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Discovery of Low-Modulus Ti-Nb-Zr Alloys Based on Machine

Learning and First-Principles Calculations
Camilo A. F. Salvador, Bruno F. Zornio, and Caetano R. Miranda*
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ABSTRACT: The discovery of low-modulus Ti alloys for

biomedical applications is challenging due to a vast number of
Downloaded via UNIV OF GOTHENBURG on December 14, 2020 at 01:39:30 (UTC).

compositions and available solute contents. In this work, machine

learning (ML) methods are employed for the prediction of the
bulk modulus (K) and the shear modulus (G) of optimized ternary
alloys. As a starting point, the elasticity data of more than 1800
compounds from the Materials Project fed linear models, random
forest regressors, and artificial neural networks (NN), with the
aims of training predictive models for K and G based on
compositional features. The models were then used to predict the
resultant Young modulus (E) for all possible compositions in the
Ti-Nb-Zr system, with variations in the composition of 2 at. %.
Random forest (RF) predictions of E deviate from the NN
predictions by less than 4 GPa, which is within the expected variance from the ML training phase. RF regressors seem to generate
the most reliable models, given the selected target variables and descriptors. Optimal compositions identified by the ML models were
later investigated with the aid of special quasi-random structures (SQSs) and density functional theory (DFT). According to a
combined analysis, alloys with 22 Zr (at. %) are promising structural materials to the biomedical field, given their low elastic
modulus and elevated beta-phase stability. In alloys with Nb content higher than 14.8 (at. %), the beta phase has lower energy than
omega, which may be enough to avoid the formation of omega, a high-modulus phase, during manufacturing.
KEYWORDS: machine learning, first-principles calculations, metals and alloys, elasticity, phase transitions

1. INTRODUCTION the physical properties of solids with reasonable accuracy. De

Despite the increasing demand for high-performance alloys by
the biomedical,1 aeronautical/aerospace,2 and oil & gas
industries,3 the traditional materials discovery process still
relies on empirical methodologies, based on significant trial
and error.4−6 Not only this has been the dominant exploration
methodology for centuries, but materials design also involves
an intricate, multidimensional optimization problem, in which
the links between parameters and specific properties of interest
are usually unknown.
Nevertheless, with the launch of The Materials Genome
Initiative (MGI), materials and data scientists have been
working together to develop multiscale computational method-
ologies to assess, evaluate, and optimize materials regarding
their fundamental properties.7 As an example, the initiative
named Materials Project consists of an open platform that has
been creating, validating, and storing data of compounds for
which experimental data may be incomplete or absent.8 At
present, there are 120,612 inorganic compounds’ data available
at the Materials Project, mainly obtained via first-principles
calculations. A full elastic description of these systems (i.e.,
elastic tensor) is defined for 13,621 entries. Based on the
previous works,9,10 this dataset is more than enough to model
Jong et al. (2016) were able to predict the elastic bulk (K) and
shear moduli (G) behavior of k-nary inorganic compounds (up
to quaternary) using a gradient-boost framework based on
local multivariate regression.9 Later on, Winter et al. (2017)
identified potential superhard materials from space groups 229
and 225 defining an elastic anisotropy parameter, which is a
function of K and G, and then confirmed their unusual elastic
properties via DFT.10
Low-modulus Ti alloys find applications as structural
biomaterials, especially among knee and hip-joint implants.
In these cases, ideally, the material must have a bonelike elastic
modulus, in order to mitigate the stress-shielding effect after
implantation and, therefore, avoid the proximal bone
degeneration around the implant.11 As a reference, Ti-Nb-
Ta-Zr alloys dominate this field of application, with an elastic
Received: October 14, 2020
Accepted: December 1, 2020

© XXXX American Chemical Society https://dx.doi.org/10.1021/acsami.0c18506

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Figure 1. Elastic property distributions for 1826 entries in the filtered database. (a) Bulk modulus (K). (b) Shear modulus (G). (c) Poisson ratio.
The values presented are Voigt−Reuss−Hill (VRH) averages. A summary of this data is compiled in Table S1 in the Supporting Information file.

modulus close to 55 GPa, at the solution-treated and water- structure, maxing out −1 or + 1% true deformation, within 8 steps,
quenched condition.12 The Ti-Nb-Zr system explored herein and single-point calculations were performed to obtain the energy of
each deformed state. The deformations were set as follows25
ij 1 y
was arbitrary chosen based on the recent literature, which
jj− δ
jj 2 0 zzzz
zz
reported a number of promising candidates from low-cost
jj zz
j
systems.13,14 Furthermore, studies with a ternary system might 0

Tetragonal: jjjj zz, with U (δ)

jj 0 − δ 0 zzzz
provide ground to incremental works in the near future, which
jjj zz
1

jjj zz
can explore a great range of quaternary systems derived from it. tetra

z
k 0 + δ z{
In the present paper, we aim to search for new, low-modulus 2
Ti alloys for biomedical applications with the aid of the MP 0
database and the matminer library.15 For exploration purposes, 3
= δ 2(C11 − C12)
we decided to test three different machine learning algorithms 4 (1)

ij 0 + δ 0 yz
jj zz
in this work: multivariate linear regression models, random

Trigonal: jjjj+ δ 0 0 zzzz, with Utri(δ) = 2δ 2C44

forest regressors, and neural networks. Later on, compositions
from a selected range were further characterized by first-
principles calculations based on density functional theory
(DFT) using special quasi-random structures (SQSs).
2. COMPUTATIONAL METHODS
Machine learning codes were implemented in python using
pymatgen,16 sci-kit learn, Keras, and TensorFlow.17 For all of the
machine learning algorithms, we performed random search
optimizations for the hyperparameters and used 5-fold cross-
validation. For the neural networks, to avoid overfitting, the root-
mean-squared error (RMSE) and mean absolute error (MAE) were
registered for each training epoch (step), and an earlier stop was
defined based on the loss function. CALPHAD calculations were
performed with the aid of the MatCalc suite, developed by
Kozeschnik.18
DFT calculations were performed using the Vienna ab initio
simulation package (VASP).19 The projected augmented wave
(PAW)20 methodology was used to treat the core electronic density,
and the Perdew−Burke−Ernzerhof (PBE) exchange-correlation
functional was employed.21 The plane-wave energy cutoff was set to
350 eV, and a 5x5x5 mesh grid sampled the Brillouin zone for all
systems, to reach the convergence criteria adopted.
To obtain an atomistic description of our body-centered cubic
(bcc) solid solutions, special quasi-random structures (SQSs) were
built with the ATAT package.22 The ATAT code aims to obtain the
best SQS for a given system size by maximizing the number of
possible radial correlations from the fully disordered state in the
supercell.23 In our case, the cells were fixed to 3x3x3 times the
primitive cell, resulting in 54 atoms. The use of SQSs in the
determination of elastic properties of random alloys has been proved
accurate for many systems in which long-range interactions are
relatively small. According to von Pezold et al. (2010), in 3x3x3 face-
centered cubic (fcc) supercells, the sampling error associated with this
technique is less than 1%, which is within the accuracy of DFT
calculations.24
From the lattice parameter optimization, we employed the
Murnaghan equation to obtain the bulk modulus of each cell. After
volume optimization, the cells were fully relaxed, until the
convergence criteria of forces smaller than 0.01 eV/Å are reached.
Then, tetragonal and trigonal strains were applied to the optimized
B https://dx.doi.org/10.1021/acsami.0c18506
jj zz
k 0 0 0{
(2)
Elastic modulus estimations were obtained based on the Voigt−
Reuss−Hill approximation, with the elastic constants being derived
from the bulk modulus considering a body-centered cubic (BCC)
system
Bulk modulus, K = 1/9(C11 + 2(C12)) (3)
Shear modulus, G = 1/15(C11 − C12 + 3(C44)) (4)
Elastic modulus, E = 9KG /(3K + G) (5)
3. MACHINE LEARNING MODELS
3.1. Initial Dataset, Screening, and Featurization. A
few considerations were made regarding the original MP
dataset before deploying the ML algorithms. From the starting
13,619 entries, the dataset was limited to compounds
containing transition metals and post-transition metals only.
The idea behind this screening was to exclude compounds in
which bonds have a predominant ionic or covalent character.
Four thousand two hundred sixty-five (4265) entries remained
after the first filtering step. Following a few modeling tryouts,
the search space was restricted to fit the elastic property range
in which Ti alloys are found, i.e., K smaller than 150 GPa, G
smaller than 100 GPa, and average Poisson ratio between 0
and 1. Only 2566 entries were kept after this step. It is worth
reminding that our approach was focused on finding elastic
minima and subtle differences in the elastic properties between
similar compositions. Therefore, we were interested in
modeling the low-modulus region as best as possible. Using
all data, the relative error associated with the low-modulus
region increases, with the model missing most of the values
from our region of interest. In other words, the model would
adjust to relatively high-modulus materials, which are prevalent
in the dataset.26
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Figure 2. Twenty most important features to predict bulk modulus K (a) and shear modulus G (b) according to a univariate feature selection
(unsupervised). An additional analysis with the incorporation of mutual information (c,d) is also presented. As a reference for this project, a score
near 10.000 would represent a correlation factor near 0.1 between the feature and target.

For the ML model parameterization, we sought composi-
tion-based descriptors suitably depicting the elastic properties.
From the matminer library, the following featurization classes
were implemented: ElementProperty(magpie), BandCenter,
ValenceOrbital, IonProperty, TMetalFraction, CohesiveEnergy,
and AtomicPackingEff iciency. A detailed description of each
feature generated with these classes can be found in Ward et al.
(2018).15 In addition to those, we also exploited the Miedema
and Yang solid solution featurizers, which are semi-empirical
models for solid solutions. The Miedema model is based on
the heat of formation of binary compounds and has shown a
high reproducibility in regard to experimental data.27 The
model proposed by Yang and Zhang is focused on multi-
component alloys and incorporates the entropy of mixing and
the effect of the atomic size differences in a free energy-based
model.28 In total, 158 descriptors were obtained.
During the remaining dataset screening for the featurization
methods, 551 entries were lost due to the absence of important
information or because one of its elements was not included in
the Miedema model. Typical compounds filtered in this step
contained Yb, Pm, and Pa in their composition. Finally, 208
entries with a single or exact oxidation state were excluded to
avoid ionic compounds, one more time. A summary of the final
1826 instances’ K, G, and Poisson ratio values is shown in
Figure 1.
3.2. Feature Analysis. An important exploratory step in
ML projects is to check which features are potentially the best
to describe a specific target property.29,30 To achieve that, we
employed a univariate feature selection method implemented
in Keras as SelectKBest.17 This technique consists of performing
one linear fit for each feature-target pair, and then, it ranks the
features based on their independent coefficient of determi-
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nation (R2). The 20 most important features obtained with this
methodology, considering K as a target, are shown in Figure 2.
For the bulk modulus (K) determination, it seems that all
features are well-balanced, being equally important, despite the
following three prominent important features: mean ground-
state volume per atom (GSVolume), the fraction of magnetic
transition metals (TMetalFraction) in the composition, and
the cohesive energy (Figure 2a). Analogous behavior was
observed by testing a mutual info regression function (Figure
2c), which considers pairs of features for the fit. As can be seen
in Figure 2c, all features have a similar score. None of them
stands out, which is an indication that only high-capacity
models, including a high number of descriptive features, would
be able to model K.
The same trend is observed when the shear modulus (G) is
set as the target variable (Figure 2b). However, relevant
features for G are not the same as for K. In this case, only the
Poisson ratio is highlighted. The Poisson ratio also stands out
during the mutual information regression analysis (Figure 2d).
It is important to remark that this was expected. After all, the
Poisson ratio and G are physically related to each other.
However, according to a recent paper, the Poisson ratio is
challenging to be modeled based on composition, with the data
currently available.31 Therefore, incorporating the Poisson
ratio to the model creates a constraint that will be further
discussed in Section 3.5.
Now that a preliminary data selection and an analysis of the
features were concluded, we present the models implemented
during this work. Based on this section, the bulk modulus (K)
and the shear modulus (G) are assumed to depend on all the
available descriptors; therefore, to avoid any bias by selecting
preferred features by hand, the initial models incorporated all
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of the 158 available features. The properties K and G were not
available as descriptors, in any case.
3.3. Linear and Random Forest Regressors. Linear
regression models are least-squares linear fits in a multidimen-
sional space. Usually, linear models establish a baseline for
more elaborate models. However, they can hardly ever solve
complex regression problems. In this case, the least absolute
shrinkage and selection operator (LASSO) regularization is
often used to create sparse solutions to the model via variable
selection and ultimately improve the prediction performance.31
On the other hand, nonlinear machine learning algorithms,
such as decision trees, have become popular across the physical
sciences.32 Decision trees are hierarchical models that aim to
find a target value by asking the fewer if-else questions. Each
node on a tree splits the dataset once according to whether a
specific parameter, or a combination of them, is above or
below a threshold value.33 Random forest (RF) regressors are
simply a combination of multiple regression trees. The
predictive power of RF regressors comes from the diversity
of the trees/branches on them. However, an excessive number
of trees, or estimators, can lead to overfitting. Other essential
parameters of RF models are the criterion to define a split
(usually, a minimization of the RMSE), the number of features
considered for splitting a node, the maximum number of nodes
(splits), and the maximum allowed depth.
At first, the predictive accuracies of linear regression and
random forest regressors were evaluated. The random forest
models were optimized based on a random search algorithm,
searching for 50 different combinations of hyperparameters. All
models used 80% of the data as the training set to predict the
unseen 20%. For the full set of features, the following RMSEs
were obtained after optimization (Table 1). More details about
each model will be discussed further on.
Table 1. Linear Models, Random Forest Regressors, and
Neural NetworksRoot-Mean-Square Errors (RMSE) for
each Target, K (Bulk) and G (Shear)a
model RMSE for K RMSE for G
LM training (testing) 11.38 (15.87) 6.49
LM+LASSO, training (testing) 12.81 (14.67) 7.48
LM+ElasticNet, training (testing) 15.05 (16.47) 11.28
RF, training (testing) 4.99 (12.39) 2.38
full NN, training (testing) 3.90 (13.62) 2.05
reduced NN, training (testing) 8.84 (12.04) 3.36
a
The RMSE of the models adopted for Figures 3 and 4 are in bold;
full and reduced configurations are presented in Figure 5.
For the linear regression models, introducing LASSO
regularization improved the test-set predictive performance
from 15.87 to 14.67 (RMSE) for K (Figure 3). However, it was
not efficient regarding the shear modulus G. The inclusion of
ElasticNet, another regularization method, did not improve
any of the models. Based on our observations, the inclusion of
regularization methods seems to be ineffective when the G is
the target variable.
For the bulk modulus (K), the random forest regressor
achieved a notably low RMSE on the training step (4.99) and a
quite good RMSE during testing (12.39) (Table 1). Recent
works also displayed the power of random forest regressors to
predict the bulk moduli of crystalline materials based on
experimental data.34
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With the random forest model optimized, we could use the
built-in Extra Tree Classifier to obtain the relative importance
of each feature to the final forest. This method roughly
estimates how important one variable (descriptor) is in terms
of predicting values in a multidimensional space. The top 20
features identified for each target for the best random forest
regressor are displayed in Figure 4. For the shear modulus (G)
prediction, the Poisson ratio seems to be a dominant
descriptor, as expected. Properties related to the ground-state
volume per atom (GSVolume), cohesive energy, and melting
temperature were selected by both models, thus being relevant
to both target variables. Other relevant properties seem to be
associated with the covalent radius, electronegativity, the
number of p-valence electrons, and the position in the periodic
table (period and group).
Having obtained two baseline models, we proceeded with
the use of neural networks (NN). However, unlike the others,
the implementation of NN is not simple, as complex networks
are prone to overfit.35,36
3.4. Neural Networks. Neural networks are nonlinear
models that mimic the operation of the human brain. A
network of neurons, also called perceptrons, takes an input
value (e.g., a variable descriptor or a combination of them),
performs basic arithmetic operations, and then subjects it to an
activation function. In our case, we implemented sequential
neural networks with three hidden layers. The number of
neurons varied between 30 and 300, which was optimized for
each case via random search. The activation function was the
rectified linear activation function, also known as ReLU, and
the optimization occurred via the stochastic gradient
descendant (adam), implemented with the default hyper-
parameters from Keras/TensorFlow.17 An illustration of the
neural networks used throughout this work is shown in the
Supporting Information file (Figure S3).
The performance of the NN is indicated in Figure 5. Models
(a) and (c) (left-hand side), which were implemented with the
full set of descriptors (147) and a higher number of neurons,
tend to overfit easily, while models (b) and (d) displayed a
reduced test-set RMSE, despite the higher dispersion for the
(7.45) training data (in blue). Although high-capacity models might
(7.58) be able to achieve remarkably low RMSE during training, they
(12.39) diverge from a generalized model, as confirmed by the
(5.91) scattering of test-set points (gray) in Figure 5a,c. In this way,
(5.97) only low-capacity neural networks could surpass the test
(5.18) prediction capabilities of the random forest regressors (Table
1). The results with NN suggest that some knowledge on
feature importance can help to obtain generalized models
avoiding overfit. On the other hand, the implementation of the
random forest method is much more straightforward since
feature selection is built into the model.
In the pursuit of ultrahard materials, Mansouri Tehrani et
al.26 employed support vector machine (SVM) regressors to
model K and G in a workflow similar to the one presented
here. The authors have demonstrated a good agreement
between SVR predictions and DFT data, especially for
compounds with bonds of metallic or covalent nature.
Regarding feature importance, our models share most of the
relevant parameters highlighted in Mansouri Tehrani et al.’s
work, corroborating with their analyses. The main difference
lies in the absence of structural parameters in our models.
Thus, in this paper, descriptors associated with the electro-
negativity, valence electrons, and cohesive energy are highly
influential for G predictions (Figure 2). It is worth noting that
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Figure 3. (a,c) Modeling the bulk (K) and shear (G) modulus with linear and (b,d) random forest regressors (in red). The performance of the RF
is notably better, especially when comparing the test-set absolute error distributions (insets). LASSO regularization was included in the linear
model displayed in (a).

Figure 4. Feature importance according to an Extra Tree Classifier for (a) bulk (K) and (b) shear (G) modulus. The final forests had an average of
1928 and 874 nodes and an average maximum depth of 22 and 18 for K and G, respectively.

despite including 14 structural descriptors to their models,
Mansouri Tehrani et al. also reported difficulty in determining
the shear modulus (G), and a cross-validated RMSE of 16.5
GPa was obtained for G. In our case, we could obtain a lower
RMSE due to the use of the Poisson ratio as a descriptor and a
much narrower dataset (low-modulus centered, excluding ionic
compounds).
3.5. Elastic Property Predictions. Using ML models to
predict the elastic properties of alloys from a system of interest
is the main goal of this study. Looking forward to G
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predictions, we assumed the Poisson ratio for all alloys in
the Ti-Nb-Zr system being proportional to the configuration
entropy.37 The idea behind it is to identify candidates far from
the diagram’s edges (pure elements). To obtain elastic moduli
(E) comparable with experimental results, it is important to set
the Poisson ratio to reasonable values. In our case, we have
interpolated the Poisson ratio between 0.25 and 0.45, typical
values among Ti alloys. While this might be considered a
methodological artifact, such assumptions are often seen in the
specialized literature, for example, when estimating the elastic
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Figure 5. (a,b) Modeling K (bulk modulus) and (c,d) G (shear modulus) with neural networks. The models (a) and (c) were implemented with
the full set of descriptors. For models (b) and (d), only the selected descriptors (Figures 2 and 4) were made available, and neurons were limited to
50.
modulus via nanoindentation measurements.38 As stated
before, the idea of this work was to make elastic predictions
based on the composition only. In this sense, the average
Poisson’s ratio is an important feature to improve the shear
modulus predictions since it carries pieces of structural
information linked with the elastic anisotropy. Given that
our models are phase agnostic, an average Poisson ratio can be
assumed (or measured) for multiphase alloys, thus enabling
one to make use of the models to explore multiphase systems
without previous structural knowledge. More information
about the Poisson ratio assumptions can be found in the
Supporting Information file.
The elastic property predictions by the RF (left side) and
NN models (right side) are depicted in the ternary diagrams
presented in Figure 6. The RF regressors do not capture well
variations of the bulk modulus (Figure 6a). Nevertheless, they
exhibit two standout regions (Figure 6c,e) with a low shear and
low resultant Young modulus. Both regions are spotted close
to the bottom line of the diagram. The first region is the Ti-Zr
near-equiatomic proportions. In a recent assessment, Shiraishi
et al. identified a minimum Young modulus for the Ti-Zr
binary system close to this region. According to the authors,
Ti-60Zr alloys present an elastic modulus of 89 GPa, with a
relatively low shear modulus, 33 GPa.39 Recently explored Ti-
Zr-Ta ternary alloys close to this composition displayed an
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impressive yield strength, higher than 1 GPa.40 The second
region of interest is located at near 80% Ti. On this island,
highlighted by a red circle (Figure 6e), the elastic modulus
seems to be homogeneous and lower than that in its vicinity.
The region is extended while Ti is being substituted with Nb,
i.e., to the northwest of the diagram. Kim et al. recently
explored Ti-Nb-Zr alloys within this compositional range and
found out a surprisingly low elastic modulus, of 39 GPa, among
Ti-14Nb-18Zr (at. %) samples.41 Also, a few commercial
alloys, such as Ti-13Nb-13Zr, and gum metals could be fit into
this region. In other words, the ML models’ results are well-
supported by previous experimental observations.
In general, variations on elastic properties predicted via NN
are more subtle. The reduced model performed well while
predicting K. On the other hand, G predictions were flat, with
no significant modulus variation along with the ternary
diagram. Therefore, since we were looking specifically for
divergent points in which the G and E could be both low, we
returned to the NN with all descriptors to make the
predictions for G, even though the test-RMSE was slightly
worse than the reduced one (test-RMSE of 5.97 > 5.18). The
minimum elastic modulus obtained for both of the models is
around 67 GPa (Table 2). Despite the lower test-set RMSE for
NN, the final predictions of each model converge in the critical
regions of the compositional space. However, we do not expect
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Figure 6. (a, c, and e) Elastic property predictions by the RF and (b, d, and f) NNs. The region of interest is highlighted in (e) and (f), in red.

Table 2. Predictions of the Ti-22Zr-Nb (at. %) Alloys’ tional theory (DFT) to evaluate the stability of the beta phase
Elastic Modulus (E) from the Selected Region in several Ti-Nb-Zr alloys selected from the optimal region
highlighted in Figure 6.
Nb content (at. %) NN E (GPa) RF E (GPa)
At RT (room temperature), pure Ti exhibits a hexagonal
0 67.0 78.3 phase known as alpha (α-phase). At 882 °C, Ti displays an
4 71.0 78.7 allotropic transformation known as β-transus, which marks the
7 72.8 78.9 transition from α-phase to β (bcc). Alloying elements
11 74.7 79.5 considered that β-stabilizers such as Nb, Ta, Mo, and V may
15 77.3 80.6 reduce the β-transus temperature, allowing the β-phase to form
18 79.6 81.4 at lower temperatures.42 However, when β-structures are fast
22 82.2 81.9 cooled, an athermal omega phase can be formed on quenching
78 137.1 130.3 due to a first-order structural transition. Athermal ω is
metastable and has a size limited to a few nanometers, and
the absolute values predicted via ML models (Table 2) to be its formation occurs by the collapse of alternate pairs of (222)
exact compared to experimental verification. β planes, through a diffusionless mechanism.43 It often has a
deleterious effect on biomedical alloys, increasing the elastic
4. FIRST-PRINCIPLES AND CALPHAD CALCULATIONS modulus.44
4.1. Phase Stability. While our ML models do not require In the compositional range explored in this work, alloys
any structural information, they also cannot predict which should present a predominant beta-phase matrix when fast
phase or crystal structure might be related to the forecast cooled to room temperature, given that omega formation can
properties shown in Figure 6. To address this limitation and be avoided.45 Therefore, an assessment of the energy
also compare the ML results with a traditional approach, we formations of metastable phases, such as the omega
employed first-principles calculations based on density func- phase,46,47 is presented. To build the omega supercells, we
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Figure 7. Phase stability of beta (bcc) relative to the omega phase. (a) Energy difference between the two phases. (b) Degree of collapse of the
omega structures after relaxation. Illustrations of omega (c) and beta (d) structures after relaxation. Note that (c) and (d) are shown in perspective
and aligned to the (110) beta zone axis, a direction in which the collapse of (222) planes is evident. The supercells use CPK standard coloring for
the atoms.

explicitly modified the position of 36/54 atoms on the <111> temperature for alloys with Zr content near 22 at. % is close
beta direction to mimic the collapse of the {111} beta planes to 700 °C (Figure 8). Below this temperature, the alpha phase
observed in the first-order beta to omega phase transition
(Figure 7). From the fully collapsed structure, we estimated
total energies before and after relaxation with the aid of DFT.
The differences in energy between beta and omega after
relaxation are presented in Figure 7a. Regarding the structures’
energies, it could be inferred that an Nb content higher than
11.1 at. % is needed to stabilize the beta phase relative to
omega.
Still, to further evaluate the omega-phase stability, we take
the omega structures after relaxation, check each atomic
position, and compare it to the prior beta structure. A degree
of collapse (DOC) of 1 means that the atoms are at the same
positions expected for a fully collapsed, standard omega crystal
structure. On the other hand, a DOC = 0 means that the
omega structure fully relaxed into beta, i.e., the atoms returned
to their original positions (as in the prior beta phase). The
DOC for Ti-22Zr alloys with Nb contents varying from 0 to
22.2 at. % can be seen in Figure 7b. As expected, the DOC
tends to 1 in compositions whose omega energy is lower than Figure 8. CALPHAD assessments (beta-transus of three selected
beta energy, such as in the Ti-22Zr binary alloy. On the other alloys with Zr = 22 at. % (from left to right) are approx. 725, 680, and
hand, if the Nb content is higher than 11.1 at. %, then a 665 °C, respectively).
partially collapsed omega is obtained after relaxation, in a
similar fashion as reported by Devaraj et al.48 Accordingly,
among these compositions, the energy of the resultant beta should be formed by rejecting Nb to the beta matrix. The beta-
phase is lower than of the omega phase, after relaxation. stabilizing effect of Nb on Ti alloys is well-documented in the
Following our results, if formed, then the omega phase should literature.42 Our results also display this effect since the
be partially collapsed in alloys Ti-22Zr-14.8Nb and Ti-22Zr- increase in Nb causes a reduction of the beta-phase energy.
18.5Nb and completely unstable if the Nb content is higher However, while beta must be the dominant phase, it is still
than 22.2 Nb (at. %). possible to find the alpha phase (hexagonal, HCP) when the
Elements like Zr and Sn may help destabilizing omega, alloys are slowly cooled from temperatures above the beta-
which is often associated with a high modulus, and benefit the transus. Therefore, to keep the elastic modulus low, alloys must
alpha” phase formation. In this case, alpha” is a metastable be fast cooled to retain as much beta phase as possible.51 Water
phase, which has composition and structure much similar to quenching may be enough to avoid the formation of alpha,
beta, and it is assumed that their elastic properties should be eventually causing a minor formation of alpha” instead.52
similar.49 According to experimental evidence, the presence of 4.3. Elastic Properties. The analyses presented in Section
alpha” is pronounced in this system because Zr might help to 4.1 suggest that it is reasonable to assume that the beta phase
stabilize the beta phase energetically but not elastically, as will be dominant among these alloys since omega is unstable in
suggested by Hu et al. (2008).50 compositions with an Nb content higher than 18.5 at. %. Also,
4.2. Beta-transus. Now let us turn our attention to the it is established that alpha-phase formation is diffusion-
formation of the equilibrium alpha phase among these alloys. controlled and can be avoided by water quenching of alloys
Thermodynamic databases indicate that the beta-transus from the beta-phase field.53 All of the elastic properties
H https://dx.doi.org/10.1021/acsami.0c18506
ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
ACS Applied Materials & Interfaces www.acsami.org Research Article

Table 3. Elastic Coefficients and the Average Elastic Modulus (E), Shear Modulus (G), Poisson Ratio, and Voigt Elastic
Anisotropy (Eanis.), Obtained via DFT
Nb content (at. %) K (GPa) C11 (GPa) C12 (GPa) C44 (GPa) E (GPa) G (GPa) Poisson ratio Eanis. (Young)
0.0 102.3 109.2 98.9 14.3 30.8 10.6 0.45 2.70
3.7 90.6 96.8 87.5 14.3 30.2 10.4 0.44 2.97
7.4 90.6 96.5 87.6 17.6 35.4 12.3 0.43 3.78
11.1 122.9 127.9 120.4 14.6 29.9 10.3 0.46 3.78
14.8 104.9 110.0 102.3 15.1 30.8 10.6 0.45 3.79
18.5 104.9 109.5 102.6 15.2 30.5 10.5 0.45 4.25
22.2 135.7 133.6 139.9 14.9 27.4 9.4 0.47 13.72
77.8 144.6 151.9 141.0 19.8 40.9 14.1 0.45 3.52

Figure 9. (a−c) 2D projections of the Young modulus, (d−f) shear modulus, and (g−i) Poisson ratio, along with the crystal orientation. For the
shear modulus and the Poisson ratio, maximum possible values are plotted in blue and minimum possible values in green. Negative values are
plotted in red (f). Since the selected alloys have similar stiffness coefficients, they are represented by only one composition, at the central column.

presented herein were modeled within 3x3x3 BCC supercells,
yielding 54 atoms, as an initial structure.
The stiffness tensor coefficients (Cij, GPa) for a given
structure are defined as the derivative of the potential energy
with respect to small strain deformations, at corresponding
local minima. For cubic structures, only three coefficients are
needed.25 In the present work, C11 and C12 were obtained via
tetragonal strains, while C44 was obtained via trigonal strains,
subjecting the structure to shear (more details are provided in
the Methods section). The elastic coefficients presented herein
were obtained based on strains from −1 to 1% of the
optimized structure and were based on the Voigt−Reuss−Hill
(VRH) approximation. As one can see in Table 3, the elastic
I https://dx.doi.org/10.1021/acsami.0c18506
constants from compositions in the optimal region identified
via ML are similar to each other. Selected alloys, with Nb
contents varying from 0 to 22 at. %, present an elastic modulus
smaller than 40 GPa, with the elastic anisotropy growing with
the Nb content. These alloys also satisfy the Born−Huang
stability criteria, i.e., C11 − C12 > 0 and C12 > C44, which points
to the high elastic stability of the beta phase in this
compositional range.
Still, the origins of such a low elastic modulus (40 GPa) are
unknown. Previous authors suggested that finding alloys with
the difference between elastic constants C11 and C22 tending to
zero is fundamental. As a consequence of that, the single-
crystal Young modulus in the <001> direction and the shear
ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
ACS Applied Materials & Interfaces
modulus along <111>, {011}, {112}, and {123} slip systems
will tend to zero.54 Also, a low elastic modulus is often
associated with the reduction of C44, which leads to a low shear
modulus.
The difference between the elastic anisotropy for the
selected alloys and the binaries Ti-Zr22 and Nb-Zr22 is
depicted in Figure 9. Two-dimensional projections were
obtained using the Marmier et al.55 representation via the
elastic tensor analysis (ELATE) suite, developed by Gaillac et
al.56 Furthermore, our results indicate that an excess of Nb
atoms in the solid solution might enhance the stiffness of the
bonds, increasing the resultant elastic constants of the beta
phase (Nb-22Zr). This is evidenced in Figure 9 while
comparing the elastic modulus (E) and the shear modulus
(G) from the right-hand column (Figure 9c,f) with the others.
In summary, both of the ML algorithms predict a relatively
extended compositional field in which low-elastic modulus
compositions can be found. There are attractive candidates
more centered in the diagram (where the TNZT alloys would
be) and also low-cost compositions, close to the binary Ti-
22Zr (at. %), which have a relatively low electron-per-atom
ratio. In fact, stability assessments here presented show that the
beta phase in Ti-Zr binary alloys should exhibit an elastic
modulus smaller than in the ternary system (Table 3);
however, omega could still be formed and compromise the
elastic modulus obtained in final products, after cooling.
The divergence between the ML predictions and DFT
calculations regarding the Young modulus (E) was within the
expected range. For example, for Ti-22Zr-14.8Nb (at. %), the
ML models predicted a minimum E between 67 and 82 GPa,
while the DFT results indicated smaller values, as low as 30
GPa. It is worth reminding that via DFT, the elastic modulus is
underestimated since it was assessed for the beta phase only.
5. CONCLUSION
Despite the previous record of experimental data addressing
bonelike modulus alloys, this work aimed to obtain generalized
models of the elastic properties of Ti alloys, to then find novel,
prospective candidates for biomedical applications in the Ti-
Nb-Zr system.
First, we could state that the current elasticity data available
at the Materials Project allows obtaining good models to
describe the elastic properties of Ti-Nb-Zr alloys. The
implementation of packages such as pymatgen and matminer
was successful, given their speed and good reproducibility
generating the features to feed the models. Both random forest
and neural network architectures were able to model the elastic
properties. Their predictions regarding the elastic modulus
converged to some areas of the compositional space.
Although there are quantitative differences between DFT
and experimental values regarding elastic constants, these
differences are systematic; thus, the models provide an effective
method for showing trends in elastic behavior as a function of
composition. However, the absolute values of elastic constants
reported here must be used with care.
Within the first-principles methodology, DFT calculations
provided relevant information on the elastic properties of the
selected alloys. Based on DFT results, the Poisson ratio range
assumed for the ML predictions (between 0.25−0.45) was
accurate for this system.
In cases such as Ti-22Zr-3.7Nb and Ti-22Zr-7.4Nb, despite
the low elastic modulus estimations via ML, DFT results point
to an omega-phase formation at low temperatures. This might
J https://dx.doi.org/10.1021/acsami.0c18506
www.acsami.org Research Article
be associated with elastic instabilities of the beta phase in these
configurations. According to our methodology, alloys with
22Zr and Nb additions higher than 14.8 (at. %) are the most
promising candidates among ternary Ti-Nb-Zr alloys for
biomedical applications. This work suggests that there are
sweet spots in the compositional map, which could be further
explored experimentally.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsami.0c18506.
Summary of the elastic properties in the starting
database, after screening; properties of nine different
supercells after relaxation obtained via DFT; Poisson’s
ratio distributions assumed for the machine learning
models; predictions without assuming a Poisson ratio;
architecture of two neural networks after random
optimization (PDF)
■
AUTHOR INFORMATION
Corresponding Author
Caetano R. Miranda − Instituto de Física, DFMT,
Universidade de São Paulo, 05315-970 São Paulo, SP,
Brazil; orcid.org/0000-0002-8008-4907;
Email: cmiranda@if.usp.br
Authors
Camilo A. F. Salvador − Instituto de Física, DFMT,
Universidade de São Paulo, 05315-970 São Paulo, SP,
Brazil
Bruno F. Zornio − Instituto de Física, DFMT, Universidade
de São Paulo, 05315-970 São Paulo, SP, Brazil;
orcid.org/0000-0002-9464-2738
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsami.0c18506
Author Contributions
C.A.F.S. and C.R.M. conceived this research. C.A.F.S. designed
the machine learning models and SQS structures. DFT
calculations and data analyses were performed by C.A.F.S.
and B.F.Z. C.R.M. supervised the study. The manuscript was
written through the contributions of all authors. All authors
have approved the final version of the manuscript.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors gratefully acknowledge the financial support from
the Brazilian National Council for Scientific and Technological
Development (CNPq) through grants 155650/2018-1,
308333/2015-2, and 307064/2019-0 and the São Paulo
Research Foundation (FAPESP, 17/02317-2). We would like
to thank Logan Ward (Argonne National Laboratory) and Qi
Wang (Lawrence Berkeley National Laboratory) for the
support regarding the matminer package.
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