Ruler儀器在潤滑脂抗氧劑含量測定中的應(yīng)用

1、living standards, poor farmers in less than complete elimination of 4600 Yuan, 8949, 19008. "Five waters rule": the County invested 2.169 billion yuan, similar counties line the city's first complete the 42 km of sewage pipe network construction, completion rate ranked first in the cit

2、y, won the provincial rural sewage treatment work better; key pollution sources such as electroplating, papermaking, chemical industry management through verification and acceptance of the municipal government, the County removed Black and odorous River, River waste, beginning of river ecological re

3、storation effects. "Three modified a split" aspects: County total demolition illegal area up 2.759 million square meters, completed City issued annual task of 153%, split against area ranking city second; completed "three modified" area 4.846 million square meters, completed City

4、 issued annual task of 403%, ranking city third, which village in the a target completed total city ranking first; County Government was named city level "three modified a split" work advanced. These achievements are hard won and should be appreciated. However, we are fully aware, the new

5、period, and work in the countryside and the environment facing higher standards and requirements, provincial party Committee offered to high level build a comprehensive well-off society goal requires "no filth, dirty environment illegal buildings, into a well-off" municipal party Committee

6、 also proposes to build into the well-off benchmark goals of the city. Compared with the superior claim, "South Gate of XX beautiful" goal, my County "San Nong" and environment there are a number of weaknesses and gaps, highlighted in the following five aspects: first, agricultur

7、e remained "low" pattern. "Low" is reflected in the quality and low; short, value added of the industry chain is low; 123 fusion yield low employee age, low quality. "Small" is reflected in smaller, specialized cooperatives throughout the County there were 3,396, but on

8、 the scale of too little. "San" is reflected in production, management, services, decentralized, centralized, standardized, brand, information and organizational level is not high. Second, the countryside is still in "dirty" phase. "Dirty" is dirty of rural sanitation s

9、ituation has not changed. "Chaos" is a village in rural housing construction planning, construction of disorder, no drawings, no construction, no vetting "four no" phenomenon, heap lying there. "Bad" is the weak rural base, village governance is poor. Thirdly, farmers c

10、ontinued to be "persistent" look. "Old" is aging, rural labor force accounted for 70% over the age of 50. "Big" is that the reform measures ground resistance, such as the transactions of property rights, land replacement; public service supply gap, rural education, heal

11、th care, pensions and other services can not meet the demand still difficult for poverty alleviation, with emphasis on poverty alleviation and 191. "Hard" is a "peasants, peasants. Four water effects still lacks線性伏安法在潤滑脂抗氧劑含量測定中的應(yīng)用谷紅寬，劉建龍 馮強(qiáng)（中國石化潤滑油天津分公司，天津 300480）摘要：通過ASTM D7527標(biāo)準(zhǔn)方法，

12、采用線性伏安法技術(shù)，對(duì)鋰基潤滑脂進(jìn)行分析，準(zhǔn)確地測量出潤滑油脂中剩余的有效抗氧化劑含量，結(jié)果表明該儀器能夠?qū)崟r(shí)便捷的測試檢測潤滑脂抗氧劑含量的變化，對(duì)進(jìn)行潤滑脂剩余使用壽命的檢測是一種有效方法。關(guān)鍵詞：潤滑脂，抗氧劑，線性伏安法隨著現(xiàn)代機(jī)械工業(yè)的發(fā)展，對(duì)潤滑脂的使用條件和使用壽命要求越來越高。高溫工作環(huán)境，有害物質(zhì)的侵入，使用時(shí)間加長，都是導(dǎo)致潤滑脂氧化的條件。由于氧化是潤滑脂失效的主要原因，潤滑脂的生產(chǎn)過程普遍采用抗氧化劑來延長潤滑脂的使用壽命。因此，潤滑油脂中抗氧劑含量很大意義決定著其使用壽命?？寡鮿└鶕?jù)化學(xué)組成主要有屏蔽酚型、芳胺型、含硫、磷、氮化合物、有機(jī)金屬化合物和復(fù)合型抗氧劑1。如

13、果能夠在潤滑脂使用過程實(shí)時(shí)便捷的測試檢測抗氧劑含量的變化，對(duì)潤滑脂產(chǎn)品的開發(fā)和使用顯得尤為重要。目前對(duì)潤滑油脂抗氧化性能的測試方法主要有：（1）高效液相色譜和氣相色譜法、（2）凝膠滲透色譜法、（3）熱分析（TGA、DSC、DTA）、（4）紅外光譜(IR)、（5）核磁共振和核磁共振紅外光譜連用、（6）化學(xué)發(fā)光技術(shù)、（7）電化學(xué)技術(shù)（包括電氣敏感氣法、伏安法和電導(dǎo)率法）2。伏安法是基于微電極上電流電壓時(shí)間三者間的關(guān)系。將潤滑劑和抗氧劑溶解在電解質(zhì)溶液中，然后插入工作、參比和輔助電極。輔助電極的電壓隨時(shí)間線性增加，當(dāng)電極電壓與抗氧劑氧化電勢相等時(shí)，抗氧劑發(fā)生電化學(xué)氧化，導(dǎo)致工作電極上電流的增加，以輔

14、助電極電壓對(duì)工作電流作圖，可得到伏安譜峰，峰的電壓值決定于抗氧劑的類型，峰的大小決定于抗氧劑的濃度3。在潤滑劑的使用過程中，抗氧化劑因與自由基和過氧化物作用而被逐漸消耗掉，直至抗氧化劑濃度達(dá)到某個(gè)臨界值時(shí)，油液開始發(fā)生加速降解反應(yīng)，此時(shí)油液已達(dá)到了其有用壽命4。因此，為了預(yù)測油液剩余有用壽命，關(guān)鍵就在于確定關(guān)鍵抗氧化劑的濃度。傳統(tǒng)的分析實(shí)驗(yàn)方法無法預(yù)示何時(shí)將發(fā)生機(jī)器性能問題，無法告知其潤滑油還可被安全地使用多久。而且，隨著現(xiàn)代潤滑油配方的復(fù)雜化，針對(duì)單個(gè)抗氧化劑的監(jiān)測將給用戶帶來極高的價(jià)值。線性伏安法通過電解液將潤滑油脂中的酚類和胺類抗氧劑萃取出來，利用抗氧劑在一定電流下發(fā)生電化學(xué)反應(yīng)的原理，

15、能夠檢測單個(gè)抗氧劑的狀態(tài)，它是當(dāng)今潤滑劑狀態(tài)監(jiān)測的一個(gè)重要手段5-7。本實(shí)驗(yàn)將采用Ruler CE520儀器按照ASTM D7527標(biāo)準(zhǔn)方法測試已知不同胺類和酚類抗氧劑添加量的鋰基潤滑脂電化學(xué)伏安峰面積，繪制驗(yàn)證曲線，得到線性歸一化方程式。將某一添加劑含量的潤滑脂在高溫下烘烤，利用Ruler CE520儀器測試其伏安峰，并通過壓力差示掃描量熱法( PDSC)檢測其氧化誘導(dǎo)期，同步分析潤滑脂抗氧劑的降解過程。1. 儀器介紹1.1 Ruler CE520儀器Ruler CE520抗氧劑含量測試儀是由比利時(shí)Fluitec International公司開發(fā)生產(chǎn)的潤滑油脂抗氧劑含量實(shí)時(shí)監(jiān)測工具。主要通

16、過測定未使用油脂和使用后油脂中的抗氧劑含量的變化，來評(píng)定潤滑油脂剩余使用時(shí)間的電化學(xué)儀器。該儀器適用于ASTM D7527標(biāo)準(zhǔn)，采用線性伏安法，利用特制的三電極探測器（包括工作、參比和輔助電極），準(zhǔn)確地測量出潤滑油脂中剩余的有效抗氧化劑含量，從而迅速且高度準(zhǔn)確地評(píng)估出潤滑油脂的剩余有用壽命。如圖1所示，該設(shè)備主要由RULER CE520設(shè)備及配套探測器，USB連接線，220 V轉(zhuǎn)換電源，油液氧剩余條件數(shù)據(jù)管理軟件R0-DMS Software 2.0，配套手提箱，一次性端頭的微量移液器以及清潔材料等。測試部分結(jié)構(gòu)如圖1所示。圖1 Ruler CE520測試儀2. 實(shí)驗(yàn)部分2.1 試驗(yàn)試劑：（1

17、） 鋰基潤滑脂基礎(chǔ)脂（自制）（2） 胺類抗氧劑、酚類抗氧劑（3） 抗氧劑電解液（Fluitec International）2.2 實(shí)驗(yàn)儀器Ruler CE520抗氧劑含量測試儀（比利時(shí)Fluitec International），壓力差示掃描量熱儀（德國NETZSCH）2.3 循環(huán)伏安法測定抗氧劑含量按照ASTM D7527標(biāo)準(zhǔn)方法將含有至少一種抗氧化劑種類的潤滑脂（準(zhǔn)確稱取100mg）溶解于Ruler CE520提供裝有電解液的測試小瓶中，溶解后的溶液（即電解槽）是由潤滑脂樣品，電解質(zhì)溶劑和固體基質(zhì)混合后而構(gòu)成的。用力搖動(dòng)小瓶后，電解質(zhì)溶劑就能將抗氧化劑從潤滑脂中分離出。將RULER測試探

18、頭插入測試小瓶中，通過向浸在被分析潤滑脂中的電極施加受控電壓信號(hào)，潤滑脂樣品中的抗氧劑在工作電極表面發(fā)生電化學(xué)反應(yīng)，所產(chǎn)生的電流在抗氧劑的氧化電位附近出現(xiàn)峰值，峰值大小與溶液中的抗氧劑的濃度有關(guān)。圖2是典型的抗氧化劑的氧化伏安圖。圖2 典型抗氧劑特征氧化伏安峰在圖2中根據(jù)電壓范圍判斷抗氧化劑類型，圖2中的兩個(gè)電流峰依次為胺類抗氧劑和酚類抗氧劑，并根據(jù)電流峰面積計(jì)算抗氧劑的濃度。2.4 潤滑脂氧化誘導(dǎo)期的測試采用ASTM D5483-02標(biāo)準(zhǔn)方法，在一定壓力的氧氣氣氛中，使試樣溫度快速升至某一設(shè)定溫度并保持恒定，測定其自恒溫開始至氧化放熱峰出現(xiàn)為止的時(shí)間間隔即氧化誘導(dǎo)期?？疾斓臏囟葹?30，升溫

19、速率100 /min，測試池壓力由氬氣提供3.5 MPa±0.2 MPa。用PDSC儀測試池出口閥調(diào)節(jié)氧氣流速至100 mL/min±10 mL/min。 樣品皿<6 mm開口鋁皿，樣品用量2.0 mg±0.1 mg。2.5 潤滑脂氧化過程試驗(yàn)將一定量的潤滑脂樣品均勻的涂抹在一塊瓷板上，厚度大約1 mm，將其放置到150 烘箱中，每隔一定時(shí)間取出一定量樣品，利用Ruler CE520測試其抗氧劑含量和氧化誘導(dǎo)期變化情況。3. 實(shí)驗(yàn)結(jié)果與討論3.1 胺類和酚類抗氧劑含量與峰面積關(guān)系標(biāo)準(zhǔn)曲線的繪制在鋰基基礎(chǔ)脂中同時(shí)加入不同比例的胺類和酚類抗氧劑，在Ruler C

20、E520儀器上測試其伏安峰，對(duì)胺類抗氧劑和酚類抗氧劑的峰進(jìn)行峰面積計(jì)算?？寡鮿┘尤氡壤头迕娣e數(shù)據(jù)如表1所示。表1 試驗(yàn)潤滑脂樣品抗氧劑加入比例和峰面積數(shù)據(jù)試驗(yàn)號(hào)抗氧劑加入量 wt%峰面積胺類酚類胺類酚類100002115578.43731.232213380.715773.443320838.825217.754425104.338743.0注：抗氧劑加入百分含量為配方內(nèi)比例。根據(jù)抗氧劑加入含量和由Ruler CE520測試得到的峰面積數(shù)值，通過歸一化法繪制標(biāo)準(zhǔn)曲線，并得到胺類抗氧劑的曲線方程為y = 6546.9x - 113.36，方程相關(guān)系數(shù)為R2 = 0.9918；酚類抗氧劑的曲線方

21、程為：y = 9897.3x - 3101.4，方程相關(guān)系數(shù)為R2 = 0.9733。上述方程曲線如圖3所示。有以上數(shù)據(jù)可知，兩個(gè)方程的線性相關(guān)系數(shù)均比較高，證明根據(jù)Ruler CE520測試得到數(shù)據(jù)描點(diǎn)繪制出來的峰面積與抗氧劑加入量的圖線趨近于一條平直線，證明線性回歸方程具有較高的可靠性。因此該儀器能夠同時(shí)快速的檢測到胺類和酚類抗氧劑的含量。圖3 胺類抗氧劑和酚類抗氧劑的標(biāo)準(zhǔn)曲線3.2 標(biāo)準(zhǔn)曲線的驗(yàn)證利用Ruler CE520測試現(xiàn)有一款鋰基潤滑脂產(chǎn)品A，并計(jì)算得到其抗氧劑的峰面積，通過3.1中得到的標(biāo)準(zhǔn)曲線，推出其抗氧劑含量，并與潤滑脂產(chǎn)品A中的抗氧劑實(shí)際加入量進(jìn)行對(duì)比。結(jié)果如表2所示.表

22、2 潤滑脂產(chǎn)品A抗氧劑含量潤滑脂產(chǎn)品A抗氧劑胺類抗氧劑酚類抗氧劑峰面積15340.212833.3曲線查得抗氧劑含量wt%2.351.61抗氧劑實(shí)際含量wt%2.501.50相對(duì)誤差-0.0600.073注：相對(duì)誤差=（曲線查得抗氧劑含量-抗氧劑實(shí)際含量）/抗氧劑實(shí)際含量由表2可知，對(duì)于鋰基潤滑脂產(chǎn)品A可以按照3.1中所繪制的標(biāo)準(zhǔn)曲線，查得其抗氧劑的加入量，對(duì)于胺類抗氧劑其相對(duì)誤差為-0.060，對(duì)于酚類抗氧劑相對(duì)誤差為0.073，誤差較小，上述標(biāo)準(zhǔn)曲線具有較高的可靠性。3.3 潤滑脂樣品氧化過程檢測分析將潤滑脂產(chǎn)品A分別烘烤（150）4h、8h、16h、24h的樣品進(jìn)行抗氧劑含量測試和氧化誘

23、導(dǎo)期測試，分析其抗氧劑衰減過程。結(jié)果如表3所示。表3 潤滑脂產(chǎn)品A抗氧劑相對(duì)含量與氧化誘導(dǎo)期變化烘烤時(shí)間/h剩余抗氧劑含量%氧化誘導(dǎo)期/min胺類抗氧劑酚類抗氧劑010010070.3880.579.950.91672.476.145.62466.973.041.14842.122.029.87由表3可知，隨著潤滑脂產(chǎn)品A烘烤時(shí)間的延長，樣品中的抗氧劑含量逐漸減少，氧化誘導(dǎo)期的縮短也驗(yàn)證了這一趨勢。實(shí)驗(yàn)表明利用上述方法得到抗氧劑相對(duì)含量數(shù)據(jù)，能有效地反映抗氧劑含量的變化，對(duì)實(shí)時(shí)跟蹤潤滑脂的使用狀態(tài)，推斷其剩余使用壽命，及時(shí)更換潤滑脂，減少設(shè)備停機(jī)具有重要參考價(jià)值和指導(dǎo)作

24、用。4. 結(jié)論根據(jù)線性伏安法的原理，通過Ruler CE520抗氧劑含量測試儀，對(duì)鋰基潤滑脂進(jìn)行了分析，繪制標(biāo)準(zhǔn)曲線，并結(jié)合壓力差示掃描量熱儀測定樣品的氧化誘導(dǎo)期的數(shù)據(jù)可以得到以下結(jié)論：（1）胺類抗氧劑和酚類抗氧劑的峰面積與其加入量成正比例線性相關(guān)，通過線性歸一化法的得到的回歸方程可靠性較高。（2）Ruler CE520抗氧劑含量測試儀可以同時(shí)、快速、比較準(zhǔn)確的測量得到胺類抗氧劑和酚類抗氧劑的含量。（3）Ruler CE520采用的線性伏安法能夠?qū)崟r(shí)監(jiān)測潤滑脂中抗氧劑含量的變化，對(duì)于潤滑脂的開發(fā)者和使用者提供了一種有效的分析方法。綜上所述，本文詳細(xì)的介紹了一種潤滑脂抗氧劑含量的測定方法，為以后

25、潤滑脂相關(guān)分析技術(shù)提供了參考數(shù)據(jù)，由于時(shí)間有限，本實(shí)驗(yàn)只提供了鋰基潤滑脂中胺類和酚類抗氧劑的分析技術(shù)，筆者建議在以后的工作中此類分析方法可以拓展到其他種類稠化劑的潤滑脂及其他種類的抗氧劑的分析任務(wù)中。參考文獻(xiàn)1 朱廷彬. 潤滑脂技術(shù)大全M. 中國石化出版社, 2005.2 夏延秋, 張新敏, 劉維民, 等.潤滑油的抗氧化性能和分析檢測技術(shù)J. 潤滑與密封, 2004, 3: 25-28.3 Kauffman R E. Development of Remain Useful Life of a Lubricant Evaluation Technique 3 Cyclic Voltammetr

26、ic Method J. Lubrication Engineering, 1999, 45(3): 709-716.4 Kauffman R E, Rhine W E. Assessment of a Remaining Lubricant Life J.2003，27：98-101.5 王德巖,黃毅,常明華. 一種測定潤滑油抗氧劑的手段伏安法J. 潤滑油, 2005, 20(3): 49-51.6 史永剛, 王德巖, 馬彥. 潤滑油抗氧劑含量的循環(huán)伏安法測定J. 1986 - DTIC Document.7 王德巖, 單慧軍. 潤滑脂剩余使用壽命的評(píng)定技術(shù)J. 合成潤滑材料, 2005,

27、32(1): 22-24.compelling." Although the "five water treatment" a lot, work very hard, but the flood of scientific enough, before the treatment and water quality improvement after the treatment effect is not obvious, county-wide focus on river still largely inferior five water, swimming

28、 the River could not be found. Five is "three to split" task still lies ahead. Notice of stock there, new construction did not receive timely treatment every year (such as ancestral hall as unauthorised repeated), contrary to the created work is very different from the provincial and munic

29、ipal standards. Meanwhile, when implementation is not in place, generally only focus on illegal construction demolished, failing that split that is clear, combined demolition, insufficient attention to reconstruction of old residential areas, urban villages, shanty towns and promote poor. To solve t

30、hese problems, we must enhance the sense of responsibility and urgency, insist on problem-oriented, to take strong measures, efforts to make up the "three agriculture" and "five water treatment", "three to split a" short Board, construction of comprehensive safeguards,

31、"South Gate of XX beautiful" goal of realizing. II, and precision Shi policy, and manpower playing good "three agricultural" work protracted "three agricultural" work is do economic social development the work of based, county levels the sector to according to "bas

32、ed agricultural, and and manpower rural, and development farmers" of requirements, insisted agricultural rural based status not shake, insisted huinong kulak policy not weakened, insisted reform innovation test not stop, efforts created new era "three agricultural" work new situation.

33、 (A) to make agriculture more. To establish the concept of agriculture around the people demand, and comprehensively promote the supply side of agriculture structural reform, strive to enhance the quality and efficiency of agriculture and competitiveness. Focus is on doing the four articles. One is the s