CHAPTER 3

PHYSICS AND CHEMISTRY OF SODIUM SILICATE AS A COLLOIDAL

MATERIAL

3.1 Introduction

Much work has been carried out to develop an explanation for the

silicate bonding in foundry sands, as has been reviewed previously in this thesis.

However, to date, little theoretical work on the physics and chemistry of the bondillg
mechanism of sodium silicate in foundry sands could bc found in the literature. No

comprehensive explanation has been given for the causes of the degradation of the silicate

bond at high humidity levels, nor has any systematic explanation been given for its poor

collapsibility. The consequence is that a trial and error approach has been adopted for

solving the problems of hygroscopicity and the poor collapsibility. However, it is known

that sodium silicate as a foundry binder is a complex colloidal system and, therefore, it

must be treated in terms of colloidal chemistry for a better understanding of the nature of

the bond itself.

This chapter offers an explanation of the basic concepts underlyinl: the physics and

,-hemistry of the bonding mechanism of sodium silicate in foundry sands. 'She bond
consists ofa precipitated gel, sodium silicate and silicic acids. These semi-solid substances

bond the in to continuous ihrcedimensional arrays known as sand m~uldsand

miis procea of forming mi-solid substances is known to chemist as gel formation.
particles. The word gel is derivd from "gelatinen, a subsbce obhined in t m fmm bone

glue by purification [39]. The word *colloid" originates from a G m k word, "kolla':

which again means glue. Colloids were let drfinrd by Gmhm (1861) [40] to mean glue-

like materials which cannot migrate through semipermeable membranes [4 I]. Colloids are

therefore glue-like substances.

Colloids are defined as those materials whose particle sir8 lies bctwccn the

dimension of a molecule and those which are just secn under an optical microscope.

Colloids are therefore consists of fine individual particles capable of remaining in a liquid

in a state of suspension for an almost unlimited time. The characteristic proprtics of

colloids result from their extremely large surface area. For instance. one grain of sand,

0.2cm in diameter, has a surface area of a 0.5 cm square; the total surface area of the same

mass of sand, ground to a particle size of one micron (0.001 mm) in diameter, is increased

a thousand times. Dipling [39] demonstrated the relationship between specific surface area

(surface area of one gram of the material) and its particle size as shown in figure I. This

correlation was based on the assumption that all individual particles are spherical in shape.

In order to cover the whole range of particle sizes present in a hydraulic mortar wnsisting

of sand with specific surface of the order of 10 sq cmlgm and gel with a spccific area of

2-3 million sq cml gm (which corresponds to a particle size ranging from 10 to 1u6cm),
Dipling found it necessary to use a system of logarithmic coordinates in Figl. All the

individual curves are in the form of straight lines, slightly displaced in relation to each

other because of the differences in the density of the different materials. The conventional

&imption that all particles are spherical in hap is, in fa,incorrect. Therefore, the

m p h m e only the themetical mean values of the various surf^^.

Figure 1. Gnin QiZC and apeelfic srr&a a m of
Sand, oeme~t~,Urn61a d gel#, srrBlee areu
ofJ.Kgmof~dal~n8Rn*m
of fLdr d & m e t e r ( s ~grvitV 32-22) Wl
 The cxkmely large s w f i e m a of colloids docs not, however, expldn the
Ob*wd in the solution of ~ l u b l silicate
e (water glass) a d its mixing with m
aid* '-&, acid, Or upon heating. The undmtanding of this p m s s r c q u i ~ n
s
ex*imti0n of sufam foras: each solid body Owes its stability 10 the p x x n a of
forces of mutual attraction between the individual constituent units. Inside the

a solid material, these forces, acting in all directions, cancel out, but unbalanced
attractive forces exists at the surface of the solids and attract and hold other materials. In a

soluble silicate (e.g., Sodium silicate), as a solid colloidal substance is formed. the

tremendous surface area which it possesses comes into play, with the result that watcr

~ o l e c u l e sare drawn to the surface of the colloidal particles and held there strongly,

thereby reducing considerably the usual mobilily of water. Furthermore, the above effect

is accompanied by the interlinking and cross linking of the constituent of the solid

material, so that a frame work is developed which is still further stiffens the gel. Such

adsorptive forces act on the adhering layer of water, but also bring about a modification of

the physical properties of the absorbed water, i.e., in the boiling point and the freczing

point. The boiling point of the water is raised so that the absorbed water can no longer bc

expelled from the gel by heating to 100 C; a higher temperature is required 1421. The
freezing point of the absorbed water is also depressed so that the water in the gel turns into

ice, not at 0 C but at a lower temperature [40~421

~h~ complexity of,the sodium silicate bond in foundry sand necessitates a detail

of the Therefore, this chapter covers silicate structures, hydrolysis P ~ ~ U C ~ S

of silicic acids, theory of gelation, the mechanism of condensation polymerization of

acid in sodium silicate solution, and the hardening mechanism of sodium silicate

binder in foundry Sand*

 3.2 Silicate Structures
The bonding mechanism in the molecular unit SiOl is based on the tetrahedral unit

coordination group (SiO4). Its inherent tendency is to bond together by complex

polymerization into chains and networks. The two fundamental facts as given above are

the basis for a structural study of the silicates [43].

The fundamental chemical unit of a silicate is the silicon tetrahedron (Fig. 2-a).

.
Since this unit is made up of free atonls of silicon and oxygen it must acquire four extra

electrons from each atom to have an octet of electrons in its valency cell. These extra

electrons must be donated by the atoms of the metals which are present in the silicate as

cations. To calculate the number of additional electrons accepted, which determines the

negative charge on the anion, chemists assume that the silicon atom is linked to cach

oxygen atom by one covalent bond. Thus, each oxygen atom is linked to the silicon atom,

then accepts one extra electron to complete its octet, and thereby the telrahedral unit as a

whole carries four negative charges and is written as : ( ~ i 0 4 ) .~In

' most silicates the SiOd

tetrahedra .are not discrete, but are part of the larger systems in which oxygcn atoms are

held in common by two tetrahedra, as shown in figure 2-b. It is possible for these

tetrahedral groups to become linked by their corners; that is, through two groups sharing

one oxygen atom. If the two tetrahedra are linked in this way at a single corner of cach, a

grouping (Si@7)results with an effective valancy of six, since the linking o f o x y ~ natom

now has no charge (Figure 2-b).

It has been shown by means of x-ray analysis, chiefly by Bragg [44] and then by
Pauling [45], that the difference between the various classes of silicates is a matter of the

siliecn-oxygen -gement and only indirectly of the remainder of the structures.

OccaPionally, the silimn-oxygen forms a closed UP, but usually t h structure

~ is endless
mrs2. The SKh Tctmldm~in the Sillcrtw
pl~urc3. ~spmmtrtbmof typlerl silicate rtr0et.m [ M 9 1
 extends w n t i n ~ u amugh
~ 1 ~ Out a given crystal, formin* "pi.nt molecules'* (Figure

2-43.

In Silicates the silicon atom in the silicates is always associated with four oxygen
atoms, M-~Ymanged with regard to the silicon. The way in which these

tetrahedral groups are arranged determines the structure of a particular silicate. Some of

these possibilities arr indicated in the formulae of figure 3, as discussed by Dunant 1461,

Parkes 1471, and Cotton and Wilkinson [48].

3.3 Products of Hvdrolvsis of Silicic Acids

Studies of the simple system of silicates, namely silica itself (Si02).involve the

boundary problem of whether or not there is crystalloid (low molecular weight particle)

solubility of silica in water. This is the central question of the existence of the so called

"monomeric" silicic acid in its ortho form, H4Si04, or as the metasilicic acid. H2Si03.

whereas one may question the directive possibility of obtaining monomeric H4Si0.1 or

H2Si03 by the intense grinding of quartz powders, the preparation of pure "monosilicic"

acid was demonstrated by Alexander [51] in a 0.1 molecular solution with pH = 3. by the

reaction of a slurry of sodium metasilicate, i.e.. sodium silicate Naz0.Si02 as the base

component, with a cation exchange resin(acidic component), at about OC. Eitcl 1431

emphasized, howewer, that the polymerization automatically sets in, even at low

temperatures, and at the optimum pH conditions for the stability of the low molecular

weight silicic acid. Eitel [43] commented that the best condition for the hydrolysis of
silicic acid is $4-3 w w the rate of condensation here is a miniInum. Much more
understanding of the automatic condensation praess :
impfia h o r n r , is a
the monomeric acids f o m oligo-acids, probably wifh a chin-fiba nnmrr, or pnhaps

also with some b&hed chain configuration,

concerning the wnstitution of the hydrolysis products of silicic acids, G l a u e r and

Rieck I521 studied the infrared abonption spectm of monomeric (single monomer) and
oligosilicic acid (few anns or branches of monorne~~)acidrand obsewed that majority of

water is present in the form of hydroxyl groups (OH).

3.4 'heorv of Gelation

It is to define cet'tain important terminology at the start of this section

for a better reading comprehension. The term "colloidal silicic acid" refers to fluid
mixtures containing hydrated silica. The term "silicic acid gel" refers to semi-solid elastic

masses which result when the gel has set. The term "silica gcl" is used only to designate

the harder, partially or entirely dehydrated product. The term "gelation" refers to the

transformation of colloidal sol into a gel. The term "colloidal micellc" is used to designate

a colloidal (high-molecular, polymerized) particle composed of its nucleus and all its ions

and molecules, which have been attracted by it. "'Thixotropy" is the property of gel to
liquefy upon mechanical agitation and to resolidify when agitation is stopped. The

phenomenon of "dilatancyWis the direct opposite ofThixotropy. A dilatant system behaves

like a liquid and flows easily under weak stresses. if, however, the system is subjected to

rapid of itr shpor to large shearing SlRSSeS, it offers inc-ing resistance to

deformation and actually solidifies. AS soon as the stress is released, the system recovers

its original fluid rnnditiOn rind properties. The term "s~neresis*is used to mean the

cbctdst.c
shrinking of a solid with the squeedng out of. liquid pha*.
 I3a-r [411 describes a "gel*' as a rigid and coherent system composed of a
dis~ersimmedim a disperse part, the lancr being w i c k of colloidal dimensions.
In a colloidal sol the disperse particles are found to bc in constant Bmwnian motion; in

contradiction to a sol, the particles of a dispersed psn of a gel a E at a standstill. Gels may

exhibit flow upon the application of a lorn suficient to overcome the bond strength

which holds the particles in place. Therefow, gels must have a measurable yield point.

3.5 The Mechanism of Condensation Polvmcrkzation of

f
In order to explain polymeri7ation ,It is appropriate to consider the co~~ccpt
of chcl~iical

bonding forces, which is based on the electron interaction of ions, as they try to satisfy

their tendency to form a saturated compound. The concepts of chemical reactions hctwccn

free gaseous atoms involve the following phenomena:

1. Electron transfer and formation of charged particles. the ions;

2. By combining cations (positive ions) with anions in a ratio whicl~causes the

sum of the charges to become zero, the cxcess charges are neutralixed;

3. The electric fields of thc cations are screened by surrounding them wit11 anions.

It is also known that the number of anions which are necessary for screening the field of a

given cation conesponds to what is known as the 'Soordination number". The

coordination requirements of cations arc much more rigid and much more important for

smcwral d y a s i s than those of the anions. The outer electrons of anions arc further

removed from the nucleus, and the nucleus chsrge is less than the negative charge of thcir
aleotmns, F~~these anions ,as a rule, are more polarivliablc than cations, and

thnefore they can adjust their electron distribution and modify their interactive f o w s to
best suit their ~ v h n m e n tConsequently,
. cloxd prked miens .rr sammon in C ~ Y S ~ ~ S .

Two cations, however, repel one another SO *mn@y hat they rarely occur close
neighbours in a crystal structwe.

The coordination requirement of a cation is the result of its demand for being

screened, that i s surrounded by negative charga. ~kcoordination requirement. therefore.

is strongly influenced by the polarizabililty of the anions. The polarizability of an anion.

inturn, depends upon its own environment.

The $i4+ ion is surrounded by four 0'. ions in all silicate minerals. 'The niolccule

SiOz. therefore, cannot exist in the vapour phase bccause the si4+ ion demands completc

screening either by polymerization or by sharing of 0'-ions, so that the inlmcdiatc

surrounding of the si4+

ion consists of atleast Four 0'.ions.

The formation of orthosilicic acid from sodium silicate leads to the replacement of

more polarizable ions of (ONa)' groups by lcss polarizable OH' ions. In contrast to the

(ONa)' group, the OH. ion group can be described as an 0

' ion into which a proton which
'

has no electron has penetrated [41]. When a cation with a high potential ficld retmains

incompletely screened, the group polymerizes by sharing some OF thc anions bctwecn two

cations, so that each cation assumes a higher coordination numbcr.

The process of polymerization of a Si(OH)4 molecule (silicic acid) leads to units in

which si4+ ion and is surroundcd octahedrally by six OH- ions. In anhydrous silica each

si4+ ion is surrounded tetrah&idly by four 0'' ions, each of which is shared by silicon

ions. The polymerization involves the interaction of three dimensional groups, but Wcyl

and Hauser [56] described the essential features of the condensation polymerization of

aquwus silioic acid by a planar scheme. This simple condensation polymerization of a

Si(OHl4 to f o m a three-dimensional network polymer of siloxane chains throughout the

solution has been advanced as the mechanism of gelling silicic acid solutions by other

investigators [57-591.

The mechanism by which polymerization takes place falls into two general

categories, "addition" and "condensation" [60]. In a addition polymerization , the

molecule obtains its reaction bond by breaking double bonds to form two single bonds

(figure 4-a). It therefore may occur without the formation of a by-product. Howcver. as a

general rule, for addition polymerization at least one double bond must esist in the

monomer (figure 4-b). In contrast to addition polymerization, which is primarily a

summation of individual molecules into a polymer. condensation polymerization forms a

second, nonpolymerizable molecule as a by-product. Usually the by-product is water or

some other simple molecule such as HCI or CHIOH.

A familiar example of condensation polymerization takes place bctwcen

formaldehyde (CH20) and phenol (C~HJOH)as shown in figure 4-c. The formaldehyde

supplies a CH2 unit which serves as a bridge between the benzene rings in two phenols.

Stripping two hydrogens from the benzene rings and one oxygen from the formaldehyde

forms water (HzO)which can volatilize and leave the system.

All experimental data now available clearly indicate that a colloidal silicic acid gel

can be formed by the condensation polymerization reaction of silicic acid to form a

polysilicic acid structure. The monomer in this polymerization rcaction is silicon

hydroxide (Si (OH)& It can be classified as amphoteric because it can release either

hydrogen or hydroxyl ions. Condensation polymerization occurs whenever the positive

and negative ions containing the silicon come in to close contact, and the released water

remains combined with the structure by adsorbtion. Hurd [57], to whom we owe this

theory, mentioned that the panicles in a sol of hydrated silica are positive in a strongly
Figure 4. Polymerization mechanisms: Addition and
Condensation Polymerization [a]
(a) Breaking double bonds to form single bonds
(c.g., ethylene)
(b) Butadiene addition polymerization into
unvulcinized rubber
(c) Condensation polymerization :phenol = C~HSOH,
formaldehyde = CH20,molecular by-product = H 2 0
acid but they become negative in weakly acid, neutral and hit solutions, In
basic the acidic type of ionization would be much i n c m d and most of the

Wideswould therefore be negatively charged. Monosilicic acid(monomer), being

unstable * combines with another monomer to form a dimmer (disilicic acid). The dimmer

then joins with another monomer to produce a trimer (ttisilicic acid). Thus, without
showing any (ONa)- groups or the COs 2- ion, but only the silicic acid. the ionic reaction

can be presented as shown in figure 5.

Figure 6 represents schematically the chain polymerizations of the ionic reactions

presented in figure 5 and thier final syneresis to silica hydrogel, a condensation

polymerization of orthosilicic acid molecules. Figure 6-1 illustrates an Si(Otil4 molcculc

as it has formed from sodium silicate solution. In an aqueous medium such a molcculc is

hydrated ; the water molecules, because of their dipolar character, are attracted by the

cation for better screening of its positive ficld. Figure 6-11 rcprescnts schematically such a

molecule of orthosilicic acid with two H20 moleculcs. The number of 1-120 molecules

which can come close to si4' is restricted by the space requirements and by thc dipole-

dipole repulsion between the oriented Ii20 molcculcs. Because of thcir lower

polarizability, water molecules cannot screen the potential ficld ol' thc si4' ion as

effectively as the same number of the more polarizable OH-ions. TWOunits of type 11 are

likely to form a dimmer by sharing two hydroxyl groups. lhis l y p 0f polymcrimtion can

continue and leads to chain-like molecules (figure 6-11!), because the end members have

incompl& coordination, but their coordination requirements can be met by reacting with

the monomer Si(OH), to form new moleculcs. The resulting chain is not likely to be

slraighg but asumes a ipg

or a spiral-like shape. The length of the chains or the s i x of

the macromo~ecu~es
depends upon a number of factors, such as the rate of pol~merimtion,
the pH ofthe solution, * mncsntntion of silica, tempnMC ~d thc presence of foreign

molecules.

Formation of these chain-like molecules, especially in close pmximity to OH-

groups within the potential fields of two si4+ions, makes it possible for a second reaction

to occur, namely, a caulensation reaction within the silicic molecules. Figure 6-IV

illustrates two joining groups of one of the polymer chains. The clearing of water fxom the

two OH-groups leads to figure 6-V,that is. the grouping which now has tllc two si4'ions
linked by an 0*-
ion. This reaction lowers thc energy of the systcnl atlenst in part. bccausc

two OH-groups are replaced by one 0**

ion which has a higher polarirahility. 'fhis

condensation process (final syneresis to a silica hydropl) shortens the si4' - si4'

distances as shown in the figure 6-V.This phenomenon has little consequence as long as

the molecule is small and mobile. However, once the polynlcrimtion process bad

advanced to such an extent that the solution of the silicic acid has fornlcd long &ins

b o u g h the development of the gel, the condensation process leads to the build-up of

tension within the chain, which consequently imparts rigidity to thc gel.

Hurd [57] pointed out that gel formation could be accounted lor by the splitting out

of a malecule of water, accompanied by the dissipation of thc charge and thc for~nationof'

an oxygen linkage between two groups, each containing one silicon ion and threc OH'

group* This is compatible with the concept that t h e &!CIS have a fribrillar structure

C O I I I ~ O S ~of
. ~ long chains of hydrated silica units (figure 7).
 0.1
1 10 100 1000 10,000
GEL TIME (Hours)

Figure 7. Condensation Polymerization and Gel Growth

(a) Condensation of silica particles into polysilicic acid molecules

may occur by the splitting out of water rnolccules containing OH
groups m ~ r 571
a

(b) Silica gels (6.8% Si02 and 1.78N HCI ) formed by neutralization
of Na20:2.5Si02 continued to increase in volumc at 23C.
A son gel was seen in 8 hours and syneresis at 214 hours
lHeymann, 611
 3.6
.-
It is now well known from the literature review on silicic r i d and gel structure that

hydrated sodium metasilicate can be written as Na2(H2Si04).8H20(65-681, and it

dissociates in this way :

-
Naz(H2Si04).8H~O+ water 2Ns' + + water

Because of the low ionization constant of silicic acid ( K , = ~ o -~~~~=, 1 0 - ' (671,
(2)
~ ' ) nlost of

~ ~ .in dilute, basic (pH 8-9) solutions hydroly~ein twn stcps :

the H Z S ~ Oions

H Z S ~ +OHzO

H,SiOi+ H20
~~ +
.-
-
___,
*---
HBi04' + Otl

114Si04 + 011

and the concentration of each ionic species depcnds upon the level of d~cpl I.
(3)

(4)

If sodium metasilicate hydrate crystals arc exposed to carhndioxidc, solutions

made from this material contain colloidal silicic acid [53.67] and geleation airrts

immediately because of the increase in viscosity. On develop~ncnlof the bond with

sodium silicate two surfaces are wetted by a fluid rncdium which then solidities. Whcn tllc

dimensions are large, we think of adhesives, whilc on a micm-scale wc may s p k of

cement, though the essential mechanisms arc the same. 'The chanp fmm liquid silicatc

solution to a solid may take place by loss of water, by saturation with solid silicates, by
chemical reaction wjth either liquid or solid reagent%by lowering the tcnlpcraturc or by a

combination 0fthe.q~p m ~ ~ ~[69].

s e sIn lenns of foundry sand application, only two Out of

four possible mechanisms are relevant:

1. ~ c v e l o p m nof
~ products as a resuIt of chemical ~ c t i o nbaause of a
by virtue of their nature function i.b o d
h.,mgC in pfithe= new

(gels);
 2. D c h y d m n P m S -c k & 0 f p b of sodium silicate fmm liquid to solid
by loss of water (glassy phase).
Thus, sodium silicate bonded sands (moulds and cores) c m k cured by either a pH

change or by a physical dehydration or by a combination of both mechanisms: one or the

other dominates depending on the individual hardeners.

3.6.1 Mechanism of cur in^ bv DHChange

This hardening mechanism involves generation of acidic species when a Iiardcner

comes into contact with the silicate solution or film (which is basic) coating the sand

grains. A decrease in the pH value by introducing acidic species causes precipitation of

the silica gel which acts as a binder between adjacent coated sand grains. A typical

example of pH change mechanism is the COZsodium silicate bonded core and mould

curing process, known as the "C02 process".

In the case of curing sand cores and moulds with C02 gas, the transformation of

the gel which bonds the sand grains togethcr can be perccived as follows : the aqucolls

solution of sodium silicate reacts with C02 gas to produce monosilicic acid and sodium

carbonate. Thus:

NazO.SiOz + 2H20 + C02 -

Putting ~ q( 5, ) in terms of an ionic balance :
Si(OH)4 + Na2CO3 (5)

Na20.2SiO2 + 5H20 ' 2 ~ a ' + 2Si(OH)4 + 20H' (6)

and

CO2 + H20 2 ~ '+ CO, 2- (carbonic acid) (7)

Then the OH-ions of fhis alkaline sodium silicate ( with pH of 10-12) 181 combine with
the H' iom fmm the carbonic acid, combining Eqs.(6) and (7)as follows:
~a20.2Sich+ c@ + 4 Hz0 - 2Si(OH)4 + NalC03
These two equations can be rewritten in the important form w shown below :
(9)

~ a ~ O . S i 0 2Hz0
. x + C02 7NazCO3 + Si02.x HzO (10)
Where x is a number of moles of water either in the sodium silicate solutioll or in thc

hydrated gel, which at present has no strength until some of the water Ins beell rctnoved

by the process of syneresis. Equations (8)to (10) are similar to Eq. (5) in which

rnonosilicic acid and sodium carbonate are the reaction products.

The ionic reaction of sodium silicate binder cured with C02 gas and including ~ a '

and C03 2- ions can be represented as shown in figure 8-a. As the above reaction indicates,

the polymerization can be truncated by the presence of ~a'ions. Any other foreign ions

which replace OH' groups attached to the si4+

cations would shorten the polymcri~ation

process, and therefore weaken the bond strength of the silica gel.

During the C02 curing process, the Na2C03has thc greatest cffcct on the rigidity

of the core or mould, but as the syneresis of the silica gel continues, the gel it self impns

some strength to the sodium silicate bonded sand. In the prcscncc of Na2CO3 and water.

overgassing with C02 causes the fomation of sodium bicarbonate (NallCO,), which has
been found by several inve~tigaton[8,22] to contribute more strength to a mould or Core.
Figurc 8, Ionic Reactions of Sodium Silicde

(a) Sodium Silicate RactingCorn

(b) Dehydration of Sodium Silicate Solution
3.6.2 Mechanism of Curinn by Physical Dehvd tion

Dehydmti0.n h n g of the silicate binder in a foundry und t a k place when there

is sufficient heat to evaporate the water content from the silicate solution. Thus, the

dehydration of sodium silicate takes place by exposure to microwave energy. convection

of hot air, or exothermic m i o n resulting from organic or inorganic compounds. The

difference between the direct dehydration process and the C@ process is that the end

products of the later or Na2CO3 andlor NaHC03 and the hydrated silica gel. where as the

former process results in a dehydrated or semi-hydrated silica gel.

A general dehydration curing of sodium silicate using either microwavc energy or

circulating hot air may have the ionic reaction shown in figure 8-b. Thc chemical reaction

can be written simply:

dehydration
NazSi03 + H20 + NazSi03 (glassy - 1120
t ( 1 1)
hydration Phase)

The Si -0 S i linkage , which is called a "siloxane" linkagc, is the only bond

which imparts rigidity to the bonded sand grains. This bond is far stronger than citlicr thc

Na2C03 bond or the hydrogel bond when cured with COz gas process. Therefore, it would

be expected that cores and moulds cured by the dehydration process would bc far stronger
than those cured by the COz gas process. Dehydration speeds up the condcnsation

polymerization p m ~by. which silicic acid is formed from the alkaline silicate solution.

Drying occurs by evaporation at the surface, and the rate is constant and indcP2ndca of

the w a h content, but is limited by the temperature, humidity and air velocity, if forced
mnv&ion is used for drying During CWhg, Warn must travel by capillary force from
me interior of the mould or COE to the surface at a rate equal to the rate of evaporation.
The *(a
loss
the mte of endensation polymeriation md iel fonnatjm.
C o l l s ~ q ~ nthe
t l s~ m
~ s i s PIY)C~SS takes place at a fater mte.

Fi~urc9 illwhtes effect of curing trmpntute on Uu bond strength of sodium

silicate when used as a binder in foundry sad. Nomully, the test m p l e s a n s o h d at

d i f f m t tempcratums for five minute and allowed to mol to mom temperature before

testing. Many investigators [5,8,70,71] have found similar results. Examination of the

curve shows that the initial strcngth is causcd by the hydraled silica gel. 'Thc pl strcngth

increases between 100 C and 300 C when all the free water has been evaporated cxccpt dlc

bonded water (water of crystallization). Following the first peak, tllcrc is a

decrease in strength caused by the release of chemically bonded water at about 3 15 C. In

the area of 450-550 C the gel bond ~ o e through

s a partially liquid state, which results in

the minimum strength. Beyond 550C the strength increases because of the fonnation of

vitreous bond and at 800 C more glass is present. This glass has a high viscosity which

produces greater strength. At 982 C more glass is fonned. According to Wales (81, with a

three-hour soak at 982 C, the hot tensile bar becomes very ductile and yields like copper.

For the purpose of making foundry moulds and cores, the silica gel rormcd at the

temperature range of 120-200 C is necessary to obtain the required strength. Eitel 1431

observed that in silica hydrogels, the difference between physically adsorbed water (free

water) and chemisorbed water (chemically bonded water) was most evident by the ease

with which the m type of 66moisture"was removed by heating in dry air at 120 C, and

th firm binding of h e hydroxyl m s in t k silanol WUp Si -OHof the surface. Uocr ct

al. [72] observed small losra of chemically bonded water (OH h ~ d r o x WuP)
~l at

150 c & a contin"(jus dehydmxylationabove 380 C. In the wne WaY that the h~droxyl

wups slmvlydismptd md nei$hbouring silanol groups undergo chcmical reactions

TEMPERATURE (C)
with re1110v.l of and the formation of condensed siloxane bindings, the ability of
the gel to absorb polar mol~culeslike water is reduced. h,
the more the hydroxyl

groups (OH) are removed from the silica gel. the more the previously strongly hydmphilic
surface character becomes hydrophobic.

3.7g -
in Foundry Sands

As a hypothis, the author proposes that the nature of sodium silicatc bonding in

foundry sands is adhesive bonding, because of the nature of the silica gel. Sodium silicate

is an efficient wetting agent. Adhesion between clean sand surfaces and bonding medium

is likely to be more complete and stronger than that with an unclear surface.

In the case of sodium silicate binder as the adhesive and the foundry sand grains as
the substrates to be bonded, little is known regarding the above factors. Most past

investigations of the strength of moulds and cores bonded with sodium silicate were

directed toward control on a day-to-day basis, rather than toward understanding thc basic

phenomenon involved in the bonding mechanism. Sodium silicate is a mctastablc

chemical compound, and it can therefore decompose fairly easily inlo monosilicic acid.

Si(OHI4 which is unstable. The latter polymerizes to polysilicic acid; polymcripalion

continues to high polymers for gel formation. The newly formed gel is hydratcd and, being

in the beginning stage , is able to adhere to the cleaned surface of the sand grains.
Polymers which are "macn)molecule$' can adhere to the interfaces by multiple paints of

physical adsoqtion, as well as extending into the adjacent phase [73]. They form a bridw

of multiple Van der Waal bonds, as they diffuse into the adjacent phases and thus can

accomplish a stitching action [74].

 dm not act @ S h h l R filling m o w &(ween the rand gmim like

a~ n c H ~O W
~ ~at. ~theS point of contact of two adjacent wd grains, the d i u m

silicate film is * l u d out d u h g compaction. This hapvns afler the sand grains have

been filly coated with the binder during the mulling pmons. AS the result of surface

tension and viscocity of sodium silicate liquid, the film forms a neck-like such structure

(bridge) to join two adjacent sand grains together (figurelo). After gassing this bridge

consists of the siloxane Si -0 -Si linkage, water. NaC03 andfor Nal.lC03. which

contribute to the rigidity of the sand core or mould. Degtyarenko and Stolyar 1751

performed a quantitative study of the resin binder distribution on n sand grain surface and

found that the strength of the sand core was directly proportional to the strcngth of thc

binder film,number of contact points on one sand grain and the area of the mininlum

section of the binder film in the contact wne. The ternary phase diagram of a sodium

silicate solution at room temperature (figure1 1) can be uscd to illustrate gel formation

from sodium silicate solution.

As an example, the sodium silicate solution, after mixing with a sand aggregate, is

rammed or vibrated into a core. At this point, it is in the state marked by rcgion "ordinary

commercial liquids" on the phase diagram. As this silicate rcacts with CO2, the Na20 is

consumed. and the gelled silicates shift on the diagram to the region of unstable liquids

and gels. This silica gel is high in SiOz. as shown in the phase diagram, and it constitutes

the bond strength of the core or mould aggregate. The phase diagram shows that the stable

forms of sodium silicate exist in the region where the silica:soda weight ratio range is 2:l
to 3,75:1. hi^ is the silicate ratio range used in the foundry industry. The silicate with the

high silica content (3.75:l) reacts f M a with C02 than docs that with low silica content

such as a silicate with a 2:l silica soda ratio-

Elgure 10. Sodium S i t e Adhesive Bonding in Foundm Sands.
Figare 11. Ternary @mediagram 8bowi.g pluae cbargea of
sodium uiUcate depending of water content 111

(1) Anhydrous d m m orthouilkate and mishrcu

witb NaOH, (2) Crgrtrlline alkaline silicata,
(3) Uneconomical partly cySt.lltzcd m i x t u q
(4) G h m , (5) UneconomicPI hydrated glmm,
(6) DehydratedUquMq ('7) Unecwolaicltl Seml-
Sdid, (8) Uneeonomid *mu Uqnid, (9) Ordim. y
Corpmercirl liqoids, (10) Wute Iiqulds, (11) Nonnally
Unstable liquids and gel&
 If a f o r d draft of hot air is used, or if evaporation is accelerated by heating.
following the direction of the arrow in figure11, it can be seen that the liquid silicate

changes first to a viscous liquid and then to a semi-solid and finally to a dehydrated liquid.

On further evaporation, possibly by heating, hydrated glass and then convenlional glass

can be obtained. Silicates of higher SiOz:Na20ratios undergo these changes more rapidly.

In the case of a conventional mould and core hardening process, however. the last changes

may not occur and the highest required strengths should bc obtained within the region of

the dehydrated liquid (Figure 11).