The influence of the dispersed oxides on the interface energy of the microcrystaliine cellulose in water suspension
The characteristics of water bounded layers in the hydrated powders and water suspensions of microcrystalline cellulose and thought containing SiO2 or TiO2 particles were investigated by 1H NMR method. It is found that the concentration of strong bounded water and the γs  value are in a...
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| Дата: | 2001 |
|---|---|
| Автори: | , , |
| Формат: | Стаття |
| Мова: | Англійська |
| Опубліковано: |
Chuiko Institute of Surface Chemistry National Academy of Sciences of Ukraine
2001
|
| Онлайн доступ: | https://surfacezbir.com.ua/index.php/surface/article/view/66 |
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| Назва журналу: | Surface |
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Репозитарії
Surface| _version_ | 1869291151245180928 |
|---|---|
| author | Shulga, O. V. Kerchhoff, J. Turov, V. V. |
| author_facet | Shulga, O. V. Kerchhoff, J. Turov, V. V. |
| author_institution_txt_mv | [
{
"author": "O. V. Shulga",
"institution": "The University of Toledo"
},
{
"author": "J. Kerchhoff",
"institution": "The University of Toledo"
},
{
"author": "V. V. Turov",
"institution": "Інститут хімії поверхні НАН України"
}
] |
| author_sort | Shulga, O. V. |
| baseUrl_str | |
| collection | OJS |
| datestamp_date | 2018-11-27T09:42:39Z |
| description | The characteristics of water bounded layers in the hydrated powders and water suspensions of microcrystalline cellulose and thought containing SiO2 or TiO2 particles were investigated by 1H NMR method. It is found that the concentration of strong bounded water and the γs  value are in a strong dependence to the concentration of cellulose in suspension. Probably, it is dictated by strong interaction between cellulose particles. At the very high concentration of suspension concentration of water inside the cellulose filament decreases in more than 3 time and (γs) value decreases from 9 to 31 J/g which is due to effect of surface forces. In the presence of dispersed particles of oxides, the concentration of bound water and γs  value in average are decrease, aseptically in the case of suspensions with TiO2 particles. |
| first_indexed | 2025-09-24T17:25:26Z |
| format | Article |
| fulltext |
TнЕ NFLUЕi\,iCЕ oF TtIЕ D-IsPЕRsЕD^o,\IDЕs
oN TtlЕ
INTЕRFAсЕ;,fтiЪi;огтйЬ"йiскo-9l\SТALLtliЕ
свььurosЕ rш wдТвк susrЕГ{slol{.
o.V. Shulga,, J. Kеrсhhoffl, and V.V. Turоv2
|DеPаrtmеп,,:I::;',:;;!k';,',:#:,l"{iftI:7#i::,|,:::,'u'o
tlJ.:i;:...i,: ::' jf w ateг b ouл9
:9 ^,^Y.,
- i n
.
thе'.,..,
: *..Ё,-j,ъfъ}i*;
-J::;i-"T:.ul,Tjt"Ц'ifu ."*:1l""Т
jl.':';trlJ:i:l"li'J-";
:ы:l*ц:*Щ:l'Jl'"''Ш1i$t***lн***.;l.".'жЦfr
*[.:*.*н*нн+*ч'ТF#i;:,T*#*"ч}ЦjiТj::#j$,"l1"*
'}:*}:l:;:ж: "ТжY;,.ff
:,t J''
" "
ln t r о d uс ti o n
е i s the o n e оf lт, : :
-l.::"il:"l,
3;:Жl"' :lНl"ЦlТii "}i:ll#F
н*:-'-нft}ggщ;f;jj#ff*;JT'.iffi i'.:'i{;il'fr
*Ёжрn'';ls;*t*".:''шn:il:'JT'Т'Hl.xT''lil{$**.iнl;
кн*шff#нЧlff*i*п**ffil
нжi;iнж;;tiн}:.iнii:ь:.','#;irlцц1;р:н:l.т';.}.{",lТi]l,n..
tr*fi д*:ffi ffн-j$flfgfffl }}gщ
,:н*'*h':'"*}:;i,itl.ЕяЁl1.n
j!""Щ"';:ii*'Цщ'l"lhl,
:'ffiН:1J,л#*iЁцdi'}:.}.Ё**'Ii.:x:
jffi Т*lЕ*'ft
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:н : l?т: ъ rь .:"l# kh: :жI xl.TЁf, T.ъТ : ;
266
USА
N TIIЕ
-LII\{Е
a:td water
): рaгtiсlеs
: oГ strоng
з:.rгation of
:: сеllulosе
:: insidе thе
:9tо31I/g
:s оf oxidеs,
:::aliy in thе
s:.rdiеd by a
:::.' data [3,41
:есrеasing оf
.:s shown that
:;s zone. This
,"-..:rrdеd watет
:.:lq with thеsе
,.:.iss might bе
...:losе maу bе
: '.ring polymеr
.r:ule in suсh a
: :; thе сеllulosе
='...еrnal
faсtors
In paгtiсulaг thе соnсеntration of sоlid phasе.in. suspеnsiоn oг pгеsеtlсс оf thе disрегsedpaгtiсlеs bеing ablе to intеra^сt rvith polymег оhains йd uff."t on tье h.ydration p.й.,.
-,
Тhe detегminatioп of thе сhaгaсtегistiсs of thе bоundеc watег l(l watrг suspеnsion
and hydratеd powdeгs of miсгoсгуstaline сеllulоsе (МCC) samplе-at thе diffеrеnt гatio ofthе сomponеnts ъ'егe thе goal oГ thе prеsent study as wеli as thе ii.rfluеnсе of thedispersеd oxides of siliсa аnd titania on thе p.o..,. оf intеraсtiоn bеtwееn watегmolесulе and МCС.
Materials
Мiсгoсrystallinе
.сеltulo^sе usеd in pharmaсеutiсal industry as a сomponеnt oftаblеt foгmulation wes сhosеn foг this study, A piсtuге of porvdег оbtainеd ьi *й"iй
еlесtгon miсrosсopе is shor.rn in fig' i In aссordanсе with fщuге 1 сеl]ulose piпiсlе havБ
a сvlindriсalshape and avегagе sizе is i0 х l00 рm, Мiсгoсгiсtallinе сеllulosе is thе suсh
tуpе of сеllulosе whiсh is paгtly hуdrolyzed by HCl tгеatment. As a sеquеnсе main paгt
of thе amoгphous sеоtions aге dеsolvеd and gгows of сгistallуnity is obsЬгvеd. Dispеisеd
siliсa (Aеrosil з00) with suгfaсе arеa 300 m2 /g and Тioz withihе рaгtiсlе sizе 0.1 цmwеrе usеd'
Fig. I
Mеthod
Thе detегrninations havе bееn donе Ьv 'F{ ]r.ъ4R spеctгosсoрy by using a freezing
of liquid phasе pгoсеdurе. Тhis mеthod has a good гесommеndation in thе dеieгminatioi
of thе сhaгaсtегistiсs оf boundеd rvatеr laуегs in suspеnsion of adsогbеnts and solutions
of biopolуmеrs [7.l0] ,Fi Nъ,fR speсtгa rvеге гесoгdеd on a high-геsolution NМR
spесtrometeг Bгukег WP-l00 SY (opегating frеquenсy 1OO МHz. tгansmission band up
to 50 k}tz). Тhе spесtгomеteг sеnsor tеmpегatuге was геmainеd сonstant to an aссuгaсy
оf +l dеgгeе with thе aid of a tеmpeгature сontгollег BVT-1O00 The intеgгatеd intеnsity
of NTr{R signals was dеtеrminеd to an aссuгaсy of +10% using an еlесtroniс integгatoi.
Thе amounts оГ intегfaсiai unfгozеn wateг (Сц2ф in the fгozеn aquеous suspеnйn oГ
267
сеllulosе at 190 <T <2.7зK wеrе еstimatеd by сomparison o{an-intеgгai intеnsitУ (1"")
;iiй Nl'{R signal of unfrozеn watеr with that (.1',,) оf watег at T = 285 K.
Cнuо = (I.*/I''X ц* / (m. + m,, )) (l)
Whеrе m* aIdи" is thе mass of watег and сеllulosе in suspеnsion bеfoге fгееzing.
тье signals oя ,uiгu.. hуdгoкуls and watег mоlесulеs from iсе wеге not detесtеd
duе to fеatuгеs of thе nl.u,uйIl1.nt tесhniquе and thе shoгt timе (*10-6 s) of сross
rеlaхation of proton in solids I l 1] Thе Gibbs frеe еnегgу changеs (АG in kJ/mol) of thе
intеrfaсial watеr wеrе сatсulateJ (with геlativr mеan еrror +15% ) using the known
o.p.nJ.n.. of thе сhangеs of tйe Gibbs frее еneгgy of iсе on thе tеmpегatuге
АG=o.0з6(2.|з _T) [12]-Wе assumе that watеr is frozеn (Т <2.7з K) at thе intегГaсе
whеn G:G, and ti,е valuе of АG:Go-G еquals АGi:G,l, ,,. -GlT) and
сoггеspondstoadесгеasеinthеGibbsf,геееnегgуof1h9intегfaсialwatеrduеtoits
intегaction with thе ,otio *u,гuсе (G. dеnotеS 1Ье Gibbs frее еnегgу of thе buik
(undisturbеd ) iсе). . t. ^г ...^1^. l''.i.ft f.aazinо the meаsllrеmеnt of sisnal
Toprеventtneovеrсoolingofwatегduгingfгeezing.thеmrasurеmеntofsigna
intensitу havе bееn ,",'uаЪ u' the hеiting of thе samplеs pге1iminarу сoolеd to T: 190 K
Rеsults
ТhеdepеndеnсеofАG(Сню)forwatеrsuspеnsion.(сuгvеs1.6)andhуdгatеd
powdеrsofсеllulosе(сuгvеs7,8)aгepresепtеdinFig2.Сoncеntгationofsolidphasе
(C,,r)insuspеnslonswasvariеdfгom6to44o/o.AsitсanbеobsеrvеdfтomFig.2,thеге
is a veгtiсal paгt of thе сurvе fоr ail dеpеndеnсiеs whiсh сorгеsponds to thе сase of thе
сonstant сonсentгation of unfrozеn watеr in widе гange of АG changеs (watеr adsorbеd
on thе surfaсе ooй'i- i...,. in a widе ,ung" oi 1empeIaturе variation). Fог thе
miсгоporous uno .",Ъpo.ou, ,nut.,iuls it was йo*n [13]' that thе prеsеnce of a suсh
vепiсal sесtion is сaused bу strong intеraсtion betwеen watег molесulе and suгfaсе. In
this tеmpеra,u,.","giJnЪ.,с*,.uJng of frее еnеrgу сaused by adsoгрtion is largег than
it сausеd ьу tе.npе.ui-,; ;;"; As strБng boundеd w*atеr is watег that fгееzеs at sufftсiеnt
tеmpегatuге сi.in..iion tт,iзl i. сaл bе сonсludеd in watег suspеnsion of сellulosе аll
adsoгbedwatегisstrongboundеdifсonсеntrationofсellulosеС,ot22Оwt%Indilutеd
suspеnsions tгie. z, с*i.1,zj.ь. sесtions сausеd by wеak bounded watеr aге appеarеd
Thеsе sесtions сan bе сharaсtегizеd bу сhangеs of /.ij.valu.е insignifiсantlу in widе гangе
of сhangеs of thе с;;;еniгation oг unf,o,еn"watеr Il2] Thе сonсеntration of stгong anс
wеak boundеd watеr (cню and С.n,I ,.,|"'tiu"iу; and. maкimцm valuе in thс
deоrеasingoffrеееnеrgyinthеlaуеrsoг,',o,gand-wеakboundеdwater(АёАG'
rеspесtivеly) сan bе dйптinеd by eхtгapolatioi of aссoгdanсе paгts of the АG(Сню
с-.Ьа.n"Ьio thе сoordinatе axis' In this сasе
C*нzo = Cn'u*Il2. - Csнzo Q)
whеге c,,o.tlJ' maximum сonсеntration of unfrozen watеr atT-+2,7з K,
ThеdataobtainedbуthiswaуarеprеsеntеdinTablеlThеTablеalsoprеsеn:
thе intеrfaсе еnеrgу р valuе'
^maхU н20
у': I AGdCнzo'о
(3)
268
.].sltу (1u"')
(1)
-g
. cеtесtеd
oГ сгoss
. ll) of thе
::з known
: ]]pеraturе
.. intегfaсе
- rТ) and
' :.rе to its
:hе bulk
оf signal
- - l90K
- rуdгated
-id phasе
] : 2' thеrе
..sе of the
.. adsorbеd
' For thе
. -^f a suсh
' .lгfaсе. In
з:gег than
.l sufftсiеnt
. ., 'u1osе all
In dilutеd
.'. appеarеd'
' ,.. rdе rangе
.:rоng and
- .е in thе
- зGS AG|''
' JG(Снzo)
(2)
. .О prеsеnts
.T'.-l -Aо.
. й"-=.Ч .
=:r
-)х'
o
o
z эLJ
175
l<n
125
1 - Cmkо = 6vЙo/o
2. Cmkc = 11wtoЬ
3-Cmkс=2oу,tto/o
4-Cmkс=23wto/o
1ф_J Ь,
o.7s _.1 ..:
050
0?5
0.ф
600,ф
I
j
,.*
I
=,1ol
; 2.Oо iУ|
I?l
o{., '*]
I
i
5. Cmkс = 43wtoЬ
6-Cmkс=44v,t|o/o
J.
4.о0
j
I
I
х
2.00
:
Non.Freezin g Water сonсЬnirаtion 1mglgD
Fig. 2. Thе dеpendеnce_of АG(Сн'o) foг watег suspensions (сurvе 1-6) and hydratedpoudeгs (сuгvе 7,8) ofсelIulose
Inteгfaсе ener,y is equal to total dесrеasing of fтее. еnеrgy of thе watег саusеd by
ffiffi|}"::,:':::?r.,watег intеrfa..,
"д;.thе
valuе o7,]."ш" suгfaсe u,"u of
еnеrgy relatеd to one -:H';ъЬTi;".,li "
value сan bе ехpгessеd in thе units
"г;;;
'.ff
'r'. ".1i,3.*",iPаo",'. J?g?,."
"
( ,i.,93i
:a
t
I
tt
!
a
0'ф --г--_._--]---._-, l*----_T
0 0o 10o ф . 2oo.oo 3ф.OoNon.Freezin g Wаtег Conсeniйion t. g/gl
7 _ Cmkc = 94.S wt %.--------"-- 8 - Cmkс =90.4vt|o/o
r-.r- "--r--
\-\ ra- \t-- e
I sl
a.7
Fig.3pгеsеntthеdeprndencaafАG(Снzo)forhуdratеdpowdегs(сuгvеsl-3)and
watеr suspеn,ion ( "u-JJъj
й, 1 : 5 7 mrхtuiJof siliсa and МCС and Fig 4 sows sцсh
depеndеnсiеs for 1 . з *i*tu.* of dispеrsеd Tioz and MCC in thе watег. In thе both сasеs
the amount of powder was a ьatf oгtЬe volumе Ьf thе сеllulose. Thе сhaгaсtеristiсs of thе
watеr boundеd laуеrs гoi tье Мсс+ Sioz + Hzo and 1\,{сC + Tioz + H2O systеms arе
listеd in tablеs 2 and 3
1 -6wt%н2o
2 - 16 'ttl
o/" H2O
3 - 21 v{t"Ь I12o
\ .\-
4.62v'ttуo|12o
\ \\-" 5 .7,r wt % н2o
1 \ 6-s,lwt%н2o
\ *\ ' 7.89wt% н2o
\ \- s.94wt%н2o\ .ч--ч
\ \\
I
5
ч
E
\
.o ol""..,"13ilЪ *"'".'3o;ll
180 0a
(mg/9)
200 c0
I,.t",,
:l
i1
\
I
I
+
I
1
-1
l
I
I
_-,]
i
l
I
l
эф
2ф
o
I
l,ф
*--- *\:
'i\
\\ -п .*'
\ \ ц\I I \r"t t d\i \. *rt
\\\
-т o6 ф
40Ф вoф , .'т:P 1ф'ф
iй.гreezlng wаtог сonс (mg/g}
Fig.3.ТhedеpеndеnceofАG(Cн2p)foгwatеrsuspensionsofсеllulosеandsiliсa5,6.1
ТhеdеpеndеnоiеsofintегГaсееnеrgуГromсonсеnt'jIi.onofsolidforwatеr
suspension for studiеd sуstеms u," p..,"niJd
.Ьn
гig 5a. This dеpеndеnсiеs has a
сompliсated shapе.
'".nЁ"Ь.*'ы"ЪЪ,
С,",,<zo*t'Й (foг sуstеms МсC+Н2o and
ьдсё+Sioz+I-I,o);,.;,,Ё,o i"l" Go|', '''.".
йс.с+Тioz) as сonсеntration of
solid inсrеasеs the р.."tu"ьu, invегsеlу p,oрoiionut dесrеasing. Thе Ys valuе bеgins tо
inсrеasе again at *".;;;;;;;;;'i;". тЬЁ t,.йсЪ*iеs oг tьe Jonсеntration of strongl1.
bound watеr agains, ё,,, ь-й*nЪn гig sь"ъ;;;;.'son of Fig. 5a and 5b it сan b.е
сonсludеd that obsегvilig сharaсtеr oгt.p"na"* " ,'ic,,l:::'*oo сhanging of Снэо'
So thе altеration "f
,;;..;;;;;i""
"г
.Ьong boundеd watеr detегminеs the intегfасе
еnergy valuе'
:lI (
'' oi
.iс]
сrn
сеl]
.^^.'
UUU
!1 4t
dеtt
surf
filar
lhе l
0.oo
2'70
:-- ' еs l-3) and
-. j sows suсh
: 'з
.эoth
сasеs
::
=
::stiсs of thе
'._ i''.stems arе
Tаblе 1
Charaсteгistiс of watег.bounded Iayeгs in thе watег suspеnsion andhydгatеd powdегs of сellulosе
Сonсеnt. of
Cе]lulosе
\Уt. oА
^G'kJimol
AG*
kJ/mol;
Cн:о*
tvldg
Cнzo Уo
3l
ZJ
LJ
l1
38
t2
2З0
160
/J
125
m{c
07з.з
l0
47A
200
v)
52
з,2
З.0
29
30
30
2.2
tl
z-)
a1.+J
9О4
945
:сa 5'6 : 1
: for watеr
,;iеs has a
- H2O and
::rtгation of
-r bеgins to
. эf stronglу
:э it сan bе
- J of Сц2pS.i intегfaсе
As сan bе obsегr,'еd fгom Fig 2 data thе сonсеntration of wеak bounded watегhas a tеnd to dесrеasе at С,,t inсгеa'.i тьi' typе оfb"";J;;;;tег has beеn aрpеarеd inthat сasе whеn thе distanсе bеtwееn сеliulosе paгtiсlеs in suspеnsion was moге thaпsomе minimal valuе. So, weak bоundеd watег is sеt up on thе еxtегnal sidе of thесеllulosе paпiсlе. For thе stгon8 boundеd watег diffеr"nt
_*;tuution
сaп be obseгvеd.Pгеsenсе of thе vегtiсal sеоtions on thе depеndenсe АG C,,|,d makes it similar toсoпespond depеndеnсe whiсh is obsегvеj foг *u'.. .u,pЬn,,on oГ hydrophiliсmiсгоporous adsorbеnts Il3] As miс.opo.еs in,и. tь.l.jluЁ,J.puniсlе сan be еithеr aсhannеls foгmеd by group of miсгofibril, o, u frее spaсе ь.i*ЪЪ" miсrofibгils availablеfor watег molесulе. It сan be сonsidегеd that соnЪеntгation-of *u.., in miсгopoгеs(volumе of miсropores) dеteгminеs by pоsiti"" of ;й; ;;;ь"r Ъ"n of thе dеpеndеnсеАG (Cнzo)
In сontrast to the сarbon adsorbеnts, thе stгong dеpеndеnсе oГ thе volumе ofmiсгoporеs against сonсеntration of solid phasе (Fig. 5b; cu.*;lj сan bе obsеrvеd. Thеvolumе of poгes сan bе геduсеd fгоm 25О ao*n'Ь is r'iti'ь^,is сuе to influеnсе of thеnеighboг paгtiсlеs. Тhе most possiЬlе геason foг thjs сan bБ influ"n.. of thе surfaсе foгсеon the volume of miсгoporеs. Тhеsе forсеs aсts in a big distanсе from thе suгfaсе ofоеllulose paгtiсles and it сan be proofеd by thе a.t tБui.iь" сonсеntгation of wеakЬoundеd watег in dilutеd suspension may ехсееds thе сoncentгatton of stгong boundedwatеr inside the fibriIs
As thе сonсеntгation of thе stгong boundеd watег in thе сеllulose filament isdеteгmined by the dеgrее of сrystalynitу oTthе poty'.. iз,+l.i''.nigь, be srrggеsted thatsurfaсе foгсes of thе neighboring jaпiсtes affесts,оn ,h;'";;;;liynrty of thе hydratеdfiiament and sign of thе intеraсtйns is dеtеrmined by thе d;';;. bеtwееn paгtiсlеs. Ifthе distanсe is grеat (dilutеd suspеnsion, left рaгt of thе сurve 1, figurе 5) thеn thе dеsrее
оf сrystаllуnitу inсгеasеs unсjеi'
сonсentration of suspеnsiоn, As o
tlttilrеПС€ сlf thе rlсlghbогirrg раriiсlеs tоgеthеr rr'ith
сОi-lsе0uеnсе thе соnсеntгation oithе stгong boundеd
7ч
с
(1
й
ttl,.=--.--
-
'lr--
a'
l-a
1.71 Wt % н2o
2-78 w1% 12О
З-83 wto/o H20
4-86 v"t% H2O
5-90 wt% HzO
-1
?
t
a
a
a
;, '.'
. т1r?I i.
lО
Е
aх
ar)
C o0 40.0C 80 00 1?0 0c
Non-fгeеzing wаteг ссlmсentrаtioп (mgig)
3 0.J --
1Оo _
l
000
ъ\
il
-i1
iф+
l
tl +
Е
ofi
3n.r."u,,i,iii.Т"*"'. "onff.i?ut,on r-JЪoj*
Fig.4.ThedеpеndenceofАG(Сн:o)fсrwatеrsuspеnsionsоГсеlluiоsеandtitania3.i
watеr in fibгils dесrеasеs, [f thе соnсеntгatiоn оf suspеnsiоn (distanсе bеtrvееn partiсlеs
геaсhеS to somе сritiсal valuе thеn suгfaсе forсеs affЪсts in oрpоsirе dirесtion _ th.
огdегlеss struсturе
"f
;;. р;l},ег сhains in fibrils is a геsult if this affесtion, Tоgеtht
with it thе сonсеntгыlon оitье strong boundеd lvatег in filamеnts inсгеasеs ( гight paГt C
thе сuгv,е 1 , fig.5). p'"p"'.с mесйnism agrееd with obtainеd in [1a] dереndenсе с
сiistattinitу andЪydration оf somе samрlеs оf сеllulosе'
The prеsеnс. oi th. disрегsеd рaгtiсlеs suсh аs Sio: and Tioz in wаIе
suspеnsiоn of сеllulos].ь,ing' thе dесrеa-sing as maxinral--соnсеntratiоn of thе stгoг'.
boundеd watег as thе ;t valuе, Thе dеpеndеnJi.s of |Ье y,(С,"l and Сн:.эS(С,,/ bесоmt
moге smooth and thе,s."tion ц.hiсh is duе to iпсrеtlsing of thе z, ll Сд.os valuеs ri;'
сonсеntгation сan bе obsегr,,еd bеttег ( Iig 5' сuг",еs 2,3)
Тhе bеgining оf this sесtion shlfts to пlоге diiutеd suspеnsiоn sidе as сan '
.usilу oБsе*.jin,й.*йpt. оf.thе SiО: ооntaining samplеs ( fig 5, сuгvе2) lJsing ti
diagгam it might bе assumеd thg |g!]g\,ving nlесhanisпl оf thе inf-luеnсe оf thе dispersеrl
212
:еihеr \\'ith
' сoundеd
:
:.:.пia3:1
" ..з partiсles]
: .. :iion _ thе
g: l Тogеthег
з :ight part oi
:....еndenсe оГ
.'. : in watег
г .: thе strong
'' ; bе"omе.
i- .',aluеs l'viti
j -. as сan bс-
- .- llsing thi'
Г : cispеrsес!
я
5
й
LI]
!r
l.r
E
l
Il
l
-t
I
l
:l
L.'
I
a
I
c
a'i1,A
\- ..'
ф>} .*\''Р\
з
.Ь
g
Oс
(J
g
!
с!
с
Ф
40 00
20 00
]-МKс+н2o
<-14кс+sio2+н2oз.Мкс+тi()2*izo
t
I
- a 11-'.r
\1
|
!.оi
I
'I
. I 2 ./
i'', \sn тt\
-.
-'-1, .,P' I.,зl
-d-_----*_,il
I
o oo -+-.-
o oo - 2o oo - ;;--;"..сonсоnt.ation ot sol.:Jjwt "z1
сU UU
з00 о0 -.
200 0о -]
I
100 0о -
oф -]--_ =---_;.-,-._*_-. -*_
U Uv
с...3iio". on ot so1ioсorh иl 60'00
Fig. 5 The dеpеndеl.i.':
9| intегfaсе еnеrgy and сonсentгation оf strong bondеd watегfгom сonсеntгation of solid foг watег susйnsion oГstudied systеms
oхidеs on thе oгdеr of thе polymeг filamеnts in thе сеllulose fibеr' Тhе oхidеs dispегsedin suspension affeсts not Ьnlу on thе dесrеasing of thе intеra"t,on, o.t,u"en сellulosеpaгtiсles but also сan гegulatе thе oгdег lni1.дolц.еr сhain йy l',-ri The main еffесt ofthis influеnсе is aгising of сrystallynlty
"г.Ё. ii;;;;;,j;";;;;"n.. of thе disрегsеdoхidеs. Тhis еffeсt сan bе bеttе^г obsЬгvм гo, ,u,p.nsion сontalning Тio2. The obsегvinsdеpеndеnсiеs д(С,"l and СнюS(С,oy' aгe dеtегminеd as a summatiЬn of thе еffесts of thiinteгaсtion bеtwееn МCС paпiсl., unа мЪё paпiсt.' Ы.l аьp.,s.a o*iс.sFоr еaсh system whiсh has bееn invеstigated thе inflесtion of the intегfaсе enегgvvalue сausеd bу intеraсtions bеtwе.n puпi.lБ, ;.iъ;.;;;;inеd as thе diffеreniЬbеtwееn maхimal and minimal uatu..oi thе intегГaс. .nф at thе vaгiаtion ofсonсеntгation of thе so,id phasе ( сun,е l-], fig. ;i-;;'",'#i'stem сontaining justМсC, МCС -t Sioz and МСC + .гiou
thls valuе is 22,, ti ;"j;й rеspесtivеly. on thеbasis of piots rесordеd on fig5a tь" uu.Ьtьn
"f
;;'i;;;;;.";;:,*, valuе сausеd Ьу
Pl:.:.."..
of thе disp^ersеd oхide сan bе dеtегminеd Тhis valuе i,.o.лn.а as diffегеnсеbеtweеn oгdinatеs of сun,еs \-2 or 1-3 whеn С,o1' valuе is лхеJ-
"
zt-)
Соnсlusions
onthеbasisofthеinvеstigationthathavebееnpегГormеditсanbесonсludеd
that lн NМR spесtгosсopу mеthoJtogеthег-with fгeez\ng of liquid рhasе proсеduгe сan
bе usrd effесtivеly to deiегmine thе bJundеd Watеr сonсеntration in watег suspеnsion of
..riuro," and intеifaсе епеrgy value in suspеnsion with diffеrеnt сonсеntration.
Conсеntration of thе stгong and wеak boundеd watег in thе watеr suspеnsions
сhangеs in sеvеral timеs with coiсеntгation of suspеnsion inflесtion. It is сausеd bу
а..iJы"g of intеrfaсe ",..gу
on lh-е
МСC/watег interfaсe' one of thе possible rеason
foг this еffесt might ь. inлuJn.е of thе neighboгing сеi1ulos.е paпiсlеs on thе ordеr in thе
p"ry.Ъ'
"й.ins
ii fibrits' Whеn thе distanсе betwеЪn partiсles (diiutеd suspеnsion) is big
thenеighboringpaгtrсlеswoцldсausrthеordеringеffесtand.thесonсеntrationofthе
stгong boundеd watеr and intегfaсе еnеrgу valuе dБсгеasеs with aгising of сonсеntгation
of suspеnsion lf thе distanсе is lеss thеn somе сгitiсal value (сonсеntгatеd suspеnsions) a
геvеrsе геgulaгitу ts oссurrеd. Thе nеarеst molесulе сan сausе thе геguiatiоn of thе
рolуmеr сhains and as a сonsеquеnсе thе h and Снэos values inсгеasеs.
Bу introduсti"" "itй.
iisрегsеd oхidеs in suspеnsion соntaining lеss thеn 20 %
of thе solid phasе
'; r, and Снzos valuеs havе bееn dесrеasеd. The intеrfaсе enrгgу
value has also bееn а..,.us.а сuusеa bу intеraсtion bеtweеn paгtiсlеs. It was state that
thе dispегsеd oхidеs;;i;i., and се1luiosе paгtiсlеs would сausе thе геgulation of thе
polуmеr сhains irl fibri1s.
Rеferеnсеs
r._кogouinZ.А''ТheChеmistryоfСеllulosеN4.Khimia,1972.5|7p.
2 Cousins S K. Brown М B- Cеliulоsе in Мiсrofibгil Assеmblу: Computational
]v{olесulaгмесьuni",вnегgуAnalуsisFavouгsBondingbуVandегWaalsFoгcеsas
thе initial st.p i,'.ё,yйt'iz"aiion // Ьolуmег . 1995 - v. 36, N 20 _ P. 3885.3888
з . Hatakе,,ama н.,
-tiшakеуama T. ]ntеrасtion Bеtwееn lvatеr and Hydrophobit
гЪryrn",' ll TеrmoсhеmiсйАсtа - 1998 _V 308. _P.з-22'
4' Hatakеyama T., Nakamura K', Hatakеуama-H Dеtегmination of Bound Watе:
Сontent in гoiу*e,,l;йA' DЬC and T,G. ll Tеrmoсhеmiса Асtа, - 1988. У ' |23 -
P. 153-16l . л...^l^11l-^ r-^ll',l^"a eг.
5.HеinегA.P.,Tеlеmano.IntеraсtionBеtwеenМonoсliniсCrystal1inеСеllulosеar.-
Watег: в,.u"оo*n oг,ь" oас,вvеn Dupliсity // Langmuir - 199,7 - v. 13, N3. - Р
5l3-5l8. .-^^ D^+..'^^. \l/atar о.
6,НеinегA.P.,KuuttiL,,Tеlemano.C^ompaгisonoj}.еIntеrГaсеBеtwееnWatегa:'-
Foцг Suгfaсеs оf Native Crуstallinе Cеllulosе bу Мolесular Dуnamiсs Simulation
Ъarbohydratе Rеsеarсh _ 1988 - V 306 -P 205.220
1. Тurov v v.' i.Ь"а. к Appliсation of lH NМR Spесtгosоopу Мetod i
Dеteгmination oiЪйu'u.teгistiсs of thit Watеr Layегs of- Watег Adsoгbеd on :,
Surfaсе oгоi,p...J.unJpo,ou, Adsorbеnts ll Аdv. Сotloid апd Intфсе Sсi. _ 19:]
_ v 79, Ьl 2-3. _P. 1,7з.211
8. Turov V.V., Mironуuk l F. Adsorption. Laу.еrs of Wаtег оn thе Surfaсе
Hуdrophobi..;;йii;Joхidеs tt сittoiаs ond Su,р,,,4. . 1998 - v. 134, N ]
P'251-26з' г.-. т ^.'^.^ ^Гll/otдr at
g.TurovV.V.,Ban,inchеnkov'N'struсtuгallyoгdеrеdS.uгfaсeLaуеrsofWatегat:
Sio2/Iсе int.,гa,..und Influenсе of Adsoгbed Мoleоulеs of Pгotеin Hуdгolysatе
thеm // Сolloidi апd Suфсе B.. . |gg7 v' 8, N з.P' 125-1з2.
.11А
|
| id | oai:ojs.pkp.sfu.ca:article-66 |
| institution | Surface |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2025-09-24T17:44:40Z |
| publishDate | 2001 |
| publisher | Chuiko Institute of Surface Chemistry National Academy of Sciences of Ukraine |
| record_format | ojs |
| resource_txt_mv | surfacezbircomua/77/720926f68883825fa9fbba73ee4bce77.pdf |
| spelling | oai:ojs.pkp.sfu.ca:article-662018-11-27T09:42:39Z The influence of the dispersed oxides on the interface energy of the microcrystaliine cellulose in water suspension The influence of the dispersed oxides on the interface energy of the microcrystaliine cellulose in water suspension The influence of the dispersed oxides on the interface energy of the microcrystaliine cellulose in water suspension Shulga, O. V. Kerchhoff, J. Turov, V. V. The characteristics of water bounded layers in the hydrated powders and water suspensions of microcrystalline cellulose and thought containing SiO2 or TiO2 particles were investigated by 1H NMR method. It is found that the concentration of strong bounded water and the γs &nbsp;value are in a strong dependence to the concentration of cellulose in suspension. Probably, it is dictated by strong interaction between cellulose particles. At the very high concentration of suspension concentration of water inside the cellulose filament decreases in more than 3 time and (γs) value decreases from 9 to 31 J/g which is due to effect of surface forces. In the presence of dispersed particles of oxides, the concentration of bound water and γs &nbsp;value in average are decrease, aseptically in the case of suspensions with TiO2 particles. The characteristics of water bounded layers in the hydrated powders and water suspensions of microcrystalline cellulose and thought containing SiO2 or TiO2 particles were investigated by 1H NMR method. It is found that the concentration of strong bounded water and the γs &nbsp;value are in a strong dependence to the concentration of cellulose in suspension. Probably, it is dictated by strong interaction between cellulose particles. At the very high concentration of suspension concentration of water inside the cellulose filament decreases in more than 3 time and (γs) value decreases from 9 to 31 J/g which is due to effect of surface forces. In the presence of dispersed particles of oxides, the concentration of bound water and γs &nbsp;value in average are decrease, aseptically in the case of suspensions with TiO2 particles. The characteristics of water bounded layers in the hydrated powders and water suspensions of microcrystalline cellulose and thought containing SiO2 or TiO2 particles were investigated by 1H NMR method. It is found that the concentration of strong bounded water and the γs &nbsp;value are in a strong dependence to the concentration of cellulose in suspension. Probably, it is dictated by strong interaction between cellulose particles. At the very high concentration of suspension concentration of water inside the cellulose filament decreases in more than 3 time and (γs) value decreases from 9 to 31 J/g which is due to effect of surface forces. In the presence of dispersed particles of oxides, the concentration of bound water and γs &nbsp;value in average are decrease, aseptically in the case of suspensions with TiO2 particles. Chuiko Institute of Surface Chemistry National Academy of Sciences of Ukraine 2001-06-10 Article Article application/pdf https://surfacezbir.com.ua/index.php/surface/article/view/66 Surface; No. 4-6 (2001): Chemistry, Physics and Technology of Surface; 266-274 Поверхность; № 4-6 (2001): Химия, физика и технология поверхности; 266-274 Поверхня; № 4-6 (2001): Хімія, фізика та технологія поверхні; 266-274 3154-8091 3154-8083 en https://surfacezbir.com.ua/index.php/surface/article/view/66/65 Авторське право (c) 2001 O.V. Shulga, J. Kerchhoff, V.V. Turov |
| spellingShingle | Shulga, O. V. Kerchhoff, J. Turov, V. V. The influence of the dispersed oxides on the interface energy of the microcrystaliine cellulose in water suspension |
| title | The influence of the dispersed oxides on the interface energy of the microcrystaliine cellulose in water suspension |
| title_alt | The influence of the dispersed oxides on the interface energy of the microcrystaliine cellulose in water suspension The influence of the dispersed oxides on the interface energy of the microcrystaliine cellulose in water suspension |
| title_full | The influence of the dispersed oxides on the interface energy of the microcrystaliine cellulose in water suspension |
| title_fullStr | The influence of the dispersed oxides on the interface energy of the microcrystaliine cellulose in water suspension |
| title_full_unstemmed | The influence of the dispersed oxides on the interface energy of the microcrystaliine cellulose in water suspension |
| title_short | The influence of the dispersed oxides on the interface energy of the microcrystaliine cellulose in water suspension |
| title_sort | influence of the dispersed oxides on the interface energy of the microcrystaliine cellulose in water suspension |
| url | https://surfacezbir.com.ua/index.php/surface/article/view/66 |
| work_keys_str_mv | AT shulgaov theinfluenceofthedispersedoxidesontheinterfaceenergyofthemicrocrystaliinecelluloseinwatersuspension AT kerchhoffj theinfluenceofthedispersedoxidesontheinterfaceenergyofthemicrocrystaliinecelluloseinwatersuspension AT turovvv theinfluenceofthedispersedoxidesontheinterfaceenergyofthemicrocrystaliinecelluloseinwatersuspension AT shulgaov influenceofthedispersedoxidesontheinterfaceenergyofthemicrocrystaliinecelluloseinwatersuspension AT kerchhoffj influenceofthedispersedoxidesontheinterfaceenergyofthemicrocrystaliinecelluloseinwatersuspension AT turovvv influenceofthedispersedoxidesontheinterfaceenergyofthemicrocrystaliinecelluloseinwatersuspension |