Dr.Ir. Gatot Trimulyadi : The adsorption behavior of chitin and its concerns with various degree of deacetylization. This high adsorption capacity was ascribable primarily to its remarkable hydrophilicity in cooperation with the relatively high amino group content. It is indicate that the importance of hydrophlicity and suggest that, in order to develop adsorbents of high capacity, it is make indicate the importance of hydrophilicity essential to make chitin derivatives highly hydrophylic and yet insoluble in water.

1. IRRADIATION GRAFTING OF HYDROPHYLIC
MONOMER
ONTO CHITIN FOR ION EXCHANGE
APPLICATION
Gatot Trimulyadi Rekso
Center for Research and Development of Isotopes and Radiation
Technology
Jl . Lebakbulus raya No 49, Jakarta 12240, INDONESIA
Fax 62 21 7691607, E-Mail : Gatot2811@yahoo.com

2. INTRODUCTION
INDONESIA DEVELOPING COUNTRY
INDUSTRIAL DEVELOPMENT
BESIDE PRODUCT
ENVIRONMENTAL PROBLEM
LIQIID WASTE WITH THE HEAVY METAL CONTENT
IN THE LARGE SCALE OF PRODUCTION CAN BE
HAZARDOUS TO ENVIRONMENTAL
ION EXCHANGE ADSORBENT
 CHEAP
 SIMPLE
 USEFFULL IN WASTE TREATMENT

3. • The natural chelating marine polymer chitin, poly(N-acetyl-
D-glucosamine) and its deacetylated derivative chitosan is
useful for removing heavy metal ion waste from discharge
water .
• Chitin , the most abundant naturally is undoubtedly one of
the most promising and attracting resources present in
quantity. Among some interesting properties of chitin ,
chelating ability arising from its characteristic structure is
especially noteworthy. Many researchers have explored the
feasibility of this approach. Kurita.K et.,all, conducted
experiments with a number of heavy metals

4. Shell seafood waste such as shrimps shell and craps are
abundantly in Inonesia
Shrimps shell Craps shell
The remarkable rapid and successful expansion of shrimps processing
industry in Indonesia suggests the possibility of utilizing shrimps-
processing waste as raw material for the manufacture of many valuable
products such as chitin and chitosan for industrial and health care
product
Indonesian shrimps production in 2006 had been projected 350.000 tons

5. SHRIMPS SHELL
NaOH, 1M
DEPROTEINATION WASTE
Organic
Fertilizer
WASTE
HCl, 1M
DEMINERALIZATION
CHITIN
Chitosan

6. The adsorption behavior of chitin and its concerns with various degree of
deacetylization. This high adsorption capacity was ascribable primarily to
its remarkable hydrophilicity in cooperation with the relatively high amino
group content. It is indicate that the importance of hydrophlicity and
suggest that, in order to develop adsorbents of high capacity, it is make
indicate the importance of hydrophilicity essential to make chitin
derivatives highly hydrophylic and yet insoluble in water.
In this present study, the purpose of the experiments is to study
graft-copolyimerization reactions as well as to study the
absorption properties as ion exchange of grafted chitin.
Hydrophilic monomers such as acrylic acid will be employed for
these experiments. The functional group of graft –copolymers is
expected to be useful in the attaching test of metal ions.

7. MODIFICATION OF CHITIN AND CHITOSAN BY IRRADIATION
TECHNIQUE
Irradiation Degradation
Degradation
・ Solid state
Polysaccharides
Polysaccharides Dilute aq. solution
Chitin/Chitosan,
Chitin/Chitosan, Pencangkokan/ grafting
and their derivatives
and their derivatives Irradiation
Applications
In Agriculture, Industry,
Food, Medicine, Cosmetic Paste-like Crosslinking
Crosslinking
Fields
condition
Carboxymethylchitin
Carboxymethylchitosa

8. WHY RADIATION TECHNOLOGY
IS IMPORTANT?
Health
Environment
Safety
New materials
Address all aspects of
Millennium Project !!!

9. HIGH QUALITY MATERIALS
Crosslinking
Grafting
Degradation

10. Electron Beam Machine
Specifications
No EPS-300 Type GJ-2 Type
1 Installation year 1984 1994
2 Origin Nissin High Shanghai Xian-
Voltage, Japan Feng Electrical
Manufacturing
Work, China
Type Cockroft- Dynamitron
3
Walton
4 Max tension 300 kV 2000 kV
5 Max energy 300 keV 2000 keV
6 Max flow 50 mA 10 mA
Sample Konveyor Konveyor
7
transportation

11. Panoramic Batch Irradiator, the Control Panel
Latex Irradiator, the Control
Panel
Gammacell-220 Gamma Chamber-4000A

12. IRRADIATION GRAFTING
GRAFTING MECHANISM
1. Initiation
Pembentukan radikal akibat radiasi
IRADIASI
a. Chit Chit• + H•
b. Chit• + M Chit-H + M•
2. Propagation
M• + nM M• n+1
3. Terminanation
Chit • + M• m grafted
Mm • + M• n+1 Homopolymer

13. Reaction of graffting acrylic acid onto chitin
H CH3
O CH3
C O H O
CH2 C O
H O H O NH CH2
H O H O NH
O
HO O O
NH CH2 O HO O
HO
NH CH2 O
C O HO
C O
CH3
CH3 n
Iradiasi
Pemanasan
.
H CH3
O CH3
C O O
CH2 C O
H O HO NH CH2
H O H O NH
O
HO O O
NH
C O
CH3
. O
CH2 O HO
NH
C O
O
.O
CH2 O
CH3 n
O
CH2 CH C
OH
O
CH C
OH
H CH3
CH2
O O CH3
C O
CH2 C O
H O HO NH CH2
H O HO NH
O
HO O O
NH CH2 O HO O
NH CH2 O
C O O
O C O
CH3
CH3 CH2
CH2 O
O CH C
CH C OH n
OH

14. EXPERIMENTAL
Material and Experiment
Chitin extracted from prawn shell (Penaeus Monodon), it was got from
Muara Karang , North Jakarta. The were initially washed by water and then
dried at 800 C overnight and conditioned at room temperature for 24 hr.
Acrylic acid monomer, and white crystalline powder, obtained from E
Merck, and other chemicals of reagent grade were used without
purification.
Radiation Source
Gamma radiation source of Co-60, IRKA batch irradiator , with irradiation
dose rate about 9,0 kGy/hr was employed in these experiments. This
radiation source is located at Pasar Jumat, Center for Application of
Isotopes and Radiation Technology, Jakarta, Indonesia.

15. Grafting reaction
• In the present experiment, the pre irradiation graft co polymerization
method was employed. In this method a sample of chitin powder of
about 500 mg , was put into a glass tube, then irradiated in air
atmosphere at room temperature.
• A monomer acrylic acid solution was deairated by bubbling with
nitrogen gas, then introduced into the pre irradiated sample and the
graft polymerization was carried out in a nitrogen atmosphere at
certain temperature . The grafted chitin obtained was washed toughly
with aquadest and soaked overnight in aquadest, then subjected to
sox let extraction with methanol for 8 hours to extract homopolymer.
The grafted chitin then was dried in vacuum until they reached a
constant weight at 500 C.
• The percentage of graft yield was calculated from the difference in
weight ;
o Graft yield = ( Wg - Wo ) / Wo x 100 %
• Where Wo and Wg are the weight before and after grafting.

16. Measuring off adsorption of metal ions by chitin and its modified
The experiment was done with chitosan with degree of the deacetylization
of 78,5 % and modified chitin were Chitin-g-Aac. Measuring the rate of
adsorption about 100 mg of powder material (chitin,chitosan and it’s
modifications) equilibrated with 100 ml 0f solutions ( HgSO4 , CuSO4.5 H2O,
K2Cr2O7) 0,1 M, at pH 4,0 and stirred for 60 min. The metal ion uptake
concentrated after equilibrating were determined by using AAS and for
Hg(II) using CV-AAS.

17. RESULTS AND DISCUSSION

18. FTIR
Evidence of grafting : The increase in weight of the extracted grafted sample, as compare with that the
original chitin and their FTIR spectra , was used as evidence of grafting.
The FTIR spectra of chitin and grafted chitin are shown in Fig 1. It can be seen that a band around at 1660
cm –1 arises from carbonyl absorption of chitin and anew band appear at 3400 cm -1 which correspond to the
hydroxyl absorption of grafted chitin with acrylic acid and at 3500 cm -1 is asymmetric stretching of NH2 for
grafted chitin with acrylamide.

19. 160
10 % Acrylamide
140
Degree of grafting (% )
20 % Acrylamide
120
30 % Acrylamide
100
40 % Acrylamide
80
60
40
20
0
0 60 120 180 240 300
Reaction time (min)
• The effect of acrylic acid and acrylamide monomer
concentration on the percentage of grafting with reaction
period of 1 hr, 2 hr, 3 hr and 4 hr are presented on
Figure above.
It can be seen that the percentage of grafting is independent of the monomer
concentration

20. Effect of grafting temperature
100 200
Temp 50 C
React. Temp 50 C
P e rc e n ta g e o f g ra ftin g (% )
80 Temp 60 C
Degree of grafting (%)
160 React. Temp 60 C
Temp 70 C
React. Temp 70 C
60 120
Temp 80 C React. Temp 80 C
40
80
20
40
0
0
0 1 2 3 4 5 6
0 60 120 180 240 300
Time of reaction (hr)
Reaction time (min)
• It is oblivious that the degree of grafting is largely
by the reaction temperature. The higher
temperature the higher of degree of grafting
obtained.
• The reason is that the increase in temperature
improves the monomer diffusibility as well as the
mobility of the monomer.
• It is recommended that the optimum reaction for
this grafting system is 70 0 C more than that the
increasing of degree of grafting is not so much,
there is a nearly constant value.

21. The ion exchange adsorption of metals ions
by grafted chitin and its derivatives
The capacity of adsorption
( mg / g)
Materials
Hg(II) Cr(VI) Cu(II) • These results clearly show that chitin modified as chitin
grafted acrylic acid have higher capacity of adsorption for
ion metal such Hg, Cr, and Cu.
Chitin 92,6 30,6 24,4
Chitosan 174,5 48,4 44,2 • The highest one is for metal ion Hg. The chitin modified
have an excellent adsorption capacity due to the
Chitin-g-Aac 294,3 109,5 180,1
advantageous location of -COOH, -OH and –NH2 group in
Chitin-g-Aam 257.3 94,8 154.6 the molecule of chitosan to form complex formation and
Chitosan-g-Aac 488,9 318,5 362,8 functional group of monomer act as ion exchger for ions
metal.
Chitosan-g-AAm 464,2 325,8 398,2

22.  Using acryl amide give percentage of
grafting higher compare with acrylic
acid.
 The presence of monomer grafted onto
chitin is demonstrated by FTIR spectrum
with the appearing of carbonyl functional
group.
 The optimal condition of monomer
acrylic acid or acryl amide concentration
was 30 %, temperature 700 C and
reaction period of 3 hours.
 Chitin grafted with acrylic acid give a
higher capacity of adsorption of metal
ion Cr, Cu and Hg compare grafted with
acryl amide.
 The high rate of adsorption is for metal
ion Hg it was found 488,9 mg/g for
chitosan-g-Aac and 464,2 mg/g for
Chitosan-g-Aam.

23. Don't worry, be happy
with nuclear