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Flynn-Wall-Ozawa法求得其反應(yīng)活化能。結(jié)果顯示，耐熱阻燃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，炭化殘重也有所增加。同時其活化能(E、)隨失重率(a)變化較復(fù)雜，a在0.2時耐熱阻燃ABS的E。相對較低，僅155.5 kJ/mol,比純ABS的低約50 kJ/mol，在a大于0.3以后其E。均比純ABS的大，最大約243.6 kJ/mol，比純ABS的E。大52 kJ/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(2015)01-06-04Analysis of thermal degradation behavior of heat resistant andfame retardant ABS resin for high temperature VRLA batteryDANG Zhi-min, LIU Tao-song(Narada Power Source Co., Ltd, Hangzhou Zhejiang 311305, China)Abstract: 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-Wal-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 (E) changes with weight loss (a) were more complex, when a is 0.2, E。of the heatresistant and flame retardant ABS was 155 kJ/mol, and 50 k.J/mol lower than that of pure ABS, when ais greater than 0.3, E。of heat resistant and fame retardant ABS was 243.6 kJ/mol, and greater than thatof pure ABS about 52 kJ/mol.Key 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)營商的移動通信基站總數(shù)已經(jīng)超過100收稿日期: 2014-08-05萬個，無人基站的數(shù)量也8益增加。目前基站大都采用VRLA電池且多建在野外高山、民房制高點(diǎn)等06 2015 No.1 Vo1.52蓄電池試驗(yàn)研究Chinese LABAT Manwww.batterychn.com高溫高濕地區(qū)。據(jù)統(tǒng)計.全年基站內(nèi)空調(diào)耗電超過。 2結(jié)果 與分析70億度V REA高料晶電4池.，用摩通熱展阻燃AABS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 °C提高圖1是耐熱阻燃ABS和普通ABS在不同升溫到35 °C,溫度提高10°C計算，整個機(jī)房的電耗，速率下的熱重 (TG) 曲線。從圖1可見，隨著升將降低60 %~80 %，在能源日益緊張舶晶蟄下溫速拳的提高，純ARS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，”實(shí)現(xiàn)書能減罪的效四晶線彤狀均先變化，但都向高溫方向偏移,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尤為必攘要但R涌電池酌壽命極大砸依賴其牲癱溫V鵑熱曄解曲線臾有血鄰隔幾A在S3萬著00PC,而溫度，當(dāng)洫搜增赫晦熱駱逸被糇的曾蝕箱失承,采電Fly耐熱阻燃)xBS的熱峰解芬兩率嬌段能一爺是茌280池鼓脹示容董恭降燃壽鄙也髓馨縮短降魯通庵隱先，但熱駱蟹迷率獎重率練穩(wěn)略溫鹿蒔周能是配券華阻燃法長期鷸雯嵩瘟所嵩溫電鬮技某盾選能里)喃嵩盂率(a瓣的然解，,別特怔溫搜范圍整38BS物F°C,電池技架昔婪就是研發(fā)箭魚阻燃ABS材料ABS的低約5尖重率為8存%大該溫度范菌葛純AB5的熱降解特本受針對新柵復(fù)的耐然阻燃AB5純梨用熱重大征溫度相寄右它是ABS對應(yīng)的熱降解溫度。經(jīng)過法比較糞彎擼通RBS黽沲槽材斡熱降解過程的差高湖06E篙瘟后池純ABS炭化殘重接近于2%，而耐異，并隸剛客裘屋動分學(xué)參數(shù),從帝韓橋保酌熱熱陪熟 編號炭化幾量約8965)01-06-04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(T&hal養(yǎng)掃撣艷清mRre積著蟄命tion速瓷曲線v i肝r-OTF倦線t否理看性n純ARY在高析法(9TAm reta李齊糴縶R傳戀備呼8r h渴下鶴先需遺青盟昂毖聲得賞ASBert縣經(jīng)歷動力學(xué)參數(shù)的差異。的溫受范圍窄，在10 C/mtn并溫速率下432 °C時DANG Zhi-min對應(yīng)最太先惠速率達(dá)16.7 %，但耐熱阻燃ABS經(jīng)1實(shí)驗(yàn)(Narada Power Source Co, Lld, Hd歷的濕麼蔣園鷹814t5, °En對應(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，另采用梨號c! GA4009e的蟄重分?jǐn)鄡xhea車氮氛nt and癡面基鼂太蟄降解速離對座的峰混囪高溻贏向偏氣氛下vR通氖流最為0dmt/rm inBs升溫速案分別ther務(wù)1村料熱穩(wěn)扇性確實(shí)有所提高tu俱同時也麗見耐為10、t4Om3@gn和AReEy/mio-I樣晶質(zhì)鼂約h1Qrn0tivation墊颶燃ARS蟄隆解開始的漏度降低l1材料熱降解溫度范園50or6QOffis下帖較耐熱阻物tAB6o與普通at th提前ia有隅論認(rèn)為這再最阻燃劑德材料提前分解成ABS電池槽林料的熱隆解行為差品da并利B FluIped, m巍aw從面隔熱隔氧dat陽止材料遞rea步熱份解租燃燒WallOaaya熱降解反庇動丸學(xué)方程求解不同先重事resid的擬聚相作展機(jī)理的體現(xiàn)A t也表朋所用的限燃體下的活化能ati該方法的優(yōu)點(diǎn)晶不露要知道詳細(xì)的反(a)系而是通過提高材料分解溫度而主要通誠減緩氧化應(yīng)過程besistant and flame retardant ABS was 155 kJ/mol, a速率達(dá)到阻燃的品的ilothat of pure ABS, when ais greater than 0.3, E。of heat resistant and flame retardant ABS was 243.6 kJ/mol, and greater than thatof pure ABS about 52 kJ/mobKey words; ABS resin; flame retardant; heat resistant; degradation; activation energy; high temperatureVRLAbattery器04-∞4◎前言02-隨著通信業(yè)的飛速發(fā)展及網(wǎng)絡(luò)覆蓋的全面性,300 400500一00三大通信運(yùn)營商的移動通信基站總數(shù)已經(jīng)超過100收稿日期: 2014-08-05溫度/C萬個，無人基站的數(shù)量也日益增加。目前基站大都圖1不同升溫速率邢用C/纜電池且多建在野外高山、民房制高點(diǎn)等06 2015 No.1 Vo1.522015 No.I Vo1.52 07蓄電池| Chinese LABAT Man溫度，K; β一加熱速率。0.00lgβ=( .0.4567E). 1 1101_ AE。-2.315 (1)RF(a))-0.005由表1和表2兩種材料TG曲線讀取的不同升g 4010溫速率下失重率和溫度的相應(yīng)值，用Flynn-Wall-Ozawa方程對兩種材料分別在升溫速率β為10、-001520、30 和40。C/min,失重率即轉(zhuǎn)化率a為0.1~00200.8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0.8 (見表1和表2)，lgβ 對1/T呈良好的線性關(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 10 °C/min下的DTG曲線過式(1)中直線斜率等于(-945675),求得不同失重率下采用Flynn-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/mol;由圖4可見，耐熱阻燃ABS的E。隨失重率A-指前因子，s; F(a)-轉(zhuǎn)化率函數(shù); T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/(°C●min'a2034斜率相關(guān)系數(shù)E/(kJ ●mol')0.1338.55350.35365.18-8.5410.9926155. 48470.2361.52 37 1 .39385 .26 390.52-8.20730.9687149.40990.3403.15 412.04421.13425.91-12.1670.9868221.49430.4422.29432.13440.74446-12.5260.9928228.0297433.77444.57453.65459.87-11.8620.998215.9419).6443.82454.1465.13470.87-11.520.9847209.716).7452.75 466.09474.7480.91-11.7030.9997213.0474.8465.35476.61 .485.22490.48-13.3810.9974243.5946表2 ABS活化能及相關(guān)系數(shù)β/(°C●min')1030.1405.33414.43422.52430.41-11.4370.9768208.205.2417.16427.84436.05444.3-11.0592013237.3423.98435.57445.63452.58-10.5590.9915192.2214.4430.81442.78452.39460.82-10.3880.9886189.1085.5436.26448.97459.72467.53-10.060.9918183.1374.6442.63455.67467.04475.77-9.68840.9889176.3726449.46463.4475.5484.02-9.45730.9914172.1655460.37472.68483.95492.27-10.5030.9872191.2021211021301351.40145150135516018s1321351.3814114 147(17)+1000K"07)=1000K"圖3經(jīng)Flynn-Wall-Ozawa法處理后的lgβ ~(1/7)X 1000圖08 2015 No.I Vo1.52