CN116496825A - Antiwear antifriction lubricating oil additive and modified lubricating oil using additive - Google Patents

Antiwear antifriction lubricating oil additive and modified lubricating oil using additive Download PDF

Info

Publication number
CN116496825A
CN116496825A CN202310447453.8A CN202310447453A CN116496825A CN 116496825 A CN116496825 A CN 116496825A CN 202310447453 A CN202310447453 A CN 202310447453A CN 116496825 A CN116496825 A CN 116496825A
Authority
CN
China
Prior art keywords
lubricating oil
additive
oil additive
friction
laser irradiation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202310447453.8A
Other languages
Chinese (zh)
Other versions
CN116496825B (en
Inventor
李伟
张文娟
邱涛
郭作波
周正
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jinan Yinhe Road And Bridge Testing And Testing Co ltd
Original Assignee
Jinan Yinhe Road And Bridge Testing And Testing Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jinan Yinhe Road And Bridge Testing And Testing Co ltd filed Critical Jinan Yinhe Road And Bridge Testing And Testing Co ltd
Priority to CN202310447453.8A priority Critical patent/CN116496825B/en
Publication of CN116496825A publication Critical patent/CN116496825A/en
Application granted granted Critical
Publication of CN116496825B publication Critical patent/CN116496825B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/20—Compounds containing nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
    • C01B21/0648—After-treatment, e.g. grinding, purification
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06—Metal compounds
    • C10M2201/061—Carbides; Hydrides; Nitrides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/0206—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04—Detergent property or dispersant property
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nanotechnology (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Lubricants (AREA)

Abstract

The lubricant additive is prepared from hexagonal boron nitride, and spherical hexagonal boron nitride nano particles are obtained by liquid phase laser irradiation of hexagonal boron nitride nano sheets and serve as the lubricant additive. The spherical hexagonal boron nitride nano-particles are prepared by adopting a simple green laser irradiation method, are used as a lubricating additive, have good dispersion stability in PAO6 base oil, and show excellent tribological properties. The one-step laser irradiation method provides a new way for preparing the spherical hexagonal boron nitride nanoparticle lubricating oil additive.

Description

一种抗磨减摩润滑油添加剂及使用该添加剂的改性润滑油Anti-wear and anti-friction lubricating oil additive and modified lubricating oil using the additive

技术领域technical field

本申请涉及一种抗磨减摩润滑油添加剂及使用该添加剂的改性润滑油。The application relates to an anti-wear and anti-friction lubricating oil additive and a modified lubricating oil using the additive.

背景技术Background technique

摩擦是自然界普遍存在的现象，通常会导致加工过程中能量的大量浪费，缩短机器寿命，甚至造成潜在的安全隐患。润滑油是减少磨损、提高机器效率的最有效策略。润滑油由基础油和添加剂组成。因此，研制新型润滑油添加剂，不断提高添加剂的抗磨、减摩性能，是提高润滑油质量的有效途径。Friction is a ubiquitous phenomenon in nature, which usually leads to a large waste of energy in the processing process, shortens the life of the machine, and even creates potential safety hazards. Lubricants are the most effective strategy for reducing wear and improving machine efficiency. Lubricating oil consists of base oil and additives. Therefore, it is an effective way to improve the quality of lubricating oil to develop new lubricating oil additives and continuously improve the anti-wear and anti-friction properties of additives.

二维层状材料因其特殊的物理化学性质而表现出优异的摩擦学性能。其中h-BN是一种具有石墨样结构的层状材料。由于具有良好的机械性、润滑性和抗氧化性，经过合理的开发有望成为绿色润滑油添加剂的首选之一。在过去的几十年里，大量关于h-BN作为润滑添加剂的研究已被报道。有研究人员发现亲脂性BN纳米片作为矿物油中的摩擦添加剂，可使摩擦系数(COF)降低20.2％。更重要的是，磨损疤痕的轨迹明显变浅。还有人研究了BN作为PAO4基础油添加剂的摩擦学性能。他们发现，在润滑油中添加h-BN层状纳米材料后，润滑油的磨损负荷比基础油提高27％。还有研究人员报道了结合180℃的水热处理和超声处理成功地剥离了BN纳米片。剥离后的h-BN纳米片具有良好的减摩和抗磨性能。然而，h-BN在矿物基础油中的分散性差限制了其使用，亲脂性h-BN的制备仍然是一个长期的挑战。Two-dimensional layered materials exhibit excellent tribological properties due to their special physicochemical properties. Among them, h-BN is a layered material with a graphite-like structure. Due to its good mechanical properties, lubricity and oxidation resistance, it is expected to become one of the first choices of green lubricating oil additives after reasonable development. In the past few decades, a large number of studies on h-BN as a lubricant additive have been reported. Researchers have found that lipophilic BN nanosheets can reduce the coefficient of friction (COF) by 20.2% as a friction additive in mineral oil. What's more, the traces of wear scars are visibly lighter. Others have studied the tribological properties of BN as a PAO4 base oil additive. They found that after adding h-BN layered nanomaterials to lubricating oil, the wear load of the lubricating oil increased by 27% compared with the base oil. Other researchers reported the successful exfoliation of BN nanosheets by combining hydrothermal treatment at 180 °C and ultrasonic treatment. The exfoliated h-BN nanosheets have good anti-friction and anti-wear properties. However, the poor dispersion of h-BN in mineral base oils limits its use, and the preparation of lipophilic h-BN remains a long-standing challenge.

根据抗磨减摩机理，由于球形颗粒分子轴承的滚动作用和摩擦副之间迅速形成摩擦润滑膜效应，使得球形颗粒具有更优异的润滑性能。目前已经对众多球形颗粒的润滑性能进行了研究，如氧化铁、碳球、二氧化钛、二硫化钨。h-BN具有强烈的(002)平面定向生长趋势，易形成不规则片状纳米颗粒，难以制备成球形。目前报道的h-BN球形颗粒的制备方法通常需要1800℃以上高温，添加尿素、硼酸、氨等化学物质，制备工艺复杂并存在一定污染，且球形度的控制仍不理想。According to the mechanism of anti-wear and anti-friction, due to the rolling action of spherical particle molecular bearings and the rapid formation of friction and lubrication film effect between friction pairs, spherical particles have more excellent lubricating properties. At present, the lubricating properties of many spherical particles have been studied, such as iron oxide, carbon spheres, titanium dioxide, and tungsten disulfide. h-BN has a strong (002) plane oriented growth tendency, and it is easy to form irregular sheet-like nanoparticles, which are difficult to prepare into spherical shapes. The preparation methods of h-BN spherical particles reported so far usually require high temperatures above 1800 °C, adding chemical substances such as urea, boric acid, and ammonia. The preparation process is complicated and there is some pollution, and the control of sphericity is still not ideal.

发明内容Contents of the invention

为了解决上述问题，本申请一方面公开了一种抗磨减摩润滑油添加剂，润滑油添加剂由六方氮化硼制备而成，将六方氮化硼的纳米片进行激光辐照后得到球形纳米颗粒作为润滑油添加剂。In order to solve the above problems, the present application discloses an anti-wear and anti-friction lubricating oil additive on the one hand. The lubricating oil additive is prepared from hexagonal boron nitride, and the nanosheets of hexagonal boron nitride are irradiated with laser to obtain spherical nanoparticles. As a lubricating oil additive.

优选的，所述纳米片按照如下方式处理：Preferably, the nanosheets are processed as follows:

将六方氮化硼的纳米片放入到去离子水中，进行磁力搅拌、超声分散得到纳米片分散液。Putting the nano-sheets of hexagonal boron nitride into deionized water, performing magnetic stirring and ultrasonic dispersion to obtain a nano-sheet dispersion.

优选的，所述激光处理按照如下方式处理：将激光束辐照到分散液当中，激光束的能量通量为460-580mJpulse-1cm-2。Preferably, the laser treatment is performed in the following manner: irradiating a laser beam into the dispersion liquid, and the energy flux of the laser beam is 460-580mJpulse -1 cm -2 .

优选的，激光辐照时间不低于30min。Preferably, the laser irradiation time is not less than 30 minutes.

优选的，激光束的波长为248nm的KrF准分子激光器作为激光辐照源；Preferably, the wavelength of the laser beam is a KrF excimer laser of 248nm as the laser radiation source;

激光束通过焦距为150毫米的凸透镜集中能量，最后辐照到分散液中，形成约0.7cm2的光斑。The laser beam concentrates energy through a convex lens with a focal length of 150 mm, and finally irradiates into the dispersion to form a spot of about 0.7 cm 2 .

优选的，所述磁力搅拌、超声分散交替进行，交替进行的次数不少于3次，每次磁力搅拌的时间不低于20min、超声分散时间不低于20min。Preferably, the magnetic stirring and ultrasonic dispersion are carried out alternately, and the number of alternating operations is not less than 3 times, and the time of each magnetic stirring is not less than 20 minutes, and the time of ultrasonic dispersion is not less than 20 minutes.

优选的，将激光辐照处理过的纳米片分散液进行过滤、干燥得到润滑油添加剂。Preferably, the nanosheet dispersion treated by laser irradiation is filtered and dried to obtain the lubricating oil additive.

另一方面，还公开了一种改性润滑油，润滑油添加剂在润滑油中的加入量为0.05-0.2wt％。On the other hand, it also discloses a modified lubricating oil, the amount of the lubricating oil additive added in the lubricating oil is 0.05-0.2wt%.

优选的，所述润滑油添加剂在润滑油中的加入量为0.1wt％。Preferably, the added amount of the lubricating oil additive in the lubricating oil is 0.1wt%.

优选的，润滑油的平均摩擦系数(COF)降低了26.1％，摩擦副磨斑直径(WSD)降低了23.2％。Preferably, the average coefficient of friction (COF) of the lubricating oil is reduced by 26.1%, and the wear spot diameter (WSD) of the friction pair is reduced by 23.2%.

本申请能够带来如下有益效果：本申请采用简单的绿色激光辐照法制备了球形六方氮化硼纳米颗粒(L-h-BN)，作为润滑添加剂，L-h-BN纳米球在PAO6基础油中具有良好的分散稳定性，并表现出优异的摩擦学性能。当L-h-BN颗粒浓度为0.1wt％时，COF和WSD分别降低了26.1％和23.2％，表面粗糙度和磨损体积分别降低了29.2％和23.8％。抗磨减摩机理主要来自两个方面。首先，L-h-BN球形纳米颗粒滚珠轴承的作用导致摩擦系数低。此外，随着摩擦过程的进行，部分L-h-BN球形纳米颗粒逐渐剥离，形成层状结构。层状L-h-BN附着在磨损表面形成摩擦膜，修复磨损表面，减少磨损。因此，L-h-BN球形纳米颗粒具有优异的抗磨和减摩性能。本申请的一步激光辐照法为制备球形L-h-BN润滑油添加剂提供了新的途径。The application can bring the following beneficial effects: the application adopts a simple green laser irradiation method to prepare spherical hexagonal boron nitride nanoparticles (L-h-BN), as a lubricating additive, the L-h-BN nanospheres have good properties in PAO6 base oil Excellent dispersion stability and excellent tribological properties. When the L-h-BN particle concentration was 0.1wt%, the COF and WSD decreased by 26.1% and 23.2%, respectively, and the surface roughness and wear volume decreased by 29.2% and 23.8%, respectively. The mechanism of anti-wear and anti-friction mainly comes from two aspects. First, the action of L-h-BN spherical nanoparticle ball bearings results in a low coefficient of friction. In addition, with the progress of the rubbing process, part of the L-h-BN spherical nanoparticles were gradually exfoliated to form a layered structure. The layered L-h-BN adheres to the worn surface to form a friction film, which repairs the worn surface and reduces wear. Therefore, the L-h-BN spherical nanoparticles have excellent antiwear and antifriction properties. The one-step laser irradiation method of the present application provides a new way to prepare spherical L-h-BN lubricating oil additives.

附图说明Description of drawings

此处所说明的附图用来提供对本申请的进一步理解，构成本申请的一部分，本申请的示意性实施例及其说明用于解释本申请，并不构成对本申请的不当限定。在附图中：The drawings described here are used to provide a further understanding of the application and constitute a part of the application. The schematic embodiments and descriptions of the application are used to explain the application and do not constitute an improper limitation to the application. In the attached picture:

图1激光一步辐照法水中制备L-h-BN球生长过程示意图。Fig. 1 Schematic diagram of the growth process of L-h-BN spheres prepared in water by laser one-step irradiation method.

图2(a)原始h-BN纳米片的TEM图像，(b)激光辐照生长的L-h-BN纳米球，(c)L-h-BN纳米球的HTEM图像。Figure 2 (a) TEM image of pristine h-BN nanosheets, (b) laser-irradiated grown L-h-BN nanospheres, (c) HTEM image of L-h-BN nanospheres.

图3(a)原始h-BN纳米片和L-h-BN纳米球的XRD光谱，(b)不同激光能量通量下生长的h-BN的拉曼光谱。原始h-BN纳米片和L-h-BN纳米球(c)N 1s核级和(d)B 1s核级的XPS谱。Fig. 3 (a) XRD spectra of pristine h-BN nanosheets and L-h-BN nanospheres, (b) Raman spectra of h-BN grown under different laser energy fluences. XPS spectra of pristine h-BN nanosheets and L-h-BN nanospheres at (c) N 1s core level and (d) B 1s core level.

图4(a)原始h-BN纳米片和L-h-BN球形纳米颗粒在PAO6基础油中的分散稳定性和(b)光学吸光度。Fig. 4 (a) Dispersion stability and (b) optical absorbance of pristine h-BN nanosheets and L-h-BN spherical nanoparticles in PAO6 base oil.

图5添加不同添加剂的PAO6基础油(a/c)COF曲线:(a)不同浓度的原始h-BN纳米片和(c)不同浓度的L-h-BN球形纳米颗粒。(b/d)与纯PAO6基础油相比，相应的平均COF和COF降幅:(b)原始h-BN纳米片和(d)L-h-BN球形纳米颗粒。Fig. 5 (a/c) COF curves of PAO6 base oil with different additives: (a) different concentrations of pristine h-BN nanosheets and (c) different concentrations of L-h-BN spherical nanoparticles. (b/d) Corresponding average COF and COF reduction compared with pure PAO6 base oil: (b) pristine h-BN nanosheets and (d) L-h-BN spherical nanoparticles.

图6PAO6基础油中不同添加剂(a)不同浓度的h-BN纳米薄片和(b)不同浓度的L-h-BN球形纳米颗粒的WSD及与PAO6基础油相比相应的WSD降幅情况。Fig. 6 WSD of different additives in PAO6 base oil (a) different concentrations of h-BN nanoflakes and (b) different concentrations of L-h-BN spherical nanoparticles and the corresponding WSD reduction compared with PAO6 base oil.

图7PAO6基础油润滑磨损表面白光干涉仪图像:(a)平面三维图像，(b)立体三维图像，(c)局部放大三维图像。0.1wt％L-h-BN球形纳米颗粒PAO6基础油润滑磨损表面的白光干涉仪图像:(d)平面三维图像，(e)立体三维图像和(f)局部放大三维图像。Fig.7 White light interferometer image of PAO6 base oil lubricated and worn surface: (a) plane 3D image, (b) stereoscopic 3D image, (c) partially enlarged 3D image. White light interferometer images of 0.1wt% L-h-BN spherical nanoparticles PAO6 base oil lubricated wear surface: (d) planar 3D image, (e) stereoscopic 3D image and (f) partially enlarged 3D image.

图8(a)纯PAO6基础油和(b)掺0.1wt％L-h-BN的PAO6基础油润滑磨损表面的光学图像，(c)图8(b)中白色框的放大图像，(d)h-BN的拉曼强度映射图像。Fig. 8 (a) Optical images of pure PAO6 base oil and (b) PAO6 base oil mixed with 0.1 wt% L-h-BN to lubricate the wear surface, (c) enlarged image of the white box in Fig. 8(b), (d) h - Raman intensity mapping image of BN.

图9(a)纯PAO6基础油和(b)0.1wt％L-h-BN润滑磨损表面的SEM图像，(c)0.1wt％L-h-BN润滑摩擦副表面的N元映射图像，(d)图9(b)中点1的EDS谱图，(e)图9(b)白框区域的N元素映射图像。Figure 9 (a) SEM image of pure PAO6 base oil and (b) 0.1wt% L-h-BN lubricated wear surface, (c) N-element mapping image of 0.1wt% L-h-BN lubricated friction pair surface, (d) Figure 9 (b) EDS spectrum of midpoint 1, (e) N-element mapping image of the white framed area in Figure 9(b).

图10 L-h-BN添加剂的润滑机理。(a)四球摩擦示意图，(b)纳米球滚动摩擦，(c)层状结构的层间滑移，(d)h-BN分子结构。Fig. 10 Lubrication mechanism of L-h-BN additive. (a) Schematic diagram of four-ball friction, (b) rolling friction of nanoballs, (c) interlayer slip of layered structure, (d) molecular structure of h-BN.

具体实施方式Detailed ways

为能清楚说明本方案的技术特点，下面通过具体实施方式，对本申请进行详细阐述。In order to clearly illustrate the technical features of the present solution, the present application will be described in detail below through specific implementation modes.

1.六方氮化硼(h-BN)球形纳米颗粒的制备1. Preparation of hexagonal boron nitride (h-BN) spherical nanoparticles

采用液相激光辐照制备h-BN球形纳米颗粒。原料为六方氮化硼。未加工的h-BN纳米片(纯度为99.9％，Macklin)呈不规则片状。将50mg h-BN加入装有30mL去离子水的玻璃烧杯中，磁力搅拌20min，超声分散20min，并往复三次，即磁力搅拌和超声分别共计3次，累积时间磁力搅拌60min，超声分散60min，得到分散均匀的h-BN溶液。采用波长为248nm的KrF准分子激光器(10Hz，25ns，Coherent，CompexPro 205)作为激光辐照源。激光束通过焦距为150毫米的凸透镜集中能量，最后辐照到溶液中，形成约0.7平方厘米的光斑。能量通量分别为460、500、540、580mJpulse-1cm-2。同时对h-BN溶液进行磁力搅拌，保证激光辐照的均匀性。激光辐照时间为30分钟。激光辐照后，粉末样品干燥，进行进一步表征。The h-BN spherical nanoparticles were prepared by liquid phase laser irradiation. The raw material is hexagonal boron nitride. Unprocessed h-BN nanosheets (99.9% pure, Macklin) were in the shape of irregular sheets. Add 50 mg of h-BN into a glass beaker filled with 30 mL of deionized water, stir magnetically for 20 min, disperse ultrasonically for 20 min, and reciprocate three times, that is, magnetically stir and ultrasonically total 3 times respectively. The cumulative time is 60 min magnetically stirred and 60 min ultrasonically dispersed to obtain Disperse h-BN solution evenly. A KrF excimer laser (10 Hz, 25 ns, Coherent, CompexPro 205) with a wavelength of 248 nm was used as the laser irradiation source. The laser beam concentrates energy through a convex lens with a focal length of 150 mm, and finally irradiates into the solution to form a spot of about 0.7 square centimeters. The energy fluxes are 460, 500, 540, 580mJpulse -1 cm -2 , respectively. At the same time, the h-BN solution was magnetically stirred to ensure the uniformity of laser irradiation. The laser irradiation time was 30 minutes. After laser irradiation, the powder samples were dried for further characterization.

2.材料表征2. Material Characterization

x射线衍射仪(XRD，D8-Advance，Bruker)以Cu-Kα线为激发源，在40kV、40mA条件下得到材料的x射线衍射图。使用配有532nm激光的拉曼光谱仪(LabRAM HR Evolution，HORIBA)记录材料的拉曼散射光谱。不同样品中N和B的结合能通过x射线光电子能谱(XPS，Thermo Fisher，Al Kαx射线源)测定。通过透射电镜(TEM，JEM-2100Plus)观察不同样品的形貌。利用白光干涉仪(GTK-A，Bruker)观察磨损表面的三维形貌和磨损体积。An x-ray diffractometer (XRD, D8-Advance, Bruker) used Cu-Kα line as the excitation source, and obtained the x-ray diffraction pattern of the material under the conditions of 40kV and 40mA. Raman scattering spectra of materials were recorded using a Raman spectrometer (LabRAM HR Evolution, HORIBA) equipped with a 532 nm laser. The binding energies of N and B in different samples were determined by x-ray photoelectron spectroscopy (XPS, Thermo Fisher, Al Kα x-ray source). The morphology of different samples was observed by transmission electron microscope (TEM, JEM-2100Plus). The three-dimensional topography and wear volume of the worn surface were observed using a white light interferometer (GTK-A, Bruker).

摩擦学性能评价：Tribological performance evaluation:

采用四球摩擦磨损试验机(MM-W1B，济南)对润滑油的摩擦磨损性能进行了测试。设备工作时，润滑油将充分渗透到四个钢球中。摩擦过程中，顶部钢球在载荷f的作用下以ω的速度旋转，底部三个钢球以支架的形式固定在一起。摩擦试验在室温下进行，转速为1000rpm，负荷为392N，试验时间为30min。钢球硬度为62HRC，直径为12.7mm，由GCr15轴承钢制成。在摩擦试验过程中，自动记录COF。为了保证COF的准确性，每一浓度重复三次摩擦实验，并对COF取平均值。The friction and wear properties of lubricating oils were tested using a four-ball friction and wear testing machine (MM-W1B, Jinan). When the equipment is working, the lubricating oil will fully penetrate into the four steel balls. During the friction process, the top steel ball rotates at a speed of ω under the action of load f, and the bottom three steel balls are fixed together in the form of brackets. The friction test is carried out at room temperature, the rotation speed is 1000rpm, the load is 392N, and the test time is 30min. The hardness of the steel ball is 62HRC, the diameter is 12.7mm, and it is made of GCr15 bearing steel. During the friction test, the COF is automatically recorded. In order to ensure the accuracy of COF, the friction experiment was repeated three times for each concentration, and the COF was averaged.

将不同能量通量(460、500、540、580mJ pulse-1cm-2)的L-h-BN球形纳米颗粒以0.05wt％的浓度加入PAO6基础油中，充分混合后进行摩擦试验。能量通量为540mJ pulse- 1cm-2时，复合材料的摩擦性能最佳，以能量通量为540mJpulse-1cm-2的h-BN球形纳米颗粒为例，进行了材料表征和摩擦学测试。在PAO6基础油中分别加入质量浓度为0.05wt％、0.1wt％、0.15wt％和0.2wt％的h-BN纳米片和L-h-BN球形纳米颗粒，得到最佳浓度。Lh-BN spherical nanoparticles with different energy fluxes (460, 500, 540, 580mJ pulse -1 cm -2 ) were added to PAO6 base oil at a concentration of 0.05wt%, and the friction test was carried out after thorough mixing. When the energy flux is 540mJ pulse - 1 cm -2 , the tribological performance of the composite material is the best. Taking the h-BN spherical nanoparticles with the energy flux of 540mJpulse -1 cm -2 as an example, the material characterization and tribological tests are carried out . Adding h-BN nanosheets and Lh-BN spherical nanoparticles with mass concentration of 0.05wt%, 0.1wt%, 0.15wt% and 0.2wt% respectively in PAO6 base oil, the optimal concentration was obtained.

摩擦试验结束后，用石油醚清洗摩擦副表面，然后用酒精清洗三次。利用白光干涉仪对磨损表面的三维轮廓进行了观测。记录了材料在磨损表面的拉曼散射光谱。采用扫描电子显微镜(SEM，FEI Quanta 250FEG)对摩擦副的表面形貌进行了观察。After the friction test, the surface of the friction pair was cleaned with petroleum ether, and then cleaned with alcohol three times. The three-dimensional profile of the worn surface was observed with a white light interferometer. Raman scattering spectra of materials on worn surfaces were recorded. The surface morphology of the friction pair was observed with a scanning electron microscope (SEM, FEI Quanta 250FEG).

3.结果与讨论3. Results and Discussion

3.1L-h-BN球的制备和表征3.1 Preparation and characterization of L-h-BN spheres

如图1所示为激光一步辐照法水中制备L-h-BN球生长过程示意图。Figure 1 is a schematic diagram of the growth process of L-h-BN spheres prepared in water by the laser one-step irradiation method.

L-h-BN球形纳米颗粒在简单激光辐照下的生长过程示意图如图1所示。在激光辐照过程中，高激光能量瞬间注入溶液中，产生解离压缩效应。并且在激光束与材料的界面上诱导产生了超高温、超高压的极端非平衡状态。粒子形态从片状到球状的转变是一步完成的。当激光束第一次击中原始h-BN片时，激光光斑立即对材料界面产生影响。在这样的冲击下，大块的h-BN***成更小的碎片。连续的脉冲激光辐照引起加热并导致h-BN颗粒表面熔化(图1中的过程I)。原始h-BN颗粒在液相环境中快速冷却，通过激光诱导光热过程重塑成纳米球(图1中的过程II)。The schematic diagram of the growth process of L-h-BN spherical nanoparticles under simple laser irradiation is shown in Fig. 1. During laser irradiation, high laser energy is injected into the solution instantaneously, producing a dissociative compression effect. And an extreme non-equilibrium state of ultra-high temperature and ultra-high pressure is induced on the interface between the laser beam and the material. The transformation of particle morphology from flake to spherical is accomplished in one step. When the laser beam hits the pristine h-BN sheet for the first time, the laser spot immediately affects the material interface. Under such an impact, large chunks of h-BN exploded into smaller fragments. Continuous pulsed laser irradiation induces heating and leads to surface melting of h-BN particles (process I in Fig. 1). Pristine h-BN particles were rapidly cooled in a liquid-phase environment and reshaped into nanospheres by a laser-induced photothermal process (Process II in Figure 1).

通过透射电镜对原始h-BN纳米薄片和L-h-BN球形纳米颗粒的形貌进行了表征，如图2所示。未加工的h-BN纳米片呈片状结构，团聚现象严重，如图2(a)所示。然而，经过简单的激光辐照，h-BN由片状结构转变为球形结构，颗粒变得更加松散。并抑制了团聚现象。这是因为在激光辐照作用下，粒子表面Zeta电位绝对值增大，粒子间的排斥力增大，从而提高了粒子的分散性。与原始h-BN粒子相比，激光诱导L-h-BN纳米球的Zeta电位绝对值增加了50％。高倍透射电镜(HTEM)图像显示了明显的晶格条纹，晶格间距为0.33nm，这是h-BN的002平面的晶格间距。The morphologies of pristine h-BN nanoflakes and L-h-BN spherical nanoparticles were characterized by transmission electron microscopy, as shown in Figure 2. The unprocessed h-BN nanosheets exhibit a sheet-like structure with severe agglomeration, as shown in Figure 2(a). However, after simple laser irradiation, h-BN transformed from a sheet-like structure to a spherical structure, and the particles became more loose. And inhibit the reunion phenomenon. This is because under the action of laser irradiation, the absolute value of Zeta potential on the particle surface increases, and the repulsive force between particles increases, thereby improving the dispersion of particles. Compared with pristine h-BN particles, the absolute value of zeta potential of laser-induced L-h-BN nanospheres increased by 50%. The high-magnification transmission electron microscope (HTEM) image shows obvious lattice fringes with a lattice spacing of 0.33 nm, which is the lattice spacing of the 002 plane of h-BN.

用XRD分析了原始h-BN纳米薄片和L-h-BN球形纳米颗粒的物相，如图3(a)所示。所有XRD衍射峰均属于BN的六方相(JCPDS编号：34-0421，P63/mmc空间基团)。h-BN晶体形态在激光辐照前后没有变化。h-BN的衍射峰分别为(002)、(100)、(101)、(004)、(110)和(112)。激光辐照后，主反射峰强度降低，这可能是由于颗粒形态由片状变为球形引起的。图3(b)为不同激光能量通量下生长h-BN的拉曼光谱。1366cm-1处的尖锐拉曼峰来自h-BN的高频特征峰。高频拉曼特征峰表现出轻微的蓝移，这可以归因于球形结构中的残余应变。The phases of pristine h-BN nanoflakes and Lh-BN spherical nanoparticles were analyzed by XRD, as shown in Fig. 3(a). All XRD diffraction peaks belong to the hexagonal phase of BN (JCPDS number: 34-0421, P63/mmc space group). The h-BN crystal morphology did not change before and after laser irradiation. The diffraction peaks of h-BN are (002), (100), (101), (004), (110) and (112), respectively. After laser irradiation, the intensity of the main reflection peak decreases, which may be caused by the particle morphology changing from flake to spherical. Figure 3(b) shows the Raman spectra of h-BN grown under different laser energy fluences. The sharp Raman peak at 1366 cm comes from the high-frequency characteristic peak of h-BN. The high-frequency Raman characteristic peaks exhibit a slight blue shift, which can be attributed to the residual strain in the spherical structure.

原始h-BN纳米薄片和L-h-BN球形纳米颗粒的XPS光谱N1s和B1s谱分别如图3(c)和(d)所示。值得注意的是，激光辐照后N1s和B1s的结合能发生了一定程度的转移。对于原始h-BN纳米片，N1s峰的位置在397.91ev，B1s峰的位置在190.29ev。而激光诱导L-h-BN纳米球的N1s峰位置为397.43ev，B1s峰位置为189.85ev。结合能降低，结果进一步证实了激光辐照后，颗粒由片状转变为球状。The XPS spectra N1s and B1s spectra of pristine h-BN nanoflakes and L-h-BN spherical nanoparticles are shown in Fig. 3(c) and (d), respectively. It is noteworthy that the binding energy of N1s and B1s shifted to some extent after laser irradiation. For the pristine h-BN nanosheets, the position of the N1s peak is at 397.91 eV, and the position of the B1s peak is at 190.29 eV. The N1s peak position of laser-induced L-h-BN nanospheres is 397.43ev, and the B1s peak position is 189.85ev. The binding energy decreased, and the results further confirmed that the particles changed from flake to spherical after laser irradiation.

纳米颗粒在基础油中的良好分散性是润滑应用的前提条件。以原料h-BN纳米片和L-h-BN纳米球为添加剂，以0.1wt％的浓度加入PAO6基础油中。对于含有L-h-BN球形纳米颗粒的油样，在30天后仍未出现明显的析出现象，说明纳米颗粒能够稳定地分散在基础油中。相比之下，含h-BN纳米薄片的油样在3天后就出现明显的析出(图4(a))。为了进一步检验分散稳定性，用紫外可见分光光度计测量了分别含有原始h-BN纳米片和L-h-BN纳米球的PAO6基础油的吸光度曲线(图4(b))。添加原始h-BN纳米片后，PAO6基础油的吸光度(λ＝430nm)随着时间的推移迅速下降。然而，含有L-h-BN球形纳米颗粒的PAO6基础油的吸光度非常稳定，这也证实L-h-BN球形纳米颗粒作为添加剂在PAO6基础油中具有良好的分散稳定性。Good dispersion of nanoparticles in base oil is a prerequisite for lubricating applications. The raw materials h-BN nanosheets and L-h-BN nanospheres are used as additives and added to PAO6 base oil at a concentration of 0.1 wt%. For the oil samples containing L-h-BN spherical nanoparticles, no obvious precipitation occurred after 30 days, indicating that the nanoparticles can be stably dispersed in the base oil. In contrast, the oil sample containing h-BN nanoflakes showed obvious precipitation after 3 days (Fig. 4(a)). To further examine the dispersion stability, the absorbance curves of PAO6 base oil containing pristine h-BN nanosheets and L-h-BN nanospheres, respectively, were measured with a UV-vis spectrophotometer (Fig. 4(b)). After adding pristine h-BN nanosheets, the absorbance (λ = 430 nm) of PAO6 base oil decreased rapidly over time. However, the absorbance of PAO6 base oil containing L-h-BN spherical nanoparticles was very stable, which also confirmed the good dispersion stability of L-h-BN spherical nanoparticles as an additive in PAO6 base oil.

采用四球摩擦学试验评价了L-h-BN球形纳米颗粒的摩擦学性能。h-BN纳米片和L-h-BN球形纳米颗粒的添加浓度分别为0.05wt％、0.1wt％、0.15wt％和0.2wt％。图5(a)为h-BN纳米片在不同浓度下作为PAO6基础油添加剂的COF曲线。纯PAO6基础油的COF有一定的波动。然而，随着h-BN纳米片的加入，COF降低。对于h-BN纳米片，当浓度小于0.15％时，COF随h-BN纳米片的增加而降低。当h-BN纳米片浓度为0.1wt％时，平均COF降幅最大，达16.2％。随着h-BN纳米片浓度的增加，COF增加。含有0.1wt％L-h-BN球形纳米颗粒的油样的COF曲线比含有0.1wt％h-BN纳米薄片的油样平滑得多，如图5(a)和(c)所示。当L-h-BN球形纳米颗粒添加浓度为0.1wt％时，COF的平均降幅最大，达到26.1％(图5d)，具有较好的减摩效果。这是因为h-BN纳米片在基础油中的分散性较差，聚集在一起的h-BN纳米片容易划伤摩擦副表面，添加剂的摩擦性能没有发挥到最佳。具有良好分散稳定性的L-h-BN球形纳米粒子在摩擦副之间传播，形成良好的润滑膜。此外，球形h-BN纳米颗粒具有良好的滚动摩擦效果，从而降低COF。The tribological properties of L-h-BN spherical nanoparticles were evaluated by four-ball tribological test. The added concentrations of h-BN nanosheets and L-h-BN spherical nanoparticles were 0.05wt%, 0.1wt%, 0.15wt% and 0.2wt%, respectively. Figure 5(a) is the COF curves of h-BN nanosheets as PAO6 base oil additive at different concentrations. The COF of pure PAO6 base oil has certain fluctuations. However, the COF decreased with the addition of h-BN nanosheets. For h-BN nanosheets, when the concentration is less than 0.15%, the COF decreases with the increase of h-BN nanosheets. When the concentration of h-BN nanosheets was 0.1wt%, the average COF decreased the most, reaching 16.2%. As the concentration of h-BN nanosheets increases, the COF increases. The COF curve of the oil sample containing 0.1 wt% L-h-BN spherical nanoparticles is much smoother than that of the oil sample containing 0.1 wt% h-BN nanoflakes, as shown in Fig. 5(a) and (c). When the L-h-BN spherical nanoparticles were added at a concentration of 0.1wt%, the average decrease in COF was the largest, reaching 26.1% (Fig. 5d), which had a better friction reduction effect. This is because the dispersion of h-BN nanosheets in the base oil is poor, the h-BN nanosheets gathered together are easy to scratch the surface of the friction pair, and the friction performance of the additive is not optimal. L-h-BN spherical nanoparticles with good dispersion stability spread between friction pairs to form a good lubricating film. In addition, the spherical h-BN nanoparticles have good rolling friction effect, thereby reducing the COF.

润滑油添加剂不仅要具有良好的抗磨性能，还要具有优异的抗磨性能。摩擦实验结束后，研究了下部固定球上的磨斑直径(WSD)数据(图6)。加入h-BN纳米薄片和L-h-BN球形纳米颗粒后，磨痕直径减小，说明添加剂起到了抗磨作用。但当浓度大于0.1wt％时，抗磨效果开始减弱。这是因为随着添加剂浓度的增加，过量的添加剂形成结块，导致磨损严重。当L-h-BN球形纳米颗粒浓度为0.1wt％时，WSD下降幅度最大，达到23.2％。然而，h-BN纳米片的分散效果不如L-h-BN球形纳米颗粒。当h-BN纳米片的浓度为0.2wt％时，WSD较纯PAO6基础油有所增加，这是团聚现象导致磨损严重的结果。优异的抗磨性能主要来自于两个方面。一是滚珠轴承效应导致摩擦系数低，从而减少磨损。另一方面，经过长时间的摩擦，L-h-BN球形纳米颗粒在摩擦和挤压过程中会逐渐剥离并转变为层状结构。随着摩擦过程的进行，层状结构会粘附在摩擦副表面，减少摩擦副表面磨损，修复摩擦副。Lubricating oil additives should not only have good anti-wear properties, but also have excellent anti-wear properties. After the friction experiment, the wear scar diameter (WSD) data on the lower fixed ball were investigated (Fig. 6). After adding h-BN nanoflakes and L-h-BN spherical nanoparticles, the diameter of the wear scar decreased, indicating that the additive played an anti-wear role. But when the concentration is greater than 0.1wt%, the anti-wear effect begins to weaken. This is because as the concentration of additives increases, excess additives form agglomerates, causing severe wear. When the concentration of L-h-BN spherical nanoparticles was 0.1wt%, the WSD decreased the most, reaching 23.2%. However, the dispersion effect of h-BN nanosheets is not as good as that of L-h-BN spherical nanoparticles. When the concentration of h-BN nanosheets was 0.2wt%, the WSD increased compared with pure PAO6 base oil, which was the result of severe wear caused by agglomeration phenomenon. Excellent anti-wear performance mainly comes from two aspects. One is that the ball bearing effect results in a low coefficient of friction, which reduces wear. On the other hand, after long-time rubbing, the L-h-BN spherical nanoparticles were gradually exfoliated and transformed into a layered structure during the rubbing and extrusion process. As the friction process progresses, the layered structure will adhere to the surface of the friction pair, reducing the wear of the friction pair surface and repairing the friction pair.

摩擦实验结束后，摩擦副表面磨损的三维图像如图7所示。未添加L-h-BN时，摩擦副表面磨损严重，沟槽更深、更宽(图7a，b)。局部放大的三维图像(图7c)显示磨损表面波动严重。加入L-h-BN球形纳米颗粒后，磨损现象得到缓解，磨损面波动大大减小，如图7(d-f)所示。局部放大的三维图像也显示磨损表面相对均匀光滑。纯PAO6基础油摩擦实验后摩擦副表面粗糙度Ra为3.012μm，L-h-BN润滑摩擦实验后摩擦副表面粗糙度Ra为2.132μm。同时，添加L-h-BN添加剂后，磨损体积由0.0021mm3减少到0.0016mm3，减少23.8％，表明L-h-BN添加剂具有良好的抗磨效果。After the friction experiment, the three-dimensional image of the surface wear of the friction pair is shown in Fig. 7. When Lh-BN was not added, the surface of the friction pair was severely worn, and the grooves were deeper and wider (Fig. 7a,b). The locally enlarged 3D image (Fig. 7c) shows that the worn surface fluctuates severely. After adding Lh-BN spherical nanoparticles, the wear phenomenon was alleviated, and the fluctuation of the wear surface was greatly reduced, as shown in Fig. 7(df). The locally enlarged 3D images also show that the worn surface is relatively uniform and smooth. The surface roughness Ra of the friction pair after the pure PAO6 base oil friction test is 3.012 μm, and the surface roughness Ra of the friction pair after the Lh-BN lubrication friction test is 2.132 μm. At the same time, after adding the Lh-BN additive, the wear volume is reduced from 0.0021mm 3 to 0.0016mm 3 , a decrease of 23.8%, which indicates that the Lh-BN additive has a good anti-wear effect.

为研究润滑机理，采用拉曼光谱仪对磨损表面进行分析。如图8所示。纯PAO6基础油润滑磨损表面的磨损痕迹深且宽(图8(a))，这与白光干涉仪观察到的磨损痕迹一致。摩擦区拉曼分析显示，在～667cm-1处出现了明显的氧化铁峰，表明摩擦副表面磨损严重。对于含有L-h-BN的试样，磨损表面光滑平整(图8(b))。磨损表面的拉曼光谱(图8(b))和拉曼平面扫描模式(图8(c，d))均显示出明显的L-h-BN信号，说明L-h-BN添加剂均匀地沉积在摩擦副上。因此，L-h-BN添加剂可以有效地形成摩擦膜，起到很好的表面修复作用，从而表现出显著的抗磨效果。To study the lubrication mechanism, the worn surface was analyzed by Raman spectroscopy. As shown in Figure 8. The wear marks on the wear surface lubricated by pure PAO6 base oil are deep and wide (Fig. 8(a)), which is consistent with the wear marks observed by white light interferometer. The Raman analysis of the friction zone shows that there is an obvious iron oxide peak at ~667cm -1 , indicating that the surface of the friction pair is severely worn. For the samples containing Lh-BN, the worn surface is smooth and flat (Fig. 8(b)). Both the Raman spectrum (Fig. 8(b)) and the Raman planar scanning mode (Fig. 8(c,d)) of the worn surface show obvious Lh-BN signals, indicating that the Lh-BN additive is uniformly deposited on the friction pair . Therefore, the Lh-BN additive can effectively form a friction film and play a good role in surface repair, thus showing a significant anti-wear effect.

图9(a、b)分别为纯PAO6基础油和L-h-BN添加剂摩擦试验后磨损表面的SEM图像。从图中可以看出，纯PAO6基础油润滑后的磨损表面不均匀，磨斑直径大。含L-h-BN添加剂的PAO6基础油润滑后的磨损表面光滑，磨斑直径小。采用能谱仪(EDS)分析磨损表面的化学成分，如图9(c-e)所示。N元素映射图像和EDS能谱显示，L-h-BN添加剂磨损表面含有N元素，证明L-h-BN添加剂成功沉积在摩擦副表面。摩擦试验后，N元素的分布呈与磨损点外观一致的球形，说明h-BN成功沉积在摩擦副表面形成摩擦膜，起到了良好的修复作用。Figure 9(a, b) are the SEM images of the wear surface after the friction test of pure PAO6 base oil and L-h-BN additive, respectively. It can be seen from the figure that the wear surface after lubrication with pure PAO6 base oil is uneven and the diameter of the wear scar is large. The lubricated wear surface of PAO6 base oil containing L-h-BN additive is smooth and the diameter of wear scar is small. The chemical composition of the worn surface was analyzed by energy dispersive spectroscopy (EDS), as shown in Fig. 9(c–e). N element mapping images and EDS energy spectra show that the L-h-BN additive wear surface contains N element, which proves that the L-h-BN additive is successfully deposited on the surface of the friction pair. After the friction test, the distribution of N elements was in a spherical shape consistent with the appearance of the wear point, indicating that h-BN was successfully deposited on the surface of the friction pair to form a friction film, which played a good repairing role.

L-h-BN作为润滑油添加剂的润滑机理如图10所示。L-h-BN纳米球作为添加剂可以很好地分散在基础油中。在摩擦过程中，球形纳米颗粒可以将滑动摩擦转化为滚动摩擦，从而降低COF，如图10(b)所示。此外，一些L-h-BN球形添加剂在摩擦副挤压过程中被剥离成片层。层状结构间较低的剪切力也能降低COF。随着摩擦过程的进行，层状结构会吸附在摩擦副表面形成摩擦膜，对摩擦副进行修复，从而减少表面磨损，发挥抗磨作用(图10(c))。综上所述，在上述两种机制的共同作用下，作为添加剂的L-h-BN球形纳米颗粒表现出优异的抗磨和抗摩擦效果。The lubrication mechanism of L-h-BN as a lubricating oil additive is shown in Fig. 10. L-h-BN nanospheres can be well dispersed in base oil as an additive. During the friction process, the spherical nanoparticles can convert the sliding friction into rolling friction, thereby reducing the COF, as shown in Fig. 10(b). In addition, some L-h-BN spherical additives were exfoliated into sheets during friction pair extrusion. The lower shear force between the lamellar structures can also reduce the COF. As the friction process progresses, the layered structure will be adsorbed on the surface of the friction pair to form a friction film, and the friction pair will be repaired, thereby reducing surface wear and exerting an anti-wear effect (Fig. 10(c)). In summary, under the combined effect of the above two mechanisms, L-h-BN spherical nanoparticles as an additive exhibit excellent antiwear and antifriction effects.

综上所述，采用简单的绿色激光辐照法制备了L-h-BN球形纳米颗粒。作为润滑添加剂，L-h-BN纳米球在PAO6基础油中具有良好的分散稳定性，并表现出优异的摩擦学性能。当L-h-BN颗粒浓度为0.1wt％时，COF和WSD分别降低了26.1％和23.2％，表面粗糙度和磨损体积分别降低了29.2％和23.8％。抗磨减摩机理主要来自两个方面。首先，滚珠轴承的作用导致摩擦系数低。此外，随着摩擦过程的进行，部分L-h-BN球形纳米颗粒逐渐剥离，形成层状结构。层状h-BN附着在磨损表面形成摩擦膜，修复磨损表面，减少磨损。因此，L-h-BN球形纳米颗粒具有优异的抗磨和减摩性能。这种简单的一步激光辐照法为制备球形L-h-BN润滑油添加剂提供了新的途径。In summary, L-h-BN spherical nanoparticles were prepared by a simple green laser irradiation method. As a lubricating additive, L-h-BN nanospheres have good dispersion stability in PAO6 base oil and exhibit excellent tribological properties. When the L-h-BN particle concentration was 0.1wt%, the COF and WSD decreased by 26.1% and 23.2%, respectively, and the surface roughness and wear volume decreased by 29.2% and 23.8%, respectively. The mechanism of anti-wear and anti-friction mainly comes from two aspects. First, the action of the ball bearings results in a low coefficient of friction. In addition, with the progress of the rubbing process, part of the L-h-BN spherical nanoparticles were gradually exfoliated to form a layered structure. The layered h-BN adheres to the worn surface to form a friction film, which repairs the worn surface and reduces wear. Therefore, the L-h-BN spherical nanoparticles have excellent antiwear and antifriction properties. This simple one-step laser irradiation method provides a new route for the preparation of spherical L-h-BN lubricant additives.

以上仅为本申请的实施例而已，并不用于限制本申请。对于本领域技术人员来说，本申请可以有各种更改和变化。凡在本申请的精神和原理之内所作的任何修改、等同替换、改进等，均应包含在本申请的权利要求范围之内。The above are only examples of the present application, and are not intended to limit the present application. For those skilled in the art, various modifications and changes may occur in this application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included within the scope of the claims of the present application.

Claims (10)

1. An antiwear antifriction lubricating oil additive is characterized in that: the lubricant additive is prepared from hexagonal boron nitride, and spherical nano particles obtained after laser irradiation of hexagonal boron nitride nano sheets are used as the lubricant additive.
2. The antiwear antifriction lubricating oil additive of claim 1, characterized in that: the nanoplatelets are treated as follows:
and (3) putting the hexagonal boron nitride nanosheets into deionized water, and performing magnetic stirring and ultrasonic dispersion to obtain nanosheet dispersion liquid.
3. The antiwear antifriction lubricating oil additive of claim 2, characterized in that: the laser treatment is performed as follows: irradiating a laser beam into the dispersion, the energy flux of the laser beam being 460-580mJpulse -1 cm -2 。
4. The antiwear antifriction lubricating oil additive of claim 2, characterized in that: the laser irradiation time is not less than 30min.
5. The antiwear antifriction lubricating oil additive of claim 2, characterized in that: a KrF excimer laser having a wavelength of 248nm as a laser irradiation source;
the laser beam is concentrated in energy by a convex lens with a focal length of 150 mm, and finally irradiated into the dispersion to form about 0.7cm 2 Is a spot of a light beam.
6. The antiwear antifriction lubricating oil additive of claim 2, characterized in that: the magnetic stirring and ultrasonic dispersing are alternately carried out, the times of the alternating are not less than 3 times, the time of each magnetic stirring is not less than 20min, and the ultrasonic dispersing time is not less than 20min.
7. The antiwear antifriction lubricating oil additive in accordance with claim 3 wherein: and filtering and drying the nano sheet dispersion liquid treated by laser irradiation to obtain the lubricating oil additive.
8. A modified lubricating oil using the lubricating oil additive according to any one of claims 1 to 7, characterized in that: the addition amount of the lubricating oil additive in the lubricating oil is 0.05-0.2wt%.
9. The modified lubricating oil of claim 8, wherein: the addition amount of the lubricating oil additive in the lubricating oil is 0.1wt%.
10. The modified lubricating oil according to claim 9, wherein: the average friction coefficient of the lubricating oil is reduced by 26.1%, and the diameter of the friction pair mill marks is reduced by 23.2%.
CN202310447453.8A 2023-04-24 2023-04-24 Anti-wear and friction-reducing lubricating oil additive and modified lubricating oil using the additive Active CN116496825B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310447453.8A CN116496825B (en) 2023-04-24 2023-04-24 Anti-wear and friction-reducing lubricating oil additive and modified lubricating oil using the additive

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310447453.8A CN116496825B (en) 2023-04-24 2023-04-24 Anti-wear and friction-reducing lubricating oil additive and modified lubricating oil using the additive

Publications (2)

Publication Number Publication Date
CN116496825A true CN116496825A (en) 2023-07-28
CN116496825B CN116496825B (en) 2025-02-07

Family

ID=87317742

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310447453.8A Active CN116496825B (en) 2023-04-24 2023-04-24 Anti-wear and friction-reducing lubricating oil additive and modified lubricating oil using the additive

Country Status (1)

Country Link
CN (1) CN116496825B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117564288A (en) * 2023-11-28 2024-02-20 华北水利水电大学 Dispersible iron-cobalt-nickel ternary magnetic nanoparticles, preparation method and application as lubricating oil nano-additive

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007210821A (en) * 2006-02-08 2007-08-23 Japan Atomic Energy Agency Method for synthesizing hard material by using laser, and method for reforming surface by laser
CN102267716A (en) * 2011-06-09 2011-12-07 济南大学 Laser liquid annealing preparation method of oxide microsphere with antifriction effect and application
CN107686761A (en) * 2017-08-16 2018-02-13 济南大学 A kind of fast preparation method in situ of Noctiluca scientillans shape graphene bag carborundum microballoon
KR20180051893A (en) * 2016-11-09 2018-05-17 울산과학기술원 Encapsulating material by using h-BN as protective layer and preparing method thereof
CN108405871A (en) * 2018-04-13 2018-08-17 济南大学 It is a kind of that the method for sub-micron metal ball particle and its application in lubricating oil are prepared based on laser ablation method
CN113252617A (en) * 2021-04-23 2021-08-13 山东大学 Glucose sensor with h-BN/Au-Pt net-shaped nano structure with photoelectric co-catalysis characteristic, preparation and application

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007210821A (en) * 2006-02-08 2007-08-23 Japan Atomic Energy Agency Method for synthesizing hard material by using laser, and method for reforming surface by laser
CN102267716A (en) * 2011-06-09 2011-12-07 济南大学 Laser liquid annealing preparation method of oxide microsphere with antifriction effect and application
KR20180051893A (en) * 2016-11-09 2018-05-17 울산과학기술원 Encapsulating material by using h-BN as protective layer and preparing method thereof
CN107686761A (en) * 2017-08-16 2018-02-13 济南大学 A kind of fast preparation method in situ of Noctiluca scientillans shape graphene bag carborundum microballoon
CN108405871A (en) * 2018-04-13 2018-08-17 济南大学 It is a kind of that the method for sub-micron metal ball particle and its application in lubricating oil are prepared based on laser ablation method
CN113252617A (en) * 2021-04-23 2021-08-13 山东大学 Glucose sensor with h-BN/Au-Pt net-shaped nano structure with photoelectric co-catalysis characteristic, preparation and application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DONGSHI ZHANG: "Perspective on how laser-ablated particles grow in liquids", 《SCIENCE CHINA PHYSICS, MECHANICS & ASTRONOMY》, vol. 7, no. 60, 12 May 2017 (2017-05-12), pages 074201 - 1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117564288A (en) * 2023-11-28 2024-02-20 华北水利水电大学 Dispersible iron-cobalt-nickel ternary magnetic nanoparticles, preparation method and application as lubricating oil nano-additive

Also Published As

Publication number Publication date
CN116496825B (en) 2025-02-07

Similar Documents

Publication Publication Date Title
Wang et al. Role of nano-sized materials as lubricant additives in friction and wear reduction: A review
Cui et al. Fabrication of carbon dots intercalated MXene hybrids via laser treatment as oil-based additives for synergistic lubrication
He et al. In situ fabrication of carbon dots-based lubricants using a facile ultrasonic approach
Wang et al. Ultralow concentration of graphene oxide nanosheets as oil-based lubricant additives
Cui et al. Fabrication of two-dimensional MXene nanosheets loading Cu nanoparticles as lubricant additives for friction and wear reduction
Wei et al. Candle soot as particular lubricant additives
Guan et al. Preparation and tribological behaviors of magnesium silicate hydroxide-MoS2 nanoparticles as lubricant additive
Wu et al. Tribological properties of chemical composite and physical mixture of ZnO and SiO2 nanoparticles as grease additives
Wang et al. Carbon quantum dots doped with silver as lubricating oil additive for enhancing tribological performance at various temperatures
He et al. Improved lubrication performance of MoS2-Al2O3 nanofluid through interfacial tribochemistry
Wu et al. Preparation and tribological properties of novel zinc borate/MoS2 nanocomposites in grease
del Río et al. Improving the tribological performance of a biodegradable lubricant adding graphene nanoplatelets as additives
Mushtaq et al. Enhancing the tribological characteristics of Jatropha oil using graphene nanoflakes
Sun et al. Tribological behaviors and lubrication mechanism of water-based MoO3 nanofluid during cold rolling process
Kumar et al. Exploration of Talc nanoparticles to enhance the performance of Lithium grease
Maheswaran et al. Experimental analysis of tribological properties of ultrasonically dispersed garnet nanoparticles in SN500 grade lubricating oil
Hao et al. Investigation on the tribological performance of functionalized nanoscale silica as an amphiphilic lubricant additive
Wang et al. Friction-induced motion evolution of reduced graphene oxide-Al2O3 at contact interface to achieve superior lubrication performance
Peng et al. An investigation into the synergistic strengthening mechanism of ionic liquid and nanoparticles as a hybrid nanofluid in friction interface
Panickar et al. Investigations on tribological properties of non-catalytic CVD synthesized carbon spheres in lubricant
Vardhaman et al. Experimental investigations to enhance the tribological behaviour of biodegradable oil by using manganese doped ZnO/FMWCNTs nanomaterials as lubricant additive
Chen et al. Extreme pressure and anti-wear properties of polycarboxylate superplasticizer modified 3D porous graphene/SiO2 as water-based lubricant additives
CN116496825A (en) Antiwear antifriction lubricating oil additive and modified lubricating oil using additive
Chen et al. Tribological properties and synergistic lubrication mechanism of 3D graphene/nano-TiO2 (G@ TiO2) composite castor oil: A microscopic view and molecular dynamics perspective
Zhang et al. The synergistic effect of MAO-treated and PAO–graphene oil on tribological properties of Ti6Al4V alloys

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant