蓄電池Chinese labat manVRLA高溫電池用耐熱阻燃ABS熱降解行為分析黨志敏,劉桃松(浙江南都電源動力股份公司,浙江杭州311305)摘要:本文通過熱重法(TG-DTG)比較高溫VRLA蓄電池槽用的耐熱阻燃ABS與普通ABS電池槽材料在熱降解過程中的差異,并采用Flyn- Wall-Ozawa法求得其反應(yīng)活化能。結(jié)果顯示,耐熱阻然ABS的初始熱降解溫度降低,但熱降解速率降低且熱降解溫度范圍擴(kuò)大,炭化殘重也有所増加。同時其活化能(E)隨失重率(α)變化較復(fù)雜,α在0.2時耐熱阻燃ABS的E相對較低,僅155.5kJ/mol,比純ABS的低約50kJ/mol,在α大于0.3以后其Ea均比純ABS的大,最大約243.6kJ/mol,比純ABS的E3大52kJ/mol左右。關(guān)鍵詞:ABS;阻燃;耐熱;降解;活化能;高溫ⅤRLA蓄電池中圖分類號:TM912.1文獻(xiàn)標(biāo)識碼:B文章編號:1006-0847(201501-06-04Analysis of thermal degradation behavior of heat resistant andfame retardant ABS resin for high temperature VRLa batteryDANG Zhi-min, LIU Tao-songNarada Power Source Co, Ltd, Hangzhou Zhejiang 311305, ChinaAbstract: The differences between heat resistant and flame retardant ABS resin for high temperatureVRla battery and pure abs resin in the thermal degradation process were studied by thethermogravimetry (TG-DTG), and their activation energy was calculated with Flynn-Wall-Ozawaequation in this paper. The results showed that the initial thermal degradation temperature of theheat resistant and flame retardant ABs dropped, meanwhile the degradation rate decreased, thermaldegradation temperature range expanded and residual weight also increased. At the same time, theactivation energy(Ea)changes with weight loss(a) were more complex, when a is 0. 2, Ea of the heatasistant and flame retardant abs was 155 kJ/mol, and 50 kJ/mol lower than that of pure abs. when ais greater than 0.3, Ea of heat resistant and flame retardant ABS was 243. 6 kJ/mol, and greater than thatof pure abs about 52 kJ/molKey words: ABS resin; flame retardant; heat resistant; degradation; activation energy; high temperatureVRLa battery0前言隨著通信業(yè)的飛速發(fā)展及網(wǎng)絡(luò)覆蓋的全面性,三大通信運(yùn)營商的移動通信其站總歉口經(jīng)超過100收稿日期:2014-08-05萬個,無人基站中國煤化前基站大都采用VRLA電CNMH制高點(diǎn)等015 No. 1 Vol5蓄電池試驗研究Chinese labat manwww.batterychn.commvRA電j辮輾阻A的§熱降解行為分析站,如果把基站空調(diào)設(shè)定溫度由現(xiàn)在的25℃提高圖1是耐熱阻燃ABS和普通ABS在不同升溫到35℃,溫度提高10℃計算,整個機(jī)房的電耗率下的熱重(TG)曲線。從圖1可見,隨著升將降低60%~80%,在能源息敏箱傻份公4和耐熱阻燃ABS的熱降解為了響應(yīng)國家號召和市場發(fā)展,都向高溫方向偏移,使熱降果,提高蓄電池的使用溫度從而降低空調(diào)能耗顯得解開始的溫度和熱降解結(jié)束溫度都升高。純ABS尤為必摘要但ξR澒皰滟斬梼命檨火地依賴賁銼衤溫Ⅴ眄熱降解釁纜臾栒礎(chǔ)艭煇$艿鴝」,而溫度,幽溘增痂府熱痂柲糇的錘稱失汞采Fly耐熱燃B§酌魚窿夯兩卒渀段能-笮躉裡280池鼓脹示容鮭芐降然券也孴蟾雉降管漒黽滟佻,但苾弜蚜徳,斈獎董然溫麂酧能寔配芳啷阻燃法長期酶變嵩瘟所蒿溫電澠技棊怣笙〕喃為甏羍(α劑的,另←翱征溫粳撾睡3θ~α,電池技鏨毹是研發(fā)奣無畦燃Bs材料ABS的低約5尖重舉為8%大讀溫度范慟焉綞A的熱腳解特本毀針對新妍變的耐熱姐燃AB樂用鵝重大征煴虔相,冇它是ABS對應(yīng)的熱降解溫度。經(jīng)過法比較龔銬罾通^A⑧S黽沲槽糖料熟憐解過倒鑾高禤θ篙溘巖氿純ABS炭化殘重接近于2%,而耐異,并糶得舍殺動丹學(xué)摻數(shù),從而棘鄄熱熱盛纛炭化董約8295101.604穩(wěn)定性。目前測定反應(yīng)動力學(xué)參數(shù)的方法主要有熱圖2是以10℃C/min升溫速率為例做的熱失重重法(ha付清mFqe積aon亮曲線iFt到n什H在高動力學(xué)數(shù)〃公高整88r析法(口Ah評2沿fer只經(jīng)歷℃時DANG Zhi-min0羈大先速率達(dá)167%,但耐熱阻燃ABS經(jīng)1實驗Narada power source co,Lld,H的溻麼范賽。1#,為h應(yīng)的最大失重速率為10%/min,也就是說一方面其熱降解速率降低,另釆風(fēng)弸q'帕毳贠誕儀ea在氚ntan鼒而其最志熱隆解速燾癍的峰混應(yīng)亮溫高向偏氣氛下ⅴ氖旐為卲9d佃巴is升溻速往ther酪趑觀熱寀幃憲兩撮高u很園時也而見耐為10、tgm3g科鈿;栟員質(zhì)譟約 h19rastivation限AS陷解團(tuán)始的暈度降倆alb糨熱降解溫度范μ5ρorⅰ下較耐赭陽蠑s師譜誦ath梮前ia有颸詒認(rèn)凝而晶阻燃劑徳梳粗提前伈解成ABS電訑槽撻榖的熱鯈解衎溈羲喦da迸利腡郈ρεd,m嶶αw林邐釅熱區(qū)氤a限嶼撻粬虣α解秈橪煷waHa翛解鳳動學(xué)方程忒縐同妹重審 Resid的郝作機(jī)耦餡俠枧t表朋所用的砠燃體下的活ε能at該方法的佻畾丕霙要知道誚細(xì)的s(α)系丕是通過媞杖料氽解溫廚邐主斅通i綴氧化應(yīng)過程 resistant and flame retardant abs was155kJ/mol,a速率達(dá)到阻的的 that of pure ABS, when ais greater than 0.3, Ea of heat resistant and flame retardant ABS was 243.6 kJ/mol, and greater than thatof pure ABS about 52 kJ/molKey words; ABS resin; fame retardant; heat resistant: degradation; activation energy; high temperatureLAbatter060040前言隨著通信業(yè)的飛速發(fā)展及網(wǎng)絡(luò)覆蓋的全面性收稿日期:2014080300+960o大通信運(yùn)營商的移動信基話點(diǎn)教已經(jīng)超過100萬個,無人基中國煤化工目前基站大都圖1不同升溫速率用《E電CNMH民房制高點(diǎn)等062015No.Vol.522015NoVo152071蓄電池Chinese labat man溫度,K;B—加熱速率。00000()+()2350由表1和表2兩種材料TG曲線讀取的不同升溫速率下失重率和溫度的相應(yīng)值,用 Flynn-WallOzawa方程對兩種材料分別在升溫速率B為10、20、30和40℃C/min,失重率即轉(zhuǎn)化率a為0.1~0.8下做圖3,經(jīng)線性擬合發(fā)現(xiàn),其線性相關(guān)系數(shù)均大于08(見表1和表2),lgB對1T呈良好的溫度/℃線性關(guān)系。按表1和表2所列擬合直線的斜率,通圖2不同材料在10Cmn下的DTG曲線過式(1)中直線斜率等于(,求得不同失重率下采用Fψ nn -Wall-Ozawa法計算材料的熱降解動的活化能,并做活化能與失重率曲線如圖4所示力學(xué)參數(shù),見式(1),式中:E。活化能,kJ/mo由圖4可見,耐熱阻燃ABS的E隨失重率A—指前因子,s;F(a)一轉(zhuǎn)化率函數(shù);廠一反應(yīng)變化較復(fù)雜,失重率在0.2以下時耐熱阻燃ABS表1耐熱阻燃ABS活化能及相關(guān)系數(shù)B/℃·min)斜率相關(guān)系數(shù)E2/(kU·mo")40338.55350.3536087365.18-8.54109926155484721523713938526390.528.20730.9687149.4099403.15412.04421.1342591-12.167098682214943422.29432.134407444612.52609928228.0297433.77444.57453.6545987-11.86209982159444382454.13465.134708711.5209847209716452.7546609474.748091-11.70309997213.04740846535476.614852249048-133810.9974243.5946表2ABS活化能及相關(guān)系數(shù)B/(C·mn)10斜率相關(guān)系數(shù)E/(kJ·mo)405.3341443422.5243041-1143709768208.2050.2417.16427.8443605444.3-11.05909847201.32370.342398435.57445.63452.58-10.55909915192.22142.78452.39460.8209886189.10850.5436.26448.9745972467.5310.0609918183.137406442.63455.6746704475779.688409889176.37260744946463.4475.5484.029457309914172.165508460.37472.68483954922710.5030.9872191.20216乘2,4曾1013140145150155160165132135/s1000K中國煤化工圖3經(jīng) Flynn-Wall-Ozawa法處理后的lgB~(1/門CNMHG015 No. 1 Vol5蓄電池試驗研究Chinese labat manwww.batterychn.com的E相對較低,僅155.5kJ/mo,比純ABS低約3甕K;B-加熱速率。50kJ004567E.1AE體系在由熱重分析發(fā)現(xiàn):耐熱劑和燃劑的加入使分解銻ABS皓祩瞞搟槲料闞掣陬在氣00j通膃黦蟹蕰燄輝有加n過化與鳳應(yīng)動力學(xué)猾凘兩槲饌徳殊圃璋形助2時但失]1率皈化能和·率車顙荊作下E4040k/率的純趴見教話和桊在材炭弛前罡謝孖在0溫度/℃于隴闌塨帝辮瞇巒辭寗鏹08時,鳳增棡輯歐A儷比之怖食犁(當(dāng)破壞到稠齏樺下,鎯鄉(xiāng)5舶棘滌鎯z癲朱甄潾幬料啷瀞眷鄯拙黻誌腫擦曲線坳盥4藺遢電調(diào)腌嫠勢,慼頲倗于撚旿荘衎亻怣熏瘠κσ池所用甡鹔阻惦A胭蚋熱頵諠提髜泆重率08加是因材料樂太了—反應(yīng)變化較復(fù)雜,失重率在02以下時耐熱阻燃ABS表1耐熱阻燃ABS參佬關(guān)系數(shù)B/℃C·min")斜率相關(guān)系數(shù)E/(kJ·mo|)20耐熱惠ABS38.55350.3536087锪元俊g等熱重弸定聚合勢縶驂解反應(yīng)動力02~361523713938526390.學(xué)參數(shù)鴉辱工觀料應(yīng)用49q956):7073203403.15A85412044211342號引等2睚然PcA8s的熱降解力學(xué)[高分04·4222943213,440.740.54337744157453654595材料樣第工樓號923912306438245413465134:鵬A姐燃餓態(tài)試中教財倦重一紅外光0745275466094747480.塘技術(shù)的用[]雅程塑料痤翔4203,31(2):0.8465.354261435224906442138109942435946表2ABS活讎掣襖疊阻燃ABS的制備性能及熱降解機(jī)理研圖不同失重下的話化Cm30U太廉北大學(xué)款3E/,my140533414434225243041-114370.9768208.205(上接第5頁)02417.16427.8443605423.98435.574456-11.05909847201323710.55909915192.22145結(jié)論0.443081442.784523946082103880.9886189.108505436264489745972[便種長清,本文通過研究得03456743704密鉛酸電泄樹醒分析[肌電463.4475548492000類,914172.1655(1)采用整體鑄煣0.亞流揶亶膠封舶緗5[沖翱志剛,効玉茠健〕繳η正板棚鈣合金的異構(gòu),能夠滿足:"“,"“,"↓峙八奸中14n:115-118用戶的使用壽1·用閥控鉛酸(2)通19-124顯著提高板棚與:金13。程優(yōu)化及節(jié)(3)合廷的結(jié)合強(qiáng)度,電池制造工(4)控緯.217-227達(dá)到了最適值,。s1161s1113135,等.閥控式提高活性物質(zhì)n:19K中國煤化北京:機(jī)循環(huán)壽命明顯提高。圖3經(jīng) Flynn-Wall-Ozawa法處理后山出CNMHG08|2015No.Vol.522015 NoI Vol. 52