermal decomposition of the
the working
envjronment
inthe foundry
molds. The smoke
and irritating
gasesaggravate
1967).
(Bloomfield,
of ammonia
Sepiolite has been attracting special interestas an adsorbent
(Dandy,
Prodas
and
Gonzalez,
1985;
lnagaki,
Fukushima,
Doi and
1968, 1971;Brueno, Sanchez,
Fukumeto
Kamigaito, 1990;Sugiura,Hayashi and Suzuki, 1991),acetaldehyde
(Sugiura,
in
1991;
and
Fukumoto,
1992,
1993).
So,
we
are
interested
effectiveand Inagaki,
Sugiura
sand.
ness
of sepiolite for reducing
smoke
and irritating
gasesliberated from resin-coated
However, if any reduction in strength occurs in the mold by adding sepiolite, the mold
cannot
be used for core making.
and
In this study, we have examined
the effect of sepiolite on the liberation
of smoke
the
bending
strength
of
the
mold.
irritating
from
resin-coated
sand,
and
on
gases
phenolic

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M Sakakibara et

al.

EXPERIMENTAL
Materiats
Sepiolitewas

into fineparticlesin the size

prepared by pulyerizingblock-sepiolite
supplied
by Turan Madencilik Sanayi
TicaretLtd., Turkey. Resin-coatedsand, which contained 100 partssilica sand and 2.9
resin formed from the novolak
resin
and
hexamethylene tetramine (R605@),
partsphenolic
was ebtained
frornHisagoya Co. Ltd.,Japan.
of

range

150-300ym. The block-sepiolite,

was

Preparation

The

of

motding

material

prepared by

resin-coa'ted
sand with the sepiolite in
O, O.5,1.0,1.5, 2.0,3.0,5,O, 10.0 and 15.0 in
its weight
percent.The moldjng material was placed in a metal die in a siliconit furnace
heated at 4000C for2min. The die was composed
of an inner part and an outer one. The
innerone was atruncated cone, while the outer one was a hollow cylinder. On remeving
from the die, a cup shape of shell mold was obtained.

wh{ch

molding

material

the amounts

Method
The

ofobservation
amoupt

was

of sepiolite added

mixing

were

ofsmDke

of smoke

iiberatedfrom the mold

every 30 sec. The degree of

observed
at
graphically
Table 1 shows the degreeof

organoleptical

Determinationofeoneentrations
(1)Fig. 1 shows the apparatus

after
smoke

strength

ofammonia,
for sampling

TABLE 1. The dcgrce of

pouringwas
was

visually and

measured

photo-

organoleptically.

of smoke.

aldehydes

and

ammonia,

organoleptical

phenots
aldehydes

strength

and

phenols in the

of

smoke

Symbel

the organoleptical

o12

METAL DIE AT 250

FiG. 1. Apparatus for sampling

no

strcngth

smoke

some

smoke

much

smoke

irritating
gascs liberatcdfrom phenolic resin-coated

sand,

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CatalyticDecomposition

smoke

in a

ofPhenolic Resin

liberatedfrom the resin-ceated sand. The

metal
die heated at 250eC. Fig.2 shows
the

sand

was

171

hardened to form

a shell

dieused inthissampling.

metal

mold

The die

steel solids, for making

six pieces of
pieces of rectangular
shell molds. The sample
gas was collected from a rectangular container. The
container
was made
of aluminium
in thickness,equipped with a gas outlet
plates ef 1 mm
connected
with
a Tefion@ tube. The die fi11ed
with resin-coated
sand
heated at 2500Cwas
placed jn the container, The sample gas-wascollected for 1.5min after packing the sand.
The bag,havinga capacity of 101,was made of aluminium foillaminatedwith polyethylene
was

of seven

composed

rectangular

terephthalate,

(2)Fig.3
smoke

the apparatus
liberatedfrom the mold

sample

gas was coilected

made

of steel

shows

plates

of

The sample

gases were
after pouring.

four minutes
The concentration

after

ammonia,

pouring

molten

from a cylindrical container

1mm in thickness, equipped

Tefion@ tube. The shell mold

container.

for sampling

of ammonia

with

molten

co11ected

was

aldehydes

aluminium

in Fig.3. The

shown

with

and
alloy

phenols in the
at

750eC. The

container

was

gas outlet connected with a

in it was plaeed in the
into four bags at intervals
of one minute
for
aluminium

determined

alloy

Kitagawa gas detector(Koumei

sucked
from the bag at a rate of

using

Co., Ltd.). The sample gas was

100mlXmin.
For the determinationof aldehydes concentration,
the gas collected in the bag was
in hydrochloricacid so that
passed through a solution of 2,4-dinitrophenylhydrazine
aldehydes
could
form hydrazone. The resulting hydrazone was extracted with chloroform.
The concentrated
solution was
analyzed
by gas chromatography.
The concentration
of
Rikagaku

Kogyo

10

10

or
FiG. 2. Metal die for sampling

phenolicresin-coated

.t-pmFtt.

irritating
from
gases liberated

sand.

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Y, Sakakibara

172

et at.

irritating
gaseslibcratedfrom

FIG.3. Apparatus for sampling

the

mold.

and propylformaldehyde, acetaldehyde

the
collected
in
the
bag
was passed
For the determinationof phenols,
aldehyde.
gas
GC@, 60-80 mesh) at roorn
through a Tenaxe tube packed with porous material (Tenax
The
were
heated
in
carrier
temperature.
condensed
gas and the resulting gaseous
phenols
The concentration
of phenols
was estimated
phenolswere analyzed by gas chromatography.
conditions
are
and
xylenol.
TTie
chromatographic
the
total
one
of
cresol
as
gas
phenol,
shown
in Table 2.
sepiolite was produced, and the liberated
For comparison,
a mold without
gases were
way
as mentioned
above.
tested inthe same
aldehydes

was

estimated

as

Determinationofmolecutar
Fig. 4 shows the apparatus
mold

after

pour{ng molten

the total one

veeight

of

distribution
oftarricmatter

for collection
aluminium

alloy at

TABLE 2.Gas

of smoke

components

750eC. The

chromatographic

conditions

Aldehydes
2%

Column

apparatus

liberatedfrom the
consisted of a glass

Phenols

OV-17

on
S% FFAP+10%
Benton 34+1%
PR
WAW,
VVAW,
DMCS 80-1oo mesh,
chromosorb
3mm in dia, 3m, glass DMCS 80-100 mesh,
3mm in dia.3m, glass
2oo- 3oooc (3oc/min)1600C160eCNitrogcn,
silicon

chromosorb

Column

tcmp.

Injectiontcmp,
Carrier gas

Detector

2500cNitrogen,

40mllmin

60 mllmin
FID

FID

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CatalyticDeeomposition

173

ofPhenolicResin

PUMP

BULB

ABSORBINGB

CHLOROFORM
ICE
SHELL CUP
FIG, 4. Apparatusforsampling

smoke

TABLE 3.GPC

cornponents

lib ratcd

from the mold.

conditiens

ColumnSolutionPumpSample
Shoden Aso1 + A801 + A8e2 in series
Chlorofolm, ltnlfmin
amount

Detector

Japan Spcc,TWINCLE
5oopt150
ml
UV

detector(254nm)

bulb and a pump. The water bath contained water and

funnel,a water bath, an absorbing
bulb
having 20ml chloroform
was
ice, in which the absorbing
put, The funnel,the
absorbing
bulb and pump were connected with a Tefion'@ tube in series. After pouring,
into
the pump was operated at a rate of 5l/min for4min, and the smoke was absorbed
attached to the funnel and innerwall
chloroforrn
through the Teflon@ tube, Tarricmatter
with
10ml of chloroform
and put in the absorbing
bulb.The
of the tube was washed
chloroform
solution was treated by gel permeation chromatography
(GPC),and the
matter
was
determined,GPC conditions are shown
molecular
weight distribution
of tarric
in Table 3. The molecular weight of the tarric matter was calibrated by using that of

polystyrene.
Measurement ofbending strength ofmotd specimen
was
measured
Bending strength of the mold, 10 10 60mm, in itssize dimensiens,
method
wi'th
a
crosshead
speed
of
1mmlmin
K
6910).
by three-point bending
(JIS
RESUIJI'S AND
Smoke
Table 4

shows

the amountof

smoke

DISCUSSION

from
liberated

the mold

after

pouring molten

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M Sakakibara et

TABLE 4. The
Amount

amount

of srnoke

liberated
from thc mold

Strength of

of

al.

smoke

after

aftcr

pouring

pouring

scpiolitein

the mold

AfterO.5minAfter1min Nter1,5rninAfter2min After3min After4min Dcgreeef

(Wt%)

odor

O.5

111'111111 oooooooo2 1ooeoooo2 111ooooo2 1oeooooo1 oooeooooo

slightly low
slightly low
1,52,O3,e5,O10.015.0o
lowlowlowlowlowlowyery
1.0

high

aluminium

less

smoke

exceeded

alloyheatedat 750eC.As shown

in this table, the

mold

with sepiolite gave off

of sepiolite
pouring than that without sepiolite. When the amount
was
liberatedas short
than 2.0wt% , only a small amount
of white smoke

after

more

pouring, but no smoke was Hberated at all after 60sec. In

odor.
addition, the mold with 2.0wt% sepiolite
gave off only a smail amount of irritating
sepiolite,
a large amount
of smoke
was continuously
ljberated
in
For the mold without
the periodfrom 30 to 240sec after pouring.
liberatedfrom the molds with 5.0wt%
Photo, 1 istwo series of photographs
of smoke
after
These
sepiolite and without
sepiolite
pour{ng.
photographswere taken at every
liberatedfrom the mold without sepiolite was clearly
30sec. Frem these, the smoke
This
while,
that
from
the
mold
with 5.0wt% sepiolite wa's' hardly observed.
observed,
liberatedfrom the mold becornessmall in the
suggests
that the particle
size of the smoke
as about

20 to 60sec

after

presence of sepiolite.
components
liberated
Fig. 5 shews the molecular
weight
distribution
of the smoke
frem the mold afterpouring molten aluminium alloy at about 750"C. As shown in the
components
liberatedfrom the mold without
figure,the molecular weight of the smoke
in the wide range of about 40 to 1ooO,while thatfrom the mold with
sepiolite distributed
5.0wt% sepiolite distributed
in the narrow range of 40 to 200.This result indicatesthat
almost all the smoke
components
higherthan 150 in the moleeular weight were decomposed
into those in the lewerone by the catalytic action of sepiolite.
These results indicatethat thermal decompositionof phenolicresin on the resin-coated
size
and that the particle
of the
sand has been promoted in the prescnce of sepielite
smoke
liberatedfrom the mold became small in the presence of sepiolite.
Emission ofammonia,

atdehydes

and

phenots

The emissien of the irritating

for the two processesof casting: (1)
gaseswas examined
heatingthe resin-coated
sand into metal
die with heating,and (2)pouring the molten
aluminium

alloy,

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Phenotic
Decomposition
Of
Resin
Catatytic

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YL Sakakibara et al.

1.5
Ta.ovt.L.1ozcabatocotn<

1.0

O.5

1000 500

200 100 50
WEIGHT

MOLECULAR
FiG. 5. Molccular

distribution
of

weight

smoke

liberated
frornthe

componcnts

mold,

Fig. 6 shows

the concentrations

of ammonia,

and

aldehydes

phenolsliberatedfrom the

heatingat 2500C. As shown in the

aldehydes
and phenols
liberatedfrom the resinof ammonia,
figure,the concentrations
sand
with 5wt% sepiolite were
1/2,1110 and 1110 times lessthan that without
coated
These results indicatesepiolite promoted thermal decompositien
sepiolite,
respectively.
rcsin-coated

of

these

sand

itwas

when

irritating
gases as

into molds

made

catalyst.

Fig,7 shows the concentratiens of

after
mold
pouring molten a]uminium
the concentrations

when

with

aEdehydes

and

phenols. For the

ammonia

and

aldehydes

for the
1 min and

mold

the

phenolsliberated from the

750'C. As shown in the figure,the times
between ammonia,
values are different
and

aldehydes

at

alloy

the maximum

reached

reached

ammonia,

without

values

maximum

5wt%

the concentrations

sepielite,

after

sepiolite, the

lmin, 2min

of
and

phenols,
3min,

phenols
3min, that of ammonia
that the decornpositionof
after 4min, This suggests
after 2min, and that of aldehydes
gases,
phenolicresin occurs more rapidly in the presence of sepiolite. As forthc irritating
and
moderately
decreased for phenols, slightly decreased for ammonia,
the emission
moderately
increased for aldehydes.

respectively,
was

almost

However,

zero

after

rnold with
reached

the maximum

value

concentration

of

after

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Cdtalytic
DecompositionofPhenolicResin

Aldehydes

150

Phenols

AEQQvz9?Ei28

177

Ammonia

100

00

50

00

100
50
o

NE

tf..m.

R.9n$*}m

grt

9.9ndicasos'IM

ig-.a.maiSme==-J
$g*m}Seo
-,}
,}

'}
'i

.;

FIG. 6.Concentrations of irritating

resin-coated
gases liberatedfrom phefiolic

Aldehydes
AEQQvZopE28go

200

Phenols

sand,

Ammonia

20000

--o--ithout

"200

rtf

sepiolite

1OO

-e--5wt%sepiolite

100

th

10000

t
xs

-,;

o
oTIME24
(min )

.,-o

24

TIME

FIG, 7.Concentrations

of

(min )

oo
TIME

24
(min )

irritating
gascsliberatedfrom the

mold.

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[.5
E

l9E6o;aZurm
3
2
1
oo

10

15

SEPiOLITE CONTENT
FtG.8, Bendingstrength

of the

20

(wt%)
mold.

.
Bending strength ofmold specimen
Fig. 8 shows the bending strength of the mold specimen
plottedas a functionof
sepiolite content. As shown,
in the figure,
the bendingstrength decreased with the
was
added,
the strength decreased
increasing
sepiolite content. When 2.0wt% sepiolite
by about 30% compared
with that witheut
sepielite, This value issufficient forstrength to
manufacture
durable aluminium
casting products.
'

CONCLUSIONS

'

In the
or

more

sand,
the mold
with
2.0wt%
processtising
phenolicresin-coated
liberatedno snioke after pouring molten
aluminfum alley. On the other
without
sepiolite, a largeamount
of smoke
was continuously
liberated

shell molding

sepiolite

hand, frem a mold

for 4min.'
Almost all the smoke components
higher than 150 in the molecular
weight
were
sand
was
decomposed into those with lovyermolecular weight. When the resin-coated
ef amrnonia,
aldehydes
and
made
into molds on heatingat 250eC,the concentrations
phenols liberatedwgre 1/2, IXIO and i/10 times lessthan that without sepiolite, respectwhen
ively,As for the gases liberatedfrom the mold with sepiolite
pouring molten
aluminium
alloy,
the, concentration
of ammonia
,decreased slightly,. that of aldehydes
These results indicate
increasedmoderately,
and that of phenols decreasednioderately.
cornponents
and
SgeaPsieOsliges
hcaatSalPyrs?.MOted
therMal decornposition of the smoke

lrhn9ttatthineg
The

bending

strength

of

the

mold

specimen

decreased with the increasingsepiolite

content.

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CatalyticDecomposition
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179

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DANDy, A.J.

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