The Forgotten – An Assessment of the Impact and Value of Non-Ionic Functional Groups in

Polymers for Deposit Control

Michael L. Standish
Chelsea L. Standish
Radical Polymers
AWT Annual Convention
September 13-16, 2017
Grand Rapids, Michigan

Abstract:

For over 40 years, additive chemists in the water treatment industry have incorporated non-ionic
functional groups to achieve targeted activity. Non-ionic monomers and functional groups can
impart distinct functionalities such as efficacy for organics and hydrocarbons, improved performance
for specific mineral scales and transition metal stabilization, activity for silica and silicate colloidal
dispersion, incorporation of wetting/surface tension reduction properties and enhancement of
crystal modification. Further, some would go as far to claim that non-ionic groups can act as
“spacers” that help direct and control polymer architecture. With these benefits to the incorporation
of non-ionic monomers there also can be drawbacks such as increased cost, decreased sequestration
capacity, and the potential for foam development at elevated concentrations.

The purpose of this paper is to provide an overview of the commonly available polymers containing
non-ionic functional groups, demonstrate both the positive and negative potential impacts upon field
performance, and provide guidance to the AWT membership as to when such materials should be
considered.

About the Authors:

Michael Standish is founder of Radical Polymers, LLC, a business designed to specifically develop
and provide technologies to the independent water treatment community. Mike has 30 years
experience in water treatment additive design, development and evaluation. Prior to forming Radical
Polymers, Mike served as Senior Business Manager for International Specialty Products and Global
Business Manager for National Starch's Alco Chemical business. Mike has served on the Board of
Directors of AWT and holds a BS in Chemistry and Masters in Business Administration from the
University of Tennessee at Chattanooga.

Chelsea Standish is the Technical Manager at Radical Polymers. She joined the company in 2016
after completing her Master of Science from the University of Tennessee at Knoxville. Chelsea began
working as a formulation chemist in the water treatment industry during her undergraduate studies
at the University of Tennessee at Chattanooga, where she obtained her BA in Chemistry and BS in
Biology. Chelsea has been heading the research of the role of surface tension in non-ionic function
groups at Radical Polymers for the past year.

© 2017 Radical Polymers, LLC – All Rights Reserved 1

A Polymer Primer in Three Paragraphs or Less

In previous papers the basics of polymers and their resulting functionality in controlling mineral
scale and deposition in process water applications have been described in significant depth. [1, 2, 3]
For the purposes of this paper and understanding the role of non-ionic functional groups in water
treatment applications, we need a working knowledge of polymers. A thirty-thousand-foot view if
you will. For this, we need to understand that polymers (Greek – poly “many”, mer “unit”) are
molecules where repeating units, called monomers, are combined. We can provide further details to
our understanding by thinking about the differences between homopolymers and copolymers.
Homopolymers utilize the same repeating units (monomers) and copolymers utilize two or more
different types of repeating units. Visually, we can picture this by thinking of a train where several
cars are connected to form a chain. This chain can either be of the same types of cars, say all
passenger cars, or one that has several types of units, such as passenger, bulk tank, flat bed, and box
cars. So, the idea of polymers is pretty simple in that we are combining chains of monomer
molecules either by utilizing one type of monomer to form a homopolymer or two or more types of
monomers to form a copolymer.

We next need to know that the delivered end-use functionality of the polymers are defined by many
variables. These include how the polymer is put together (polymerization technique), the length of
the polymer (molecular weight), and the types of monomers utilized (composition.) In the purest
sense, the polymerization technique is mainly of interest to the polymer chemist since it defines the
strategy of how to put the monomer(s) together to form a desired polymer. Polymerization
technique can have a profound impact on both cost and performance. Molecular weight of a polymer
can, and will, also have a dramatic impact on polymer performance. As a rule of thumb, most
polymers employed for mineral scale and deposit control have an average molecular weight (Mw) of
less than 10,000 Daltons. Further, we can add an additional rule of thumb that polymers with a M w of
about 3,000 or greater tend to be good solids dispersants and polymers with a M w of less than 3,000
tend to be better suited for increasing the solubility (threshold inhibitors) of common scale forming
minerals such as calcium carbonate.

Polymer composition is the remaining variable to consider. We know from previous papers that
while there are many types of compositions, each can be boiled down to polymers that contain
carboxylate (COO-), sulfonate (SO3 -), and/or non-ionic (various non-charged) functional groups. For
perspective, the overwhelming majority (estimated to be greater than 80-90%) of all monomer
utilized is carboxylate in type. This includes predominantly acrylic, methacrylic and maleic acid
monomers. These monomers provide base functionality for calcium carbonate scale, help build
molecular weight for solids control and dispersion (specifically acrylic or methacrylic acid), and
provide a relatively low cost source of functionality. Sulfonated monomers are the second most
widely utilized monomers in mineral scale and deposit control. The sulfonate functional group
primarily provides good stabilization properties for transition metals and calcium phosphate. Non-
ionic monomers are somewhat sparingly utilized. Well known non-ionic containing polymers are
utilized for enhanced phosphate and iron stabilization in both cooling and boiler applications.
However, the role of non-ionic monomers has largely been neglected by polymer chemists due to
limited incorporation capabilities in aqueous techniques, cost, and paradigms around functionality.
When thoughtfully and carefully incorporated, non-ionic monomers can enhance attributes of
carboxylate and sulfonate containing copolymers and expand efficacy for difficult to control scales or
deposits.

© 2017 Radical Polymers, LLC – All Rights Reserved 2

Put Me in Coach, I’m Ready to Play

Non-ionic monomers are woefully underutilized in scale and deposit control polymers. Less than
20% of all polymer offerings incorporate non-ionic functionality and, where utilized, non-ionic
monomers are typically incorporated into polymers at levels between 5-10% on a molar basis.
Given this, only about 1-2% (molar basis) of all polymer utilization for scale and deposit control
contain non-ionic functionality. There are a few exceptions where incorporation is greater than
10%. These polymers tend to have noticeably enhanced properties in a wide variety of areas such as
calcium carbonate crystal modification, enhanced performance for phosphate and transition metal
stabilization, expansion of functionality to include organic debris and deposits, on-line cleaning, silica
and magnesium silicate control, and surface tension reduction/wetting.

Benefits of Non-Ionic Monomer Incorporation:

▪ Improved Crystal Modification

▪ Increase Polymer Stability in Harsh Waters
▪ Enhance Phosphate Stabilization
▪ Excellent Transition Metal (Fe, Zn, Mn) Stabilization
▪ Expansion of Dispersion Functionality to Include Organics
▪ On-Line Cleaning
▪ Colloidal Silica Stabilization
▪ Magnesium Silicate Control
▪ Surface Tension Reduction and Surface Wetting

With so many added benefits, why are non-ionic monomers utilized so sparingly? Cost is certainly a
factor. Simple non-ionic monomers such as acrylamide are economical but have limited benefits.
More highly differentiated non-ionic monomers, which provide noticeable performance
enhancements, can cost 2X or more than carboxylates such as acrylic and maleic. However, cost
never holds a good polymer scientist back. More practically, the utilization of non-ionics can require
a very different polymerization strategy or technique that may not be available to the producer on a
commercial scale. Said differently, non-ionic monomers by nature have limited or no water
solubility. Given that most polymers utilized for mineral scale control are produced using aqueous
polymerization techniques, the use of non-ionic monomers can be very difficult or impractical.

When non-ionic monomers are incorporated in at appreciable amounts a primary benefit can be
surface tension reduction and wetting. In simple terms, wetting refers to the ability of a liquid to
maintain contact with a solid surface. We have all heard the terminology of “making water wetter”
in the context of surfactants (surface active agents). The idea here is that the additive is making the
water more surface active by helping it wet the surface more thoroughly. The same principle is
applied with certain non-ionic containing polymers where there are distinct advantages to improving
the wetting properties of water in a process application. Specifically, we can relate to the benefits of
additives wetting solid surfaces and particulates as a means of improving performance. For
dispersion of solids, it is critical that the additive can adsorb and interact with the solid surface.
Similarly, for on-line cleaning, wetting is required to help lift scale from a surface into the bulk water
such that it can be removed from the system. Wetting and surface tension reduction are also a
necessity for functionality in controlling hydrophobic materials such as hydrocarbons or organic
debris. The surfactant-like properties incorporated into high non-ionic monomer containing
polymers can produce extraordinary results when applied properly.

© 2017 Radical Polymers, LLC – All Rights Reserved 3

Understanding Surface Tension - Psychologist Not Needed

The phenomenon of surface tension can be observed in everyday life. The beading of morning dew
on a flower petal (Figure 1) and the formation of the meniscus in a graduated cylinder (Figure 2) are
two examples one might see on a regular basis out in nature or in the field as a water treater. Surface
tension is the result of the attraction of the molecules in a liquid. In the bulk of the liquid the
molecules are pulled evenly in all directions (cohesive forces), which results in a net force of zero.
The water molecules at the top of a glass of water do not have neighboring water molecules above
them, only air. Therefore, the water molecules on top are attracted to neighboring water molecules
to the right,left and bottom. This results in a stronger bond between the water molecules on top and
is what causes extra energy being required to move an object through the surface of water. These
forces can be between two liquids, or a liquid and a solid (interfacial tension); between a liquid and a
gas (surface tension), or between a solid and gas (surface free energy). [4]

Figure 1: Water droplets beading on the petals Figure 2: The formation of a meniscus in a glass
of a flower. graduated cylinder.

Surface tension can be strictly defined as “The attractive force exerted upon the surface molecules of
a liquid by the molecules beneath that tends to draw the surface molecules into the bulk of the liquid
and makes the liquid assume the shape having the least surface area”- Merriam-Webster.

Mathematically, it can be characterized as:

F
Eq. (1) σ=
L ∙ cos θ

where σ is surface tension, F equals force, L is the wetted length, and θ is the contact angle. Surface
tension is commonly reported in millinewtons per meter (mN/m) or dynes/cm.

Contact Angle and the Wettability of Solids

A lot of valuable information can be gathered from surface tension data. Specifically, the
determination of contact angle can provide insight into the behavior of a liquid as it interacts with a
particular solid. Contact angle is the angle between the surface of a liquid and a solid with which it is
in contact. Thus, we can use the contact angle as a measurement of the wettability of a solid by a
liquid. The term wettability means that a solid will form a common interface with a liquid that it
encounters. A contact angle, θ, of 0° would mean complete wetting. If a solid has a contact angle
between 0°-90° the solid is considered wettable by the liquid of interest. If θ is greater than 90° the
solid is not wettable by the liquid of interest (Figure 3).

© 2017 Radical Polymers, LLC – All Rights Reserved 4

 Figure 3: Visual of decreasing contact angle and
increased wetting.

When the contact angle of a solid in relation to a liquid is calculated, the surface free energy of that
solid can be determined. Surface free energy, simply put, is the surface tension of a solid and is
reported in the same units as surface tension of liquids, mN/m (σ). Surface free energy can be
further broken into dispersive and polar parts. Dispersive and polar parts can apply to both solids
and liquids when looking at surface free energy and surface tension, respectively. The polar parts of
the solid or liquid is related to the polar interactions of that substance. These forces are like those
between water molecules which are strong dipole-dipole interactions where the electron density of
the oxygen atom in the water molecule is much greater than that of the hydrogen atoms. These
interactions are a permanent, not temporary, dipole moment. The dispersive parts of a solid or
liquid are related to the dispersive interactions of that substance. Dispersive interactions are static,
temporary and weak. [5] These weak interactions are also known as London forces. The polar parts
plus the dispersive parts equal the total surface tension (liquid) or surface free energy (solid) as seen
in equation 2.

Eq. (2) 𝜎 = 𝜎𝑝𝑜𝑙𝑎𝑟 + 𝜎𝑑𝑖𝑠𝑝𝑒𝑟𝑠𝑖𝑣𝑒

Wait A Minute, I Thought We Were Discussing Non-Ionic Monomers!

Now that surface tension and contact angle have been defined in a general technical manner, we can
apply these thoughts to water treatment and non-ionic functional groups. Pure water has a reported
literature surface tension of 72.86 mN/m. This is the highest surface tension of any liquid except for
mercury, which is 486.5 mN/m at room temperature. It is important to note that the surface tension
of liquids decrease as temperature increases. Another important relationship is between the polar
nature of a liquid and surface tension. The greater the polar nature, the greater the surface tension of
the liquid. As stated in the previous paragraph, polar parts of a substance are the stronger and
permanent forces. This is where our non-ionic functional groups come in to play. Non-ionic moieties
can decrease the surface tension of the water they are dissolved in by creating a steric barrier. The
non-ionic functional groups exert a pressure on the surface of the water which in turn reduces the
surface tension. [6]

So, why do we care about these properties in the context of water treatment. As stated, non-ionic
groups can and will impact the tendency of a liquid to wet a solid surface and provide resulting
performance benefits. However, this is not just blind luck. It can be both designed and demonstrated
mathematically. As an example, we can take the most common water treatment scale, calcium
carbonate, and look at how surface free energy, polar and dispersive parts of the solid and of a New
Polymer can impact surface adsorption.

© 2017 Radical Polymers, LLC – All Rights Reserved 5

Calcium carbonate has a surface free energy of 33.10 mN/m which is made up of 22.9 mN/m
dispersive part and 10.20 mN/m polar part. [7] Water has a σ of 72.8 mN/m with a dispersive part
21.8 mN/m and a polar part of 51.0 mN/m. [8] Now imagine a New Polymer that has a surface
tension of 26.50 mN/M with dispersive parts equaling 25.2 mN/m and polar parts are 11.3 mN/m
(Figure 4).

Calcium Carbonate Calcium Carbonate

Water New Polymer

Calcium Carbonate Calcium Carbonate

Water New Polymer

Figure 4: Visual representation of solid liquid interaction between calcium carbonate (solid) and
water (liquid, left) and a New Polymer (liquid, right).

Eq. (3) σl > σ s

Eq. (4) σl ≈ σs

σl is the surface tension of the liquid and σs the surface free energy of the solid. In equation 3 where
the surface tension of the liquid is greater than the surface free energy of the solid, less wetting
occurs. In Equation 4 where the surface tension of the liquid is roughly equal to the surface free
energy of the solid, wetting is more likely to occur. As the contact angle decreases, the liquid is being
adsorbed on to the solid.

The contact angle (wettability) can be calculated using the following equation:

𝑚2 𝑐 ∙ 𝑝2 ∙ 𝜎 ∙ cos 𝜃
Eq. (5) =
𝑡 𝜂

where m is the mass, t is the time flow, c is the capillary constant of the solid being tested, p is the
density of the liquid of interest, σ is the surface tension of the liquid, θ is the contact angle, and ƞ is
the viscosity of the liquid.

In the example above, Figure 4, the solid and liquid on the right would have a smaller contact angle.
Therefore, the liquid containing the New Polymer would be able to wet out on to the solid more than
the untreated water illustration on the left. Furthermore, because the New Polymer in the example
above has similar dispersive and polar parts to that of the calcium carbonate, this increases its ability
to wet out on the surface of the calcium carbonate compared to that of the untreated water.

© 2017 Radical Polymers, LLC – All Rights Reserved 6

Methodology of Surface Tension Determination

There are many ways to determine surface tension: pendant drop method, ring tear-off method, the
rod method, and the (Wilhelmy) plate method. The last three methods can be performed using a
tensiometer, an instrument specifically used to determine surface tension. For our experiments a
Krüss K-100 force tensiometer was used. The Krüss K-100 force tensiometer can be used to
determine not only surface tension but interfacial tension, surface free energy, and contact angle. [4]

The Wilhelmy plate method was used for determining surface tension in our experiments. In this
method 100 mL of the liquid being tested is placed in clean glass vessel with a known volume of
121.5 mL. A roughened platinum plate probe is handled carefully with gloves, flamed until slightly
orange to remove any impurities on the surface, and placed on to a probe holder at the top of the
Krüss K-100. The glass vessel is raised until the reflection of the plate can be seen in the liquid in the
vessel (Figure 5). The Krüss Laboratory Desktop program is run, and the surface tension is
determined by measuring the tensile force that is acting against the plate as it comes in contact with
the liquid it is measuring. After the test is finished the probe is rinsed thoroughly with DI water,
isopropyl alcohol, DI water again, and flamed before being placed back into its casing.

Figure 5: Wilhelmy plate test configuration.

In this method force is used to determine the surface tension reduction of the polymers being tested.
Looking back at equation 1 and at figure 6 below, surface tension can be determined by force if L, the
wetted length (perimeter of the plate), is known as well as the contact angle of the liquid to the plate
being used. [5] In this test, a plate made of platinum is used, due to the fact that the contact angle of
any liquid to platinum is 0°. The cosine of 0° is 1; therefore, by measuring the wetted length of the
plate and knowing that the contact angle of the liquid to the plate will be 0°, the force exerted on the
liquid can be used to determine σ, contact angle. [4]

© 2017 Radical Polymers, LLC – All Rights Reserved 7

 F = Force, mN/m

L = Wetted length, mm

θ= Contact angle of liquid to plate

Figure 6: Surface tension determination factors used for calculations for the Wilhelmy plate method.

Methodology of Contact Angle Determination

The contact angle (wettability) of powder can be determined, using the Washburn method, by
utilizing the Krüss K-100. In this method, a powder of interested (e.g. mineral scale such as calcium
carbonate, organic pitch deposit samples from a paper mill, etc.) can be packed into a glass sample
holder. This holder is hollow, and contains a replaceable filter base at the bottom so that when it is
suspended over a liquid of interest (in this case a non-ionic surfactant at an appropriate dosage that
is in the glass vessel described above for the determination of surface tension), the liquid can be
slowly raised to the sample holder and the liquid sample can be pulled up into the sample holder via
capillary forces as illustrated Figure 7. To determine contact angle (wettability) of the liquid to the
powder equation 5 from above is used.

Powder
Replaceable
filter base

Figure 7: Washburn method test configuration.

© 2017 Radical Polymers, LLC – All Rights Reserved 8

The capillary constant for the solid being tested is first determined. The following equation is used:

2σ ∙ cos θ
Eq. (6) h=
ρgr

Where h is the height that the liquid rises within the sample holder, σ is the surface tension of the
liquid, θ is the contact angle, ρ is the density of the liquid, g is the acceleration due to gravity, and r is
the radius of the sample holder (capillary). By using an optimal liquid with a contact angle of 0° (cos
θ is equal to 1), as well as a known density and surface tension, the capillary constant can easily be
determined. Returning briefly to the theory on dispersive and polar parts and low surface tension in
relation to contact angle to achieve a contact angle of 0°, a liquid with no polar parts must be used.
For this experiment, hexane was used. With this information, the capillary constant can then be
determined and used for following tests to determine contact angle of the solid with liquids with
unknown contact angles. The information can then be used to determine the surface free energy of
the solid using different models provided in the Krüss Laboratory Desktop program. For the
Washburn method, there is a limiting contact angle for a liquid in the sample holder of 90°. If the
contact angle is greater than 90°, cos θ is negative and the liquid is unable to rise into the capillary.
Both the contact angle and the capillary constant of the powder being tested are the results of the
linear regression of mass2 vs. time. [4]

Methodology of Dispersive and Polar Parts Determination

Once the contact angle is determined with at least one liquid with a known surface tension, the
surface free energy of the solid regarding dispersive and polar parts can be determined in the Krüss
Laboratory Desktop program.

To determine the dispersive and polar parts of a liquid a few steps must be taken. First the surface
tension of the liquid of interest must be determined. This was done using the methodology described
above for surface tension determination. Once the surface tension is known, the contact angle of that
liquid to a solid can be determined. To determine contact angle and subsequently dispersive and
polar parts, a solid with no polar parts must be used. In this experiment polytetrafluoroethylne
(PTFE, Teflon) was used. It has a reported literature surface free energy of 20.70 mN/m, meaning it
has 20.70 mN/m of dispersive parts and 0.0 mN/m polar parts. [9] The contact angle of the liquid to
the solid can then be determined using a similar set up to that in Figure 5 where a small plate of PTFE
is suspended above the liquid of interested which is then slowly raised to the PFTE probe while the
force is measured. These values can then be used to determine the contact angle of the liquid to the
solid as well as the dispersive and polar parts of the liquid using the Krüss Laboratory Desktop
program. [5]

© 2017 Radical Polymers, LLC – All Rights Reserved 9

Data and Results

Surface Tension Reduction

In the following graph, a reduction in surface tension by polymers with increasing non-ionic can be
observed. With an increase in reduction of surface tension as the active concentration of the polymer
increasing. As stated before, water has the highest surface tension of any liquid at room temperature
(excluding mercury). In Graph 1, below, the polymer AA:SA, which does not contain any non-ionic,
has little reduction in surface tension even at increasing dosages, with only a reduction of 1.352
mN/m from water. The two polymers with the AA:SPME:SMS:MMA and AA:SA:t-BAM I compositions,
reduce surface tension by roughly 4.287 mN/m and 4.483 mN/m, respectively, below water with a
slight increase in reduction seen as concentration increases. The polymer with the AA:SA:t-BAM IV
composition reduces surface tension significantly more than the previous three polymers containing
non-ionic, as well, by 7.354 mN/m. A New Polymer described as AA:SA:NI contains the highest level
of non-ionic monomer in its class. This composition reduces surface tension the most significantly,
by 9.38 mN/m. This is expected due to the significant increase in non-ionic functional groups in the
composition of the polymer.

Graph 1: Surface Tension Reduction By Non-Ionic Functional Groups.

© 2017 Radical Polymers, LLC – All Rights Reserved 10

In Table 1 below the results of the sample polymers tested above were tested for the surface tension
of the neat product. The same trend as above is seen in the neat samples where an increase in non-
ionic monomer in the polymer results in a decrease in surface tension.

Table 1
Liquid Surface Tension (Neat Sample)
Water 72.80 mN/m
AA:SA 69.63 mN/m
AA:SA:t-BAM I 49.22 mN/m
AA:SPME:SMS:MMA 46.19 mN/m
AA: SA: t-BAM IV 44.17 mN/m
New Polymer: AA:SA: NI 38.36 mN/m

Decreasing Contact Angle (Increasing Wettability)

The contact angle of the various polymers of interest was determined using the Krüss K-100 in
relation to a solid with no polar parts (PTFE). This allowed for further determination of the
dispersive and polar parts of said polymers. A reduction in contact angle was seen, as the increase in
non-ionic increased in the polymer samples (Table 2). This reduction in contact angle is an increase
in wetting of the polymer on to the solid surface.

Table 2
Liquid PTFE Contact Angle
Water 116.62°
AA:SA 105.50°
AA:SA:t-BAM I 100.04°
AA:SPME:SMS:MMA 97.14°
AA: SA: t-BAM IV 93.08°
New Polymer: AA:SA: NI 81.81°

Photographs were taken of the polymer that did not contain any non-ionic functional group as well as
the polymer that contains the highest amount, seen in Image 1 below. Visually, a difference can be
seen between the two polymers. The polymer on the left, which contains high levels of non-ionic has
a smaller contact angle as well as increased wetting on to the PTFE surface. The polymer on the right
has an increased contact angle to the PTFE, resulting in decreased wetting of the surface by the
polymer.

AA:SA:NI AA:SA

Image 1: Contact angle of AA:SA:NI and PTFE (Left), Contact angle of AA:SA and PTFE (Right).

© 2017 Radical Polymers, LLC – All Rights Reserved 11

The contact angles of the polymers on the PTFE surface was visually confirmed using the software
ImageJ, as seen in Image 2 below. These contact angles are consistent with those reported using the
Krüss K-100.

AA:SA:NI AA:SA
PTFE Contact Angle: 80.86° PTFE Contact Angle: 105.25°

Image 2: Contact angle determination of AA:SA:NI and PTFE (Left), Contact angle determination of
AA:SA and PTFE (Right) using ImageJ Software.

Dispersive and Polar Parts of Liquid and Solids

Table 3, below, shows the distribution of dispersive parts and polar parts for each liquid tested. As
the non-ionic content increases in the polymer, the polar part decreases as well.

Table 3
Liquid Dispersive Part Polar Part
Water 21.82 mN/m 50.98 mN/m
AA:SA 35.18 mN/m 34.45 mN/m
AA:SA:t-BAM I 22.32 mN/m 26.90 mN/m
AA:SPME:SMS:MMA 22.12 mN/m 24.08 mN/m
AA: SA: t-BAM IV 23.61 mN/m 20.56 mN/m
New Polymer: AA:SA: NI 25.96 mN/m 12.40 mN/m

The surface free energy of calcium carbonate has literature values of 25.10 mN/m and 33.10 mN/m,
with the latter resulting in dispersive parts equal to 22.90 mN/m and 10.20 mN/m polar parts.
When determining the surface free energy of calcium carbonate using the Washburn method on the
Krüss K-100, results showed 28.3 mN/m total with dispersive parts equal to 21.7 mN/m and polar
parts equal to 6.6 mN/m. This was consistent with reported literature values. When calcium
carbonate was tested with water, the contact angle was found to be 84.2°, meaning the water has
poor wettability onto the calcium carbonate. When calcium carbonate was tested with diiodo-
methane, the contact angle was found to be 72.1°, meaning that diiodo-methane has better
wettability onto the surface of the calcium carbonate. This is in line with the idea that substances
with similar surface free energy/surface tension, dispersive and polar parts can adsorb onto one
another better than those with vastly different surface energy make up.

Other reported literature values for surface free energy of typical scale inducing components reflect a
similar trend: high dispersive parts, low polar parts. Talc (magnesium silicate) has a reported
surface free energy of 42.90 mN/m which is comprised of 42.20 mN/m dispersive parts and 0.70
mN/m polar parts. Iron oxide has a reported surface free energy of 32.90 mN/m with dispersive
parts making up 20.00 mN/m and polar parts making up 12.90 m/m. With this in mind, the increase
of non-ionic functional groups resulting in an increase of in calcium phosphate stabilization, iron
stabilization, crystal modification, as well as increased wetting and surface tension reduction makes a
lot of sense when broken down into surface free energy, dispersive and polar parts.

© 2017 Radical Polymers, LLC – All Rights Reserved 12

Calcium Phosphate Stabilization Properties

It is well understood that the incorporation of sulfonate functionality is required to provide calcium
phosphate stabilization properties. The functionality can be greatly enhanced by the addition of
certain non-ionic monomers. Graph 2 shows the dramatic enhancement in efficacy that can be
derived when a non-ionic monomer is added to a standard AA:SA copolymer. The data show calcium
phosphate stabilization for a new AA:SA:NI versus standard AA:SA copolymers of varying ratios.

Graph 2: Calcium Phosphate Stabilization – Non-Ionic Enhancement

Iron Stabilization

Images 3-5 show the iron stabilization properties of three non-ionic containing polymers relative to a
blank (No Treatment.) In these images, the amount of iron captured on the 0.2μm membrane filter
can be visually observed with increasing dosage. Less color collected on the membrane surface is an
indication that the iron has been effectively stabilized and particles sufficiently less than 0.2μm in
size. It can be observed that the New Polymer, which contains a higher level of non-ionic monomer,
functions more effectively at a lower overall dosage. This comparison is especially prominent when
AA:AMPS:NI - Iron Stabilization
observing the 9, 12, and 15 mg/l treatments for each polymer.

Blank 9 mg/l 12 mg/l 15 mg/l 18 mg/l 24 mg/l

Image 3: AA:SA:t-BAM I – Iron Collection on 0.2μm membrane filter

© 2017 Radical Polymers, LLC – All Rights Reserved 13

 AA:NI:SMS:ABS - Iron Stabilization

Blank 9 mg/l 12 mg/l 15 mg/l 18 mg/l 24 mg/l

HPSP - Iron Stabilization
Image 4: AA:SPME:SMS:MMA – Iron Collection on 0.2μm membrane filter

Blank 9 mg/l 12 mg/l 15 mg/l 18 mg/l 24 mg/l

Image 5: NEW POLYMER (AA:SA:NI) – Iron Collection on 0.2μm membrane filter

Crystal modification

In cases where effective crystal habit modification is observed, the mechanism requires the polymer
to adsorb onto the surface of a forming crystal lattice (Figure 8). This allows the polymer to impede
the directional growth of the lattice and subsequently promote the formation of precipitated crystals
that are abnormal in shape, size, and overall appearance. The incorporation of non-ionic
functionality can play an important role in impacting the degree to which crystals are modified by
impacting both wetting and the conformation of adsorption onto a forming crystal surface. This can
be seen empirically in Image 6 where an enhanced polymaleic acid containing non-ionic functional
groups shows exceptional distortion of calcite (cubic calcium carbonate.)

Figure 8: Polymer Interaction – Adsorption onto Forming Crystal Lattice

© 2017 Radical Polymers, LLC – All Rights Reserved 14

Image 6: Calcite Crytal (Left) and Calcite Crystal Modification Using an Enhanced Polymaleic Acid
(Right).

Conclusions

© 2017 Radical Polymers, LLC – All Rights Reserved 15

The focus of this paper was intended to provide an introduction and basic reasoning behind the
increased benefits of non-ionic functional groups with respect to the surface properties they impart.

The benefits of the use of non-ionic monomers can be seen by considering the sampling of
information presented in this paper . Though there can be drawacks such as increase in cost, a
decrease in sequestration capacity, and the potential for foam in overfeeding situations, the use of
non-ionic functional groups add a wide range of distinct functionalities:

Benefits of Non-Ionic Monomer Incorporation:

▪ Improved Crystal Modification

▪ Increase Polymer Stability in Harsh Waters
▪ Enhance Phosphate Stabilization
▪ Excellent Transition Metal (Fe, Zn, Mn) Stabilization
▪ Expansion of Dispersion Functionality to Include Organics
▪ On-Line Cleaning
▪ Colloidal Silica Stabilization
▪ Magnesium Silicate Control
▪ Surface Tension Reduction and Surface Wetting

The authors plan significant additional work to explore other variables that specifically impact water
treatment applications and the best use of such polymers. These data will be presented in future
publications.

References

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[2] M. L. Standish, Rules of Three – Simplifying the Selection of Polymers, 2015.
[3] M. L. Standish, Extending Performance: A New Product Treatment in ‘No Man’s
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[4] "Krüss: Advancing Your Surface Science," 2017. [Online]. Available:
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[5] Krüss Laboratory Desk Software, 2.2 ed., vol. 3, Hamburg: Krüss GmbH, 2015.
[6] M. Bumiller, Dispersing Powders in Liquid, Horiba, 2013.
[7] C. K. Schoff, "Wettability Phenomena and Coatings," in Modern Approach to
Wettability: Theory and Applications, NY: Plenum Press, 1992, pp. 375-395.
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© 2017 Radical Polymers, LLC – All Rights Reserved 16