Abstract
Superlubricity is generally classified as solid superlubricity and liquid superlubricity according to the lubricants involved at the interfaces, and is a popular research topic in tribology, which is closely linked to energy dissipation. Significant advancements in both experimental studies and theoretical analysis have been made regarding superlubricity in the past two decades. Compared with solid superlubricity, liquid superlubricity has many advantages; e.g., it is more easily achieved at the macroscale and less sensitive to the surface smoothness and atmospheric conditions. In the present study, the advancements in liquid superlubricity at the macroscale are reviewed, and the corresponding mechanisms for various types of liquid lubricants are discussed. This investigation is important for engineering traditional mechanical lubricating systems. Finally, the issues regarding the liquid superlubricity mechanism and the future development of liquid superlubricity are addressed.
Introduction
Because the energy consumption and material losses derived from friction and wear in mechanical systems place large economic and environmental burdens on all nations (Erdemir and Eryilmaz, ), studies on lubrication technology and mechanisms are very important for energy conservation and emission reduction. Since it was invented in the early 1990s (Shinjo and Hirano, ), superlubricity has attracted extensive concentration from researchers in many fields (Tisza, ; Meyer and Gnecco, ; Baykara et al., ; Li et al., ,). It describes a phenomenon where the friction force between two sliding surfaces nearly vanishes ideally (Hirano, ) or a state in which the sliding coefficient of friction (COF) is <0.01 in actual mechanical lubricating systems (Erdemir et al., ).
Superlubricity is generally classified as solid superlubricity and liquid superlubricity according to the lubricants involved at the interfaces (Baykara et al., ; Berman et al., ; Sinclair et al., ). Solid superlubricity at the nanoscale or microscale is easily achieved with two-dimensional materials, such as molybdenum disulfide (Martin et al., ), graphite flakes (Liu et al., ), boron nitride (BN) (Song et al., ), and graphene (Feng et al., ). It has also been achieved at dissimilar interfaces, including the crystalline gold/graphite interface (Cihan et al., ), graphene nanoribbons/gold interface (Kawai et al., ), and silica/graphite interface (Li et al., ). However, solid superlubricity at the macroscale is rarely achieved (Li et al., ), owing to the strict requirement of atomically smooth contact in these materials. In contrast to solid superlubricity, many liquid lubricants have been found to possess a macroscale superlubricity property, such as water (Xu and Kato, ; Zhou et al., 2005), oils (Bouchet et al., ; Matta et al., ), and polymers (Muller et al., ; Zhang et al., 2017). The superlubricity mechanism of these lubricants accounts for the formation of a hydrogen-bond network, a tribofilm, a hydration layer, or a molecular brush, depending on the properties of the lubricants. Recently, our group found that a phosphoric acid aqueous solution (H3PO4(aq)) as a liquid lubricant could achieve superlubricity at the Si3N4/SiO2 interface with an extremely low COF of 0.004 under maximum initial contact pressures of 700 MPa (Li et al., , , ). According to the superlubricity mechanism of H3PO4(aq), a series of acid-based lubricants composed of different polyhydroxy alcohols and acids were established (Li et al., ,). Among these acid-based lubricants, the one composed of polyethylene glycol (PEG) and boric acid (BA) allows superlubricity to be achieved under neutral conditions, avoiding acid corrosion (Ge et al., ). Room-temperature ionic liquids (RTILs) are well-known as eco-friendly lubricants and lubricating additives (Ge et al., ; Jiang et al., ). Research into the superlubricity property of RTILs has been performed by experts recently (Espinosa et al., ). Because RTILs can be designed by combining a variety of cations and anions, it is possible to develop RTILs possessing not only the superlubricity property but also special properties for different operating conditions. One of the issues for liquid lubricants is that the wear is severe during the wearing-in period. To alleviate this defect, a mixture of short-chain dihydric alcohol and graphene-oxide nanoflakes (GONFs) is explored, making it possible to achieve macroscale superlubricity and super-low wear simultaneously.
To better illustrate the differences of the superlubricity materials and their corresponding superlubricity mechanisms, these superlubricity materials are classified into 6 main types based on the main functioning materials during superlubricity period. The “Water” section describes the first discovery of superlubricity at a ceramic interface. The “Polymers” section reviews the superlubricity property of polymers. The “Acid-Based Aqueous Lubricants” section presents the development of a single phosphoric acid into a series of acid-based lubricants composed of acids and polyhydroxy alcohols. The “RTIL Lubricants” section outlines recent advances in RTILs, focusing on their superlubricity mechanism. The “Oil-Based Lubricants” section describes the superlubricity achieved with oils and oil-like liquids. The “Nanomaterial-Based Lubricants” section focuses primarily on the feasibility of macroscale superlubricity achieved with nanomaterials (like GONFs, BN, NaOH-modified black phosphorus (BP-OH), layered double hydroxide nanoplatelets (LDH), and nanodiamonds) as additives. The “Conclusions and Outlooks” section concludes the paper, offering perspectives and suggestions for future research on macroscale liquid superlubricity.
Water
The first liquid superlubricity phenomenon was discovered by Tisza with helium II in 1938 (Tisza, ); it was called superfluidity at that time. In 1987, water was found to provide superlubricity at the Si3N4/Si3N4 interface, and an extremely low COF—even <0.002—was achieved after a wearing-in period (Tomizawa and Fischer, ). The wearing-in process provides ultra-smooth surfaces and a very low contact pressure. The smooth surfaces make the lubrication enter the elastohydrodynamic lubrication (EHL) regime, in which a thin water film exists at the interface and provides low viscous friction. In addition to smooth surfaces, tribochemical reactions contribute to the superlubricity. Induced by shear, a tribochemical film is formed on the surfaces via tribochemical reactions, as indicated by Equations (1, 2) (Spikes and Tysoe, ; Khajeh et al., ). This film has extremely low shear resistance and can be maintained on the surfaces during the rubbing process. Analysis shows that this tribofilm is composed of colloidal silica, which can produce the electrical double layer, leading to very low friction in boundary lubrication (BL). Therefore, an extremely low friction is achieved in the mixed lubrication (ML) regime (EHL + BL) under a low contact pressure. Later, several studies on ceramic lubrication, e.g., using SiC, were performed under water lubrication (Chen et al., , ). These studies report that the COFs under water lubrication can decrease to 0.01 or even less, but the wearing-in period is significantly longer than that for a Si3N4/Si3N4 tribopair, as depicted in Figure 1. Their superlubricity mechanism is similar to that of Si3N4/Si3N4 tribopairs: the large friction reduction results from the decrease of the contact pressure and the formation of the colloidal silica tribofilm as indicated by Equations (2, 3).
Figure 1
However, there are two issues for ceramic tribopairs under water lubrication. First, the wear on ceramic surfaces is too large. To solve this issue, amorphous carbon nitride coatings (a-CNx) are deposited on the surface of a Si3N4 disc. For an a-CNx/ Si3N4 tribopair, after a wearing-in period under water lubrication, an average stable COF of ~0.007 is achieved at a sliding speed of 160 mm/s and a normal load of 5 N (Zhou et al., 2007). Moreover, the wear rate of the Si3N4 ball in an a-CNx/Si3N4 tribopair is only 1/35 of that in a Si3N4/Si3N4 tribopair under water lubrication. The wear mechanism of a-CNx/Si3N4 is the formation of a carbonaceous transfer film on the a-CNx coatings via a tribochemical reaction between the a-CNx coatings and water induced by friction. The second issue is that the superlubricity of ceramic tribopairs under water lubrication can hardly be achieved under a high contact pressure; thus, laser texturing technology is applied to SiC/SiC tribopairs to improve the load-carrying capacity of their surfaces (Wang et al.,
Polymers
Because they can be both solid-like to sustain a normal load and liquid-like to shear easily (Baykara et al.,
Figure 2

Effects of (A) the molecular weight of the PEG side chains, (B) the Lys/PEG grafting ratio, and (C) the molecular weight of the PLL backbone on the COF. The lubricant film thickness was measured with respect to the speed using an MTM and ultrathin-film interferometry. Muller et al. (
Recently, researchers reported a new grafting method for acquiring hydrophilic polymer brushes on poly(dimethyl siloxane) (PDMS) surfaces (Ron et al.,
Figure 3

(A) Coating of a substrate with a PDMS film. (B) Crosslinked PDMS matrix incorporating diblock copolymers and a skin layer. (C) High water contact angle is attributed to the PDMS skin layer formation. (D) Tribostress shears off the skin layer and induces brush segregation with charges and counter ions. H is the brush height. Ron et al. (
Recently, poly(vinylphosphonic acid) (PVPA) with salt ions was found to achieve superlubricity on a Ti6Al4V/polytetrafluoroethylene tribopair. Research into the superlubricity mechanism reveals that the cations and anions function together to achieve the superlubricity even under harsh conditions (Zhang et al., 2017). This finding makes PVPA-modified Ti6Al4V a potential material for artificial implants. It is concluded that when used as lubricants, polymers must be accompanied by a good solvent. In this way, solvent molecules can improve the stretching of polymer brushes for inducing a permeation pressure to sustain a normal load and provide low friction.
Similar to polymers, macroscale superlubricity could be achieved with hydrated alkali metal ions (Li+, Na+, K+) based on hydration effect (Han et al.,
Acid-Based Aqueous Lubricants
Phosphoric acid as a lubricant was first found to achieve superlubricity at the Si3N4/glass interface in 2011 (Li et al.,
Figure 4

(a) Evolution of the COF with time under lubrication with an H3PO4 aqueous solution (pH = 1.5). Inset is the ball-on-disk model for friction testing. The tribopair is Si3N4/glass, the load is 3 N, and the sliding velocity is 75 mm/s. (Li et al.,
In the first wearing-in stage, H+ ions play a key role in the rapid reduction of the COF from 0.45 to 0.05. Because there are ≡ SiOH bonds on the surfaces of glass and Si3N4, the H+ ions in H3PO4 can be adsorbed on the contact surfaces via the protonation reaction (Sjoberg,
Although H+ ions strongly affect the friction reduction in the first wearing-in stage, they cannot realize superlubricity directly. Among the acids, only H3PO4 is found to realize superlubricity after the second wearing-in stage; the COF decreases from 0.05 to 0.004 gradually. For other acids, there is no second wearing-in stage, and the COF remains larger than 0.01 (Li et al.,
Figure 5

Effects of the temperature and humidity. (A) Evolution of the COF with time under lubrication with H3PO4 (pH = 1.5) at different temperatures, at a humidity of 25%. (B) Evolution of the COF with time under lubrication with H3PO4 (pH = 1.5) at different humidity values, at a temperature of 25°C. The tribopair is Si3N4/glass, the load is 3 N, and the sliding velocity is 75 mm/s.
Based on the foregoing analysis, the superlubricity model of H3PO4 is proposed. In the first wearing-in stage, H+ and H2 ions are adsorbed on the contact surfaces, forming the stern layer. After the second wearing-in stage, the hydrogen-bond network is adsorbed above the stern layer and plays a key role in sustaining load. In addition to providing load support, an important function of the hydrogen-bond network is locking water molecules in the contact region. It is inferred that a thin hydrated water layer is adsorbed on the surface of the hydrogen-bond network because of the strong hydrogen-bond effect of the H3PO4 molecules, similar to a water layer adsorbed on the top of surface of ice (Dash et al.,
The superlubricity model of H3PO4 indicates that this type of superlubricity is dominated by two factors: the positively charged surfaces formed by the adsorption of H+ ions and the hydrogen-bond network of H3PO4 and water molecules. Accordingly, it is possible to achieve superlubricity with a mixture of acid and polyhydroxy alcohol, because the H+ ions from the acid can satisfy the first factor and the hydroxyl groups from the polyhydroxy alcohol can satisfy the second factor, as depicted in Figure 6A.
Figure 6

(A) Illustration of promoting phosphoric acid to a mixture of glycerol and acid. (B) Schematic of the possible lubrication model between the two friction surfaces. The red and white spheres represent oxygen and hydrogen atoms, respectively. Li et al. (
To prove this hypothesis, mixtures of acids (H2SO4, HCl, H2C2O4, and H3NO3S, pH = 1) and polyhydroxy alcohols (glycerol, 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, and 1,5-pentanediol) were prepared and tested. If the tests are performed with these polyhydroxy alcohols only, the minimum COF would be larger than 0.05. If the tests are performed with the mixtures, the friction behavior of the mixtures is similar to that of H3PO4: the COF decreases to ~0.05 during the wearing-in period and then gradually decreases to <0.01 (Li et al.,
Table 1
| No acid | H2SO4 | HCl | H2C2O4 | H3NO3S | |
|---|---|---|---|---|---|
| 1,2-ethanediol | 0.05 | 0.004 | 0.004 | 0.004 | 0.003 |
| 1,3-propanediol | 0.07 | 0.004 | 0.003 | 0.003 | 0.003 |
| 1,4-butanediol | 0.06 | 0.004 | 0.005 | 0.005 | 0.004 |
| 1,5-pentanediol | 0.06 | 0.004 | 0.006 | 0.004 | 0.003 |
Lowest COF under lubrication with four kinds of polyhydroxy alcohols and their mixtures with four kinds of acid lubricants (H2SO4, HCl, H2C2O4, and H3NO3S, pH = 1).
The tribopair is Si3N4/glass, the load is 3 N, and the sliding velocity is 75 mm/s. Data are obtained from Li et al. (
The superlubricity of these mixtures is affected by the concentration of polyhydroxy alcohol in the mixture. Superlubricity can be achieved if the concentration of polyhydroxy alcohols is less than a critical value, which is 40, 50, 40, and 30% for 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, and 1,5-pentanediol, respectively. The superlubricity mechanism of these acid-based mixtures is as follows: the hydrogen-bond network formed by polyhydroxy alcohols and water molecules is adsorbed onto the surface of the stern layer (induced by H+ ions) during the wearing-in period; thus, a hydrated water layer is formed, yielding superlubricity, as depicted in Figure 6B (Li et al.,
To check whether all the alcohols can be mixed with acid to achieve superlubricity, three key characteristics of alcohols that affect their physicochemical properties are investigated: the number of hydroxyl groups, the position of the hydroxyl groups on the C-C skeletal chain, and the length of the C-C skeletal chain (Li et al.,
Figure 7

COF under lubrication with mixtures of H2SO4 solution and polyhydroxy alcohols (A) with 3 carbon atoms in its carbon chain; (B) with various carbon chain length. The volume ratio of the polyhydroxy alcohols to the H2SO4 solution (pH 1) is 10:1. Li et al. (
As mentioned previously, the two factors for superlubricity are the H+ ions and the hydrogen-bond network. The first factor can be satisfied for all mixtures because of the existence of acid, but if the alcohol has only one hydroxyl group in its molecular structure, it cannot form a hydrogen-bond network with water molecules and thus cannot satisfy the second factor for superlubricity. If the alcohol has more than one hydroxyl group in its molecular structure, it can form the hydrogen-bond network with water molecules, yielding superlubricity. The position of the hydroxyl groups and the number of carbon atoms in the C-C skeletal chain have no effect on the hydrogen-bond network formation and thus have no obvious effect on the superlubricity.
Analysis of the superlubricity behavior of H3PO4 and the mixtures of polyhydroxy alcohols and acids reveals that their superlubricity mechanism is the same and that the two critical factors for superlubricity are the H+ ions and the hydrogen-bond network. The H+ ions help to form the stern layer on the surfaces via the protonation reaction, which requires the pH of the lubricant to be <2. The hydrogen-bond network provides load support and locks water molecules in the contact region, which requires the existence of at least two hydroxyl groups in the lubricant molecular structure. The authors proved that these two factors are required for achieving superlubricity. The steady COF achieved with only H+ ions (e.g., acid, except for H3PO4) is >0.03, and that achieved with only the hydrogen-bond network (e.g., glycerol only) is >0.02. The superlubricity mechanism of the acid-based lubricants is attributed to both the formation of the hydrogen-bond network and the stern layer. The friction results and mechanism indicate that if a liquid lubricant satisfies two criteria—possessing H+ ions (pH ≤ 2) and at least two hydroxyl groups in its molecule—liquid superlubricity can be achieved. Therefore, a novel system of liquid superlubricity based on H+ ions and hydroxyl groups is established, and this study offers a new method for achieving liquid superlubricity.
However, the strong acidity of these acid-based lubricants limits their applications in a practical mechanical system. Recently, a new type of acid-based lubricant, which is a mixture of BA and a PEG aqueous solution (PEG(aq)), was synthesized and found to provide superlubricity (COF ≈ 0.004) in neutral conditions (pH ≈ 6.4) at Si3N4/SiO2 interfaces, as depicted in Figure 8 (Ge et al.,


Figure 8

(A) COFs and (B) wear scar diameter (WSD) of the mixtures of PEG and several acids: BA, acetic acid, tartaric acid, lactic acid, and citric acid. Ge et al. (
Rtil Lubricants
RTILs are a series of well-known lubricants and lubricant additives in surface science and engineering (Ye et al.,
Recently, as depicted in Figure 9, researchers explored the robust superlubricity of a 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ([EMIM]TFS) aqueous solution between a Si3N4/SiO2 tribopair (Ge et al.,
Figure 9

COF of the [EMIM]TFS aqueous solution. The inset shows the proposed superlubricity model. Ge et al. (
Oil-based Lubricants
In general, friction for liquid lubrication depends on the lubrication regime, which transitions from BL to ML and then to EHL. Moreover, the liquid friction is generally the lowest during the transition to EHL, where the thickness of the fluid film is perfect for separating the surfaces completely and providing extremely low viscous friction (Baykara et al.,
Figure 10

(a) Relationship between the COF and the rotational speed. Bouchet et al. (
In addition to surface coating, alloys are typically used in mechanical engineering applications for different conditions. Some alloy tribopairs, such as Nitinol 60 alloy/steel tribopairs, are also used to study superlubricity. Superlubricity can be achieved under lubrication with castor oil in the boundary regime. Researchers examined the influence of the sliding speeds and normal loads on the friction in detail (Zeng and Dong, 2013). The results showed that the influence of the sliding speed on the lubricity is greater than that of the load owing to the chemical structure of castor oil, which is not suitable at high sliding speeds, because of its poor oxidation stability. Therefore, maintaining the sliding speed in an appropriate range is very important for achieving the superlubricity of the Nitinol 60 alloy. The same researchers compared castor oil, turbine oil, seed oil, and paraffin oil, and the results showed that only castor oil can achieve superlubricity for a Nitinol 60 alloy/steel tribopair (Zeng and Dong, 2014). Therefore, the hydroxyl groups branched on the acid chain may be necessary for superlubricity. The main chemical structure of castor oil has three long-chain fatty acids with an alkyl ester group, as depicted in the inset of Figure 11a. Thus, castor oil has the ability to form a thin film as an intermolecular layer and reduces the friction between the interfaces (Zeng and Dong, 2013). Analysis shows that tribochemical reactions occur during rubbing motion, including the decomposition of castor oil, the formation of iron oxy-hydroxide, and the triboformed OH-terminated surface with iron oxy-hydroxide. The authors propose a new superlubricity model, as depicted in Figure 11b. Here, a lamellar structure is formed by the intercalation of hexanoic acid molecules between Ni and iron oxy-hydroxide, which can provide strong repulsive electrostatic forces, contributing to the achievement of the superlubricity state (Zeng et al., 2016). As a good vegetable oil, castor oil is an eco-friendly lubricant owing to its excellent properties, such as its high biodegradability, renewability, and superlubricity performance. Therefore, the superlubricity achieved with castor oil makes it suitable for practical engineering applications in many fields, including biotechnology.
Figure 11

(a) Evolution of the COF with time. The inset shows the main chemical structure of castor oil. (b) Lubrication diagrammatic sketch of the tribopair under castor-oil lubrication. Zeng et al. (2016) Copyright 2016, Nature.
Researchers also achieved superlubricity with silicone oil between a Si3N4/glass tribopair by pre-treating the interface with H2SO4 (Li et al.,
Figure 12

(A) COF under lubrication with 100 mPa·s silicone oil, H2SO4 (pH = 1), and 100 mPa·s silicone oil after wearing-in with H2SO4 (pH = 1). (B) Final COF of silicone oils between the original surfaces (Si3N4/glass) and the surfaces after wearing-in with H2SO4 (pH = 1). The error bars represent the standard deviations of five measured values. Li et al. (
Nanomaterial-Based Lubricants
One common feature of liquid superlubricity is that a wearing-in process is required before the achievement of superlubricity, which usually leads to severe wear. It has been proven that graphene-oxide (GO) materials can provide wear protection. Through the generation of a GO-adsorption film on the contact surfaces, GO can separate the contact surfaces and reduce the wear (Wu et al.,
Our group achieved a macroscale superlubricity state through the synergy effect of GONFs and ethanediol (EDO) at ceramic tribopairs including Si3N4/SiO2, Si3N4/Si3N4, and Si3N4/Sapphire (Ge et al.,
Figure 13

Characterization of GONFs: (a) atomic force microscopy image; (b) high-resolution transmission electron microscopy (HRTEM) image; (c,d) XPS spectra; (e) Raman spectra. (f,g) Friction and wear testing results for GONFs-EDO. (h) HRTEM image of the cross-sectional area of the worn surface. (i,j) Proposed superlubricity and anti-wear mechanism of GONFs-EDO. Ge et al. (
Other nanomaterials like BP-OH, BN, LDH, and nanodiamonds were also found to help the base lubricants achieve superlubricity. The superlubricity mechanism for BP-OH aqueous solution is attributed to the effective lubricating layer formed by the attachment of water molecules on BP-OH nanosheets in the silica-gel (Wang et al.,
Conclusions and Outlooks
Studies on liquid superlubricity at the macroscale are focused on the mechanism, which differs for different lubricants and is usually attributed to multiple factors, such as the silica layers and hydrodynamic lubrication for water, the tribochemical layer, and hydrogen-bond network for viscous lubricants, and the stern layer and hydrogen-bond network for acid-based lubricants. The mechanism of liquid superlubricity is very complicated and should be further investigated. Because of the limitation of the present technology, the structure, and arrangement of liquid molecules in the contact region, which play the dominate role on the superlubricity, are still not clear. In addition, the kinds of materials for liquid superlubricity are limited; only a few materials exhibit superlubricity behavior. The possibility of other liquid materials with superlubricity properties remains to be investigated. Furthermore, there are many factors that limit the application of liquid superlubricity, such as the severe wear, acidic conditions, and complexity of manufacturing ideal surfaces. However, the prospects for liquid superlubricity in industrial applications are excellent. For instance, hydrophilic polymer brushes may be suitable for silicone rubbers in microfluidics, marine paints (antifouling), biomedical devices, etc. Acid-based lubricants and ionic liquids may be suitable for Si3N4 bearings, who have strong resistance to acidic corrosion. Oil-based lubricants may be suitable for the mechanical parts like gears and bearings, who are made of steels and alloys. PVPA-modified Ti6Al4V is a potential material for artificial implants. Therefore, research in the near future should focus on the development of new liquid lubricants to offer lubricating performance with extremely low friction and wear, as well as be associated with practical operating conditions in mechanical systems.
Statements
Author contributions
JLu and JLi gave the guidance on the structure and content of this review. XGe completed this review.
Acknowledgments
The work is financially supported by the National Natural Science Foundation of China (51775295, 51527901, and 51335005).
Conflict of interest
The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.
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Summary
Keywords
macroscale superlubricity, liquid lubricants, polymers, acid-based lubricants, room-temperature ionic liquids, oil-based lubricants, nanomaterial-based lubricants
Citation
Ge X, Li J and Luo J (2019) Macroscale Superlubricity Achieved With Various Liquid Molecules: A Review. Front. Mech. Eng. 5:2. doi: 10.3389/fmech.2019.00002
Received
17 December 2018
Accepted
17 January 2019
Published
05 February 2019
Volume
5 - 2019
Edited by
Valentin L. Popov, Technische Universität Berlin, Germany
Reviewed by
Wenling Zhang, University of Alberta, Canada; Ali Erdemir, Argonne National Laboratory (DOE), United States
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© 2019 Ge, Li and Luo.
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*Correspondence: Jinjin Li lijinjin@mail.tsinghua.edu.cnJianbin Luo luojb@tsinghua.edu.cn
This article was submitted to Tribology, a section of the journal Frontiers in Mechanical Engineering
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