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Predicting Young’s Modulus of Linear Polyurethane and

Polyurethane−Polyurea Elastomers: Bridging Length Scales with
Physicochemical Modeling and Machine Learning
Joseph A. Pugar, Calvin Gang, Christine Huang, Karl W. Haider, and Newell R. Washburn*
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ABSTRACT: Predicting the properties of complex polymeric

Downloaded via UNIV DEL PAIS VASCO on December 16, 2022 at 08:07:54 (UTC).

materials based on monomer chemistry requires modeling physical

interactions that bridge molecular, interchain, microstructure, and
bulk length scales. For polyurethanes, a polymer class with global
commercial and industrial significance, these multiscale challenges
are intrinsic due to the thermodynamic incompatibility of the
urethane and polyol-rich domains, resulting in heterogeneities
from molecular to microstructural length scales. Machine learning
can model patterns in data to establish a relationship between the
monomer chemistry and bulk material properties, but this is made
difficult by small data sets and a diverse set of monomers. Using a
data set of 63 industrially relevant and complex elastomers, we
demonstrate that accurate machine learning predictions are possible when monomer chemistry is used to estimate interactions at
interchain length scales. Here, these features were used to accurately (r2 = 0.91) predict the Young’s modulus of polyurethane and
polyurethane−urea elastomers. Furthermore, by a query of the trained model for compositions that yield a target modulus within the
range of accessible values, the capabilities of using this methodology as a design tool are demonstrated. The presented methodology
could become increasingly useful in building models for materials with small data sets and may guide the interpretation of the
underlying physicochemical forces.
KEYWORDS: Young’s modulus, thermoplastic polyurethane, machine learning, small datasets, multiscale modeling

1. INTRODUCTION heterogeneous and multiphase copolymers. As a result, the

An unmet challenge in polymer chemistry and polymer physics
is predicting bulk material properties solely on the basis of a
knowledge of the monomers and the synthesis conditions,
particularly in predicting properties that emerge across
multiple length scales. Previous multiscale modeling of both
amorphous and semicrystalline polymers has demonstrated the
ability to accurately describe behaviors from the atomic to the
macroscale,1−3 and strategies such as quantum chemical
calculations, molecular dynamic simulations, and continuum
mechanics treatments have provided substantial insight into
the physicochemical basis of many scale-specific phenomena.
However, the primary challenge remains the integration of
these models, in which the predictions must accurately cascade
from molecular constituents to bulk physical properties.
In modeling the multiscale phenomena in polymeric
materials, polyurethanes (PUs) present a particularly signifi-
cant challenge. PUs are structurally diverse and tunable to
many applications, including their use in adhesives, coatings,
rigid and flexible foams, and elastomers in the automotive,
furniture, insulation, construction, sporting goods, and medical
device industries, among others. However, the diversity of
material properties possible for PUs is due to the formation of
variety of competing physicochemical forces within the
material lead PUs to be fundamentally dissimilar from their
polyolefin counterparts, making them an important system for
the development of modeling methodologies.4−6 The micro-
structures of resulting PUs will in part dictate the mechanical
response of the bulk material to an external stress or load, and
here the material’s Young’s modulus (E) is used as an
important property that is modeled. While there have been
numerous works on modeling the linear elasticity and/or
viscoelastic mechanical responses of polymers with continuum
mechanics, many of these models have been derived and
validated for simpler single-phase homopolymer (polyolefin,
polyester, etc.) systems and thus have limitations in the
treatment of complex heteropolymers.7,8
Received: December 21, 2021
Accepted: March 14, 2022
Published: March 30, 2022

© 2022 American Chemical Society https://doi.org/10.1021/acsami.1c24715

16568 ACS Appl. Mater. Interfaces 2022, 14, 16568−16581
ACS Applied Materials & Interfaces
Figure 1. Polyurethane elastomer microstructure illustrated as a colored schematic. The legend in the bottom right corner of the figure identifies
each unique chemical structure in the polymer morphology.
In this study, we focus on one particular class of PU, linear
polyurethane and polyurethane−polyurea elastomers. In the
interest of brevity, we will at times refer to these systems
simply as polyurethanes or PUs, but it should recognized that,
in cases where a diamine chain extender was employed, they
are actually polyurethane−polyureas. Like many PU systems,
these materials are incompatible with many theoretical
investigations of viscoelasticity because they do not have a
defined homogeneous reference state and microphase
segregation alone has not been shown to adequately describe
the elastic mechanical response of the system. Other
approaches have used neo-Hookean models with series of
Maxwell elements aimed to combine the differing mechanical
responses, but these do not incorporate the thermodynamic
forces known to be present between the hard and soft
segments.9,10 The mechanical responses in polyurethanes stem
from both enthalpic and entropic forces and consequently yield
a distribution of relaxation and retardation time scales.11
However, the development of a model which is parametrized
by experimentally tunable variables, such as the chemical
structure of the polymer itself, that adequately captures the
complex modalities which exist on different length scales and
accurately predicts bulk mechanical response has not yet been
demonstrated.
Machine learning (ML) introduces the capabilities needed
to leverage the multiscale modeling of materials and has
become an increasingly popular strategy in the field of material
science.12,13 ML can be used to build predictive models from
sets of training data and learn behaviors and trends in
materials. The conversion of structural information into
chemical and physical parameters to predict material properties
was developed long before the use of data-driven techni-
ques.14,15 Transformations through functional group contribu-
tion methods and the generation of quantitative structure−
property relationships (QSPR) have been used to predict the
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thermodynamic and electronic properties of materials accu-
rately.16−18 More recently, Ramprasad et al. have presented
models that predict bulk polymer properties such as the glass
transition temperature (Tg) and band gap (Eg) and have
captured influential trends such as side-chain length and
aromaticity degree.19,20 In addition to informatics, other
descriptor sources such as quantum chemical calculations,
thermodynamic calculations, and experimental/process varia-
bles have also been used to parametrize training data sets
spanning atomic, micro, and bulk scales.21−23 These additional
strategies can offer a more precise approximation of parameters
and can provide insight into material trends through varying
driving forces and/or using different scales. However, tradi-
tional ML methodologies often rely on large data sets, and the
resulting models are built from a significant number of unique
material instances. Most of these works used data sets of 150+
unique data points (and in some cases 500+), which can be
time-intensive when traditional experimental methods are
used. Building models that incorporate state of the art
multiscale modeling mentioned previously, while not depend-
ing on large data sets to learn from, remains a significant
challenge.
Hierarchical machine learning (HML) is a methodology that
introduces an additional layer of physiochemical latent
variables to traditional input−output ML modeling, creating
a hierarchy of data and providing constraints on the structure
of the response surface. This approach has been shown
previously to overcome problems associated with having a
limited number of training samples by modeling the system
response with parameters describing the underlying forces in
the material.24,25 The model then predicts the responses from
those physical forces (“descriptors” or “features”), rather than
simple material input information (structure or formulation
data). A hierarchy is generated in which chemical variables are
converted into physical descriptors through a series of
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equations or transformations, and a second learned trans-
formation of these physical descriptors is used to predict the
response variable. This series of transformations allows the
model to capture physically realizable trends, rather than just
statistical significance and can overcome the challenge of small
data sets.26 Not only has this approach demonstrated improved
accuracy on model test sets, but the interpretability of the
model increases because physically meaningful features are
parametrized. This model architecture can also lead to the
discovery of new trends that may govern material properties
beyond the instances used to train the model and therefore
may also be used as a design tool to tailor a formulation to the
desired properties. Through the utilization of HML, here we
show a methodology for the prediction of the Young’s modulus
of PUs from a small data set of 63 unique samples using
physicochemical data that additionally can provide insight into
chain interactions. We propose that this approach can allow
data-driven algorithms to predict bulk material properties from
smaller data sets more accurately than black-box modeling.
2. METHODS
2.1. Material Library. Polyurethane and polyurethane−polyurea
elastomers are a product of a polyaddition process, involving the
copolymerization of three major components: macrodiols, also known
as polyols, diisocyanates, and low-molecular-weight diol or diamine
chain extenders. During the polyaddition process, the alcohol and
isocyanate groups of the monomers react to yield polymer chains with
many urethane and/or urea junctions (i.e., polyurethanes or
polyurethane−polyureas, respectively). While the polymerization
proceeds, the product phase segregates into “hard” (urethane-rich
regions resulting from the reaction of the diisocyanate and chain
extender organized by hydrogen bonding) and “soft” (amorphous or
semicrystalline backbone of the macrodiol) segment domains (Figure
1). This thermodynamic and kinetic phase segregation results in
atomic-scale interactions between monomers that govern complex
intra- and intermolecular arrangements of growing chains, ultimately
yielding complex microstructures as a result. In this work, a material
training library was synthesized using systematic variations in the
chemical structures of the polyurethane monomers and the
composition of the formulations. A total of 63 unique linear
polyurethane or polyurethane-polyurea formulations were prepared
that spanned six polyols (including polyethers, polyesters, and
polycarbonate), five diisocyanates (including aromatic and aliphatic),
and two chain extenders (diol and diamine). The full list of product
names and structures can be found in Table S.4 and Figure S.1 in the
Supporting Information. Each sample was synthesized using a
standard two-step polyaddition method. In the first of two synthesis
steps, a prepolymer was made by mixing the polyol and diisocyanate
in a reaction beaker heated to 110 °C for 2 h with constant
mechanical stirring. By introducing a stoichiometric excess of
diisocyanate to the polyol (at least 2:1), the product of the first
step was a mixture of isocyanate-capped chains and excess
diisocyanate, typically referred to as a prepolymer. In a second
reaction step, the prepolymer was allowed to react with a
stoichiometrically predetermined amount of chain extender, and a
linear, high-molecular-weight network of chains was formed. The ratio
of isocyanate groups to alcohol and/or amine groups in the second
step is referred to as the NCO:OH index, and for this sample library,
the index was kept constant at 1.05 (slight isocyanate functional group
excess). Similarly, the hard segment content, defined as the weight
percent of the chain extender and diisocyanate in the formulation, was
also varied by adjusting the reagent amounts, to prepare polyur-
ethanes with 25%, 35%, and 45% hard segments. After the chain
extender was introduced and stirred into the prepolymer for 3 min,
the increasingly viscous and exothermic mixture was poured into a
100 × 20 × 2 mm Teflon mold and cured in an oven at 100 °C for 24
h. All but one sample class in the training library were synthesized
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without the use of catalysts or solvents. For the series of samples that
included polypropylene glycol (PPG), 100 ppm of catalyst the
dibutyltin dilaurate (DBTDL) was used to accommodate the slower
relative reactivity of the secondary hydroxyl group on the terminal end
of the polyols, ensuring that the reactions yielded high-molecular-
weight polymers. Once each sample was removed from the vented
oven 24 h postreaction, they were left to completely cure at room
temperature for 1 week before mechanical testing began.
2.2. Measurements. Once each sample was cured, Fourier-
transform infrared (FT-IR) spectroscopy was performed with a
Frontier spectrometer (PerkinElmer) in the 4000−700 cm −1
wavenumber range. The spectra indicated the loss of the free
isocyanate peak (2200 cm−1) and urea group formation (1690−1640
cm−1) for the polyurethane−polyurea systems and a lack thereof for
the polyurethane systems. Then, the Young’s modulus of each sample
was measured by measuring stress−strain data in tensile mode using a
rheometer (Discovery HR-2) at room temperature. The strain rate
during tensile measurements was kept constant at 0.05 mm/s for all
samples to avoid deviations in mechanical response due to different
deformation rates.27 The samples were analyzed with the TRIOS
software package, and the modulus was documented using the onset
slope from the stress−strain data. Each sample modulus value was an
average of five tensile experiments, and the final reported values had
standard deviations of 5 MPa or less.
2.3. Data Set Generation. 2.3.1. Chemical Variables. Each
sample in the data set was initially accompanied by the chemical
structure, formulation, or known chemical data. This initial feature
space represents the explicit representation of the chemical structure
and is similar in format to popular molecular fingerprinting techniques
in which functional groups were represented by placeholding integers
in a unique sequence that represents the molecule/repeating unit.18 In
addition to the chemical structure, the formulation and known
chemical data were also included. These are values that can be found
on the isocyanate or polyol’s technical data sheet, such as density and
molecular weight. In addition, stoichiometry that was directly
calculated during the synthesis of each sample was also included,
e.g. the NCO index of the prepolymer. In total 18 chemical variables
OH
were used to represent the simplest parameters that determine
chemical structure and formulation (the data set is provided in the
Supporting Information). Throughout the remainder of the manu-
script the models (Ê = f(xi)) trained on just these 18 chemical
variables {xi} were compared to models (Ê = f(yi)) trained on just the
physical variables {yi}, which were mapped from the chemical
variables f: {xi} → {yi} using the methods discussed in the following
sections.
2.3.2. Cheminformatics. By representation of the hard and soft
segments as simplified molecular-input line-entry system (SMILES)
strings, physicochemical features were computed using the RDKit
database.28 The software uses patterned algorithms that employ a
series of filtering mechanisms based on topology and electronic
similarity to generate features for each unique input.29 The SMILES
strings for each unique PU repeating unit can be found in Table S.1 in
the Supporting Information. Every feature calculation was performed
on the polymerized unit structure: i.e., terminal urethane groups on
the hard segment structure with one chain extender structure
included. The soft segment structure calculations were performed
on the repeat unit of the polyols, and all repeating-unit structures were
capped with hydrogen atoms.
2.3.3. Density Functional Theory (DFT) Calculations. The
ground-state electronic parameters of each hard-segment repeating
unit were calculated as additional features. Using the Gaussian 16W
software, each structure’s HOMO/LUMO gap, electric dipole
moment, ionization potential, polarizability (α), and hyperpolariz-
ability (β) were calculated.30 The B3LYP/6-31G* basis set was
employed because of its previous utilization in quantum chemical
calculations with polyurethanes.31 Then the five descriptors were
extracted from the calculation output files and were tabulated into the
feature set.
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2.3.4. Thermodynamic Models. The underlying thermodynamic
driving forces are implicit to phase segregation and mechanical
response and have been historically used to describe polyurethanes
theoretically and analytically.32,33 On the basis of work by Ginzburg et
al. in their analytical PU Young’s modulus model,34 thermodynamic
and phase interaction descriptors were added to the feature set. Each
feature was calculated from either chemical structure or formulation
information. They include features such as the Hildebrand solubility
parameters (δ), the densities (ρ), and equivalent and molecular
weights (E and M, respectively) of the hard and soft segments and the
phase incompatibility parameter (χ) for a multiblock copolymer
ÅÄ ÑÉ
(δ − δS)2 ÅÅÅÅ MH E ÑÑÑ
derived from the Flory−Huggins approach shown in eq 1.
ÅÅ + S ÑÑÑ
ÅÅ 2ρ ρS ÑÑÑÖ
ÅÇ H
χN = H
RT
(1)
2.3.5. Experimental Data. FT-IR absorbances have been shown to
estimate the relative degrees of hydrogen bonding in polyurethanes.35
For each sample, 10 spectral features were extracted to be included in
the model training space. The peak wavenumber and intensity of the
hydrogen-bonded carbonyl (∼1700 cm−1), free carbonyl (∼1750
cm−1), and amine (∼3300 cm−1) peaks were used alongside the peak
wavenumber and intensity of the hydrogen-bonded and free urea
peaks (1640 and 1690 cm−1, respectively).36
2.4. Machine Learning. The complete chemical and physical data
sets were finalized by compiling and sorting each unique feature
vector with the corresponding modulus that was experimentally
measured. The validation set containing samples with 35% by weight
hard segment was then removed from each data set and was withheld
during the training and testing of each model. The set, now consisting
of 54 unique PUs, was randomly split into training and test sets
containing 80% and 20% of the data points, respectively. All modeling
was performed in Python using the Scikit-Learn library and using data
standardized about a zero-centered mean.37 The model performance
was measured using the coefficient of determination (r2) and the root-
mean-squared error (RMSE) metrics of each output prediction
against the experimentally determined modulus.
2.4.1. Modeling Strategies. Once the chemical to physical
descriptor transformations were completed, the ML modeling from
the physicochemical descriptors to the material response variable was
performed. Any experimental or empirical data, e.g., FT-IR features,
that could not be directly mapped from chemical data using the
processes mentioned previously were subject to sequential ML
models within the overall HML structure: i.e., the values ultimately
used were output from models built from the curated or measured
data that were parametrized by the chemical variables.
Two regression approaches were compared in this study: linear
regression and nonparametric Bayesian estimation. The two modeling
types provide different strengths and weaknesses that were leveraged
for specific tasks in building the model hierarchy. Linear regression
determines a function of best fit about a response variable (y) by using
least-squares approximations to regress to a sum of optimal linear
coefficients (β) of independent variables (x). Subsequently,
regularized linear regression, with the least absolute shrinkage and
selection operator (LASSO), is a popular tool in forming a linear
function that relates the response variable to a subset of the total
feature space.38 LASSO introduces an L1 penalty term to the least-
squares linear regression, which effectively removes parameters with
lower correlation to responses, and the weight of the penalty can be
optimized through cross-validation. The primary benefits of using
LASSO modeling are (1) it prevents overfitting from the use of too
many variables in the model, (2) the result is interpretable with the
physical form of E = ∑i βi xi , (3) modeling parameters are easy to
tune, and (4) the final model is sparse (reduced dimensionality).
However, one key disadvantage is that LASSO is poor at capturing
nonlinear or nonlocal trends in the data and, as mentioned previously,
such trends may be crucial in creating a robust model for a complex
physical system.
The second modeling type employed was Gaussian process
regression (GPR). This is a Bayesian modeling approach found to
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be useful with small data sets containing data characterized by
nonlinear behavior.39,40 This nonparametric model generates a prior
distribution of the latent function space using a mean function
(typically the average value of the response variable) and a covariance
kernel describing the similarities in the training data features. The
model then makes predictions for test data on the basis of a normal
distribution of values parametrized through the covariance matrix.
GPRs are typically excellent with nonlinear data and interpolating on
a complex feature space, allowing for improved interpretation on a
continuous and multivariate Gaussian distribution. GPR has the
following differences from LASSO. (1) The model’s hyperparameters
are strictly dependent on the kernel(s) and are automatically
optimized during the covariance computation. (2) It does not have
an inherent regularization capability: i.e., it uses the entire sample
feature vector to generate the posterior distribution and may overfit
unless a feature-ranking method is used to decrease the dimension-
ality of the feature space manually. Here, through a combination of
both LASSO and GPR models, a low-dimensional feature space of
physicochemical forces was also developed to model and predict the
Young’s modulus.
2.4.2. Feature Selection and Model Tuning. Two different feature
selection methodologies were employed during the modeling. Doing
this reduced the dimensionality of the models and avoided them from
becoming susceptible to overdetermination due to the number of
available features (88) being greater than the number of training
points (43 after train/test split). The first method was to use the
regularization inherent to LASSO linear regression to select a small
subset of features to the modulus response. As was mentioned
previously, through the incorporation of an L1 norm, the linear
regression cost function was adapted to sparsify the available feature
space while regressing to a linear function of best fit (eq 2). In the
equation, the cost (J) is minimized as a function of the coefficients
(β) about a linear function (y = ∑i βi xi).
J(β) = ||y − h(x , β)||2 + λL1(β) L1 = ∑ |βi |
i (2)
In all LASSO feature selections, leave-one-out cross-validation
(LOOCV) was employed. The regularization tuning parameter (λ)
corresponding to a minimized mean-squared error (MSE) from the
cross-validation was specified to the model, and the resulting
coefficients from the regression were a sparse list of features that
most accurately predict the response through linear trends in the data.
This process was performed over 15 different separations of the
training and testing data during the train/test splitting process.
Averaging feature frequency and performance metrics over 15 unique
splits ensured that features unimportant to a generalizable model were
not kept as artifacts of a particular or convenient split. For each split,
the 10 features with the highest coefficients were stored and the top
five most frequent descriptors from the 15 lists were chosen as the
final sparse set of LASSO-selected features. Due to the variability
limitations to a data set of this size, this rigorous methodology for
feature selection was performed to maximize each feature’s ability to
demonstrate a robust and general relationship to the target property.
However, it is very likely that, in modeling a physical system, that
nonlinear relationships exist between input and output variables.
Through the use of GPR and a permutation importance (PI) ranking
algorithm (GPR-PI), a sparse list of features that may represent
nonlinear and linear trends was computed. In GPR, the kernel
determines the distance metrics between points in the model. There
are numerous choices for kernels, but in practice, that which yields the
most accurate predictions in training and testing is used. The models
were tuned by performing cross-validation of the data set over various
kernels and kernel combinations, and the PI algorithm ranked the
importance of each feature by randomly shuffling the values of each
feature and measuring the model performance each time. The features
that decrease the model’s r2 score most significantly throughout the
shuffling process were selected to have greater predictive utility.
Similarly to LASSO, the GP feature selection was performed over 15
unique train/test splits and the most frequent features of high
importance were pooled in a final sparse feature space. The kernel, the
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ACS Applied Materials & Interfaces
measure of covariance between features, found to most frequently fit
the data most accurately is shown in eq 3.
ij d(xi , xj)2 yz
σ 2 ijj 2ν
k(x , x′) = σ 2 expjjjj− zz +
z
zz j
j z
Γ(ν)2ν − 1 jk lM
j
k {
2
d(xi , xj )
2lRBF
ji 2ν zy
K νjjj d(xi , xj)zzz + noise
j lM z
k {
It is a summation of kernels including the radial basis function (RBF),
the Matern function, and a white noise function.37,39 In the first two
terms d(xi, xj)2 is the Euclidean distance between features, σ is the
signal standard deviation, and l is the length scale of each kernel (RBF
and Matern, respectively) and represents the separation length at
which the features become uncorrelated to the response. In the
Matern expression, Γ(ν) and Kν are γ and modified Bessel (second
kind) functions, respectively, and are used in combination to create a
“less smooth” RBF parameter. The smoothing parameter (ν) was
always optimized to a value of 1.5 in this model, indicating that the
function is once-differentiable. The simplified kernel expression
including what is often called the 3 Matern is shown in eq 4.
ij d(xi , xj)2 yz i 3 d(xi , xj)2 yzz
k(x , x′) = σ 2 expjjjj− zz + σ 2jjj1 +
2 GPR models showed sufficient predictive capabilities using the
zz jj
j 2lRBF z j zz
k { k {
2
lM
jij 3 d(xi , xj)2 zyz
expjjj− zz + noise
zz
j
k {
lM
The combined kernel computed the covariance for each feature pair
and forms a covariance matrix n features by n features in size. The
feature covariance matrix and the feature mean vector were then used
to parametrize the normal posterior distribution to predict modulus
values, as shown in eq 5.
ij E yz
jj zz≈ Ν(μ ⃗ , Κ⃗)
j ̂z
k E{
2.4.3. Optimization. After a trained and validated model was
created, all 63 data points were used to train a final model aimed at
designing new formulations within the chemical boundaries of the
sample library. The new model was subjected to a chemical variable
design grid (∼700 theoretical formulations) and predicted the
modulus of samples with fixed chemical structure as a function of
changing prepolymer stoichiometry (NCO/OH index). The trans-
formation of the chemical variable grid to a physical variable grid
(both grids are provided in the Chemical and Physical Data set in the
Supporting Information) was analogous to the previously mentioned
transformations. Thus, the trained model made predictions for every
point in the grid, yielding an accessible chemical structure and
prepolymer stoichiometry for a desired modulus. Three formulations
were chosen to demonstrate the HML model as a design tool,
targeted to have Young’s moduli of 10, 40, and 50 MPa, respectively.
A discussion in section 3 covers the three chemical structures explored
and the accuracy of the model at those points.
3. RESULTS AND DISCUSSION
3.1. Machine Learning Models Parameterized by
Composition. To benchmark our modeling approach, we
began by using linear regression and GPR to predict the
Young’s modulus of the PUs in the data set as a function of the
blend of monomers that comprised each polymer alongside
stoichiometric information that described the formulation.
Both linear regression and GPR with the entire chemical
variable feature set were performed, which represented a
traditional “black box” approach to machine learning. The
performance metrics of each model on the training and testing
sets are presented in Table 1. In these models, the original data
set comprised of 63 samples was divided into a portion for
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Table 1. Average Performance Metrics of Models Predicting
the Modulus As a Function of Monomer Composition and
yz
zz
Stoichiometry: i.e., Using Only the Chemical Variablesa
z
ν
{
train RMSE test RMSE
train r2 test r2
model (MPa) (MPa)
linear regression 0.84 0.63 12.71 14.60
(3) Gaussian Process 0.86 0.65 9.01 14.47
Regression
a
These performances represent a “black box” approach to machine
learning. The results, obtained over 15 unique train/test splits,
indicate a high level of overfitting as evidenced by the reduction in r2
from training to testing. In all 15 splits the same 18 features in the
chemical descriptor set were used to train the models.
training, in which 80% of the data (selected at random) were
used to optimize the parameters or hyperparameters in the
models and the remaining 20% were used to test the
performance of the model. Neither linear regression nor
zz
chemical features exclusively. While statistical benchmarks vary
with requirements, having a test r2 value of at least 0.7 can be
considered necessary for obtaining meaningful predictions
from the model. Furthermore, the reduction in r2 from training
to testing suggests that both models were overfitting the data
(4) used to train the algorithms, resulting in a lower value when
new data were used to test.
3.2. Machine Learning Models Parameterized by
Physicochemical Forces. Physicochemical forces represent
latent variables that determine the system responses. Selecting
a set of forces for data-driven modeling requires a mechanistic
understanding of the factors that determine the modulus, but
here tools of statistical learning were used to identify those that
(5)
are most strongly correlated with the responses. The
mechanical response of a polymeric material involves a
complex interplay between competing enthalpic and entropic
forces, where the tensile force required to perform work upon
and deform the material can be described by first principles as
the change in free energy of the system when elongated. This
general relationship among tensile force, enthalpy, and entropy
is shown in eq 6, where f is the force required to deform the
material, enthalpy (H) and entropy (S) change are in response
to elongation (∂L), with constant pressure (P) and temper-
ature (T):8
i ∂H yz i ∂S y
f = jjj zz − T jjj zzz
k ∂L { P , T k ∂L { P , T
(6)
For the theoretical “ideal” polymer (nonpolar, homogeneous,
and isotropic), the elastic response of the material can be
approximated by the entropic portion of this equation alone,
assuming it to have no change in cohesive forces while being
stretched. The mechanical behavior of ideal Gaussian networks
are thus functions of the conformational and configurational
entropy of the material and temperature and are simply
governed by component mixing. In heteropolymers such as
PUs, the multiphase microstructure results in a thermodynamic
competition between the two free energy terms mediated
through many physicochemical interactions. The focus of this
work is on the methodologies to generate modeling descriptors
across multiple scales and processes to capture these factors are
discussed.
3.3. Training Set and Associated Physicochemical
Descriptors. The 63 samples in this data set were a
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chemically diverse group of industrially relevant linear
polyurethane and polyurethane−polyurea elastomers that
contain complex intra- and intermolecular interactions, multi-
phase incompatibilities, and dispersion, dipole, and hydrogen-
bonding forces. The use of cheminformatics through the
RDKit library allowed the chemical structure of the polymers
to be represented by electronic, shape, and topological
descriptors. Quantum chemical DFT calculations offer a
second approach to describing the unique electronic behavior
of varying hard segment chemical structures. Thermodynamics
and analytical equations based on Flory−Huggins theory can
provide information on the phase interaction and describe the
nonequilibrium state of the PUs. Finally, the frequency shifts
and the relative intensities of the FT-IR peaks can describe
hydrogen bond strength. The final physicochemical feature
vector was generated to provide information beyond the
atomic scale by describing the molecular-range interactions.
3.4. Feature Selection with Physicochemical Forces.
LASSO and GPR-PI were then performed on the multiscale
physicochemical features (“physical feature set”) generated by
computational and experimental methods. The selected
features from both strategies are represented in eqs 7 and 8.
These sparse feature sets were determined using their
frequency over multiple data splits as mentioned previously.
At this point in the analysis, the other features were removed
from the physical feature set and the model performance
statistics presented in the following tables are for models
parametrized by only those features shown. The average
performances over 15 different divisions of data did not have
different feature groupings. The functional form of each model
is different due to the mathematical differences presented in
section 2.4. LASSO yields a linear equation of best fit with
optimized coefficients, while GPR yields a feature vector that
most effectively describes the variance in a normal distribution
formed about the known modulus values.
LASSO: E ̂ = − 0.33qed HS + 0.19COW,free − 0.39PPPP
+ 0.17Tm,SS + 0.12Hyperpolar(β) (7)
GPR: P(E|̂ wHS, qed HS, CO W,free , DPPP , Tm,SS , U,i MPC HS
− MPCSS) (8)
Immediately apparent is the degree of overlap in selected
features between both modeling strategies; both contain the
lump electronic molecular property of the hard segment
(qedHS),the wavenumber of the free carbonyl peak (COW, free),
the degree of polymerization of the prepolymer (DPPP), and
the melting temperature of the soft segment (Tm,SS). However,
the model performances with the GPR-PI model selected
features outperformed LASSO in accurately predicting the
responses in the test data by a significant margin (Table 2).
The GPR selected three additional features compared to the
LASSO: the hard segment weight fraction (wHS), a urea binary
classification variable (Ui), and the difference in maximum
absolute partial Gasteiger charges of the hard and soft
segments (MPCHS − MPCSS). Through the utilization of
modeling with a probabilistic function more suitable for small
nonlinear data sets and the incorporation of these three
additional features, using a GPR for predicting the modulus as
a function of the physical feature space was chosen as the top
half of the model hierarchy. However, two items should be
noted. (1) The sequential models mapping chemical structure
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Table 2. Average Performance Metrics of Machine Learning
Models Predicting the Modulus as Parametrized by the
Physical Features in Eqs 7 and 8 over 15 Unique Train/Test
Splitsa
model train r2 test r2 train RMSE (MPa) test RMSE (MPa)
LASSO 0.78 0.76 11.21 11.67
GPR-PI 0.99 0.92 2.72 5.89
a
This feature space included descriptors derived from cheminfor-
matics, quantum chemistry, thermodynamics, and experimentally
determined values of FT-IR and curated values for the soft segment
melting temperature.
to both the FT-IR feature and the soft segment Tm had not yet
been included in the HML architecture. (2) The GPR model
may have been overfitting due to the high training accuracies of
r2 = 0.99 and RMSE = 2.72 MPa, most likely due to the
complexity of the kernel employed. While this iteration of the
model was not entirely parametrized by the chemical variables,
the goal of this first iteration was to evaluate the model
predictive performance when it was supplemented with a
sparse set of physical descriptors.26 The next iteration
presented will include the sequential models mentioned
previously. The overfitting caused by the RBF + Matern
kernel was initially chosen because it outperformed all other
covariance expressions when the testing data were fitted.
Therefore, feature selection and cross-validation were
performed with this specific kernel and a further dimension-
ality reduction significantly decreased the performance metrics
(Δr2 ≈ −0.12). While the model adopted may be overfit, the
primary aim of this work was to explore the incorporation of
physical variables in the model framework. A more in-depth
analysis of the sparse parametrization of the model across other
kernels and modeling techniques will be the subject of future
work.
In the final modeling step, the sequential models were
created and added to the hierarchy. In summary, the chemical
variables were transformed into the physicochemical variables
through three different transformations: (1) known equations
to directly calculate DPPP and wHS from stoichiometry from
eqs 9 and 10, (2) cheminformatics determination of qedHS and
MPCHS − MPCSS, from the SMILES input (Supporting
Information), and (3) GPR modeling of COW, free and Tm, SS
from the chemical variable feature space. The results of the
regression models in predicting the IR and melting temper-
ature features were both sufficiently accurate to use in the
broader model (average test scores of at least r2 = 0.85). A
schematic of the final model hierarchy is presented in Figure 2.
OH
( NCO )PP
DPPP = 1 + OH
1 − ( NCO )
PP (9)
miso + mce
wHS =
mpoly + miso + mce (10)
Figure 3 compares testing performances of the chemical
(“black box”) model and the final physicochemical model. The
HML model had average training scores of r2 = 0.98 and
RMSE = 2.72 MPa and testing scores of r2 = 0.91 and an
RMSE = 6.88 MPa, which were slight dropoffs in comparison
to the models which without reparametrizing the output (with
measured or documented values of COW, free and Tm,SS,
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Figure 2. Final HML model schematic. Chemical structure and formulation variables are transformed into physical and latent forces spanning
multiple length scales through a series of transformations. The transformations include two sequential GPR models, two RDKit computations, and
two outputs from the known equations “Chemical Descriptors”, all from chemical layer inputs (xi). The physical layer is then used to parametrize a
GPR which estimates each sample’s Young’s modulus.

Figure 3. Performance comparison of test data using Gaussian process regression with chemical variables to model the sample modulus and the
HML approach with the physiochemical hierarchy. The plots show the actual E value in comparison to the E value predicted. The 45° blue line has
been added to show where predictions of perfect accuracy would have been. These plots show one unique training test split instance included in the
average score value reported.

respectively) by chemical composition. This was expected,
given that each regression model contained error contributions
to the overall model due to synthetic and experimental
variance in the empirically determined COW, free feature as well
as limitations of the chemical feature space to fully capture a
continuous function output that Tm,SS has in the latent space.
The limited accuracy of the sequential models results in an
error that propagates to the final modulus prediction in the
final hierarchy. However, by introduction of regression as a
mode of transformation to obtain additional physicochemical
16574
descriptors, the final HML model can make predictions solely
from the chemical structure and formulation input. Addition-
ally, by using the multiscale physicochemical descriptors in the
final model, a significant increase in model performance was
still observed between the physicochemical model and the
original baseline model despite being parametrized by nine
fewer features (16-parameter feature vector in the chemical
space vs 7-parameter feature vector in the physicochemical
space). The average RMSE of the final model was comparable
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Figure 4. Black box versus HML modeling comparison. On the left, the chemical variables are used to directly predict the modulus, resulting in a
test score of r2 = 0.65 and RMSE = 14.47 MPa, whereas on the right, the chemical variables are transformed into physical variables on the molecular
scale through a series of transformations, resulting in a test score of r2 = 0.91 and RMSE = 6.88 MPa. The physical layer is then used to parametrize
a GPR that estimates each sample’s Young’s modulus.

Figure 5. Performance comparison of validation data using Gaussian process regression with chemical variables to model the sample modulus and
the HML approach with the physiochemical hierarchy. The plots show the actual E value in comparison to the E value predicted. The 45° blue line
has been added to show where predictions of perfect accuracy would have been. These plots show one unique training test split instance included
in the average score value reported.

to the standard deviation observed in measuring the moduli of
the samples experimentally.
3.5. Validation Set. Demonstrating the model’s ability to
capture trends outside of the original data space is essential in
applications. By withholding nine samples from the total data
set that were formulated with 35% hard segment by weight, the
model predicted the modulus without requiring any prior
instances of such formulations in the training process. While
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“black box” models would rely on statistical interpolation,
HML utilizes the physicochemical trends learned from the
training data, and the model was able to predict the validation
set with r2 = 0.91 and an RMSE of 4.15 MPa accuracy on
average (Figure 4). Figure 5 shows the performance
comparison between the baseline and HML model prediction
of the validation set on one particular training test split. Table
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Table 3. Average Performance Metrics of the Baseline Chemical Variable-Exclusive GPR Model and the Final Physicochemical
HML Model over 15 Unique Training Test Splitsa
feature space train r2 test r2 validation r2
chemical 0.86 0.65 0.65
physicochemical 0.98 0.91 0.91
a
The “physicochemical” feature space here refers to the features shown in eq 8 and in the hierarchy represented in Figure 2. The difference between
the “physicochemical” scores here and the “GPR-PI” scores reported in Table 2 is the incorporation of the sequential models to parametrize all
layers of the model using the original 18 chemical features.
3 shows the average performance comparison between the
models.
The accuracy observed can be due to mapping the modulus
to continuous physical variables rather than fitting it to
chemical structure fingerprints. Thus, the HML model
demonstrates the ability to generalize to new formulations by
leveraging their molecular-scale latent forces. It should be
noted that predicting test set values may be more challenging
than predicting validation set values for some training test
splits, hence the lower validation RMSE. For example, the
model may have received the data for PPG/MDI/BDO/25%
during training, may or may not have had predicted PPG/
MDI/BDO/45% during testing, and then predicted PPG/
MDI/BDO/35% during validation. Therefore, it is expected
that the validation set outperformed the test set on average,
given that the validation extrapolations spanned less distance in
the learned feature space.
In addition to increasing the accuracy and generalizability of
models, building models from physicochemical feature spaces
enhances interpretability. Using physically and chemically
meaningful features, one can subject those selected to cross-
analysis with domain knowledge and the literature to observe
correlations or discrepancies. These observations can aid in
understanding what drives system responses in the material
and may become crucial in expanding material searches
beyond what is experimentally available in existing data sets,
thus providing new design principles as well as extending our
knowledge of complex materials.
3.6. Physical Significance of Selected Features. The
final sparse feature space included seven variables describing
various underlying driving forces in PUs. The interpretation of
the selected features can be separated into two length scale
categories: microstructure and molecular interaction. Figure 6
shows the final permutation importance scores for the features
in descending order.
The hard segment weight fraction (wHS) and average degree
of polymerization of the prepolymer (DPPP) have direct
implications on the amount, size, and dispersion of the hard
and soft segment phases. The two features are highly
correlated, both being functions of the equivalent weight of
the monomers and ratio of OH contributions from the polyol
and chain extender, respectively. Despite their correlation,
when wHS is removed from the final feature set, the
corresponding coefficient of determination decreased by Δr2
= −0.02 for the average test score and Δr2 = −0.11 for the
average validation score, suggesting its importance on
interpolating across the relevant chemical space. It has been
consistently observed that by increasing wHS, the entropic
mixing of the phases decreases and larger, more phase-
segregated structures form and percolate into the bulk
microstructure, increasing the modulus.41,42 Second, additional
trends mapped through the DPPP values, which were unique
for each prepolymer, became the second most important
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train RMSE (MPa) test RMSE (MPa) validation RMSE (MPa)
9.01 14.47 8.30
2.72 6.88 4.15
Figure 6. Permutation feature importance box and whisker plot of the
final seven features in descending order of importance to the final
Gaussian process model. Notched boxes in red represent features on
the microscale. Notched boxes in blue represent structural features on
the intermolecular scale. Notched boxes in green represent electronic
features on the intermolecular scale.
feature in the model. The effects of soft segment length and
concentration have been systematically studied for their effects
on bulk properties and are highly sensitive to varying ether,
ester, and carbonate groups in the polyol backbone.43,44
By a capture of the degree of entropic phase mixing in each
sample with these two features, the model was able to leverage
the other features describing smaller length scales to map
trends more enthalpic in nature. The urea variable (Ui) is a
simple binary identification of whether the sample was
synthesized with a diamine chain extender or not: i.e., the
feature was simply 0 for BDO formulations, and 1 for MOCA
formulations. The differences between polyurethane and
polyurethane/polyurea were significant, most notably in
intermolecular hydrogen bonding in the hard segment, and
have been extensively studied elsewhere.36,45 The presence of
urea linkages in the hard segment may allow bidentate
hydrogen bonding to occur, in comparison to monodentate
bonding in urethane groups. The increase in hydrogen-
bonding potential led to polyurethane−polyurea having more
order in the hard segment and an increase in phase
segregation, resulting in larger but more compact physically
cross-linked structures, imparting a higher resistance to
deformation to the material. The wavenumber of the carbonyl
peak (COW,free) can also be attributed to the extent of
hydrogen bonding and phase segregation in PUs. Previous
studies have directly estimated the degree of phase segregation
(DPS) from IR data.46 However, in PUs with varying degrees
of crystallinity and hydrogen bonding in the soft segment, the
hard segment characteristics did not exclusively correlate with
descriptors associated with order and secondary bonding. The
vibrational shift patterns provided by this feature may be
providing the model with features associated with hydrogen-
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Figure 7. Schematic representation of the TPU microstructure with highlighted regions pertaining to some of the final features in the
physicochemical model. The soft segment melting temperature (Tm,SS) and free carbonyl peak wavenumber (COW,free) (subschematics on the left
side of the figure) represent intermolecular parameters aiming to capture order and secondary bonding characteristics in both the hard and soft
phases. The COW,free visualization represents the lack of hydrogen bonding between the carbonyl functional group in the polyol backbone and the
urethane linkage in the hard segment. The lump molecular property of the hard segment (qedHS) and difference in maximum partial charges
(MPCHS − MPCSS) (middle and top right of the figure, respectively) aim to capture the electronic nature and interfacial polarizability between
phases. The degree of polymerization of the prepolymer (DPPP) at the bottom of the image represents entropic mixing as well as hard segment
dispersion in the multiphase system. The hard segment weight fraction (wHS) and the urea identification (Ui) features are not present in this
visualization.

bonding degree and phase segregation information as functions
of implicit chemical structure effects on secondary bonding in
both the hard and soft segments. In contrast, the melting
temperature of the soft segment (Tm,SS) likely provided the
model with crystallization trends through dispersion forces in
the soft segment. The manipulation of the soft segment
structure has been previously studied for how the resulting
crystallization in the phase affects the mechanical properties.47
Crystallization through intermolecular dispersion forces in the
polyol backbone is a major source of enthalpic strength in the
bulk material and has also been found to lead to an increased
phase segregation in PUs.48 The model found high importance
in these intermolecular features that aim to describe how the
hard and soft segments order through dispersion and
secondary forces and how segregated they may become as a
result.
The two electronic features in the final model computed by
cheminformatics capture interactions between the chemical
units and offer an atomic-scale measure of the internal energy
in the polymer. The difference in maximum absolute partial
Gasteiger charges between the segments (MPCHS − MPCSS) is
a measure of the interfacial polarizability, which contributes to
the cohesive energy. It is interesting to note that this feature
was highly correlated with the other DFT-computed features
and the highly collinear hyperpolarizability (β) feature was
present in the final LASSO equation. By use of the difference
between the two individual informatics values, the model
identified the importance of the relative electrostatic
16577
interaction between unique structures. The dielectrics of the
soft/hard segment boundary have previously been related to
PU behavior.49 Finally, the most important feature in the
model was the quantitative estimation of druglikeness of the
hard segment (qedHS), which is an empirical lump parameter
of characteristic structural and electronic molecular properties
of the repeating unit. While this informatics descriptor was not
designed for polymers, qedHS is a function of the molecular
weight, partition coefficient, polar surface area, hydrogen bond
donors and acceptors, and aromaticity, among others.50 It
characterizes the hard segment with this series of relevant
electronic and size parameters spanning molecular and
electronic length scales. The HML model leveraged a final
feature space that contained seven unique physicochemical
terms that can be interpreted to govern the mechanical
response of the complex material across multiple length scales.
Five of the final seven features are depicted within the PU
elastomer microstructure in Figure 7.
3.7. Application of HML as a Design Tool. While
predicting the properties in virtual experimentation is an
important assessment of a model, experimental validation of
ML models as a design tool is becoming a standard approach
to demonstrating capabilities.51 When the GPR trained on all
63 data points was subjected to a grid of ∼700 unique PU
formulations, modulus predictions were made throughout the
grid and the desired responses could be mapped to structure
and stoichiometry. Here the design aim was to identify unique
samples that would yield three different modulus values while
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Table 4. Target, Closest Model Conditions Found on the Grid, and Experimentally Measured Moduli Observed during the
Experimental Validation and Designa
target modulus model prediction experimental modulus chain NCO/OH index of
(MPa) (MPa) (MPa) polyol diisocyanate extender prepolymer
10.0 9.54 8.30 PTMEG 2000 HMDI BDO 2.70
40.0 40.34 46.20 PEA 2000 TDI MOCA 2.44
50.0 51.19 60.40 PHMC 2000 HDI BDO 5.30
a
All three samples were constrained to a 1.05 NCO/OH index for the entire polymer: i.e., including the chain extender stoichiometry. The index of
the prepolymer was chosen as the independent variable for the optimization study.

Figure 8. GPR model’s learned relationship for each chemical structure combination explored during the experimental validation study. The blue
points are data points the model trained on with the corresponding uncertainty being represented by the blue error bars. The green points are the
grid used to determine the trend the model learned, where the light green shaded region represents the uncertainty throughout the trend. The red
points are the experimentally measured values of the design samples, coinciding with the NCO/OH index of the prepolymer used in their synthesis.
Perfect design accuracy would be represented by the red point falling on the green point trend.

spanning differing polyol, diisocyanate, chain extender, and
prepolymer indexes: 10, 40, and 50 MPa, respectively. The
specific formulations provided by the model, along with the
experimentally measured moduli of each synthesized in
practice, are provided in Table 4.
Figure 8 shows the learned trend for each fixed chemical
composition combination alongside the sample instances the
model either trained on or designed. The 10 and 40 MPa
samples both fall within the model’s confidence interval,
whereas the 50 MPa sample falls slightly outside of it,
suggesting that the model has more accuracy when it
generalizes to modulus values in the lower regime of the
data set, albeit the small sample size chosen here. It should also
be noted that the distribution of modulus values in the training
set was skewed to contain many more instances in a low-
modulus regime (45 of the 63 data point had E < 36 MPa). In
general, the model has learned that for fixed compositions the
relationship between the modulus and NCO/OH prepolymer
index resembles a rooted power function. Other systematic
studies of varying prepolymer stoichiometry (or a similarly
hard segment weight fraction) have reported experimental
results describing a variety of different trends including root,52
high-order,41 and linear53 relationships between the modulus
and prepolymer stoichiometry (hard segment content). While
the experimental validation accuracy demonstrates the design
applicability of the method presented, there is an insufficient
amount of data for each unique structure to further elucidate
the learned trends of the model.
3.8. Future Directions. This work presents modeling
materials that are heterogeneous at multiple length scales using
physicochemical modeling in a framework of machine learning.
This multiscale physicochemical approach to predicting
Young’s modulus in PUs has provided insights into how
modeling efforts in the future may be improved and expanded.
First, the design of the experiment (or organization of the data
16578
set) could be constructed in ways to better capture the
underlying forces of interest: for example, eliminating
categorical features such as the presence of urea groups (Ui)
to parametrize the entire physical feature space in continuous
variable forces to improve generalizability. Similar to the way
we varied polyol and isocyanate structures in this study, others
have found that a variation of the chain extender has significant
effects in polyurethane systems.54 By introducing more
structural diversity to the chain extender and having
descriptors that represent the physicochemical forces corre-
sponding to those structural changes, we may be able to
elucidate the effects of the hard segment further. Second, while
the physical feature space employed in this work spanned
length scales from electronic to microstructural, the prediction
of a latent morphology was not apparent. As was mentioned
previously, modeling the complexities in PU microstructure is
a significant challenge and often requires rigorous experimental
determination through small-angle X-ray scattering
(SAXS).55,56 To truly bridge the gap from the chemical
structure to bulk behavior, the inclusion of a physicochemical
determination of the intermediate length scales may be crucial.
We propose that direct measurements of the microstructure
(SAXS) accompanied by other experimental descriptors, such
as COW,free, may allow the model to construct a latent
morphology and thus better equip the model for more
challenging prediction and design tasks. Finally, the method-
ology can also be augmented by incorporating sampling
approaches into data set construction. Specifically, it has been
well demonstrated that Bayesian optimization throughout data
set creation is an effective tool for identifying the data points of
highest model importance.57 Simply put, the model can
identify which sample should be synthesized next to decrease
uncertainty in the learned feature space. A methodology as
such, coupled with a structure-to-continuous and physical
latent force feature space presented here, introduces the
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ACS Applied Materials & Interfaces
potential for ML-based models to extrapolate beyond learned
material spaces and become invaluable tools in the fields of
material discovery. The combination of increased structural
diversity improved the featurization of the physical space
across larger length scales, and exploration into state of the art
modeling approaches is the basis of proposed work.
4. CONCLUSION
The model hierarchy presented here uses the frequency of
chemical functional units in the monomers and stoichiometry
exclusively as the input. Then, through the use of a rich
literature base on phenomenological forces in PUs, a series of
physicochemical descriptors were generated to parametrize a
Gaussian process ML model. Through transformations, which
include established equations, cheminformatics, and predictive
sequential models, the HML model predicted the modulus of
tests sets with an average of r2 = 0.91 and RMSE = 6.88 MPa
accuracy, which was greater than the performance of the “black
box” model parametrized solely by the monomer composition.
While it improved the prediction accuracy and interpretability
through parametrization via multiscale physical variables, the
model also showed the capability of interpolating through the
data space and accurately predict the modulus of unseen
formulations (r2 = 0.91, RMSE = 4.15 MPa). The final feature
space contained seven parameters spanning electronic to
microstructural length scales, and the identification of how
each had been previously linked to PU behavior was discussed.
Finally, the model was experimentally validated through a
design exercise to target three specific moduli values within the
model’s learned trends between chemical structure and
stoichiometry. The presented methodology and resulting
performance suggest the importance of incorporating multi-
scale physicochemical parameters into complex material model
design with small data sets.
■
ASSOCIATED CONTENT
*
sı Supporting Information
Table S.1 The Supporting Information is available free of
charge at https://pubs.acs.org/doi/10.1021/acsami.1c24715.
Repeating units and SMILES, full physical descriptor list,
GPR hyperparameters, commercial reagents, and chem-
ical structures (PDF)
NCO/OH and E values (XLSX)
■
AUTHOR INFORMATION
Corresponding Author
Newell R. Washburn − Department of Materials Science and
Engineering, Carnegie Mellon University, Pittsburgh,
Pennsylvania 15213, United States; Department of
Chemistry, Carnegie Mellon University, Pittsburgh,
Pennsylvania 15213, United States; Department of
Biomedical Engineering, Carnegie Mellon University,
Pittsburgh, Pennsylvania 15213, United States; orcid.org/
0000-0001-7843-8860; Email: washburn@
andrew.cmu.edu
Authors
Joseph A. Pugar − Department of Materials Science and
Engineering, Carnegie Mellon University, Pittsburgh,
Pennsylvania 15213, United States
Calvin Gang − Department of Chemistry, Carnegie Mellon
University, Pittsburgh, Pennsylvania 15213, United States
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www.acsami.org Research Article
Christine Huang − Department of Chemistry, Carnegie
Mellon University, Pittsburgh, Pennsylvania 15213, United
States
Karl W. Haider − Covestro LLC, Pittsburgh, Pennsylvania
15205, United States
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsami.1c24715
Notes
The authors declare the following competing financial
interest(s): N.R.W. has started a company to explore the
industrial application of these methods and discloses a
potential conflict of interest.
■
ACKNOWLEDGMENTS
The authors thank James A. Thompson-Colón (Covestro
LLC) for help in designing the feature space and Professor
Stephanie Sydlik (CMU) for access to the experimental
equipment. C.G. was supported by ARPA-E (DE-AR0001138).
J.A.P. and N.R.W. gratefully acknowledge support from a
Covestro Science Award.
■
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