郭萬(wàn)民,白清順,竇昱昊,郭永博,杜云龍
石墨烯在不銹鋼材料應(yīng)用中的減摩和耐磨特性研究進(jìn)展
郭萬(wàn)民,白清順,竇昱昊,郭永博,杜云龍
(哈爾濱工業(yè)大學(xué) 機(jī)電工程學(xué)院,哈爾濱 150001)
材料間的摩擦和磨損會(huì)產(chǎn)生能源和經(jīng)濟(jì)上的損耗,高強(qiáng)度的石墨烯為提高材料的減摩和耐磨特性提供了新的途徑。不銹鋼材料已經(jīng)在工業(yè)領(lǐng)域獲得廣泛的應(yīng)用,根據(jù)石墨烯和不銹鋼材料的結(jié)合方式分類(lèi),總結(jié)了國(guó)內(nèi)外關(guān)于石墨烯應(yīng)用于不銹鋼材料減摩降損的研究進(jìn)展,從不銹鋼材料的加工到應(yīng)用,揭示了石墨烯降低不銹鋼摩擦因數(shù)的規(guī)律。石墨烯納米顆粒作為切削液添加劑,可以極大降低不銹鋼和刀具摩擦界面的摩擦因數(shù),從而提高不銹鋼工件表面加工質(zhì)量。先制備后轉(zhuǎn)移仍是當(dāng)前石墨烯應(yīng)用于不銹鋼表面的主要方式,石墨烯以固體潤(rùn)滑劑的形式作用于摩擦界面,不銹鋼表面的磨損率可以實(shí)現(xiàn)下降。激光熔化增材制造技術(shù)的不斷發(fā)展,為石墨烯增強(qiáng)不銹鋼復(fù)合材料提供有效途徑,極大地推動(dòng)該材料的工程應(yīng)用進(jìn)程,也為石墨烯降低不銹鋼材料的摩擦磨損提供了新的研究方向。最后,通過(guò)對(duì)石墨烯降低不銹鋼材料摩擦磨損的研究總結(jié),指出了當(dāng)前研究存在的部分問(wèn)題并提出了解決措施,展望了該方向的應(yīng)用前景。
石墨烯;不銹鋼;摩擦磨損;機(jī)械性能;激光熔化增材制造
不銹鋼是一種具有高強(qiáng)度的低成本合金,而且不銹鋼材料軋制到0.01 mm仍能保持良好的性能,這些特性使得不銹鋼材料成功應(yīng)用于眾多領(lǐng)域,比如機(jī)械結(jié)構(gòu)的外殼、醫(yī)用手術(shù)刀以及電氣設(shè)備中的電極部分[1]。特別對(duì)于工業(yè)領(lǐng)域,不銹鋼材料是十分常見(jiàn)的應(yīng)用材料,然而摩擦和磨損一直都是機(jī)械故障和材料損傷的主要原因,如何最大程度地減少這一影響是當(dāng)前工業(yè)領(lǐng)域的重大挑戰(zhàn)之一,復(fù)合材料、涂層和潤(rùn)滑油是解決這一問(wèn)題的重要方法[2-3]。其中最為簡(jiǎn)單有效的方法就是在滑動(dòng)界面上使用固體和液體潤(rùn)滑劑[4]。但是,隨著社會(huì)對(duì)環(huán)境的關(guān)注度不斷提高,綠色摩擦的定義被提出,如何實(shí)現(xiàn)降低材料磨損的同時(shí)對(duì)環(huán)境造成的污染最小,甚至不對(duì)環(huán)境產(chǎn)生污染,成為新的關(guān)注點(diǎn)。許多低維納米材料的出現(xiàn),由于其本身獨(dú)特的化學(xué)性質(zhì)和結(jié)構(gòu)特性,以及對(duì)環(huán)境污染較小的優(yōu)點(diǎn),為降低摩擦磨損提供了新的解決方案[5]。
石墨烯材料作為二維材料的代表,自2004年被發(fā)現(xiàn)就因本身優(yōu)良的特性成為研究熱點(diǎn)[6]。石墨烯是一種由碳原子sp2雜化的蜂窩晶格結(jié)構(gòu)二維碳納米材料[7-8],由于其本身結(jié)構(gòu)的特殊性,石墨烯材料有著良好的機(jī)械性能[9],彈性模量、固有強(qiáng)度和摩擦特性更是遠(yuǎn)優(yōu)于其他材料[10-13]。所以,將石墨烯材料與現(xiàn)有材料結(jié)合成為了新的研究熱點(diǎn)[14-18],進(jìn)一步推動(dòng)石墨烯材料研究的同時(shí)也拓展了現(xiàn)有材料的應(yīng)用領(lǐng)域。對(duì)于不銹鋼材料,摩擦磨損一直是限制其應(yīng)用的重要因素,為此,諸多學(xué)者對(duì)于石墨烯和不銹鋼材料的結(jié)合,特別是耐磨性的提高展開(kāi)了許多研究[19]。
石墨烯用于不銹鋼材料減摩耐磨性提高,不僅體現(xiàn)在不銹鋼材料的應(yīng)用過(guò)程,而且在不銹鋼的生產(chǎn)制造過(guò)程中也十分有效。由于石墨烯的作用環(huán)節(jié)不同,與不銹鋼材料的結(jié)合方式也有所區(qū)別,為此根據(jù)兩者的結(jié)合方式對(duì)石墨烯提高不銹鋼減摩耐磨性進(jìn)行闡述,為后續(xù)石墨烯用于不銹鋼材料耐磨性提高的研究提供一定的指導(dǎo)。
不銹鋼作為諸多機(jī)械零件的基體材料,常見(jiàn)的機(jī)械加工過(guò)程都會(huì)應(yīng)用于不銹鋼材料本身,由于對(duì)加工精度有較高要求,多數(shù)情況下都需要高速加工,然而加工區(qū)域產(chǎn)生大量熱會(huì)限制切削速度的提高,所以切削液在高速切削中起著重要作用[20]。但是隨著對(duì)環(huán)境問(wèn)題的不斷關(guān)注,切削液的大量使用已不符合當(dāng)今的加工理念,所以最小量潤(rùn)滑的概念被提出,并且在此基礎(chǔ)上提出了納米流體微量切削技術(shù)[21]。具有優(yōu)良機(jī)械性能和導(dǎo)熱性的石墨烯,成為了納米添加劑的理想材料。為此,Amrit等人[22]探究了添加石墨烯納米顆粒的植物油基切削液對(duì)于不銹鋼鉆削的影響規(guī)律,隨著石墨烯納米顆粒濃度的增加,鉆區(qū)內(nèi)潤(rùn)滑膜的抗摩擦和承載能力有所增強(qiáng),鉆頭與不銹鋼之間的摩擦因數(shù)越小,不銹鋼材料表面粗糙度有明顯的降低。圖1為納米石墨烯SEM(Scanning electron microscope)圖,納米石墨烯整體上為質(zhì)量較差的多層石墨烯結(jié)構(gòu),說(shuō)明石墨烯納米流體切削液對(duì)于石墨烯本身的質(zhì)量要求較低。圖2為不同石墨烯濃度下摩擦因數(shù)以及工件鉆削加工表面粗糙度對(duì)比,具體的鉆削參數(shù)為:鉆頭直徑8 mm,鉆孔深度30 mm,切削速度7.91 m/min,進(jìn)給量0.125 mm/r。
圖1 石墨烯納米顆粒形貌的掃描電子顯微鏡圖[22]
圖2 不同石墨烯濃度切削液作用下AISI321不銹鋼與M35高速鋼間摩擦因數(shù)的變化規(guī)律及加工后工件表面粗糙度的對(duì)比[22]
石墨烯納米流體切削液用于不銹鋼的其他加工工藝時(shí)[23],同樣可以觀察到摩擦力明顯降低,以及對(duì)不銹鋼加工表面質(zhì)量的提高。對(duì)于不銹鋼加工過(guò)程摩擦力的降低作用,不僅體現(xiàn)在石墨烯作為單一納米添加劑時(shí),混合納米粒子中石墨烯的存在也展現(xiàn)出良好的性能。目前針對(duì)混合納米粒子添加的研究相對(duì)較少,特別是石墨烯作為混合納米粒子組成成分時(shí),但現(xiàn)有的初步研究中仍表明石墨烯納米粒子良好的降低摩擦力能力[24]。圖3為氧化鋁/石墨烯復(fù)合納米流體切削液用于不銹鋼材料切削時(shí)摩擦因數(shù)的變化規(guī)律,相比于氧化鋁納米顆粒,石墨烯顆粒降低摩擦力的作用在切削穩(wěn)定后才得以體現(xiàn)。圖4為氧化鋁/石墨烯復(fù)合納米流體切削液作用下工件磨損圖像。
圖3 氧化鋁/石墨烯復(fù)合納米顆粒對(duì)切削過(guò)程摩擦因數(shù)的影響[24]
圖4 氧化鋁/石墨烯復(fù)合納米流體切削液作用下工件磨損圖像[24]
石墨烯納米顆粒添加到切削液中,導(dǎo)熱系數(shù)為3000 W/(m–1·K–1)的石墨烯材料提高了整體切削液的導(dǎo)熱能力,可以降低不銹鋼加工表面溫度,進(jìn)而提高加工表面質(zhì)量。其次石墨烯納米顆粒在工件表面不均勻分布,石墨烯納米顆粒填充表面微坑,而凸起部分石墨烯納米顆粒分布密度較低,這樣形成的石墨烯納米膜降低了不銹鋼工件表面粗糙度,而且對(duì)不銹鋼材料起到了保護(hù)作用。圖5為石墨烯納米顆粒填充效應(yīng)示意圖。
圖5 石墨烯納米顆粒的填充效應(yīng)[22]
對(duì)于納米流體切削液的研究已有大量的報(bào)道[25],但是對(duì)于石墨烯作為納米添加劑的研究相對(duì)較少,特別是用于加工不銹鋼材料的研究更少。宏觀尺度的研究表明:石墨烯可以有效地降低不銹鋼加工過(guò)程中的摩擦力,而且對(duì)于不銹鋼表面質(zhì)量的提高也十分有利,雖然對(duì)于石墨烯納米顆粒如何降低摩擦力以及提高不銹鋼加工質(zhì)量的機(jī)理有所揭示,但是石墨烯和其他納米顆粒對(duì)于不銹鋼加工過(guò)程的復(fù)合作用仍需進(jìn)一步研究,特別是納米尺度上機(jī)理的解釋有待研究。綜上所述,石墨烯納米切削液對(duì)于不銹鋼加工過(guò)程摩擦力的影響規(guī)律仍有待研究。
前文所述中,石墨烯是以添加劑的形式存在于切削液中,而且作用于不銹鋼材料的加工,切削液本身仍是降低摩擦力的主要因素。事實(shí)上,石墨烯作為主體材料直接作用不銹鋼工件摩擦表面時(shí),無(wú)論是降低摩擦力還是對(duì)不銹鋼材料的保護(hù),同樣展現(xiàn)出良好的效果。根據(jù)石墨烯的制備工藝以及和不銹鋼材料的結(jié)合形式,可以將不銹鋼表面的石墨烯分為兩類(lèi):一類(lèi)是已經(jīng)制備好的石墨烯轉(zhuǎn)移到不銹鋼表面[26],另一類(lèi)為直接在不銹鋼表面原位制備石墨烯。
事實(shí)上,自石墨烯被發(fā)現(xiàn)開(kāi)始,石墨烯的制備工藝一直就是眾多科研人員關(guān)注的重點(diǎn),因?yàn)楸WC高質(zhì)量和高產(chǎn)量石墨烯的獲取,才能保證石墨烯應(yīng)用的繼續(xù)研究。所以,根據(jù)石墨烯的結(jié)構(gòu)特點(diǎn),常見(jiàn)的石墨烯制備工藝除了包括機(jī)械和化學(xué)剝離[6-7,27]以及SiC外延生長(zhǎng)[28-30],化學(xué)氣相沉積法被認(rèn)為是可以兼顧石墨烯質(zhì)量和尺寸的有效工藝手段[31-36]。在諸多石墨烯的制備工藝中,不銹鋼都不是理想的基底材料,特別是獲取大面積石墨烯的化學(xué)氣相沉積法中,表面質(zhì)量、晶格尺寸以及融碳度合適的銅成為理想制備基底材料[37-39]。
因此,不銹鋼表面的石墨烯主要通過(guò)轉(zhuǎn)移的方式實(shí)現(xiàn)。美國(guó)阿貢實(shí)驗(yàn)室通過(guò)轉(zhuǎn)移石墨烯的方式,首先開(kāi)展了石墨烯對(duì)于不銹鋼材料減摩耐磨性影響規(guī)律的研究[2]。由于實(shí)驗(yàn)本身探究的是石墨烯降低不銹鋼表面磨損和摩擦的宏觀影響規(guī)律,對(duì)石墨烯的質(zhì)量和尺寸要求較低,所以選用高定向熱解石墨制備的石墨烯(SPG)[40],以乙醇為涂敷載體實(shí)現(xiàn)石墨烯和不銹鋼材料的結(jié)合。圖6和圖7為不銹鋼表面摩擦因數(shù)的變化規(guī)律以及不銹鋼表面磨損狀態(tài)對(duì)比。
圖6 不銹鋼摩擦副在不同溶液中和間歇供應(yīng)SPG時(shí)的摩擦因數(shù)以及有無(wú)初始SPG層的鋼的COF結(jié)果[2]
Berman的實(shí)驗(yàn)結(jié)果表明,在不銹鋼摩擦界面添加石墨烯,可以使不銹鋼的磨損率最高下降3~4個(gè)數(shù)量級(jí),摩擦因數(shù)的降低也很顯著,并且能夠抑制氧化鐵的形成[2]。所以,石墨烯的鈍化作用,不僅有助于不銹鋼表面摩擦磨損,而且對(duì)于不銹鋼耐腐蝕性的提高也十分有利。在此基礎(chǔ)上,研究人員認(rèn)識(shí)到環(huán)境因素會(huì)影響石墨烯對(duì)不銹鋼的減摩效率,阿貢實(shí)驗(yàn)室后續(xù)又探究了氣體氛圍下石墨烯對(duì)于不銹鋼減摩的規(guī)律[41-42]。實(shí)驗(yàn)結(jié)果也證實(shí)了研究人員的猜想,不銹鋼表面石墨烯通過(guò)石墨烯乙醇分散液獲取(SPGF),不同氣體氛圍下不銹鋼表面石墨烯的損壞時(shí)間相差明顯,特別是氮?dú)夥諊惺?duì)不銹鋼材料的保護(hù)時(shí)效相對(duì)較短,而氫氣氛圍中石墨烯對(duì)于不銹鋼材料的保護(hù)時(shí)效相對(duì)較長(zhǎng)。理論計(jì)算中指出氫原子會(huì)與破損的石墨烯邊緣碳成鍵,進(jìn)而對(duì)石墨烯破損處起一定程度的修補(bǔ)作用,對(duì)氣體環(huán)境的影響給出了解釋。圖8為氮?dú)夥諊率?duì)不銹鋼表面摩擦因數(shù)的影響規(guī)律。
圖7 磨損后不銹鋼表面磨損痕和軌跡光學(xué)顯微圖[2]
圖8 氮?dú)夥諊虏讳P鋼摩擦副在有無(wú)石墨烯下摩擦因數(shù)對(duì)比[42]
先制備石墨烯后轉(zhuǎn)移的方式,簡(jiǎn)化了石墨烯用于不銹鋼減摩的實(shí)驗(yàn)流程,也擴(kuò)展了石墨烯的應(yīng)用領(lǐng)域,但是這種方法的缺點(diǎn)是石墨烯的質(zhì)量難以保證[43]。對(duì)于尺寸較大的高質(zhì)量石墨烯,轉(zhuǎn)移過(guò)程會(huì)導(dǎo)致石墨烯的質(zhì)量下降[44-46],甚至引起石墨烯破損,導(dǎo)致微尺度上探究石墨烯對(duì)不銹鋼減摩耐磨影響規(guī)律十分不利。盡管石墨烯的轉(zhuǎn)移工藝在不斷進(jìn)步,包括轉(zhuǎn)移支撐材料的不斷嘗試[47],但是石墨烯的轉(zhuǎn)移過(guò)程仍會(huì)對(duì)后續(xù)的摩擦實(shí)驗(yàn)產(chǎn)生干擾。
因此,不銹鋼表面原位制備石墨烯不僅能夠排除轉(zhuǎn)移過(guò)程帶來(lái)的干擾,而且相比于轉(zhuǎn)移型石墨烯與不銹鋼之間通過(guò)范德華力維持,原位制備型石墨烯與不銹鋼結(jié)合更穩(wěn)定。但是由于不銹鋼材料本身性質(zhì)限制,傳統(tǒng)的化學(xué)氣相沉積法很難得到高質(zhì)量的石墨烯[1],所以為實(shí)現(xiàn)不銹鋼表面制備較高質(zhì)量石墨烯,研究人員對(duì)化學(xué)氣相沉積法進(jìn)行了優(yōu)化[48-49]或者改變不銹鋼基底形貌[50]。E. C. Romani1等人[51]在此基礎(chǔ)上,探究了化學(xué)氣相沉積法在不銹鋼表面制備石墨烯的摩擦規(guī)律,實(shí)驗(yàn)結(jié)果表明無(wú)石墨烯不銹鋼表面摩擦因數(shù)約為有石墨烯不銹鋼表面摩擦因數(shù)的3倍。圖9為不同載荷下有無(wú)石墨烯不銹鋼表面摩擦力的變化規(guī)律。
盡管直接在不銹鋼表面制備石墨烯的質(zhì)量相對(duì)較差,制備得到的石墨烯多為單層到3層的混合物,但摩擦曲線上依然保持了良好的平穩(wěn)性,這是轉(zhuǎn)移型石墨烯無(wú)法保證的結(jié)果。主要原因有兩點(diǎn),第一,維持足夠的生長(zhǎng)時(shí)間,可以實(shí)現(xiàn)石墨烯對(duì)不銹鋼基底的全覆蓋;第二,石墨烯與不銹鋼之間不僅有范德華力作用,甚至?xí)谐涉I。為了證實(shí)這一點(diǎn),Xu等人[52]在不銹鋼球表面機(jī)械剝離原位制備石墨烯涂層,同樣證明了石墨烯可以有效降低不銹鋼表面摩擦力,也證實(shí)了Cr—C鍵的存在。圖10為制備樣品的拉曼光譜圖和XRD衍射圖。
圖9 不同摩擦表面摩擦因數(shù)變化規(guī)律[51]
圖10 Gr/SS樣品的拉曼光譜圖及SS 304和Gr/SS的XRD衍射圖[52]
不銹鋼材料磨損的形成是摩擦累計(jì)的結(jié)果,特別是出現(xiàn)局部磨損后會(huì)進(jìn)一步加快材料磨損,石墨烯在摩擦表面的存在,會(huì)均勻地承載法向載荷,進(jìn)而使得表面磨損分布均勻,對(duì)于整體材料的耐磨性提高十分有利。轉(zhuǎn)移型石墨烯與不銹鋼表面主要通過(guò)范德華力約束,摩擦過(guò)程中石墨烯和不銹鋼會(huì)發(fā)生相對(duì)滑動(dòng),而且石墨烯材料本身導(dǎo)熱系數(shù)較高,所以石墨烯在降低摩擦界面摩擦力的同時(shí)會(huì)減低摩擦界面溫度,抑制了氧化鐵的形成,對(duì)于不銹鋼表面起到了保護(hù)作用。在不銹鋼表面原位制備型石墨烯中,由于Cr—C鍵的存在,表面石墨烯與不銹鋼結(jié)合緊密,而且覆蓋率較高,無(wú)論是抑制氧化鐵的形成還是石墨烯的承載能力,都略高于轉(zhuǎn)移型石墨烯。圖11為有無(wú)石墨烯不銹鋼表面磨損軌跡輪廓高度對(duì)比。
圖11 不銹鋼表面磨損軌跡輪廓高度對(duì)比[2]
綜上所述,無(wú)論是轉(zhuǎn)移型石墨烯還是原位生長(zhǎng)型石墨烯,對(duì)不銹鋼表面減摩耐磨性能的提高都十分有效,而且也為石墨烯在不銹鋼表面的應(yīng)用提供有效的指導(dǎo)。但是目前研究中,對(duì)于降低不銹鋼表面摩擦力所轉(zhuǎn)移的石墨烯存在低質(zhì)量碎片化問(wèn)題,也就出現(xiàn)了實(shí)驗(yàn)結(jié)果中摩擦曲線波動(dòng)明顯的現(xiàn)象,這同樣也限制了從微尺度上對(duì)石墨烯降低不銹鋼表面摩擦力進(jìn)行機(jī)理性研究。直接在不銹鋼表面制備石墨烯解決了石墨烯碎片化的問(wèn)題,但高質(zhì)量的石墨烯仍很難獲取,而且由于制備工藝本身對(duì)溫度有較高的需求,這導(dǎo)致了不銹鋼材料發(fā)生滲碳和析碳[53],對(duì)不銹鋼材料本身的性能產(chǎn)生了較大的影響。所以,雖然兩種方法都證明了石墨烯可以有效降低不銹鋼表面摩擦力,但都因自身的工藝限制存在一定的局限性,對(duì)石墨烯降低不銹鋼表面摩擦的機(jī)理性解釋不充分。
無(wú)論是轉(zhuǎn)移型石墨烯還是原位制備型石墨烯,石墨烯僅存在于不銹鋼材料的表面,石墨烯也僅作用于不銹鋼發(fā)生摩擦的界面上,而且不銹鋼和石墨烯之間主要通過(guò)范德華力約束,由于這些條件的限制,石墨烯無(wú)法對(duì)不銹鋼進(jìn)行長(zhǎng)效保護(hù)。美國(guó)阿貢實(shí)驗(yàn)室[2]也指出,間歇性添加石墨烯可以實(shí)現(xiàn)對(duì)不銹鋼減摩耐磨性的持續(xù)提高,但是在工程應(yīng)用的多種場(chǎng)合下,間歇性添加石墨烯材料很難實(shí)現(xiàn),所以此類(lèi)的實(shí)驗(yàn)研究仍存在一定的局限性。針對(duì)以上問(wèn)題,國(guó)內(nèi)研究人員針對(duì)石墨烯增強(qiáng)不銹鋼復(fù)合材料進(jìn)行了進(jìn)一步研究。
粉末冶金是金屬材料和零件制備的常用方法[54-56],整個(gè)工藝過(guò)程已經(jīng)十分成熟和完善,針對(duì)各種金屬粉末原材料的冶金工藝都有大量研究[57-60]。對(duì)于不銹鋼材料,研究人員很早就認(rèn)識(shí)到粉末冶金的優(yōu)點(diǎn),同樣也開(kāi)展了大量的研究[61-63]。然而,由于粉末冶金材料的相對(duì)密度較低,導(dǎo)致粉末冶金不銹鋼的機(jī)械強(qiáng)度和耐腐蝕性都低于鍛制不銹鋼[64],所以一直限制了粉末冶金不銹鋼材料的應(yīng)用。但隨著對(duì)粉末冶金以及各種材料性質(zhì)的研究,人們發(fā)現(xiàn)其他金屬、金屬化合物或陶瓷添加劑均可提高粉末冶金不銹鋼材料的相對(duì)密度[65-67]。所以,石墨烯作為添加劑增強(qiáng)粉末冶金不銹鋼材料的性能引起了研究人員的關(guān)注,同時(shí)伴隨著金屬3D打印技術(shù)的發(fā)展也為此提供了新途徑[68]。
石墨烯增強(qiáng)金屬基納米復(fù)合材料技術(shù)主要應(yīng)用于純金屬,對(duì)于不銹鋼材料的相關(guān)研究相對(duì)較少[69-70]。西安交通大學(xué)[71]開(kāi)展了粉末冶金制備石墨烯納米片增強(qiáng)不銹鋼材料的相關(guān)工作,石墨烯的原材料也選用了相對(duì)經(jīng)濟(jì)的石墨紙,對(duì)制備的不銹鋼復(fù)合材料進(jìn)行了基本機(jī)械性能的檢測(cè),并指出石墨烯對(duì)不銹鋼復(fù)合材料摩擦性能有所改善。圖12為粉末冶金制備石墨烯納米片增強(qiáng)不銹鋼的實(shí)驗(yàn)流程。
粉末冶金石墨烯納米片增強(qiáng)不銹鋼相比于粉末冶金不銹鋼,相對(duì)密度以及顯微硬度等有所提高,但是由于石墨烯和不銹鋼密度相差較大,所以石墨烯在不銹鋼中分布的均勻性較差,易產(chǎn)生石墨烯的團(tuán)簇現(xiàn)象,降低了對(duì)材料摩擦性能的改善效果。武漢科技大學(xué)[72]針對(duì)石墨烯和不銹鋼密度相差大的問(wèn)題提出了新的解決方案,通過(guò)引入銅顆粒和石墨烯結(jié)合,進(jìn)而減少兩者之間的密度差,最終制備了Gr-Cu/SS復(fù)合材料。圖13為Gr-Cu/SS復(fù)合材料制備工藝過(guò)程。
圖12 粉末冶金制備石墨烯納米片增強(qiáng)不銹鋼[71]
圖13 Gr-Cu/SS復(fù)合材料制備工藝(a原始氧化石墨烯納米片,b氧化石墨烯-銅,c原始不銹鋼粉末,d石墨烯-銅,e石墨烯-銅/不銹鋼混合粉末,f石墨烯-銅/不銹鋼復(fù)合樣品)[72]
石墨烯質(zhì)量分?jǐn)?shù)僅為0.2%的Gr-Cu/SS復(fù)合材料的抗拉強(qiáng)度和屈服強(qiáng)度約為之前的2倍,材料耐磨性能有所提高,但是對(duì)于摩擦因數(shù)沒(méi)有開(kāi)展詳細(xì)的實(shí)驗(yàn)。所以,對(duì)于該類(lèi)材料的摩擦性能仍有待研究,而且由于銅的引入也對(duì)探究石墨烯減摩效果產(chǎn)生干擾[73],其摩擦學(xué)的內(nèi)在機(jī)理仍有待深入研究。
激光熔化增材制造技術(shù)出現(xiàn)之初,主要集中應(yīng)用于定制金屬部件生產(chǎn)上[74],但隨著技術(shù)的發(fā)展以及對(duì)材料性能要求的提高,研究人員認(rèn)識(shí)到激光增材技術(shù)為金屬性能的改善提供了途徑。對(duì)于不銹鋼和不銹鋼復(fù)合材料,激光熔化增材制造在提高耐磨性和強(qiáng)度性能方面也取得了許多研究和發(fā)現(xiàn)[75-78]。石墨烯和不銹鋼密度相差明顯,粉末冶金難以克服這一個(gè)問(wèn)題,由于激光熔化增材是多層堆疊方式加工,而且單層材料很薄,可以保證石墨烯的均勻分布,為石墨烯增強(qiáng)不銹鋼復(fù)合材料研究提供了新的途徑。
中科院寧波工業(yè)技術(shù)研究院[79]首先通過(guò)激光熔化增材制造技術(shù)開(kāi)展了多層石墨烯增強(qiáng)不銹鋼復(fù)合材料的研究,探究了不同含量石墨烯對(duì)不銹鋼復(fù)合材料顯微組織和力學(xué)性能的影響。圖14為實(shí)驗(yàn)所用不銹鋼復(fù)合材料的工藝流程。針對(duì)復(fù)合材料進(jìn)行了機(jī)械性能的檢查,摩擦因數(shù)隨著石墨烯含量的增加而降低,而且特定含量石墨烯增強(qiáng)不銹鋼復(fù)合材料展現(xiàn)出極優(yōu)的機(jī)械性能。圖15為不同石墨烯含量下的摩擦因數(shù)變化規(guī)律。
圖14 石墨烯增強(qiáng)不銹鋼復(fù)合材料工藝流程[79]
圖15 不同石墨烯含量下復(fù)合材料的摩擦因數(shù)曲線(G0代表無(wú)Gr,G1代表含1%Gr,G2代表含2%Gr,G3代表含3%Gr)[79]
Ajay Mandal等人[80]在此基礎(chǔ)上,制備了尺寸更大的石墨烯增強(qiáng)不銹鋼復(fù)合材料柱體樣件,系統(tǒng)地研究了復(fù)合材料的顯微組織結(jié)構(gòu)以及機(jī)械性能,并在不同載荷和速度的條件下檢測(cè)了材料的摩擦因數(shù),證明了石墨烯能夠改善不銹鋼材料的減摩性和耐磨性。圖16為不同載荷條件下摩擦因數(shù)隨滑移速度的變化曲線。
不銹鋼材料的磨損機(jī)理主要是微犁耕,普通不銹鋼表面發(fā)生磨損時(shí),會(huì)觀察到微小的磨損碎片,即滑移過(guò)程中材料被犁削并形成深溝。添加石墨烯的不銹鋼復(fù)合材料,石墨烯會(huì)在界面處形成墊狀結(jié)構(gòu),提供了更平滑的接觸表面,阻止了犁耕效應(yīng)的產(chǎn)生[75]。圖17為不同含量石墨烯增強(qiáng)的不銹鋼復(fù)合材料與普通不銹鋼磨損界面對(duì)比。
通過(guò)對(duì)材料顯微組織的分析,也證明通過(guò)激光熔化增材技術(shù)實(shí)現(xiàn)了石墨烯在不銹鋼中的均勻分布,同時(shí)由于激光能量較高,晶體表現(xiàn)為多層之間連續(xù)和隨機(jī)取向,保證了整體材料的均勻性,而且避免了碳化鉻的形成,石墨烯能夠充分發(fā)揮自身優(yōu)良的機(jī)械性能,顯著提高復(fù)合材料的力學(xué)性能。相比于粉末冶金,激光熔化增材制造解決了石墨烯和不銹鋼密度相差大導(dǎo)致的團(tuán)簇現(xiàn)象,但是所制備的復(fù)合材料中,石墨烯缺陷明顯增加,石墨烯的力學(xué)性能下降明顯,實(shí)驗(yàn)結(jié)果與理論計(jì)算之間存在較大誤差。綜上所述,雖然制備復(fù)合材料的機(jī)械性能有了一定的提升,石墨烯可以有效地提高不銹鋼的減摩性和耐磨性,但是由于對(duì)該復(fù)合材料的研究較少,未能對(duì)其機(jī)理獲得統(tǒng)一的認(rèn)識(shí),大量的實(shí)驗(yàn)結(jié)論仍需探究。
圖16 法向載荷分別為6、8、10 kg時(shí)摩擦因數(shù)隨滑移速度的變化曲線[80]
圖17 8 kg法向載荷下不銹鋼石墨烯復(fù)合材料磨損界面形貌[80]
不銹鋼材料是工業(yè)領(lǐng)域的重要應(yīng)用材料,實(shí)現(xiàn)低摩擦條件下高精度加工不銹鋼零件是先進(jìn)制造領(lǐng)域重要的發(fā)展方向。在最小潤(rùn)滑量的條件下石墨烯納米流體切削液的使用,可以有效地提高不銹鋼零件的表面質(zhì)量。但是,包括石墨烯納米顆粒尺寸均勻度和分布均勻度的均勻性特征是影響不銹鋼工件整體加工質(zhì)量的關(guān)鍵,局部石墨烯納米顆粒尺寸過(guò)大或濃度過(guò)高會(huì)引起工件局部粗糙度值的增加。同樣,石墨烯作用于不銹鋼工作摩擦界面時(shí),其分散均勻性也對(duì)不銹鋼減摩和耐磨特性的提高起到關(guān)鍵的作用。因此,無(wú)論對(duì)于石墨烯用于不銹鋼切削加工,還是石墨烯用于不銹鋼的界面材料,控制石墨烯納米顆粒或納米片的尺寸均勻性特征,實(shí)現(xiàn)穩(wěn)定的石墨烯減摩和耐磨,都是未來(lái)研究的重點(diǎn)。
創(chuàng)新的石墨烯制備工藝是石墨烯在不銹鋼材料應(yīng)用中實(shí)現(xiàn)長(zhǎng)效的減摩和耐磨特性的基礎(chǔ)。不銹鋼表面制備石墨烯,提高了石墨烯和不銹鋼的結(jié)合程度,但卻帶來(lái)了表面石墨烯的缺陷增加以及層數(shù)均勻性下降的問(wèn)題。石墨烯/不銹鋼復(fù)合材料是極大提高長(zhǎng)效性的重要途徑,但是石墨烯和不銹鋼密度相差顯著以及石墨烯團(tuán)簇現(xiàn)象的出現(xiàn),極大地限制了該材料的發(fā)展。增材制造工藝可以解決石墨烯和不銹鋼高密度差引起的分布不均問(wèn)題,同時(shí)也減少了團(tuán)簇現(xiàn)象的出現(xiàn),但是增材制造工藝本身會(huì)造成材料機(jī)械性能的下降。所以改善和發(fā)展不銹鋼表面制備石墨烯工藝仍是未來(lái)研究的關(guān)注點(diǎn),石墨烯/不銹鋼復(fù)合材料的制備技術(shù)革新和工藝改進(jìn),是實(shí)現(xiàn)兩種材料工程應(yīng)用的關(guān)鍵所在。
由于石墨烯具有優(yōu)良的機(jī)械性能,充分利用石墨烯的機(jī)械性能對(duì)現(xiàn)有材料進(jìn)行優(yōu)化成為材料學(xué)發(fā)展的新方向,而不銹鋼作為工業(yè)領(lǐng)域重要的應(yīng)用材料,減摩耐磨性提高會(huì)帶來(lái)巨大的經(jīng)濟(jì)效益,所以將石墨烯和不銹鋼結(jié)合實(shí)現(xiàn)這一目標(biāo)成為學(xué)術(shù)界和工業(yè)界共同的追求。經(jīng)過(guò)多次的實(shí)驗(yàn)嘗試,石墨烯與不銹鋼兩個(gè)結(jié)合實(shí)現(xiàn)減摩和耐磨仍需在機(jī)理上開(kāi)展深入研究,同時(shí)需要解決其工程應(yīng)用的技術(shù)難題。本文根據(jù)近年來(lái)石墨烯應(yīng)用于不銹鋼材料減摩耐磨性提高的研究進(jìn)行總結(jié),證實(shí)了石墨烯對(duì)不銹鋼減摩耐磨性的提高十分有效,特別是激光熔化增材制造技術(shù)的應(yīng)用,為石墨烯增強(qiáng)不銹鋼復(fù)合材料的工程應(yīng)用提供了條件。
雖然已經(jīng)得到了許多石墨烯對(duì)不銹鋼摩擦力影響的規(guī)律,但是多數(shù)實(shí)驗(yàn)仍處于宏觀領(lǐng)域,微尺度上開(kāi)展的研究很少,微觀上的實(shí)驗(yàn)結(jié)果還不能通過(guò)內(nèi)在的機(jī)理進(jìn)行科學(xué)解釋。而且由于激光熔化增材制造技術(shù)應(yīng)用于石墨烯增強(qiáng)不銹鋼復(fù)合材料的研究尚處于初期,實(shí)驗(yàn)結(jié)果和理論計(jì)算之間存在分歧,所以材料的工程應(yīng)用仍需進(jìn)一步研究。高質(zhì)量石墨烯的獲取以及和不銹鋼材料的結(jié)合仍是關(guān)鍵問(wèn)題,此類(lèi)問(wèn)題的解決才能進(jìn)一步揭示微觀機(jī)理,因此基于原子和分子計(jì)算的理論仿真也將是解決當(dāng)前存在問(wèn)題的有效途徑。
石墨烯和不銹鋼材料的結(jié)合是拓展兩種材料應(yīng)用的重要方式,提高不銹鋼材料減摩耐磨性對(duì)拓展新材料的應(yīng)用領(lǐng)域,提高不銹鋼零件的經(jīng)濟(jì)性,降低能量消耗具有重要的意義。本文總結(jié)了近年來(lái)石墨烯應(yīng)用于不銹鋼材料減摩耐磨性提高的研究,對(duì)于該方向的研究具有一定的指導(dǎo)意義。
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Research Progress in Friction Reduction and Wear Resistance of Graphene in Stainless Steel Applications
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(School of Mechatronics Engineering, Harbin Institute of Technology, Harbin 150001, China)
Friction and wear of stainless-steel materials is a great waste of economy and energy. Graphene with high strength provides a new way, to improve the wear resistance of stainless-steel materials. The combination of the two materials is of great significance to the industrial field. According to the combination mode of graphene and stainless-steel materials, the research progress on the application of graphene in the friction and wear of stainless-steel materials was summarized. From the processing to the application of stainless-steel materials, the law of graphene reducing the friction coefficient of stainless steel was revealed. As a cutting fluid additive, graphene nanoparticles can greatly reduce the friction coefficient of the friction interface between stainless steel and the tool, thus improving the surface quality of stainless-steel workpiece. Preparation followed by transfer is still the main way for graphene to be applied to stainless steel surface. Graphene acts on the friction interface in the form of solid lubricant, and the wear rate of stainless-steel surface can be reduced by an order of magnitude. The continuous development of laser melting additive manufacturing technology provides an effective way for graphene reinforced stainless steel composites, greatly promotes the process of engineering application of the material, and provides a new research direction for graphene to reduce the friction and wear of stainless-steel materials. Finally, through the research on the reduction of friction and wear of stainless-steel materials by graphene, some problems existing in the current research are pointed out and possible solutions are proposed, and the application prospect of this direction is prospected.
graphene; stainless steel; friction and wear; mechanical properties; selective laser melting
2021-03-31;
2021-04-13
GUO Wan-min(1994—),Male, Ph. D. candidate, Research focus: carbon nanomaterials.
白清順(1974—),男,博士,教授,主要研究方向?yàn)槌芗庸づc微納制造。郵箱:Qshbai@hit.edu.cn
Corresponding author:BAI Qing-shun(1974—), Male, Doctor, Professor, Research focus: ultra-precision machining and micro/nano manufacturing technology. E-mail: Qshbai@hit.edu.cn
郭萬(wàn)民, 白清順, 竇昱昊, 等. 石墨烯在不銹鋼材料應(yīng)用中的減摩和耐磨特性研究進(jìn)展[J]. 表面技術(shù), 2021, 50(4): 43-55.
TH117
A
1001-3660(2021)04-0043-13
10.16490/j.cnki.issn.1001-3660.2021.04.003
2021-03-31;
2021-04-13
國(guó)家自然科學(xué)基金項(xiàng)目(51775146,51535003,52075129)
Fund:Supported by the National Natural Science Foundation of China (51775146, 51535003, 52075129)
郭萬(wàn)民(1994—),男,博士生,主要研究方向?yàn)樘技{米材料。
GUO Wan-min, BAI Qing-shun, DOU Yu-hao, et al. Research progress in friction reduction and wear resistance of graphene in stainless steel applications[J]. Surface technology, 2021, 50(4): 43-55.