C* Semidilute Solutions - SWSCC · Thixotropy • Wall slip • Shear banding • These all should...

Sem

idilu

te S

olut

ions

Dilu

te b

lobs

C*

Net

wor

k of

mes

h SC

C SW

CHA

PTER

111

8 P

olym

ers i

n Co

smet

ics10

1

Sem

idilu

te S

olut

ions

Net

wor

k of

mes

h co

nsist

s of b

lobs

of r

adiu

s r=

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

102

Poly

mer

s in

good

solv

ent i

n se

mi-d

ilute

so

lutio

n

Blo

b ra

dius

For r

> th

at is

out

side

the

blob

For r

> th

at is

out

side

the

blob

The

repu

lsiv

e in

tera

ctio

ns

betw

een

mon

omer

s are

sc

reen

ed o

ut

The

blob

s con

nect

in a

rand

om fl

ight

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

103

Sum

mar

y

g(r)

rC

*cros

sove

r

Sing

le sw

olle

n ch

ains

g(r )

=r-4

/3a-5

/3

insi

de th

e bl

ob

R IS

TH

E C

OIL

SI

ZE

g(r )

= c

/r

outs

ide

the

blob

g(r )

0

for r

> R

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

104

DIL

UTE

SO

LUTI

ON

VI

SCO

SITY

DIL

UTE

SO

LUTI

ON

VI

SCO

SITY

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

105

Poly

mer

Sol

utio

n Vi

scos

ity

The

visc

osity

of a

solu

tion

depe

nds u

pon

the

prop

ensi

ty o

f the

solv

ent t

o flo

w

In a

pol

ymer

solu

tion,

the

poly

mer

mol

ecul

e ‘s

low

s’ th

e flo

w o

f the

solv

ent

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

106

Poly

mer

Sol

utio

n Vi

scos

ity IF T

HE

SOLV

ENT

DO

ES

NO

T FL

OW

TH

RO

UG

H

THE

CO

IL –

IT IS

C

ALL

ED A

NO

N-F

REE

D

RA

ININ

G C

OIL

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

107

Poly

mer

Sol

utio

n Vi

scos

ity IF T

HE

SOLV

ENT

FLO

WS

THR

OU

GH

TH

E C

OIL

–IT

IS C

ALL

ED A

FR

EE D

RA

ININ

G C

OIL

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

108

Visc

osity

Visc

osity

tube

tube

flow

ing

liqui

dflo

win

g liq

uid

O

OO

O

O

O

O O O

flow

fast

est i

n ce

nter

of t

ube

flow

fast

est i

n ce

nter

of t

ube Flow

is s

tatio

nary

at w

all

Flow

is s

tatio

nary

at w

all

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

109

Poly

mer

Sol

utio

n Vi

scos

ity

The

Mar

k-H

ouw

ink

Equa

tion

Intri

nsic

Vis

cosi

ty, [

]=K

Ma

[] i

s the

hy

drod

ynam

ic

size

of t

he

poly

mer

mol

ecul

e in

solu

tion

(dl/g

)

A fa

ctor

that

de

pend

s upo

n th

e ‘s

wol

len’

size

of

the

poly

mer

m

olec

ule

a =

0.5

for n

on-f

ree

drai

ning

a =

1.0

for F

ree

drai

ning

For G

auss

ian

Cha

ins

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

110

Mea

sure

men

t of V

iscos

ityM

easu

rem

ent o

f Visc

osity

Mea

sure

tim

e of

sol

vent

flo

w th

roug

h vi

scom

eter

t o

Mea

sure

tim

e of

sol

utio

n flo

w th

roug

h vi

scom

eter

t

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

111

Visc

osity

Visc

osity

•We

mea

sure

solu

tion

(an

d so

lven

t (vi

scos

ity se

para

tely

•Rel

ativ

e Vi

scos

ity =

(r

•th

at re

veal

s how

muc

h m

ore

visc

ous t

he so

lutio

n is

com

pare

d to

the

solv

ent

•Spe

cific

Visc

osity

= [(

r -1

•sp

•re

mov

es th

e so

lven

t visc

osity

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

112

Dete

rmin

ing

the

Intr

insic

Visc

osity

•Tim

e th

e flo

w o

f sol

vent

and

pol

ymer

solu

tions

th

roug

h a

capi

llary

•The

spec

ific

redu

ced

visc

osity

,

sp/c

=(

-o)

/ oc

•Mea

sure

the

(sp

/c) f

or a

serie

s of d

ilute

po

lym

er so

lutio

ns

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

113

Wha

t is

the

Intr

insi

c Vi

scos

ity?

Wha

t is

the

Intr

insi

c Vi

scos

ity?

•The

uni

ts a

re d

ecili

tre/

gram

•vo

lum

e pe

r uni

t wei

ght

•Th

e in

trin

sic v

iscos

ity g

ives

the

volu

me

occu

pied

by

one

gram

of p

olym

er in

so

lutio

n

•[].M

= th

e vo

lum

e oc

cupi

ed b

y on

e m

ole

of p

olym

er in

solu

tion

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

114

Redu

ced

Spec

ific

Visc

osity

Redu

ced

Spec

ific

Visc

osity

hydr

odyn

amic

inte

ract

ion

thro

ugh

the

solv

ent

hydr

odyn

amic

inte

ract

ion

thro

ugh

the

solv

ent

sp/c

= [

] +

k[]2

csp

/c =

[]

+ k[

]2 c

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

115

Visc

osity

Visc

osity

•Red

uced

Spe

cific

Visc

osity

=

sp/c

•a

mea

sure

of t

he sp

ecifi

c cap

acity

of t

he p

olym

er to

incr

ease

the

rela

tive

visc

osity

•Bu

t it c

onta

ins t

he h

ydro

dyna

mic

inte

ract

ion

cont

ribut

ion

•Rem

ove

this

cont

ribut

ion

by e

xtra

pola

ting

to in

finite

dilu

tion

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

116

Dete

rmin

ing

the

Intr

insic

Visc

osity

sp/c

Cpo

lym

er

[]

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

117

Visc

osity

–H

uggi

ns P

lot

sp/c

Cpo

lym

er

[]

Dilu

te S

olut

ion-

Poly

mer

Mol

ecul

es d

o no

t tou

ch

Sem

i-Dilu

te S

olut

ion-

Poly

mer

Mol

ecul

es d

o in

terp

enet

rate

C*

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

118

Rept

atio

n•A

bove

the

chai

n en

tang

lem

ent t

hres

hold

•The

pol

ymer

mol

ecul

es w

riggl

e pa

st e

ach

othe

r •L

ike a

snak

e m

ovin

g al

ong

a tu

be m

ade

up o

f sna

kes

•Visc

osity

= (c

oncn

)2.2

-3.4

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

119

The

Gla

ss T

rans

ition

Tem

pera

ture

, Tg

•Bel

ow th

e Tg

,•

Chai

ns h

ave

insu

fficie

nt e

nerg

y to

rept

ate

past

eac

h ot

her

•Abo

ve th

e Tg

•Po

lym

er ch

ains

‘wrig

gle’

and

hav

e en

ough

exc

lude

d vo

lum

e to

wrig

gle

past

ea

ch o

ther

•Pla

stici

zers

are

smal

l mol

ecul

es th

at lo

wer

the

Tg o

f a p

olym

er o

r po

lym

er sy

stem

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

120

Plas

ticiza

tion

•Sm

all m

olec

ules

inte

rspe

rsed

bet

wee

n th

e po

lym

er m

olec

ules

can

assis

t rep

atat

ion

•Th

is is

plas

ticiza

tion

•The

re is

a ti

me

elem

ent

•If

the

appl

ied

forc

e m

ust l

ast l

ong

enou

gh fo

r the

po

lym

ers t

o m

ove

•If

the

forc

e is

of sh

ort d

urat

ion,

ela

stic

defo

rmat

ion

and

reco

very

will

occ

ur•

Debr

a Nu

mbe

r

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

121

The

Mar

k H

ouw

ink-

Saku

rada

Equ

atio

n.

[] =

KMa

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

122

Rheo

logy

of P

olym

er

solu

tions

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

123

Ther

mal

Beh

avio

r of G

els

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

124

http

://w

ww

.bre

nnta

g-sp

ecia

lties

eu

rope

.com

/en/

dow

nloa

ds/F

ood_

pres

s_re

view

/TB

_Hyd

roco

lloid

s_FN

FN20

1009

.pdf

Ther

mal

Beh

avio

r of G

els

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

125

http

://w

ww

.bre

nnta

g-sp

ecia

lties

eu

rope

.com

/en/

dow

nloa

ds/F

ood_

pres

s_re

view

/TB

_Hyd

roco

lloid

s_FN

FN20

1009

.pdf

Ther

mal

Beh

avio

r of G

els

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

126

http

://w

ww

.bre

nnta

g-sp

ecia

lties

eu

rope

.com

/en/

dow

nloa

ds/F

ood_

pres

s_re

view

/TB

_Hyd

roco

lloid

s_FN

FN20

1009

.pdf

Ther

mal

Beh

avio

r of G

els

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

127

http

://w

ww

.bre

nnta

g-sp

ecia

lties

eu

rope

.com

/en/

dow

nloa

ds/F

ood_

pres

s_re

view

/TB

_Hyd

roco

lloid

s_FN

FN20

1009

.pdf

RHEO

LOGY

SCC

SW

CH

APT

ER 1

118

Pol

ymer

s in

Cos

met

ics

128

STR

ESS

RAT

E O

F ST

RA

IN

New

toni

an

Pseu

dopl

astic

Dila

tant

RHEO

LOGY

SCC

SW

CH

APT

ER 1

118

Pol

ymer

s in

Cos

met

ics

129

STR

ESS

RAT

E O

F ST

RA

INBIN

GH

AM

B

OD

Y

ELLI

S

Thixo

trop

y

SCC

SW

CH

APT

ER 1

118

Pol

ymer

s in

Cos

met

ics

130

Vis

cosi

ty

Tim

e

Cea

se sh

ear

Rheo

pexy

SCC

SW

CH

APT

ER 1

118

Pol

ymer

s in

Cos

met

ics

131

Vis

cosi

ty

Tim

e

Cea

se sh

ear

Elas

tic a

nd V

iscou

s

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

132

http

://w

ww

.jero

n.je

/ang

lia/le

arn/

sec

/sci

ence

/forc

emot

/pag

e08.

htm

A S

prin

g is

an

elas

tic so

lidH

ooke

's la

wFo

r a N

ewto

nian

Liq

uid:

http

://fin

earta

mer

ica.

com

/feat

ured

/po

urin

g-liq

uid-

tom

isla

v-

Visc

oela

stic

ity

•Pol

ymer

s are

visc

oela

stic

mat

eria

ls•P

urel

y el

astic

mat

eria

ls de

form

whe

n st

ress

is a

pplie

d an

d co

mpl

etel

y re

cove

r the

ir or

igin

al sh

ape

whe

n th

e st

ress

is re

mov

ed.

•Pur

ely

visc

ous l

iqui

ds d

efor

m w

hen

a st

ress

is a

pplie

d bu

t rem

ain

defo

rmed

whe

n th

e st

ress

is re

mov

ed•

The

high

er th

e st

ress

, the

gre

ater

the

rate

of s

trai

n•

The

visc

osity

is th

e pr

opor

tiona

lity

fact

or th

at re

late

s the

mag

nitu

de o

f the

ap

plie

d st

ress

to th

e ra

te o

f str

ain.

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

133

Visc

oela

stic

ity•i

f the

stre

ss is

hel

d co

nsta

nt, t

he st

rain

incr

ease

s with

tim

e (c

reep

);•i

f the

stra

in is

hel

d co

nsta

nt, t

he st

ress

dec

reas

es w

ith

time

(rela

xatio

n);

•the

effe

ctiv

e st

iffne

ss d

epen

ds o

n th

e ra

te o

f ap

plica

tion

of th

e lo

ad;

http

://w

ww.

yout

ube.

com

/wat

ch?v

=f2X

Q97

XHjV

w•i

f cyc

lic lo

adin

g is

appl

ied,

hys

tere

sis (a

pha

se la

g)

occu

rs, l

eadi

ng to

a d

issip

atio

n of

mec

hani

cal e

nerg

y;

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

134

Visc

oela

stic

ity

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

135

Line

ar v

isco

elas

ticity

Appl

ied

stre

ssIm

med

iate

st

rain

Cree

pss

Appl

ied

stra

inIm

med

iate

st

ress

Rela

xatio

n

•tis

time,

is

stre

ss,

is

stra

in

•is

inst

anta

neou

sel

astic

mod

ulif

or c

reep

, I

s

inst

anta

neou

sel

astic

mod

ulif

or re

laxa

tion

•K(t)

is th

ecr

eep

func

tion,

F(

t)is

the

rela

xatio

n fu

nctio

n

Stor

age

and

Loss

Mod

uli

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

136

Stor

age

Mod

ulus

(th

e el

astic

co

mpo

nent

)

Loss

Mod

ulus

(th

e vi

scou

s co

mpo

nent

)

The

elas

tic

com

pone

nt ca

n be

m

odel

ed a

s a sp

ring

of sp

ring

cons

tant

E

The

visc

ous c

ompo

nent

ca

n be

mod

eled

as a

da

shpo

t hav

ing

a liq

uid

of v

iscos

ity η

Sprin

gs a

nd D

ashp

ots

•The

Max

wel

l Mod

el SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

137

http

://up

load

.wik

imed

ia.o

rg/w

ikip

edia

/com

mon

s/d/

db/M

axw

Pred

icts

strai

n in

crea

sing

with

tim

e fo

r con

stan

t stre

ss..

But

real

pol

ymer

s usu

ally

sh

ow st

rain

rate

dec

reas

ing

with

tim

e

•Th

e Ke

lvin

-Voi

gt M

odel

Goo

d fo

r mod

elin

g cr

eep

Not

so g

ood

for m

odel

ing

rela

xatio

n

Sprin

gs a

nd D

ashp

ots

•The

Sta

ndar

d Lin

ear S

olid

Mod

el

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

138

http

://up

load

.wik

imed

ia.o

rg/w

ikip

edia

/com

mon

s/d/

db/M

axw

Mor

e ac

cura

te th

an M

axw

ell a

nd K

elvi

n-Vo

igt f

or m

ater

ial

reso

nses

……

but

inac

cura

te fo

r spe

cific

load

s

In R

ealit

y th

ere

is a

Dist

ribut

ion

of R

elax

atio

n Ti

mes

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

139

http

://up

load

.wik

imed

ia.o

rg/w

ikip

edia

/com

mon

s/d/

db/M

axw

ell_

dia

Part

icul

ate

Gel

s

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

140

Part

icul

ate

Gel

s

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

141

Rheo

logy

of '

gel’

stru

ctur

es a

t equ

ilibr

ium

ωSC

C SW

CHA

PTER

111

8 P

olym

ers i

n Co

smet

ics14

2

Yiel

d St

ress

Flu

ids

and

failu

re o

f the

Cox

-Mer

zRul

e•

At lo

w st

rain

s , th

e st

ruct

ured

‘gel

s’ sh

ow e

last

ic re

cove

ry•

That

is, t

hey

beha

ve li

ke e

last

ic so

lids

•Ho

wev

er, u

nder

stea

dy sh

ear,

thes

e ge

ls flo

w li

ke li

quid

s•

Whe

reas

solid

s wou

ld fr

actu

re•

Ther

efor

e, st

ruct

ured

gel

s beh

ave

like

solid

s at l

ow st

rain

s•

Abov

e a

cert

ain

stre

ss (y

ield

stre

ss) t

hey

flow

like

liqu

ids.

•Th

e em

piric

al C

ox-M

erzr

ule

stat

es th

at th

e vi

scos

ity/r

ate

of st

rain

beh

avio

r is

com

para

ble

to th

e co

mpl

ex v

iscos

ity/f

requ

ency

beh

avio

r•

The

Cox –

Mer

zrul

e is

obey

ed fo

r man

y so

lutio

ns•

How

ever

, str

uctu

red

gels

usua

lly d

isobe

y th

e Co

x-M

erzr

ule

•Be

caus

e th

ey ce

ase

to b

e flo

wab

leflu

ids b

elow

the

yiel

d st

ress

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

143

CON

SIDE

R A

POLY

MER

AS

A ST

ICKY

PAR

TICL

E

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

144

Stic

ky P

olym

er P

artic

les

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

145

Rela

xatio

n Pr

oces

s A

–Di

ffusi

on b

etw

een

enta

ngle

men

t poi

nts

The

Mod

ulus

at

tim

e t

Initi

al

Mod

ulus

Rela

xatio

n fu

nctio

n at

tim

e t

From

the

Rous

e M

odel

, The

initi

al

mod

ulus

= k

Tpe

r cha

ini.e

. (nu

mbe

r den

sity

of ch

ains

).kT

(ρN

o/M

).kT

For e

ntan

gled

syst

ems

M b

ecom

es M

e

Stra

in te

nsor

in th

e di

rect

ion

of th

e ve

ctor

bet

wee

n en

tang

lem

ents

,Th

e m

olec

ule

is ou

tsid

e its

equ

ilibr

ium

con

form

atio

n.

The

rela

xatio

n m

odul

us

for t

he A

pro

cess

The

initi

al R

ouse

Mod

ulus

dep

ends

on

the

dens

ity o

f cha

ins i

n th

e en

tang

lem

ent r

egio

n (B

lob)

Long

rela

xatio

n tim

es co

ntrib

ute

to a

hi

gher

mod

ulus

at t

ime

t.SC

C SW

CHA

PTER

111

8 P

olym

ers i

n Co

smet

ics14

6

Rela

xatio

n Pr

oces

s B

–Re

trac

tion

of th

e ch

ain

to it

s orig

inal

den

sity

For r

e-eq

uilib

ratio

n ac

ross

slip

-link

sRe

trac

tion

in th

e co

nfin

ed

geom

etry

is d

omin

ated

by

the

low

est o

rder

R-Z

mod

e

Retr

actio

n re

laxa

tion

time

dep

ends

on

the

sam

e pa

ram

eter

s as p

roce

ss A

AND

THE

NUM

BER

OF

ENTA

NGLE

MEN

TS P

ER C

HAIN

Retr

actio

n M

odul

us d

epen

ds o

n th

e sa

me

para

met

ers a

s R-

Z b

ut th

e slo

wer

R-Z

mod

es d

omin

ate.

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

147

Rela

xatio

n Pr

oces

s C –

Reco

very

of t

he o

rigin

al c

onfo

rmat

ion

by re

ptat

ion

The

char

acte

ristic

tim

e fo

r a re

puta

tion

mot

ion

is:

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

148

Cellu

losic

thic

kene

rs

Hyd

roxy

ethy

lcel

lulo

se H

EC

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

149

•Deg

ree

of S

ubst

itutio

n (0

-3) a

nd M

olar

su

bstit

utio

n

•Non

ioni

c th

icke

ner

•She

ar-th

inni

ng R

heol

ogy

http

://or

igin

-ars

.els

-cdn

.com

/con

tent

/imag

e/1-

s2.0

-S00

0888

4612

0006

95-g

r2.jp

g

Rel

axat

ion:

Proc

ess A

:

Proc

ess B

Proc

ess C

:

The

Rheo

logy

of A

queo

us S

olut

ions

of

Hyd

roxy

ethy

lcel

lulo

se

Tanδ

is G”

/G’.

Ther

efor

e al

l HEC

solu

tions

>3%

ar

e m

ore

elas

tic th

an

visc

ous

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

150

The

Rheo

logy

of A

queo

us S

olut

ions

of

Hyd

roxy

ethy

lcel

lulo

se

151

Rel

axat

ion:

Proc

ess A

:

Proc

ess B

Proc

ess C

:

Fast

el

astic

re

spon

se

Slow

vi

scou

s re

spon

se

The

slow

visc

ous r

espo

nse

arise

s fro

m:

The

long

est

Rous

e-Zi

mm

Mod

es

The

coil

wou

ld b

e ex

pect

ed to

st

retc

h un

der s

hear

(De

Genn

es).

Th

e ‘d

ashp

ot’ r

elax

atio

n in

this

case

wou

ld b

e th

e st

retc

hing

and

re

-form

atio

n of

the

coil.

Rept

atio

nis

prob

ably

not

sig

nific

ant i

n di

lute

solu

tion.

It

may

be

impo

rtan

t in

conc

entr

ated

solu

tions

.

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

Rheo

logy

and

Sen

soria

l Att

ribut

es

•For

Hyd

roge

ls, g

el-li

ke su

spen

sions

/em

ulsio

ns•

Rheo

logi

cal p

aram

eter

s tha

t can

be

corr

elat

ed w

ith se

nsor

y pe

rcep

tion

inclu

de•

Yiel

d st

ress

•

Thixo

trop

y•

Wal

l slip

•Sh

ear b

andi

ng

•The

se a

ll sh

ould

be

mea

sure

d fo

r cor

rela

tion

of rh

eolo

gy w

ith

sens

oria

l pro

pert

ies

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

152

S. O

zkan

, T. W

. Gill

ece,

L. S

enak

and

D. J

. Moo

re, C

hara

cter

izat

ion

of y

ield

stre

ss a

nd sl

ip b

ehav

iour

of s

kin/

hair

care

ge

ls us

ing

stea

dy fl

ow a

nd L

AO

S m

easu

rem

ents

and

thei

rco

rrel

atio

n w

ith se

nsor

ial a

ttrib

utes

, In

tern

atio

nal J

ourn

al o

f Cos

met

ic S

cien

ce, 2

012,

34,

193

–201

Exte

nsio

n of

coi

ls an

d ro

ds

A co

oper

ativ

e co

il-ro

d tr

ansit

ion

occu

rs a

t a

criti

cal e

long

atio

nal

shea

r rat

e

Orde

red

stru

ctur

es sh

ow u

p as

bi

refr

inge

ntsh

ear b

ands

Ther

e is

no cr

itica

l she

ar ra

te

for r

ods -

--th

ey sh

ow

incr

easin

g al

ignm

ent w

ith th

e sh

ear f

ield

as t

he sh

ear r

ate

incr

ease

s

The

alig

nmen

t sho

ws u

p as

a

gene

raliz

ed b

irefri

ngen

ce in

th

e hi

gh sh

ear r

egio

ns o

f the

4-

roll

mill

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

153

Cellu

losic

thic

kene

rs: H

ydro

xypr

opyl

cellu

lose

HPC

SCC

SW

CH

APT

ER 1

118

Pol

ymer

s in

Cos

met

ics

154

•Deg

ree

of S

ubst

itutio

n (0

-3) a

nd M

olar

subs

titut

ion

•Non

ioni

c th

icke

ner

•She

ar-th

inni

ng R

heol

ogy

•Low

LC

ST (4

0C)

2-ph

ase

1-ph

ase

met

asta

ble

bino

dal

spin

odal

T max

and

Tmin

arise

from

chan

ge in

chai

n fle

xibi

lity

with

tem

pera

ture

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

155

The

Mas

ter C

urve

for R

elax

atio

n un

der

exte

nsio

nal f

low

for H

ydro

xypr

opyl

cellu

lose

Norm

alize

w.r.

t, De

bra

Num

ber

Stre

ss re

laxa

tion

time

=Ti

me

of o

bser

vatio

n

Belo

w Tp

Sam

e re

laxa

tion

proc

ess a

t diff

eren

t te

mps

.

Abov

e Tp

Diffe

rent

rela

xatio

n pr

oces

ses:

th

e cu

rves

do

not f

it on

a

singl

e m

aste

r cur

ve

Mas

ter c

urve

wrt

shea

r rat

e in

dica

tes s

ame

rela

xatio

n pr

oces

s at

diff

eren

t tem

pera

ture

s SC

C SW

CHA

PTER

111

8 P

olym

ers i

n Co

smet

ics15

6

Hyd

roxy

prop

ylce

llulo

se

The

hydr

odyn

amic

vo

lum

e de

crea

ses w

ith

T in

crea

se

(bel

ow T

p)i.e

. the

Kuh

n le

ngth

get

s sh

orte

r

Criti

cal s

train

rate

indi

cate

s co

il-ro

d tra

nsiti

on b

elow

Tp

Tran

sitio

n to

rod

alig

nmen

t i.e

. rod

s pre

sent

prio

r to

shea

r in

met

asta

ble

regi

on

In tw

o ph

ase

regi

on a

bove

Tp,

th

e ro

d al

ignm

ent i

s mor

e pr

omin

ent

The

criti

cal s

train

rate

in

crea

ses w

ith T

unt

il the

ph

ase

tran

sitio

n (K

uhn

Leng

th D

ecre

asin

g)

The

criti

cal s

train

rate

di

sapp

ears

at t

he b

inod

alte

mp

( the

pol

ymer

be

com

es ro

d-lik

e)

Bire

fring

ence

du

e to

coil-

rod

tran

sitio

n

durin

g ex

tens

ion

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

157

Coop

erat

ive

Tran

sitio

ns w

ith T

empe

ratu

re

kT/ε

0Va

n De

r W

aals

H-Bo

nd

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

158

Zipp

er m

odel

for t

he fo

rmat

ion

of ju

nctio

n zo

nes

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

159

Zipp

er m

odel

for t

he fo

rmat

ion

of ju

nctio

n zo

nes

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

160

Zipp

er m

odel

for t

he fo

rmat

ion

of ju

nctio

n zo

nes

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

161

K-CA

RRAG

EEN

AN

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

162

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

163

Carr

agee

nan

AFM

2-su

lfate

pr

even

ts

crys

talli

zatio

n of

the

doub

le

helic

es

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

164

Carr

agee

nan

–th

e ro

le o

f ion

s in

hier

arch

ical

stru

ctur

e fo

rmat

ion

•Ab

ility

to fo

rm g

els f

ollo

ws t

he se

quen

ce:

Thes

e se

em

to b

e sp

ecifi

c st

ruct

urin

g io

ns

Helix

form

atio

n ca

n be

follo

wed

by

mea

surin

g sp

ecifi

c op

tical

ro

tato

ry p

ower

Hyst

eres

is be

twee

n ge

lling

and

m

eltin

g –

aggr

egat

ion

of h

elice

s.

No h

yste

resis

/no

gel w

ith N

aCl–

but h

elice

s for

m!

Spec

ific

ion

effe

cts.

–se

e ne

xt

slide

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

165

Carr

agee

nan

–th

e ro

le o

f ion

s in

hier

arch

ical

stru

ctur

e fo

rmat

ion

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

166

Carr

agee

nan

–th

e ro

le o

f ion

s in

hier

arch

ical

stru

ctur

e fo

rmat

ion

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

167

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

POLY

ELEC

TRO

LYTE

S &

INTE

RACT

ION

BE

TWEE

N IO

NIC

ION

ASS

OCI

ATIO

N

PRO

PERT

IES

POLY

ELEC

TRO

LYTE

S &

INTE

RACT

ION

BE

TWEE

N IO

NIC

ION

ASS

OCI

ATIO

N

PRO

PERT

IES

168

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

PPoly

elec

trol

yte

Mod

elPo

lyel

ectr

olyt

e M

odel

Fuos

s, R.

M.;

Katc

halsk

y, A.

; Lifs

on, S

.; Pr

oc. N

at. A

cad

Sci.

1951

, 37,

579

Man

ning

, G.S

.; Q

uart

erly

Rev

iew

s of B

ioph

ysics

, 197

8, 2

, 179

Gao,

J.Y.;

Dub

in, P

.L.;

Sato

, T.;

Mor

ishim

a, Y.

; J. C

hrom

atog

raph

y, A;

199

7, 7

66,2

36

+--

____

____

__

____

__

_

__

__

___

__

___

+ +

+ +

+ +

+ + +

++

++

++

+

+ +

+ +

+ +

+ +

+

++

+

+ +

+ +

++

+ +

+ ++

++

+

+ +

+ +

+ +

+ +

+ +

+ +

+

+

+ + +

++

++

+

169

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

Coun

terio

nDi

strib

utio

nCo

unte

rion

Dist

ribut

ion +

++fre

e in

solu

tion

free

in so

lutio

n++

Donn

an

Equi

libriu

mDo

nnan

Eq

uilib

rium

Boun

d &

Hydr

ated

+

Boun

d &

Dehy

drat

ed

Oosa

wa,

F.; P

olye

lect

roly

tes,

Mar

cel D

ekke

r Co.

; NY.;

197

117

0

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

Poly

elec

trol

yte-

Coun

terio

n

Int

erac

tion

Poly

elec

trol

yte-

Coun

terio

n

Int

erac

tion

•Tw

o th

eorie

s:

•Ce

ll T

heor

y (P

oiss

on-B

oltz

man

n)

•M

anni

ng th

eory

(Co

unte

rion

Cond

ensa

tion)

171

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

Poiss

on-B

oltz

man

n M

odel

Poiss

on-B

oltz

man

n M

odel

+--

____

____

__

____

__

_

__

__

___

__

___

+ +

+ +

+ +

+ + +

++

++

++

+

+ +

+ +

+ +

+ +

+

++

+

+ +

+ +

++

+ +

+ ++

++

+

+ +

+ +

+ +

+ +

+ +

+ +

+

+

+ + +

++

++

+

l

ra

R

leng

th

infin

ite

172

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

Poiss

on-B

oltz

man

n M

odel

Poiss

on-B

oltz

man

n M

odel

•Inf

inite

ly lo

ng ro

d, ra

dius

‘a’

•med

ium

of c

onst

ant d

iele

ctric

•fixe

d po

lyio

nch

arge

spre

ad e

venl

y al

ong

the

rod

•cou

nter

ions

cont

aine

d w

ithin

a co

ncen

tric

cylin

der,

radi

us ‘R

’

•Inf

inite

ly lo

ng ro

d, ra

dius

‘a’

•med

ium

of c

onst

ant d

iele

ctric

•fixe

d po

lyio

nch

arge

spre

ad e

venl

y al

ong

the

rod

•cou

nter

ions

cont

aine

d w

ithin

a co

ncen

tric

cylin

der,

radi

us ‘R

’

173

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

Man

ning

The

ory

Man

ning

The

ory

belo

w

crit

belo

w

crit

174

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

Man

ning

The

ory

Man

ning

The

ory

abov

e cr

itab

ove

crit

free

free

boun

dbo

und

175

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

Man

ning

The

ory

Man

ning

The

ory

•Tw

o-st

ate

theo

ry

•co

unte

rions

free

or b

ound

•Dim

ensio

nles

s cha

rge

dens

ity is

redu

ced

to u

nity

by

coun

terio

nco

nden

satio

n

•

•Tw

o-st

ate

theo

ry

•co

unte

rions

free

or b

ound

•Dim

ensio

nles

s cha

rge

dens

ity is

redu

ced

to u

nity

by

coun

terio

nco

nden

satio

n

•kT

lzkT

lz

176

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

Man

ning

The

ory

Man

ning

The

ory

llcr

it=

crit

= z iz i

177

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

Man

ning

The

ory

Man

ning

The

ory

•For

vin

yl m

onom

er h

omop

olye

lect

roly

tes:

•l =

0.2

5nm

•P b

= 1-

(

)

•65%

of m

onov

alen

t ion

s con

dens

e•8

2% o

f div

alen

t ion

s con

dens

e

•For

vin

yl m

onom

er h

omop

olye

lect

roly

tes:

•l =

0.2

5nm

•P b

= 1-

(

)

•65%

of m

onov

alen

t ion

s con

dens

e•8

2% o

f div

alen

t ion

s con

dens

e

zz

178

Gel

/net

wor

k fo

rmat

ion

from

hel

ical

junc

tion

zone

sIn

ord

er to

from

a g

el, h

elica

l ‘ju

nctio

n zo

nes’

mus

t be

conn

ecte

d in

to a

effe

ctiv

e ne

twor

k; T

wo

poss

ible

ne

twor

k st

ruct

ures

are

show

n be

low.

Intr

amol

ecul

ar h

elice

s•

the

junc

tion

zone

is

form

ed b

y a

doub

le

helix

bet

wee

n tw

o ch

ains

;•

The

bran

chin

g is

form

ed a

t ‘ki

nks’

in

the

chai

n th

at ca

nnot

be

wou

nd in

to th

e he

lical

stru

ctur

e

Aggr

egat

ion

of fu

lly

deve

lope

d he

lices

•br

anch

ing

is fo

rmed

by

ben

ding

of t

he

helic

es to

form

ju

nctio

ns b

etw

een

the

aggr

egat

ed

‘junc

tion

zone

s’

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

179

Evid

ence

for G

ellin

g by

Hel

ix A

ggre

gatio

n

Non-

gel h

elica

l k-

carr

agee

nan

In 0

.3M

LiCl

0.3M

KCl

dial

yze

gelle

dk-

carr

agee

nan

Now

add

0.

3M Li

Cl

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

180

‘Sta

te D

iagr

am’ f

or

K-Ca

rrag

eena

nDe

grad

ed k

-ca

rrag

eena

n

Inta

ct k

-ca

rrag

eena

n

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

181

Note

the

shar

p di

vidi

ng li

ne a

t xC

s:Na

= 0.

4Do

es th

is im

ply

spec

ific b

indi

ng?

Spec

ific

site

bin

ding

of

ions

on

K-Ca

rrag

eena

n?

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

182

Spec

ific

site

bin

ding

of

ions

on

K-Ca

rrag

eena

n?

Cf12

.7kJ

/mol

for n

on-s

pecif

ic sa

lts

Use

Poiss

on-B

oltz

man

n Ce

ll th

eory

and

law

of

Mas

s Act

ion

to ca

lcula

te

the

chem

ical p

oten

tial o

f po

lyio

nsfre

e an

d bo

und

to co

il an

d he

lix–

calcu

late

the

enth

alpy

an

d en

trop

ies o

f bin

ding

SC

C SW

CHA

PTER

111

8 P

olym

ers i

n Co

smet

ics18

3

Spec

ific

site

bin

ding

of

ions

on

K-Ca

rrag

eena

n?

Cf12

.7kJ

/mol

for n

on-s

pecif

ic sa

lts

The

OH

grou

ps o

n k-

Carr

agee

nan

are

not w

ell

conf

igur

ed to

com

plex

with

the

coun

terio

ns–

How

ever

, in

a do

uble

-hel

ical c

onfo

rmat

ion,

the

OH

grou

ps w

ould

be

conf

igur

ed c

orre

ctly

and

the

doub

le h

elica

l con

form

atio

n w

ould

be

stiff

.

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

184

Conc

lude

that

ag

greg

atio

n (a

nd g

ellin

g)

is ca

used

by

spec

ific

bind

ing

of io

ns to

the

asse

mbl

ed h

elix

( ra

ther

th

an to

the

coil)

Zipp

er M

odel

Algi

nate

s and

Pec

tin

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

185

Algi

nate

s

•Ex

opol

ysac

char

ides

ext

ract

ed fr

om b

row

n se

awee

ds a

nd so

me

bact

eria

•Lin

ear b

lock

copo

lym

ers o

f man

nuro

nate

and

gulu

rona

telin

ked

with

alte

rnat

ing

resid

ues

•Bi

osyn

thes

is Pa

thw

ay•

Man

nuro

nan

is po

lym

erize

d an

d th

en p

ost-m

odifi

ed b

y ep

imer

ase

enzy

mes

whi

ch co

nver

t m

annu

rona

teto

gul

uron

ate

•Ep

imer

ase

enzy

mes

are

now

bei

ng u

sed

indu

stria

lly to

crea

te a

lgin

ates

with

opt

imum

pro

pert

ies

for s

pecif

ic a

pplic

atio

ns.

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

186

Algi

nate

s•T

he g

ulur

onat

ere

sidue

s sel

ectiv

ely

bind

alk

alin

e ea

rth

met

als

•The

egg

-box

mod

el*:

•Th

e G-

bloc

ks fo

rm a

2/1

hel

ical c

onfo

rmat

ion

and

diva

lent

catio

nsar

e co

ordi

nate

d w

ithin

the

cavi

ties f

orm

ed th

ereb

y•

The

‘egg

-box

’ dim

er se

quen

ces a

ssoc

iate

late

rally

•To

form

junc

tion

zone

s

*SC

C SW

CHA

PTER

111

8 P

olym

ers i

n Co

smet

ics18

7

Algi

nate

s

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

188

Algi

nate

s

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

189

Algi

nate

s

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

190

Algi

nate

s

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

191

Pect

ins

•Pec

tin is

com

pose

d of

long

se

quen

ces o

f par

tially

met

hyl

este

rifie

d (1

-4)-l

inke

d α-

D-gl

actu

rona

tere

sidue

s•G

alac

turo

nate

is st

ruct

ural

ly th

e m

irror

imag

e of

gul

uron

ate

•The

refo

re, s

imila

r egg

-box

st

ruct

ures

to a

lgin

ate

may

be

expe

cted

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

192

Pect

insc

.f.Al

gina

tes

Sim

ilar i

nitia

l bi

ndin

gSe

cond

ary

bind

ing

(egg

-box

) is m

uch

mor

e en

erge

tical

ly

favo

rabl

e fo

r al

gina

te

(gul

uron

ate)

than

fo

r pec

tin

(gal

actu

rona

te)

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

193

Pect

insc

.f.Al

gina

tes

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

194

Chai

n St

iffne

ss o

f Pol

ysac

char

ides

1: g

lucu

rona

n, 2

: man

nuro

nan,

3: g

ulur

onan

, 4: g

alac

turo

nan.

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

195

Mod

elin

g G

elat

ion

of A

lgin

ates

The

antip

aral

lel c

hain

pai

ring

gave

rise

to a

n ef

ficie

nt h

ydro

gen

bond

net

wor

k w

ith tw

o co

mpl

emen

tary

hyd

roge

n bo

nds:

O2â

ââO

6, 2

.73

Å (2

.88

Å), a

nd O

3âââ

O5,

2.8

7 Å

(2.9

1 Å)

. It a

lso p

rovi

ded

a un

ique

per

iodi

c ch

elat

ion

site

for c

alciu

m io

ns.

It is

not p

ossib

le to

disc

rimin

ate

betw

een

the

two

form

s of t

hese

chai

n pa

iring

s bas

ed o

n to

tal

ener

gy; h

owev

er, t

he a

ntip

aral

lel a

rran

gem

ent i

s pr

obab

ly fa

vore

d in

the

gel s

ince

it h

as b

een

repo

rted

that

ure

a su

bsta

ntia

lly w

eake

ns th

e ge

l.Th

e sh

ape

of th

is st

ruct

ure

is c

lose

to th

at o

f the

pop

ular

“eg

g bo

x m

odel

”.

Cal

cium

coo

rdin

atio

n: o

nly

four

liga

nds f

rom

the

chai

ns, O

2 an

d O

6 of

bot

h ch

ains

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

196

Mod

elin

g G

elat

ion

of P

ectin

sirr

espe

ctiv

e of

the

helic

al fo

rm, t

he a

ntip

aral

lel

arra

ngem

ent w

as th

e m

ost f

avor

able

one

.

this

bes

t ant

ipar

alle

l ass

ocia

tion

is si

mila

r to

the

“egg

box

stru

ctur

e”.

But

……

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

197

Mod

elin

g G

elat

ion

of A

lgin

ates

and

Pec

tins

For P

ecta

te, t

he c

aviti

es fo

rmed

by

the

join

ed c

hain

s do

not

have

the

prop

er si

ze fo

r cal

cium

ions

; the

y ar

e fa

r too

larg

e (F

igur

e 6b

).

The

pres

ent c

alcu

latio

ns c

lear

ly d

emon

strat

e th

at th

e “e

gg b

ox

mod

el”

cann

ot c

orre

spon

d to

the

pairw

ise

asso

ciat

ions

of

pect

ate

chai

ns th

at fo

rm th

e ju

nctio

n zo

nes i

n ca

lciu

m p

ecta

tege

ls.

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

198

SCC

SW C

HAPT

ER 1

118

Pol

ymer

s in

Cosm

etics

199

CaBE

REx

tens

iona

l Rhe

omet

er

http

://w

ww.

cam

poly.

com

/file

s/81

13/5

216/

6124

/CaB

ER.p

dfSC

C SW

CHA

PTER

111

8 P

olym

ers i

n Co

smet

ics20

0