121
Nematic Ordered Cellulose Templates
highly. engaged. intermolecular. hydrogen-bonded. domains. or. the. junction.
zone,. as. indicated. in. Figure 6.3a.. In. addition,. polarized. Fourier. transform.
infrared. spectroscopy. (FTIR). combined. with. the. vapor-phase. deuteration.
was.enabled.to.reveal.orientation.of.the.cellulose.main.chains.to.the.stretching.direction.in.both.the.crystalline.domains.and.the.noncrystalline.regions.
of.NOC.films..The.NOC.film.was.also.considered.to.have.both.the.oriented.
main.chains.and.the.nonoriented.OH.groups.as.the.side.chain..This.flexible.
state.of.the.OH.groups.might.further.hinder.the.oriented.crystallization.in.
the. NOC. preparation. process. and. yet. induce. the. unique. properties. in. the.
surface.of.the.NOC.film.(Higashi.and.Kondo.2012;.Kondo.2007;.Kondo.et.al..
2002,.2012)..In.Figure 6.5a,.the.CP/MAS. 13 C.NMR.spectra.for.NOC.samples,.as.
well.as.amorphous.(a.noncrystalline.state.without.any.preferred.orientation. ).
cellulose. prepared. from. cellulose-SO 2 -dimethylamine-dimethyl. sulfoxide.solution.(Isogai.and.Atalla.1991).and.CF11.cellulose.powder.(Whatman.
International.Ltd.).are.shown.in.the.range.from.50.to.80.ppm.where.chemical. shifts. at. the. C6. position. appear.. The. chemical. shift. of. CF11. appears. at.
65 ppm,.corresponding.to.tg.conformation,.indicating.that.CF11.is.a.native.
cellulose..Our.NOC.sample.exhibits.a.broader.signal.similar.to.amorphous.
cellulose.within.the.range.of.the.type.of.the.hydroxymethyl.conformation,.
gg,. which. also. supports. our. suggestion. that. NOC. is. noncrystalline. even.
though.it.is.well.ordered.
The. orientation. parameter. calculated. from. wide-angle. X-ray. diffraction. (WAXD). photographs. (Figure 6.5b). became. 0.88,. which. indicated. a.
high.degree.of.orientation..However,.the.crystallinity.did.not.significantly.
follow. the. increase. of. the. orientation. by. stretching. (Kondo. et. al.. 2001)..
Simultaneous.orientation.and.crystallization.did.not.occur.as.is.often.seen.
with.crystalline.polymers.(Ward.1997),.which.agrees.with.the.infrared.(IR).
analyses. of. deuterated. NOC. samples. based. on. the. ratio. of. the. remaining.
OH.groups.in.the.drawn.films.corresponding.to.the.crystallinity.index..The.
crystal. linity. was. approximately. 14.8%. and. 16.8%. before. and. after. stretching,.respectively.(Kondo.et.al..2001;.Togawa.and.Kondo.1999)..IR.spectra.of.
deuterated.samples.also.supported.a.low.crystallinity.of.the.film.based.on.
the.ratio.of.the.remaining.OH.groups.in.the.drawn.films.that.corresponds.
to.the.crystal. linity.index..Figure 6.5b.also.shows.WAXD.intensity.curves.in.
both.the.equatorial.and.meridional.directions.of.NOC.(B).together.with.cellulose.II.fibers.(A)..In.the.equatorial.diffraction.of.NOC,.typical.crystalline.
diffraction.patterns.representing.cellulose.II.were.not.observed..The.diffuseintensity. .equatorial.profile.for.NOC.indicated.that.it.contains.considerably.
more. “amorphous”. regions.. The. meridional. scan. of. WAXD. indicates. the.
lulose.are.affected.by.the.disorder.of.the.neighboring.chains,.which.is.symmetrical.for.the.chain.axis..In.general,.cellulose.polymorphs.provide.almost.
the.same.meridional.patterns;.that.is,.two.strong.distinct.reflections.of.the.
(002).and.(004).planes.(2θ.=.17.2°,.d.=.0.516.nm;.2θ.=.34.7°,.d.=.0.259.nm,.respectively)..The.present.results.demonstrate.that.NOC,.which.is.highly.ordered.
Nematic Ordered Cellulose Templates
highly. engaged. intermolecular. hydrogen-bonded. domains. or. the. junction.
zone,. as. indicated. in. Figure 6.3a.. In. addition,. polarized. Fourier. transform.
infrared. spectroscopy. (FTIR). combined. with. the. vapor-phase. deuteration.
was.enabled.to.reveal.orientation.of.the.cellulose.main.chains.to.the.stretching.direction.in.both.the.crystalline.domains.and.the.noncrystalline.regions.
of.NOC.films..The.NOC.film.was.also.considered.to.have.both.the.oriented.
main.chains.and.the.nonoriented.OH.groups.as.the.side.chain..This.flexible.
state.of.the.OH.groups.might.further.hinder.the.oriented.crystallization.in.
the. NOC. preparation. process. and. yet. induce. the. unique. properties. in. the.
surface.of.the.NOC.film.(Higashi.and.Kondo.2012;.Kondo.2007;.Kondo.et.al..
2002,.2012)..In.Figure 6.5a,.the.CP/MAS. 13 C.NMR.spectra.for.NOC.samples,.as.
well.as.amorphous.(a.noncrystalline.state.without.any.preferred.orientation. ).
cellulose. prepared. from. cellulose-SO 2 -dimethylamine-dimethyl. sulfoxide.solution.(Isogai.and.Atalla.1991).and.CF11.cellulose.powder.(Whatman.
International.Ltd.).are.shown.in.the.range.from.50.to.80.ppm.where.chemical. shifts. at. the. C6. position. appear.. The. chemical. shift. of. CF11. appears. at.
65 ppm,.corresponding.to.tg.conformation,.indicating.that.CF11.is.a.native.
cellulose..Our.NOC.sample.exhibits.a.broader.signal.similar.to.amorphous.
cellulose.within.the.range.of.the.type.of.the.hydroxymethyl.conformation,.
gg,. which. also. supports. our. suggestion. that. NOC. is. noncrystalline. even.
though.it.is.well.ordered.
The. orientation. parameter. calculated. from. wide-angle. X-ray. diffraction. (WAXD). photographs. (Figure 6.5b). became. 0.88,. which. indicated. a.
high.degree.of.orientation..However,.the.crystallinity.did.not.significantly.
follow. the. increase. of. the. orientation. by. stretching. (Kondo. et. al.. 2001)..
Simultaneous.orientation.and.crystallization.did.not.occur.as.is.often.seen.
with.crystalline.polymers.(Ward.1997),.which.agrees.with.the.infrared.(IR).
analyses. of. deuterated. NOC. samples. based. on. the. ratio. of. the. remaining.
OH.groups.in.the.drawn.films.corresponding.to.the.crystallinity.index..The.
crystal. linity. was. approximately. 14.8%. and. 16.8%. before. and. after. stretching,.respectively.(Kondo.et.al..2001;.Togawa.and.Kondo.1999)..IR.spectra.of.
deuterated.samples.also.supported.a.low.crystallinity.of.the.film.based.on.
the.ratio.of.the.remaining.OH.groups.in.the.drawn.films.that.corresponds.
to.the.crystal. linity.index..Figure 6.5b.also.shows.WAXD.intensity.curves.in.
both.the.equatorial.and.meridional.directions.of.NOC.(B).together.with.cellulose.II.fibers.(A)..In.the.equatorial.diffraction.of.NOC,.typical.crystalline.
diffraction.patterns.representing.cellulose.II.were.not.observed..The.diffuseintensity. .equatorial.profile.for.NOC.indicated.that.it.contains.considerably.
more. “amorphous”. regions.. The. meridional. scan. of. WAXD. indicates. the.
lulose.are.affected.by.the.disorder.of.the.neighboring.chains,.which.is.symmetrical.for.the.chain.axis..In.general,.cellulose.polymorphs.provide.almost.
the.same.meridional.patterns;.that.is,.two.strong.distinct.reflections.of.the.
(002).and.(004).planes.(2θ.=.17.2°,.d.=.0.516.nm;.2θ.=.34.7°,.d.=.0.259.nm,.respectively)..The.present.results.demonstrate.that.NOC,.which.is.highly.ordered.