Chemistry Everyday for Everyone

How To Learn and Have Fun with Poly(Vinyl Alcohol)

and White Glue
V. de Zea Bermudez, P. Passos de Almeida, and J. Féria Seita*
Secção de Química, Universidade de Trás-os-Montes e Alto Douro, Quinta de Prados, Apartado 202,
5001 Vila Real Codex, Portugal

For the past three years, the content of this paper has Main Concepts (1–6 )
been presented as a class guide in the practical laboratory of
the one-semester materials science course. This course is taken Viscosity is a physical property that characterizes the flow
by first-year students in the Civil Engineering program. The resistance of simple fluids. Well-known fluids present a range of
work described here always elicits much enthusiasm among viscosities: anyone can easily conclude that the viscosity of
students, who find it very amusing and instructive. Its intent is water is quite low, whereas the viscosity of honey, mayonnaise,
to provide a rather simple theoretical approach to some of syrups, ketchup tomato sauce, or motor oils is considerably
the most fascinating aspects of the rheology of certain fluids. higher. We are all also aware of the fact that the control of
Students prepare two popular viscoelastic materials that viscosity is of extreme importance to industry. The consis-
exhibit unusual flow properties. One of them is derived from tency of shaving creams, some toothpastes, and artist’s paints
poly(vinyl alcohol), PVA, a synthetic analogue of a product needs to be properly adjusted for easy flow from the customers’
sold by Mattel Corporation (California, USA) and commer- tubes. Medical and food manufacturers, as well as dairy, flour,
cialized as a toy under the name of “Slime”. The other is a and starch industries constantly require viscosity measurements.
poly(vinyl acetate)-based emulsion similar to a product also The viscosity of most common fluids depends exclusively
marketed as a toy named “Silly Putty”. After synthesizing the on the temperature; increasing the latter reduces viscosity and
gels, the students must carry out a series of suggested mechani- vice versa. The flow of these particular fluids, named
cal tests with both fluids and explain their intriguing and Newtonians, is completely understood and widely docu-
unique behavior. At the end of the laboratory work, students mented. Such a property is not characteristic for all fluids.
are expected to answer several questions connected not only with There are some whose viscosity can be altered by other means,
these materials, but also with common fluids encountered in for example, by submitting the fluid to shear stresses (stirring,
everyday life. The results have always been very satisfactory. pouring, squeezing, or spreading). Their behavior may be an
As a rule, students enthusiastically try to discuss the observed advantage or it may become a nuisance. Many household and
properties in full detail. industrial liquids lie in this class and their usefulness depends
Apart from being undeniably entertaining and educational, largely on their non-Newtonian character.
the experiment, which can be done by pairs of students, is Fluids are divided into four main categories, depending
inexpensive and easy to perform and can be accomplished in on the way they flow:
less than two hours. It does not require special glassware or Type I. Time-independent or purely viscous fluids
equipment. The chemicals involved have no known toxic Newtonian fluids
effects. No special safety measures need to be adopted when non-Newtonian fluids
handling the gels formed, but the use of gloves and goggles shear-thinning fluids
is strongly advisable because of the nature of the cross-linking shear-thickening fluids
agent. Most students wish to take the putties away with them plastic fluids
and they are allowed to do so. The instructor makes sure first Bingham fluids
that the putties are kept in a sealed plastic bag and then warns Type II. Time-dependent fluids
the students not to touch the putty or to let children play thixotropic fluids
with it or ingest it. negative thixotropic fluids
In addition, the gelation experiment involves a series of Type III. Viscoelastic fluids
other interesting concepts, such as cross-linking, gel chemistry, Type IV. Complex rheological fluids
polymer networks, fiber production by the extrusion process,
We will discuss the Newtonian, shear-thinning, shear-
water solubility, hydrogen bonding, and glass transition tem-
thickening, thixotropic, negative thixotropic, and viscoelastic
perature, all directly or indirectly associated with polymer
fluids with some detail in this work.
science and therefore quite appropriate for the subject of
Materials Science. Time-Independent or Purely Viscous Fluids (1–3 )
In spite of the fact that the gelation experiment has been
widely discussed in the literature, we propose some changes Viscosity is independent of the duration of flow. Provided
in the preparation of the gels which improve both their di- the temperature and pressure remain constant, the shear rate
mensional stability and workability. depends only on the shear stress.
Newtonian Fluids
*Deceased. The other authors wish to express their distress for Let us consider a fluid contained between two large par-
the loss of a friend and eminent researcher, who died while this allel plates of area A separated by a small distance H. The
manuscript was being revised. system is initially at rest, but at time t = 0 the upper plate

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 Chemistry Everyday for Everyone

(A) is set in motion in the x-direction at a constant speed v. F

As time proceeds, the fluid gains momentum and finally the (A) moving plate
steady-state velocity profile shown in Figure 1 is established.
It is thus assumed that the layer in contact with the station-
ary plate (B) does not move (v = 0), but that each successive H
h
adjacent layer of fluid moves at a rate that increases with the
distance to plate B in a linear fashion. When this final state of x
steady motion is attained, the constant shearing force F, re- (B) stationary plate

quired to maintain the motion of the upper plate, can be Figure 1. Scheme of the flow of a thin layer of a Newtonian fluid
expressed as follows, provided the flow is laminar: between two plates

F =ηv
(1)
A h
shear thickening (n>1)
where v/h represents the rate of change of velocity with dis- log σ
tance from plane. The factor η is called the viscosity of the Newtonian (n=1)
fluid. It is constant at a given temperature for a particular
fluid. The units of η in the cgs system are g cm᎑1 s᎑1, also
known as poise. Most viscosity data are reported either in this
unit or in centipoises (1 cp = 0.01 poise).
The use of another constant, the kinematic viscosity, is shear thinning (n<1)
sometimes preferred. This quantity, which has units of cm2
s᎑1, is defined by
η
ν= ρ (2)
where ρ is the mass density of the fluid. log (dv/dh)
If the shear stress is designated as σ and if the shear rate
Figure 2. Logarithmic plot of the shear stress and shear rate for
is given by the velocity gradient d v/dh, one obtains:
Newtonian, shear-thinning, and shear-thickening fluids

σ = η dv (3)
dh
For Newtonian fluids n = 1. If n < 1, ηa decreases with
This formula is known as Newton’s law of viscosity. The increasing shear rate and the fluid is called shear thinning.
fluids that behave in this fashion have a viscosity that is inde- When n > 1, the fluid is named shear thickening, since ηa
pendent of the shear rate. They are termed Newtonian fluids. increases with increasing shear rate. The logarithmic plot of
All gases, most simple liquids, and solutions of low molecular shear stress vs shear rate for Newtonian and non-Newtonian
weight materials are described by Newton’s equation. Examples fluids is shown in Figure 2.
of common Newtonian fluids are water, acetone, carbon
tetrachloride, mercury, and some oils. Shear-Thinning (Pseudoplastic) Fluids
According to one of the theoretical models which have been
Non-Newtonian Fluids proposed to explain the behavior of shear-thinning fluids, with
Non-Newtonian fluids are those able to show a wide range the increase of the shear rate, the molecules are progressively
of viscosity depending on the shear rate. It is thus preferable aligned along the stream lines, causing a decrease in ηa. The
to use the term apparent viscosity, ηa, defined as the ratio of degree of alignment will depend on the shear rate and will
shear stress to shear rate: occur immediately or within a nonmeasurable period of time.
As soon as the major axes of the molecules lie along the stream
ηa = σ
(4) lines, the apparent viscosity will reach a steady value. Dilute
dv polymer solutions, polymer melts (rubbers, cellulose, acetate,
dh napalm), suspensions (paints, paper pulp, detergent slurries),
and dilute suspensions of inert solids are examples of shear
The following empirical relationship between shear stress thinning fluids.
and shear rate has been proposed to describe the flow of non-
Newtonian fluids: Shear-Thickening (Dilatant) Fluids
n Shear thickening is far less common than shear thinning.
σ = k dv (5) Osborne Reynolds was the first to recognize shear thickening
dh fluids in 1885. He termed them dilatant fluids, because the
model he used to describe their behavior involves a dilatancy
where k and n are constants for a particular fluid. or expansion on shearing. A very simple and enlightening
The apparent viscosity ηa may be expressed in terms of demonstration of Reynolds’s model of wet sand mixtures was
k and n by substituting eq 5 into eq 4, giving later suggested by R. E. Berg (2). Berg partly filled a plastic
n–1 bottle with sand and fitted it with a stopper and a glass tube
ηa = k d v (6) at the top. He then added water until the level of the liquid
dh reached the top of the tube. By gently squeezing the sides of

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 Chemistry Everyday for Everyone

the bottle, he observed that the inside mixture offered con- “curtains” on the finished material. A paint is judged by the
siderable resistance. When he squeezed the same bottle hard extent to which the brush marks disappear during drying. A
and suddenly, the resistance became so great that it was not good paint should lose consistency rapidly but be capable of
possible to deform the bottle significantly. Berg also noticed rebuilding very slowly, allowing complete leveling for a perfect
in the second experiment that the level of the water had and smooth finish.
changed, contrary to what he would have expected: instead Thixotropic foodstuffs include honey and “mayonnaise”.
of going up, the level of the water dropped appreciably. Shaving cream, some toothpastes, and artist’s paints are also
Let us see how the Reynolds model accounts for the thixotropic fluids.
observed features.
Negative Thixotropic Fluids
Increase in resistance to squeezing. When the bottle is sud-
denly squeezed and the fluid dilates, the amount of water One of the models that account for the negative thixo-
between the grains is not enough to lubricate them. Sudden tropic nature of some fluids postulates that a larger number of
shearing causes additional friction between the grains and an intermolecular bonds is formed in the course of motion than
increase in the apparent viscosity of the suspension. The faster in the system at rest. Since ηa increases with shear rate and
one squeezes, more the grains will tend to move over one duration of shear, negative thixotropy is treated as a reversible
another, leaving their initial closely packed state, and the less sol-gel-sol transformation. During flow, both the frequency of
efficient lubrication will be. The mixture will then offer extra collisions between different polymer molecules and the cross-
resistance to shearing. On the contrary, low shear rates allow linking increase, leading to the formation of a gel. Gelation
the water to occupy the additional space between the grains, induces in turn an increase of ηa. In solution at moderate
keeping the friction low. shear rates, this building process masks the destruction of the
Decrease of the water level. Initially, because the grains of three-dimensional structure, which occurs at the same time
sand are packed as closely as possible, water cannot be pulled because shearing breaks weak bonds. Once the shear stress is
through the voids between them. By squeezing the sides of removed, the original sol is reformed.
the bottle some grains lift over one another and the distance Very few negative thixotropic fluids are known. Owing
to their closest neighbors increases. The total volume occupied to their negative thixotropic nature some lubricating greases
by the grains is increased and water is allowed to flow between may be pumped from the tanks, where they are stored in a
them. Therefore, although the sides of the bottle are pushed relatively fluid state, to bearings. On shearing, they gel, pre-
inward, the flow of water in the container makes the water venting leakage.
level go down. Negative thixotropy is generally a hindrance in industry.
The Reynolds model applies to all suspensions of solids In all those processes that involve the rapid transport of fluids
in liquids, when the solid content is high. Besides the wet the increase of ηa diminishes the efficiency of the process.
sands mentioned, other such fluids are wheat starch solutions, Luckily, at high shear rates the phenomenon does not occur,
some paints, printer’s ink, and gum arabic in water. making possible the transport of fluids in a runny state by
pumping them through the pipes at very high speed. At inter-
Time-Dependent Fluids (2, 4 ) mediate shear rates, negative thixotropy becomes a very serious
Viscosity depends on the duration of flow. The shear drawback.
stress depends on the shear rate and on the duration of shear.
Time-dependent fluids are similar to shear-thinning and Viscoelastic Fluids (2, 5, 6 )
shear-thickening fluids, except that a measurable amount of Properties
time is needed for the viscosity to regain its initial value once
the shearing has ceased. Time-dependent fluids can have a Shear rate and viscosity depend both on the shear stress
wide range of viscosity for each shear rate and for this reason and on the extent of the deformation of the fluid.
the term apparent viscosity is applied here as well. If the In addition to being fairly viscous, viscoelastic fluids are
apparent viscosity decreases with shearing, the fluid is said elastic. Their inherent elasticity is responsible for a series of
to be thixotropic; if the apparent viscosity increases, the fluid astonishing properties. Solutions and melts of high polymers
is negative thixotropic. fall into this category of fluids. The viscoelastic effect, which is
more marked when the molecular weight is high, as in jellies,
Thixotropic Fluids artificial fibers, and flour dough, may be analyzed on the basis
Thixotropic fluids are essentially time-dependent shear- of the properties of the individual chain molecules. However,
thinning fluids. They become runny when stirred (a sol is the cause of the viscoelasticity depends on the solution under
formed) and recover the initial structure when left to stand (a study. It should be also noted that the involvement of long-
gel is formed). Thixotropy (literally “change by touch”) may chain molecules is not compulsory for elasticity to appear.
be understood as a reversible gel-sol-gel transformation. It re- It is also present when a Newtonian fluid is dispersed through-
quires anisotropic particles loosely packed. Particles in the out another fluid to form an emulsion.
shape of needles or thin discs and polymeric particles are more The following list of properties includes some of the most
efficient in producing it than are particles with uniform shape, striking effects displayed by viscoelastic fluids which have been
such as spheres. Also, the particles responsible for thixotropy demonstrated and extensively discussed by Collyer (6, 7 ):
must be large, for the collisions between small particles or mol- Elasticity. If a viscoelastic fluid is extruded through a tube
ecules generally give rise to Newtonian behavior. forming a ball at the exit opening and the pressure is sud-
Thixotropy is of great importance in the industry of denly removed, the fluid will recoil along the tube and may
paints. It is a desirable property because paints are required eventually regain the initial position. This feature is usually
to be easily spread at high shear rates but not to drip or cause called flow elasticity. A similar elastic recoil can be observed

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 Chemistry Everyday for Everyone

whenever a viscoelastic fluid is stirred in a container. If after tubes must be properly designed in order to give fibers with
some time the stirring is stopped, the direction of the swirling the desired size and required shape.
will reverse and the air bubbles trapped in the fluid will re- Spinability. Polymer solutions and melts are capable of
trace their movements. If a stream of fluid is poured from an being drawn out into long, fine, and stable threads (see Fig.
elevated beaker into a second beaker another uncommon me- 4). Technically this property is called spinability.
chanical property produced by elastic recoil will be illustrated. Let us first consider the case of a loaded metal wire. The
If the hanging stream of fluid is interrupted for some rea- tensile strength will be greater at the local points of weakness—
son, the falling stream will fall into the lower beaker, while that is, the regions of smaller diameter. These unstable regions
the upper stream will recoil upward and back to the beaker. cause wire breaking. This phenomenon, named localized
Self-Siphoning Effect. It is possible to induce some fluids striction, occurs in Newtonian fluids as well as in elastic solids.
to siphon themselves out of a beaker once the falling stream Under analogous experimental conditions many viscoelastic
is initiated. Once the length of suspended mass is consider- threads do not break, owing to a sort of strain-hardening pro-
able, the elasticity of the material is enough for the hanging cess which opposes striction. The stability of the viscoelastic
fluid to pull more of the polymer from the elevated beaker, thread increases with polymer weight and the concentration
first up the lip of the beaker and then over to its side. If a of the polymer. Therefore it depends on the absolute length
fluid is emptied from one beaker into another, the direction of the polymer chain, on the number of repeat units, and on
of the flow may be reversed by decreasing the length of the the degree of interaction of the macromolecules.
falling fluid, that is, by slowly raising the lower beaker. A Spinability is crucial to the fiber industry; otherwise it
similar climbing tendency is observed when filling a syringe would not be possible to prepare nylon or rayon yarns. It is
with certain fluids. It is sometimes more convenient to lift of fundamental importance in nature, as it allows spiders to
the syringe out of the fluid surface while sucking it up. A make webs!
stream of fluid will flow from the surface into the syringe. Weissenberg Effect. When tea is stirred in a cup, a steep
Die-Swell. Forcing a certain amount of a viscoelastic fluid vortex is formed. If the procedure is repeated with a viscoelas-
into a tube and pushing it through it displays one of the most tic fluid, it does exactly the opposite: it climbs up the stirrer
characteristic features of these fluids. Contrary to what hap- (see Fig. 5). This climbing behavior is known as the
pens to Newtonian fluids, the viscoelastic mass emerging from Weissenberg effect.
the tube will expand; its diameter will tend to increase by as When a viscoelastic fluid is sheared in one direction, its
much as three or four times the diameter of the hole (see Fig. structure causes additional forces to arise perpendicularly. The
3). The expansion may be due to a sudden recoiling of the shearing set up by the stirring rod creates a force radially inward
polymeric chains against the shearing when they are forced toward the rod, pushing the fluid to and then up the rod.
to go through the tube and out of it. The long-chain mol- The surface of the fluid may be seen as a system of concentric
ecules traveling inside the tube are stretched. When they emerge elastic bands. When the bands turn at different speeds, because
from the tube, they relieve their internal stresses by con- of the fluid’s viscosity, they create shearing forces between
tracting and the diameter of the fluid increases. themselves, which in turn create the radial forces that attempt
Die-swell constitutes a very serious hindrance in the to make the elastic bands contract towards the center. Examples
manufacture of synthetic fibers. It is imperative to know be- of common viscoelastic fluids that produce this surprising
forehand the amount of die-swell likely to occur in the die effect are the thick portion of egg white, gelatin, some condensed
under the conditions of extrusion because the orifice of the milks, some types of honey, and some types of motor oil.

Figure 3. Die-swell effect using the PVA Figure 4. Spinability using the PVA gel Figure 5. Weissenberg effect using the
gel prepared in this work prepared in this work PVA gel prepared in this work

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Chemistry Everyday for Everyone

The laboratory experiment proposed in this work involves Nevertheless, B(OH)3 cannot produce polyol gels, since
the production of two viscoelastic fluids: a slime obtained the complexation reaction occurs through the attachment of
from an aqueous solution of PVA and a putty prepared with boron to adjacent alcohol groups of the same polymeric chain
white glue, a poly(vinyl acetate)-based emulsion. Structurally, and this prevents cross-linking from taking place (see eq 8).
the fluids are thermoreversible hydrogels. The gelation of the Borate Ion. In the presence of the tetrafunctional
aqueous solutions of both polyhydroxy polymers is caused B(OH)4᎑ ion the cross-linking between different PVA chains
by the presence of the borate anion, B(OH)4᎑, which plays (or between parts of the same PVA chain) is made possible,
the role of a cross-linker among the polymer chains. As the leading to the creation of a tridimensional network. When
principles governing the unusual behavior displayed by these the concentration of cross-linked chains is high, the network
materials are the same, the discussion that follows will focus immobilizes the solvent and a semisolid gel is obtained.
on the PVA slime. It has long been accepted that the B(OH)4᎑ ion has the
ability to react with many polyols in aqueous solution to form
Gelation of PVA
anionic complexes. The following two reactions are believed
The addition of an aqueous solution of borax to an aque- to be involved in the diol–borate complexation:
ous solution of PVA, followed by vigorous stirring of the mix-
ture, immediately initiates the process of gelation of PVA. A+B AB᎑ + 2H2O (9)
The material acquires a consistency reminiscent of a slime. ᎑
2A + B A2B + 4H2O (10)
Once prepared, the elastic and semirigid mass will display a ᎑ ᎑
number of quite intriguing properties: when the fluid is slowly where A, B, AB , and A2B represent, respectively, the free
pulled apart it stretches; if it is suspended from a hand, it polyol, the B(OH)4᎑ ion, and the polyol–borate complexes
will also stretch; if suddenly pulled apart, it breaks; if placed with 1:1 and 2:1 stoichiometry.
on a flat surface, it flows and forms a film. For a linear hydrocarbon chain containing 1,3-type hy-
The chemical basis for this very popular experiment has droxyl substituents, such as PVA, complexes with structure
been extensively investigated (7–11). A behavior similar to 1 (for AB᎑) or 2 (for A2B᎑) result. Cross-linking caused by
that found for PVA has been observed with several other poly- the formation of 2:1 complexes has been usually cited as the
hydroxy polymers (12–14). Most of the studies reported have cause for the enhanced viscosification in borax/PVA solutions.
aimed at elucidating the alcohol–borax complex formation
mechanism, which still cannot be regarded as settled.
CHOH CHOH CHOH
Role of Borax in Formation of Polymeric Gels
from Linear Polymeric Molecules CH2 CH2 CH2

Borax, the common designation of sodium borate, CH O OH CH O O CH

Na2B4O7ⴢ10H2O, is the salt of a strong base and a weak acid. – –
CH2 B CH2 B CH2
In aqueous solution it is hydrolyzed, yielding a boric acid/
borate buffer at a pH close to 9. The buffer equilibrium is CH O OH CH O O CH
described by the equation CH2 CH2 CH2
B(OH)3 + 2H2O B(OH)4᎑ + H3O+ (7) CHOH CHOH CHOH

In the gelation experiments, for which the borax con-

centrations employed are low (≤0.025 M), trigonal planar 1 2
B(OH)3 and tetrahedral B(OH)4᎑ exist as monomeric species.
Boric Acid. The tendency of B(OH)3 solutions to form The influence of polymer and B(OH)4᎑ concentrations,
diol complexes in the presence of organic polyols, such as ionic strength, pH, and temperature on the thickening of PVA
many water soluble natural products (e.g., guar and other has been examined by many authors (7, 8, 10, 11). Sinton
gums) which contain long chains with 1,2-diol groups, is well (9) has demonstrated that a particularly useful technique to
known: study the chemistry of PVA–borate complexes in water is 11B
NMR because 11B chemical shifts are sensitive to the oxygen
OH
C OH C O OH
symmetry (trigonal or tetrahedral) about boron and to the
+
–
+ H 3O +
size of polynuclear rings in 1:1 and 2:1 complexes.
HO B B
(8) One the most important contributions to the under-
C OH C O OH
OH standing of the borate–PVA complexation mechanism is
attributed to Nickerson (7), who has argued that even though
B(OH)3 is also capable of complexing PVA, a synthetic borate ester links between chains might be expected to be
water-soluble polymer presenting a predominant pattern of responsible for the viscosification and gelation observed, it
–OH groups linked to alternating carbon atoms of the poly- is more likely that cross-linking occurs through hydrogen
mer backbone (1,3-diol structure) and a minor percentage bonding between PVA and the B(OH)4᎑ ions. The uncommon
(about 1–2%) of 1,2-diol structures: properties exhibited by borate cross-linked gels—associated
with the ease with which the bonds break, reform, and break
CH CH CH CH CH CH CH CH CH CH CH CH
again—indeed suggest that the networks are in dynamic equi-
OH H OH H H OH OH H OH H OH H
librium and that the cross-linkages are not covalent. Several
n n'
experimental observations support Nickerson’s claim: (i) the
1,3 diol normal sequence 1,2-diol sequence 1,3-diol normal sequence unexpected solubility of the PVA in water, attributed to

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 Chemistry Everyday for Everyone

hydrogen bonding between the –OH groups of the main Reagents

chains and the water molecules; (ii) the decrease of the solu-
poly(vinyl alcohol), [CH2CH(OH)]n, (Mw 124,000–
bility of PVA in water caused by heating, due to the break- 186,000, 99+% hydrolyzed), supplied by Aldrich
down of the network of hydrogen bonds; (iii) the formation
of a gel instead of an insoluble complex of borate, due to the white glue (e.g., marketed by Bostik, shop available)
cooperative effect of a large number of –OH groups; (iv) the solid borax, Na2B4O7ⴢ10H2O, supplied by Riedel
easy disruption of the cross-linkages by shearing, reflecting commercial acetone, CH3COCH3
their weakness. The proximity between –OH groups and the Vaseline
borate ions assures their reformation. Only extreme dilution tap water
in water will stop the gel from being rebuilt.
The scheme that follows is thus preferred to explain the Procedure: PVA
behavior of PVA gels. Part A: A day before the gelation experiment
Preparation of 4% aqueous solution of PVA. Add 40 g of
H
PVA to 1 L of tap water at 70 °C. Stir the solution for about
O H
24 hours, keeping the temperature at 70 °C. The final polymer
O
CH H H CH
solution should be clear, nearly colorless and considerably
O
–
O viscous.
CH2 B CH2 Remarks:
O O
CH H H CH
1. It is highly recommended (8) to slowly sprinkle the
O H O powder onto the surface of the stirred water. This will
insure the individual wetting of the grains of the poly-
H mer and their swelling through solvent imbibition.
Failure to stir during the addition of the powder will
It is then not surprising that the success of the gelation result in the formation of a sticky mass of wet polymer
experiment depends primarily on the use of the appropriate which immediately clings to the walls of the beaker
PVA. For the creation of a stable gel, a highly hydrolyzed and resists dissolution.
PVA is desired. Such a polymer will possess a large number 2. Moderate heat at temperatures never higher than 70 °C
of alcohol groups regularly distributed along the backbone. accelerates dissolution. Cassaca et al. (8) name 90 °C
Equally important is the molecular weight of PVA, which as the maximum temperature allowed. At this tempera-
ture we were unable to speed dissolution. Instead, the
should be high in order to assure the mechanical strength of opposite effect was observed: the solution formed into
the cross-linked network. For the reasons presented, a 99– clots. Overheating should be avoided for two reasons:
100% hydrolyzed PVA having a molecular weight of at least (i) forced evaporation of the water will lead to formation
100,000 should be purchased for gelation purposes (8). of a crust of polymer at the surface of the solution,
and (ii) excessive heat will interfere with the dispersion
Experimental Details of the polymer whose solubility is partially imparted
by the presence of hydrogen bonds established with
Materials the solvent.
one 50-mL glass beaker 3. The PVA solution can be stocked in a closed container
two 150-mL glass beakers for one year at room temperature without losing any
two 500-mL glass beakers of its appearance or properties.
two 1000-mL glass beakers Part B: Gelation experiment
25-mL glass tube Preparation of 4% aqueous borax solution. Dissolve 40 g
glass tube (1.5-cm i. d. and about 3 cm long) of borax in about 1 L of tap water at room temperature. Stir
5-mL plastic syringe (without needle) the solution until complete dissolution.
Petri dish PVA Gelation. Slowly add 16 mL of the 4% borax solu-
tion to 500 mL of the PVA solution with rapid and vigorous
hot-plate magnetic stirrer
mixing. Continue mixing until the mixture gels. Air bubbles
magnetic stirring bar will probably be formed and stay trapped in the gel. Remove
thermometer the solid material, discarding any excess liquid.
pair of tweezers Remarks:
polystyrene spatula
1. The PVA mass will initially be sticky. Its properties
aluminium foil (30 × 30 cm) can be improved if the freshly prepared solid material
pair of gloves picks up foreign matter, such as dust or other particles
glass stirring rod found on the floor. Small pieces of paper towel may
mechanical stirrer act as fillers and provide stiffness to the PVA mass.
paper towel 2. The PVA mass should be worked with one’s hands for
a while before performing any of the mechanical tests
hammer described below. Before each new test the mechani-
support base with rod and clamps cally broken chunks of PVA should be reworked into
pair of scissors a single mass and rolled into a ball.

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 Chemistry Everyday for Everyone

3. The PVA mass tends to harden with age. Within one the falling stream in a second 500-mL beaker placed on the
week after the gelation experiment, the material will table top. Slowly raise the second beaker to decrease the length
have turned brownish and will exhibit better mechani- of the hanging fluid. The direction of flow will be reversed.
cal properties.
Test 3
4. If 500 mL of a 4% PVA solution prepared a year be-
fore is used, only 11 mL of the 4% borax solution will
Transfer the PVA mass to a 500-mL beaker. With the
be needed to produce the gel. help of a support base and a clamp, keep the beaker about
60 cm above the level of the table top and tilt it slightly to
Cassaca et al. (8) concluded that the volume of borax
allow the fluid to slowly fall from its lip. Stick a small dark
solution needed to gel the 4% PVA solution was 1/10 or 1/5
piece of paper on the falling stream close to the lip of the
the volume of the 4% PVA solution. In our case this ratio is
beaker in order to follow any change in the direction of the
approximately 1:31. We also note that Stroebel et al. (15)
flow. Cut the falling stream with a pair of scissors, coated
proposed a novel method of obtaining the PVA gel by using
with vaseline, a few centimeters below the lip of the beaker.
an 8% solution of PVA rather than the 4% one. They claim
The upper stream will recoil upward and back to the beaker.
that a less sticky and more viscous the gel is obtained by com-
bining the 8% PVA solution and the 4% borax solution in Test 4
volume ratios of 1:1 or 1:2. We tried this alternative but the 1. Stuff a quantity of PVA into the glass tube furnished.
results were unsatisfactory; the gel thus prepared is a rigid mate- Push the mass through the tube until it emerges at the
rial whose behavior is far from the typical viscoelastic one. other end. It will expand.
More recently McLaughlin et al. (11) investigated the in- 2. Suddenly release the pressure. The mass will recoil and
fluence of borate concentration on the degree of cross-linking regain the initial position.
of PVA by titrating with sulfuric acid a series of gels prepared Test 5
by standard procedures. They concluded that the titration of Suck the PVA mass into a syringe by first dipping the
the slimes (mixtures of a 4% PVA solution and a 4% borax syringe into the fluid surface and then lifting it about 20–40
solution in volume ratios of 20:1, 10:1, 20:3, and 5:1) corre- cm above the fluid surface as the plunger is slowly pulled
sponds essentially to the neutralization of the basic solution back. A stable thread will be formed.
produced by the dissolution of borax. Through protonation
the borate species available for keeping the PVA chains to- Test 6
gether become disabled and the gel structure is destroyed (see 1. Transfer the PVA mass to a 500-mL beaker. Attach a
eq 6). Addition of excess sodium hydroxide to the neutral- glass rod to the mechanical stirrer. Stir the PVA mass
using care to keep the turning rod at the same point
ized free-flowing solution allows reconstitution of the gel.
and not too deep. Rotate it at close to 1000 rpm. The
Mechanical Properties of PVA (2, 5, 6, 8) mass will climb up the stirrer.
2. Stop stirring. The direction of swirling will be reversed.
Test 1
1. Suspend the PVA mass from your hand. It will stretch. Production and Plastification of PVA Fibers
2. Place the PVA mass on a flat, unbounded surface (for The extrusion of polymer solutions into a coagulating
instance a table top) and leave it at rest for a few min- medium is feasible with many systems. Because PVA is in-
utes. It will flow very slowly and form a film. soluble in acetone, it is possible to remove PVA fibers from
3. Stick the PVA mass on a glass window. It will slowly this solvent. Through slight moistening, the dry fibers be-
slide down the glass like a highly viscous fluid. come more flexible. The plasticizing effect of water, which
4. Place the PVA mass in a beaker. It will assume the shape results from the presence of numerous highly hydrophilic –
of the container. OH groups along the main chains of PVA, is accompanied
5. Place the PVA mass on a table top and squeeze it gently. by a decrease of the glass transition temperature of the poly-
It will flatten. mer, the temperature that marks the frontier between glasslike
6. Roll the PVA mass into a ball and drop it on the floor. properties and rubbery or flexible behavior.
It will bounce like a rubber ball, with a fairly high elas- For the extrusion process (16 ), fill the syringe with the
tic recovery. 4% solution of PVA. Slowly extrude the PVA solution into a
7. Slowly pull the PVA mass apart. It will stretch, form- Petri dish containing acetone. Wait a few seconds and then
ing strands. carefully remove the fiber formed with a pair of tweezers.
Place the fiber in a 150-mL beaker containing acetone and
8. Place the PVA mass on a table top and hit it with your
hand. It will hardly be deformed, showing almost no elas- let it harden for several minutes. Remove the fiber from the
ticity. beaker and lay it on a paper towel to dry. Dip one fiber briefly
in tap water. Record any change in the flexibility of the fi-
9. Place the PVA mass on a table top and hit it with a
hammer. It will shatter. ber. It becomes elastic. NOTE: Fibers longer than 50 cm have
been obtained in this way. Rodriguez (16 ) used a 5% solu-
10. Sharply pull the PVA mass apart. It will break like a
tion of PVA to produce fibers, usually 10–20 cm long.
metal rod when stretched under tremendous strain.
An alternative process (17 ) is to pour the 4% PVA
Test 2 solution into a 150-mL beaker to a depth of about 2 cm.
Transfer the PVA mass to a 500-mL beaker. With the Add an equal depth of acetone, which will form a layer on
help of a support base and a clamp, keep the beaker about the top of the PVA solution. Using a pair of tweezers, pick
60 cm above the level of the table top and tilt it slightly to up the white interfacial layer formed and pull it slowly straight
allow the fluid to slowly fall. The hanging fluid will siphon upward out of the beaker. A fiber 50–70 cm long can be pulled
itself out of the beaker, up its lip and then over to its side. Collect out. Lay the fiber on the aluminium foil and let it dry. Pull

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 Chemistry Everyday for Everyone

more fibers out of the beaker until complete exhaustion of 3. The ink of ball-point pens is probably the best example
the PVA layer. Dip one fiber briefly in tap water. Record any of a property displayed by certain fluids. Identify these
change in the flexibility of the fiber. It becomes elastic. NOTE: fluids. What is required from the ink of ball-point
Producing long, thin fibers according to this method demands pens? The ink of ball-point pens belongs to the class of
shear-thinning fluids. Ink should flow freely when one
some skill and training, and certainly a lot of patience! Most
writes (i.e., when it is being sheared), but should not flow
times we only managed to pick the whole layer of PVA solu- when the pen is kept in one’s pocket, briefcase, or bag.
tion. HINT: Pick the interfacial layer in such a way that you
can start building a thread and then pull it upward as slowly 4. Remember when you happened to walk by the sea-
shore, across the stretch of sand still wet but where
as you can.
the grains can no longer float. You probably noticed
Procedure: White Glue that if you walked quickly your footsteps looked dry
and white immediately afterwards and only after some
Add 25 mL of tap water to 25 mL of white glue. Stir time did the sand look wet again. However, if you
the solution until complete dissolution. For gelation, slowly walked slowly, your foot was left in place longer and
add 16 mL of 4% borax solution to the white glue solution you did not observe that effect. Interpret the phenom-
with rapid and vigorous mixing. Remove the solid material, ena just described and classify the fluid. When one walks
discarding any excess liquid. quickly, the sand under the feet is sheared because of one’s
Remarks: weight. The grains, initially closely packed, will occupy
more volume, the sand will expand, and the water level
1. Both the concentration of the aqueous solution of will decrease. Friction between the grains will be high and
white glue and the concentration of the borax solu- their lubrication low, and the grains will not slide. The
tion indicated here are different from the ones pro- surface will then look dry. Water will eventually climb
posed by Katz (18). The changes we have introduced, up and reach the surface, making the sand look wet. When
which allow the putty to display its viscoelastic behavior one walks slowly, the shearing rate is slow and the effect
in a much more apparent way, are probably connected just explained is lost, because water can move into the
with the nature of the white glues used by Katz (18) voids between the grains, lubricating them and keeping
and by us to produce the putty. In Portugal, as in the the friction low. The wet sand on the beach belongs to
United States, white glue is a poly(vinyl acetate)-based the class of dilatant fluids.
emulsion. The “Bouncing Putty” reported by the British
researchers Armitage et al. (19) is derived from di- 5. The mode of flow of some foodstuffs has certainly been
methylsilicone oil, [(CH3)2SiO]n. Katz’s putty has ex- of annoyance to you at some time during your life.
actly the same origin. You have surely needed to vigorously shake a bottle of
ketchup tomato sauce before being able to pour it over
2. Unlike PVA-derived slime, white-glue putty rapidly
your food. Imagine that you help yourself to ketchup
loses its properties when left standing in the open air.
sauce just after someone else. If you then keep the
The effect is particularly noticeable in summertime.
bottle at rest for a period of time and help yourself to
To avoid this inconvenience the putty should be kept
it once more, do you expect the fluid to display the
in a closed container after being handled.
same mechanical properties as before? Why? In what
3. We totally disagree with Katz’s classification (18), class of fluids do you include Ketchup? In general, when
which includes this putty in the class of “dilatant” or we pour ketchup from a bottle immediately after some-
shear-thickening fluids. According to Walker (2) it is one else, we find the fluid runny, because that person prob-
a viscoelastic material. The properties exhibited by the ably needed to shake the bottle vigorously in order to de-
putty confirm unambiguously its viscoelastic nature. crease the ketchup’s consistency. Yet, if we help ourselves
To investigate the mechanical properties of this mate- to it again some time later, it will have become consider-
rial, perform tests 1 to 6 with the white-glue-derived putty. ably more viscous. Ketchup is therefore a thixotropic fluid.
Its viscosity decreases if stirred or mixed, regaining the
Results and Discussion initial value after a measurable amount of time.
6. The feared quicksands are suspensions of sand in water
1. (a) Describe and interpret the tests you have performed whose hazards results from their non-Newtonian be-
on the PVA gel, designating the mechanical property havior. Suspensions of sand in water are quick when-
or properties responsible for the particular behaviors ever the water is under pressure because of a small in-
exhibited by this fluid. flux of water coming from below the surface, such as
(b) The glass transition temperature of PVA in the a natural spring. If the additional water pressure at any
dried state is approximately 85 °C. Do you expect this depth is equal to or slightly greater than the pressure
value to remain constant after slight moistening? Jus- of the sand at that depth, then a heavy object placed
tify your answer. R: No. When dried, the fiber is rigid. on the top will sink to the bottom. Once submerged,
With slight moistening, it becomes elastic because of the any attempts to free it through sudden movements will
plasticizing action of water, which lowers the glass tran- only increase the pressure of the sand about it, lead-
sition temperature. ing ultimately to its complete immobilization. If the
2. Chemically, the putty derived from white glue is a object is a human being, the experience may have very
poly(vinyl acetate)-based emulsion. Classify this fluid unpleasant consequences, often ending with the death
and explain its unique mechanical behavior. The white- of the person.
glue putty is a viscoelastic fluid whose properties are inti- (a) Explain the behavior of quicksands. Name the class
mately associated with the formation of hydrogen bonds of fluids they belong to. When quicksand is rapidly
between the borate ion and the oxygen atoms of the sheared, its viscosity increases because at the moment of
pendant acetate moieties of the polymer chains, in a way shearing the grains are almost in their closest packing. A
similar to that described for the PVA slime. sudden dilation of the suspension also occurs; and because

JChemEd.chem.wisc.edu • Vol. 75 No. 11 November 1998 • Journal of Chemical Education 1417

Chemistry Everyday for Everyone

the amount of water between the grains is not enough to Universidade de Trás-os-Montes e Alto Douro, for the pho-
lubricate them and allow them to slide, additional fric- tographic work, and to António José Monteiro, from Bostik-
tion between the grains is produced. Consequently they Cola e Vedantes, Lda., for useful information regarding the
will offer more resistance to shearing. If an object is com- white glue.
pletely submerged in quicksand, the pressure about the
object will be greater, making its motion even more diffi- Literature Cited
cult. Quicksands belong to the class of dilatant fluids.
(b) Propose ways to escape from quicksand, in case you 1. Collyer, A. A. Phys. Educ. 1973, 8, 333.
are ever caught in it. Struggling should be avoided by 2. Walker, J. J. Sci. Am. 1978, 8, 186.
all means. If the person is caught in quicksand up to the 3. Bird, R. B.; Stewart, W. E.; Lightfoot, E. N. Transport Phenom-
knees, the best thing to do is to lie backward, spread the ena; Wiley: New York, 1960.
arms along the surface and slowly try to free the legs, one 4. Collyer, A. A. Phys. Educ. 1974, 9, 38.
at a time. Movements should be as slow as possible at this 5. Collyer, A. A. Phys. Educ. 1973, 8, 111.
stage. Once both legs are free, the next step is crawling 6. Collyer, A. A. Phys. Educ. 1974, 9, 313.
backwards to shore. The arms and feet should now hit 7. Nickerson, R. F. J. Appl. Polym. Sci. 1971, 15, 111.
the surface with sudden movements because the shear 8. Cassassa, E. Z.; Sarquis, A. M.; Van Dyke, C. H. J. Chem. Educ.
thickening effect will produce a more resistant quicksand, 1986, 63, 57G.
which will help the person to reach shore. 9. Sinton, S. W. Macromolecules 1987, 20, 2430.
7. In spite of their considerable viscosity, it is relatively 10. Koike, A.; Nemoto, N.; Inoue T.; Osaki, K. Macromolecules 1995,
easy to spread margarine or mustard on a slice of bread. 28, 2339.
In which class of fluids do margarine and mustard lie? 11. McLaughlin, K. W.; Wyffels, N. K.; Jentz, A. B.; Keenan, M. V.
Why? Both household products are included in the class J. Chem. Educ. 1997, 74, 97.
of thixotropic fluids, but the thixotropic effect is more 12. Oertel, R. P. Inorg. Chem. 1972, 11, 544.
marked with margarine. These fluids have a fairly high 13. Pezron, E.; Ricard, A.; Lafuma, F.; Audebert, R. Macromolecules
viscosity, which is fortunately decreased when they are 1988, 21, 1121.
sheared with a knife across the slice of bread. If margarine 14. Sato, T.; Tsujii, Y.; Fukuda, T.; Miyamoto, T. Macromolecules 1992,
and mustard did not behave this way, they would be more 25, 3890.
difficult to spread. Once shearing is removed, the viscos- 15. Stroebel, G. G.; Whitesell, J. A.; Kriegel, R. M. J. Chem. Educ.
ity of both substances gradually regains the initial value. 1993, 70, 893.
16. Rodriguez, F. J. Chem. Educ. 1992, 69, 915.
Acknowledgments 17. Sherman, M. C. J. Chem. Educ. 1992, 69, 883.
18. Katz, D. Educ. Chem. 1993, 30 Infochem 4.
We wish to express our gratitude to Isabel Martins 19. Armitage, D. A.; Hughes, M. N.; Sinden, A. W. J. Chem. Educ.
Sequeira, from the Serviço de Audiovisuais of the 1973, 50, 434.

1418 Journal of Chemical Education • Vol. 75 No. 11 November 1998 • JChemEd.chem.wisc.edu