ADVANCED ORGANIC COATING

Eco-formulations

P. Gronchi
AA 2014-2015

1
 Goldschmidt/Streitberger
2
Basics of Coating Technology
To formulate eco friendly coatings, HIGH SOLID
formulations to SOLVENT FREE COATINGS require:

1. the binders for the high solid content coatings

have to be highly fluid initially and then to become
very solid;
2. the binders for powder are to be very solid
initially to retain solids then fluid to coalesce in a
smooth film.

In each case severe demands are placed on its

design.

A further requirement is that an inorganic or solid

particle amount over 70% may cause a severe loss
of fluidity.
3
 The solid content and the binder
content

4
 The limit derives from a balance between the surface area
of particles and the volume of the binder.

Vp

Vp Vb Va
The Packing Factor is the maximum
Volume fraction of internal phase that
can be fit into the system when the
particles are randomly close packed
And external phase just fills all the
interstices between the particles

Vp
PVC
Vp Vb

5
6
 Metodi di determinazione del CPVC

Considerando un film per unit di peso:

se PVC<CPVC, the density of a film*
1
f (1)
w

1 w
p b

Da cui the specific volume is

1 1 1 1
w (2)
f b
b p

con w = frazione in peso.

Remember: I cannot add density values that are intensive values and
not extensive ones.

7
 Metodi di determinazione del CPVC

Considerando un film per unit di peso:

se PVC>CPVC
1
f
w (3)
p * CPVC
1 w

f p * CPVC (4)

Nelle condizioni limite w = 1 1

f p * CPVC
1

f
CPVC w=1 (5)
p

Allintersezione S( vedi grafico curve eq. 2 e 4) invece

w f
CPVC (6)
p

o meglio
w
p
CPVC
1 w
w (7)
8 p b
Latex: concentrated suspensions of discrete, spherical and relatively tacky,
resinous particles in water, with a particle size range that may compare closely
with that of pigment. Spherical latex particles fail to completely wet the pigment particles.
They may also deform and micro voids are formed leading to reduced film densities.

9
10
Oil adsorption nd CPVC

OA = oil adsorption (linseed oil)

0,935 = linseed oil density
= pigment density

11
 Prediction of packing arrangement depends on :

Size, Shape, Surface, Spacing, Structure, Spread, Stirring

The binder amount increases with area surface.

What happens when the dimension of particles (pigment) is nanometric?

Discussion:
The packing factor decreases almost proportionally to the average diameter of
particles. Then particles become resistant to dense packing. The packing
becomes fluffier. As an example the packing compactness of the finer
(precipitated) CaCO3 (0,01-0,5 m) is about the half of the coarser (ground) one
(2-10 m). Gypsum, Cement, pigment give the same results.

By this way, it is permitted to hypothesize that at, nanometric dimension, at the same
PVC, considering the figure PVC-, the straight line on the PVC<CPVC side, is
less inclined, and the safe area is more small. The PCV and relations changes.

12
13 Plot pag 131 Patton
 Nodular (irregularly rounded in shape, approximately spherical)
Blocky ( roughly rectangular, chunky, or boxlike)
Platy ( leafy, lamelliform, flaky, Sheetlike)
Acicular (needlelike, bristlelike)
Fibrous (threadlike)

Sphericity value =
surface area of sphere equal in volume to nonspherical particle
surface area of non spherical particle

Da considerazioni puramente geometriche

14
15
 Use and the meaning of Spacing
Hiding power (HP) of TiO2 (rutile) (contrast unit = 0,98 ft2/lb):

= 370 (empirical formula)

Where c = s + d.
The model is validated if there is a tetrahedral spacing ( = 0,740).
Example 1-
Spacing vs. s
Hiding power
d
c

When PVC< CPVC at maximum of packing: 3 = 3

Then HP at PVC =15%. 0,15 (d+s)3 = 0,740 d3
From which s = 0,702d
and then c =d+s= 1,702d
and consequently HP =153 ft2/lb.

ASTM D6441 - 05(2010)

Contrast units
Significance and Use
Contrast ratio at a specified film thickness
is a useful hiding power parameter for production
control and purchasing specifications.
The greater the hiding power, the less coating
is required per unit area to obtain adequate hiding.
Knowledge of hiding power is therefore important
16 in regard to coating costs and for comparing coating value
 0.18
0.16
0.14
0.12
0.1
s/(s+d)
0.08
0.06
0.04 Figure 1. s vs. s/(s+c). An arbitrary
0.02
value of d has been chosen
0
0 0.5 1 1.5
Spacing

Comment: since s increases at a relatively faster rate than (s+d),

it follows that the ratio s/c = s/(s+d) must increase with an increase in s.
This means that tha HP , expressed in ft2/lb increases as the particles
become further separated. Conversely, bringing the TiO2 particles
closer together ( by increasing the PVC) reduces the HP.

Actually the introduction of an excessive concentration of TiO2

to achieve whiteness can be self-defeating

17
 From: Zeno-Wicks)

18
 Example 2 Spacing vs. Anticorrosion

19
 Mean= Chain or grapelike clusters

Examples: carbon black, pyrogenic silica, fine pigments.

Nodular polymer spherical particles chain from dispersibility

+ dispersibility until
Texture Rating = 12-15
- jetness, gloss

Empirical equation

Texture rating= S( d 0,4)

S = Specific surface area

d = Structure index
(Packing factor for bare pigments)

20
Distribution pattern

21
 Implies a disturbance of the relative positions of pigment particles,
by (mainly)
-Vibratory motion (shaking)
-Continuous circular movement (milling, grinding, dispersing)

REARRANGEMENT TO A MORE DENSE AND UNIFORM PACKING

5% volume reduction

Vibration is used e.g. to determine the oil absorption value.

22
 The binder features (binder design)

23
 HIGH SOLIDS AND SOLVENT FREE BINDERS binder design

Liquid or Powder

To design high solid coatings there are some parameters to respect

and some corollaries to discuss.

1. Molecular weight and polydispersity

2. Viscosity (Tg, NV)
3. Functionality (crosslinking).

Parameter objectives at the end

High Tg (as that of conventional coatings) and as High
as possible molecular weight.

Functionality but limited interactions between of pre-polymers.

24
 binder design
MEMO

25
 binder design

Molecular weight

kM w Mark Houwink Sakurada

0,5 e 0,8 for flexible macromolecules
1-2 for rigid macromolecules
3,4 below and above respectively the entanglement molecular weight
Discontinuities are present in the values

Above a certain polymerisation degree we have a strong increase of the

viscosity that may limit the solid content.

26
 binder design

Polydispersity Mw/Mn

From the Houwink eq.,

highest fractions have a dominating effect on
viscosity.

Paul Flory experiment:

The same number of moles (n1) of two polyester with different
Molecular weight. Let stand at high temperature in order
to reach the equilibrium from exchange reactions.

Initially
DPn= n1100+n150 =n1150
Memo
After heating to make interchange: DPn= Mn/Mi
Where
DPn = 2 (n1 75) = n1150 Mn = mean numerical molecular weight
Mi = molecular weight of the monomer i
Result: the viscosity at the melting point dramatically decreased.
The DP is unchanged, the polydispersity decreased.
27
 binder design

The rheological behaviour of polymeric systems is profoundly influenced by their molecular

weight and molecular weight distribution (MWD). The relationship between viscosity
and shear rate is sensitive to the polymer polydispersity, especially in the high
molecular weight region. ..
.. For linear polymers, the relationship between viscosity and shear rate
shows two distinct regions.
At low shear rates the viscosity is a constant, 0 , but when
the shear rate increases above a certain critical value the viscosity begins to decrease and
continues to decrease with increasing shear rate. At still higher shear rates, a lower
limiting viscosity appears mostly for dilute systems. In concentrated systems including
melts this region is seldom observable.

Viscosity model for polydisperse polymer melts

D. Nichetti and I. Manas-Zloczower

J. Rheol. 42~4!, July/August 1998

28
 binder design
Viscosity during the film
formation
Doolittle eq.
Theory of polymer free volume
Vo = occupied volume
Vf = free volume
A, B system constant
The chemical-physical parameter that describe the film formation process is the

GLASS TRANSITION TEMPERATURE

that is related to the polymer segment mobility

A(T Tg )
Viscosity at the beginning
C1 (T Tr ) of glass transition 1012
ln ln r 27.6
C2 (T Tr ) B (T Tg )

A = depends on the difference in thermal expansion coefficients above and below the Tg.
None study on the relation with structural factor that control these coefficients
B = (Tg- T) at which viscosity goes to infinity. 51,6 universal constant but it varies
29
with composition
 Williams Landel Ferry binder design

40.2 (T Tg )
ln 27,6 Wicks/Hill (1982)
51.6 (T Tg ) Approximate form of WLF
WLF eq. No density change is considered

Generally a low Tg is required to have a low viscosity.

Dry to Touch
At Room Temperature (25C)

Blocking If =103 (T-Tg) = 54 C i.e. Tg=-29 C,

per un film che deve essere secco al tocco

if =107 Pa.s Tg=4 C

Attention: the Tg values from WLF are arbitrary. Take some reserve.

30
 binder design

The Tg of a polymer is controlled

By the composition and molecular weight

Mathematical relationship for resin solutions

lg k M n NV
It takes into account the NV fraction
that changes during the film formation

31
 binder design

Flory-Fox eq.
K
Tg Tg
Mn
Tg
is the vitrification* temperature at
molecular weight approaching the
infinity.

K
Is a system-specific constant typically
105

* Gillham

32
 binder design

Functionality
From the above considerations, HS formulations require:
low molecular weight
low polydispersity (asap near 1)
high flexible oligomers

But the Tg values must be similar to those of conventional binders,

so a crosslinking adequate must be made. This can be
accomplished controlling the polar interaction among group.
So maximise crosslinking, minimise interactions

The imperfections in a network can derive from not telechelic chain.

(in a telechelic molecule, all the chain ends bear required reactive
group)

Functionality plays a relevant role.

33
 binder design
Two cases related to the crosslinking action:

F F F F F F

F HS binder
F F
F F F
Reduced Molecular weight
The same functionality F Reduced Molecular weight
Reduced equivalent weight
Lowered functionality
The same equivalent weight

F FF FF
HS binder
FF

functional.group
f
molecule.number

34
 binder design
Radiate and stars structures.
Is often inappropriate to reduce molecular weight or Tg beyond a
certain point and alternative approaches may have to be adopted.

A star shaped molecule extends over a much smaller

volume than the corresponding linear species so
reducing entanglements and friction.

The branches have more freedom than the centre of the

molecule, so the Tg medium and the viscosity, is
further reduced.

The possibility to introduce more reactive groups allows

low equivalent weight and high functionality
(POLYTELECHELIC MOLECULES).

The molecules have a compact structure with a low

polydispersity.

35
 binder design

Star polymers
Obtained from caprolactone and a polyol

OH

36
 Hyperbranched moleculesbinder design
The logical conclusion of star molecules is the dendrimer
type molecule.
Dendrimers impart fluidity also at high molecular weight and none discontinuity appears for the
alpha values of the Mark Houwink eq..
They are used as processing aids.
An A-B2 monomer polymerization is necessary

Degree of branching= (dendritic moieties+ terminal moieties)/ total units> 0,5

Hyperbranched polymers have a very large number of branches. They can be prepared in several ways, but most commonly from AB2 monomers
or from combining A2 and B3 monomers. When prepared from AB2 monomers, gelation does not occur. The polymer molecules have a
single A terminus (the focus) and many B termini (the chain ends). Individual monomers can react at 1, 2, or 3 sites.
Monomers that react at only 1 site (the A site) have two free B sites and are considered terminal (T).
Monomers that react at 2 sites (the A site and 1 B site) have one free B site and are considered linear (L).
Monomers that have reacted at 3 sites (the A site and both B sites) are considered dendritic (D).
Hyperbranched polymers are characterized by a degree of branching (DB) which represents the percentage of
dendritic and terminal monomers among the total monomers in the polymer:
DB = D + T/ (D + T + L)
Statistical treatments show that batch polymerization of AB2 monomers gives a DB of ~0.5.
Higher degrees of branching can be obtained using special reaction conditions (slow addition of monomer, addition of a core).
Perfect branching (DB = 1) can be found in the dendritic polymers

37
 OH binder design
H C H
O
HO C C CH2 OH
O OH
H
O O
Dimethylolpropionic acid OH
O O OH

O OH
OH
A-B2 monomer O O OH

O OH
DENDRIMER 2 generation

Dimethylpropionic acid can be esterified under conventional condition

When it leads to molecules with a preponderance of hydroxyl groups.
The products have low viscosity and high functionality.
The ester group is hindered and so stabilised while OH are relatively reactive

The OH group can be modified with oil-fatty acids to provide

high solids alkyds
38
 binder design

39
Corollaries
Mechanical properties: defecting cohesive
may arise

Reaction rates: high rates may arise but a

long curing time may be necessary without
physical drying

Toxicology: low molecular weight (300-500)

are requested initially.

40
 Specific HS binders
Polyesters.
Polyester are very adaptable molecules. The polymerization
degree can be reduced at the monomer level, the chain can
allocate methylene repeating units to reduce Tg and to offer
minimum frictional resistance, interrupted by ester functions.

They can be completely telechelic increasing the starting diol

(excess).

The viscosity can be adjusted inserting pendant methyl groups;

the danger is the high Mn macromolecules that affect viscosity.

Unfortunately the polydispersity will still be at least 2 for

conventional polymerisation, the functionality is limited at 2
and can be OH or COOH.

The groups have strong tendency to form H-bonds.

41
 Specific HS binders
Polyesters (alkyds).

The pendant fatty acids provide the crosslinking sites.

Chain stopper of the radical reaction between the DB can be inserted to

control the molecular weight.

Long oil alkyds increases solid content so the technology moves towards
increasing fatty acid content.

The other fatty acids are used to crosslink.

It is important to select fatty acid mixture with high number allylic
unsaturation.

Phtalic anhydride can be substituted with adipic acid.

Other polyol can be used to avoid severe condition necessary to esterify

the secondary OH of glycerol.

Solids may be increased by making resins with narrower molecular weight

distribution. For example, one can add a transesterification catalyst near
the end of the alkyd cook uniform molecular weight + lower viscosity

42 Zeno /Wicks
Pg. 274
 Alkyd resins for HS paint: some discussion.

Solvent choice:
Hydrocarbon solvent promote intermolecular hydrogen bonding, expecially
between carboxylic acids, hydroxyl groups thereby increasing viscosity.
Use of at least some hydrogen-bond acceptor solvent gives a significant
reduction of viscosity.

Molecular weight:
Must be low. Low Dibasic acid/ polyol ratio and going towards longer oil.
This means lower functionality and lower ratio of aromatic to aliphatic
chains and then to an increase of the time for drying. We have to use drying
oils with a higher average functionality but whose amount is limited by their
tendency to discolor. Safflower oil better than soybean oil. Proprietary oils
can be used but take attention to yellowish and embrittlement.

43
Alkyd resins for HS paint: some discussion.

Mw dispersion: a narrow molecular weight distribution may increase

the solid. It can be obtained adding a transesterification catalyst near
the end of the alkyd cook.

Use of tripentaerytritol. High rate of crosslinking with a short oil lenght.

Reactive diluents.
Styrene that copolymerise with unsaturaed chain so
VOC is used.

44
 Specific HS binders

Acrylics
The binders are in striking contrast with polyesters.
Chain growth and addition reaction. It is very
difficult to have low Mw.

Functionality is a very critical parameter for acrylics

Notwithstanding the variety of monomers the

structural variations are limited.

45
 Alcohol ester vs tg

150

100
Tg (C)

50 Acrilati
0 Metacrilati
0 5 10 15 20
-50

-100
carbon number

46
 Acrylics
Bulky monomers for high Tg.

Attention to the backbone that may be aparted.

Other vinyl esters (that may undergo free radical

polymerisation) may be used.

Photooxidative degradation reduce weathering.

Polyacrilate more susceptible to radical combination

leading to a doubled molecular weight. The
solution is the chain transfer agents (thiols).

47
Crosslinking chemistry

It is essentially a polymerisation although one

whose monomers may themselves be polymeric,
and whose product is an intractable network.

The same process Chain-growth and step-growth

processes characterise it.

The differences exist if the coating has to

develop its properties at ambient temperatures
or it can be stoved (table).

48
 Crosslinking chemistry

At first functions have to be exactly calculated in order to do not create

gelification or vetrification through H-Bonds.

The viscosity of the system increases with the increasing of polar groups and
their interaction.

The chain-growth polymerisation is the most useful process.

The condensation process creates VOC (activation of polar groups)

Pinhole, popping

The crosslinlink process has to be <<dense and efficient>>

49
 Crosslinking chemistry

The crosslinker molecules have many groups at a high

reactivity, but they cannot reacts before the application.
(tripentaerytritol)

The right bonds however have to develop to give the hard

coating avoiding H bonds or all those of second order.

The second order linkages have to appear after the true

crosslinking reaction.

50
Photochemistry
Why radiation curing
(UV and EB)?
(pag 607 BASF Handbook)
1. ENERGY
2. HEAT

51
 Fractions of a second with normal energy inputs of approx. 1
J/cm2 in the UVA radiation range.
Pigmented systems with sufficient transparency require roughly
double energy input. Depending on the formulation of the UV
coating, pre-drying to release the solvent or water at approx. 70-
90C is beneficial to produce smooth and defect free surfaces.

First generation was limited in speed by the use of unsaturated polyester resins and styrene
as reactive diluents. Monomers free acrylic resins, which have a higher reactivity, permit
coating lines up to 4 times faster. Even higher production and coatings speeds are attained
in foil production, e.g. for the furniture industry in a reel-to reel production process
similar to the coil coatings process.
In all the case the coatings lines are much shorter than is the case with thermal curing.

52
 Chemical vs. photoinduced crosslinking
Radical Initiators. Generally used

Three mechanism for UV curing:

radical, cationic, charge transfer

Condensation polymerisation. USE of catalyst and additives.

Siccatives

Additives for isocyanate crosslink increase of reactivity

53
 Chemical vs. photoinduced crosslinking
UV-Photoinitiators or sensitizer

Longwave UV range

54
 Chemical vs. photoinduced crosslinking

Mechanism of UV curing
For epoxy resins

This mechanism is rae and

limited to few polymers.

55
New type of photonitiators

56
Chain growth crosslinking

The initiation step , is not an efficient process.

It requires an <<initiator>>.
Generation of free radicals
1. I 2A* (direct transfer of energy)
( Trought a sensitizer
2a. S S* or
S*+I (S+I)*
2b S S*
(S+I)S-H + I* S*+I S+I*
I* 2A

I= initiator
S= sensitiser (is used in conjunction with initiator)
A= half initiator

57
Crosslinking chemistry
 Step-growth crosslinking

Desiderata: crosslinker with low molecular weight and low viscosity

1.Monomeric Curing agent.
Toxycological problems of amines that are CH2OCH3 CH2OCH3
substitued by polymides or epoxy-
amine adducts. H3COH2C N
N
N CH2OCH3

The viscosity ratio between binder and

crosslinker must be adjusted on the N N
equivalent weight base.

HMMM hexamethoxymethylamine (can be N

obtained in a monomeric form not H3COH2C CH2OCH3
oligomerised and more suitable for HS
formulation)

2.Amines as Alternative to hydroxyl H

groups N O
Amines are markedly weaker H-bond
donors than hydroxyls but have basic
character that may hinder the acid role. OMe
They have high reactivity with isocyanates.
COOMe

58
Crosslinking chemistry
 Step-growth
crosslinking S

H N
NCO + SH
N H

3. Thiols as alternative to amines and hydroxyl O

S
groups.

4. Thiol-ene chemistry

5. Acetoacetate chemistry

59
Crosslinking chemistry
 Photochemistry

Type of radiation:UV, -radiation, EB.

-rays (80-500Gev)>E.B. (3-12Mev)>U.V.( 3-120 ev)

The actual choice falls on the UV radiation due to the great

improve in the technology.

The effect of UV is almost istantaneous, energy requirements

are low and reactions can be carried out at ambient
temperature.

1 ev=1.60217657 10-19 joules

60
Crosslinking chemistry
 Photochemistry

The two basic principles:

The only radiation absorbed by the reacting system is

effective in producing chemical range (Grotthuss-
Draper).

Each molecule taking part in a chemical reaction absorbs

one quantum of radiation causing the reaction (Stark-
Einstein)

61
Crosslinking chemistry
Photochemistry

hc
E Nh N

N avogadro number

2.86x10 5
E kcal mol 1

I
log( ) elc
I0
Number of moles converted or consumed

number of einstein absorbed

62
Crosslinking chemistry
Photochemistry

= 1 every quantum adsorbed produces one chemical reaction

< 1 others reactions compete with the main photochemical
reaction
> 1 a chain reaction takes place

=efficiency may be high as 1x106, signifying that a radical

chain reaction is operating.

Three mechanism have been used for UV curing:

1. Free radical
2. Cationic
3. Charge transfer

63
Crosslinking chemistry
Photochemistry

Limitations
The critical points are: thickness, flatness, pigment
amount, pigment darkness

Air inhibition: diradical oxygen may terminates chain

growth prematurely and leaves a sticky surface.
The solutions are:

-- to work in inert atmosphere.

-- to increase the radical flux towards the point

where oxygen works (surface).

-- to use allyl ethers

64
Crosslinking chemistry
Photochemistry

65
Photochemistry

66
Crosslinking chemistry
Photochemistry

67
 Photochemistry

Po

a. Standard Hg lamp
b. Low irradiance in the photoinitiator absorption bands. (extended exposure).
c. Flash lights (short exposure)
68
Crosslinking chemistry
 Photochemistry

Energy output

For a Hg standard light:

About
35% in UV range (9% UV-A; 12% UV-B; 9% UV-C)
20% vis
30% IR
20% heat loss

Energy to which the coating is exposed

69
70
Photochemistry

71
Crosslinking chemistry
Chemically initiated
crosslinking

72
Crosslinking chemistry
Chemically initiated chain growth
crosslinking

Auto-oxydation is a redox process. The radical

polymerization might initiate the methacrylate
crosslinking.
Redox chemistry is mainly used for unsaturated polyesters.
At the high temperatures used, the acids are all in the trans
form , like fumarate, that is more reactive than maleate.
Styrene is substituted by vinyltoluene due to its mutagenic
potential .
The preferred redox initiator is the
Co++ octoate + MEK hydroperoxyde.
The salt is usually mixed with the polymer and the
hydroperoxyde added at the point of use.

73
Crosslinking chemistry
 Chemically initiated chain growth crosslinking

Co 2+ + ROOH RO. + OH - + Co 3+
Co 3+ +ROOH RO. + O2 + H+ + Co 2+
RO. +R1H R1. + ROH

Problem of unsaturated polyesters (the same of UV-Cured acrylate):

oxygen inhibition sticky surface

Solution for wood application:

incorporation of wax in the formulation
(floates on the surface and can be removed)

74
Crosslinking chemistry
 Powder coating

Compounding

Calender. The elements of a FORMULA are BLENDED,

HEATED and GELLED to PASS between several successive
CYLINDERS of a
calender, which will produce gauges and lay flat. An
EMBOSSING CYLINDER can also CUSTOMIZE the FINISH in
imprinting a relief on the sheet.
The resultant film is then COOLED, ROLLED or SLIT,
according to the required widths.
PARAMETERS This sheet can also be DOUBLED with other material or
LAMINATED or COATED to give complementary qualities.
Size
Shape
Dispersity of particles
Ability to promote the development of electrostatic charge.
Stability at the temperatures of coalescence and those of
ambient.
75
Crosslinking chemistry
Powder coating

Thermoplastic Powders.
The advantage on the thermosetting resins is that there is
no crosslinking, the film is more flexible.
The drawbacks is the high viscosity that produce
dishomogeneity of thickness and difficult
compounding.
Low molecular weight are preferred.

Typical: PE, PPE, PVC, Polyamide(Nylon-11, 12)

Their application is:
-by fluidised (200-300C) bed because is very difficult to
grind them into small particles.
-by flame spraying (1,5mm thick film)

76
Crosslinking chemistry
Powder coating

Reactive binders for Powders.

Epoxies: Bisphenol-A-epichlorydrin

Bisphenol-A epichlorydrin

Polyesters: Terephtalic and isophtalic acids. Low level of adipic

acids (acids termination are preferred for the crosslinking).

Acrylics: a niche production. Problems of cross contamination with

polyesters, of molecular weight and functionality. It is necessary
to use much solvent

77
Crosslinking chemistry
Non-aqueous dispersion
Disperse phase polymer science

Low production.
Monomer soluble in a solvent polymerization Polymer
insoluble in the same solvent colloidal suspension

The stabilisation can be exclusively of the steric type due to

the aliphatic solvent frequently used.

USE of CO2 supercritical

78
Crosslinking chemistry
HS non-aqueous dispersion

Very HS formulation:
-bimodal distribution of spherical
particles with a polymer content of 80%
and the diameter ratio is 12:1 and 70%
of volume is occupied by the larger
particles.

-BP 1,157,630 tetramodal distribution to

gain up to 95% of the theoretical packing
factor

79
Non-aqueous
dispersion

Plastisols (from 1946: resin plasticiser system)

PVC and/or co-polymers of vinyl chloride with diethyl

malonate to accept plasticisers (tributyl phospate).

The advantage is that plastisols overcome the viscosity

costraints regarding polymer concentration.

They can be used in vHS formulation.

80
Crosslinking chemistry