Tribochemistry Od Bismuth Salts For Solid Lubrication

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Tribochemistry of Bismuth and Bismuth Salts for Solid Lubrication
Pablo Gonzalez Rodriguez, Karin van den Nieuwenhuijzen,
Walter Lette, Dik Schipper, and Johan E. ten Elshof
ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.6b02541 • Publication Date (Web): 03 Mar 2016
Downloaded from http://pubs.acs.org on March 3, 2016
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Page 1 of 20 ACS Applied Materials & Interfaces
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4 Tribochemistry of Bismuth and Bismuth Salts for Solid Lubrication
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6 P. Gonzalez-Rodriguez 1-2, K.J.H. van den Nieuwenhuijzen 2, W. Lette 3, D.J. Schipper 3, J.E. ten
7 Elshof 2,*
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9 Materials innovation institute (M2i). Elektronicaweg 25, 2628 XG Delft, the Netherlands.
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Inorganic Materials Science, MESA+ Institute for Nanotechnology, University of Twente, P.O. Box 217, 7500 AE
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12 Enschede, The Netherlands.
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Surface Technology and Tribology, Faculty of Engineering Technology, University of Twente, P.O. Box 217, 7500 AE
14 Enschede, The Netherlands
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19 ABSTRACT
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21 One of the main trends in the last decades is the reduction of wastage and the replacement of toxic
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23 compounds in industrial processes. Some soft metallic particles can be used as non-toxic solid lubricants
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25 in high temperature processes. The behavior of bismuth metal particles, bismuth sulfide (Bi2S3), bismuth
26 sulfate (Bi2(SO4)3) and bismuth oxide (Bi2O3) as powder lubricants was studied in a range of temperatures
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28 up to 580 °C. The mechanical behavior was examined using a high temperature pin-on-disc set-up, with
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30 which the friction force between two flat-contact surfaces was recorded. The bismuth-lubricated
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surfaces showed low coefficients of friction (µ ≈ 0.08) below 200 °C. Above the melting temperature of
33 the metal powder at 271 °C, a layer of bismuth oxide developed and the friction coefficient increased.
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35 Bismuth oxide showed higher friction coefficients at all temperatures. Bismuth sulfide exhibited partial
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37 oxidation upon heating but the friction coefficient decreased to µ ≈ 0.15 above 500 °C, with the
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formation of bismuth oxide-sulfate, while some bismuth sulfate remained. All surfaces were studied by
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40 X-ray diffraction (XRD), confocal microscopy, high resolution scanning electron microscopy (HR-SEM) and
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42 energy-dispersive X-ray spectroscopy (EDS). This study reveals how the partial oxidation of bismuth
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44 compounds at high temperatures affects their lubrication properties, depending on the nature of the
45 bismuth compound.
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48 Keywords: solid lubricant, high temperature, bismuth, bismuth oxide, bismuth sulfide, bismuth sulfate,
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pin on disk, friction coefficient
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52 INTRODUCTION
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Solid lubricants are used in many industrial processes, especially related to metal processing. Although
56 metals as structural materials are in some cases being replaced by more lightweight or sustainable
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ACS Applied Materials & Interfaces Page 2 of 20
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3 solutions, like composites or ceramics,1,2 the production of high-end products is still linked to the
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5 mechanical properties and workability of metals. Metal-metal sliding contacts are present in a wide
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7 variety of applications, including conduits,3 automotive gears,4 sliding electrical contacts5 and biological
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implants.6 In the upstream industry, the production of steel requires the use of large amounts of
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10 lubricants and nowadays the most common products are aqueous suspensions of graphite, molybdenum
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12 disulfide or polytetrafluoroethylene (TeflonTM).7,8 Nevertheless, some problems are associated with their
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14 use, for instance pitting corrosion on the steel surface caused by partial decomposition of the lubricants
15 at high temperature, and, more in general, a dirty working environment.9 Bismuth has been used for
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17 many years as an active part in self-lubricating alloys10 because of its natural softness and as an additive
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19 for lubricating oils.11-13 This element has found its major applications as an alternative for lubricants
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21 based on lead. Both metals have a high density, malleability, softness and low melting temperature.14
22 The one important difference between the two is that bismuth is not toxic for living organisms, in
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24 contrast to its counterpart lead.15 Despite both being heavy metals, bismuth may be considered as a
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26 green alternative to lead. Bismuth has already been used in protective lubricating coatings for solid
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lubrication.16 It has been found that bismuth particles can form non-bonded films on steel that are easily
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29 removed from lubricated surfaces, and which are due to the poor solubility of bismuth in iron.17,18 Other
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31 compounds of bismuth have also been studied as active additives in lubricants. The presence of sulphur
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33 has a synergetic effect on the lubricating properties of bismuth. Bismuth sulfide (Bi2S3) is known to have
34 lubricious properties, forming a stable tribolayer on lubricated pairs.19 Bismuth organometallic
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36 compounds are used as additives in oil-lubricated systems, together with sulphur carriers that promote
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38 the formation of a Bi2S3 tribolayer between the interfaces of metal-oil-metal. However, under conditions
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where the use of organic-based products is unfavorable, i.e. at high temperatures, employing solid
41 lubricants in the form of powders is a solution to reduce friction and energy consumption.9 Powders are
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43 typically applied in the form of a suspension in a liquid solvent or compressed to act as a part on the
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45 sliding system.20 Application of the lubricant together with treatment of the waste after its use should be
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performed in a controlled manner. Therefore, it is important that the lubricant itself is not toxic in small
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48 concentrations for living organisms. Bismuth is present as additive in cosmetics and paints,21,22 anti-
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50 inflammatories23 and dental resins,5 so it can be considered as a non-toxic material for humans. Exposure
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52 to bismuth at high temperatures is not known to have toxic effects. Bismuth metal has a low vapor
53 pressure and is just slightly absorbable by the respiratory and intestinal tracts.24 Therefore, in this
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55 research we explore the applications of bismuth and several bismuth compounds as high temperature
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57 lubricants. Bismuth and bismuth salts have hardly been studied as lubricants in the form of free powders
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3 and little is known about the chemical modifications that bismuth undergoes when present in the
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5 contact between two sliding surfaces.
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10 EXPERIMENTAL
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13 Preparation of bismuth suspensions. Bismuth metal powder (Bi, ABCR, 99.9 %), bismuth (III) sulfide
14 (Bi2S3, ABCR, 99.9 %), bismuth (III) oxide (Bi2O3, Alfa Aesar, 99 %) and bismuth (III) sulfate (Bi2(SO4)3, Alfa
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16 Aesar, 99 %) were used as received, without further purification. The powders were suspended in water
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18 to a concentration of 2 w% in closed bottles. The suspensions were placed on a rolling bench with
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zirconium oxide beads (φ = 1 mm) for 48 h in order to reduce the particle size of the powders, as a
21 standard procedure to grind suspended powders. The suspensions were then transferred to a steel pin
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23 and dried on a hot plate at 90 °C. Typically, a quantity of 200 µL of each suspension was transferred with
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25 the help of a pipette and dried on the surface of the measuring steel pin.
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27 Characterization.
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30 Pin-on-Disc: The lubricating properties of the bismuth and bismuth salt powder films were assessed by
31 the use of a High-Temperature Pin-on-Disc (PoD) tribometer of CSM instruments. This technique allows
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33 to record friction forces between two sliding surfaces when a lubricant is present in between them. The
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35 granular nature of the lubricant made it necessary to adapt the classical PoD configuration, because the
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use of a bearing ball implies a single contact point between the two metal surfaces. In our experiments
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38 the balls were flattened so that the lubricant could be applied on the surface of the pins and could be
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40 employed when the discs had reached the set temperatures. The pins consisted of flattened steel
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42 bearing balls (10 mm diameter, SKF). The surface of the steel pin was 27 mm2 (disc diameter of φ = 5.9
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mm), giving a surface concentration of lubricant of 75 µg/mm2 (or 75 g/m2). The applied load was 10 N,
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45 resulting in an effective contact pressure of 370 kPa. The rotating disk was made of EN 10278 steel and
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47 was polished, as well as the flattened bearing balls, with SiC paper with a maximum mesh of 2000 and
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49 diamond paste of 3 µm particle size. The calculated arithmetic roughness of the steel surfaces was Ra =
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0.90 ± 0.25 µm. The measurements consisted of recording of the friction force for a maximum of one
52 rotation of the pin over the disc, at a velocity of 1 mm/s. Data were collected from the first data points
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54 after contact between the pin+lubricant and the disc at temperatures varying from 25 to 580 °C. The
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56 coefficient of friction (CoF) was averaged over a minimum of 5 repetitions. The typical time scale of an
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3 experiment lasted up to 30 s, since the powder films were susceptible to be worn out due to the limited
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5 testing surface.
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The measurement of particle size was performed using a laser diffraction particle size analyzer
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9 (Mastersizer 2000). The particle size distributions (PSDs), i.e., particle size at 10% (D10), 50% (D50), and
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11 90% (D90) of the volume distribution were all calculated automatically using the Mastersizer 2000
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13 software. The characterization of the crystallographic changes by X-ray diffraction (XRD) was conducted
14 with an X’Pert Powder Pro (PANalytical) using Cu-Kα irradiation (λ = 1.5418 Å) and recorded with a 1D
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16 PIXcel detector. Scans from 2θ = 20-70° were measured with step sizes of 0.013° and 150 s per step.
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18 High-resolution scanning electron microscopy was executed on a Merlin field emission microscope
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(Zeiss) coupled with elemental analysis performed by energy-dispersive X-ray spectroscopy (EDS; TEAM™
21 EDS system). Further surface analysis was performed with a laser confocal microscope VK 9700 from
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23 Keyence at a magnification of 10 times and a z-axis resolution of 1 nm. Surface images of different
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25 tribofilms were obtained and the profile roughness parameters were determined.
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27 RESULTS AND DISCUSSION
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30 The performance of bismuth metal (Bi) and bismuth compounds as lubricants was studied by means of
31 Pin-on-Disc (PoD) measurements. The diverse compounds have different melting/softening points that
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33 may influence the tribological properties. The lowest melting point is that of bismuth metal at 271 °C,
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35 followed by Bi2(SO4)3 at 405 °C, Bi2O3 at 817 °C and Bi2S3 at 850 °C. Only the two first compounds have
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37 melting points below the maximum testing temperature in this study (580 °C). The powders of all
38 bismuth compounds were suspended in water and grinded for 48 h and the particle size distributions in
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40 volume are displayed in table 1. The thicknesses of the dried films varied from 100 to 300 µm for the
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42 different films. The thickness difference was caused by density differences between the individual
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compounds, while keeping the mass of the powders constant.
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46 Table 1. Summary of particle size distributions by volume of the different lubricants.
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Particle size distributions (PSDs)
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50 Compounds D10 (µm) D50 (µm) D90 (µm)
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52 Bi 2.09 6.42 20.462
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54 Bi2O3 1.38 11.14 69.56
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Bi2S3 1.51 11.51 67.14
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3 Bi2(SO4)3 1.86 11.71 45.67
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The friction properties of Bi were directly compared with those of Bi2O3, see Figure 1. The recorded
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11 35 °C to 580 °C using eq. 1.
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13 F μ ∙ F (eq.1)
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15 Where Fd, µ and Fn are the dynamic friction force, CoF and the normal force, respectively.
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40 Figure 1. Variation of the average coefficient of friction of bismuth metal (Bi) and bismuth oxide (Bi2O3) with
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temperature. The red bands represent the average range of the CoF upon contact between the two bare metal
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43 surfaces, and the CoF of graphite lubricant, respectively.
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The CoF of the contact between the unlubricated surfaces of the pin and the disc were recorded as
47 reference, resulting in values of 0.32 ± 0.02 at different temperatures. The CoF of graphite as the state-
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49 of-the-art lubricant was also determined, with values of 0.050 ± 0.005. For the sake of clarity and
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51 simplicity, the data points of both reference measurements are represented in Figure 1 in the form of
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colored bands. The measured values can be found in Figure S1 in the supplementary information section.
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54 The average CoF of the Bi films was lower than the metal-to-metal contact at all temperatures below 500
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56 °C. The maximum effectiveness of Bi as lubricant was reached in the low temperature range (up to 200
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58 °C) with a reduction of the CoF by a factor of 3 compared to the reference. This is due to the fact that
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3 bismuth metal has a closed packed quasi-metallic layered structure at room temperature.25 This
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5 structure may be at the basis of its enhanced properties as solid lubricant. When a force is applied the
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7 atoms slide along the same crystallographic direction, forming a slip system where dislocations can
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propagate. The value of the CoF increased steadily between 200 and 500 °C, to reach typical values of
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10 metal-metal contact eventually. The variation of the recorded values also increased with temperature,
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12 which could be related to changes experienced by the Bi film. Above the melting temperature (271 °C),
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14 liquid bismuth can wear out faster compared to the solid powder form. Thus, the performance of
15 bismuth metal as lubricant was only comparable with graphite at temperatures below 200 °C. On the
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17 other hand, the CoF of Bi2O3 was higher than the metal-metal contact for all tested temperatures.
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19 Bismuth atoms in the structure of Bi2O3 are not completely screened by the surrounding oxygen atoms
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21 due to their large size (117 pm). The lack of surrounding makes that the metal cations can interact with
22 each other and form covalent or ionic bonds leading to a network that is difficult to shear.26
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25 The variation in the friction properties of Bi powders can be directly linked to changes in the chemistry
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and crystallography of the lubricant. The friction experiments led to the formation of transferred films
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28 from the surface of the pin to the surface of the discs and the Bi powders underwent crystallographic
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30 changes within the measurement time. Figure 2 shows the X-ray diffraction patterns of the Bi transferred
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32 films at different temperatures, up to 580 °C. It was found that, upon heating, partial oxidation of the Bi
33 film resulted in Bi2O3. The oxidation happened even at room temperature and was accelerated in
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35 samples tested at 300 °C and higher. Figure 2b displays the 2Θ region from 26 to 28.5°. It can be seen
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37 that three Bi2O3 peaks emerged from the background, i.e. the (110), (120) and (012) peaks, resulting in
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39 an overall intensity decrease of the Bi (012) peak with increasing temperature. The intensity of the (012)
40 peak increased up to 400 °C as an artifact of the irradiated surface. Bismuth metal seemed to adhere
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42 stronger to the surface of the disc after measurement around and above the melting point. The
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44 measurements at high temperature also induced the oxidation of the surface of the steel discs, and
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peaks of iron (III) oxide (Fe2O3) were present in samples tested above 400 °C. Evidence of intermetallic
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47 compounds of bismuth and iron were not found in the employed films, which could be due to the short
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49 measurement times. The transferred Bi powders may not have had enough time to react with the
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51 surface of the steel before the samples had cooled down. The lubrication mechanism at low
52 temperatures (below the melting point) is not based on the formation of a bound layer of lubricant and
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54 substrate, but on the deformation and sliding of Bi particles between the two sliding metal surfaces.
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56 Previous reports in literature found the same behavior when using Bi as additive in lubricant oils.11,17
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3 Bismuth has a low melting point compared to the majority of metals in the periodic table.25 The
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5 oxidation of Bi was accelerated above the melting point, as can be seen by the XRD data in figure 2. The
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7 partial oxidation of the lubricant films beyond the melting point could be related to the higher friction
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coefficients at higher temperatures. The CoF of Bi powders increased upon heating and approached the
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10 behavior of Bi2O3 films, as can be seen in Figure 1. Apparently, the formation of a stiffer oxide phase
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12 decreased the deformability of the bismuth film, hindering its good friction properties. In addition, the
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14 molten bismuth was worn out faster, which implied a friction increase when a thinner bismuth film is
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48 Figure 2. (a) Powder XRD patterns of transferred Bi films after heating to temperatures between 35 and 580 °C. (b)
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Close-up range from 26 to 28.5 °, where the main peaks of Bi and Bi2O3 are located. The diffractograms were
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51 normalized to the main peak of the Fe-Cr substrate at 2Θ = 44°. The phases are represented as follows: Bi metal (Bi,
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53 ♦, JCPDS 00-044-1246), bismuth (III) oxide (Bi2O3, *, JCPDS 00-006-0294), stainless steel (Fe-Cr, •, JCPDS 03-065-
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7775) and iron (III) oxide (Fe2O3, ○, JCPDS 01-073-0603).
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3 The melting of Bi could also be seen in the morphology of the transferred films. Confocal microscopy
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5 imaging of Bi samples after investigation above 300 °C showed regions with varying light refraction and
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7 amorphous shapes that could be attributed to molten Bi powder, see Figure 3. A close-up of the molten
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droplets showed that their core was formed by microcrystals and not by a glassy structure. The molten
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10 areas may have been the nucleation points for the accelerated oxidation of Bi. Despite the formation of
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12 molten Bi, the increasing CoF with increasing temperature can be directly linked to the formation of
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14 Bi2O3 crystals in the matrix of molten Bi droplets. The transferred Bi films at 300 °C had thicknesses in the
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range of 30 – 50 µm and a roughness of 0.8 µm, in contrast to Bi2O3 transferred films that had
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17 thicknesses in the range of 70 – 110 µm and an average roughness of 3.9 µm, see Figure 3. The lower
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19 film thickness and roughness of Bi could be linked to the plasticity of the metallic phase in comparison to
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21 the more brittle behavior of Bi2O3.
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Zenithal view of a typical Bi transferred film at x10 magnification. Inset: view of a molten droplet at x50
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54 magnification. Clear grey: steel, dark brown: bismuth, elongated dark-edged drops: molten bismuth; (b)
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56 Topographic representation of the surface of a Bi film at x10 magnification and line profile of the roughness; (c)
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3 Zenithal view of a typical Bi2O3 film with x10 magnification; (d) Topographic representation of the surface of a Bi
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5 film at x10 magnification and line profile of the roughness.
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7 In another series of friction experiments, the compounds Bi2S3 and Bi2(SO4)3 were compared. Results of
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9 the average CoF for both compounds are displayed in figure 4. Both ceramic materials performed above
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11 the metal-metal contact for the majority of friction tests at different temperatures. Nevertheless, Bi2S3
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showed a steady decrease of the average CoF from 100 °C. The coefficient of friction dropped abruptly
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14 above 500 °C, and the lubricant showed values of only half of the CoF of metal-metal contact. The spread
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16 in the measurement data increased at 500 °C, which may be considered as a transition temperature for
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18 the lubricant, and reached more reproducible values at 580 °C. Bi2(SO4)3 showed more erratic behavior,
19 and no trend could be deduced from the measured values of friction. The ceramic showed friction forces
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21 well above normal metal-metal contact and the scatter in the measurement data was high. The relatively
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23 large scatter in the data may be an indication of the lack of deformability of these ceramic powders. The
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25 particles tend to slide and roll between the asperity contact of the metal surfaces. The stiffness of the
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50 Figure 4. Variation with temperature of the average coefficient of friction of bismuth (III) sulfide (Bi2S3) and bismuth
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(III) sulfate (Bi2(SO4)3). The red bands represent the average CoF for contact between two bare metal surfaces, i.e.
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53 pin and disc, and the CoF of graphite.
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56 The crystallographic changes of Bi2S3 upon heating were studied by XRD and the patterns are displayed in
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Figure 5. The transferred films consisted exclusively of Bi2S3 up to 400 °C. At 500 °C and higher, new
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3 peaks resulting from a partially oxidized species of bismuth and sulfur emerged. On the basis of its
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5 crystallographic reflections the new compound corresponded to bismuth oxysulfate [Bi28O32(SO4)10], with
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7 65 % of Bi2S3 oxidized. The disappearance of some reflections of Bi2S3 and the increase in intensity of the
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peaks of the new phase suggests that its formation was directly linked to the partial oxidation of Bi2S3
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10 during the tribological tests. The effect of oxidation was especially visible by prolonging the typical
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12 experiment from 1 cycle (or 60 s) to 5 cycles (or 5 min); these samples are denoted 580 °C (s) and 580 °C
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14 (m), respectively. The peaks of the oxidized [Bi28O32(SO4)10] phase increased in intensity with prolonged
15 thermal treatment, as can be seen in Figure 5. None of the growing peaks could be attributed to the
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17 Bi2O3 phase. It is known in the literature that Bi2S3 undergoes oxidation in both Bi and S sites upon
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19 heating, leading to mixed oxides-sulfates at these temperatures.27 The peaks of the stainless steel
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21 substrate are visible in the patterns, accompanied by ferrite (Fe2O3) and magnetite (Fe3O4) peaks. The
22 oxidation in both Bi and S sites may have influenced the difference in performance between Bi2S3 and its
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24 oxidized form [Bi28O32(SO4)10] compared with Bi2(SO4)3. Bi2(SO4)3, a typical ionic bonded ceramic, showed
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26 more ‘ceramic’ behavior, with less plastic films, leading to higher CoFs and more scatter in the
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measurement values.
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33 Figure 5. Powder XRD patterns of Bi2S3 transferred films after treatment between 35 to 580 °C. The phases are
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represented as follows: Bismuth (III) sulfide (Bi2S3, ♦, JCPDS 01-084-0279), bismuth oxysulfate (Bi28O32(SO4)10, •,
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36 JCPDS 01-077-1727), stainless steel (Fe-Cr, ○, JCPDS 03-065-7775), iron (III) oxide (Fe2O3, *, JCPDS 01-073-0603) and
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38 iron oxide magnetite (Fe3O4, *’, JCPDS 01-086-1358).
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43 The transferred films were also studied by means of HR-SEM and EDS. The analysis resulted in values of
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45 63 mol% of the bismuth atoms combined with oxygen which is in line with the oxygen composition of
46 [Bi28O32(SO4)10], with 65 % percent of Bi2S3 oxidized. The HR-SEM image of the surface of the film and the
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48 elemental analysis can be found in the supplementary information, figure S2. The morphology of the Bi
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50 films was studied by means of confocal microscopy. The transferred Bi2S3 films at high temperature had
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52 thicknesses in the range of 15 – 20 µm and a roughness of 2.7 µm. Despite being rougher than Bi films,
53 the low thickness of the Bi2S3 films is also related to the plasticity of that lubricant. The topographical
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55 profile of a Bi2S3 model film at 300 °C can be found in the supplementary information, figure S3.
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CONCLUSIONS
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60 11
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3 The effectiveness of Bi and Bi2S3 as solid free-standing powders for lubrication has been demonstrated.
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5 The morphological, crystallographic and chemical characterization of all Bi compounds helped to
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7 describe their behavior as lubricants. Bi powders perform better at temperatures below 500 °C, with an
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overall reduction of the CoF by a factor of 3 compared to the reference metal-metal contact. In contrast,
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10 Bi2S3 performed best as a lubricant above 500 °C with a reduction in CoF by a factor of 2. The oxidation of
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12 both lubricants influenced their tribological behavior in a different way. Despite oxidation of the
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14 lubricants, no reaction with the substrate was found, which makes the cleaning process of the lubricant
15 from the surface easier. This may help to avoid wastage of water and other cleaning agents, and thus
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17 help the sustainability of high temperature processes. This study allowed to choose the best solid
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19 lubricant for processes occurring at different temperatures.
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21 ASSOCIATED CONTENT
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24 Supporting Information
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26 The Supporting Information is available free of charge on the ACS Publications website at DOI:…
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28 Pin-on-disc measurements of unlubricated metal surfaces and graphite; HR-SEM of a Bi2S3 transferred
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30 film; confocal micrographs of a Bi2S3 transferred film (PDF).
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32 AUTHOR INFORMATION
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34
35 Corresponding Author
36
37 *E-mail: j.e.tenelshof@utwente.nl
38
39 Notes: The authors declare no competing financial interest.
40
41
42
AKNOWLEDGEMENTS
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44 This research was carried out under the project number M41.7.11434 in the framework of the Research
45
46 Program of the Materials innovation institute (M2i) Delft, the Netherlands. The authors thank E.G. de
47
Vries for technical assistance during friction data acquisition and M. Smithers for all the advices during
48
49 HR-SEM imaging.
50
51
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Tribochemistry Od Bismuth Salts For Solid Lubrication

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