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Diamond-like carbon films for tribological modification of rubber

  • Jiaqi Liu , Tao Yang , Huatang Cao , Qiaoyuan Deng , Changjiang Pan and Feng Wen EMAIL logo
Published/Copyright: September 30, 2022
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Nanotechnology Reviews
From the journal Nanotechnology Reviews Volume 11 Issue 1

Abstract

The service conditions of rubber seals are primarily in the dynamic sliding state, with a high coefficient of friction, which can seriously compromise the equipment’s safety and the services’ lifespan. Diamond-like carbon (DLC) films have been the ideal candidate for tribological modification of rubber surfaces due to their excellent tribological properties over the last two decades. This field can be widely discussed as a hard film on soft substrates, where the challenge is the mismatch of mechanical properties, leading to the exfoliation of DLC films in friction. Early work developed the DLC films with a segment structure to solve this critical issue, illustrating the possibility of wear-resistant rubber. In recent years, researchers have paid attention to further increasing the coated rubber’s lifetime in friction, focusing on adhesion. These research achievements were reviewed on the aspects of structurization, adhesion, and doping in this article. It proposed an alternative direction of understanding the surface wear mechanism for designing wear-resistant DLC films on rubber.

Keywords: DLC films; rubber; tribology; wear; adhesion; doping

1 Introduction

Wear is inevitable in most mechanical components, e.g., bearings, gears, brakes, and piston rings [1]. Rubber is routinely used with prominent oil-resistant features to seal rods, pistons, and valves in engineering applications. However, when seals work primarily in dynamic sliding conditions [2], rubber exhibits high friction characteristics when interacting with other engineering materials (steel counterparts, etc.) that can easily lead to rubber wear and tear, while the frictional heat generated by high friction can intensify the process, prompting premature failure of rubber seals and leakage, which seriously affects the safety and reliable service of equipment [3]. Therefore, it is essential to conduct anti-wear tests on rubber materials to reduce friction and increase the wear resistance of rubber seals.

Surface physical modification is a green methodology to modify the surface of rubber. In most cases, the rubber surface macromolecules undergo a chemical structure change after physical treatment, which is still a chemical modification. For example, plasma treatment was applied to change the physical and chemical properties of the rubber surface to improve friction and wear performance [4,5]. However, the chemical and physical treatments of the rubber surface have limitations on enhancing the tribological performance of rubber due to the high coefficient of friction (CoF) of the modified layer, which cannot meet the low friction requirement yet.

A film is a layer with unique functions attached to the rubber substance after depositing the film on the rubber surface. The rubber surface macromolecules still maintain their original structure, which is a physical modification of the surface. The formation of a selected protective film on the rubber surface can reduce the CoF between the rubber and its counterpart, thus reducing the wear of the rubber. So far, various films, including organic polymers and inorganic hard ones, have been used on the rubber to modify the tribological performance. Polytetrafluoroethylene films were prepared on acrylonitrile-butadiene rubber substrates, possessing high stability in the friction process with low CoFs [6]. Tashlykov et al. used their ion-assisted ion plating to deposit metal films (Ti, Cr, Mo, etc.) on the rubber surface to improve its tribological properties [7,8]. It was found that the high adhesion characteristics of metal films and steel counterparts have a significant influence on the improvement of the tribological properties of the rubber surface. Cadambi and Ghassemieh deposited ceramic film (tungsten carbide) on the rubber surface and found that the ceramic film can effectively reduce hysteresis friction [9].

Diamond-like carbon (DLC) is a class of amorphous materials possessing superior chemical inertness, corrosion resistance, and low CoF [10]. The superlow CoF of DLC could reach 0.001 [11], making it one of the most promising solid lubricants in engineering. The research on DLC/rubber has been activated over the last two decades due to its good chemical compatibility (the main components are carbon and hydrogen). The value of DLC films on rubber substrates is actively explored [12,13,14]. The application of DLC films deposited on rubber substrates is considered promising in O-rings for zoom cameras, ball bearings, and rubber seals in the aerospace, automotive, and rural water supply industries [15,16,17]. Considering the mismatch in mechanical properties between rigid films and soft substrates, earlier work developed DLC films with segmented structures to address this critical issue and is reviewed in related review articles [18,19]. In recent years, researchers have noted that the focus for further improving the service life of coated rubber in friction is adhesion, and to address this vital issue, researchers have discussed the improvement of adhesion properties from different aspects, such as the influence of substrate [20], the choice of plasma pretreatment gas [21], the optimization of film formation methods [22,23], intermediate transition layers [24], and doping [25], and some progress has been made.

This review summarized the typically updated processes of modified DLC films on rubber surfaces in recent years, categorized into structurization, adhesion, and doping. It proposes an alternative direction of understanding the surface wear mechanism for designing wear-resistant DLC films on rubber, reveals the critical problems of current studies, and discusses potential future research trends that still need to be resolved.

2 DLC and its tribology

DLC is composed of sp2 and sp3 carbon bonds (which may also contain a small amount of sp1), where different bonds are cross-linked to form an amorphous carbon network [26]. Based on the elemental composition of DLC, it can be divided into hydrogen-free DLC and hydrogen-containing H-DLC. As shown in Figure 1a, hydrogen-free DLC films include tetrahedral amorphous carbon films (ta-C) and graphite-like amorphous carbon films (a-C). Hydrogenated DLC films can be prepared by the physical-assisted chemical vapor deposition method using hydrocarbon gases (C2H2, CH4, etc.) as carbon precursors, which have low friction and wear [27]. The sp3 and sp2 content and hydrogen ratio affect DLC films’ physicochemical and mechanical properties. The higher the proportion of sp3/sp2 DLC within a specific range, the higher the hardness of the DLC coating will get [12]. While preparing DLC films, the carbon structure in the DLC films can be adjusted by controlling the deposition method and conditions, which determines the mechanical properties of the films.

Figure 1 (a) Ternary phase diagram for various DLC films concerning their sp2, sp3, and hydrogen contents [35]. (b) The proposed nonadhesive interface model is based on surface hydrogen passivation [36].
Figure 1

(a) Ternary phase diagram for various DLC films concerning their sp2, sp3, and hydrogen contents [35]. (b) The proposed nonadhesive interface model is based on surface hydrogen passivation [36].

The DLC films were found to have a low CoF due to their wear-induced graphitization [28]. Erdemir et al. accomplished a breakthrough in superlubricity in highly hydrogenated amorphous carbon films [29]. By comparing the function of hydrogen in DLC films, the non-hydrogenated DLC films are constantly subjected to high CoF and wear rates, which is usually attributed to the solid interactions between the carbon dangling bonds and their counterpart [30]. In terms of the microscale (Figure 1b), Erdemir proposed that the redistribution of charge density and the repulsive forces generated between two positively charged hydrogen protons along the sliding interface are the origins of suppression adhesive interactions and hence friction [31]. This hydrogen passivation interface is satisfactory to cancel out the friction forces and avoid material wear. Maintaining the hydrogen-covered surface is vital due to the inevitable loss of hydrogen.

The surface topology plays a crucial role in tribology. Mechanical interlocking can occur among surface asperities and lead to high frictional losses (especially during sliding tests’ run-in or initial stages) [32]. Typically, the roughness of amorphous DLC films relies on their substrate topology. Thus, the rubber substrate raises the difficulty of reaching an ultralow CoF. The tribochemical interactions between DLC and its surroundings have been intensively investigated [33]. Under dynamic sliding contacts, DLC surfaces may interact with counterparts and gaseous molecules in the surroundings. The interaction will remain stable along with substrate changes. The transfer layers on the sliding surfaces commonly affect the frictional behavior of DLC films [34], which comes from DLC counterparts’ debris. This debris will react with the surface and result in tribochemical interactions.

3 Development of DLC films on rubber

Early studies date back to around 2004 when Nakahigashi et al. in Japan used radio frequency plasma assisted chemical vapor deposition to deposit flexible DLC films on rubber and started the application of DLC in rubber seals [12], and in the same year, Takikawa et al. [14] and Miyakawa et al. [37] used T-filtered arc deposition system in the preparation of DLC films on ethylene propylene diene monomer substrates without introducing gas. They also investigated the tribological properties of the rubber surface after depositing DLC films and compared them with uncoated rubber, but only at low loads. After that, Japanese scholars generally agreed that the presence of surface cracks in DLC films on rubber surfaces was the main reason for their flexibility, but the mechanism of crack formation was not described in detail. Since then until 2008, a large number of relevant studies have been conducted in this area, Yoshida et al. [38], Martinez-Martinez and De Hosson [19], Lubwama et al. [18], and Pei et al. [13] contributed to the study of DLC-coated modified rubber. It was found that film flaking did not occur even in the deformation of soft substrates. However, the cracks generated in the films affected the final frictional properties. Martinez-Martinez et al. [39] investigated the effect of different plasma pretreatment and film deposition bias on the DLC film bonding on the rubber surface. They found that both affected the film crack formation density by changing the temperature difference before and after the film deposition. They obtained the temperature difference and film crack density by controlling the temperature difference before and after the film deposition. Lubwama et al. [40] investigated the tribological behavior of DLC and Si-doped DLC films coated on the surface of nitrile butadiene rubber (NBR). The prepared films exhibited a crack-like microstructure with hydrophobic properties and a dense non-columnar microstructure under a certain negative bias pressure. The dry and wet environments and the presence or absence of the Si–C interlayer had significant effects on the tribological properties and bond strength of the coatings. The presence of the Si–C interlayer greatly enhanced the bonding force of the films and provided general design rules for depositing ultra-low friction DLC films on rubber. The loss of the protective layer due to wear in long-term friction leads to an increase in CoF, as researchers have been working to further reduce the CoF of coated rubber materials and improve their service life in harsh friction environments.

3.1 Examples of DLC films on rubber

Different vapor deposition techniques have been used to deposit DLC films on various types of rubber [41]. Table 1 summarizes the classification and characteristics of typical deposition techniques for DLC films on different rubber surfaces and reviews information on the corresponding deposition techniques over the past two decades. It illustrates that CVD and physical vapor deposition (typical magnetron sputtering) are two prevalent methods due to their relatively low deposition temperatures. In general, the elastomers cannot withstand high temperatures, a critical limitation on the synthesis methods of films on rubber. Meanwhile, temperature control, the crucial factor influencing the film quality, becomes unavailable in DLC films on rubber.

Table 1

Deposition details and characteristics of DLC coatings on rubber

Technique category Classical deposition process Characteristics Deposition details References
Substrates Film Gases and precursors Interlayer
PVD MS Substrate diversification FKM, HNBR, ACM W–DLC Ar + C2H2 W–C [47]
Low deposition temperature FKM, HNBR W–DLC Ar + C2H2 Cr (optional)W–C [48]
Large deposition area NBR DLC Ar (Graphite) [22]
Stable deposition rate NBR DLC Ar (Graphite) Ti–C [24]
Uniform film layer HNBR DLC Ar + C2H2 [49]
Stable process HNBR Ti–DLC Ar + C2H2 [50]
Good repeatability TPU DLC Ar, C4H10, C2H2 [51]
PLD Fast film growth MVQ DLC Frozen C5H11OH [38]
High-resolution film deposition
Easy to realize micro-zone deposition
CVD Low deposition temperature CR, NBR, MVQ DLC CH4 [12]
Good winding property
PECVD Uniform film layer
PACVD Low internal film stress
Good adhesion\linefeed\High cost
Challenging to obtain pure products
Most of the reaction substances are flammable, explosive, and toxic
Butyl rubber DLC CH4 [52]
ACM DLC Ar + C2H2 [16,39,53,54,55]
NBR DLC Ar + C4H10 Si–C (optional) [15,40,44,56]
Si–DLC
NBR, FKM, TPU DLC Ar + C2H2 [42]
NBR DLC Ar + C2H2 [57,58]
HNBR DLC Ar + C2H2 [13,17,46,59,60,61]
T-FAD EPDM, MVQ DLC None, H2, Ar, C2H2, C2H4, CH4 [14,37]
PBII FKM Si–DLC Si (CH3)4 [62]

Abbreviations: ACM, acrylic rubber; CR, chloroprene rubber; EPDM, ethylene propylene diene monomer; FKM, fluororubber; HNBR, hydrogenated nitrile butadiene rubber; MVQ, silicone rubber; MS, magnetron sputtering; NBR, nitrile butadiene rubber; PACVD, plasma-assisted chemical vapor deposition; PBII, plasma-based ion implantation; PECVD, plasma-enhanced chemical vapor deposition; PLD, pulsed laser deposition; PVD, physical vapor deposition; T-FAD, T-shaped filtered arc deposition; TPU, thermoplastic polyurethane.

As for the rubber substrate, it plays a vital role in the ultimate tribological performance. The NBR and fluororubber present excellent tribological performance after coating DLC films [42]. The surface interaction between rubber and counterpart is modified with the coating of DLC. Therefore, the CoF dramatically decreases. However, the mechanical property of rubber determines the degree of deformation being loaded, which also affects the tribological behavior based on the contact area [43]. Besides, the surface roughness of coated rubber relies on the original roughness of the rubber substrate. In most studies, one typical way to estimate the surface roughness is via an atomic force microscope, with an analyzed area of less than 10 μm2 × 10 μm2. It should be noted that the actual contact area between rubber and counterparts is significantly larger than this size. The contact area at around millimeter level should be considered according to the size of the friction counterpart.

As for the category of DLC films, most cases are hydrogenated DLC films due to the merit in the frictional interactions. However, the interlayers and doping strategies have been rarely used in the DLC films on rubber. Lubwama et al. [44] systematically studied the function of Si–C interlayers between DLC films and rubber and suggested that interlayers can enhance adhesion. The doping technique has been used to modify the hardness, tribological properties, internal stress, and adhesion of DLC films on hard substrates [45]. It has enormous potential to apply doping on the DLC films to rubber substrates due to the prominent issues related to the film adhesion and internal stress between the DLC and soft rubber materials. The doped DLC films on the rubber substrate are discussed in the latter part.

The tribological properties of films are generally evaluated by tribotests, consisting of repeated movements of the film in contact with the counterpart (usually a ball) under a specific load, speed, and atmospheric conditions. Table 2 summarizes the test conditions and CoF of DLC films deposited on rubber substrate surfaces. The coated rubber exhibits a low CoF (∼0.2) compared with the raw rubber (∼0.8), which benefits from the excellent tribological properties of DLC films. However, the various friction conditions make it difficult to make comparisons. Pei et al. [46] proposed an analytical model to simulate the viscoelastic behavior of rubber in cyclic friction tests, as shown in Figure 2. It reveals the variation law of two friction elements in friction tests under different conditions. The adhesive friction mainly depends on the frictional contact area. In contrast, hysteresis friction relies on the contact surface force (or torque magnitude), which reveals the adhesive and hysteresis contributions to friction in the rubber tribology. According to the proposed theory, the tribotest condition can be briefly understood. The loading force has both effects on the contact area and the contact surface force. Thus, it is critical for CoF value. The contact area could also be determined by the rubber deformation (hardness), the size of the counterpart, and surface roughness. The morphology of coated rubber is shown in Table 2. The deposition method and rubber category lead to different morphology, which has a distinct influence on friction. As a result, it is necessary to control these parameters for comparing the tribology performance fairly.

Table 2

Characteristics of DLC films on kinds of rubbers

Substrate Technique Morphology Performance References
NBR PACVD + DC–MS 100Cr6 stainless steel ball [42]
10,000 cycles; load 1 N
CoF ∼0.3
NBR PACVD Brass counterpart (reciprocating) [63]
645 cycles; load 10 N
CoF ∼0.5
NBR MS GCr-15 stainless-steel ball [20]
10,000 cycles; load 1 N
CoF ∼0.2
HNBR CVD 100Cr6 stainless steel ball [60]
10,000 cycles; load 1 N
CoF ∼0.14
ACM PACVD 100Cr6 stainless steel ball [16]
10,000 cycles; load 1 N
CoF ∼0.22
ACM PECVD 100Cr6 stainless steel ball [55]
30,000 cycles; load 1 N
CoF ∼0.08 (oil)
NBR MS + PACVD 100Cr6 stainless steel ball [58]
10,000 cycles; load 1 N
CoF ∼0.2
PU PCAD Annual chrome steel disk [64]
Load 50 N
CoF ∼0.3
NBR MS Tungsten carbide ball [22]
7,500 cycles; load 0.3 N
CoF ∼0.25
NBR PECVD GCr15 steel ball [65]
12,000 cycles; load 3 N
CoF ∼0.2
Figure 2 (a) Sketch of the mattress model composed of standard linear solid (SLS) units under deformation by a ball. The detailed SLS arrangement is enclosed. (b) Strain evolution of an SLS under static loading. (c) Strain evolution of an SLS under cyclic loading. (d) A closer view of a loading–unloading cycle in the steady state. Schematic overview of the influence of the increase in shear strength (from (e) to (f)), normal load (from (f) to (g)) on the contact area, and friction contributions of DLC film-coated rubber (a–g) [46].
Figure 2

(a) Sketch of the mattress model composed of standard linear solid (SLS) units under deformation by a ball. The detailed SLS arrangement is enclosed. (b) Strain evolution of an SLS under static loading. (c) Strain evolution of an SLS under cyclic loading. (d) A closer view of a loading–unloading cycle in the steady state. Schematic overview of the influence of the increase in shear strength (from (e) to (f)), normal load (from (f) to (g)) on the contact area, and friction contributions of DLC film-coated rubber (a–g) [46].

3.2 Structured DLC films on rubber

When the DLC films are deposited onto the rubber, the deformation of the soft substrate tends to cause catastrophic failures of the DLC films [66]. Extensive works focus on the segment-structured DLC films addressing the incongruous deformation between hard films and soft substrates [52]. The mesh wire was employed to fabricate the segment-structured DLC films on a substrate (Figure 3a1). The wear resistance of the new structure was significantly improved compared with that of the conventional unsegmented DLC films due to effective stress relaxation (Figure 3a2).

Figure 3 (a1) Film method for producing segment-structured DLC films. (a2) Schematic illustration of segment-structured DLC film, (a1 and a2) [52]. (b1) Evolution of measured substrate temperature versus time of plasma cleaning (open symbols) and deposition (close marks), with the solid fitted curves. (b2) Sizes of film segments as measured and predicted versus temperature variation ΔT during deposition. (b3) Surface morphology of DLC films on hydrogenated nitrile butadiene rubber (HNBR) deposited at temperature variations: ΔT = –46.3 °C. (b4) CoF of 300 nm thick DLC films on HNBR with segment sizes indicated, (b1–b4) [13]. Sketch of the segmentation mechanism in different regimes of temperature variation during deposition: (b5) positive ΔT and (b6) negative ΔT. The length of the arrow pairs indicates the rubber substrate’s thermal expansion or contraction rate at different moments of deposition from t 1 to t 4. The cooling phase after deposition is from t 4 to t f, (b5 and b6) [59].
Figure 3

(a1) Film method for producing segment-structured DLC films. (a2) Schematic illustration of segment-structured DLC film, (a1 and a2) [52]. (b1) Evolution of measured substrate temperature versus time of plasma cleaning (open symbols) and deposition (close marks), with the solid fitted curves. (b2) Sizes of film segments as measured and predicted versus temperature variation ΔT during deposition. (b3) Surface morphology of DLC films on hydrogenated nitrile butadiene rubber (HNBR) deposited at temperature variations: ΔT = –46.3 °C. (b4) CoF of 300 nm thick DLC films on HNBR with segment sizes indicated, (b1–b4) [13]. Sketch of the segmentation mechanism in different regimes of temperature variation during deposition: (b5) positive ΔT and (b6) negative ΔT. The length of the arrow pairs indicates the rubber substrate’s thermal expansion or contraction rate at different moments of deposition from t 1 to t 4. The cooling phase after deposition is from t 4 to t f, (b5 and b6) [59].

Pei et al. developed another approach to deposit flexible DLC films on rubber via self-segmentation based on the unique structural design [61]. They tuned the substantial thermal mismatch between the DLC film and rubber substrate to form a dense network of cracks in the DLC film, contributing to its flexibility. The size of the micro-segments can be controlled by tuning the substrate temperature variation during deposition by varying the bias voltage (Figure 3b1 and b2). When DLC films are deposited on the rubber surface, cracks are initialized due to the mismatch of thermal stresses and form a dendritic network of cracks, dividing the films into micron-scale areas (Figure 3b3). The decreased size of the film segments and the opening gap between the segments give rise to excellent tribological performance (Figure 3b4). This method exhibited a creative mentality for designing structures with excellent tribology. A reasonable estimation of the less size of film segments, such as nanoscale, will provide better tribology performance. Because the property of rubber limits the temperature range, the other strategy should be considered.

The mechanism of crack formation is schematically depicted in Figure 3. Under a positive temperature difference (the difference between the plasma cleaning temperature and the deposition temperature is above zero; Figure 3b5), the films are separated from each other due to the thermal expansion of the rubber substrate. As the temperature tends to be stable, the expansion rate of the films decreases, while the growth rate of films remains constant throughout the deposition process. Therefore, the film continuously grows from a certain point. As the temperature increases, the rubber substrate expands, resulting in cracks in the films due to tensile stress.

In contrast, the negative temperature difference (Figure 3b6) does not affect the continuous growth of the film. The compressive stress acts from the beginning of the deposition, which promotes the formation of continuous films, resulting in a higher crack density and smaller size patches on the surface after cooling. The inward shrinkage of the rubber occurs during the final cooling, which causes the inward bending of the crack edges. Hence, the film formed at the positive temperature difference is relatively flatter than at the negative temperature difference. The cracks in the DLC film on the rubber surface bend inward regardless of the positive or negative temperature difference. This inwardly curved and closed crack avoids the interaction between the patches and the severe wear caused by the generated abrasive chips.

3.3 Adhesion between DLC films and rubber

The adhesion between film and substrate critically determines the reliability and service lifespan of the film application and is also a common concern in the manufacturing process. The primary damage to the films during wear is the inconsistent deformation between the film and substrate, resulting in exfoliation of the films. Therefore, the key to improving DLC films’ tribological performance on rubber substrate lies in enhancing the adhesion. So far, there are two common ways to enhance adhesion.

3.3.1 Plasma pretreatment

A clean surface fosters good adhesion between the films and the substrate. The strict temperature limitation of rubber makes plasma cleaning an alternative method to obtain a clean surface. An argon plasma was used to treat the rubber surface before the deposition of DLC films [49]. The morphology difference under strain between plasma-treated and untreated rubber reveals that plasma treatment strengthens interfacial adhesion (Figure 4). When the stress is released, all cracks return to their initial microstructure. Thus, no delamination of the film patches was observed. It indicates that the DLC film adheres well to the rubber substrate after plasma treatment. The modification of the rubber morphology and changing the temperature at the start of the deposition are responsible for enhanced adhesion. If the adhesion between the rubber substrate and the DLC films is sufficiently high, many cracks could form on the surface after stretching; the film flakes off at the crack edges to release the stress. A method to quantify the adhesion of DLC films on rubber surfaces was also developed based on the in situ tensile tests [53]. During the strain, the film breaks, and the patch size decreases until it reaches the maximum adhesion value; the patch size keeps constant. Therefore, the relationship between the final patch size ( l ) and the adhesion strength (interfacial shear strength [ τ ]) can be found as follows:

(1) τ = 4 t σ l ,

where t and σ are the thickness and tensile strength [67] of the DLC films, respectively. A better estimation of l is given by average patch size L ̅ as follows [68]:

(2) l = 4 L ̅ / 3 .

Figure 4 Morphology of DLC film deposited on untreated (left column) and −400 V Ar plasma pretreated HNBR (right column) after being stretched to: (a and d) 20% strain; (b and e) 50% strain; and (c and f) unloaded from the maximum strain. A pair of arrows indicates the stretch direction (a–f) [49].
Figure 4

Morphology of DLC film deposited on untreated (left column) and −400 V Ar plasma pretreated HNBR (right column) after being stretched to: (a and d) 20% strain; (b and e) 50% strain; and (c and f) unloaded from the maximum strain. A pair of arrows indicates the stretch direction (a–f) [49].

Furthermore, various gas combinations for plasma treatment have been investigated recently. Four plasma gases were used to treat the rubber surface before deposition, and the adhesion difference was studied [21]. The X-cut method was utilized to estimate the adhesion, revealing that NBR with N2 and Ar plasma pretreatment has the optimal adhesion with DLC films (Figure 5a–d). The X-cut method uses a blade to cut X-shaped cuts on the sample’s surface and then utilizes a specific tape to adhere and tear the cuts. The peeled films are evaluated qualitatively in the X-cut region using microscopy to assess the adhesion level of the films [69,70]. Furthermore, the observed stable friction curve with a CoF of 0.2 is ascribed to forming a compact layer on the rubber surface, originating from the Ar pretreatment (Figure 5e).

Figure 5 SEM images of X-cuts after peel tests for DLC/rubber with different plasma pretreatments: (a) Ar–O2; (b) Ar–H2; (c) Ar–N2; and (d) Ar–Ar. (e) CoF of virgin NBR and DLC/rubber with different plasma pretreatments, (a–e) [21]. The carbon and oxygen element mapping images of NBR rubber pretreated by Ar plasma at the various times of (f) 0, (g) 15, (h) 30, and (i) 75 min. (j) CoF and acoustic signal function as the DLC film’s loading force (f–j) [71].
Figure 5

SEM images of X-cuts after peel tests for DLC/rubber with different plasma pretreatments: (a) Ar–O2; (b) Ar–H2; (c) Ar–N2; and (d) Ar–Ar. (e) CoF of virgin NBR and DLC/rubber with different plasma pretreatments, (a–e) [21]. The carbon and oxygen element mapping images of NBR rubber pretreated by Ar plasma at the various times of (f) 0, (g) 15, (h) 30, and (i) 75 min. (j) CoF and acoustic signal function as the DLC film’s loading force (f–j) [71].

The effects of separate treatment times were investigated to clarify more structure information caused by Ar pretreatment [71]. The two main influences of Ar pretreatment were proposed: One is the removal of surface contaminants; the other is the creation of free radicals on the surface. The following method was used to investigate the surface-free radicals well: Comparing the captured molecular O2 and H2O from the air atmosphere. The results of element mapping (Figure 5f–i) reveal that the free radicals increase with the prolonged pretreatment time. Meanwhile, the other method, the scratch test, was used to adjust the critical adhesion quantitatively (Figure 5j). Therefore, the optimal time for Ar pretreatment was established. The scratch test is simple, intuitive, quantitative, and can simulate the actual working conditions to a certain extent. The acoustic signal renders the estimation of critical adhesion more reliable.

3.3.2 Interlayers

Designing an intermediate transition layer can also be an effective way to improve adhesion by decreasing residual stress. The interlayers should have good adhesion to both rubber and DLC films. Typically, the hardness of interlayers needs to be in between rubber and DLC films so that there is a gradient deformation, which is beneficial for eliminating stress. Considering the element composition of rubber and DLC, the carbon-based interlayer is favorable.

The Ti–C films were interlayers between DLC and the rubber substrate to enhance the tribological performance [24]. Compared to the wear tracks after the friction test, the samples with Ti–C interlayers exhibit better abrasion performance (Figure 6a), attributed to improved adhesion. Meanwhile, the structure of interlayers is also essential. The interlayers under higher bias voltage possess lower I D/I G and strong adhesion, supporting superior tribological performance.

Figure 6 (a) SEM images showing the wear tracks of NBR, DLC coated on NBR (DLC, DT1, DT2, DT3, and DT4). The DLC films with a Ti–C interlayer under substrate bias voltages of 0, −50, −100, and −150 V are referred to as DT1, DT2, DT3, and DT4, respectively [24]. (b) Process design for DLC and Si–DLC films deposited on NBR substrate. Vickers hardness (at 147.1 mN indentation load) and adhesion levels for DLC and Si–DLC films without and with Si–C interlayer [56]. (c) The residual stress of films deposited on NBR and Si wafer substrates. The terms “DLC-1 film, DLC-2 film, DLC-3 film, DLC-4 film” were used to denote the Si–DLC films on different Si interlayers with a deposition time of 0, 5, 15, and 35 min [25].
Figure 6

(a) SEM images showing the wear tracks of NBR, DLC coated on NBR (DLC, DT1, DT2, DT3, and DT4). The DLC films with a Ti–C interlayer under substrate bias voltages of 0, −50, −100, and −150 V are referred to as DT1, DT2, DT3, and DT4, respectively [24]. (b) Process design for DLC and Si–DLC films deposited on NBR substrate. Vickers hardness (at 147.1 mN indentation load) and adhesion levels for DLC and Si–DLC films without and with Si–C interlayer [56]. (c) The residual stress of films deposited on NBR and Si wafer substrates. The terms “DLC-1 film, DLC-2 film, DLC-3 film, DLC-4 film” were used to denote the Si–DLC films on different Si interlayers with a deposition time of 0, 5, 15, and 35 min [25].

The Si–C interlayers were also investigated on the NBR substrate [56]. The DLC films with Si–C interlayers give rise to better adhesion levels than bare DLC films. In contrast, this kind of interlayer induces a decrease in hardness simultaneously (Figure 6b). Eventually, the Si–C interlayer does not improve tribological performance. The thickness of the interlayer is also very sensitive to tribological performance. The thick interlayer will cause enormous residual stress, while the thin interlayer will only result in negligible residual stress. The thickness-related research was conducted on the Si interlayers [25]. It was found that there was an optimal thickness for the lowest residual stress (Figure 6c). Therefore, the thickness of the interlayer is a critical factor to consider when introducing an interlayer.

3.4 Doped DLC films on rubber

Incorporating certain doping elements into DLC films may significantly affect the tribochemical mechanisms [72]. These different elements can participate in various reactions and tune the tribological action of DLC films. From the mechanics’ aspect, doping can modify the sp2 and sp3 structures, leading to changes in the mechanical properties. Due to the mismatching mechanical properties between rubber and DLC films, it is critical to decrease the internal stress to enhance tribological performance. Many dopants have been used to decorate DLC films, achieving excellent friction performance [73,74,75]. The typical strategies related to the DLC films are summarized in Figure 7. The doping elements can be divided into three groups according to different chemical states. The difference in the valence electrons’ number will induce different types of potential for electrons. As far as we know, the research on electrostatic tribology, like hydrogenated DLC [36], is limited. Most research suggests that incorporating doping elements changes the environment of C, leading to changes in hardness and stress [76,77]. Besides, doping concentration is also vital for the tribological performance of DLC films. When the doping concentration is low, the doping atoms will substitute the C sites or enter interstitial sites [78]. However, phase segregation occurs as the doping concentration rises. The elements with valencies lower than 4 typically form the metal nanocrystalline [79] rather than the carbide phases when the doping elements have high chemical states [80,81]. Phase segregation is a disadvantage for tribology due to the rough interface and abrasive wear [82]. Therefore, doping with low concentration is promising for optimizing the tribological performance of DLC films.

Figure 7 The typical doping strategy of DLC films.
Figure 7

The typical doping strategy of DLC films.

The doped DLC films have been less applied on the rubber substrate. In the early days, Ti–DLC [50], W–DLC [48], and Si–DLC [62] were fabricated on the rubber, exhibiting enhanced tribological performance compared with bare rubber. However, the structural changes caused by doping have not been thoroughly investigated. Lubwama et al. reported the Raman analysis (Figure 8) of Si–DLC compared with DLC [40]. The residual stress was calculated as follows [83]:

(3) σ = 2 G 1 + ν 1 − ν Δ w w 0 ,

where Δ w is the shift in Raman wavenumber of the G peak, w 0 is the Raman wavenumber of reference, G is the shear modulus (G = 70 GPa), and ν is the Poisson’s ratio ( ν = 0.3) [84]. The residual stress estimation of these films indicated that the inclusion of Si dopant reduced the compressive stress.

Figure 8 Raman spectra at 488 and 325 nm for (a) DLC, (b) Si–DLC, (c) DLC with Si–C, and (d) Si–DLC with Si–C films deposited on nitrile rubber (a–d) [40].
Figure 8

Raman spectra at 488 and 325 nm for (a) DLC, (b) Si–DLC, (c) DLC with Si–C, and (d) Si–DLC with Si–C films deposited on nitrile rubber (a–d) [40].

Another Si–DLC film on rubber was studied by Liu et al. [85]. The various Si compositions were designed to investigate the structure of Si–DLC films. It was found that the incorporated Si probably exists in the form of Si–C bonds [86] at a high Si concentration (Si–DLC1) (Figure 9). As the Si concentration decreases further, the Si 2p peak could be fitted into two peaks at ∼100.3 eV for Si–C bonds and ∼101.3 eV for SiO x C y bonds [87], indicating that the incorporated Si probably exists in the form of SiC and SiO x C y at relatively low Si concentration. The Si–DLC films with appropriate Si content produce excellent tribological performance, attributed to the counterpart’s protection, even with relatively low hardness.

Figure 9 (a) The Si 2p spectra of the Si–DLC films deposited at different CH4 flow rates on NBR, and the fitted Si 2p spectrum of (b) Si–DLC1 film, (c) Si–DLC2 film, (d) Si–DLC3 film, (e) Si–DLC4 film, and (f) Si–DLC5 film. The Si concentration gradually decreases from Si–DLC1 to Si–DLC5 films [85].
Figure 9

(a) The Si 2p spectra of the Si–DLC films deposited at different CH4 flow rates on NBR, and the fitted Si 2p spectrum of (b) Si–DLC1 film, (c) Si–DLC2 film, (d) Si–DLC3 film, (e) Si–DLC4 film, and (f) Si–DLC5 film. The Si concentration gradually decreases from Si–DLC1 to Si–DLC5 films [85].

Some other materials were also used to modify the DLC films. The F-DLC was fabricated by introducing the C4F8 gas precursor [88], wherein the mass loss was measured to compare with the wear resistance. The results show that the incorporation of fluorine has little influence on the CoF (Figure 10a). Furthermore, as a solid lubricant, transition metal dichalcogenides (TMDs) such as MoS2 or WS2 have been widely used to accompany DLC [89,90]. Various DLC/MoS2 ratios were deposited on elastomeric substrates, and the tribological performance was compared. The thick films keep intact after friction compared to the severely damaged thin films (Figure 10b and c).

Figure 10 Coefficients of friction and film mass loss after tribotests of (a) uncoated NBR, deposited DLC and F-DLC films on UBR substrates [88]. Microscopic images of wear tracks: (b) 300 nm hybrid_B coated thermoplastic polyurethane (TPU) and (c) 150 nm hybrid_B coated TPU (b and c) [91].
Figure 10

Coefficients of friction and film mass loss after tribotests of (a) uncoated NBR, deposited DLC and F-DLC films on UBR substrates [88]. Microscopic images of wear tracks: (b) 300 nm hybrid_B coated thermoplastic polyurethane (TPU) and (c) 150 nm hybrid_B coated TPU (b and c) [91].

4 Summary and perspective

Rubber has been widely used as a common sealing material in the environment of friction. The DLC film significantly improves the friction and wear performance of the rubber surface, which dramatically reduces the CoF of the rubber surface. However, applying hard films to a soft substrate is still challenging. The deformation in the soft rubber induces the fracture of hard films, and afterward, the exfoliation of DLC films may cause severe wear. The structured films, plasma pretreatment, and interlayers yield satisfying results in improved tribological performance. Film adhesion is a focal point in improving the tribology performance of DLC-coated rubber to avoid DLC films’ peel-off. Meanwhile, the doped DLC films exhibit the potential to eliminate residual stress, which is also beneficial for adhesion. The doped DLC films could be well utilized on the rubber substrate according to the comprehensive mechanism.

Even though the DLC films exhibit the low CoF on the rubber surface, the wear consumption of DLC layers is the main factor determining the lifetime of protection. The increased thickness is an alternative way to prolong the lifetime of DLC films. Nevertheless, considerable stress will be generated with the increase in thickness. In this case, the advantage of the doping method in eliminating stress is significant. Besides, further decreasing the wear despite the evident deformation should be the other pathway in this field. The wear mechanism of DLC films is responsible for designing more wear-resistant films [92]. Due to the lack of sophisticated investigation of surface revolution in the friction process on a rubber substrate, a method for enhancing the wear-resistant property needs to be developed. With the development of characteristic technology, the in situ structure characteristic combining the tribotest is promising to explore the wear mechanism of DLC films on rubber, such as in situ XPS and Raman.

After enhancing the wear-resistant property, the increasing loading force might not be a challenge for DLC-coated rubber. Thus, the rubber can bear severe harsh friction conditions. Due to the extensive application of soft materials in the friction environment, this field is vital in decreasing the waste caused by friction.

# These authors contributed equally to this work and should be considered as first co-authors.

  1. Funding information: This work was supported by the Key Projects of Hainan Province (ZDYF2019206) and the Natural Science Foundation of Hainan Province (420RC525).

  2. Author contributions: All authors have accepted responsibility for the entire content of this manuscript and approved its submission.

  3. Conflict of interest: The authors state no conflict of interest.

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Received: 2022-05-05
Revised: 2022-07-14
Accepted: 2022-08-09
Published Online: 2022-09-30

© 2022 Jiaqi Liu et al., published by De Gruyter

This work is licensed under the Creative Commons Attribution 4.0 International License.

Articles in the same Issue

  1. Research Articles
  2. Theoretical and experimental investigation of MWCNT dispersion effect on the elastic modulus of flexible PDMS/MWCNT nanocomposites
  3. Mechanical, morphological, and fracture-deformation behavior of MWCNTs-reinforced (Al–Cu–Mg–T351) alloy cast nanocomposites fabricated by optimized mechanical milling and powder metallurgy techniques
  4. Flammability and physical stability of sugar palm crystalline nanocellulose reinforced thermoplastic sugar palm starch/poly(lactic acid) blend bionanocomposites
  5. Glutathione-loaded non-ionic surfactant niosomes: A new approach to improve oral bioavailability and hepatoprotective efficacy of glutathione
  6. Relationship between mechano-bactericidal activity and nanoblades density on chemically strengthened glass
  7. In situ regulation of microstructure and microwave-absorbing properties of FeSiAl through HNO3 oxidation
  8. Research on a mechanical model of magnetorheological fluid different diameter particles
  9. Nanomechanical and dynamic mechanical properties of rubber–wood–plastic composites
  10. Investigative properties of CeO2 doped with niobium: A combined characterization and DFT studies
  11. Miniaturized peptidomimetics and nano-vesiculation in endothelin types through probable nano-disk formation and structure property relationships of endothelins’ fragments
  12. N/S co-doped CoSe/C nanocubes as anode materials for Li-ion batteries
  13. Synergistic effects of halloysite nanotubes with metal and phosphorus additives on the optimal design of eco-friendly sandwich panels with maximum flame resistance and minimum weight
  14. Octreotide-conjugated silver nanoparticles for active targeting of somatostatin receptors and their application in a nebulized rat model
  15. Controllable morphology of Bi2S3 nanostructures formed via hydrothermal vulcanization of Bi2O3 thin-film layer and their photoelectrocatalytic performances
  16. Development of (−)-epigallocatechin-3-gallate-loaded folate receptor-targeted nanoparticles for prostate cancer treatment
  17. Enhancement of the mechanical properties of HDPE mineral nanocomposites by filler particles modulation of the matrix plastic/elastic behavior
  18. Effect of plasticizers on the properties of sugar palm nanocellulose/cinnamon essential oil reinforced starch bionanocomposite films
  19. Optimization of nano coating to reduce the thermal deformation of ball screws
  20. Preparation of efficient piezoelectric PVDF–HFP/Ni composite films by high electric field poling
  21. MHD dissipative Casson nanofluid liquid film flow due to an unsteady stretching sheet with radiation influence and slip velocity phenomenon
  22. Effects of nano-SiO2 modification on rubberised mortar and concrete with recycled coarse aggregates
  23. Mechanical and microscopic properties of fiber-reinforced coal gangue-based geopolymer concrete
  24. Effect of morphology and size on the thermodynamic stability of cerium oxide nanoparticles: Experiment and molecular dynamics calculation
  25. Mechanical performance of a CFRP composite reinforced via gelatin-CNTs: A study on fiber interfacial enhancement and matrix enhancement
  26. A practical review over surface modification, nanopatterns, emerging materials, drug delivery systems, and their biophysiochemical properties for dental implants: Recent progresses and advances
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https://doi.org/10.1515/ntrev-2022-0481
Keywords for this article
DLC films; rubber; tribology; wear; adhesion; doping
Creative Commons
BY 4.0

Articles in the same Issue

  1. Research Articles
  2. Theoretical and experimental investigation of MWCNT dispersion effect on the elastic modulus of flexible PDMS/MWCNT nanocomposites
  3. Mechanical, morphological, and fracture-deformation behavior of MWCNTs-reinforced (Al–Cu–Mg–T351) alloy cast nanocomposites fabricated by optimized mechanical milling and powder metallurgy techniques
  4. Flammability and physical stability of sugar palm crystalline nanocellulose reinforced thermoplastic sugar palm starch/poly(lactic acid) blend bionanocomposites
  5. Glutathione-loaded non-ionic surfactant niosomes: A new approach to improve oral bioavailability and hepatoprotective efficacy of glutathione
  6. Relationship between mechano-bactericidal activity and nanoblades density on chemically strengthened glass
  7. In situ regulation of microstructure and microwave-absorbing properties of FeSiAl through HNO3 oxidation
  8. Research on a mechanical model of magnetorheological fluid different diameter particles
  9. Nanomechanical and dynamic mechanical properties of rubber–wood–plastic composites
  10. Investigative properties of CeO2 doped with niobium: A combined characterization and DFT studies
  11. Miniaturized peptidomimetics and nano-vesiculation in endothelin types through probable nano-disk formation and structure property relationships of endothelins’ fragments
  12. N/S co-doped CoSe/C nanocubes as anode materials for Li-ion batteries
  13. Synergistic effects of halloysite nanotubes with metal and phosphorus additives on the optimal design of eco-friendly sandwich panels with maximum flame resistance and minimum weight
  14. Octreotide-conjugated silver nanoparticles for active targeting of somatostatin receptors and their application in a nebulized rat model
  15. Controllable morphology of Bi2S3 nanostructures formed via hydrothermal vulcanization of Bi2O3 thin-film layer and their photoelectrocatalytic performances
  16. Development of (−)-epigallocatechin-3-gallate-loaded folate receptor-targeted nanoparticles for prostate cancer treatment
  17. Enhancement of the mechanical properties of HDPE mineral nanocomposites by filler particles modulation of the matrix plastic/elastic behavior
  18. Effect of plasticizers on the properties of sugar palm nanocellulose/cinnamon essential oil reinforced starch bionanocomposite films
  19. Optimization of nano coating to reduce the thermal deformation of ball screws
  20. Preparation of efficient piezoelectric PVDF–HFP/Ni composite films by high electric field poling
  21. MHD dissipative Casson nanofluid liquid film flow due to an unsteady stretching sheet with radiation influence and slip velocity phenomenon
  22. Effects of nano-SiO2 modification on rubberised mortar and concrete with recycled coarse aggregates
  23. Mechanical and microscopic properties of fiber-reinforced coal gangue-based geopolymer concrete
  24. Effect of morphology and size on the thermodynamic stability of cerium oxide nanoparticles: Experiment and molecular dynamics calculation
  25. Mechanical performance of a CFRP composite reinforced via gelatin-CNTs: A study on fiber interfacial enhancement and matrix enhancement
  26. A practical review over surface modification, nanopatterns, emerging materials, drug delivery systems, and their biophysiochemical properties for dental implants: Recent progresses and advances
  27. HTR: An ultra-high speed algorithm for cage recognition of clathrate hydrates
  28. Effects of microalloying elements added by in situ synthesis on the microstructure of WCu composites
  29. A highly sensitive nanobiosensor based on aptamer-conjugated graphene-decorated rhodium nanoparticles for detection of HER2-positive circulating tumor cells
  30. Progressive collapse performance of shear strengthened RC frames by nano CFRP
  31. Core–shell heterostructured composites of carbon nanotubes and imine-linked hyperbranched polymers as metal-free Li-ion anodes
  32. A Galerkin strategy for tri-hybridized mixture in ethylene glycol comprising variable diffusion and thermal conductivity using non-Fourier’s theory
  33. Simple models for tensile modulus of shape memory polymer nanocomposites at ambient temperature
  34. Preparation and morphological studies of tin sulfide nanoparticles and use as efficient photocatalysts for the degradation of rhodamine B and phenol
  35. Polyethyleneimine-impregnated activated carbon nanofiber composited graphene-derived rice husk char for efficient post-combustion CO2 capture
  36. Electrospun nanofibers of Co3O4 nanocrystals encapsulated in cyclized-polyacrylonitrile for lithium storage
  37. Pitting corrosion induced on high-strength high carbon steel wire in high alkaline deaerated chloride electrolyte
  38. Formulation of polymeric nanoparticles loaded sorafenib; evaluation of cytotoxicity, molecular evaluation, and gene expression studies in lung and breast cancer cell lines
  39. Engineered nanocomposites in asphalt binders
  40. Influence of loading voltage, domain ratio, and additional load on the actuation of dielectric elastomer
  41. Thermally induced hex-graphene transitions in 2D carbon crystals
  42. The surface modification effect on the interfacial properties of glass fiber-reinforced epoxy: A molecular dynamics study
  43. Molecular dynamics study of deformation mechanism of interfacial microzone of Cu/Al2Cu/Al composites under tension
  44. Nanocolloid simulators of luminescent solar concentrator photovoltaic windows
  45. Compressive strength and anti-chloride ion penetration assessment of geopolymer mortar merging PVA fiber and nano-SiO2 using RBF–BP composite neural network
  46. Effect of 3-mercapto-1-propane sulfonate sulfonic acid and polyvinylpyrrolidone on the growth of cobalt pillar by electrodeposition
  47. Dynamics of convective slippery constraints on hybrid radiative Sutterby nanofluid flow by Galerkin finite element simulation
  48. Preparation of vanadium by the magnesiothermic self-propagating reduction and process control
  49. Microstructure-dependent photoelectrocatalytic activity of heterogeneous ZnO–ZnS nanosheets
  50. Cytotoxic and pro-inflammatory effects of molybdenum and tungsten disulphide on human bronchial cells
  51. Improving recycled aggregate concrete by compression casting and nano-silica
  52. Chemically reactive Maxwell nanoliquid flow by a stretching surface in the frames of Newtonian heating, nonlinear convection and radiative flux: Nanopolymer flow processing simulation
  53. Nonlinear dynamic and crack behaviors of carbon nanotubes-reinforced composites with various geometries
  54. Biosynthesis of copper oxide nanoparticles and its therapeutic efficacy against colon cancer
  55. Synthesis and characterization of smart stimuli-responsive herbal drug-encapsulated nanoniosome particles for efficient treatment of breast cancer
  56. Homotopic simulation for heat transport phenomenon of the Burgers nanofluids flow over a stretching cylinder with thermal convective and zero mass flux conditions
  57. Incorporation of copper and strontium ions in TiO2 nanotubes via dopamine to enhance hemocompatibility and cytocompatibility
  58. Mechanical, thermal, and barrier properties of starch films incorporated with chitosan nanoparticles
  59. Mechanical properties and microstructure of nano-strengthened recycled aggregate concrete
  60. Glucose-responsive nanogels efficiently maintain the stability and activity of therapeutic enzymes
  61. Tunning matrix rheology and mechanical performance of ultra-high performance concrete using cellulose nanofibers
  62. Flexible MXene/copper/cellulose nanofiber heat spreader films with enhanced thermal conductivity
  63. Promoted charge separation and specific surface area via interlacing of N-doped titanium dioxide nanotubes on carbon nitride nanosheets for photocatalytic degradation of Rhodamine B
  64. Elucidating the role of silicon dioxide and titanium dioxide nanoparticles in mitigating the disease of the eggplant caused by Phomopsis vexans, Ralstonia solanacearum, and root-knot nematode Meloidogyne incognita
  65. An implication of magnetic dipole in Carreau Yasuda liquid influenced by engine oil using ternary hybrid nanomaterial
  66. Robust synthesis of a composite phase of copper vanadium oxide with enhanced performance for durable aqueous Zn-ion batteries
  67. Tunning self-assembled phases of bovine serum albumin via hydrothermal process to synthesize novel functional hydrogel for skin protection against UVB
  68. A comparative experimental study on damping properties of epoxy nanocomposite beams reinforced with carbon nanotubes and graphene nanoplatelets
  69. Lightweight and hydrophobic Ni/GO/PVA composite aerogels for ultrahigh performance electromagnetic interference shielding
  70. Research on the auxetic behavior and mechanical properties of periodically rotating graphene nanostructures
  71. Repairing performances of novel cement mortar modified with graphene oxide and polyacrylate polymer
  72. Closed-loop recycling and fabrication of hydrophilic CNT films with high performance
  73. Design of thin-film configuration of SnO2–Ag2O composites for NO2 gas-sensing applications
  74. Study on stress distribution of SiC/Al composites based on microstructure models with microns and nanoparticles
  75. PVDF green nanofibers as potential carriers for improving self-healing and mechanical properties of carbon fiber/epoxy prepregs
  76. Osteogenesis capability of three-dimensionally printed poly(lactic acid)-halloysite nanotube scaffolds containing strontium ranelate
  77. Silver nanoparticles induce mitochondria-dependent apoptosis and late non-canonical autophagy in HT-29 colon cancer cells
  78. Preparation and bonding mechanisms of polymer/metal hybrid composite by nano molding technology
  79. Damage self-sensing and strain monitoring of glass-reinforced epoxy composite impregnated with graphene nanoplatelet and multiwalled carbon nanotubes
  80. Thermal analysis characterisation of solar-powered ship using Oldroyd hybrid nanofluids in parabolic trough solar collector: An optimal thermal application
  81. Pyrene-functionalized halloysite nanotubes for simultaneously detecting and separating Hg(ii) in aqueous media: A comprehensive comparison on interparticle and intraparticle excimers
  82. Fabrication of self-assembly CNT flexible film and its piezoresistive sensing behaviors
  83. Thermal valuation and entropy inspection of second-grade nanoscale fluid flow over a stretching surface by applying Koo–Kleinstreuer–Li relation
  84. Mechanical properties and microstructure of nano-SiO2 and basalt-fiber-reinforced recycled aggregate concrete
  85. Characterization and tribology performance of polyaniline-coated nanodiamond lubricant additives
  86. Combined impact of Marangoni convection and thermophoretic particle deposition on chemically reactive transport of nanofluid flow over a stretching surface
  87. Spark plasma extrusion of binder free hydroxyapatite powder
  88. An investigation on thermo-mechanical performance of graphene-oxide-reinforced shape memory polymer
  89. Effect of nanoadditives on the novel leather fiber/recycled poly(ethylene-vinyl-acetate) polymer composites for multifunctional applications: Fabrication, characterizations, and multiobjective optimization using central composite design
  90. Design selection for a hemispherical dimple core sandwich panel using hybrid multi-criteria decision-making methods
  91. Improving tensile strength and impact toughness of plasticized poly(lactic acid) biocomposites by incorporating nanofibrillated cellulose
  92. Green synthesis of spinel copper ferrite (CuFe2O4) nanoparticles and their toxicity
  93. The effect of TaC and NbC hybrid and mono-nanoparticles on AA2024 nanocomposites: Microstructure, strengthening, and artificial aging
  94. Excited-state geometry relaxation of pyrene-modified cellulose nanocrystals under UV-light excitation for detecting Fe3+
  95. Effect of CNTs and MEA on the creep of face-slab concrete at an early age
  96. Effect of deformation conditions on compression phase transformation of AZ31
  97. Application of MXene as a new generation of highly conductive coating materials for electromembrane-surrounded solid-phase microextraction
  98. A comparative study of the elasto-plastic properties for ceramic nanocomposites filled by graphene or graphene oxide nanoplates
  99. Encapsulation strategies for improving the biological behavior of CdS@ZIF-8 nanocomposites
  100. Biosynthesis of ZnO NPs from pumpkin seeds’ extract and elucidation of its anticancer potential against breast cancer
  101. Preliminary trials of the gold nanoparticles conjugated chrysin: An assessment of anti-oxidant, anti-microbial, and in vitro cytotoxic activities of a nanoformulated flavonoid
  102. Effect of micron-scale pores increased by nano-SiO2 sol modification on the strength of cement mortar
  103. Fractional simulations for thermal flow of hybrid nanofluid with aluminum oxide and titanium oxide nanoparticles with water and blood base fluids
  104. The effect of graphene nano-powder on the viscosity of water: An experimental study and artificial neural network modeling
  105. Development of a novel heat- and shear-resistant nano-silica gelling agent
  106. Characterization, biocompatibility and in vivo of nominal MnO2-containing wollastonite glass-ceramic
  107. Entropy production simulation of second-grade magnetic nanomaterials flowing across an expanding surface with viscidness dissipative flux
  108. Enhancement in structural, morphological, and optical properties of copper oxide for optoelectronic device applications
  109. Aptamer-functionalized chitosan-coated gold nanoparticle complex as a suitable targeted drug carrier for improved breast cancer treatment
  110. Performance and overall evaluation of nano-alumina-modified asphalt mixture
  111. Analysis of pure nanofluid (GO/engine oil) and hybrid nanofluid (GO–Fe3O4/engine oil): Novel thermal and magnetic features
  112. Synthesis of Ag@AgCl modified anatase/rutile/brookite mixed phase TiO2 and their photocatalytic property
  113. Mechanisms and influential variables on the abrasion resistance hydraulic concrete
  114. Synergistic reinforcement mechanism of basalt fiber/cellulose nanocrystals/polypropylene composites
  115. Achieving excellent oxidation resistance and mechanical properties of TiB2–B4C/carbon aerogel composites by quick-gelation and mechanical mixing
  116. Microwave-assisted sol–gel template-free synthesis and characterization of silica nanoparticles obtained from South African coal fly ash
  117. Pulsed laser-assisted synthesis of nano nickel(ii) oxide-anchored graphitic carbon nitride: Characterizations and their potential antibacterial/anti-biofilm applications
  118. Effects of nano-ZrSi2 on thermal stability of phenolic resin and thermal reusability of quartz–phenolic composites
  119. Benzaldehyde derivatives on tin electroplating as corrosion resistance for fabricating copper circuit
  120. Mechanical and heat transfer properties of 4D-printed shape memory graphene oxide/epoxy acrylate composites
  121. Coupling the vanadium-induced amorphous/crystalline NiFe2O4 with phosphide heterojunction toward active oxygen evolution reaction catalysts
  122. Graphene-oxide-reinforced cement composites mechanical and microstructural characteristics at elevated temperatures
  123. Gray correlation analysis of factors influencing compressive strength and durability of nano-SiO2 and PVA fiber reinforced geopolymer mortar
  124. Preparation of layered gradient Cu–Cr–Ti alloy with excellent mechanical properties, thermal stability, and electrical conductivity
  125. Recovery of Cr from chrome-containing leather wastes to develop aluminum-based composite material along with Al2O3 ceramic particles: An ingenious approach
  126. Mechanisms of the improved stiffness of flexible polymers under impact loading
  127. Anticancer potential of gold nanoparticles (AuNPs) using a battery of in vitro tests
  128. Review Articles
  129. Proposed approaches for coronaviruses elimination from wastewater: Membrane techniques and nanotechnology solutions
  130. Application of Pickering emulsion in oil drilling and production
  131. The contribution of microfluidics to the fight against tuberculosis
  132. Graphene-based biosensors for disease theranostics: Development, applications, and recent advancements
  133. Synthesis and encapsulation of iron oxide nanorods for application in magnetic hyperthermia and photothermal therapy
  134. Contemporary nano-architectured drugs and leads for ανβ3 integrin-based chemotherapy: Rationale and retrospect
  135. State-of-the-art review of fabrication, application, and mechanical properties of functionally graded porous nanocomposite materials
  136. Insights on magnetic spinel ferrites for targeted drug delivery and hyperthermia applications
  137. A review on heterogeneous oxidation of acetaminophen based on micro and nanoparticles catalyzed by different activators
  138. Early diagnosis of lung cancer using magnetic nanoparticles-integrated systems
  139. Advances in ZnO: Manipulation of defects for enhancing their technological potentials
  140. Efficacious nanomedicine track toward combating COVID-19
  141. A review of the design, processes, and properties of Mg-based composites
  142. Green synthesis of nanoparticles for varied applications: Green renewable resources and energy-efficient synthetic routes
  143. Two-dimensional nanomaterial-based polymer composites: Fundamentals and applications
  144. Recent progress and challenges in plasmonic nanomaterials
  145. Apoptotic cell-derived micro/nanosized extracellular vesicles in tissue regeneration
  146. Electronic noses based on metal oxide nanowires: A review
  147. Framework materials for supercapacitors
  148. An overview on the reproductive toxicity of graphene derivatives: Highlighting the importance
  149. Antibacterial nanomaterials: Upcoming hope to overcome antibiotic resistance crisis
  150. Research progress of carbon materials in the field of three-dimensional printing polymer nanocomposites
  151. A review of atomic layer deposition modelling and simulation methodologies: Density functional theory and molecular dynamics
  152. Recent advances in the preparation of PVDF-based piezoelectric materials
  153. Recent developments in tensile properties of friction welding of carbon fiber-reinforced composite: A review
  154. Comprehensive review of the properties of fly ash-based geopolymer with additive of nano-SiO2
  155. Perspectives in biopolymer/graphene-based composite application: Advances, challenges, and recommendations
  156. Graphene-based nanocomposite using new modeling molecular dynamic simulations for proposed neutralizing mechanism and real-time sensing of COVID-19
  157. Nanotechnology application on bamboo materials: A review
  158. Recent developments and future perspectives of biorenewable nanocomposites for advanced applications
  159. Nanostructured lipid carrier system: A compendium of their formulation development approaches, optimization strategies by quality by design, and recent applications in drug delivery
  160. 3D printing customized design of human bone tissue implant and its application
  161. Design, preparation, and functionalization of nanobiomaterials for enhanced efficacy in current and future biomedical applications
  162. A brief review of nanoparticles-doped PEDOT:PSS nanocomposite for OLED and OPV
  163. Nanotechnology interventions as a putative tool for the treatment of dental afflictions
  164. Recent advancements in metal–organic frameworks integrating quantum dots (QDs@MOF) and their potential applications
  165. A focused review of short electrospun nanofiber preparation techniques for composite reinforcement
  166. Microstructural characteristics and nano-modification of interfacial transition zone in concrete: A review
  167. Latest developments in the upconversion nanotechnology for the rapid detection of food safety: A review
  168. Strategic applications of nano-fertilizers for sustainable agriculture: Benefits and bottlenecks
  169. Molecular dynamics application of cocrystal energetic materials: A review
  170. Synthesis and application of nanometer hydroxyapatite in biomedicine
  171. Cutting-edge development in waste-recycled nanomaterials for energy storage and conversion applications
  172. Biological applications of ternary quantum dots: A review
  173. Nanotherapeutics for hydrogen sulfide-involved treatment: An emerging approach for cancer therapy
  174. Application of antibacterial nanoparticles in orthodontic materials
  175. Effect of natural-based biological hydrogels combined with growth factors on skin wound healing
  176. Nanozymes – A route to overcome microbial resistance: A viewpoint
  177. Recent developments and applications of smart nanoparticles in biomedicine
  178. Contemporary review on carbon nanotube (CNT) composites and their impact on multifarious applications
  179. Interfacial interactions and reinforcing mechanisms of cellulose and chitin nanomaterials and starch derivatives for cement and concrete strength and durability enhancement: A review
  180. Diamond-like carbon films for tribological modification of rubber
  181. Layered double hydroxides (LDHs) modified cement-based materials: A systematic review
  182. Recent research progress and advanced applications of silica/polymer nanocomposites
  183. Modeling of supramolecular biopolymers: Leading the in silico revolution of tissue engineering and nanomedicine
  184. Recent advances in perovskites-based optoelectronics
  185. Biogenic synthesis of palladium nanoparticles: New production methods and applications
  186. A comprehensive review of nanofluids with fractional derivatives: Modeling and application
  187. Electrospinning of marine polysaccharides: Processing and chemical aspects, challenges, and future prospects
  188. Electrohydrodynamic printing for demanding devices: A review of processing and applications
  189. Rapid Communications
  190. Structural material with designed thermal twist for a simple actuation
  191. Recent advances in photothermal materials for solar-driven crude oil adsorption
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