磁控濺射法制備防水透濕織物

1、第19卷第4期高分子材料科學(xué)與工程V o l.19,N o.42003年7月POL Y M ER M A T ER I AL S SC IEN CE AND EN G I N EER I N G Jul.2003磁控濺射法制備防水透濕織物孫銀潔,馬林,齊宏進(jìn)(青島大學(xué)化工系,山東青島266071摘要:利用磁控濺射法制備了防水透濕織物。主要研究了功率、靶距、工作壓力和沉積時(shí)間四個(gè)工藝參數(shù)對織物應(yīng)用性能的影響。結(jié)果表明這四種參數(shù)對PET基防水透濕織物的拒水性能變化規(guī)律和改變程度各有不同,但對織物透氣性,透濕性影響不大,基本上保持了原有織物的透氣性及透濕性。關(guān)鍵詞:磁控濺射;防水織物;透氣性;透濕性

2、;聚四氟乙烯;聚對苯二甲酸乙二酯中圖分類號:O646.8文獻(xiàn)標(biāo)識碼:A文章編號:100027555(20030420188204近年來,我們采用離子束濺射技術(shù)使織物在其表面生成了一層含氟高分子拒水膜1,2。由于膜僅附著于纖維表面,故織物保存了原有的孔隙及透氣、透濕性5;因?yàn)R射能量大,足以使PT FE靶斷裂成以C2F4為主的小基團(tuán)3,4,進(jìn)而與織物表面基團(tuán)反應(yīng),聚合成膜,故牢度好;且膜薄透明、柔韌,使織物保持了原有的風(fēng)格、手感和顏色,克服了傳統(tǒng)防水透濕織物加工復(fù)雜,耐水壓低,附著牢度差,柔軟性差,有機(jī)溶劑回收費(fèi)用高且易造成環(huán)境污染及成本高等致命弱點(diǎn)?？紤]到其簡單的一步法工藝及連續(xù)化加工的應(yīng)用前景

3、,與傳統(tǒng)方法相比,具有明顯的特點(diǎn)和優(yōu)勢。這是一種新理念的防水透濕織物,在學(xué)術(shù)上及應(yīng)用方面都具有重要意義。最近我們利用磁控濺射技術(shù),以聚四氟乙烯等物質(zhì)作靶材,制備了一系列防水透濕織物。本文對其應(yīng)用性能進(jìn)行了研究。1實(shí)驗(yàn)部分1.1實(shí)驗(yàn)材料PET織物:20c m×20c m,30塊,市售,前處理及具體過程見文獻(xiàn)5。1.2實(shí)驗(yàn)工藝條件從碳氟膜的制備研究來看,對于一定的濺射設(shè)備,影響膜性質(zhì)的因素主要有功率、時(shí)間、壓力和基底與靶之的間距離,因此選取四種不同工藝參數(shù)來制備防水透濕織物,具體工藝參數(shù)見T ab.1。Tab.1D ischarge condition sN um ber Pow er(

4、WP ressure(PaT i m e(m inD istance(mm 12005×10-11207023005×10-11207034005×10-11207045005×10-11207056005×10-11207063001×10-11207073003×10-11207083005×10-11207093008×10-1120701030010×10-112070113005×#215;10-16070133005×10-19070

5、143005×10-112070153005×10-115070163005×10-112050173005×10-112060183005×10-11207070193005×10-112080203005×10-1120901.3拒水性能的研究利用承德試驗(yàn)機(jī)廠生產(chǎn)的JY282型靜態(tài)接觸角測定儀。試驗(yàn)條件:溫度20.0,濕度65%。1.4透氣性能的測試收稿日期:2002209217;修訂日期:2003201218基金項(xiàng)目:國家自然科學(xué)基金(50,173013和山東省自然科學(xué)基金(Y99F04資助項(xiàng)目作者簡介:孫銀潔(197

6、5-,女,碩士生.聯(lián)系人:齊宏進(jìn).利用日本KA TO T ECH 公司生產(chǎn)的KES 2F 82A P 型透氣儀進(jìn)行測定。1.5透濕性能的測試采用日本KESP 2TL II 型精密熱物性測試儀進(jìn)行測試。測試條件:溫度19.520,濕度66%67% 。F ig .1Relation between power and con tact an -gle (F ig .2Relation between pressure and con tactangle (F ig .3Relation between ti m e and con tact angle(2結(jié)果與討論2.1拒水性能從F ig .1F

7、 ig .4可以看出,除有一條件下的織物接觸角為82.5°,其它的接觸角均大于90°,表現(xiàn)出良好的拒水性能, 但各工藝條件對拒水性能影響不一。F ig .4Relation between distance and con tactangle (1功率對接觸角的影響最大。當(dāng)功率從200W 變化到600W 時(shí),接觸角從137.5°減小到105.1°。由前面XPS 的研究2可知,這是由于功率的增大導(dǎo)致氟碳比的減小,氟碳比的減小是碳氟膜表面結(jié)構(gòu)中富氟的-CF 3和-CF 2-的數(shù)量的減少。因?yàn)樵跒R射時(shí),靶材首先被入射的氬離子破壞成CF x 類型碎片,入射離子的

8、能量不同使得CF x 類型碎片分布也不相同;同時(shí),靶材仍有可能局部受熱產(chǎn)生少量的碎片離子,特別是低分子量離子碎片增多,同時(shí),碎片離子在等離子區(qū)域會(huì)產(chǎn)生各種各樣的自由基、正離子、負(fù)離子等活性離子。功率的增大使得各種基團(tuán)碎片產(chǎn)生碰撞的幾率增大,最終形成的碳氟膜中-CF 3、-CF 2-、-CF -、-C -CF -和-C -也呈現(xiàn)復(fù)雜變化。功率增大,所需能量高的碳的問題增加。而在提高拒水性上,各種含氟基團(tuán)排列順序?yàn)镃F 3>CF 2>CF ,因?yàn)榉窃魉曰鶊F(tuán),含氟越少,拒水性越差。(2壓力增加有利于提高拒水性能。這是因?yàn)閴毫υ黾?轟擊靶材的離子增多,同時(shí)對基底的轟擊也增強(qiáng),使-C -

9、類型的比例減小。與功率的影響相比,增加幅度不是太大,從117.4°到138.8°,這與XPS 2研究中壓力對提高氟碳比的程度不大的結(jié)果是一致的。(3時(shí)間從60m in 增加到150m in ,除11號樣品,其它的拒水性能基本變化不大,時(shí)間主要影響成膜厚度,而不是組成。對11號樣品,拒水性能差可能是由于時(shí)間短,碳氟膜還未能覆蓋基底所造成的。981第4期孫銀潔等:磁控濺射法制備防水透濕織物(4靶距對拒水性能影響較為復(fù)雜。在60 mm80mm之間拒水性能較好,而靶距過小或過大時(shí)拒水性差,這說明靶距過近或過遠(yuǎn)對成膜不利,60mm到80mm是合適的靶距,其防水透濕織物的拒水性能最佳。

10、2.2透氣性能織物的透氣性決定于織物的經(jīng)緯紗線間以及纖維間空隙的數(shù)量與大小,亦即與經(jīng)緯密度、經(jīng)緯紗線特?cái)?shù)、紗線捻度等因素有關(guān),此外還與纖維性質(zhì)、織物厚度、體積、質(zhì)量等因素有關(guān)6。對于經(jīng)濺射處理的織物的透氣性不僅與以上因素有關(guān),而且還與沉積在纖和靶距的透氣性數(shù)據(jù)的不規(guī)律性也有關(guān)。由于我們選用的是同一組織結(jié)構(gòu)的織物,在研究透氣性時(shí)可忽略織物本身的影響。Tab.2Gas per m eability of PETs at differen tpowers before and af ter sputter i ng(kPa s mN um ber12345Befo re0.02290.02290.0

11、2290.02290.0229A fter0.01760.01900.01950.01990.0204Tab.3Gas per m eability of PETs at differen t pres-sures before and af ter sputter i ng(kPa smN um ber678910Befo re0.02290.02290.02290.02290.0229A fter0.02090.02070.01900.01970.0199Tab.4Gas per m eability of PETs at differen t ti m e before and af t

12、er sputter i ng(kPa s mN um ber1112131415Befo re0.02290.02290.02290.02290.0229A fter0.02170.02030.01900.01900.0184Tab.5Gas per m eability of PETs at differen t dis-t ance before and af ter sputter i ng(kPa smN um ber1617181920Befo re0.02290.02290.02290.02290.0229A fter0.02260.01870.01900.01940.0184從

13、T ab.2看出,功率增加,透氣性略有上升,盡管沉積速率的研究表明碳氟膜厚度隨功率增加而增加,但織物在濺射過程中經(jīng)歷了離子轟擊、沉積、刻蝕等復(fù)雜的變化,使得纖維變形,纖維與纖維間的孔隙擴(kuò)大,并超過了厚度的增加,有利于透氣性的改善。T ab.2、T ab.3、T ab.4、T ab.5表明壓力、時(shí)間和靶距對透氣性的影響更為復(fù)雜,從影響幅度看,功率和靶距影響較大,時(shí)間和壓力影響較小?？偟膩碚f,濺射后織物的透氣性與原織物相比變化不大,基本上不影響織物的舒適性。Tab.6M o isture-per m eability of PETs at dif-feren t powers before and

14、 af ter sput-ter i ng(W (m2 KN um ber12345 Befo re1.4601.4601.4601.4601.460A fter1.4331.4331.4331.4161.365 Tab.7M o isture-per m eability of PETs at differen t pressures before and af ter sputter i ng(W(m2 KN um ber678910 Befo re1.4601.4601.4601.4601.460A fter1.3781.4401.4331.4601.416 Tab.8M o istur

15、e-per m eability of PETs at differen t ti m e before and af ter sputter i ng(W (m2KN um ber1112131415 Befo re1.4601.4601.4601.4601.460A fter1.4361.3851.4161.4331.460Tab.9M o isture-per m eability of PETs at differen t dist ance before and af ter sputter i ng(W(m2 KN um ber1617181920 Befo re1.4601.46

16、01.4601.4601.460A fter1.4731.4661.4331.4401.4092.3透濕性能從T ab.6,T ab.7,T ab.8,T ab.9中數(shù)據(jù)可以看出,處理后織物的透濕性隨工藝條件變化不大,因此可以得出結(jié)論:在所選定工藝條件范圍內(nèi),PET基底上沉積碳氟膜不影響織物原有的透濕性,這一點(diǎn)對保持防水透濕織物的舒適性是非常重要的。3結(jié)論(1功率、壓力、時(shí)間和靶距對PET基防水透濕織物的拒水性能的影響規(guī)律和影響程度不同。拒水性隨功率的增加而減小,影響幅度最大;壓力增加使拒水性增加,但幅度不大;在一定時(shí)間之后拒水性變化不大;靶距的影響較為復(fù)雜。(2濺射后的織物透氣性、透濕性變化

17、不091高分子材料科學(xué)與工程2003年大,基本上保持了原有的透氣性。參考文獻(xiàn):1Q i H J ,Sui K Y ,Fu Y B ,et a l .AA TCC ,Chalo tter ,U .S .A .,1999:524.2Q i H J ,Fu Y B ,Sui K Y ,et a l .Second A sian 2Euro 2pean Internati onal Conference on P las m a Surface Engi 2neering ,Beijing ,Ch ina ,1999:131.3H ishm eh G A ,Barr T L ,Sk lyarov A

18、.J .V ac .Sci .T echno l .,1996,A 14(3,M ay June :13301338.4M arechal N ,Pauleau Y .J .V ac .Sci .T echno l .,1992,A 10(3,M ay June :477483.5王東(W AN G Dong ,劉萍(L I U P ing ,齊宏進(jìn)(Q I Hong 2jin .青島大學(xué)學(xué)報(bào)(Journal of Q ingdao U niver 2sity ,1999,14(4:13.6趙書經(jīng)(ZHAO Shu 2jing 主編.紡織材料實(shí)驗(yàn)教程(T extile M aterial Ex

19、peri m ent T uto rial .北京:中國紡織出版社(Beijing :Ch inese T extile P ress ,1994:436.STUDY OF D ISCHARGE PARAM ETERS ON APPL IED PROPERT IES OF FL UOROCARB ON COAT INGS D EPOSITEDON PET FABR I CS B Y M AGNETRON SPUTTER INGSUN Y in 2jie ,M A L in ,Q I Hong 2jin(D ep .of Che m .E ng in .,Q ing d ao U n ivers

20、ity ,Q ing d ao 266071,Ch ina ABSTRACT :W aterp roof and m o istu re 2p er m eab le fab rics w ere p repared by m agnetron sp u ttering po lytetrafluo roethylene (PT FE target on to po lyethylene tereph thalate (PET sub strate .Effect of discharge p aram eters (pow er ,p ressu re ,ti m e ,distance o

21、n app lied p roperties of fluo rocarbon coatings depo sited on PET fab rics w as studied .T he w ater con tact angle of the w aterp roof b reath 2ab le fab ric w as found to decrease rem arkab ly w ith pow er bu t to rise w ith p ressu re due to the changes in the coating com po siti on .T he depo s

22、iti on ti m e m ain ly affects coating th ickness o ther than com po siti on .T he m o istu re per m eab ility of these coated fab rics is near that of the uncoated fab rics since on ly the fiber su rface has been individually covered w ith the coated grain s w h ile the fab rics still rem ain o rig

23、inal num erou s po res .T he T SD has been cho sen to be 60mm ,at w h ich has good hydrop hob icity and gas 2m o istu re p er m eab ility of coatings .It p roved to be feasib le that p reparing w aterp roof and m o istu re 2p er m eab le fab rics by m ean s of m agnetron spu ttering .Keywords :m agn

24、etron spu ttering ;w aterp roof fab rics ;gas per m eab ility ;m o istu re p er m eab ility ;PT FE ;PET(上接第187頁。continued from p .187PREPARAT I ON AND STUDY ON PROPERT IESOF THE PPy MM T COM POSITESZHAO J in 2ling ,W AN G L i 2x in ,R EN L i ,W U Chun 2ru i ,SON G Fang(Institu te of P olym er S cience and E ng neering ,H ebei U n iversityof T echnology ,T ian J in 300130,Ch ina ABSTRACT :Po lyp yrro le M on tm o rillon ite (PPy MM T com po sites have been p repared by chem 2ical po lym erizati on of