Ecole Doctorale Sciences et Ingénierie des

Molécules Procédés Produits et Énergie

Rapport annuel de progression de la thèse

Juillet / 2023

DEVELOPPEMENT DE NOUVELLES TECHNOLOGIES DE

FERTILISATION CONTROLEE EN UTILISANT DES

M. Mehdi KHOULOUD

ème
doctorant(e) en 2 année de thèse

LCPM,
1 rue Grandville, BP20451,

Sommaire

I. THESIS
OBJECTIVES: .......................................................................
......................................................... 3
II. STATE OF THE
ART: ..............................................................................
.................................................. 3
II. 1. Modified
clays: ............................................................................
................................................... 4
II. 2. Stimuli-responsive smart
fertilizers: ......................................................................
....................... 4
II. 3. Chitosan and poly( -caprolactone)
systems: ..........................................................................
...... 5
II. 4. Chitosan (CS) and clay composite
materials : .......................................................................
........ 6
III. METHODOLOGY / WORK
UNDERTAKEN: .......................................................................
...................... 6
III. 1. Pillared
clays: ............................................................................
.................................................... 6
I 1 P l r g r l :
. . i a i t i
s ................................................................................
.............................................. 8
l n a
I 2 R s l s n d c s i
n ................................................................................
................................ 8
. . e u a d i u s :
t s o
III. 2. Development of amphiphilic pH responsive CS-g-PCL
copolymers: ......................................... 10
I I 2 1 P l m r a i n r l :
I . . . o e i t t i
s ................................................................................
............................. 11
y z o a
I I 2 2 R s l s n S H l
I . . . e u o C - C

t ..................................................................
................................................. 12
I I 2 3 R s l s n o o y e s
I . . . e u o c p l m
r ................................................................................
........................... 12
t
IV. THREE-YEAR THESIS
TIMELINE: .........................................................................
................................. 15
V. THESIS
PROGRESS: .........................................................................
...................................................... 16
VI. PROFESSIONAL
OBJECTIVE: ........................................................................
........................................ 16
2

I.
 Approach 4
Regulation of foliar fertilizer
The intermittent
release via encapsulation using
nature of solar

photosensitivity.
for regulation of the

release.

Approach 2
Control of fertilizer release through coating with

The decrease in pH levels

pH-sensitive materials. (CS-g-PCL)

within the rhizosphere

Approach 3 pH

synchronized release of
Use of clay modified by CS intercalation as a

nutrients with the

« fertilizer carrier »
Approach 1 NPK

plant's needs.
Use of clay modified by bridging as a
II.
« fertilizer carrier »
Figure 1: Soil and foliar targeted
controlled release concepts

II. 1.
 Figure 2: Layered structure of
smectites

II. 2.

4
II. 3.

II. 4.
III.
III. 1.

6
 Figure 3: Pillaring and fertilizer
production protocol

Acid washed sand

Water
for 24 hours then thoroughly
washed with distilled
feeding:
Pump
water until a negative AgNO3
test was obtained.
@ 5ml/min Fertilizer
granules (5g)

5 cm

20

Figure 4: Set-up for evaluating the release kinetics

through sand columns

I 1 P l r g t i l :
 . . i a i r s
l n a

T° Calcination ratio % w/w Water mmol total

pillaring AlCl3.6H2O NaOH pillaring
Clay (g)
(°C) OH-/Al suspension (ml) Al/g clay Al (mol)
Trial 1 200 2 10 3 323,3 10 0,1
250 500 750
Trial 2 300 2 10 3 323,3 10 0,1
250 500 750
Trial 3 400 2 10 3 323,3 10 0,1
250 500 750
Trial 4 500 2 10 3 323,3 10 0,1
250 500 750

I 2 R s l s a d d c s i n
. . e u n i u s :
t s o

Pillared Clay
Normal Clay

200°C

300°C

400°C

500°C

Figure 5: FTIR analysis of pillared and

non-pillared clays treated at different temperatures.

These results
suggest the potential use of this
Moroccan clay in CO2 capture. The clay samples were also analyzed using scanning
electron

revealed the typical morphology of smectites, the calcined intercalated clay

samples at 400 and 500°C
exhibit a less dense structure with more visible pores.

Ghassoulite Clay PILC Calcined @ 200°C PILC Calcined @ 300°C PILC

Calcined @ 400°C PILC Calcined @ 500°C
 Figure 6: Scanning Electron Microscopy (SEM) Images of Treated
and Untreated Clay Samples

On the other hand, EDX

Normal
the detection of localized
clay

the case of pillared clays.

Pillared
F r i z r p o u t n a d
e t i e r d c i n
l o
clay
a s s m n :
s e s e t
Figure 7: EDX
analysis of clay samples.
In these trials, we investigated

primarily monocalcium phosphate as its source of phosphorus, monoammonium

phosphate (MAP), diammonium phosphate(DAP), and an NPK ((NH4)2HPO4,

with clay in an 80:20 fertilizer to PILC ratio and cogranulated. Figure 8 gives
an
illustration of a granulated product.

on the physical properties of the granules as illustrated in figure 9,

specifically

Figure 8: Cogranulated PILC-

the caking tendency was eliminated and the crushing strength of the granules
Fertilizer granules

27,5 Caking tendancy (KgF) Crushing

strength (kgF)
30
25 21

15
10
2 2,5
1 0 0 0 1 0 1 0
0

MAP DAP TSP NPK

Figure 9: Fertilizer granules physical properties

assessement:Caking tendancy (left), Hardness (right)

With regards to the release kinetics, which constitute the primary objective of
this study, we conducted
an evaluation of the phosphorus release from the four phosphate fertilizers. The
trials are underway,

good sign (figure 10).

Figure 10: Ongoing release kinetics assessement using

sand columns protocol.

Hydration
Pillared Clay

Hydration Dehydration
Clay Dehydration

(Fertilizer) (Fertilizer+Clay)
(Fertilizer+PILC)
Figure 11: Swelling behavior of fertilizer
granules.

The fertilizer co-granulated with untreated clay had in most cases the fastest
nutrient release due to the
swelling behavior (as it did not have interlayer pillars, as illustrated in figure
11) that lead to the
 hypothesis through static disintegration tests in water. These trials are ongoing
and will be continued
for at least one month.

III. 2.

Deacetylation

Concentrated NaOH

Figure 12: Deacetylation of chitin.

Chitosan exhibits a pH-responsive behavior thanks to its amino groups and can be
utilized for the
development of smart materials for the controlled release of fertilizers by taking
advantage of the pH

10
 Protonation
Diluted HCl
(Oct) Sn, 120°C
2

Basic
environment Acidic environment

R = H or

The grafting/polymerization process

is performed through ring opening Sn(Oct)2 + R-OH OctSnOR +
OctH
following the
OctSnOR + R-OH ROSnOR +
OctH
mechanism described below :

R-OH represents chitosan with

its primary hydroxyl group

I I 2 1
I . . .
Protonation of chitosan was carried out using hydrochloric acid, considering the
degree of
deacetylation. After protonation, chitosan becomes soluble in water and is
recovered through
lyophilization. Freshly cryodistilled -caprolactone was introduced into a reaction
vessel containing dried
chitosan under a controlled atmosphere. Mass polymerization was conducted at 120°C
using different
ratios of chitosan to caprolactone. The reaction kinetics were analyzed using
nuclear magnetic

The molar ratio of catalyst (tin octoate) to -caprolactone is fixed at 1/100;

however, with respect to the
primary OH groups of chitosan, targeted as grafting sites, this ratio varies from
one experiment to

2% 3% 5% 7% 10%
100 100 100 100
100
0,750 0,500 0,300 0,214
0,150
11

I I 2 2
I . . .
The degree of deacetylation of CS was determined using
1
by comparing the integrals of resonance peaks at
approximately 2 ppm, corresponding to the protons of the
group of the acetyl moiety, with the integral

ring, located between 3 and 4.4 ppm (figure 13). The

degree of acetylation of the chitosan used is 24.2%, which

By subjecting chitosan to stoichiometric protonation using

diluted HCl, a clear solution was obtained, as illustrated in Figure 13:
Evaluation of the degree of acetylation of
chitosan by H NMR
spectroscopy.
1

+
NH3 and enabling solubility of chitosan. After

FTIR spectroscopy was utilized to validate the protonation process, and the results
indicated a band
-1
, which confirms the successful protonation of amine
groups (figure 14).

1560 1520
CS

CS-HCl
a

b
FTIR analysis
Figure 15:(a) "Protonated chitosan solution", ( Figure 14:
of chitosan and protonated chitosan.
 b) "Chitosan-HCl after lyophilization".

The measured molar mass by size exclusion chromatography (SEC) of the CS-HCl
sample, was
estimated as follows: = 1900 g/mol, = 1390 37.
The characterization
was performed in LCPM using a double detection equipment (DRI-LS) with an aqueous
eluent (NaNO3

I I 2 3
I . . .
The produced copolymers were assessed
Physical blend

Physical blend
CS-HCl in CS-HCl-
g-PCL
for solubility in water, dichloromethane, PCL in CH Cl
PCL+CS_HCl in PCL+CS_HCl in
2 2 H O in CH
Cl /H O
2 2 2
2 CH Cl /H O CH Cl

2 2 2 2 2
made with PCL, CS-HCl and physical

in water and PCL in DCM, resulting in clear

solutions. The physical blend gives also
clear non-miscible solutions. The

visible interfacial layer at the solvent

and amine function protection (figure 16).

Figure 16 : Amphiphilic
behavior assessment in solvent mixtures.

12

The kinetics of polymerization were

1
solvent. The conversion yields for each
experiment were determined by tracking the
of the and ' protons, which
appeared at 4 ppm 4.2 ppm,
-
caprolactone) and monomer. The
using
following formula:
Where are the integrals of the
peaks.
Figure
17 : H NMR conversion assessment

The kinetics of bulk heterogeneous polymerization are challenging to characterize

due to the complexity
and heterogeneity of the reaction mixture. Due to this issue, several experiments
have been carried out

are illustrated in figure 18.

Figure 18: Polymerization kinetics of CS-HCl-g-PCL

copolymers.

SEC analyses were conducted on filtered copolymer solutions in THF and were
performed at IMED-
Lab using equipment equipped with dual RID and UV (254 nm) detections calibrated
using polystyrene

increased grafting sites, and shorter grafts chains. D

50000 2,2
2
40000
CS-HCl-g-PCL
Mw
1,8
Mn
30000
1,6
20000
1,4
10000 1,2
CS_HCl Content w/w%
CS_HCl Content w/w%
0 1
0% 2% 4% 6% 8% 10% 12% 0% 2% 4% 6%
8% 10% 12%
Figure 19: Mw & Mn of CS-HCl-g-PCL copolymers as function of CS-HCl
Figure 20: Dispersity
of CS-HCl-g-PCL copolymers as function of CS-
content.
HCl content.
13

suggesting moderate to broad molecular weight distribution. Increasing CS content

(2% to 10%)
correlates with lower molecular weight, as illustrated in figure 20, and narrower
dispersity in grafted

Solubilizing amphiphilic copolymers such as CS-g-PCL

both hydrophobic PCL grafts and
hydrophilic chitosan backbone is challenging. While PCL

THF[35], chitosan is mostly insoluble, except in acidic

aqueous solutions [36]. Previous studies have reported

g-PCL dissolution [37][38]. However, solubility may vary

based on CS-g-PCL parameters. Although prepared
1
DMSO-d6 predominantly reveal PCL proton peaks, with
an interfering peak at 3.3 ppm due to absorbed moisture.
(or CS-HCl) was
observed (figure 21).

FTIR analysis was performed on all samples. The

characteristic band for the ammonium group in CS-HCl
-1
-1
in PCL exhibited a distinct peak at 1720 cm . These

copolymers (figure 22).

Figure 21: Top to bottom: H-

NMR spectrum of -Caprolactone using CDCl3
1
as solvent, H-NMR spectrum of
Poly( -Caprolactone) using CDCl3 as solvent,
1
H-NMR spectrum of CS-HCl-g-
PCL copolymer (7%CS-HCl) using DMSO-d6 as
1
1

PCL

CS-g-PCL
(2%CS HCl)

CS-g-PCL
(3%CS HCl)
 CS-g-PCL
(5%CS HCl)

CS-g-PCL
(7%CS HCl)

Figure 22:
Evolution of CS-HCl-g-PCL (7%CS HCl) FTIR
spectrum with
progression of polymerization.
CS-g-PCL
(10%CS HCl)

During FTIR
analysis monitoring (as
CS-HCl
the intensity of
such ammonium band
.
This phenomenon
suggests the partial
Figure 23 : FTIR spectra of neat PCL, CS-g-PCL with different CS-
HCl ratios and neat CS-HCl.
initiating sites
14

Solubilization tests at 10% w/w in THF were CS-HCl content

in copolymer
performed on copolymers with CS-HCl content 2%
5% 7%

90,67 91,65 93,10

were centrifuged, at 10k rpm for 5min, to

9,32 8,34 6,90

evaluate the soluble fraction compared to the

polymers. The mass distribution is reported in the table.

1
The two parts were characterized using H NMR with DMSO-d6
as solvent (figure 25). The spectra obtained only show chemical

Supernatant
hand, FTIR characterizations indicate the presence of PCL
in the soluble fraction. In the precipitate, both
(figure 24).

Pellet

Figure 24
: H NMR Spectra of soluble (supernatant) and

1
insoluble
(pellet) fractions of CS-HCl-g-PCL (5%CS-HCl)

Figure
25: FTIR analysis of soluble (supernatant) and
insoluble
(pellet) fractions of CS-HCl-g-PCL (5%CS-HCl)

Films of the obtained materials were prepared using a

hydraulic press at 60°C (melting temperature of PCL)

in figure 23). With an increasing amount of CS, the

resulting films exhibit greater fragility due to the presence

previously discussed. Only the sample with a 2% wt CS

allows for the measurement of the mechanical properties.

to assess their properties.

Figure 26: CS-HCl-

g-PCL films preperation with hydraulic
press.

IV.

st
1 year Natural clay crosslinking and characterization of the pillared
clays
Cogranulation of the pillared clays with fertilizers

Amine protection of CS by protonation

nd
2 year Synthesis and characterization of CS-HCl-g-PCL amphiphilic
copolymers
Coating of fertilizers with CS-HCl-g-PCL amphiphilic copolymers

15