(一) 製品的凍結
溶液速凍時(每分鍾降溫10~50℃),晶粒保持在顯微鏡下可見的大小;相反慢凍時(1℃/分),形(xing)成(cheng)的(de)結(jie)晶(jing)肉(rou)眼(yan)可(ke)見(jian)。粗(cu)晶(jing)在(zai)升(sheng)華(hua)留(liu)下(xia)較(jiao)大(da)的(de)空(kong)隙(xi),可(ke)以(yi)提(ti)高(gao)凍(dong)幹(gan)的(de)效(xiao)率(lv),細(xi)晶(jing)在(zai)升(sheng)華(hua)後(hou)留(liu)下(xia)的(de)間(jian)隙(xi)較(jiao)小(xiao),使(shi)下(xia)層(ceng)升(sheng)華(hua)受(shou)阻(zu),速(su)成(cheng)凍(dong)的(de)成(cheng)品(pin)粒(li)子(zi)細(xi)膩(ni),外(wai)觀(guan)均(jun)勻(yun),比(bi)表(biao)麵(mian)積(ji)大(da),多(duo)孔(kong)結(jie)構(gou)好(hao),溶(rong)解(jie)速(su)度(du)快(kuai),便(bian)成(cheng)品(pin)的(de)引(yin)濕(shi)性(xing)相(xiang)對(dui)也(ye)要(yao)強(qiang)些(xie)。
藥品在凍幹機中預凍在兩種方式:一種是製品與幹燥箱同時降溫,;另一種是待幹燥箱擱板降溫至-40℃zuoyou,zaijiangzhipinfangru,qianzhexiangdangyumandong,houzhezejieyudongyumandongzhijian,yinerchangbeicaiyong,yijiangudongganxiaolvyuchanpinzhiliang。cifadequedianshizhipinruxiangshi,kongqizhongdeshuizhengqijiangxunsudiningjiezaigebanshang,erzaishenghuachuqi,ruobanshengwenjiaokuai,youyudamianjideshenghuajiangyoukenengchaoyueningjieqidezhengchangfuhe。cixianxiangzaixiajiyouweixianzhu。
zhipindedongjiechuyujingzhizhuangtai。jingyanzhengming,guolengxianxiangrongyifashengzhishizhipinwendusuiyidadaogongjingdian。danrongzhirengbujiejing,weilekefuguolengxianxiang,zhipindongjiedewenduyingdiyugongjingdianyixiayigefanwei,bingxubaochiyiduanshijian,yidaizhipinwanquandongjie。
(二) 升華的條件與速度
冰在一定溫度下的飽和蒸汽壓大於環境的水蒸氣分壓時即可開始升華;比製品溫更低的凝結器對水水蒸氣的抽吸與捕獲作用,則是維護升所必需的條件。
氣qi體ti分fen子zi在zai兩liang次ci連lian續xu碰peng撞zhuang之zhi間jian所suo走zou的de距ju離li稱cheng為wei平ping均jun自zi由you程cheng,它ta與yu壓ya力li成cheng反fan比bi。在zai常chang壓ya下xia,其qi值zhi很hen小xiao,升sheng華hua的de水shui分fen子zi很hen容rong易yi與yu氣qi體ti碰peng撞zhuang又you返fan回hui到dao蒸zheng汽qi源yuan表biao麵mian,因yin而er升sheng華hua速su度du很hen漫man。隨sui著zhe壓ya力li降jiang低di13.3Pa以下,平均自由程增大105倍,使升華速度顯著加快,飛離出來的水分子很少改變自己的方麵,從而形成了定向的蒸汽流。
真空泵在凍幹機中起著抽除永久氣體的作用,以維護升華所必需的低壓強。1g水蒸氣在常壓下為1.25L而在13.3Pa時卻膨脹為10000升,普通的真空泵在單位時間內抽除如此大量的體積是不可能的。凝結器實際上形成了專門捕集水蒸氣的真空泵。
製品與凝結的溫度通常為-25℃與-50℃。冰在該溫度下的飽和蒸汽壓分別為63.3Pa與1.1Pa,因而在升華麵與冷凝麵之間便產生了一個相當大的壓力差,如果此時係統內的不凝性氣體分壓可以忽略不計,它將促使製品升華出來的水蒸氣,以一定的流速定向地抵達凝結器表麵結成冰霜。
冰的升華熱約為2822J/克ke,如ru果guo升sheng華hua過guo程cheng不bu供gong給gei熱re量liang,那na末mo製zhi品pin隻zhi有you降jiang低di內nei能neng來lai補bu償chang升sheng華hua熱re,直zhi至zhi其qi溫wen度du與yu凝ning結jie器qi溫wen度du平ping衡heng後hou,升sheng華hua也ye就jiu停ting止zhi了le。為wei了le保bao持chi升sheng華hua與yu冷leng凝ning來lai的de溫wen度du差cha,必bi須xu對dui製zhi品pin提ti供gong足zu夠gou的de熱re量liang。
(2)升華過程
在升溫的第一階段(大量升華階段),製zhi品pin溫wen度du要yao低di於yu其qi共gong晶jing點dian一yi個ge範fan圍wei。因yin此ci擱ge板ban溫wen要yao加jia以yi控kong製zhi,若ruo製zhi品pin已yi經jing部bu分fen幹gan燥zao,但dan溫wen度du卻que超chao過guo了le其qi共gong晶jing點dian,此ci時shi將jiang發fa生sheng製zhi品pin融rong化hua現xian象xiang,而er此ci時shi融rong化hua的de液ye體ti,對dui冰bing飽bao和he,對dui溶rong質zhi卻que未wei飽bao和he,因yin而er幹gan燥zao的de溶rong質zhi將jiang迅xun速su溶rong解jie進jin去qu,最zui後hou濃nong縮suo成cheng一yi薄bo僵jiang塊kuai,外wai觀guan極ji為wei不bu良liang,溶rong解jie速su度du很hen差cha,若ruo製zhi品pin的de融rong化hua發fa生sheng在zai大da量liang升sheng華hua後hou期qi,則ze由you於yu融rong化hua的de液ye體ti數shu量liang較jiao少shao,因yin而er被bei幹gan燥zao的de孔kong性xing固gu體ti所suo吸xi收shou,造zao成cheng凍dong幹gan後hou塊kuai狀zhuang物wu有you所suo缺que損sun,加jia水shui溶rong解jie時shi仍reng能neng發fa現xian溶rong解jie速su度du較jiao慢man。
在大量升華過程,雖然擱板和製品溫度有很大懸殊,但由於板溫、ningjieqiwenduhezhenkongwendujibenbubian,yinershenghuaxirebijiaowending,zhipinwenduxiangduihengding。suizhezhipinzishangerxiacengcengganzao,bingcengshenghuadezulizhujianzengda。zhipinwenduxiangyingyehuixiaofushangsheng。zhizhiyongrouyanyibudaobingjingdecunzai。cishi90%以yi上shang的de水shui分fen已yi除chu去qu。大da量liang升sheng華hua的de過guo程cheng至zhi此ci已yi基ji本ben結jie束shu,為wei了le確que保bao整zheng箱xiang製zhi品pin大da量liang升sheng華hua完wan畢bi,板ban溫wen仍reng需xu保bao持chi一yi個ge階jie段duan後hou再zai進jin行xing第di二er階jie段duan的de升sheng溫wen。
剩sheng餘yu百bai分fen之zhi幾ji的de水shui分fen稱cheng殘can餘yu水shui分fen,它ta與yu自zi由you狀zhuang態tai的de水shui在zai物wu理li化hua學xue性xing質zhi上shang有you所suo不bu同tong,殘can餘yu水shui分fen包bao括kuo了le化hua學xue結jie合he之zhi水shui與yu物wu理li結jie合he之zhi水shui,諸zhu如ru化hua合he的de結jie晶jing水shui結jie晶jing、danbaizhitongguoqingjianjiehedeshuiyijigutibiaomianhuomaoxiguanzhongxifushuideng。youyucanyushuifenshoudaozhongyinlideshufu,qibaohezhengqiyazeshibutongchengdudejiangdi,yinerganzaosudumingxianxiajiang。suirantigaozhipinwenducujincanyushuifendeqihua,danruochaoguomoujixianwendu,shengwuhuoxingyekenengjijuxiajiang。baozhengzhipinanquandezuigaoganzaowenduyaoyoushiyanlaiqueding。tongchangwomenzaidierjieduanjiangbanwen+30℃左zuo右you,並bing保bao持chi恒heng定ding。在zai這zhe一yi階jie段duan初chu期qi,由you於yu板ban溫wen升sheng高gao,殘can餘yu水shui分fen少shao又you不bu易yi氣qi化hua,因yin此ci製zhi品pin溫wen度du上shang升sheng較jiao快kuai。但dan隨sui著zhe製zhi品pin溫wen度du與yu板ban溫wen逐zhu漸jian靠kao攏long,熱re傳chuan導dao變bian得de更geng為wei緩huan慢man,需xu要yao耐nai心xin等deng待dai相xiang當dang長chang的de一yi段duan時shi間jian,實shi踐jian經jing驗yan表biao明ming,殘can餘yu水shui分fen幹gan燥zao的de時shi間jian與yu大da量liang升sheng華hua的de時shi間jian幾ji乎hu相xiang等deng有you時shi甚shen至zhi還hai會hui超chao過guo。
(四)凍幹曲線:將擱板溫度與製品溫度隨時間的變化記錄下來,即可得到凍幹曲線。
比較典型的凍幹曲線係將擱板升溫分為兩個階段,在大量升華時擱板溫度保持較低,根據實際情況,一般可控製在-10至+10之zhi間jian。第di二er階jie段duan則ze根gen據ju製zhi品pin性xing質zhi將jiang擱ge板ban溫wen度du適shi當dang調tiao高gao,此ci法fa適shi用yong於yu其qi熔rong點dian較jiao低di的de製zhi品pin。若ruo對dui製zhi品pin的de性xing能neng尚shang不bu清qing楚chu,機ji器qi性xing能neng較jiao差cha或huo其qi工gong作zuo不bu夠gou穩wen定ding時shi,用yong此ci法fa也ye比bi較jiao穩wen妥tuo。
如ru果guo製zhi品pin共gong晶jing點dian較jiao高gao,係xi統tong的de真zhen空kong度du也ye能neng保bao持chi良liang好hao,凝ning結jie器qi的de製zhi冷leng能neng力li充chong裕yu,則ze也ye可ke采cai用yong一yi定ding的de升sheng溫wen速su度du,將jiang擱ge板ban溫wen度du升sheng高gao至zhi允yun許xu的de最zui高gao溫wen度du,直zhi至zhi凍dong幹gan結jie束shu,但dan也ye需xu保bao證zheng製zhi品pin在zai大da量liang升sheng華hua時shi的de溫wen度du不bu得de超chao過guo共gong晶jing點dian。
若製品對熱不穩定,則第二階段板溫不宜過高。為了提高第一階段的升華速度,可將拉板溫度一次升高至製品允許的最高溫度以上;待(dai)大(da)量(liang)升(sheng)華(hua)階(jie)段(duan)基(ji)本(ben)結(jie)束(shu)時(shi),再(zai)將(jiang)板(ban)溫(wen)降(jiang)至(zhi)允(yun)許(xu)的(de)最(zui)高(gao)溫(wen)度(du),這(zhe)後(hou)兩(liang)種(zhong)方(fang)式(shi)雖(sui)然(ran)使(shi)大(da)量(liang)的(de)升(sheng)華(hua)速(su)度(du)有(you)一(yi)些(xie)提(ti)高(gao),但(dan)其(qi)抗(kang)幹(gan)擾(rao)的(de)能(neng)力(li)相(xiang)應(ying)降(jiang)低(di),真(zhen)空(kong)度(du)和(he)製(zhi)冷(leng)能(neng)力(li)的(de)突(tu)然(ran)降(jiang)低(di)或(huo)停(ting)電(dian)都(dou)可(ke)能(neng)會(hui)使(shi)製(zhi)品(pin)融(rong)化(hua)。合(he)理(li)而(er)靈(ling)活(huo)地(di)掌(zhang)握(wo)第(di)一(yi)種(zhong)方(fang)式(shi),仍(reng)是(shi)目(mu)前(qian)較(jiao)常(chang)用(yong)的(de)方(fang)式(shi)。
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