Not f or Publication

Presented Before the Di vi si on of Gas and Fuel Chemistry

American Chemical Society
Atl anti c Ci ty, New J ersey, Meeting, September 1?-18, 1959
Coal Acids - Raw Materi al f or Foundry Resins
BY
Wesley L. Archer, James B. Louch and Robert S. Montgomery
"he Dow Chemical Company - Midland, Michigan
LnJ TRODUCTION :
Aromatic polycarboxylic aci ds derived from the control l ed oxidation of coal(')
have been used t o prepare thermosetting resi ns Of i nterest t o the foundry i ndustry.
The monoethanolamine, diethanolamine, ethylenediamine, diethglenetriamine and penta-
erythri tol adducts of these coal aci ds were i nvesti gated as shel l molding resi n
bi nders.
The current uses of a phenol-formaldehyde resi n i n the foundry i ndustry i l l ustrated
some of the market potenti al s f or the new coal aci d resi ns. The l argest market i s
found i n shel l molding where some 17 mi l l i on pounds of phenol-formaldehyde resi n was
used i n 1957.
i n steel cores i s another market wi th good growth potenti al .
The increased use of the phenol-formaldehyde resi n with cereal binders
Sand bri quettes bonded with the coal aci d resi ns were tested f or tensi l e strength
and the resi ns of parti cul ar i nterest evaluated i n shel l molding.
pentaerythri tol preadvanced resi n was outstanding i n overal l performance as a shell
molding binder and thus w i l l be the resi n of prime i nterest i n thi s paper.
Resin Preparation
The coal aci d -
The resi n adducts of i nterest i n thi s i nvesti gati on were homogeneous sol uti ons
of the coal aci ds and reactant i n water. The coal aci d - pentaerythri tol resi n was
parti al l y advanced i n water to gi ve a sti l l water soluble homogeneous sol uti on.
water sol uti ons afford an easy and economical method of applying the resi n to the sand.
I n most cases, equivalent rati os of the reactants were used i n the resi n preparati on
and resi n adduct concentrations of 60-7@ gave sol uti ons of workable vi scosi ti es.
resi ns as water sol uti ons have an unlimited storage l i f e.
These
"he
Requirements of a Shel l Molding Resin
The fi rst requirement of a shel l molding resi n i s that it must give a f ree flowing
resi n coated sand which on heati ng thermosets to fi rml y bond the sand grai ns together.
The resul tant shel l mol d must have suffi ci ent heat resi stance to withstand the shock
of molten metal and hold cl ose tol erances unti l the metal has set. A t the proper time
i n the metal set cycle the shel l must al so burn out t o give col l apse of the shel l and
a cl ean casti ng.
concentration, e. g . urea formaldehyde gives a low temperature col l apse for magnesium
and aluminum casti ngs.
used f or malleable i ron and steel casti ngs.
The temperature of col l apse can be governed by the resi n type and
Phenolic resi ns afford higher heat real stance and are commonly
The potenti al resi n binder must be effecti vel y and easi l y dispersed i n a sand mix
by means of a Simpson or si mi l ar type muller.
resi n has been popular i n the past, but it i s rapi dl y being replaced by a mor e effecti ve
l i qui d resi n coati ng procedure.
the mulling operati on to dry the resi n coated sand unti l it i s f ree flowing.
of thi s free flowing condi ti on duri ng storage i s necessary f or optimum pattern per* -I ormance
l ater.
Dry blending of the sand and powdered
In thi s procedure a source of hot ai r may be used duri ng
Maintenance
-u7-
I t i s important that the resi n binder be cured and thermoset within a reasonable
period of t i me.
typi cal shel l molding procedure given below.
The approximate time and temperature l i mi t s are i l l ustrated i n the
(1)
The dry resi n coated sand i s dropped onto a preheated (400-500'F.) metal
pattern and allowed to remain f or 15-55 seconds.
the coat or dwell time determines the thi ckness of the shell.
A t the end of the proper dwell time the enti re pattern i s inverted 180 degrees
allowing all the excess and unbonded sand to f al l back i nto the dump box. A
dough l i ke shel l of resi n bonded sand i s l eft adhering to the metal pattern.
The metal pattern and parti al l y cured shel l i s then placed i n an el ectri c or
gas furnace (800-1J +00~.) where the cure i s completed i n 40-60 seconds.
The thermoset shel l mold I s then ej ected from the metal pattern by hydraul i cal l y
operated ej ecti on pi ns.
This time period born as
( 2 )
( 5 )
(4)
The fabri cati on performance and pouring behavior of the shel l mold i s greatl y de-
pendent on the shel l having suffi ci ent tensi l e strength at a reasonable resi n concentration,
e.g. 5.5-% resi n sol i ds. Factors that af f ect the tensi l e strength of the resi n bonded
sand include the resi n's actual composition, the effi ci ency of the coating operation,
the degree of resi n flow before thermoset and the temperature range necessary f or thi s
flow. A l l of these factors and the conditions necessary f or the optimum tensi l e strength
can be evaluated by preparing bri quettes from the dri ed resi n coated sands.
Preparation of the Coal Acid - Pentaerythri tol Resin - ( ET- 400)
Most of the coal aci ds used i n thi s work were prepared at the Dow Chemical Company.
These coal aci ds were similar to those made by the Carnegie I nsti tute of Technology (2)
and had an equivalent weight of 80-85 and average functi onal i ty of approximately three.
The f i rst parti al l y esteri f i ed coal aci d - pentaerythri tol resi ns were prepared by
The reacti on of a
sti rri ng and refl uxi ng the mixture f or a period of 5-6 hours. The degree of advancement
was determined by ti trati on of the avai l abl e carboxylic aci d groups.
75% sol i ds sol uti on of 1 equivalent coal aci ds - 1 equi val ent pentaerythri tol during the
f i rst two hours of refl ux i s rapi d. An equi l i bri um esteri f i cati on of 5% was obtained
af ter 8 hours. When 0.9 equi val ent of pentaerythri tol ( 7% sol i ds sol uti on) i s used an
equilibrium esteri f i cati on of 52% is reached af ter 8 hours.
Concentration on the esteri f i cati on rate i s shown by the f act that a 9 6 sol i ds sol uti on
of ET-400-85 (contai ns 0.85 equivalent pentaerythri tol ) gi ves 2% esteri f i cati on at the
end of the f i r st twenty minutes of refl ux.
The ef f ect of sol i ds
The parti al l y advanced resi n is a viscous sol uti on which does not exhi bi t any
preci pi tati on on standing i f the advancement i s greater than 12%.
at 60- 6s cal cul ated reacted sol i ds gave a very workable vi scosi ty.
Physical Properti es of the Coal Acid - Pentaerythri tol Resins -(ET-400)
The resi n sol uti on
Preparati on of one quarter inch bri quettes from the dri ed resi n coated sand allowed
a study of the physi cal properti es of the, coated sands as they were rel ated t o the resi n
composition and pretreatment. The sand coati ng operati on was done i n a "Kitchen Aid"
mixer or i n l arge batches i n a Simpson Mul l er. A source of hot ai r di rected onto the
sand mix shortensthe time requi red f or the mulling operati on.
sand through a 42 mesh screen it was dropped i nto a quarter i nch deep bri quette mold
preheated t o 425F. The coated sand was allowed t o stand f or 10-15 seconds and then
the excess unbonded sand scraped off wi t h a thi n metal stri p.
at 650'~. f or 2 minutes gave the fi ni shed test specimen.
motor dri ven Di etert Tensi l e Tester.
After screening the coated
Curing of the bri quette
These were then tested on a
b
s
a
n
A.
,
a.
/
I
I
C.
. .
_ - . .
. . .
I .
-l l &
OptimumPentaerythri tol Concentration i n ET-400
Tensi l e strengzh determinations have shorn that the pentaerythri tol concen-
trati on can be dropped t o 0.9 equi val ent pentaerythri tol to 1.0 equivalent coal
aci ds without reducing the resi n's bonding strength. Use of a 1: l rati o of hydroxyl
to carboxylic acid groups would seemunnecessary si nce steri c hinderance;undoubtedly
prevents the reacti on of some of the carboxylic aci d groups.
mysi cel Strength vs. Resin Concentration
A pl ot of the percent of reacTed resi n sol i ds on a coarse.0ttawa sand vs. the
resul tant tensi l e strengths i s shown i n Figure 1. The bri quettes were bonded with
an ET-400-9 resi n with a preadvancement of 17.5% and cured f or 2 minutes at 650"~.
A tensi l e strength of 360 psi . i s obtained at the 4%resi n l evel commonly used i n
commercial shel l molds. Natural l y, the strength at a certai n resi n l evel w i l l vary
with the si ze di stri buti on of the sand, the cl ay content of the sand, the resi n
composition and the coati ng techniques.
l ater.
Effect of Resin Preadvancement
Each of these factors will be discussed
The tensi l e strength of the ET-400 resi n coated sand has been found to be a
functi on of the resi n preadvancement. The preadvancement necessary f or optimum
tensi l e strength appears to be i n the range of 1?-18$.
of preadvancement on the tensi l e strengths of two di fferent resi n coated sands.
This parti cul ar data was obtained on small one and a half pound batches of sand
coated i n a "Kitchen Aid" mixer.
muller demonstrates that higher tensi l e strengths may be expected from the more
effecti ve coati ng obtained with a Simpson Mul l er.
Figure 2 shows the effects
The one tensi l e strength value i n Figure 2 marked
The presence of cl ay and other nonsi l i ca i mpuri ti es i n the Vasser bank sand
could expl ai n the di fferences i n tensi l e strength of the Vasser bank AFS 100 sand
as compared with the high si l i ca content Wedron AFS 116 sand. The cl ay and si l t
i mpuri ti es could indeed decrease the flow of the resin before the thermoset.
flow of the resi n coating on a sand grai n to the surrounding sand grai ns and
formation of a complete bond would be decreased.
The most important property control l ed by resi n advancement i s the rate and
Thus,
temperature at which the resi n flows. The improved flow behavior of the resi n on
coated sands with l ess preadvancement i s di rectl y refl ected i n the improved tensi l e
strengths. The temperature at which the resi n fi l m on a sand grai n w i l l start to
f l ow can be determined and is referred to as the sti ck poi nt.
ment of the ET-400 resi n gives a l ower sti ck poi nt and a resul tant higher tensi l e
strength.
A lower preadvance-
Preliminary observations have shown that the amount of moisture pickup by the
resi n coated sand i s another f actor control l ed parti al l y by the degree of resi n
advancement.
coated sand wi l l remain i n a f ree flowing condi ti on before actual use.
coated i n 3. Simpsor Mulier with a resi n of at l east 1% preadvancement wi l l give a
stabl e f ree flowing sad.. This range of resi n preadvancement may al so be expected
tol gi ve uearly optimum tensi l e strengths.
Thus, adequate resi n advancement i s necessary so that the resi n
Sand
Shell Mold m d Core ?&xication
The E1'-4CO resi n with optimum sand binding prop, -rti es was thel? examined i n the
The smal l :hree prong cover pl ate type
actual fabri cati on 3f shel l molds and cores.
stel l mold that - a s presared on a small dump box machine is shown i n Figure 5 .
shel i cores have al so been prepared on a commercial Shalco core blowiag machine.
Hollow
Both
d'
I .
1
h
I
1
pieces of equipment employ the same basi c pri nci pl es of investment, removal of excess
unbonded sand and f i nal cure as outl i ned earl i er.
A. Sand Coating Procedure
The proper mulling procedure i s second only to the resi n i n determining the
f i nal behavior of the coated sand i n shel l mold fabri cati on. The resi n formu-
l ati ons f or actual shel l fabri cati on were applied to 20 pound batches of sand
contained i n a Simpson Muller.
A typi cal coati ng operation f or the Simpson Muller i s given below:
(1)
Charge 9000 grams of sand and 550 grams of l i qui d ET-400-9 resi n
(4% reacted sol i ds on sand) and 20 grams Acrawax (0.22q6) to the muller.
(2) MUU f or 1 minute.
( 5 ) Hot ai r supply
started and continued unti l coated sand went through the
agglomeration stage.
Mulling continued f or an addi ti onal 15 minutes with hot ai r.
Coated sand dumped and screened through a 40 mesh screen.
( 4)
(5)
The Acrawax serves as a l ubri cant f or the f i nal resi n coated sand and helps
the sand retai n i ts f ree flowing character.
was furnished by a small modified hai r dryer with a maximumnozzle temperature of
500F.
The hot ai r for the mulling operation
During the agglomeration stage it was found necessary to stop the muller
several times and manually break up the pl asti c l i ke sand mass. Coating of 720
pound batches of Nugent AFS 75 sand wi th ET-400 i n a commercial si ze muller di d
not give thi s problem. The enti re cycl e from resi n addi ti on to coated sand di s-
charge required 14 minutes i n the commercial setup. Total time f or the coati ng
operati on i n the small Simpson Muller was 55 minutes.
B. Shel l Mold Properti es
A Nugent AFS 75, coarse Ottawa or Wedron AFS 116 sand coated with 4% of ET-
400-9 resi n gave good three prong cover pl ate shel l molds at a pattern temperature
of 450-50OoF., investment time of 15 seconds and cure time of 40-60 seconds.
resi n preadvancement of approximately 15% i s preferred f or maximumtensi l e strength
and pattern performance at a low pattern temperature of 450F. Moisture stabi l i ty
of the ET-400-9 coated sand appears to be good si nce no buildup of coated sand on
the back si de of the shel l and/or peel back of a porti on of the shel l occurs. An
excessive amount of moisture al so tends to cause the agglomeration of the i ndi vi dual
sand parti cl es i nto uni ts of several parti cl es. These small agglomerates give poor
packing of the sand parti cl es at the pattern surface and the resul ti ng poor surface
hardness and strength.
A
The di fferences i n tensi l e strengths of a high si l i ca sand and bank sand shel l
mold i s again i l l ustrated by the following val ues.
4% ET-400-9 (advanced 16$) coated Nugent sand averaged 515 psi . as compared to the
value of 795 psi . f or the resi n on Wedron sand. Hardness as measured by a Di etert
Hardness Tester was 80 f or the Nugent shel l s and 90 f or the Wedron sand shel l s.
The tensi l e strength of the
Recent work has shown that the addi ti on of a nonionic surfactant, e.g. 0.25%
Tri ton X-100, to the resi n coated Nugent or Vasser sand w i l l give a 2% strength
i ncrease. Replacement of 5C$ of the pentaerythri tol i n the ETA00 resi n with a
-120-
gl ycol or ethylene oxide adduct w i l l also gi ve a 25-4& i ncrease i n the resi n
strength.
can be expecced t o average 400--b50 psi .
Thus the tensi l e strength of a modified 4%ET-400-9 coated Nugent sand
A f i el d test of the ET-400-9 resi n as 2 shel l molding bi nder has been attempted
at a malleable i ron foundry. The resi n used i n thi s test was one of the earl i er
~~- 400- 9 formulations preadvanced to 28.5%. The performance of the resi n i n the
coati ng of the Nugent sand i n 720 pound batches was good.
inck:ss i n si ze were fabri cated at a pattern temperature of 500F. , investment time
of 34 seconds, and cure time of 50-60 seconds.
i nch shel l molds being ej ected from the pattern after cure.
casti ngs weighing 11 pounds a pi ece were successful l y cast without ady major metal
breakouts.
tensi l e strength. Tensi l e bars prepared from thi s coated sand gave an average
tensi l e strength of 170 psi .
some 400 psi . strength on Nugent sand may gi ve the needed addi ti onal strength f or
a completely successful commercial test.
Shel l rnolds of 20 x 50
Figure 4 shows one of the 20 x 50
Approximately 25
The major poi nt f or improvement appeared to be the need f or increased
The abi l i ty of the newest ET-400 formulation t o give
C. Shell Core Properti es
Acceptable commercial hollow shel l cores ( 25 inches i n l ength and 2i 5 inches
i n width) have been fabri cated on a Shalco core blowing machine using a 5. 5$ ET-
400-9 coated Wedron sand, The resi n had been advanced to 28. $ esteri fi cati on.
Shel l cores with excel l ent hardness (90 on Dietert Tester), detai l and strength
were prepared at 600'~. wi t h an investment time of 3-15 seconds and cure time of
1.5-2.0 minutes. These conditions correspond t o cure conditions used with a
commercial phenol-formaldehyde resi n coated hi gh si l i ca sand.
Core Binders
The foundry i ndustry's i nterest i n improved core bi nders has encouraged the use
of the urea formaldehyde and phenolic formaldehyde resi ns. Pri nci pl e use of the phenolic
resi n i n sol i d foundry cores has been l i mi ted mostly to steel cores. The need f or a
more heat resi stant binder f or steel cores has l i mi ted the resi n t o a phenolic type.
The cheaper urea formaldehyde type resi n fi nds wide use i n the nonferrous and ferrous
type foundri es. Both resi ns are used i n conjunction with various cereal fl ours and core
oi l bi nders.
Preliminary data i ndi cates that several of the coal aci d type resi ns may fi nd
uti l i ty i n foundry cores.
been prepared from an Ottawa AFS 60 sand bonded vi th 1.e ET-400-9, I..@ Mogul B 2i 1
f l our and 5$ water. Core mixes of thi s type have been successful l y core blown with
commercial machines.
paper al so suggests the possi bl e use of these i n the core binder appl i cati on.
Speci fi cal l y, cores with tensi l e strengths of 570 psi . have
The tensi l e data of other coal aci d resi ns given i n the preceding
Preparati on of bri quettes from a moist resi n coated sand and allowing the bri quettes
to stand at room temperature l eads t o the development of considerable green strength.
This green strength i s the resul t of the ai r drying of the resi n film to gi ve a "dry"
water pl asti ci zed resi n f i l m surrounding and bonding each sand parti cl e.
amine resi n adduct f or example, yi el ds an optimum strength of 525 psi . at a 6%resi n
concentration while @ of the diethylenetriamine adduct gives a green strength of
240 psi . af ter only 20 hours at roomtemperature.
al so be of i nterest i n sand core fabri cati on.
CONCLUSIONS :
The diethanol-
Thi s green strength property could
I ncreasi ng foundry i nterest i n new synzhetic thermosetti ng sand bi nders has opened
markets f or resi n binders that have new and improved physi cal properti es.
sand bi nder f or thi s purpose may be deri ved f rom the oxi dati on products of bituminous
A new t;rpe of
ii t
).
,
h
-121-
coal .
alkanolamine, polyhydroxy1 or polyamine reactant.
Speci fi cal l y, thermosetting resi ns may be prepared from these coal aci ds and an
The coal aci d - pentaerythri tol resi n (ET-400-9) preadvanced t o lJ-l@% esteri f i cati on
i s of parti cul ar i nterest i n shel l molding work. A 13-18$ preadvancement w i l l produce
a free flowing sand with optimum tensi l e strength. Experimental shel l molds have been
prepared with thi s ET-400-9 resi n at a pattern temperature of 450-50GF., investment
time of 15 seconds and cure tiffie of 40-60 seconds. Both high si l i ca content sands and
bank sands have been used i n the shel l mold fabri cati on.
515 psi . of tensi l e strength can be expected with a medium f i ne, unwashed Sank sand.
The addi ti on of a surfactant to the resi n i ncreases the strength of the resi n bonded
bank sand to 400 psi .
tensi l e strength to 795 psi .
A t a 48 resi n concentrati on
Use of a f i ne, washed high si l i ca content sand i ncreases the
One attempt to use ET-400-9 as a commercial shel l molding binder i ndi cated that
a somewhat greater tensi l e strength is necessary.
advancement nay afford the needed strength improvement. Tensi l e strengths of the
uri gi nal resi n bonded sand were 170 psi . as compared to the later tensi l e strengths
of 4C0 m i . (contai ns 0.2% surfactant). Commercial shel l cores have al so been
A new formulation wi t h only l 5$
..
fabri cated with ET-400-9.
XFEWiTCES :
1. Montgomery, R. S., Holly, E. D. and Gohlke
Montgomery, R. S., Holly, E. D. , i bi d. 36
2. Franke, N. W. , Kiebler, M. W. , Ruof, C. E.
I nd. Eng. Chem., 2784 - 2792 (1952).
R. S., Fuel , Lond., 55 (1956) 60
1957) 63
Sovich, T. R., and Howard, E. C.,
-122-
Figure 1
I RESIN CONTENT VS. TENSILE STRENGTH I
6 7 8 9
REACTED RESIN SOLIDS, */ .
Ti owe 2
PRE-ADVANCEMENT VS. TENSILE STRENGTH
0
0 5 10 15 20
1
0 WEDRON AFS 116
0 VASSER BANK AFS 100
4 % REACTED RESIN SOLIDS
X PRE-ADVANCEMENT
?
\
-123 -
- TiLwe 3
P