Rheology of Toothpaste

Prepared by:
Oral Car group, Research and Development Unit;
Eng. Ahmad Masdar & Eng. Mahdi Salehi

Toothpaste has three main functions:
- Removing stains on tooth through abrasion.
- Cleaning and refreshing oral cavity through flavors and detergents
- Acting as a carrier for releasing special therapeutic or cosmetic compounds
A tooth cleanser comprises of a simple mixture of tooth abrasives, flavoring material,
and surfactant (and special combinations if required). Principally, tooth powders are
all-out tooth cleaners, but despite this fact, most consumers prefer to use toothpaste
instead of tooth powder or other tooth cleaners. This caused the toothpaste changes
itself from a simple mixture of main necessary materials to very complicated products
having unique compounds and appearance, and improved the production and
distribution of toothpaste significantly. This research describes the scientific principle
and technology governing the toothpaste industry.
The cleaning function of toothpaste can be divided into two parts: removing tooth
plaques as a one function, and cleaning the stains on tooth as the other.
Plaque is a mass of bacteria forms on teeth and in case it is not removed or controlled
causes tooth diseases including tooth decay, periodontal diseases, and formation of a
great mass of calculus and tartar.
Tooth stain is however some thing different. When organic pellicle (secreted by the
saliva) forms on tooth after a few seconds to few minutes polishing, this pellicle reacts
with coloring agents (such as cigarette smoke, beverages, colored fruits, special
pigmented bacteria and ) and stains the teeth.
At the beginning of the formation of plaque (i.e. before calcification), it is soft and can
be effectively removed using tooth cleaning materials or by tooth brushing.
Removing spots and stains faces serious problems. Stained pellicle sticks firmly to the
teeth and resist against removing. Stained pellicle can be cost-effectively and
harmlessly removed by tooth brushing and rubbing materials used in toothpaste.

As mentioned above, classical toothpastes were simple products in terms of their
function and applications, and toothbrush was able to remove the plaque, and even a
dry rubbing powder (such as tooth powder) was an appropriate material to remove the
stained pellicle. As long as toothpaste was only a carrier of abrasives and a little
flavoring material, Rheology of toothpaste was not regarded as an exiting field of
study.
Since American Dental Association (ADA) accepted fluoride toothpaste as anticavity
toothpaste, the market of toothpaste expanded rapidly. The fast growth leads to
variation and improvement of various types of toothpaste. Significant researches have
been done on the color, flavoring material, rheology, and other properties of toothpaste
and its optimization.
In fact, the manufacturers of toothpaste discovered the benefits gained from more
attractive toothpastes having better flavors, appearance, packaging, and other
characteristics related to some extent to the rheology of toothpaste.
The main ingredients of toothpaste are liquid, polymerized material used for increasing
the viscosity and stability of rheology, abrasive system, flavoring agent, surfactants,
pharmaceutical agent such as fluoride, and other active materials.
Up to the late 1960s abrasive agents formed almost half of toothpaste's formulation,
and included calcium salt (such as dehydrated dicalcium phosphate or calcium
carbonate). In those days, the compound of fluoride and abrasive used in famous
brands of toothpastes was not chemically stable.
The abrasive interacted with fluoride and caused the resulted compound not to be
solved, and therefore the anti-cavity effect of toothpaste was reduced. This problem
was solved using sodium monoflourophosphate instead of sodium fluoride or tin
fluoride. Another solution is to use a more compatible abrasive with more effective
abrasion quality named amorphous hydrated silica having relatively low concentration.
This innovation is used often in the market of USA and brought loads of benefits.
These benefits include the capability of formulating the toothpastes, which have new
appearance (such as transparency), use broadly pharmaceutical materials (preventing
tooth decay and periodontal diseases), enhance and improve flavors, are refreshing,
more functional and cost effective. Hence, silica abrasive was used immediately by the

manufacturers of toothpaste and welcomed by the public and entered markets in two
forms of transparent and opaque toothpastes. Toothpastes are formulated using silica
abrasive and traditional abrasives according to the different methods. The toothpastes
containing silica consist of a high content of humectants and they are called toothpaste
type1. The rheology of toothpastes type 2 is based on a high content of abrasives,
while the rheology of toothpastes type 2 is principally based on the
humectant- polymer system and the content of the abrasives used in these types of
toothpastes are too low to be significant in terms of rheology.

The properties pertaining to the rheology of toothpaste
Sodium Carboxy methylcellulose (CMC), is the polymer in common use for
condensation of the toothpaste type 2. Movement towards using silica abrasives entails
to develop new polymer systems. The toothpastes using silica for condensation are not
so dependant on abrasives than the toothpaste type 2.
The key properties of toothpaste dependant on rheology are as follows:
- monotonous extrusion of the paste through pressing the tube
- non-extrusion or non-overflow of the paste without pressing the tube
- minimum energy for extruding the paste from tube
- the capability of being sheared after the paste is rubbed on the brush
- proper stand-up of the paste on the brush and non-penetration of the paste
into the hair of the brush
- fast dispersing of paste in the oral cavity after brushing the teeth
- fast release of flavors
- pleasant quality and appropriate volume of foam
- capability of being fast and completely washed after brushing the teeth, and
not to be slimy and gooey
- capability of being easily washed and spit the foam out of the mouth
into the sink
- Physical stability during the term of storage and distribution until
delivery to consumers

The toothpastes distributed in the markets during the last two or three decades ago
lacked one of the above-mentioned properties. After emergence of new ideas related to
the formulation of toothpastes, the tables were turned. Nowadays, the market is under
control of the brands using the ideas to optimize the rheological properties (as set
forth) required for the formulation of new toothpastes.
The required properties of a toothpaste behavior expressed by the rheological terms are
as follows:
- to be viscous
- to be pseudo-plastic
- while the shear rate is low, it shows a high yield stress
- to be thixotropic
- immediate restructuring after deformation
The aforesaid properties is dependent on the fully regular three-dimensional structure
of toothpaste to provide the functional properties and stability of toothpaste, and to
only on the viscosity increase, which can be achieved by using more abrasives in the
system containing only humectant.
The pseudo-plastic property has some advantages, which allow the toothpaste to retain
its high viscosity required for stability and other aspects, but after the paste is extruded
from the tube of toothpaste and during teeth brushing, the said viscosity reduces. It
leads to an easier extrusion of the paste from the tube and faster spread of the paste in
the oral cavity, and results in pleasant and light foam disperse and immediate release
of flavors.
Fast restructuring ability after deformation caused by extruding from the tube or other
forces is of high importance, because the toothpaste preserves its original rheological
status for the next push out, and causes the pushed out paste to resist against being
dispersed on the brush. At last, the stress relaxation rate after extrusion is to be so fast
that the shear stress lowers itself than the yield point (in case the toothpaste has yield
point), or shear stress, in which the flow is zero or lower. Figure 1 demonstrates the
possible situations. Graph "A" is preferred, while the graph "B" is not so.

Well-formulated toothpaste does not flow automatically, unless a certain amount of
stress is applied. In this case, this product tends to change itself to liquid state and
loose its solid state.


The toothpastes lacking this property tend to flow out when the tube is open (unless it
is very viscous), or is not placed on the brush in a static state. In the toothpaste type 1,
the extruded paste shows immediately rheological properties of a liquid, and its solid
structure (such as being in a static state) begins to weaken. The immediate
restructuring of the paste until it reshapes itself to a solid state strengthens the structure
of the paste and therefore creates the capability of staying in a static state. Principally,
in case the deformation from liquid state to solid behavior is faster, the system can
reach earlier to the relative steady state.
To have the aforementioned properties requires developing an appropriate three-
dimensional network, which is a key factor for selection of polymer-solvent systems of
the toothpastes type 1. The said three-dimensional networks in the toothpaste are
formed through polymeric chains connected to the larger or smaller chains existing in
the configuration of solid structure, depending on the type of polymer, concentration,
dryness degree of the solvent used, etc. The three-dimensional polymeric chain in the
toothpaste or any other similar products is defined primarily through the structure of
polymer, interaction of the polymer with its surrounding environment, various parts of
the polymer, range of the connections of the polymeric chain and other configurations.
One of the most important properties of the useful polymers is that their structure
fractures immediately after being sheared (e.g. compression) and recovers completely
right away after the shear process ends. (Fig. 1)

In fact, it is possible that some parts of the paste, which has been sheared, would be
recovered from the adjacent parts and conversely. It shows that how ideal toothpastes
behave.

Toothpaste different formulations
As said above, after introduction of silica xerogel, and silica abrasives the nature of the
formulation of toothpastes has been totally changed. While the previous toothpaste
(type 2) were full of abrasives (40-50%) and had a relatively low content of
humectants, the toothpaste containing silica (type 1) have a low content of abrasives
(10-15%) and a high content of humectants. Moreover, the toothpaste containing silica
can be supplied in the form of transparent and opaque, based upon the similarity of the
refractive index and humectants, and the other factors. The opaque toothpaste
containing a high content of abrasives are called usually "paste" and the semi-
transparent or full transparent products called "gel". In the table 1 and 2, some
examples of the gel or pasty toothpaste have been gathered.
As the toothpastes containing silica xerogel have all the positive rheological properties
above-mentioned, they satisfy the consumers. In the experiments done by the
consumers without their knowledge, the gel toothpastes were evaluated twice as much
better than the traditional toothpastes, and this was a criterion confirming the obvious
difference between the properties of the both products. Some years later, the products
containing silica abrasive possessed ultimately three forth of the toothpaste market.
One of the most important rheological improvements of toothpaste was achieved by
using the silica abrasives to control the rheological properties of toothpaste, after the
advantages of fine sedimentary silica was observed. The last one of these silica
abrasives was aerogel and fine sedimentary silica to the content of 5 to 15 percent,
quantified according to the regulated amount of the abrasives and fine silica. The low
content of the pyrogenic silica was used sometimes to modify the rheology of the
toothpaste type 2, but its effects on rheological properties were resulted from the
satisfaction of the consumers from the paste.



Regulating the rheological properties of a toothpaste
A- definition of the most important rheological criteria
The most important rheological criteria related to toothpaste are viscosity, pseudo-
plasticity, thixotropy, and yield point. As the system of toothpaste is very complicated
therefore, the criteria selected for toothpaste shall be defined exactly. Among all the
states that can be covered by the term rheology (gas, liquid, and solid), it is very hard
to explain the properties of some kinds of liquids and soft solids. Diluted liquids can
be considered as Newtonian fluid, which are easy to define. Concentrated and soft
solids such as toothpaste are Non-Newtonian fluid. They show the properties of
viscosity and elasticity, can be decomposed only through advanced and complicated
methods, and are not rheologically ideal. Toothpaste belongs to the class of viscous
and gooey materials.
The meaningful description of toothpaste behavior requires gathering a significant
amount of date. For example, simple measurement of viscosity of one point will give
us a number, which can be deemed never a complete and useful description of the
rheology of toothpaste. Toothpaste should be examined from an appropriate
rheological perspective, so that the relation among its rheology and its production and
its usage can be well understood. The behavior of fluid used in toothpaste covers both
time-dependent and time-independent properties. The fluid behaviors are four
parameters of viscosity, pseudo-plasticity, thixotropy, and yield point, which define
practically the rheology of toothpaste.
Viscosity is the ratio of shear stress to the shear rate, which is defined using poises
unit, and can determine the concentration, heaviness or resistance against free flow.
These terms are qualitative and abstract, which can be useful but they are not definite
enough for the process of formulation. High viscosity is not the only factor, which can
guarantee that the paste does not overflow and extrude when the tube is open or the
paste does not penetrate into the hairs of the brush. In contrary, if the viscosity is high,
it will be very hard to push out and extrude the paste from the tube, the paste will tend
to be filiform and nematic instead of being sheared, and therefore it will disperses too
slowly in the mouth, and a sticky and thick foam form and saliva forms in the oral
cavity, which makes washing the mouth from foam and saliva hard. This properties

maybe does not influence the function of toothpaste, but it prepares an unpleasant
situation for tooth brushing, especially for some age groups such as old people, the
disabled, and children.
Pseudo-plasticity is a phenomenon independent of time. Pseudo-plastic flow is
somehow related to the hybrid flow, since it simulate in middle up to high shear rates
pseudo-plastic flow and in low shear rates Newtonian flow. Pseudo-plastic liquids
have the properties of Non-Newtonian flow. As you see in the graph B in the figure 2,
they are Non-Newtonian and immediately after being cut off, recover their viscosity.
Viscosity changes when the shear stress applies in a certain period. Pseudo-plastic
flow is the property of some of the emulsions. For example, emulsion dyes are fully
pseudo-plastic. Their structure is broken to be easily dispersed at the time of being cut
by the painting brush, but the painted layer becomes immediately viscous so that the
dye does not drop and flow on the wall.
Pseudo-plasticity is one of the most important properties of toothpaste. When shear
rate is low, the viscosity of toothpaste is to be so high to avoid overflow of the paste
from the tube or penetration into the hairs of the brush. When shear rate is high, for
example during teeth brushing, viscosity shall be low so that the paste can be dispersed
in the oral cavity.


Thixotropy is a phenomenon dependent on the time. The viscosity of thixotropic
systems is decreased because of shear, but this does not occur instantly. When the
sheared system is left by itself, the apparent viscosity will change. Some times, the
system can increase in the gellylike strength. Figure 3 shows the thixotropic behavior
of toothpaste.

Restructuring during relaxation time can help keeping the abrasive solids in a
suspension. The advantages of thixotropic behavior are not similar to pseudo-plastic
behavior in some cases. It has been empirically observed that it is hard to find a
difference between a pseudo-plastic liquid (which viscosity reduced by increase in
shearing) and a thixotropic substance (which stress reduces by the constant shear
during the passage of time).
The thixotropy of a system such as toothpaste can be depicted by a rheogram. When
the shear rate curve (vertical axis) is depicted against shear stress (longitudinal axis),
the thixotropic system of a hysteresis loop like what is shown in the figure 3 will be
formed. The measures of the closed areas of the loop will show us the degree of the
thixotropy of the system.



The more gradient the ascendant branch of the hysteresis loop is, the more sensitive is
the liquid structure against shear. Generally, the reduction of water in the system of
solvent causes the thixotropy to be increased, it means that the areas of the loop
expands, which leads to the increase in the time required for restructuring. Thixotropic
behavior indicates that the three-dimensional structure of polymer has been formed.
Yield point is a stress, which begins before flow applies. We can consider the yield
point as the stress required by a system having the solid rheology to behave like a
system having liquid rheology. Yield point can be whether a property of a thixotropic
system or not. The high yield point (but not too high) is a good solution for suspension

of the materials used in toothpaste such as abrasives. Some of the gums and resins
used in the solvent system of toothpaste demonstrate high gelation strength, which is
appropriate for the suspension of the abrasive particles, which are principally
motionless. Applying more stress than the yield point (e.g. by pressing) causes the
system demonstrates some rheological properties of a liquid (e.g. streaming). The
systems with high yield point are especially appropriate for the formulation of
toothpaste. The fluids demonstrating the thixotropic behavior with high yield point are
particularly suitable. Up to now, we described the most important rheological
properties of toothpaste; from now on, we are able to show how to use these properties
to manufacture a privileged product. Ideally, the key primary materials shall be
selected, analyzed, and after that mixed. Unfortunately, this is not easily possible in
case the rheological relations of the materials shall be considered. The interaction of
the materials is so complicated that it cannot be supposed that the presupposed
rheological behavior of a substance in a separate aqueous system will be reoccurring in
the end products without any change. One of the proper solutions is that to test the
certain phases of toothpaste, and then develop the structure of toothpaste phase by
phase.
B- Comparing Toothpaste Type 1 vs. Type 2
The composition of the toothpaste type 1 and 2 are different. (Table 1 & 2). The
rheological properties of the both systems have been developed using different
mechanisms. Adding abrasives to liquid part of the toothpaste type 2 changes tangibly
some rheological properties including viscosity. Adding abrasives to the toothpaste
type 1 (which consists only not more than 15 percent of the toothpaste) does not
influence largely the rheology of toothpaste. According to Iler, this is not well
understood in some cases that the dispersion of the significant portions of the separate
particles and completely diffused in a liquid does not increase significantly the
viscosity and thixotropy . This phenomenon is occurred only when the particles
form a colloidal network in the liquid; in such case, the concentrations effects can be
observed. The quantity and the type of the abrasive used in the toothpaste type 1 are
not sufficient to form a strong three-dimensional structure based on polymer.


C- toothpaste structure
The preferred structure of toothpaste shows a balance between rheological properties.
We cannot rely on only one separate and independent rheological property of
toothpaste to evaluate its structure. For example, a stable product can be formulated
easily by increase in its viscosity. Such a product can be regarded from any aspect
toothpaste, but the discriminating consumers and formulators do not believe that.
Stability may be based on high yield point, but this is not applicable when the liquid is
below yield point and is felt exceedingly diluted and watery in the mouth. Therefore,
balance among the rheological properties is the key point for preparing the reliable
structure of toothpaste. The liquid past of toothpaste can be considered as the base of
the structure of toothpaste. The first substance, which has a direct role in the rheology
of toothpaste, is humectant system usually containing glycerin, sorbitol (separately or
jointly) as well as water. Propylene glycol and polyethylene glycol are used too. The
ratio of these materials is regulated based on the functional, apparent, microbiological
and economic parameters. The content of the glycerin and sorbitol to the water shall be
so regulated that the toothpaste has less capacity to be contaminated by germs.
Glycerin and sorbitol have both Newtonian behavior, and while they increase the
viscosity of toothpaste, but do not influence the rheological properties. Polyethylene
glycols can change the viscosity based on molecular weight, the amount and
interaction with the other ingredients. The content of water (or the degree of leanness)
has a critical role in the rheology. For example, the reduction of water ratio to the
polymer in carboxymethyl cellulose leads to the inclination to reduce thixotropy.
By selecting a humectant system, the rheological properties of this system can be
regulated broadly through a proper selection of the gums, resins, thickeners,
concentrators. These materials are polymers able to form three-dimensional structures
only in the solvent systems. It is necessary to have knowledge on the behavior of
polymers in the aqueous systems, and do empirical experiments to judge and evaluate
polymers. Providentially, the rheology of the aqueous solutions of polymers gives us a
good forecast of the system.
The third effective factor in the structure of toothpaste is the abrasive. Abrasive is a
unique ingredient used in the toothpastes type 2. The size of the particles, the

appearance and the content of the abrasive are effective in the rheological behavior of
toothpaste. The way the particles are dispersed, is an important factor in their
capability to resist against releasing from suspension during the time of storage.
Polymeric network has an important role in suspension of abrasive particles.
The behavior of dispersed particles can be precisely observed in a Newtonian fluid. As
the behavior of the particles in a pseudo-plastic fluid is very complicated, and even
when the fluid has a yield point, it is too hard to understand it theoretically.
The properties of silica in the toothpaste type 1 and type 2 are different from various
points of view. The limited solubility of silica in water can be effective in the structure
of polymer. The presence of alkali metals in silica can influence the behavior of silica
and its interaction with the other ingredients in the process of thermal behavior. The
Change in the process of high temperature reflects probably the change in the behavior
of polymer. This part of toothpaste technology, especially having only solvent,
requires to understand the principles of abrasive law in the rheology of silica
toothpaste.
The type and amount of surfactant may influence significantly the structure of
rheology, or as it reoccurs alternatively, it may reduce the viscosity. Polyethylene
glycols may create strong viscosity in some systems, such as those, which contain the
thickening hydrated amorphous silica (due to the hydrogen bonds between the silica
surface and PEG).
Shear is effective in the rheology of some formulas during the process of agitating.
Obviously, there are some factors such as humectants, abrasives, and chemistry of
polymers, which are to be rheologically controlled, so that the predictable and
reoccurring rheological properties can be achieved.
Detergents such as SLS do not influence viscosity, or may reduce it (especially in the
toothpaste type 1). It is hard to predicate the effects of detergents. This will vary by the
change in the manufacturing method, type of formulation, type and concentration of
polymer, shear rate during agitation process and the other related factors. Probably, the
main effect of detergent is to wet polymer and influence the solubility of polymer. The
rheology of toothpaste type 1 is dependent on the compound of humectants. The
polymer behavior, which is especially useful in the rheology of the toothpaste type 1,

depends completely on the degree of leanness of the solvent. Briefly, the formulation
of toothpaste having good rheology depends on the optimization of viscosity, pseudo-
plasticity, thixotropy, and yield point. The said factors are changed based on the
primary materials used in toothpaste, and external forces including shear during
manufacture, and temperature. Rheology is involved with the property of polymers in
the only-solvent systems, the multiple forces interacting simultaneously, and the
formation and fracturing of the polymeric structure during manufacture, filling
process, and use.
D- Toothpaste polymers
Abrasives play an important role in the toothpaste type 2. This importance is
undermined in the toothpaste type 1 and instead the role of polymer is underpinned.
Such polymers are preferred for the toothpaste type 1 that can form a strong structure
in the only- solvent system, and create a high pseudo-plasticity, thixotropy, and yield
point. In addition, it is important for a polymer to stabilize the phase of water and does
not allow water be divided into 2 phase. Therefore, the number of useful polymers is
restricted. Moreover, it is necessary to use the mixture of polymers to optimize their
effects. Nowadays, all kinds of the toothpaste type 1 are manufactured by using a
mixture of appropriate polymers. Some of the toothpaste type 2 uses only one
polymer.
Interaction between polymer and solvent, or the strong effect of the solvent on the
structure of polymer is not very odd. For example, it has been reported that the use of
polyethylene glycol in the solvent of a special toothpaste type 1 is required to form the
structure, when carboxymethyl cellulose is used, but in case of using special hydroxy
ethyl cellulose, there will be no need to use PEG. Physical chemistry of toothpaste
type 1 is relatively a new subject and there are too many things, which can be studied.
After emergence of the toothpaste type 1, five polymers have attained importance:
sodium carboxymethyl cellulose, hydrated silica, gum xanthenes, carbopol, and
carrageenan. These days, all kinds of the toothpaste type 1 contain hydrated silica. The
kinds of silica used in the toothpastes change from Xerogel to pyrogenic silica.
Xerogel are similar to the classic teeth abrasives in terms of size, inertness, and lack of
the ability to form a three-dimensional network in the only-solvent systems.

Pyrogenic silicas are very important in forming the network. Aerogel silica and other
sedimentary silicas in small size, large area, and middle absorption capacity are
located between aerogel silica and fine pyrogenic silica, and can easily form three-
dimensional lattices with glycerin aqueous solutions, sorbitol, and other ingredients
such as PEGs.
Fine silicas are the only mineral product used broadly in the structure of toothpaste.
Magnesium and aluminum silicas and so are able to form the structure in the only-
solvent systems, but they are used in a limited manner. An excellent paper on the
chemistry of silica has been prepared by Pader. The chemistry of organic polymers
useful in toothpastes is discussed by Pader and Davidson. Fine silicas are available in
the form of aerogel, sedimentary, pyrogenic, and fumed. Their behavior has been
described just in the only-solvent systems. The low content of the particles and their
high porosity can increase the viscosity in the only-solvent systems, and create gels,
creams, and pastes, which can be easily extruded from the tube. Figure 4 shows the
relation of the concentration of a aerogel silica to the viscosity of the sorbitol solution
(since the refractive index of silica powders, glycerin, and sorbitol are close to each
other 1.46, the products are transparent). Depending on the properties of the silica
particles, solvent system, presence or absence of the other polymers, the particles can
form three-dimensional lattices having different strength, and high thixotropy. The
toothpastes type 1 formulated by using the appropriate silica powders have high
pseudo-plasticity, and yield point. The toothpastes type 1 need a high content of silica
(approx. 5 to 15 percent) to form a network-like structure. Vice versa, a relatively low
amount of fine silica powder (pyrogenic of fumed) is needed to modify the toothpaste
type 2.
Carbomers (such as Carbomer 934) are excellent for formation of three-dimensional
structures in the toothpaste type1. These polymers form strong and transparent gels
when using with the only-solvent systems in a very low concentrations (less than 1
percent) and almost neutral pH. These polymers form structures, which have a
relatively high yield point. These structures can effectively suspend the abrasive
particles.




The toothpaste formulated by using an appropriate carbomer and other rheological
modifiers show an excellent stability, easy flow after stress, and immediate
restructuring upon stress cut-off. These can be observed through uniform and
monotonic ribbon, complete cut-off after extrusion (not to be filiform), good stand on
the brush, and immediate dispersion in the mouth. The speed of restructuring can be so
fast that the fracturing and restructuring happens simultaneously. Stress relaxation is
so fast that a stress below yield point happens almost non-simultaneously.
Carrageenan is available in the form of Iota, Kappa, and Lambda. They have different
physicochemical properties, which have been described by Pader. They can tolerate
the solvent soluble in water and therefore are useful as concentrator in toothpaste.
Lambda type of carrageenan is not gel, while Kappa and Iota types are gel (such as
carrageenan gel
2+,
Iota Ca)
Kappa type is mixed with the gum of locust bean, and this is economically cost-
effective for the formulation of toothpaste. Carrageenans can control effectively the
rheological properties. They can provide range of fluid properties from Newtonian
(with carrageenan having low molecular weight) to different level of pseudo-plasticity,
and thixotropy (with Iota calcium carrageenan). Xanthene gum can be useful a
stabilizer of the suspension of toothpaste, since it has yield point and its viscosity is
almost independent from temperature and pH. Xanthene gum is chemically neutral and
does not react with the ingredients of toothpaste. The solution of xanthene gum is
highly pseudo-plastic and its viscosity is instantly reduced proportional to the shear

stress. This behavior is attributed to the spiral structure of xanthene. One of the
advantages of xanthene gum in comparison to the others is that it creates a more
limited apparent viscosity under the high stress circumstances like pumping.

The other gums and resins (with or without yield point) can be used in the formulation
of toothpaste to achieve some special properties such as stability of foam, or pleasant
feeling in the oral cavity. Hence, hydroxy ethyl cellulose, gum of locust bean and other
gums and resins has been introduced for the effects more than formation of a stable
structure of abrasive particles in an only-solvent system. It is preferred to use two or
more polymers. The mixture of polymers is in general necessary to remove the
existing differences with the various humectants, therapeutic factors (such as high
concentration of potassium nitrate or sodium bicarbonate) or for the price.
E- Toothpaste production
The rheological properties of toothpaste play a key role in selection of its
manufacturing process. The other factors involving in the selection of the process are
as follows: the quantity of production, labor charges, process control, accessible
promises, ancillary facilities, and local or national standards for HSE. Anyhow, the
main process depends largely on the theology of toothpaste and its ingredients (such as
resins and gums). Toothpaste can be produced in the ambient temperature or more or a
mixture of both, through fast or slow shearing agitation.
Manufacture of toothpaste can be divided into 5 parts:
- preparation of liquid mixture
- Compounding the said mixture with abrasive powders
- Adding surfactants and sensitive materials
- Storage
- Filling
The air content can be controlled through agitation under vacuum state or by
de-aeration in the production line. Using the resins and gums, which create yield point
are useful because pumping will be easier and filling will be cleaner (pumping
pressure shall be more than yield point). In such case, the product will create a hard
structure after stress relaxation, and therefore the abrasive will be motionless in the

suspension, and can be saved for a long time. Restructuring upon stress relaxation
during filling process has two advantages:
- The paste can be easily cut off, and it does not tend to be filiform when
flowing out of the nozzles, makes no trouble for punching.
- The paste can keep its uniformity and homogeneity in the tube.
The rheological properties of toothpaste can be influenced by the conditions of
manufacture, which are as follows: permanent fracture of polymer because of
additional shear; a factor that can influence the behavior of polymer in molecular
level; degradation of polymer by the temperature applied in the mixers; storage tanks
or tubes, and irrevocable degradation of the three-dimensional structure of polymers.
Principally, toothpastes are manufactured through cold or warm process.
The advantages of warm process are as follows:
- Better microbial control;
- Easier stirring;
- Easier pumping and filling of the paste because of decrease in viscosity;
The advantages of cold process are as follows:
- spending lower costs for energy
- avoiding adverse effects occurred during high temperature
The disadvantages of warm process are as follows:
- possibility of reduction or decomposition of flavors
- interaction of ingredients and permanent or temporary change in rheology
In both processes, the stability of polymer existing in the end product may be at risk.
This is because of high dependency of the system on polymers. Fortunately, these
effects can be predicted from the behavior of the polymer in the model of the only-
solvent systems. These models have shown that the differences of the behaviors of the
polymers used in toothpaste can be useful.
Sodium carboxymethyl cellulose has been studies in both warm and cold processes in
the only-solvent systems. Sodium carboxymethyl cellulose is available in various
varieties. Most of the CMC solutions are pseudo-plastic, but some of them are not so,
as some of the CMC solutions are thixotropic and some of them are not. Thixotropy is
a function of substitution degree as well as substitution uniformity. It has been argued

that CMC passes some phases before being dispersed in an only-solvent system. In a
cold process (approx. 25 C), the apparent viscosity increases in an only-solvent
system until it becomes swollen, after that when the polymer is relaxed from
aggregation and restate itself to solution, the viscosity will reduces to a balanced
degree.
In the warm process (approx. 50 80 C), the apparent viscosity of polymer is reduced
in an only-solvent system by increase in the temperature, and after passages of time
the viscosity is decreased. The range of these effects depends on the ratio of water in
the only-solvent system, presence of salts, concentration, composition of the polymeric
compounds and the time.
Therefore, the viscosity of CMC solutions (and the mixtures of CMC with other
polymers) depends not only on the beginning of the shear, but also on the time after
shear occurs. However, this can be problematic for quality control during production
process. CMC can show the problems occur because of insufficient time of stirring or
shearing. The speed differences of polymer hydration, various behaviors in different
intermediates, etc. shall be harmonized during the manufacturing process.
Hydration of some polymers is very harder than that of the others. There is
competition among the ingredients used in the mixture of toothpaste to access to the
existing water. The time spent for production of toothpaste shall be used
conservatively. It means that the system should have time enough to reach the ultimate
equilibrium state. This ensures the reproducibility of the product. Carbopols are the
polymers of acrylic acid, which are cross-linked with a polyalkenyl polyether. These
are spiral molecules, which are supplied with pH 3 to the markets. They create the
highest viscosity during neutralization with alkali. The proper method for obtaining a
solution in an only-solvent system is to disperse dry resin in a polar solvent (such as
polyol) and then to disperse this mixture in water and neutralize it until pH reaches 5
to 10. Polymer is sensitive to the monovalent, divalent, and trivalent cations. The
degree of sensitivity changes by the type of resin and the concentration of salt. The
viscosity of the most carbopol solutions is a little sensitive to heat increase, but some
of them causes the viscosity reduces irreversibly.

Block has described some of the rheological properties of toothpaste considered by
consumers as follows:
Required pressure for preliminary extrusion: For this purpose, a Tension-meter
instrument is used. By using this instrument, the required energy for extruding the
paste from the tube can be measured in different shear rates. Among the 8 systems
tested by this instrument, one of them showed reduction of preliminary energy
required for extruding the paste, together with increase in rate. The toothpaste
manufactured by using xanthene gum or without CMC needed relatively less energy
for extrusion of paste from the tube of toothpaste. The differences were observable
when the temperature or the diameter of the orifice of the tube was changed. Although
the results of the tests were very different, this method was useful to demonstrate the
differences in the formulations of toothpaste.
By measuring the tensile strength by an extrusion rheometer, it was observed that there
is a reverse relation between extrusion capability and tensile strength. In most of the
tested pasts tensile strength increased when storage time enlarged. The other method
introduced by Block was based on assessment of the adhesion-cohesion properties of
paste. The sample was placed between to discs and the vertical force required for
pulling the discs from each other was measured. Subsidence or SAG is another
parameter that can be understood by consumers. Its measuring tool has been developed
in some of the industries interested in rheological principles.
Such methods so far explained are not precise methods, and one reason is related to the
differences of empirical methods and the other is related to the expired date of
toothpaste or temperature, etc, and the data offered by these methods depends on the
understanding of the most important rheological properties of toothpaste, which can
restrict the acceptability of the products for the purpose of control on behalf of the
consumer.

F- Toothpaste Stability
The responsibility of the ingredients regarding the rheological properties of toothpaste
includes stability too. In this case, the stability of toothpaste is influenced by two main
factors:

- The ability of polymer system to preserve the abrasive in the suspension
- The ability of polymer system to prevent from synersis in an only-solvent
system
The type of toothpastes (with high of low content of abrasives) is one factor to ensure
stability. The toothpaste containing low content of abrasives based on hydrated silica
is fully stable because their three-dimensional structure does not change. However,
they are unable to stabilize the liquid and the separation of liquid is observable, unless
they are completed with a hydrophilic polymer. Sodium carboxymethyl cellulose,
which is not only enough to form the structure, can stabilize the toothpastes containing
silica very well. Some complementary polymers are useful to for achieving the
advantages of yield point and thixotropy and reaching an excellent rheological
formulation. However, these polymers are not required for formation of the toothpaste
type 2, which structure needs mostly a high content of abrasives. The toothpaste type 2
containing a high amount of abrasives can be stabilized and keep its stability during
storage period by using polymers, which are not significant in creating yield point or
pseudo-plasticity.
Well-formulated toothpaste shall preserve the uniformity of the structure of toothpaste
for more than 3 years under normal conditions of storage, and for more than one
month under the temperature of 45 to 50 C (flavors and other properties will be lost).
Some of the polymers used in toothpaste have been gradually lost their usage in
commercial level, and only the polymers, which can keep their rheological properties
together with detergent used in toothpaste, are common.

Reference
Rheological Properties of Cosmetics and Toiletries, Dennis Laba, 1993