1 s2.0 S0300944022007007 Main

Progress in Organic Coatings 177 (2023) 107403
Contents lists available at ScienceDirect
Progress in Organic Coatings

journal homepage: www.elsevier.com/locate/porgcoat
Review
Correlations of rheological methods to coatings’ performance

Shun Xing Zheng a, *, Hua Shan Chen b
a
Department of Material and Engineering, Nanjing University of Aeronautics and Astronautics, Nanjing, China
b
Shuang Rui Anticorrosion Engineering Technology Co., Ltd, Luoyang, China
A R T I C L E I N F O A B S T R A C T
Keywords: Most basic issues of organic coatings are related to rheology. The paper extracts rheological methods from the
Steady rheology references to establish correlations with coating performance, which sets a framework for coating rheology. The
Transient rheology low-frequency parameters obtained in oscillatory tests can be used to predict rheological properties in very slow
Oscillatory rheology
processes, such as pigment settlement and sagging. Fractal analysis is used to investigate pigment flocs in
Organic coatings
coatings, but the affinity of medium to pigment particles determines whether fractal structures of flocs form and
Controlled shear-stress rheometer
which formation mechanism to take. During curing processes, an increase in storage modulus G′ and a decrease
in the inclination of G′ -ω plots are used to measure and indicate crosslink density. The product of intrinsic
viscosity and boundary concentration where polymer coils start to entangle, C*[η], regardless of the molecular
weight, is used to assess the chain configuration in polymer solutions. Extensional viscosity and the elastic
modulus in nonlinear regime are used to investigate roll spatter and spray atomization. The sagging and levelling
performance of coatings can be characterized by the empirical Leneta flow test, simple 3ITT, and quantitative
falling wave method. Stress ramp loop can be used to directly measure static yield stress and identify the for
mation mechanism of fractal structures, revealing internal change within coatings. Rheology modifiers are
introduced in detail.
(continued )
List of symbols
GX crossover modulus (G′ =G′′ )
CSR controlled shear rate rheometer DMA dynamic mechanical analysis
CSS controlled shear stress rheometer HMHEC hydrophobically modified hydroxyethylcellulose
γ̇ shear rate, rate of strain γcr critical strain
σ shear stress Ec cohesive energy [=(G′ × γ2cr)/2]
η coefficient of viscosity ( = σ/γ̇) Geq equilibrium modulus
σ0 yield stress df mass fractal dimension
η(0) zero shear viscosity Tg glass transition temperature
η(∞) infinite shear viscosity X crosslinking density
R2 coefficient of determination SCA sag control agents
ηr relative viscosity, ratio of a solution viscosity to the solvent viscosity ηsp specific viscosity
Φ effective particulate fraction HEC hydroxyl ethyl cellulose
Φm particulate fraction of maximum packing HEUR hydrophobically modified ethoxylated urethane
ω angular frequency RLA reaction-limited aggregation
G′ or E′ storage modulus DLA diffusion-limited aggregation
G′′ or E′′ loss modulus C* critical concentration
tanδ loss factor (=G′′ /G′ ) [η] intrinsic viscosity
η* dynamic viscosity AT’s associative thickeners
POSS polyhedral oligomeric silsesquioxane 3ITT three interval thixotropy test
Mn number average molecular weight cgel critical concentration at gel point
weight average molecular weight WFT wet film thicknesses
Mw
SPP sequence of physical processes
DoS dripping-onto-substrate rheometry
(continued on next page)
(continued on next column)
* Corresponding author.
E-mail address: [email protected] (S.X. Zheng).
https://doi.org/10.1016/j.porgcoat.2022.107403
Received 4 July 2022; Received in revised form 22 December 2022; Accepted 29 December 2022
Available online 27 January 2023
0300-9440/© 2023 Elsevier B.V. All rights reserved.
S.X. Zheng and H.S. Chen Progress in Organic Coatings 177 (2023) 107403
(continued ) on the chains’ conformation in solution [6]. The long free polymeric
CaBER capillary break-up extensional rheometry chains tend to adopt a disordered coil state to reduce the entropy of the
at final amplitude of surface disturbance system. Thus, long-chain polymers form a highly entangled structure in
a0 initial amplitude of surface disturbance the solutions, which causes shear thinning (pseudoplastic) behavior
DSC Differential Scanning Calorimeter
HASE hydrophobic alkali-swellable emulsion polymer
shown in Fig. 1. Very slow flow destroys the entangled network within
polymer solutions, but the destroying speed is equal to the forming
speed; the viscosity remains constant at maximum value η(0). When
1. Introduction shear makes the entangled polymers orientate along the flow direction,
the viscosity decreases with increasing shear rate, exhibiting shear
Most organic coatings begin as a liquid in bulk and then form a thin, thinning behavior.
solid film by crosslink or solvent evaporation or both. The fundamental When pseudoplastic fluids are disturbed, the fluids show very rapid
issues of the coatings include interaction among components, selection recovery of viscosity after the disturbance, and the viscosity-shear rate
of components or additives, crosslink and gelation, storage stability, flow curve presents a high η(0) plateau, following shear-thinning
coating application, levelling and sagging, and so on. The issues can be behavior and η(∞) plateau. Most coatings are pseudoplastic fluids. If it
investigated by rheological techniques. takes a measurable time for the viscosity to recover, thixotropic (time-
Rheological techniques measure the response of coatings to external dependent) behavior is observed.
forces. Based on this response, one can study consistent control of flow
and deformation properties of coatings. Each coating type and each 3. Interaction of components in solvent-borne coatings
application method have its particular rheological requirements
respectively. In order to produce the films with required performance, it Organic coatings are multi-component systems generally composed
is essential to adjust and control the rheological properties of the coating of polymer, pigment, solvent, and additives. The interaction among the
used, and then rheological measurement is used throughout the components determines rheological behavior of coatings.
manufacturing and application processes of coatings [1]. In fact, in the For solvent-borne pigmented coatings, the factors affecting rheo
coating industry at least half the cost of new product development is logical behavior include the molecular weight of polymer, the interac
consumed in “getting the rheology right” [2]. tion between polymer chains, the concentration of polymer solutions,
However, Richard R. Eley [2] commented on the application status of the pigment loading, and the dispersants used. It is well known that the
rheological techniques, “Many rheological measurements are of little higher the molecular weight of polymer, the higher the viscosity of its
help for quality control and research of coatings.” The paper will analyze solution. In solvent-borne coatings, the most used are prepolymers or
the situation in the Section 5. “It is often unclear how to connect rheo oligomers, and then it is not necessary to discuss the effect of molecular
logical (measurement) data with the real-world performance of paints.” weight on rheological behavior.
Thus, how to correlate rheological measurement results to coating per
formance is an important issue. 3.1. Interaction among macromolecules
The present paper extracts rheological methods from the cited ref
erences to establish correlations with coating performance, which pro Two typical resins used in coatings are urethane oil and alkyd resin.
vides an accessible way for employing the rheological techniques in The urethane oil is prepared with a partial glyceride mixture and toluene
coating fields. Specifically, the rheological methods elucidate how to (a) diisocyanate (TDI), and the glyceride mixture has hydroxyl value 141.5
characterize the storage stability of pigmented coatings; (b) follow and mg KOH/g, acid value 2.0 mg KOH/g, and monoglyceride 21.8 %. The
measure crosslink processes of coatings; (c) use fractal analysis for alkyd resin with oil length of about 50 % is prepared with sunflower oil,
identifying structures of flocs and formation mechanisms; (d) assess phthalic anhydride, and glycerol. The two resins are diluted with xylene
chain configuration in polymer solutions; (e) control application pro to 60 % solid content, and the viscosities are determined using a
cesses of screen-print, roll and spray coating; (f) investigate the perfor Brookfield viscometer in the range of 1–100 s− 1. The experimental re
mance of levelling and sagging; and (g) select suitable rheology sults are listed in Table 1 [7]. The power-law equation is expressed as:
modifiers. The rheological methods are also discussed in depth to pro
vide insights into rheological measurements of coatings. σ = K γ̇n (2)
2. Basic concepts
The most used shear rheology is characterized by using a rotary

rheometer in a simple shear stress field. A steady rheological state is
independent of how it is reached. In steady-state rheological tests, when
a constant shear rate γ̇ is applied to a system, the shear stress is
measured, but the shear stress varies with time, and gradually reaches a
steady value that is denoted the shear stress σ. The viscosity of a fluid (η)
is a measure of its resistance to deformation caused by stress:
η = σ /γ̇ (1)
Only Newtonian fluids can be defined by a single value for viscosity.
Apparent viscosity (ηa) of non-Newtonian fluids varies with shear rate.
Non-Newtonian fluids require more parameters to be set and measured,
such as yield stress (σ 0), zero shear viscosity η(0), and infinite shear
viscosity η(∞) [3]. Yield stress (or yield value) is defined as the minimum
stress required to produce permanent flow.
In a polymer solution, a transient network of polymer chains is
formed due to the presence of temporary junctions like entanglements or
weak hydrogen bonds between the chains [4,5]. The dynamics of the
network depend on the rates at which the chains leave and rejoin it and Fig. 1. Flow curve of pseudoplastic fluids.
2
Table 1
Fitting parameters of 60 wt% polymer solutions at 25 ◦ C [7]
Polymer solution Mn Mw Tg (◦ C) Power-law equation Casson equation
2
n K (Pa s) R σ0 (Pa) η∞ (Pa s) R2
Urethane oil 3170 5928 4.1 0.823 0.29 0.999 0.29 0.09 0.999
Alkyd resin 4876 26,817 0.9 0.986 0.21 0.999 0.0013 0.19 0.999
where K is consistency, and n is the power law index. Fluids with n = 1 complete change in solution structure, but at very slow flow, the
are Newtonian fluids; fluids with 0 < n < 1 show shear thinning structure could be only disturbed, not completely destroyed. Since the
behavior. The alkyd resin solution is close to Newtonian fluid, while the solutions at slow or high flow have different structures, they have
urethane oil solution has n in the range of 0.795–0.832, showing shear different shearing histories.
thinning behavior. Casson equation is expressed as:
(√̅̅̅ √̅̅̅̅̅ √̅̅̅̅̅̅̅̅ ) 3.3. Interaction caused by pigment and dispersant
σ = σ 0 + η∞ γ̇ (3)
Viscosity is a measure of resistance to flow. High viscosity at low
where σ0 is yield stress and η∞ is infinite shear viscosity. Only urethane shear rates indicates strong interaction among components in coatings.
oil solution has a defined yield stress [7]. The presence of H bonding in Fig. 3 presents the flow curves of the inks that are composed of pigment
the urethane oil solution results in strong interaction among the mac (12.1 vol% TiO2 powders, TP), dispersant (0.90 vol% lauric acid, LA),
romolecules, resulting in shear-thinning behavior and yield stress. and vehicle containing 85.3 vol% solvent (terpineol, T) and 1.70 vol%
binder (ethyl cellulose, EC) [9].
The measurements are performed using a controlled-stress rotational
3.2. Effect of solvent concentration rheometer (Bohlin C-VOR 120, Malvern) by sweeping over 22 values of
shear rates in the range of 0.01–158 s− 1, and a pre-shear of 2 min at 0.01
A pure solvent presents Newtonian behavior, while concentrated s− 1 is first applied to eliminate shearing history.
polymer solutions display typical non-Newtonian flow curves. Fig. 2 The curves (T + EC + LA) and (T + EC) have far lower viscosities than
shows the flow curves of polymer solutions in the whole concentration the curves (TP + T + EC + LA) and (TP + T + EC), respectively, espe
range [8]. In concentrated solutions, strong interaction enables macro cially at low shear rates. Thus, the addition of TiO2 particles dramati
molecules to move as a whole, resulting in spurt. Spurt is the loss of cally increases the inks’ viscosities, suggesting that there is very strong
contact between the solution and the surface of measuring device at high interaction between TiO2 particles and cellulosic chains. The very strong
shear rates. Only >70 % concentration shows defined spurt stresses σs. interaction between pigment particles and polymer chains has also been
The presence of spurt also reveals the elasticity of the concentrated so reported in the references [10,11].
lutions. Since thermosetting coatings use oligomers and have solid Similarly, the dispersant lauric acid significantly decreases the vis
contents of 40–60 %, they do not generally present the spurt cosities by comparing the curves of (T + EC + LA) − (T + EC) and the
phenomenon. curves of (TP + T + EC + LA) − (TP + T + EC), respectively. Lauric acid
In the case of rheological measurement, a high shear rate can cause a acting as an effective dispersant forms a repulsive barrier around the
particles’ surface, decreasing the viscosity of paints by acting against the
formation of a network.
The rheological behavior of pigment in coatings is described by the
Fig. 2. Viscosity dependency of solids for poly-p-benzamide in dimethyl acet

amide solutions [8] Fig. 3. Effect of TiO2 and lauric acid on shear viscosity [9]
3
Krieger-Dougherty equation: from experimental data using non-linear regression analysis.

The most used in oscillatory measurements are strain sweep and
ηr = (1 − Φ/Φm ) − kΦm
(4) frequency sweep. In Fig. 4(a), the strain sweep test at a constant tem
perature and a fixed frequency obtains a linear viscoelastic range where
where k is a constant (intrinsic viscosity, often close to 2.5). A high
the moduli are independent of the applied strain. Using a strain in the
effective particulate fraction Φ value (i.e., close to Φm) leads to an abrupt
linear viscoelastic region a frequency sweep is performed in Fig. 4(b) so
increase in the relative viscosity ηr.
that we can obtain G′ , G′′ , G*, tanδ, and cross-over modulus (G′ = G′′ ).
In general, in polymer solutions the orientation of entangled poly
The critical strain (γcr) is the maximum strain above which the structure
mers and the chain interaction cause shear thinning behavior. The rare
starts to “break down”, and then cohesive energy [Ec = (G′ × γ 2cr)/2]
cases in coatings are that strong chain interaction between polymer
represents the gel strength of the structure.
leads to yield stress, and concentrated polymer solution results in spurt.
The frequency sweep with a strain beyond the linear viscoelastic
But in organic coatings, there is strong interaction between pigment
region becomes very complicated; even the above definitions about
particles and polymer chains. Consequently, the strong interaction
moduli are no longer applicable.
among coating components causes shear thinning behavior and yield
stress, while weak interaction leads to zero shear viscosity.
(2) Indicators of storage stability
Organic coatings require strong interaction to prevent pigment set
tlement, and then they need to form a network structure with gel
Natural stability test1 and accelerated stability test2 are used to
strength. The term “gel strength” indicates the interaction magnitude.
assess pigment sedimentation of coatings, but the tests are time-
consuming and complex [12]. Oscillatory rheological tests have been
3.4. Storage stability correlated to the storage stability of coatings. The higher cross-over
modulus, the better the paint stability [13]. The high values of G′ at
Pigment particles move downward for the coatings at rest. The low frequency indicate long-term stability [13]. Low-frequency tanδ < 1
coating viscosity at very low shear rates approximately indicates viscous appears to be a sufficient criterion to prevent sedimentation [14,15].
resistance to the particle settlement, but steady-state measurement at a A high value for tanδ shows that viscous flow dominates in coatings,
very low shear rate needs very long time. The advantage of oscillatory and the interaction between pigment particles is so weak that particle
rheology is that viscoelastic response of a material at different time deposition cannot be prevented. A low tanδ value indicates that the
scales (1/ω) be directly obtained by frequency (ω) sweep. The low- interaction between pigment particles is too strong, such that they form
frequency regime corresponds to a long time measurement. Thus, large clusters to deposit. In general, the value of tanδ for coatings is in
oscillatory rheology is very suitable for investigating pigment the range of 0.5–1.5. Low-frequency <1 shows that the coatings have
settlement. higher values of at low frequency than.
A specific example is the coatings containing 50 % oil-length dehy
(1) Oscillatory technique drated castor oil alkyd resin and red iron oxides [16]. The wetting/
dispersing agents in Table 2 are used to prevent flocculation and sedi
When a sample is constrained in a rotational rheometer, an oscil mentation. The test results in Table 3 show that the parameters except
lating strain at a given ω (rad s− 1) is applied to the sample by γ (t) = γ 0 sin yield stress agree well with natural stability results.
(ωt) with small amplitude γ0 in the linear viscoelastic region. After an It should be noted that the measurement method of yield stress in
initial start-up period, stress develops in response to the applied strain, Table 3 is questionable; namely, the viscosity vs. shear stress plot is
with σ(t) = σ0 sin (ωt + δ), shifted by the phase angle δ. obtained at the constant low shear rate 0.1 s− 1 for a time interval of
In the range of 0 < δ < 90◦ , storage modulus (G′ ), loss modulus (G′′ ), 3000 s, and the yield stress is the maximum shear stress observed over
loss factor (tanδ) and dynamic viscosity (η*) can be calculated from γ0, the whole time scale. The test method cannot represent the transition
σ 0 and δ: from solid-like to liquid-like behavior, and then the yield stress is not
( ) ( ) √̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
( ′ )2 ( ′′ )2 true in Table 3.
′ σ0 ′′ σ0 G′′ * G G Since viscous flow dominates at low-frequency regimes (long-time
G = cosδ • G = sinδ • tanδ = ′ • η = + .
γ0 γ0 G ω ω experiments), the low-frequency parameters can approximately char
acterize gel strength of the coatings at rest. The low-frequency param
The moduli, G′ and G′′ , indicate the elastic properties and viscous eters used are η(0), low-frequency G′ and tanδ, cross-over modulus, and
properties of the sample, respectively. The materials with the same tan cohesive energy Ec. The parameters are the indicators of the storage
(δ) value exhibit similar viscoelastic behavior, regardless of the magni stability of paints. The parameters are used to evaluate stability of
tude of their moduli. Dynamic viscosity (η*) is proportional to flux waterborne coatings in the following two examples.
resistance, and its magnitude represents the overall strength of visco One example is that four dispersants with different lipophilic hy
elastic response. drophilic balance values are used to disperse iron oxide yellow in a
According to the Cox-Merz rule, when frequency (ω) and shear rate waterborne coating. Water, glycol, and one of the dispersants are mixed
(γ̇) are equal, the η* is equal to the apparent viscosity η(γ̇) , that is, η*=η(γ̇) thoroughly. After the addition of pigment, the system with ~50 %
at ω = γ̇. In this case, the frequency is expressed in radians. At low shear pigment loading is dispersed at ~3000 rpm for about 30 min using a
rates, the low-frequency dynamic viscosity is close to the apparent high-speed disperser (VMA Getzmann GmbH, Germany). Finally, the
viscosity. remaining water and additives are added and mixed well. It is found that
( )/( )
For the Cross model [ η − η(0) η − η(∞) = Kγ̇m ], when the very the cohesive energy Ec value determined only at 55 ◦ C agrees with the
small η(∞) is omitted, the model can be expressed as η = η(0) /(1 + Kγ̇m ). accelerated stability test performed at 55 ◦ C [17].
The frequency dependence of η* can be expressed as: Another example is that the use of soy protein replaces HEC thick
ener in the latex paint. The values of G′ at 0.1 rad/ s obtained from
η(0)
η* = [ ] (5)
1 + (ω/ωC )β
1 1
Natural stability test: the samples were stored in metallic containers at
where ωC is the critical shear frequency at which the viscosity decreases ambient conditions for one year.
to half its initial value; β is the material constant that depends on the 2
Accelerated stability test based on ASTM D 1849: the samples were kept in
nature of the dispersion. With the use of Eq. (5), η(0) can be obtained an oven at 55 ◦ C for one month.
4
Fig. 4. Oscillatory sweep test.
Fig. 5(a).
Table 2
Winter-Chambon criterion is the presence of frequency-independent
Wetting dispersants used in alkyd primers [16]
tanδ (=G′′ /G′ ) at gel point. For example, the tanδ of PUDs is frequency-
Wetting dispersants (%) SP1 SP2 SP3 SP4 independent at 17 min, indicating that the waterborne system reaches
Calcium octoate 0.9 0.3 0.3 0.3 its gel point in Fig. 5(b) [21].
Soya lecithin 0.3 0.4 0.4 0.4 Winter-Chambon criterion is also used to investigate the gelation
Oleate salt of tallow 0.3
behavior of solvent-borne N-phenylaminomethyl–POSS (polyhedral
triethylamine
Anionic phosphate ester 0.3
oligomeric silsesquioxane)/PU (polyurethane) nanocomposites [22] and
Total amount 1.2 0.7 1.0 1.0 the physical gelation of carbon black/isotactic polypropylene melt [23].
Storage stability Zero Rapid Soft Soft The two systems all follow Winter-Chambon criterion. The latter system
settling settling settling settling [23] is similar to the heating and melting of powder coatings. The above
examples show that the coating systems (solvent-borne type, water-
frequency sweep indicate that the latex paints using soy protein have borne type, and powder type) all show frequency-independent charac
good long-term stability [18]. The cohesive energy Ec value correlates teristics at gel point.
well with the experimental results of the latex paints in accelerated heat-
age stability test [19]. 4.2. Fractal analysis
4. Coating transformations A widespread phenomenon is that small particles tend to stick

together to form agglomerates or flocs, and each floc is composed of self-
Organic coatings cover a wide variety of non-reactive and reactive similar structures (fractal structures). The dispersed pigment particles
systems. The section only discusses gelation and chemical crosslink of spontaneously form larger-size clusters (flocs) because of the attractions
coatings. between particles in pigmented coatings. For this reason, pigment dis
persants are used to prevent the flocculation.
4.1. Concept and criteria of gelation
(1) Microstructure of physical gel
There are chemical-crosslink gels and physical gels. Physical gels can
be constructed based on weak interactions like hydrogen bonding, In term of physical gels, the affinity of medium to particles is of vital
charge transfer, or electrostatic interactions. For chemical-crosslink gel, importance for the formation and morphology of fractal structures.
a wet paint film is suddenly unable to flow when its crosslink degree Carbon black (CB) is a typical pigment used to investigate flocculated
reaches gel point. Because macromolecules with infinite molecular structures in coatings. The primary particles of carbon black are strongly
weight are formed at the gel point, but sols (monomers and small bonded together to form structures called aggregates, and an agglom
molecular-weight oligomers) still swell the macromolecules. erate is a group of aggregates bound together through van der Waals
At gel point, the systems have an equilibrium modulus (Geq) and force. The structure of agglomerates breaks up under shear flow. The
follow Winter-Chambon criterion [20], which is elucidated by the networks consisting of CB agglomerates can be investigated by fractal
following examples. analysis.
For aqueous polyurethane dispersions (PUDs) with 40 wt% PU, an In CB dispersions, the affinity of medium to CB particles determines
oscillatory time sweep is carried out to determine the influence of whether fractal networks can form. When the affinity is too small (such
gelation process on G′ at a constant shear frequency (1 rad/ s) in the as in a polystyrene/di-butyl phthalate solution medium), a dense
linear viscoelastic range [21]. A dramatic increase in G′ is observed at network is fully developed at small CB content so that there is no fractal
70 ◦ C, and then the value of G′ becomes time-independent. The plateau network. The CB particles hardly agglomerate and are randomly
of G′ is called Geq, a typical criterion for forming an elastic gel shown in dispersed if the affinity is too high (such as in the alkyd solution
Table 3
Measurement results by oscillatory test [16]
PVC Storage stability Frequency sweep Amplitude sweep
G′ (Pa) G′′ (Pa) tanδ η(0) (Pa s) G′ = G′′ (Pa) σ0 (Pa)

SP1 37.3 % Zero settling 4.19 4.90 2.07 135.0 43.36 1.345
SP2 68.9 % Rapid settling 0.42 1.00 3.21 61.3 23.07 1.374
SP3 68.9 % Soft settling 1.19 1.81 2.72 85.8 29.97 1.698
SP4 68.9 % Soft settling 2.35 4.38 2.41 124.0 30.72 0.857
5
Fig. 5. Geq plateau and Winter-Chambon criterion at gel point [21]
medium). Only moderate affinity, such as rosin-modified phenol resin, increasing water content.
allows the formation of flocculated network [24]. The fractal structure has two formation mechanisms: DLA and RLA.
When CB is dispersed in a rosin-modified phenol resin varnish. With When df = 1.8, fractal structures become much more open by diffusion-
the increase in its concentration, the system progressively forms weakly limited aggregation (DLA). In this case, the clusters move by Brownian
flocculated gels. At a given temperature, there is a critical CB concen motion and adhere to each other upon contact, which is a fast process.
tration (cgel) at its gel point. The frequency-independent behavior at the Greater values of df (≥2.1) indicate denser agglomerates formed via
gel point is expressed as: G(ω)′ = Aωn and G(ω)′′ = Bωn, and then reaction-limited aggregation (RLA). RLA is a slow process of cluster
/ ′ / aggregation under a repulsive barrier, and clusters collide many times
tanδ = G′′(ω) G(ω) = B A = tan(nπ/2) (6) before actually sticking together.
For the inks containing 77 %, 67 %, and 48 % water, their df values
Critical relaxation exponent (n) is equal to 2δ/π. When the hydro
decrease from 2.1 to 1.7 with decreasing water content, suggesting that
dynamic interaction is completely screened, and excluded volume effect
low fractal agglomerates are formed via DLA. The ink containing 89 %
is dominant, the mass fractal dimension (df) is:
water has df = 2.6 and forms compact agglomerates, which is consistent
df = (d/n) − 2 (7) with the RLA results [26]. The experimental results mean that the me
dium environments determine the formation mechanisms of the fractal
where d denotes space dimension (d = 3). Oscillatory measurements are agglomerates.
carried out with a controlled strain rheometer in the linear viscoelastic However, if the distinct stress ramp curves of DLA and RLA in Fig. 14
region. The cgel, n, and df at different temperatures are listed in Table 4. (b) were used to differentiate the systems, the above conclusion would
With increasing temperature, the fractal structure of carbon black is be more convincing.
more open, changing from plane-like to straight-line structure [25]. Fractal analysis not only can identify the microstructures of the
physical gels, but also figure out their forming mechanism.
(2) Formation mechanism of physical gel
(3) Chemical gelation
The medium environments determine whether fractal networks form
and which formation mechanism to take. The following example reveals By comparison, chemical-crosslink gels have completely different
the influence on forming mechanism. formation mechanisms, and crosslink density determines whether the
The Pt/C inks use 5.5 wt% ionomer and medium consisting of water systems reach gel points.
and 1-propanol in a ratio of 48: 52, 67:33, 75:25, and 89:11, forming As for N-phenylaminomethyl-POSS/PU composites, POSS acts as a
strongly agglomerated structures [26]. Strain sweep (0.01 %–1000 %) at crosslinker. At 140 ◦ C, the critical gel concentration is 2.7 wt% POSS,
1 Hz is performed using a cone-plate rheometer. The plateau storage and fractal structures are formed only between 2.5 wt% and 6 wt%
modulus (G0′ ) is obtained by extrapolating from the data corresponding POSS. This is to say that the systems cannot gel below 2.5 wt% POSS,
to 0.01–0.03 % strain. The Pt/C inks display G0′ with a power-law while the crosslink density is significantly increased above 6 wt% POSS,
dependence on the particle volume fraction φ: (G0′ ∝ φA). deviating far from the structure at 2.7 wt% POSS [22]. Thus, the fractal
The fractal dimension (df) is determined by the scaling exponent A: structures of chemical-crosslink gels exist only around their critical gel
concentrations.
(d − 2) + (d + x)(1 − α) 1 + (3 + x)(1 − α)
A= = (8)
d − df 3 − df
4.3. Chemical crosslink
Here, d = 3; x is fractal dimension of cluster backbone, which is
assumed to be between 1.0 and 1.3. Three different gel regimes are Chemical crosslink causes the molecular weights of resins rapidly
identified: strong-link gel (α = 0), weak-link gel (α = 1), and transition increase, resulting in high viscosities. Bubble viscometer3, called
gel (0 < α < 1). In Table 5, the scaling exponent A decreases with Gardner-Holdt viscometer, are routinely used for controlling the
endpoint of resin synthesis. Most coatings are thermosetting, and they
Table 4
need to undergo chemical crosslink to form dry films.
Carbon black in rosin-modified phenol resin varnish [25]
Temperature cgel A B (n) df 3
Standard liquids with different viscosities and the samples are put in a set of
30 ◦ C 31 wt% 790 1700 0.70 2.29 glass tubes of the same size. They all are turned over at the same temperature,
40 ◦ C 32 wt% 140 370 0.76 1.95 and the moving velocities of the bubbles are compared. The viscosity is indi
50 ◦ C 32 wt% 30 100 0.80 1.75
cated by the specification letter of the standard liquid whose bubble velocity is
60 ◦ C 31 wt% 5.3 24 0.84 1.57
closest to that of the sample.
6
Table 5 4.4. Glass transition temperature

Fractal analysis for agglomerate of Pt/C inks [26]
Water content Scaling exponent, A Regime Fractal dimension, df The most important parameter of solid polymer is glass transition
temperature (Tg), above which its stiffness drops dramatically with an
48 % water ink 4.0 Strong-link gel 1.7 (α = 0; x = 1.3)
67 % water ink 4.0 Strong-link gel 1.7 (α = 0; x = 1.3) increase in viscosity.
75 % water ink 3.3 Transition gel 2.1 (α = 0.5; x = 1.0)
89 % water ink 2.2 Weak-link gel 2.6 (α = 1; x = 1.0) (1) Interaction in solid films
In solid coating films, there are pigment and cured polymer. DMA
Although chemical crosslink can greatly increase the viscosities of
test can indicate the changes in polymer network and characterize the
wet films, the following factors also make the viscosities rise: (i) solids
interaction between pigment and polymer.
increase due to solvent evaporation, (ii) the reduction in levelling shear
The modulus is expressed as “E” in DMA tests. There are Emin′ , Emax′′
stress with the decrease in roughness amplitude, and (iii) thixotropic
and Ttanδ max around Tg, and they all represent a measure of Tg, but they
structural recovery [2]. Thus, viscosity is not a suitable indicator of
differ on the temperature scale a few K. Among them, loss modulus (E′′ )
crosslink degree for coatings.
depends on the interaction of strain and motion resistance, and then
Oscillatory techniques are used to follow chemical crosslink process
Emax′′ and Ttanδ max are very sensitive indicators for changes in the
of coatings, revealing cure details at any point in the curing process.
polymer network. They are used to measure the variations of paint
formulation or polymer chain degradation caused by, for example,
(1) Liquid systems
weathering effects [29,30].
Like crosslinking, pigments decrease the freedom degree for
The following studies show that both G′ and inclination of G′ vs. ω
segmental motions and restrict the molecular response to temperature
plots can be regarded as two measurements of crosslinking density in
change, resulting in a decrease in Emin′ of coatings. Consequently, Emin′ is
liquid coatings, although they cannot differentiate chemical crosslink
used to investigate the interaction between pigment and polymer in
and physical gel.
solid films.
The drying processes of 2 K waterborne hydroxyl acrylic coatings are
determined by a rotational viscometer. Without the isocyanate hard
(2) Glass transition in solid films
ener, there is no cross-over point between the G′ curve and the G′′ curve
in Fig. 6(a). An increase in G′ with time is clearly observed due to the
Crosslink density is directly related to storage modulus in liquid
presence of an isocyanate hardener in Fig. 6(b). Thus, the G′ can be
systems, but crosslink in solid films makes the relationship become
regarded as a measurement of crosslinking density of the coatings.
complicated.
Accordingly, tanδ (=G′′ /G′ ) gradually decreases during the curing pro
When crosslink density (υe) is regarded as moles of elastically
cess [27].
effective network chains per cubic centimeter, the equation is: E′ =
Fig. 6(c) shows G′ vs. ω plots of POSS/PU composites, and the moduli
3υeRT. This equation is effective for elastomers above Tg that contain
are shifted by a factor of 10N for comparison. Since POSS acts as a
chains connected at both ends of the network at different junction
crosslinker, the content of POSS can be regarded as a measurement of
points.
crosslink density for the POSS/PU composites. The inclination (i.e.,
Since alkyd resins contain fatty acids, which can be considered
gradient or slope) of the G′ vs ω plots decreases with increasing crosslink
dangling chains, the equation E′ = 3υeRT is not elastically effective.
density, and that of the composites with 8 wt% POSS is close to zero
Using a lattice model and assuming a Gaussian behavior of the chains
[22].
between crosslink points, DiMarzio equation is used to describe the
Pure elasticity is a time-independent process, as the strain appears
change in Tg caused by the formation of crosslink points:
the moment the stress is applied, without any time delay. In the case of
( )/( )
pure elasticity, the slope of G′ vs ω plots is equal to zero. Consequently, X = Tg − Tg,u k2 Tg (9)
the inclination of G′ vs ω plots can be regarded as a measurement of
crosslinking density. where Tg is glass transition temperature of a crosslinked polymer, Tg, u is
However, Fig. 12 shows a similar decrease in the inclination of G′ vs. that of the unreacted polymer, k2 is a constant of 1.2 for crosslinked
ω plots of PUDs with increasing content of polyurethane dispersions systems, X is crosslink density, defined as the moles of chains between
(PUDs), accompanying the transition from a fluid to an elastic gel. The crosslink points divided by the total number of moles of segments. X can
transition is a physical process, which suggests that the inclination of G′ be regarded as the inverse of the number of rotatable bonds per elastic
vs ω plots cannot differentiate chemical crosslink and physical gel. chain.
DiMarzio equation (Eq. 9) is only suitable for the systems with low
(2) Solid thermoset crosslink density. It is used to investigate modified alkyd coatings. When
10 % triethoxysilane-modified alkyd resin is added into long linseed oil
Dynamic mechanical analysis (DMA) follows the chemical crosslink alkyd resins, the Tg values of the cured films increase from 25 ◦ C of the
process of solid thermosets. DMA and Differential Scanning Calorimeter alkyd resin to 37 ◦ C of the modified alkyd resin. Consequently, the
(DSC) tests of an epoxy-amine powder coating are shown in Fig. 7. The crosslink densities increase from 0.051 to 0.081, and the number of
coating evolves from powder at 75 ◦ C to liquid intermediates at rotatable bonds per elastic chain decrease from 19.61 to 12.35 [31].
100–130 ◦ C and finally to cured solid at over 160 ◦ C. The fully cured As for highly crosslinked coating films, the multiple non-ideological
coating has the Gmax′ of 1.24 MPa at 160.4 ◦ C [28]. effects of crosslink should be considered, such as decrease in chain-end
Gelation estimated by tan(δ) = 1 represents the incipient stage of concentration and departure from Gaussian behavior. Based on the
crosslinked network formation. At the gel point, the temperature is considerations, a complex model has been developed [32], but it is not
129.6 ◦ C, and the degree of cure (alpha) is 49.1 %. However, we cannot easy to use the model, because more parameters need to be measured in
decide whether the gel point is the same as that determined by having an advance. However, the point is that highly crosslinked systems un
equilibrium modulus and following the Winter-Chambon criterion. dergoes a very sharp increase in Tg at high conversions.
7
Fig. 6. Rheological methods for measuring crosslink density.
5. CSR and CSS rheometers 5.1. Stress ramp loop
Since cheap controlled shear rate (CSR) rheometers are simple in Stress ramp loop test can reveal what is going on within the micro
construction and convenient in use, shear rate as a variable is present in structure of coatings and give accurate results of the yield stress. The
most flow curves reported. Unless otherwise specified, rheological protocol for the test is that the sample is subjected to increase in torque
measurements are made with CSR rheometers. There is no difference to a selected maximum torque (“up-ramp”), immediately followed by
between controlled shear stress (CSS) and CSR data for equilibrium flow. decrease in torque (“down-ramp”). A typical stress ramp loop shown in
However, when CSR rheometers are used to characterize fresh Fig. 8 is used to characterize Carrageenan stabilized milks whose in
cement mortar, it is found that at very low shear rates, the rheometers ternal structures tend to collapse readily under even small deformations.
display abrupt flow and stop. With the increase in shear rate, in the Carrageenan stabilized milks starts with a very small stress applied to
intermediate shear-rate range, the part of the material near the rotor is the quiescent systems. The shear stress at the initial point of measurable
sheared, while the rest remains un-sheared (or immobile). Only at suf viscosity is called static yield stress. From that point, a 30-fold decrease
ficiently high shear rates, the entire material is sheared, and shear stress in viscosity is followed by a short plateau terminating at a critical stress,
becomes a function of shear rate. Thus, the shear behavior of the cement beyond which precipitous shear thinning occurs [36]. The presence of
mortar differs depending on the magnitude of applied shear rate [33]. structural viscosity plateau is ascribed to that the network structure can
The extreme example [33] shows that the sample is not in steady state at undergo significant strain before overall collapse.
the low and intermediate shear rate regimes. In the case, transient CSS rheometer upgrades experimental capability on rheology by
rheology is needed for investigating the systems. amplifying viscosity differences of weak gel systems. Carbopol is a high
Transient behavior depends on whether the sample is exposed to a molecular weight poly(acrylic acid) in gel-like solution crosslinked by
constant shear rate or a constant stress [34]. CSS rheometer is suited to ionic interactions. The viscosity-shear stress curves of two Carbopol
measure transient behavior of strain-sensitive fluids. Stress ramp test by dispersions with slightly different concentrations of 1.1 wt% and 1.3 wt
CSS rheometer provides information about breakdown and buildup % have the down-ramp viscosity ratio of about 250:1 shown in Fig. 9(a),
(recovery) of network structures in coatings [35]. Richard R. Eley whereas the viscosity-shear rate plots in Fig. 9(b) are bland and
elaborates on why and how CSS rheometer is used in coating field [2]. featureless, and the viscosity ratio is only about 2:1 [2].
8
Fig. 7. DMA profiles of G′ , G′′ , and tan (δ) for an epoxy powder.
coating [28]
Fig. 8. Loop of viscosity vs shear stress [36]
9
Fig. 9. Flow curves of Carbopol dispersions of 1.1 % and 1.3 % as a function of shear stress (a) and shear rate (b) [2]
By the way, since stress ramp curves in Fig. 14(b) can show typical entirely miss the rheological domains where application and film-
features of DLA flocs and RLA flocs, the tests can be used to identify the forming flows take place. Since the measurement results of CSR
formation mechanism of pigment flocs. viscometer cannot assess and control these key flow processes, Richard
R. Eley commented that the measurements are of little help for quality
control and research of coatings [2].
5.2. Viscosity-stress flow curve Another advantage of using CSS viscometer is that shear stress is
easily calculated, and the calculation methods of levelling stress, sagging
Shear stress dominates flow process, but shear rate is a dependent stress and gravitational stress are available [2].
variable—the resultant of the driving stress and the resisting viscosity
[2]. The viscosity-shear stress flow curves can be obtained by using CSS 5.3. Discussion on yield stress
rheometer, which is steady-state measurement. The stress data in the
flow curves permit quantitative assessments and control for the flow Yield value, the minimum stress required to produce permanent
processes. flow, indicates the transition stress at which a system changes from
A typical example is shown in Fig. 10. The curves of two latex paints having a solid behavior to having a fluid behavior or the converse
mark out shear stress ranges of critical flow processes: 1– 4 Pa for sag changing process.
ging, 2– 50 Pa for levelling, 500– 700 Pa for brush, and 200– 400 Pa for Static yield stress measured by stress ramp loop is the stress that must
roller application [2]. However, the viscosity-shear rate flow curves do be overcome for flow to initiate. During coating application, the
not provide such useful information. For instance, one cannot predict microstructure responsible for yield behavior is broken, and the rate of
the relative levelling rates of two different paints from their viscosity structural recovery leads to what is termed a dynamic yield stress.
values at a shear rate of 1 s− 1 or at any other shear rate. Dynamic yield stress is the stress below which flow ceases, and it is
The typical CSR rheometers are constant-speed “ICI” cone and plate obtained by fitting flow data to model equations which contain a yield
(ASTM D 4287) and Krebs-Stormer paddle viscometers (ASTM D 562) stress term, such as Casson equation (Eq. 3) or Herschel–Bulkley model
used for laboratory Q/C. Stormer viscometer only provides viscosity for (σ = σ0 + kγ̇ n ), or by extrapolating a shear stress-shear rate flow curve to
a single shear stress value (80 Pa). In Fig. 10, the CSR viscometers almost zero shear rate. Since there are many factors affecting the measurement
of dynamic yield stress, only when a well-defined procedure (tempera
ture, shear rate, shear time, measuring geometry) is used, the obtained
values are comparable. Dynamic yield stress may differ significantly in
magnitude with static one or the one from oscillatory tests [37,38].
Yield behavior itself is complicated. During measurement of yield
behavior, there are three transitions with the increases in applied stress
(or strain): the first is a transition from linear to nonlinear viscoelastic
behavior, followed at a higher stress by the yield point, above which the
material flows as a fluid [39]. Moreover, materials with apparent yield
behavior are found instead to exhibit irreversible flow at very low
stresses [40].
Despite all this, yield value is still a meaningful concept. Yield stress
is denoted as the transition stress at which a material behaves either as
elastic solid-like or viscous liquid-like. This transition usually occurs
within a range of stresses, in which the material exhibits viscoelastic
behavior [41,42]. Most coatings show apparent yield behavior where
the viscosity can precipitously drop several orders of magnitude over a
narrow range of stress.
Typical flow characteristics of some commercial paints are given in
Table 6. The data are obtained at the same shear rate using a Stormer-
Fig. 10. Flow curves of latex paints using CSS rheometer in steady state test [2] type concentric cylinder rheometer. The paints all have viscosities of
10
Table 6 “water”). A dilution plot of a latex paint is indicated as “latex” for

Flow properties of some commercial paints [43] comparison.
Product Viscosity, η/Pa Yield value, σ0/ Degree of The linear curve of “tert-butyl alcohol” indicates a typical polymer
s Pa thixotropy solutions with good solvents. In latex paints, polymer particles and
Enamel, gloss 0.14–0.39 0–3 Nil to slight pigment particles are suspended in aqueous phase, and the rheological
Enamels, semi-gloss 0.10–0.35 5–12 Slight behavior can be described by Krieger-Dougherty equation (Eq. 4). Only
Flat or matte paints 0.06–0.10 2–10 Slight to marked at larger than about 50 % v/v polymer has lower viscosities than
Wall water 0.02–0.14 1–10 Slight to marked pigment, because the deformation of polymer particles leads to a larger
dispersible
Primers, metal 0.03–0.12 0–10 Nil to marked
packing density at maximum packing.
Varnishes 0.09–0.29 0 Nil The “water” curve in Fig. 11 shows complex rheological behavior.
Addition of water first separates the ion pairs of the polymer, resulting in
sharply decreasing viscosity. Secondly, more water causes the polymer
<0.4 Pa⋅s and yield values not exceeding 12 Pa [43]. separate out from the dispersion to produce swollen clusters. The
swollen clusters orient along the shear field, displaying low viscosity.
6. Waterborne coatings Thirdly, further dilution makes more polymer enter the swollen clusters,
and then collision of swollen clusters forms aggregates, yielding a
The pressure to reduce air pollutants promotes development of pseudo polymeric network, exhibiting the maximum viscosity. Finally,
waterborne coatings. The widely used waterborne coatings are latex further dilution causes more solvent enter water phase, producing less
paints and water-reducible dispersions whose polymers are dispersed in deformable clusters, the viscosity decreases rapidly [3]. In a word, the
water in the form of viscous particles. Latex particles are dispersed with change in volume fraction and swelling degree of swollen clusters
the help of surfactants, while water-reducible resins are often prepared determine the viscosity profiles of the dispersions on dilution.
in organic solvents, and hydrophilic groups are introduced into the
resins as internal emulsifiers [3].
6.2. Water dispersions
6.1. Rheological behavior of waterborne coatings The complex rheological behavior of water dispersions comes from
ionic interaction and the presence of swollen clusters.
A 54 % tert-butyl alcohol solution of carboxyl acrylic resin with 75 %
neutralization degree is prepared. When the solution is diluted by water, (1) Concentration of dispersions
it becomes a dispersion. When the solution is diluted by tert-butyl
alcohol, it is still a polymer solution. Fig. 11 shows influence of dilu The change in modulus of polyurethane dispersions (PUDs) on
tion on the solution (solution “tert-butyl alcohol” and dispersion dilution is shown in Fig. 12. At PU ≤ 42 wt%, the frequency-dependent
dispersions have much lower G′ than G′′ . At PU ≥ 44 wt%, the disper
sions behave as critically gelling systems. The 44 wt% dispersion shows
a liquid-like consistency, while the frequency-independent PUD with 46
wt% has Geq, becoming an elastic gel [44]. Thus, dilution by adding
more water makes the PUD undergo the transition from an elastic gel to
a fluid.
In the water dispersions, hydrophilic groups of polymer is on the
surface of viscous particles, whereas the hydrophobic chains are within
the particles [3]. At very high solids, the viscous particles are close to
each other, the counter ions of hydrophilic groups attract polymer
chains together, forming an elastic gel, exhibiting gelation at high solids.
(2) Master curve
Fig. 12. Modulus change of PUDs with polymer concentration [44](x-Axis is

shifted to higher frequency range by a factor “a” ranging from 1 to 10
Fig. 11. Dilution viscosity curves of acrylic solution, dispersion and latex [30] for comparison).
11
Master curve can predict rheological behavior under deformation The molecular weight of AT is in the range of 103–104 g/mol, which
and flow conditions that are experimentally inaccessible. The master does not significantly increase viscosity of latex paints. The typical AT’s
curve of PUDs have been constructed based on oscillatory measure include hydrophobic alkali-swellable polymer [HASE], hydrophobically
ments. Zero-shear viscosity η0 can be calculated by fitting complex vis modified hydroxyethylcellulose [HMHEC], and hydrophobically modi
cosity η* vs ω data to Cross model (Eq. 5): η0 = η*[1 + (ω/ωC)β], where fied ethoxylated urethane [HEUR].
ωC is critical frequency, β is material constant. In Fig. 14(a), the hydrophobes of most HEURs adsorb to colloidal
The calculated parameters (η0, ωC, and β) are used to construct the surfaces of hydrophobic polymer to create a repulsive layer, while the
master curve of PUD by normalizing relative viscosity (ηr) by η0 and ω by minority of HEURs bridges the polymer colloids together into a tem
ωC for each concentration [45,46]: porary network [50]. The hydrophobe–hydrophobe association created
( )β by AT molecules decreases water mobility, thickening the systems [51].
ηr ω In Fig. 14(b), the two types of thickeners produce different pigment
=f (10)
η0 ωC flocs by using stress ramp curves [52]. The cellulosic-thickener HEC
promote formation of DLA floc structures, while an associative thickener
where f(ω/ωC)β is assumed to be independent of molecular weight,
produces RLA floc structures [53]. The DLA process produces a loose,
concentration and temperature.
open floc structure with lower fractal dimension (F) by using the
The master curve of PUDs in Fig. 13 is similar to the shear-thinning
cellulosic thickener. The DLA floc easily breaks down under shear to
curve in Fig. 1. There is a plateau at small frequencies (or low shear rate)
smaller flocs, showing a high initial viscosity that decreases steeply over
followed by shear-thinning region at higher frequencies. This suggests
a small range of stress.
that the orientation and motion of swollen clusters in the water dis
The RLA process produces a dense, spherical floc structure with
persions have similar rheological effect to that of the entangled poly
higher F. The RLA floc gradually breaks down under shear to smaller
mers in polymer solutions.
flocs, showing a low initial viscosity that decreases gradually over a
As for modified PUDs, incorporation of water-soluble lignosulfonate
wide range of stress [53]. The influence of non-AT and AT on application
with a rigid structure into castor oil-based polyurethane enhances me
of latex paints will be discussed in Section 7.2.
chanical and thermal properties, and the dynamic viscosity increases
significantly with increasing lignosulfonate content [47].
Samy A. Madbouly and Joshua U. Otaigbe systematically investi 6.4. Configuration of polymer in solutions
gated rheological behavior of PUDs and presented an excellent review
[45]. Now PUDs can be prepared and used in a controlled and repro Chain configuration of polymer in solutions can be characterized by
ducible manner. C*[η], the product of intrinsic viscosity and boundary concentration
where polymer coils start to entangle.
6.3. Latex paints Guar gum [GG] as one of the most effective natural thickeners has
been chemically modified to overcome its incomplete hydration at room
As for latex paints, viscous polymer particles suspend in aqueous temperatures and a poor clarity of solution. Its derivatives used include
media, which causes two issues: (i) pigments settling due to low vis hydroxypropyl guar [HPG], hydroxypropyl-methyl guar [MHPG] and
cosity of water; and (ii) poor levelling ascribed to the presence of latex methoxyl guar [MG].
particles and pigment particles. Both of the issues can be solved by
selecting thickeners. In fact, suitable thickeners imparts good pigment
stability, good levelling and high fullness to latex films.
There are non-associative thickener (non-AT) and associative thick
ener (AT). They have different thickening mechanisms. Non-AT with
molecular weight in the range of 105–106 g/mol contains many hydroxyl
groups along its molecular chains, such as hydroxyl ethyl cellulose
(HEC) or guar gum. The unusually high viscosity of non-AT in water
come from the large hydrodynamic volume in solution and its entan
glements [48,49].
Specific viscosity, ηsp = ηr − 1, is obtained by capillary viscometer,
suggesting that the internal friction effect between solvent molecules
has been deducted. A plot of logηsp vs logC in Fig. 15 is obtained using
rotational viscometer, where C indicates concentration. In the dilute
region, ηsp increases linearly with concentration by ηsp~C5/4, but at
higher concentrations, the gradients shift to much higher values
(ηsp~C15/4). The critical concentration (C*) can be assumed as the
boundary concentration of the two regions where polymer coils start to
entangle.
The C* is sensitive to the intrinsic properties of polymers, such as
chain stiffness and solvent-polymer interaction. The lower C* values of
GG and MHPG in Table 7 suggest a more expanded chain configuration.
Intrinsic viscosity [η] is the viscosity at the solution concentration
close to zero, and the [η] measured by capillary viscometer is propor
tional to the hydrodynamic volume of each chain. Since concentration C
is proportional to the number of chains present in the solution, C[η] is
the occupied hydrodynamic volume of all polymer chains. The insert of
Fig. 15 shows the well-defined linear dependence of ηsp as a function of
the product C[η] in all the concentration regime.
Since the C*[η] value, regardless of the molecular weight, is an index
Fig. 13. Master curves of PUDs [45] of the total volume occupied by all coils at the boundary concentration,
12
Fig. 14. Thickeners in latex paints.
following Section 8.
Steady state means that all transience has died away. The steady-
state metrics used for describing coatings are shear thinning behavior
or dynamic yield stress. When they are used to describe instantaneous
properties in coating application, the results are questionable at best and
misleading at worst. Thus, coating application mainly employs transient
rheology and oscillatory rheology.
7.1. Screen printing
Screen-printing technique is used to prepare thin films used in high

tech fields, such as solid oxide fuel cells (SOFC) components of electrode
and electrolyte. The films with thickness in the range of 10–100 μm are
prepared by pressing an ink through a mesh in contact with the
substrate.
Screen printing process begins with the flooding step, in which the
ink is distributed evenly across the screen via a flood bar. The screen-
printed ink need to be sufficiently fluidized in the flooding step so that
Fig. 15. Specific viscosity vs concentration (C) plots of guar gum and its de
it fills the openings on the screen backside without dripping through.
rivatives solutions [34]
When a squeegee applies pressure against the screen, the screen touches
the substrate, and the ink is transferred onto the substrate. The screen
Table 7
springs immediately back after the squeegee has passed.
Parameters of guar-gum and its derivatives [54]
(1) Transient rheology
Mw [η] C* C* [η]
Guar gum 2.4 × 106 8.5 0.25 1.91 For the screen-printed zirconia-based inks, doped zirconia is
Methoxyl guar 2.6 × 106 8.5 0.35 2.95
dispersed in vehicles of terpineol and ethyl cellulose. The contents of
Hydroxypropyl guar 5.0 × 106 4.7 0.43 2.0
Hydroxypropyl-methyl 1.0 × 106 7.4 0.30 2.95 ethyl cellulose are 0, 0.14, 0.36 and 0.50 vol%, while that of ZrO2 is
about 36.5 vol%, and terpineol content is about 55 vol% [55]. Two
transient rheological experiments, shear jump test and creep experi
it is a better index than C* for characterizing chain configuration. The ment, are performed for the inks.
higher C*[η] values of methoxyl guar and hydroxypropyl-methyl guar in In Fig. 16(a) of shear jump tests, the inks undergo 120 s preshear at
Table 7 suggest that introduction of methyl groups leads to the coil 0.1 s− 1, followed by 120 s rest, the shear rate jump sequence is 1, 10, 1,
shrinkage [54]. 100, and 1 s− 1. After each shear rate jump, the 120 s rest is the period of
Since the guar derivatives form water solution and the C*[η] values structure rebuilding. Shear rate jump from 10 s− 1 to 1 s− 1 is selected to
are used for comparing chain configuration, these suggest that C*[η] as a fit the formula:
criterion can be used for comparing the chain configuration of polymer
used in solventborne coatings. σ = σs [1 − exp( − Kt) ] − η∞ γ̇exp( − Kt) (11)
where σ s is steady-state shear stress, and K is a fitted coefficient which

7. Coating application
provides recovery rate.
In Fig. 16(b) of creep experiments, when a constant stress is applied
Film formation processes include application (e.g., rolling, spraying)
on an ink at t1, the strain J (= γ/σ, Pa− 1) is followed as a function of time
and post application (e.g., levelling, sagging). Perfect coating films
for a period of t. At t2, the stress is removed, and the strain J is followed
require a high degree of flow control over application and post appli
for another period t until t3. The extent of recovery R (%) is given by R
cation. How to achieve this goal is discussed in the Section 7 and the
(%) = (JOR/J3) × 100, and the deformation is indicated as [(J3 − J1)/J3].
13
sintering.
(2) Sequence of physical process (SPP) approach
In conventional oscillatory tests, the time is equal to 2π/ω for 1 cycle

of oscillation. The timescale of 10 rad/s is 0.63 s. Since several oscilla
tions need to be performed before the response is even recorded and
analyzed, the time resolution of the oscillatory test is on the order of
6–10 s at a frequency of 10 rad/s. However, the resolution are not suf
ficient to characterize the fast transfer process (on the order of milli
seconds) in screen printing.
A new oscillatory technique, called sequence of physical processes
(SPP) approach, has been developed and used to characterize the screen-
printed inks [57]. The SPP approach combines large oscillatory ampli
tude sweep (i.e., beyond the linear viscoelastic regime) with transient
viscoelastic response. The transient response is obtained by using a
numerical differentiation method. The large oscillatory amplitude cau
ses the microstructure undergo orientational and conformational
changes, resulting in complex nonlinear flow behaviors.
The test protocol is three consecutive oscillatory steps at a fixed
frequency, with the strain amplitude of the first step at the maximum
extent of the linear viscoelastic regime. The strain amplitude in the
second (e.g., the high strain condition) is chosen, for example, so that
tan(δ) is either 0.5 or 1. The third step returns to the same linear con
dition as the first step in Fig. 17(a). The GX is crossover modulus
(G′ =G′′ ).
When a sinusoidal strain input is applied on the sample, transient
response is determined by an ARES G2 strain-controlled rheometer via
transient data collection mode of TA Instruments’ TRIOS software
[57,58]. The resolution is limited only by the data acquisition time, and
then the SPP approach can gain information at microsecond level.
Fig. 16. Transient rheological measurements of zirconia inks for screen print
The meanings of the terms used for the transient response in
ing [55]
nonlinear regime are not exactly the same as those used in traditional
rheology. The term “yielding” here refers to inelastic deformation of
A stress of 2 Pa is applied for 120 s, and the recovery is monitored for
solids, while the “reformation” or “recovery” suggests forming stress-
120 s, while frequency sweeps are conducted at a stress amplitude of 1
bearing structures or jamming (i.e., shear thickening). For the screen-
Pa [55]. The obtained results of transient rheology and the results of
printed inks, yielding is a very fast process (~20 ms), while recovery
oscillatory tests are listed in Table 8.
is a slow process (~200 ms).
A higher recovery rate suggests the presence of a stronger elastic
Transient moduli are thought of as partial derivatives of the stress
network structure. With increasing ethyl cellulose content, the rate of
with respect to strain and strain rate, respectively. Fig. 17(b) represents
recovery R(%) and extent of recovery (K) increase, but deformation (J3
transient stress responses to an oscillatory strain where tan(δ) = 1 and at
− J1)/J3 decreases. At higher binder content, stronger network struc
a frequency of 10 rad/s.
tures are formed and the ink is less deformable, suggesting stronger
In Fig. 17(c) of Cole–Cole plot, the frequency is parametrically
adhesion within the ink. However, the stronger adhesion leads to stencil
eliminated. The deltoid red solid line exhibits the change in the transient
clogging, a reduction in ink “rolling,” and an increase in the extent of
G′ and G′′ . In linear regime, each point in a Cole–Cole plot marks the
missing prints. It is observed that the surface roughness and thickness of
response of an entire oscillation and the red deltoid is absent. In non-
the screen-printed films increase with increasing binder content. Zir
linear regime, the larger the amplitude applied, the larger the deltoid
conia ink containing 0.14 vol% binder shows superior screen-printing
area.
performance [55].
Fig. 17(d) shows Cole–Cole plots of two commercial screen-painted
A review [56] summarizes the correlations between ink rheology and
inks (stiff sample A and soft sample B) where tan(δ) = 0.5 [59]. The
properties of screen-printed films for SOFC components [56]. The inks
shaded gray area represents solid-like region. The average moduli ob
must have satisfactory thixotropic properties for improving surface
tained from normalized moduli (G′ /GX and G′′ /GX) pierce through the
evenness of the films, while oscillatory properties are used to evaluate
boundary at a shallow angle. The instantaneous moduli curves have
particle network strength within the inks. Electrolyte ink with a com
three separate transitions: yielding (apices 1 to 2); recovery (apices 2 to
bination of a high solid content (>30 vol%) and a low binder content
3); and hardening (apices 3 to 1). In the yielding step, there are a rapid
(<1 wt% of powder) is used to produce a dense film with minimum
decrease in G′ and a moderate increase in G′′ , suggesting that the
defects. Electrode ink with a higher binder content (>1 wt% of powder)
yielding transition is dominated by structural breakdown. The recovery
is preferred to improve the film porosity after the binder burnout during
Table 8
Rheological properties and screen-printing properties of zirconia inks [55]
Binder content Deformation, (J3 − J1)/J3 K (1/Pa) R (%) η(0) (Pa⋅s) tanδ G* (Pa) Stencil clogging Ink rolling Missing Slumping
0 0.990 0.222 3.36 53 1.28 106.5 Good Good Good Bad

0.14 0.754 0.057 60.2 1.4 × 104 0.57 267.9 Good Good Good Good
0.36 % 0.669 0.118 80.9 8.0 × 104 0.40 628.3 Good Bad Good Good
0.50 % 0.657 0.179 93.3 1.2 × 104 0.40 849.6 Bad Bad Bad Good
14
Fig. 17. High shear recovery test by amplitude sweep and transient moduli response [57]
indicates a steep decrease in G′′ , while the hardening transition shows a difference in rheological properties by the high time resolution. First,
rapid increase in G′ . since sample B has faster recovery rate, it will maintain line shape much
Fig. 17(e) shows a full view of amplitude sweep from the projection quicker after the ink transfer step. Secondly, sample A shows stronger
of Fig. 17(b). At the low frequency regime, the point of maximum strain hardening than sample B, and then sample A cannot transfer well
is the reversal point of strain around (apex 1), where the strain rate is through the line opening, resulting in more line discontinuities [57].
close to zero. When the strain is close to zero, the strain rate approaches
to a maximum. The recovery occurs during the process of an increase in 7.2. Roll and spray application
strain rate, while the hardening transition occurs with a decrease in
strain rate. Yielding transition begins at (apex 1) shortly after the ma Complex flows like forward roll coating and spraying generate
terial passes the point of maximum strain and is followed sequentially by droplets via the extension and breakup of filaments. The term “pinch-
the recovery and hardening transitions twice within the course of a off” refers to final breakup of fluid fibers.
period of oscillation. During spray painting, small coating droplets are generated, which is
Fig. 17(d) and (e) shows that the SPP approach developed by Rogers referred to as atomization. The smaller the paint droplets, the better the
SA [59] provides a quantitative method to identify when, and by how appearance and quality of the paint films. Since solventborne coatings
much, a material response stiffens, softens, thickens, or thins while that often use oligomers as the binder, and various high-efficiency
being deformed. atomizing equipment can be selected and used for spraying applica
Two commercial inks, samples A and B, are used in fine line printing. tion, rheological properties of the thermoset coatings will no longer pose
Stiff sample A produces slightly more line imperfections such as peaks a problem for atomization. For example, an electrostatic rotating bell
and valleys and discontinuities than soft sample B. They are quite similar atomizer combining compressed air technique and high-speed rotating
in the linear regime, but the SPP approach tests distinguish their bell technique promotes atomization [60,61].
15
For roll coating, elongated fibers break at one or more points extensional relaxation time, namely, a high extensional viscosity [72].
generating tiny droplets, known as misting or spatter. The spatter ten Thus, extensional viscosity can be tuned by changing the ratio of stiff AT
dency of paint is qualitatively assessed by ASTM D4707.4 to flexible AT.
Extensional viscosity and the elastic modulus in nonlinear regime are
used to investigate roll spatter and spray atomization of coatings, (2) Storage modulus in nonlinear zone
especially latex paints.
Droplet formation is related to extensional elasticity. Storage
(1) Extensional viscosity modulus and first normal stress difference of latex paints govern elas
ticity of filaments, but normal stresses have no correlation with spatter
Extensional relaxation time is the time constant of an exponential ratings [73,74]. Storage modulus of latex paints can be tuned to promote
return of a system to equilibrium after a disturbance. The longer the filament breakup and suppress spatter [75]. However, for high-speed
relaxation time, the stronger the elasticity of the system. Low exten deformation of coatings during application, the used elastic modulus
sional viscosity requires the extensional relaxation time to be as short as should be in nonlinear zone and it is frequency-dependent.
possible. There is an inverse correlation of frequency-dependent elastic
The measurements by Dripping-onto-Substrate (DoS) rheometry5 modulus (2 Hz) with observed spatter resistance of latex paints thick
indicate that extensional flow field results in progressive stretching and ened with HEC and HMHEC [76]. That is to say that the low elastic
orientation of polymer in semi-dilute poly(ethylene oxide) (PEO) solu modulus retards spatter.
tions shown in Fig. 18(a). The terminal extensional viscosity value is The elastic modulus outside the linear viscoelastic regime (i.e., strain
reached before all the chains are completely stretched out. amplitude of 10 %) at a frequency of 1 rad s− 1 is used to investigate
In Fig. 18(b) extensional viscosity increases with both polymer spatter of latex paints with Stormer viscosity in the range of 95–110 KU.
concentration and molecular weight [62]. Moreover, the extensional At the same volume solids, the higher the elastic modulus, the more
viscosity is orders of magnitude larger than the shear viscosity in dilute observed spatter [77], which agrees with the test results [76]. But when
polymer solutions [63]. Latex paints are dilute solutions of thickeners, the volume solids vary for the same paint, the observed spatter increases
and the effect of thickeners on extensional viscosity is very important for with decreasing the elastic modulus [77].
latex paints, especially using high molecular weight non-associative In addition to roll spatter, the elastic modulus outside linear regime
thickeners. High extensional viscosity leads to spatter and poor atomi is used to investigate spray atomization [77].
zation of latex paints.
In roll application, excessive spatter correlates with high extensional (3) Glass flake
viscosity, especially for cellulosic-thickened paints [64]; roll spatter can
be prevented using fluids with low extensional viscosity [65]. In general, low extensional viscosity suggests good atomization, but
In spray application, the formulations with higher extensional vis glass flake has opposite effects on extensional viscosity and spray
cosity have lower degree of atomization for latex paints [65]. When atomization.
extensional viscosity is measured by a liquid jet breakup technique and Fig. 18(c) shows that filament thinning time increases with
dilute aqueous PEO solutions are sprayed by air-assisted atomization, a increasing concentration of aluminum flakes for waterborne automobile
decrease in extensional viscosity leads to a decrease in the particle sizes basecoats by Capillary break-up extensional rheometry (CaBER)6 [72].
[66]. When glass flakes are dispersed in an alkali-soluble acrylate associative
Associative thickeners (ATs) have lower extensional viscosity than thickener solution, 3.5 vol% of glass flakes results in a 4-fold increase of
non-associative thickeners due to their lower molecular weights. Thus, the extensional relaxation time without significantly affecting the shear
ATs reduce spatter of latex paints, though at a cost penalty. The hy flow properties [72]. However, although adding glass flakes into latex
drophobic groups of ATs form intermolecular associations or micelles paints increases extensional viscosity, flake-shaped pigment particles
with hydrophobic latex particle surfaces, creating thickening effect within coatings act as breaking points inside the ligaments, improving
[67,68]. The hydrophobes have rapid viscoelastic stress relaxation so atomization [78].
that extensional stresses fast decay, which limits the formation of long The above-mentioned SPP analysis [59] as a new technique can gain
liquid fibers that produce excessive spatter [69,70]. insights about transient viscoelastic response, but the responses are
Stiff AT has a lower extensional viscosity than flexible AT [71]. For different at low, medium, and high frequency regions. When the SPP
two alkali-soluble acrylate associative thickeners, addition of the flex approach is used to investigate roller spatter and spray atomization, it
ible AT into the solution of the stiff AT leads to a significant increase in should first find out the ranges of strain and stain rate that can correlate
the SPP test results to the application methods.
4 8. Levelling and sagging

The test paint is applied on nonabsorbing Leneta paper [42 cm × 16.5 cm]
with 150 μm wet film thickness applicator. Immediately after application, the
paper is mounted on a vertical wall, following which 10 cycles of the notched
High end coating films (glossy films with a high quality appearance)
spool roller are completed over the wet paint film in approximately 20 s to require a high degree of control over film formation processes, especially
generate the spatter. The spattered paint is collected on a nonabsorbing paper levelling and sagging. Sag results from gravity driven flow, and this flow
and left to dry. After natural drying, the spatter droplets are rated on the scale causes unsightly accumulation of coating at substrate edges and ac
of 0–10 by visual observation. Due to the qualitative nature of ratings, they are centuates imperfections in the substrate itself [2].
person-specific. Sagging and levelling performance of coatings can be empirically
5
DoS rheometry protocol is that the fluid is pumped at a low and fixed flow
rate through a nozzle that has an outer and inner diameter respectively. A finite
volume of the liquid is released onto a substrate at a fixed distance H below the
6
nozzle, and the aspect ratio selected is H/D0 = 3. A stretched liquid bridge is In CaBER experiment, a fluid drop is placed between two plates and sub
created between the nozzle and a sessile drop on substrate. The liquid bridge sequently exposed to an extensional step strain thus forming a liquid filament. A
undergoes capillary-driven instability and thinning followed by the pinch-off at CaBER extensional rheometer is equipped with plates of diameter D(0) = 6 mm.
the necked region of fluid. Movies of the self-thinning process are captured, and Plate separation is changed (e.g. from Linitial = 6 mm to Lfinal = 16 mm within
the neck radius is determined for analyzing thinning and pinch-off dynamics. If 40 ms) so that the necking of liquid bridge is controlled by the balance of
the fluid can wet the nozzle, the outer diameter of nozzle (D0) is used for scaling capillary and viscoelastic forces. The only measured quantity during filament
the neck diameter. necking is the change in the midpoint diameter D(t) with time.
16
Fig. 18. Measurement of extensional rheological properties of polymer solutions.
characterized by Leneta flow test.7 The frequently-used method for (1) Sagging
characterizing sagging and levelling performance is falling wave method
shown in Fig. 19(a). Paints are applied onto a substrate with a well- Sagging occurs at low shear rates, which is confirmed by the
defined initial surface roughness, created by using a sinusoidal rippled following example. The elastic moduli of polyurethane paints are
application bar. The inclined angle of substrate and coating thickness determined by amplitude sweep at 10 rad/s in the linear regime. There is
are variables in falling wave method. At smaller inclined angles, the a linear correlation (R2 = 0.94) between Anti-Sag Index from Leneta
resolution is greatly enhanced owing to a reduction in the shear stress flow test and elastic moduli G′ measured immediately after pre-shear at
difference between adjacent coated lines [79]. a shear rate of 1000 s− 1 for 1 min [81]:
(12)
′
8.1. Influencing factors and models Anti − Sag Index = 0.19G + 4.0
Since the G used for characterizing gel strength occurs at low-
′
An early study outlines basic requirements for levelling and sagging frequency region, Eq. 12 suggests that sagging occurs at low shear
of latex paints. Latex paints with low yield stress (<0.25 Pa) exhibited rates. Similarly, the other parameters for characterizing gel strength can
better levelling, while those with higher values of low-shear viscosity also be used to predict sagging, such as η(0), low-frequency tanδ < 1,
showed better sag resistance [80]. cross-over modulus and Ec.
In case of checking for consistency in sag resistance between batches
of the same coating or ranking sag resistance of different coatings, the
measurements should be carried out at the smallest permissible angle in
7
Fig. 19(a). When the test is used to identify initial thickness range for
Leneta blade has eleven engraved slots of graduated depth from 4 to 24 mils
sag-free coating, it should run at angle of intended application [79].
in 2-mil increments, so that paint stripes of varying thickness are produced,
roughly equal in thickness to half the slot depth. Paints were drawn down on
Leneta sag and levelling test chart of 194 mm × 289 mm dimension using (2) Levelling
levelling test blade. The flow-levelling is evaluated by visually comparing the
dried drawdowns with Leneta levelling standards in ASTM D4062. Extent of A paint film with a well-defined initial surface roughness created by a
levelling is rated in a flow-levelling index scale of 0–10 where 10 indicates sinusoidal rippled application bar in Fig. 19(a). Orchard equation is used
complete levelling. After drawdown, the substrate is hung vertically to allow to describe levelling process of a wet horizontal sinusoidal film on a
sagging flow. Sag index (highest thickness of the stripe where no visual sag is smooth substrate shown in Fig. 19(b).
noticed) was then noted down according to ASTM 4400. An Anti-Sag Index (or
Sag index) is referred to as the notch depth of the thickest of a stripe that has
resisted crossing the spacing to touch the next lower stripe.
17
Fig. 19. Measurement methods for levelling and sagging.
a low shear rate (0.1 s− 1) period of 200 s followed by a high shear rate
∫
a0 16π 4 σ h3 dt
(13)
(500 s− 1) interval lasting 60 s, and then recovery period of 200 s at 0.1
ln =
at 3λ4 η
s− 1. The influence of contents of rheology modifier and pigment type on
where average film thickness is h, low viscosity η, high surface tension σ , the degree and rate in viscosity recovery after removing the high shear
wavelength of sinusoidal model λ; a0 is initial amplitude, and at is final rate is investigated [84].
amplitude. The levelling standard is divided into 9 grades. The best
levelling grade (at = 0.5 μm) is that at which the surface disturbances (2) Quantitative application of falling wave method
cannot be perceived by the human eye [3].
Levelling is favoured by a small wavelength (λ), low viscosity (η), Rheology modifiers used are called thickeners in latex paints and sag
high surface tension (σ), and high film thickness (h). During levelling, control agents (SCAs) in solventborne coatings. Coatings containing
the viscosity increase by several orders of magnitude causes the greatest SCAs maintain a low viscosity for a short time after application, thus
influence on the final amplitude. Solvent evaporation results in allowing good levelling, but thicken fast enough to prevent sagging.
shrinkage of film thickness and of amplitude, which contributes signif Falling wave method can quantitatively describe levelling and sag
icantly to the final amplitude. However, the influence of gravity and ging so that it can identify the cause and nature of a poor coating
surface tension change during flash-off period on the final amplitude can appearance caused by flow. The SCA (di-urea of HDI and benzylamine)
be neglected [82]. is added into an automotive clearcoat [85]. The degree of levelling is
described by (lnat/a0). The plot in Fig. 20(a) shows that under same
levelling degree, the clearcoat with 1.1 % SCA requires much less total
8.2. Rheological measurement film flow than the clearcoat without SCA.
The wave-shift (movement of the waves towards the panel bottom) is
In addition to empirical Leneta flow test and falling wave method, denoted as degree of sagging. The plot of wave-shift vs time in Fig. 20(b)
sagging and levelling performance of coatings can be characterized by shows that the clearcoat with 1.1 % SCA stops sagging in <150 s (2.5
simple 3ITT. The film levelling after spray application is also studied by min), while the clearcoat without SCA keeps sagging until 900 s (15
numerical simulation. min). Thus, the coatings containing SCAs maintain a low viscosity for a
short time after application, thus allowing good levelling, but thicken
(1) Three interval thixotropy test (3ITT) fast enough to prevent sagging. The coatings containing SCA is called
thixotropic coatings or high build coatings.
3ITT consists of two different deformation types, imposed by a Falling wave method is also used to investigate sag and levelling in
change in shear rate or shear stress. A typical 3ITT curve in Fig. 19(c) powder coatings [86], but the quantitative test is laborious and time-
presents an empirical prediction for levelling and sag resistance. A latex consuming.
paint is subjected to three different shear rates in a stepwise fashion for a
defined time: ① 0.01 s− 1 for 100 s, ② 3000 s− 1 for 100 s and ③ (3) Numerical simulation
switching back to 0.01 s− 1 for 300 s. The viscosity instantly drops once
high shear rate is applied, and the subsequent viscosity recovery after A numerical simulation program has been developed for investi
high shear is removed indicates rheological properties of the latex gating film levelling after spray application [87]. Since it is beyond
paints. coating rheology scope, it is simply introduced. There are two compli
The concept “percent viscosity recovery” is widely used in 3ITT, but cated cases handled by the numerical simulation:
100 % recovery may fail in Leneta sag test, because it only correlates
with degree of viscosity recovery. Correct prediction of levelling and sag (a) solvent evaporation The evaporation rate of solvents is deter
behavior requires both degree and rate in the viscosity recovery after mined first by solvent transport in the gas phase and followed by
removing the high shear rate. The 100 s is a reasonable time for the paint solvent diffusion inside the film. When the viscosity change with
to flow completely. The viscosity after 100 s recovery is indicated as η100 time is expressed as the form η = k1 exp (k2t) + k3 exp (k4t), the
s. The difference in viscosity during recovery at 100 s and 10 s, (η100 s − error between the calculated and the measurement amplitudes is
η10 s), is used as a measure of recovery rate in viscosity. The empirical only 5 %.
rheology limits for good flow-levelling and acceptable sag resistance are (b) thixotropic coatings The dependence of moduli on frequency is
36 < η100 s < 70 Pa s and 28 < (η100 s − η10 s) < 47 Pa s for cellulosic measured by frequency sweep in linear viscoelastic region to
thickener (HEC) based latex paint; the limits are 3 < η100 s < 13 Pa s and obtain the relaxation time spectra of a thixotropic coating. The
2 < (η100 s − η10 s) < 6 Pa s for HEUR thickener based paint [83]. relaxation time spectra are used to calculate the levelling
3ITT is also conducted on solventborne acrylic paints. The protocol is
18
Fig. 20. Measurement of levelling and sagging by falling wave method [85]
viscosity and levelling velocity of the coating [87]. The simula 9. Conclusion
tion results agree with the experimental results.
Organic coatings are generally low-viscosity, multi-component sys
Three additional sub-programs in numerical simulation program tems. For polymer solutions, shear thinning behavior comes from
were applied to calculate the behavior of multilayer systems, e.g., paints orientation of entangled polymers and strong interaction among the
with skin formation or wet-on-wet systems, and the formation of corner chains. Pigment particles have strong interaction with polymer chains in
defects [88–90]. paints, greatly increasing the viscosity, while dispersants form a repul
sive barrier around dispersed particles to decrease the viscosity.
8.3. Experimentally selecting SCAs Rheology modifiers used are called thickeners in latex paints and sag
control agents (SCAs) in solventborne coatings. Rheological methods are
The type and dosage of SCAs can be selected by rheological tech extracted from the references to establish reliable correlation between
niques. Various SCAs with a concentration of 0.6 % are incorporated the parameters and coating performance. The correlations between
into epoxy primer and polyurethane topcoat [91]. The rating for rheological parameters and coating performance set a framework for the
pigment settling is performed in an oven stability test at a temperature of coating rheology that handles fundamental issues of organic coatings.
53 ± 2 ◦ C for 10 days. Sag resistance is expressed by the wet film
thicknesses (in μm) that can satisfy the requirements for sag resistance. (1) The parameters used for characterizing gel strength are low-
The test results in Table 9 are used to evaluate anti-settling and anti- frequency G′ and tanδ, cross-over point (tanδ = 1), zero shear
sagging properties of paints. 3ITT test and low-frequency G′ correlate viscosity η(0), and cohesive energy (Ec). They can predict rheo
well with the observed storage and application properties for both logical properties of very slow flow processes, such as pigment
paints. settlement, sag.
For epoxy primers, the overall performance of surface-modified clay (2) At gel point the coating systems have Geq and follow Winter
is better than other additives. Similarly, for PU paints, the polyurea- Chambon criterion. Fractal dimension can be calculated from the
based SCA shows the best results. frequency-independent behavior at gel point. Fractal analysis can
identify fractal structures of pigment flocs and formation mech
anisms of the flocs. To use fractal analysis for coatings, it is
required to select suitable medium environments for the
Table 9 dispersed particles. Because the medium environments determine
Influence of sag control agents on paint properties [91]. whether fractal networks form and which formation mechanism,
Sag control Low shear viscosity Rating for anti- Sag resistance (wet
DLA or RLA, to take. Stress ramp curves in Fig. 14(b) show typical
agents (Pa⋅s) settling (10 = best, film thickness in features of DLA flocs and RLA flocs, and they can be used to
0 = worst) μm) identify the formation mechanisms of the flocs.
Epoxy PU Epoxy PU Epoxy PU (3) During curing process, the change in elastic modulus G′ and
primer topcoat primer topcoat primer topcoat inclination of G′ -ω plots can be regarded as measurements of
Castor oil 2060 89.5 8 6 500 300 crosslinking density of coatings, although they cannot differen
derivative tiate chemical crosslink and physical gel. DMA follows chemical
Organoclay I 720 3.8 10 8 300 180 crosslink process of solid thermosets, and DiMarzio equation (Eq.
Organoclay II 110 6.3 6 8 150 150 9) is used for characterizing crosslinking density for coatings with
Organoclay 1330 1.9 6 4 250 60
low crosslink density.
III
Polyurea 2300 160 8 10 250 300 (4) Polyurethane dispersions gelate at high concentration regimes,
Surface- 3590 4.3 8 8 500 180 and the master curves can be constructed using Cross model (Eq.
modified 5) to predict rheological behavior under deformation and flow
clay
conditions that are experimentally inaccessible. The complex
Polyolefin 195 0.7 6 6 300 90
Fumed silica 1920 13.0 8 8 300 150
rheological behavior of PUDs on dilution comes from ionic
Polyamide 870 ** 6 ** 150 ** interaction and the presence of swollen clusters.
** Suitable thickeners impart good pigment stability, good
Maximum value in bold.
19
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Progress in Organic Coatings 177 (2023) 107403

Contents lists available at ScienceDirect

Progress in Organic Coatings

Correlations of rheological methods to coatings’ performance

The most used shear rheology is characterized by using a rotary

Fig. 2. Viscosity dependency of solids for poly-p-benzamide in dimethyl acet­

Krieger-Dougherty equation: from experimental data using non-linear regression analysis.

Fig. 4. Oscillatory sweep test.

4. Coating transformations A widespread phenomenon is that small particles tend to stick

G′ (Pa) G′′ (Pa) tanδ η(0) (Pa s) G′ = G′′ (Pa) σ0 (Pa)

Fig. 5. Geq plateau and Winter-Chambon criterion at gel point [21]

Table 5 4.4. Glass transition temperature

Fig. 6. Rheological methods for measuring crosslink density.

5. CSR and CSS rheometers 5.1. Stress ramp loop

Fig. 8. Loop of viscosity vs shear stress [36]

Table 6 “water”). A dilution plot of a latex paint is indicated as “latex” for

(2) Master curve

Fig. 12. Modulus change of PUDs with polymer concentration [44](x-Axis is

Fig. 14. Thickeners in latex paints.

7.1. Screen printing

Screen-printing technique is used to prepare thin films used in high

where σ s is steady-state shear stress, and K is a fitted coefficient which

(2) Sequence of physical process (SPP) approach

In conventional oscillatory tests, the time is equal to 2π/ω for 1 cycle

0 0.990 0.222 3.36 53 1.28 106.5 Good Good Good Bad

4 8. Levelling and sagging

Fig. 18. Measurement of extensional rheological properties of polymer solutions.

Fig. 19. Measurement methods for levelling and sagging.

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Fig. 2. Viscosity dependency of solids for poly-p-benzamide in dimethyl acet