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Original Article

Biomimetic microtextured surfaces to improve


tribological and antibacterial behaviors of 3Y-TZP
ceramics

Jinyang Xu a,*, Xiaoming Zhang a, Jingyu Dai a, Dedong Yu b, Min Ji c,


Ming Chen a
a
State Key Laboratory of Mechanical System and Vibration, School of Mechanical Engineering, Shanghai Jiao Tong
University, Shanghai 200240, PR China
b
The Second Dental Center, Shanghai Ninth People's Hospital, College of Stomatology, Shanghai Jiao Tong University
School of Medicine, Shanghai 201999, PR China
c
School of Mechanical and Automotive Engineering, Qingdao University of Technology, Qingdao 266400, PR China

article info abstract

Article history: Surface texturing has been a powerful means to improve the service performance of
Received 25 November 2022 various engineering materials. The 3 mol% yttria-stabilized tetragonal zirconia polycrystal
Accepted 6 January 2023 (3Y-TZP) represents the most-used ceramic oxide in restorative dentistry due to its
Available online 17 January 2023 excellent esthetic effects, good chemical stability and superior biocompatibility. However,
such materials show the limited ability of tribological and antibacterial performance for
Keywords: dental applications. In the present work, a bio-inspired design of textured surfaces was
3Y-TZP ceramics conducted based on the microstructural analysis of butterfly wings, peacock tail feathers,
Biomimetic textures and dolphin skins to improve the service performances of 3Y-TZP ceramics for dental
Wettability behavior applications. Three types of microtextures, including micro-grids, micro-feathers, and
Tribological performance micro-grooves, were fabricated onto the 3Y-TZP ceramics using the laser ablation tech-
Antibacterial properties nique. The effects of different microtextures on the wettability, tribological and antibac-
terial behaviors of 3Y-TZP ceramics were studied. The results indicate that all the
biomimetic microtextures can effectively improve the service performance of 3Y-TZP.
Wettability acts as a decisive factor for the tribological and antibacterial performances of
textured ceramic surfaces. The bio-inspired microtextured surfaces all show hydrophobic
behavior, thus yielding an effective improvement of antibacterial properties for 3Y-TZP.
Moreover, the micro-grids inspired by the butterfly wings basically perform the best in
tribological and antibacterial tests compared with the other counterparts.
© 2023 The Author(s). Published by Elsevier B.V. This is an open access article under the CC
BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

* Corresponding author.
E-mail address: xujinyang@sjtu.edu.cn (J. Xu).
https://doi.org/10.1016/j.jmrt.2023.01.039
2238-7854/© 2023 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://
creativecommons.org/licenses/by-nc-nd/4.0/).
j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 3 ; 2 3 : 1 3 6 0 e1 3 7 4 1361

analyzed in principle that surface texturing by laser ablation


1. Introduction can reduce corrosion (such as C element content) and increase
surface hydrophobicity by changing the surface chemical
With the increased awareness of oral health, bioceramics composition. In sum, wettability is firmly related to surface
have emerged and gradually substituted conventional poly- morphology, surface free energy, and surface chemical
mers and metals in dentistry to improve clinical performances composition. Additionally, surface texturing shows benefits in
[1]. Among bioceramic families, 3 mol% yttria-stabilized reducing friction and wear amount at the contact interfaces
tetragonal zirconia polycrystal (3Y-TZP) represents the most- [22e24]. The phenomena are attributed to the reduced contact
used ceramic oxides for fabricating dental prostheses due to length and entrapment of wear debris for textured surfaces
its excellent esthetic effects, desirable chemical stability, and during the sliding process, according to Wu et al. [25]. To date,
superior biocompatibility [2e9]. Additionally, since zirconia- various textured surfaces have been applied to many engi-
based ceramics are nearly inert biomaterials composed of neering fields with the aim of enhancing tribological behavior
high-purity zirconia and possess the advantages of tooth-like or improving anti-wear ability. For instance, Ryk et al. [26]
color, high corrosion resistance, and good biocompatibility, reported a 30% friction reduction of reciprocating automotive
they have become very popular in clinical dental prostho- components by using textured surfaces. Wu et al. [27] ach-
dontics to fabricate inlays, implant crowns, and fixed bridges ieved a remarkable reduction of cutting forces and friction
[10e12]. Despite their superior mechanical and physical work when using textured cutting inserts for machining tita-
properties, 3Y-TZP ceramics show a very limited ability of nium alloys. Xing et al. [28] confirmed the feasibility of func-
antibacterial and tribological performances for realistic dental tional textures in reducing friction coefficient and wear rate
applications. This is attributed to the harsh service environ- for Si3N4/TiC ceramic sliding against steel under dry friction.
ment and tough interactions with human soft and hard tis- Kümmel et al. [29] prepared different microtextures on un-
sues in the oral cavity. Under the action of the masticatory coated WC/Co cutting inserts and stated that introducing
muscles, the ceramic dentures and periodontal tissue tend to desired textures could significantly inhibit the built-up edge
promote rhythmic movements, including cutting, horizontal formation and decrease wear progression. Fang et al. [30]
grinding, and smashing, which causes excessive wear on highlighted the benefits of texturing dimple patterns on
tooth surfaces. Additionally, the oral cavity, serving as an tungsten carbide parts in enhancing anti-wear properties and
absolute bacterial environment, often provides suitable reducing friction. Concerning the dental applications, very
reproduction conditions for the formation of plaques, which limited studies [5,18,31] are reported in the literature to apply
in turn causes dental caries, gum atrophy, and various oral textured surfaces to improve the anti-wear performance of
inflammations [13,14]. The above evidence highlights the zirconia ceramics.
importance of anti-wear and antibacterial abilities for ceramic Moreover, surface texturing has unique advantages in
dentures. enhancing antibacterial behavior for denture materials. Con-
To improve the service performances of target materials, ventional antibacterial methods such as brushing teeth are
surface texturing has become a powerful means in surface difficult for ordinary people to achieve cleaning standards,
and interface engineering to create various nano/micro tex- which are greatly affected by individuals’ living habits. Drug
tures. The most important feature of a surface texture lies in sterilization will destroy the balance of oral flora and even
its functionality. With the help of interface and scale effects, cause poisoning. Long-term use of drug sterilization will pro-
significant changes in optical, acoustic, thermal, electrical, duce drug-resistant bacteria and cause a decline in the effect.
magnetic, mechanical, and biological properties of texture Differing from the above two methods, surface texturing in-
surfaces can be realized. Previous studies have indicated that hibits plaques by reducing the attachment of bacteria, which
surface texturing can alter surface characteristics, induce the works from the first step when bacteria enter the human
transition of wettability and promote tribological enhance- mouth. To design effective microtextures, the bionic design
ments [14e18]. Thus, desired functional surfaces can be would be a feasible tool. After hundreds of millions of years of
created by the modification of surface structures. evolution, the surfaces of biological skins have evolved into
Regarding denture materials, wettability, wear resistance, anti-wear, antibacterial, and super-hydrophobic structures,
and antibacterial properties are crucial indicators for evalua- which have been widely used in engineering fields [21]. Some
tion. Surface texturing can alter the wetting properties of natural surface topographies, such as insect wings, moth eyes,
zirconia surfaces. In general, hydrophilic surfaces are favor- and geckos skin, have been proved to be antibacterial. Chung
able for cell adsorption, while hydrophobic surfaces are un- et al. [32] designed a surface microstructure based on the shark
favorable. Traditional dentures consist of implants, skin to disrupt bacterial biofilm formation without the use of
abutments, and restorations. The surface treatment of im- fungicides, which achieved a 50e80% reduction in coloniza-
plants should be aimed at enhancing the osseointegration tion. The antibacterial behaviors of these biological surfaces
process, so a super-hydrophilic surface is required; for abut- rely mainly on the effect of micro-nano structures on bacterial
ments, the antibacterial properties need to be considered adhesion rather than the chemical composition of the surface.
since plaque attachment can cause diseases such as peri- Besides, bacterial adhesion and inhibition are also influenced
implantitis. Zirconia ceramics are featured by a high surface by the wetting behavior of target surfaces [14,20,33]. The
free energy, and thus they exhibit a hydrophilic nature [19,20]. adsorption capacities of hydrophilic and hydrophobic surfaces
The experimental work done by Ji et al. [5] has proved that the for specific bacterial flora are quite different. The use of trapped
surface wettability can be changed or even reversed by air layers on the hydrophobic surface can inhibit and prevent
modifying the shape of the microtexture. Jing et al. [21] the adhesion of certain bacteria.
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Fig. 1 e The SEM images of microstructures of wing surfaces for (a) Stibochiona nicea (Gray) (1 mm) [35]; (b) Vanessa indica
Herbst (10 mm) [36]; (c) Pieris rapae (10 mm) [36].

To develop anti-wear and antibacterial surfaces for 3Y-TZP and other pollutants are mixed, the surfaces of butterfly wings
ceramics, the bionic design method was adopted in the cur- can always keep clean and dry [20]. Previous studies have
rent work. The paper attempts to prepare functional textures found that the unique ultrastructure of the butterfly wing
using laser ablation method to enhance the service perfor- scale surface is the key factor for its hydrophobic and self-
mances of 3Y-TZP for dental use. The topographical features cleaning performance [21]. Fig. 1 shows the scanning elec-
of three microtextures, including micro-grids, micro-feathers, tron microscope (SEM) images of microstructures of wing
and micro-grooves, were inspired by the microstructural surfaces for Stibochiona nicea (Gray) [35], Vanessa indica
analysis of butterfly wings, peacock tail feathers, and dolphin Herbst [36] and Pieris rapae [36]. These butterfly scales have
skins. Considering the high machining efficiency and grid-like micro-textures on the surface and are regularly ar-
noncontact characteristics of the laser ablation method [34], ranged, with ridges and ribs parallel to each other distributed
the picosecond laser processing system was used to prepare between the scales. Inspired by the closely-arranged grid
the designed microtextures onto the 3Y-TZP samples. The structure on the surface of butterfly scales, the biomimetic
contact angle measurements and tribological tests were car- model of micro-grids was established. The bionic surface was
ried out to compare the wettability and anti-wear behaviors of closely arranged with regular grid-like groove structures to
laser-textured 3Y-TZP samples. Staphylococcus aureus was also improve the hydrophobic performance. Additionally, previous
cultured on the nontextured and laser-textured samples to studies indicate that when the laser processing pitch
evaluate the antibacterial properties of different micro- increased to 100 mm, the surface structure was gradually
textures. The paper clarifies the mechanisms of different revealed, and the grid structure was not yet apparent. When
microtextures affecting the service performance of zirconia the laser pitch was increased to 150 mm and 200 mm, the sur-
ceramics for dental applications. face structure could be fully revealed [23]. Based on the sur-
face structure of butterfly wings and the characteristics of
laser processing technology, the texture model was designed,
2. Experimental design, implementation and as shown in Fig. 2.
measurement Peacock tail feathers are proved to possess exceptional
wetting properties. As depicted in Fig. 3(a) [37], the droplets
2.1. Bionic design of microtextures exist in an approximately spherical shape and can roll freely
at a certain inclination angle on the surface of the peacock
Butterfly wings have strong hydrophobicity and self-cleaning feather. This is due to the unique structure formed by the
properties. In the natural environment, where rain, dust, growth and arrangement of the feathers. Fig. 3(b) is a peacock

Fig. 2 e The schematic diagram of the geometrical features of the designed micro-grid textures (Unit: mm).
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Fig. 3 e The microstructure of the peacock feathers [37].

feather structure magnified 10 times under an optical micro- reduction. While for water striders that can stand and walk on
scope. As shown in Fig. 3(c), when increasing the observation the water surface, their legs must have super-hydrophobic
magnification, the branches of peacock feathers are structures to hinder water infiltration. It can be seen from
composed of closely arranged scale-like structures, and there Fig. 5 (c) and (d) that their leg setae also have irregular groove-
are tiny gaps between each column of feathers. In contrast, like structures [40]. These grooves are not in the same direc-
there is a larger gap between rachides. The width of each quill tion but staggered from each other at an angle. Therefore, the
is about 40 mm, and the width from the rachis to the edge of surfaces of the above three organisms all have or can be
the quill is about 300 mm [37]. Considering the characteristics simplified into parallel grooves, and a biomimetic model can
of laser ablation methods, the bionic model shown in Fig. 4 be derived as shown in Fig. 6. The grooves in the model are not
was established, in which the microstructure characteristics rectangular grooves but have evenly distributed arc-shaped
of the peacock feathers were preserved, and some geometrical depressions with a radius of 300 mm, which is to simulate
parameters were adjusted appropriately. the uneven state of the grooves on the biological surface. It is
The dolphin surface is very smooth, containing an average speculated that this surface may be hydrophobic and friction-
roughness of only 5.3 mm. As can be seen from Fig. 5 (a), the reducing.
dolphin skin is not a perfectly smooth surface but has folds all
over the body [38]. These folds can be simplified as grooved 2.2. Fabrication of microtextures
microtextures with equal spacing and depth. The shark sur-
face is made up of numerous overlapping scales called The 3Y-TZP powders were purchased from a commercial
“dermal denticles”. It can be seen from Fig. 5 (b) that these company to fabricate the zirconia workpiece samples. At the
protrusions are a segment of ridges along the shark's initial stage, the powdery 3Y-TZP was firstly dry pressed with
advancing direction. They are oriented in the same direction a pressure of 90 MPa and then hot pressed at 300  C with a
but not strictly along a straight line [39]. The groove-type pressure of 240 MPa to form the green-compact billets [41].
microtexture can be obtained by simplifying the protrusions Then, the ceramic blocks were sintered inside a sintering
that are not along the same line as the protrusions are con- furnace at the sintering temperatures of 1500  C under the
nected in sequence. The approximate groove-type micro- atmospheric environment. The bulk density and Vickers
textures of dolphins and sharks are mainly used for drag hardness of the fully-sintered 3Y-TZP samples are 6.04 g/cm3

Fig. 4 e The schematic diagram of the geometrical features of the designed micro-feather textures (Unit: mm).
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Fig. 5 e The organisms with grooved microtextures: (a) dolphins and their folds across the skin surface [38]; (b) sharks and
their surface ridges [39]; (c) SEM image of water strider leg bristles [40]; (d) SEM image of grooves on the surface of water
strider leg bristles [40].

and 1295 HV, respectively [41]. The fully-sintered 3Y-TZP evaporate the solid material for chip separation. The method
sample is composed of 98.75% tetragonal phase and 1.25% is more flexible and can realize the mapping of 2D data to the
monoclinic phase, and its grain size is within 522.60 nm surface of the 3D model, generate 3D data, and realize the
through our previous XRD analysis [41,42]. Before the laser marking of the physical surface. The laser processing tech-
treatment, all the ceramic samples were carefully polished to nology can be seamlessly connected with the AutoCAD soft-
have the identical size of 10 mm (length)  10 mm ware without complex conversion and has a powerful
(width)  5 mm (thickness). To create designed microtextures secondary development interface, which is suitable for a
onto the 3Y-TZP samples, the laser processing method was broad range of applications. In the present study, the ultra-
adopted. It is a very promising and powerful manufacturing violet picosecond processing system was used for the surface
method being extensively used in various engineering fields. texturing operation. The relevant geometrical parameters of
Its principle lies in projecting the laser beam onto the surface the three types of microtextures are listed in Table 1, in which
of the material to obtain highly-localized energy to melt or the texture density signifies the ratio of the area cut by the

Fig. 6 e The schematic diagram of the geometrical features of the designed micro-groove textures (Unit: mm).
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of the friction coefficients with the number of cycles was


Table 1 e The geometrical parameters for the designed
analyzed. Finally, the wear morphologies of each textured 3Y-
surface textures.
TZP surface were examined by the JSM-7800F SEM.
Texture Side length/ Interval Depth Texture
To evaluate the antibacterial properties of textured 3Y-TZP
type diameter (mm) (mm) density
samples, Staphylococcus aureus (S. aureus, ATCC 25923) was
(mm) (%)
selected as the test strain. The strains were provided by the
Micro-grids 440/300 200 35 76.69
China General Microbiological Culture Collection Center
Micro- 420/100 138/130 35 69.45
feathers
(CGMCC). After activating and cultivating the strains pre-
Micro-grooves 300/80/600 170 35 53.29 served on the slant, the bacterial liquid of P2 generation in the
growth logarithmic phase was obtained. The 60 mL of Staphy-
lococcus aureus suspension (107 CFU/mL) was inoculated on the
surface of each sample. It was diluted 10, 100, and 1000 times
laser to the nominal texturing area. Figs. 7 and 8 show the with normal saline. Afterward, 100 mL of the diluted bacterial
photographs and SEM morphologies of the original and three solution was taken to inoculate in a nutrient agar petri dish
textured 3Y-TZP surfaces after laser processing, respectively. and placed in a constant temperature incubator at 37 C for
It is noted that despite the existence of certain defects and 24 h. Then, photographs were taken by a gel imaging system,
burrs along the edges of textured surfaces, the geometrical and the number of colonies in each petri dish and the anti-
boundaries and contours of the microtextures are very clear. bacterial rate of each group of samples were calculated. Note
The SEM equipment used in this study is a JSM-7800F super- that the antibacterial rate is defined as (A-B)/A  100%, where
resolution field microscope made by JEOL Ltd. A signifies the average bacterial colony number of the non-
textured ceramic surface, and B denotes the average bacterial
2.3. Surface performance testing colony number of the textured ceramics. Finally, bacterial
adhesion was examined by the fluorescence microscope
For wettability evaluation, the DSA 100 drop-shape analyzer (OLYMPUS GX71, Japan).
was used to measure the liquid contact angle of the three
biomimetic surfaces. The used liquid was deionized water,
and each drop was 5 mL. After the drop was stabilized on the 3. Results and discussion
tested surface for 15s, the contact angle was photographed by
a CCD camera and then automatically calculated by the image 3.1. Wettability assessment
identification software.
To assess the tribological properties of textured zirconia Wettability is an important property to characterize the
ceramics, the reciprocating frictional tests, as shown sche- interaction between a solid surface and a liquid, closely
matically in Fig. 9, were conducted for the textured 3Y-TZP related to phenomena such as capillary action. A direct mea-
surfaces. To meet the simulation conditions, the experiments surement of surface wettability is the contact angle formed by
were carried out under the lubricated sliding condition using the liquid on the surface. The larger the contact angle, the
distilled water as the medium, and the natural teeth shown in more hydrophobic the surface becomes. The hydrophobic
Fig. 10 were selected as an antagonist body to perform 2000 surfaces can inhibit the adhesion of bacteria and reduce the
cycles of friction with the 3Y-TZP samples to replicate the infiltration of lubricating liquid in wet friction so that the
mutual movement between the occlusal ceramic restorations. lubricating liquid can fully function and reduce the friction
A vertical load of 4 N was set to simulate the state of contact coefficient. According to the calculation of the Young's equa-
between the natural teeth in the oral cavity and the surface of tion, the intrinsic contact angle of zirconia ceramic is about
the material, according to the literature survey [5,43]. The one- 75 , which belongs to a hydrophilic material, so it is necessary
way friction stroke of 3 mm and the reciprocating frequency of to introduce microtexture to change its wettability. In this
2 Hz were adopted to model the chewing process of the clin- test, the static contact angle test was used to identify the
ical conditions. Note that the sliding direction was set parallel change in surface wettability of textured zirconia ceramics.
to the microtexture direction, as shown in Fig. 11. The varia- Fig. 12 shows the contact angle measurements of original and
tion of frictional forces during the sliding process was recor- textured 3Y-TZP surfaces with deionized water. It is clear that
ded in-situ by the high-precision force sensor, and the change the introduction of the three microtextures has changed the

Fig. 7 e The photographs of the original surface and the three kinds of the microtextured surfaces.
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Fig. 8 e The SEM morphologies of the original surface and microtextured surfaces.

original hydrophilic zirconia surface into a hydrophobic sur- remains on the surface, and the grooves are completely filled
face, in which the micro-grid texture changes the most, and with air, as illustrated in the Cassie model of Fig. 13.
the contact angle reaches over 150 . According to the formula of the Wenzel model, the theo-
On an ideal smooth and flat surface, the intrinsic contact retical contact angle of the microtextures can be calculated, as
angle of the zirconia ceramic surface can be obtained ac- listed in Table 2. By comparing the test values, it is found that
cording to the Young's equation, which is about 75 . However, the contact angle error of the micro-groove texture is very
the zirconia ceramic samples used in the experiments cannot small, while the micro-grid and micro-feather textures have
reach the ideal state, and the surface has a certain roughness.
Therefore, from the test results in Table 2, it can be seen that
there is a specific error between the surface contact angle and
the theoretical intrinsic contact angle for the textured 3Y-TZP
samples.
When analyzing the wettability of a workpiece sample,
surface roughness needs to be considered. For non-ideal sur-
faces, the contact angle of the material surface can be cor-
rected according to the Wenzel and Cassie models shown in
Fig. 13. The Cassie model assumes that the liquid fills all the
groove structures on the solid surface, and in this case, the
surface roughness amplifies the wetting behavior of the ma-
terial itself. When the roughness is large, the air will form an
air cushion in the groove and cause the failure of the Wenzel
model. In this case, it will create a situation where the liquid
Fig. 9 e The schematic diagram of the frictional tests.
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conditions. In contrast, the original reference surface yields a


much higher average friction coefficient of 0.342, which is
approximately 1.91 times that of the micro-gird surface. The
phenomenon suggests that using the original 3Y-TZP for the
fabrication of dentures cannot yield a very reasonable anti-
friction behavior, and there is still a lot of room for improve-
ment via the introduction of microtextures. Additionally, the
frictional curve of the original surface tends to rise up within
250 cycles relative to the other three textured surfaces, which
denotes a running-in stage, as shown in Fig. 15. The phe-
nomenon may be due to the fact that the original surface has a
Fig. 10 e The natural teeth used in the frictional tests.
smaller contact area with the natural teeth and possesses
larger frictional stress than the textured surfaces. Conse-
large contact angle errors. The possible reason may be due to quently, the friction coefficient increases faster. When the
the fact that the actual contact angles for the micro-grid and sliding process becomes stable, the friction coefficient still
micro-feather surfaces are in an intermediate state between fluctuates greatly due to the fact that the natural tooth surface
the Wenzel and Cassie models, as shown in Fig. 14, where the is uneven, and the friction coefficient changes significantly
Wenzel model is not fully applicable at this time. On the other during the reciprocating sliding contacts. In addition, the
hand, the formula of the Wenzel model results from experi- micro-grid yields the lowest value of friction coefficient, fol-
ence and modeling, and the different topographic parameters lowed by the micro-feather and micro-groove, the order of
of the actual texture surface will have complex effects on its which is roughly opposite to that of the texture density, as
contact angle. depicted in Table 3. This is because the higher the density of
Through the above analysis, it can be concluded that the the surface texture, the smaller the contact area with the
surface microtexture can change the wettability of 3Y-TZP friction member during the reciprocating sliding cycle. This
ceramics. By adjusting the microtexture parameters, the means that the actual distance reduction of sliding friction in
wetting effects of textured 3Y-TZP surfaces can be enhanced. each cycle leads to a decrease in friction. Therefore, a smaller
The micro-grid structure has the largest contact angle and, friction coefficient is produced when the sliding contacts
thus, the best hydrophobicity, while the micro-feather texture enter a steady state [31].
is affected by factors such as surface roughness. Its actual Additionally, the wear morphologies of different textured
contact angle is smaller than that of the micro-groove texture, 3Y-TZP samples after the frictional tests were also charac-
and its hydrophobicity is relatively the lowest. terized by the SEM. The obtained results are shown in Fig. 16.
It is noted that all the textured surfaces have experienced a
3.2. Friction and wear performances certain degree of wear under the action of reciprocating fric-
tion. The micro-feather basically undergoes the largest level of
The reciprocating frictional experiments were conducted on wear during the sliding contacts under the similar clinical
the original ceramic surface and micro-textured surfaces conditions. It is seen that most of the micro-feature bound-
against the natural teeth under wetting conditions. Fig. 15 aries have been severely damaged, and fragments and broken
shows the variation curves of the friction coefficients of bars become very prevalent after the wear tests, which makes
different surfaces within the 2000 cycles of reciprocating the microtexture lose the proper functionality. Additionally,
sliding, and Table 3 lists the comparison of the average friction the micro-groove undergoes a relatively lower extent of wear
coefficients between different 3Y-TZP surfaces. Results indi- damage, where the main damage types are cracks initiated at
cate that under the lubricated frictional conditions, all the the corner of the microtextures. In contrast, the micro-grid
designed biomimetic microtextures show the ability to reduce exhibits the lowest amount of wear, where only very few
friction coefficient compared with the original surface, which broken bars are identified on the worn surface. The results
indicates the beneficial effect of the surface texturing on suggest that the micro-grid has more advantages in resisting
improving the friction behavior of 3Y-TZP ceramics during wear, maintaining its own shape accuracy, and is more able to
rubbing against the natural teeth under the similar clinical serve in the chewing environment of the oral cavity.

Fig. 11 e The schematic diagram showing the friction direction during the tribological tests.
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Fig. 12 e Results of the contact angle measurements of 3Y-TZP samples.

Table 2 e Comparison of the theoretical and test values of


surface contact angle.
Texture pattern Original Micro- Micro- Micro-
surface grids feathers grooves
Contact Theoretical value 75.0 135.0 128.0 114.3
angle Test value 33.1 151.2 103.2 114.1
(o)

Through the comparison of the friction coefficient, it can


Fig. 14 e The intermediate state between the Wenzel and
be found that different surface microtextures exhibit dispa-
Cassie models.
rate wear resistance, and the results are firmly related to the
texture density and structural strength. The structural
strength determines the fracture resistance of the textured
surfaces and provides the corresponding mechanical strength addition, as shown in the contact model of Fig. 17, the distilled
to withstand the external force caused by the chewing water continuously moves through the surface of the sample,
movement of the oral cavity. The greater the structural which brings out the wear debris stored inside the texture and
strength, the slight the damage, and the anti-friction effect is enters the friction surface during the subsequent friction
enhanced to a certain extent. The micro-feather texture un- process, forming a cycle to increase the wear extent. More-
dergoes noticeable wear due to its edge structural strength. In over, due to the influence of structural strength and wear

Fig. 13 e The schematic diagram of the Wenzel and Cassie models.


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Table 3 e Comparison of the friction coefficients of


different surfaces.
Original Micro- Micro- Micro-
surface grids feathers grooves
Average friction 0.342 0.179 0.210 0.239
coefficient
Decrease ratio 0 0.477 0.386 0.301
Texture density / 76.693 69.450 53.292
(%)

debris, the friction and wear severity of micro-feather textures


tend to get intensified.
Based on the above analysis, it can be concluded that the
surface texture can reduce friction and wear to a certain
extent under the influence of wettability changes by control-
ling the degree of surface porosity and structural strength. The
Fig. 15 e The variation curves of the friction coefficient of three textures designed in the work have yielded obvious anti-
original and textured 3Y-TZP surfaces. friction effects. Among them, the micro-grid texture shows

Fig. 16 e The wear morphologies of the microtextured 3Y-TZP ceramic surfaces.


1370 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 3 ; 2 3 : 1 3 6 0 e1 3 7 4

Fig. 17 e A schematic diagram of the contact between the


textured 3Y-TZP ceramics and the natural tooth.

Fig. 19 e The bacterial colonies number and antibacterial


rate in terms of different samples.
the most significant impact on reducing friction and wear,
being the preferred choice for clinical applications followed by
the micro-feather and micro-groove textures. hydrophilic surface, bacteria are more likely to adhere to the
bottom edge of the texture for the maximum contact area,
3.3. Antibacterial properties while for the hydrophobic surface (Fig. 20(b)), it is difficult for
the liquid to contact the bottom end of the textured gap due to
The culture dishes of Staphylococcus aureus were placed in a the existence of a large amount of air in the textured gap, thus
constant temperature incubator at 37  C for 24 h. After the reducing the bacterial adhesion. Moreover, a capillary pres-
cultivation, the bacteria inoculated on the surface of each sure difference could exist between medium in the texture
sample were diluted and transferred to an agar petri dish for groove and the surrounding that helps to prevent the adher-
cultivation, and the distribution of bacterial colonies in the ence of the bacteria on the sample surface. This also explains
petri dish is shown in Fig. 18. The number of colonies on the why the micro-grid texture shows the highest hydrophobicity
surface of each sample was counted using the plate counting and yields the best antibacterial properties.
method, and then the antibacterial rate of each sample was Using the fluorescent staining properties of DAPI, the
calculated, as shown in Fig. 19. The results indicate that all the bacterial adhesion on the textured surfaces was examined by
designed microtextures show noticeable antibacterial effects a fluorescence microscope (Ref. Fig. 21). It is found that the
compared with the original reference surface. Among them, texture shape could be vaguely seen through the fluorescent
the micro-grid texture exhibits the best antibacterial proper- spots on the textured surface, and the clarity reflects the
ties, followed by the micro-feather and micro-groove, and its number of colonies. The bacterial distribution on the original
antibacterial rate reaches about 65.14%. This suggests that the surface is uniform and dense, and there are certain accumu-
micro-grid would be the preferred texture type for clinical lation and overlapping phenomena. But there are few and no
applications to achieve the best antibacterial behavior of obvious regularity in the distribution position. Compared with
dentures. the original surface, the bacteria distribution on the three
Regarding the mechanisms of bacterial adhesion, the ulti- textured surfaces is less, but all have aggregation phenomena
mate form of bacteria on teeth is the formation of biofilm. The to a certain extent, mainly concentrated at the top edge of the
bacteria have to experience several periods, including initial textured surface. Among them, the bacterial aggregation be-
reversible adhesion, irreversible adhesion, as well as biofilm comes more pronounced on the micro-groove surface. The
growth, maturation, and dissemination [30]. For the initial density is high, and there is an obvious overlapping phe-
reversible adhesion, the wettability of textured surfaces usu- nomenon. This indicates the existence of a certain tropism for
ally poses a significant influence. As shown in Fig. 20(a), for the bacterial growth. The phenomena are related to the bacteria

Fig. 18 e The photographs showing the bacterial colony distribution in the petri dish.
j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 3 ; 2 3 : 1 3 6 0 e1 3 7 4 1371

Fig. 20 e The schematic diagram of bacterial adhesion for (a) the hydrophilic surface and (b) the hydrophobic surface.

Fig. 21 e The fluorescence staining characteristics of bacterial adhesion for different 3Y-TZP surfaces.

Fig. 22 e The schematic diagram of bacterial rupture on a microtextured surface.


1372 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 3 ; 2 3 : 1 3 6 0 e1 3 7 4

adsorption on the textured surfaces with different wettability, friction and anti-wear performances. The micro-feather
where hydrophobic surfaces cause bacteria to concentrate on shows a better effect on reducing friction than the
the top edge of the textures. As seen in Fig. 22, when bacteria groove-like texture, but due to the influence of structural
tend to adhere onto the textured surface, the suspended part strength and debris, its wear is more severe than that of the
will rupture and eventually collapse due to the effects of micro-groove texture.
multi-level textured structures [44]. The bacterial cell wall  The adhesion and reproduction of bacteria are disturbed
attaching to the surface often undergoes a large stretch and due to the changes in surface wettability and the presence
deformation, resulting in an instant extreme increase in the of roughness. All the biomimetic surfaces designed in the
surface area. Then the irreversible mechanical rupture of cell study have an obvious inhibitory effect on Staphylococcus
walls occurs, leading to the decline of the bacterial population aureus compared with the original reference surface.
[45]. The phenomena make the bacteria more directional in Among them, the micro-grid texture exhibits the best
distribution to ensure their survival. antibacterial properties, followed by the micro-feathers
In sum, the designed biomimetic microtextures can and micro-grooves, and its antibacterial rate reaches
change the wettability of zirconia ceramics and consequently about 65.14%. It is confirmed to be the most preferred
affect bacterial adhesion. The Staphylococcus aureus in the texture type amongst the examined textures for clinical
experiment prefers to adhere to the hydrophilic surface, so applications to achieve the best antibacterial behavior of
the use of the air film generated by the super-hydrophobic dentures.
surface can inhibit and reduce the bacterial adhesion [46].  The hydrophobic surfaces designed in this work all
Meanwhile, the existence of surface texture also influences exhibit excellent wear resistance and antibacterial prop-
the adhesion, extension, and reproduction of bacteria and erties due to their influence on friction debris movement
thus exerts an antibacterial effect. This implies that the use of and bacterial adhesion. The micro-grid performs better
hydrophobic microtextures can possess the advantage of than the other two microtextures in terms of hydropho-
improving the antibacterial behaviors of dentures for the bicity, friction and wear properties, and antibacterial
clinical applications. Finally, due to the super-hydrophobic behaviors.
properties, the micro-grids yield the most outstanding anti-  Finally, the current research work is limited to the perfor-
bacterial ability, followed by the micro-feathers and micro- mance evaluation of microtextures prepared on planar
grooves. surfaces of fully-sintered 3Y-TZP ceramics, not the actual
denture surfaces. To better approach realistic clinical ap-
plications, more endeavors should focus on preparing
4. Conclusions biomimetic microtextures on realistic curved tooth sur-
faces. Additionally, future research on optimizing the
The present work proposes the bio-inspired design of textured texture topographies should be carried out through inter-
surfaces based on the microstructural analysis of butterfly disciplinary research. Finally, more clinical trials are
wings, peacock tail feathers, and dolphin skins to improve the required to comprehensively evaluate the service perfor-
service performances of 3Y-TZP ceramics for dental applica- mance of textured 3Y-TZP denture surfaces.
tions. Three types of biomimetic microtextures, involving
micro-grids, micro-feathers, and micro-grooves, were pre-
pared onto the 3Y-TZP ceramics to improve their service
performances. The paper addresses the impacts of different Author statement
microtextures on the wettability, tribological and antibacterial
behaviors of textured 3Y-TZP ceramics. Based on the results Jinyang Xu: Conceptualization, Methodology, Investigation,
acquired, some key conclusions can be drawn. Funding Acquisition, Writing - Original Draft; Xiaoming
Zhang: Investigation, Data Curation, Formal analysis; Jingyu
 The original reference surface basically yields a 33.1 Dai: Investigation, Data Curation, Formal analysis; Dedong
contact angle, which suggests the intrinsic hydrophilic Yu: Writing - Review & Editing; Min Ji: Writing - Review &
behavior of the nontextured 3Y-TZP ceramics. The intro- Editing; Ming Chen: Writing - Review & Editing.
duction of biomimetic microtextures has been confirmed
to have different degrees of influence on the wettability of
the 3Y-TZP surface. The micro-grid structure yields the Declaration of competing interest
largest contact angle of 151.2 and, thus, the best hydro-
phobicity. While the micro-feather is affected by factors The authors declare that they have no known competing
such as surface roughness, and its actual contact angle is financial interests or personal relationships that could have
103.2 , being smaller than that of the micro-groove appeared to influence the work reported in this paper.
texture. Therefore, its hydrophobicity is relatively the
lowest.
 The original reference surface achieves the highest average Acknowledgments
friction coefficient of 0.342, indicating a very poor anti-
friction behavior of the nontextured 3Y-TZP ceramics. The work was supported by the National Natural Science
Additionally, the micro-grid texture yields the best anti- Foundation of China (Grant Nos. 52175422 and 52175425).
j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 3 ; 2 3 : 1 3 6 0 e1 3 7 4 1373

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