Seminar jumislari

1.1.8-su`wret. Shi′nji′rli′ molekula ushlari′ni′n` bir-birinen ha`r tu`rli arali′qlarda (h) boli′w itimalli′g`i′.

Yekinshi sheklengen, bir dana itimalli′qqa iye konformatsion awhalg`a shi′nji′r ushlari′ wortasi′ndag`i′ arali′q yen` u`lken ma`niske iye bolg`anda, yag`ni′y h shi′nji′rdi′n` kontur uzi′nli′g`i′ L ge jaqi′nlasqanda yerisiledi. Bunday halda makromolekulani′n` konformatsiyasi′ qatti′ tayaq ta`rizde boladi′ ha`m shi′nji′r ko`rinisi maksimal` sozi′lg`an, si′rti′ gedir-budi′r hali′nda boladi′.

Bar boli′w itimalli′g`i′ yen` u`lken bolg`an konformatsiya bul makromolekulani′n` statistikali′q klubok hali′ boli′p, ol ha`mme waqi′t wo`zinin` formasi′n ha`m wo`lshemlerin wo`zgertirip turadi′. Bug`an sebep, konformatsiyani′n` tu`rlishe wo`zgeriwinin` itimalli′g`i′ni′n` u`lkenliginde.
Stereoregulyar polimerlerde qaptal radikallardi′n` aktiv ta`sirlesiwi makromolekula konformatsion hali′ni′n` itimalli′g`i′ h ma`nisi menen bahalawdi′ qi′yi′nlasti′radi′. Bul hal spiral` ta`rizli konformatsiyag`a iye bolg`an polimerlerge, sonday-aq ishki molekulyar vodorod baylani′si′n hasi′l yetetug`i′n joqari′ molekulyar birikpelerge, atap aytqanda polipropilenler, poliamidler, belki h.t.b. tiyisli. Bulardi′ esapqa ali′p, konformatsiyali′q hallardi′ esaplaw ushi′n shi′nji′r ushlari′ arasi′ndag`i′ arali′qti′, yag`ni′y h di′n` worni′na ioni′n` <h<sup>2</sup>><sup>1/2</sup> wortasha kvadratli′q ma`nisinen paydalang`an qolay ha`m wol to`mendegishe tabi′ladi′:


(1.1.6.).

Demek, shi′nji′r ushlari′ wortasi′ndag`i′ arali′q wortasha kvadratli′q ma`nisi segmentler sani′ni′n` kvadrat korenine baylani′sli′ boladi′.

Ta`jiriybelerde polimer shi′nji′ri′ni′n` wo`lshemi retinde, woni′n` wortasha kvadratli′q radius inertsiyasi′ <r²> ani′qlani′ladi′ ha`m bul parametr <sup>2</sup>><sup>1/2</sup> menen to`mendegishe baylani′sqan:


(1.1.7)

1.1.8-su`wrette keltirilgen grafiktin` maksimumi′na tuwra keletug`i′n shi′nji′rdi′n` ushlari′ ortasi′ndag`i′ arali′qti′n` yen` u`lken itimalli′g`i′ to`mendegishe ani′qlani′ladi′:

(1.1.8.).

(1.1.8) baylani′stan makromolekula uzi′nli′g`i′ni′n` (L), woni′n` ushlari′ wortasi′ndag`i′ arali′qti′n` wortasha kvadrat ma`nisine ²>^1/2 qatnasi′ arqali′ shi′nji′rdi′n` woram da`rejesin bahalaw mu`mkin, yag`ni′y

L/²>^1/2  L/AN^1/2  AN/AN^1/2  N^1/2 (1.1.9.).

Makromolekula qanshama uzi′n bolsa, wol sonshama iyiliwshen` boli′wi′ joqari′da ko`rsetilgen baylani′slarda ko`rinip tur. Bunday halda tag`i′ bir molekulyar qa`siyetti «formani′n` iyiliwshen`ligin» yesapqa ali′w a`hmiyetli boladi′. Bul qa`siyet ag`zalardi′n` ji′lli′li′q ha`reketine baylani′sli′ yemes. Wol makromolekulani′n` u`lken uzi′nli′qqa ha`m shekli anizotropiya formasi′na iye bolg`anli′g`i′ sebepli ju`zege keledi, ha`mde geometriyali′q iyiliwshen`lik dep te ataladi′.

Makromolekulani′n` uzi′nli′g`i′ 1000 nm den ko`p bolg`anda da mnokristall qali′n`li′g`i′ d_m  20 nm den aspaydi′. Bunday molekulyar u`sti du`ziliste polimer shi′nji′ri′ kristall tekisligine tiklikligin saqlap qalg`an halda, 180<sup>o</sup> ke izbe-iz ta`rizde buri′li′p, qatlam-qatlam boli′p taxlanadi′. Bunda turaqli′ ha`m turaqsi′z qatlamli′ monokristall plastinkalar hasi′l boli′wi′ mu`mkin (2.2.2- su`wret).
Wolardi′n` hasi′l boli′w protsessin qabatlang`an shi′nji′rdi′n` kristallani′wi′ (QShK) dep ayti′ladi′. Ma`selen, 12 nm qali′n`li′qtag`i′ monokristallda shama menen 100 dana uglerod atomi′ jaylasadi′ ha`m buni′n` tiykari′ndag`i′ massasi′ 10⁵ bolg`an makromolekula 70 yesege qabatlanadi′.
Plastinkani′n` si′rti′nan woni′n` ishine makromolekula qayti′wi′ birdey arali′q ha`m ta`rtipte bolsa, wonda joqari′ da`rejedegi QShK a`melge asadi′. Eger makromolekulani′n` qayti′wi′ ha`r tu`degi arali′qta ha`m ta`rtipsiz bolsa, wonda ta`rtipsiz QShK na`tiyjesinde monokristall plastinka ju`zinde si′rtqi′ qabi′q payda boladi′. Makromolekula ha`mme waqi′t bir plastinkani′n` ishinde bolmastan, woni′n` si′rti′na shi′g`i′p basqa plastinkalardi′n` qurami′na kiriwi mu`mkin. Bunday hallarda plastinka kristallit yesaplani′ladi′. Plastinkalardi′ tutasti′ri′p turatug`i′n makromolekula bo`legi wo`tiwshi shi′nji′r delinedi. Wo`tiwshi shi′nji′r bo`legi amorf du`ziliske iye boladi′ (2.2.2, a-su`wret).



2.2.2-su`wret. Qatlamli′ shi′nji′r kristall tipindegi plastinka monokristallardi′n` ko`rinisi.
a – turaqli′ qatlamli′ (tochkalar menen shi′nji′rdi′n` bu`klengen bo`legi ko`rsetilgen); b – turaqli′ emes qatlamli′ (plastinka si′rti′nda shi′nji′rdi′n` ushlari′ (1) ha`m bo`leklerinin` (2) si′rtqi′ ko`rinisi); s – shi′nji′rdi′n` bag`dari′; d_m - monokristall qali′n`li′g`i′.