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      泰州科德橡膠機械-密煉機:膠制品耐寒性原理及通用解決辦法概述

      發布時間:2019-08-22 10:45:00 點擊:    關鍵詞:密煉機,捏煉機,開煉機,橡膠機械

      泰州科德橡膠機械-密煉機開煉機捏煉機廠家2019年8月22日訊  橡膠的耐寒性,即在規定的低溫下保持彈性和正常工作的能力。硫化橡膠在低溫下,由于松弛過程急劇減慢,硬度、模量和分子內摩擦增大,彈性顯著降低,致使橡膠制品的工作能力下降, 特別是在動態條件下尤為突出。

           硫化膠的耐寒性能主要取決于高聚物的兩個基本特性:玻璃化轉變和結晶。兩者都會使橡膠在低溫下喪失彈性。

           對于非結晶型(無定形)橡膠而言,隨溫度降低,橡膠分子鏈段的活動性減弱,達到玻璃化溫度( Tg)后,分子鏈段被凍結,不能進行內旋轉運動,橡膠硬化、變脆,呈類玻璃化態,喪失了橡膠特有的高彈性。因此,非結晶型橡膠的耐寒性,可用玻璃化溫度(Tg)來表征。實際上,即使在高于玻璃化溫度的一定范圍內, 橡膠也會發生玻璃化轉變過程,使橡膠喪失彈性體的特征。這一范圍的上限稱為脆性溫度( Tb),也即硫化膠只有在高于脆性溫度時才有使用價值。因此工業上常以脆性溫度作為橡膠制品耐寒性的指標, 但是脆性溫度不能反映結晶性橡膠的耐寒性。

      一般情況下,經硫化后的橡膠所擁有的彈性與溫度間的關系圖如下:

      密煉機,開煉機,捏煉機,橡膠機械

            從上圖得知,經硫化后的橡膠在室溫附近很大的溫度區域內都擁有彈性,隨著溫度下降,微粒的布朗運動減弱,橡膠會因內部粘性的增加而呈現出皮革狀。當溫度進一步降低微粒的布朗運動完全停止,橡膠就會產生凍結現象,既進入脆化玻璃狀區域。這就是結晶性橡膠的結晶現象。這種現象表明:通過將橡膠置于適當的溫度下,橡膠內部的不規則分子結構中的一部分將會出現重新排列,其結果造成模量增加,永久變形擴大,并且隨時間的延長橡膠的彈性也慢慢喪失。

            從以上橡膠的分子運動規律可知:要使橡膠具有良好的耐寒性必須使其分子間的凝集能量相對得小,熔融熵較大,也就是要求分子間的運動相對地容易而且結晶性低。

         耐寒配方考慮:

        一、生膠品種的選擇;

       二、耐寒橡膠的軟化體系;

       三、硫化體系的選擇;

      3.1交 聯密度對硫化溫度 Tg的影響;

      3.2交聯密度對耐寒系數的影響;

      3.3交聯鍵類型對耐寒性的影響

       四、填充體系的選擇

          填充劑對橡膠耐寒性的影響, 取決于填充劑和橡膠相互作用后所形成的結構。活性炭黑粒子和橡膠分子間會形成不同的物理吸附和牢固的化學吸附鍵, 會在炭黑粒子表面形成生膠的吸附層(界面層)。該界面層的性能與玻璃態生膠的性能十分接近, 一般被吸附生膠的玻璃化溫度 Tg上升。填充劑的加入會阻礙鏈段構型的改變, 因此,不能指望加入填充劑來改善橡膠的耐寒性

            一般情況下,在主鏈上有雙鍵或醚鍵的橡膠的耐寒性較好,但雖有雙鍵且在側鍵上同時又擁有極性基的橡膠( NBR、CR 等),或主分子鏈雖為單鍵但側鍵上同時有極性鍵的橡膠(氯磺化聚乙烯、丙稀橡膠、氟橡膠等)的耐寒性較差。結晶性橡膠在分子結構上具有規則性,特別是反式結構更為顯著,例如:古塔膠( GUTTA PERCHA )即使在室溫下也表現為結晶固體, CR 的分子結構中反式結構也占大部分,相對于它們,脆化溫度低的 BR、NR 也有規則性的順位結構, 所以其結晶速度不如擁有反式結構的橡膠那樣快, 特別是擁有順位結構多的 BR 結晶速度也很快。硅橡膠既有耐熱性也有良好的耐寒性,這是因為其分子結構的主鏈上為 -Si-O-Si- ,而與其它橡膠的主鏈( -C-C-C-)完全不同。

           因此提高橡膠耐寒性也可采用增加橡膠分子間的架橋密度的方法。提高架橋密度橡膠的耐低溫效果當然會提高但并非十分顯著,相反橡膠的結晶速度卻會顯著下降。所以,相對于二烯烴系橡膠也可適當多加點硫磺(不可超過 5phr),作為硫化促進劑, MBT 的性能最優, CBS 次之。采用過氧化物架橋的橡膠在低溫條件下具有優異的耐彎曲性,但與硫磺硫化的橡膠相比其結晶速度似乎要快一些。

            當在橡膠配方中添加了作為填充劑的高補強碳黑后,普遍認為在其周圍會形成一種稠密的分子結構,表現為準玻璃狀態。所以將此類橡膠置于低溫狀態時,其分子運動會受到束縛,表現出較高的分子模量因此其耐低溫效果會變弱。另外,由于其周圍的橡膠分子易獲得穩定規則的結構,從而使得結晶速度加快。在這點上白色的填充劑由于與橡膠的凝結量及結合力都要小,會出現因拉伸變形而造成橡膠與填充劑脫離,從而可減少遭受象前者那樣不良影響的危險。

           在選擇增塑劑上,必須考慮:

      ①相溶性好;

      ②揮發少;

      ③具有優良的低溫柔軟性;

      ④不易被抽提這四個條件。

            現在常用的增塑劑可分為溶劑型和非溶劑型兩種,溶劑型增塑劑與橡膠的相容性特別好分散到橡膠中間后具有很強的親和力能把橡膠間的物理網線理開,而非溶劑型的相容性雖然差一點但摻入到橡膠內后可擴大其分子間的間隔,起到使分子運動變得容易的作用。

           一般來說,對于 NR、SBR、BR 等橡膠采用石油系碳氫類溶劑型增塑劑擴提高其相容性;但是對 NBR 和 CR 等橡膠來說采用 DBP、TCP 等增塑劑其的相容性會更好。TP-95、DOS、DOA 等增塑劑對改善低溫性也不錯,但在配方中前者的使用量不可超過 10phr,后者不可超過 20phr,不然會在橡膠的表面析出, 所以建議在使用時倂用少量相溶性好的 DBP、DOP等增塑劑效果會更好。

      總結:

      ( 1)從生膠品種的選擇上耐寒橡膠一般主鏈含有雙鍵和醚鍵。

      (2)硫化體系的選擇在滿足使用條件情況下應選擇交聯密度小,用硫磺硫作為硫化劑劑,這樣形成牢固度較小、長度較大的多硫鍵,從而提高橡膠的耐寒性能。

      (3)增塑劑的選擇遵循相似相溶的原則:既極性橡膠選用與其極性相近、溶解度參數相近的塑劑。非極性橡膠選擇石油系碳氫化合物作為軟化劑。

      (4)填充劑對玻璃化溫度 Tg 的影響不大,但在高于 Tg 的溫度時,還是有一定影響的。


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