1. Evaluation of Radiation Dose from Powder and Bulk Hydroxyapatite for Routine Dosimeter
Presented by
Ms. Kanokwan Boonsook
Date: 8 June, 2016
Department of Physics, Faculty of Science
King Mongkut’s University of Technology Thonburi
Good morning ladies and gentlemen. It’s pleasure to be here with you today. First, I’d like to introduce myself. I’m Kanokwan Boonsook. I am a master student in department of Physics at King’s mongkut university of technology thonburi. Today I would like to present the topic about nuclear and radiation physics. In the title is Evaluation of Radiation Dose from Powder and Bulk Hydroxyapatite for Routine Dosimeter
(33 sec)

2. Outlines Introduction Objectives Experiment Results & Discussion
Conclusions
Next, this is outline of my presentation. It consists of 5 main parts. First of all, I will be presenting an introduction of this work. Then, I will talk about objectives, experiment. After that, explain about results and discussion and lastly is conclusions.
(25 sec) 2

3. Introduction Bone Functions of the bone
Framework for support and movement
Protection
Storage of minerals
Production of blood cells
When I talk about the organ system of your body, one of the most importance organ is bone. Because the bone serve a variety of mechanical functions. Together with other bones in the body.
The Functions of the skeleton For example, it is - Structural support for heart, lungs and marrow  - Protection for brain, and other internal organs  - Mineral reservoir for calcium and phosphorus  - production of blood cells 
As mention above, you know that the bone has a lot of function and they are very strong. So, the bone are strong like this due to the composition within the bone.
Ref : 3

4. Introduction (cont.) Composition of bone Calcium Phosphate
Collagen and hydroxyapatite
Fibres
Fibre patterns
Bone tissue
Mineralized collagen fibrils
Osteons and Haversian canals
Ref :
Bone structure
Ok, in the human bone is mainly composed of 65%w of inorganic substances and the remaining 35%w of organic compound which the most is collagen. The inorganic substances in bone as apatite calcium phosphate. The form of calcium phosphate in your bone which is in hydroxyapatite form.
35% Organic
28% collagen
5% protein
65% Inorganic (hydroxyapatite)
Mostly Calcium and inorganic orthophosphate deposited between collagen
Calcium Phosphate 4

5. Introduction (cont.) Osteoporosis Bone fractures Types of fractures
In the daily life of human. Sometimes it may be accidents that result in our bones fracture or brittle. The main cause of the bone fracture caused by trauma due to an injury and spontaneous fracture that cause by a disease (ดีซีซ). In Thailand, there are a lot of patients with this disease, Most of the elderly that is osteoporosis.
Types of fractures
1. Traumatic fracture (cause by an injury)
2. Spontaneous fracture (cause by a disease)
Osteoporosis 5

6. Introduction (cont.) Medical Technology Bone replacement material
Calcium supplement
Bioceramic material
Bioresorbable ceramic
Bioinert ceramic
Bioactive ceramic
“Hydroxyapatite”
In the present, there are many medical technologies which have a role in the treatment of bone disease, such as a calcium supplement, drug inhibits bone destruction, bone replacement surgery with the patient's own bone parts and the other one is the surgery to replace the damaged bone with the artificial bone or bioceramic. Especially, hydroxyapatite that has the ability to bind in the human bone. It is also capable of promoting bone regeneration and bonding directly to regenerated bone without intermediate connective tissue at a faster rate than other materials.
Ref:
Glucosamine 6

7. Introduction (cont.) Effect of radiation
In the future, the patients who had been treated with bone replacement with implanted bones from hydroxyapatite may be work about radiation or diagnose and radiotherapy by radiation. Then, hydroxyapatite from synthesis must be investigate the effect of radiation on hydroxyapatite.
In the future, the patients who had been treated with bone replacement with implanted bones from hydroxyapatite may be work about radiation or diagnose and radiotherapy by radiation. Then, hydroxyapatite from synthesis must be investigate the effect of radiation on hydroxyapatite. So in this research has studied the effects of radiation exposure hydroxyapatite synthesized from quail eggshell using electron spin resonance spectroscopy in order to serve a based medical information and develop new dosimeter for routine dosimetry.
Ref: 7

8. Objectives
To study characteristic ESR signal on hydroxyapatite synthesized from quail eggshell before and after gamma irradiation.
To evaluate gamma radiation dose response on hydroxyapatite synthesized from quail eggshell.
To study fading time on hydroxyapatite synthesized from quail eggshell after irradiation.
Next, the purpose (เพอเพิร์ส) of this work consists of 3 points. The first point is to study characteristic ESR signal on hydroxyapatite synthesized from quail eggshell before and after gamma irradiation. The second point is to evaluate gamma radiation dose response on hydroxyapatite synthesized from quail eggshell. And finally, to study fading time on hydroxyapatite synthesized from quail eggshell after irradiation. (35sec) 8

9. Hydroxyapatite powder
Experiment : Sample Preparation
Samples preparation
Hydroxyapatite synthesis
adjust pH
Remove membrane, clean and crush into powder
NH4OH sol.
6M (NH4)2HPO4 sol.
adjust pH
Quail eggshell
CaO + HNO3
10M Ca(NO3)2 sol.
Heat at temp C
Precipitated
CaCO CaO+CO2
In this part is about experiment. For this work is divided into 2 experimental step. First step is sample preparation and second step is analysis the effect of radiation of the samples.
For the process of sample preparation, first the quail eggshell were removed membrane and cleaned in distilled water. After dried, the quail eggshell were crushed into powder and annealed at 1300 C for 4 hr. at room temperature. After sintering, you can get the eggshell heated at 1300 C that so-called calcium oxides. The calcium oxides were mixed with nitric acid and became to calcium nitrate solution. Then, Phosphate solution was prepared from di-ammonium hydrogen orthophosphate mixed with distilled water and dropped it into calcium nitrate solution. The both of solution were adjusted pH with ammonium hydroxide. After stirring, the solution will precipitate. Hence, it was washed with distilled water over and over times, filtered and dried in oven at 100C for 48 hr. After that, grinded it into the powder. You can get the hydroxyapatite that synthesized from quail eggshell. (2.14 min)
Keep at room temp. for 8 hr.
Filtered
Dry at 100ºC 48 hr.
Sample:
Quail eggshell heated at 1300 C (CaO)
Ground into powder
Hydroxyapatite powder 9

10. Experiment : Characterization
0.5 cm
Irradiation
pellet mold
Gamma ray
Varies dose 0.1 – 10.0 kGy
0.065 g
Hydroxyapatite
Quail eggshell hydroxyapatite
(QS-HAp)
Hydraulic hand pump
Results
Characteristic of ESR signal
Ionizing Radiation - induced free radicals
Results
Dose response
Fading time
post-irradiation fading affects the attainment of high accuracy in dosimetry measurements
Continue from previous slide, in this slide show the experiment for characterization, the samples such as powder and bulk hydroxyapatite were synthesized from quail eggshell. For bulk hydroxyapatite, was prepared from hydroxyapatite g molded (โมวเดิด) with force 300 psi of hydraulic hand pump. The dimension of pellet about 0.5 centimeters (เซนติมิเดิลซ์). After that, all of samples were irradiated with gamma ray at varies dose from 0.1 to 10 kGy. For the results, there are 3 points to study. The first, the characteristic of ESR signal. Second, evaluate dose response on hydroxyapatite and the last study fading time after irradiation. All of the results were investigated by electron spin resonance spectroscopy or ESR. (1.28 min)
Electron spin resonance spectroscopy 10

11. Results & discussion Characteristic ESR signal of HAp
Part 1-1 : Hydroxyapatite
g - value
Free radical
2.0027
CO-
2.0020
Axial CO2-
2.0016
CO33-
1.9987
QS-HAp
CO33-
Axial CO2-
10 kGy
CO-
Fig.2 The model of paramagnetic center in HAp
(Rokhmistrov, D.V. et al.,2012)
Next part is about results and discussion. It’s divided into 3 parts. For this slide is the first part about characteristic of ESR signal of hydroxyapatite. In this figure show ESR signal of QS-HAp before and after gamma irradiation. The ESR signal before irradiation has only a background signal. And after irradiation, there are mainly three components contributing to the ESR spectra. The center peak of ESR is four molecules ions of CO2-, CO3- and CO33-. The g value of center peak of Hap show in the table. The results shows that the characteristic of Hap from quail eggshell is similar to Hap from bone and tooth enamel of human. Moreover, it also appears 2 peaks beside the center peak that assigned to the features of HAp synthesis in the aqueous solution, when the water molecules enter into the formatting HAp crystal lattice consists of water molecules and free electron formed by gamma irradiation of HAp. During the motion the free electron interacts with four protons of water molecules located inside of HAp crystal lattice. For the model of paramagnetic center in hydroxyapatite show in figure2. (1.22min)
before irradiation
The new paramagnetic center in HAp was found. Its formation is assigned to the features of HAp synthesis in the aqueous solution, the free electron of HAp that formed by gamma irradiation interacts with the four photons of the four water molecules during its motion circular trajectory
Fig.1 ESR signal QS-HAp before and after gamma irradiation 11

12. Results & discussion (cont.)
Dose response of hydroxyapatite
Part 2-1
Table.1 Intensity of ESR signal on powder hydroxyapatite dose range kGy
Dose (kGy)
Intensity (a.u.)
0.1
0.2
0.4
0.8
1.0
2.0
4.0
8.0
10.0
Powder QS-HAp
Gamma ray
Varies dose 0.1 – 10 kGy H
Peak-to-peak intensity
Next part is about dose response of powder hydroxyapatite that was irradiated with gamma ray at dose 0.1 to 10 kGy and investigated by ESR. In figure 3 show the effect of the radiation dose of QS-HAp irradiated at various dose and peak to peak intensity or H shows in table 1. from this figure showed that the intensity ESR signal of carbonate radical was increased with increasing radiation dose.
Fig.3 Effect of the radiation dose of powder QS-HAp irradiated with  radiation at various dose
Electron spin resonance spectroscopy 12

13. Irradiation dose (kGy) Dose from calibration curve
Results & discussion (cont.)
Dose response of hydroxyapatite
Part 2-1 : Powder QS-HAp (linear function.)
Table 2. Comparison of radiation dose of powder QS-HAp
Irradiation dose (kGy)
Dose from calibration curve
(kGy)
%error
0.1
-0.121 -
0.2
0.145
27.566
0.4
0.516
28.918
0.8
0.599
25.093
1.0
0.883
11.722
2.0
2.527
26.346
4.0
4.982
24.560
8.0
8.338
4.220
10.0
10.729
7.289
Next, in this slide show dose response curve of powder QS-HAp irradiated with gamma radiation at dose kGy. The relation between radiation dose and intensity of ESR was plotted and show in Fig. 4. The dose response curve obtained in case of gamma irradiation was tried to fit by a linear function of the applied dose as y = mx+c.
From this function we can calculate new radiation dose from calibration curve and compare with Fricke solution dose and show results in table 2. The results show that the percentage errors of powder hydroxyapatite was less than 29%
Fig.4 Dose response curve of powder QS-HAp irradiated with  radiation at room temperature 13

14. Results & discussion (cont.)
Dose response of hydroxyapatite
Part 2-2
Table.3 Intensity of ESR signal on bulk hydroxyapatite dose range kGy
Dose (kGy)
Intensity (a.u.)
0.1
0.2
0.4
0.8
1.0
2.0
4.0
8.0
10.0
Bulk QS-HAp
Gamma ray
Varies dose 0.1 – 10 kGy H
Peak-to-peak intensity
In this part is same as the previous part but change from the powder hydroxyapatite samples into the bulk hydroxyapatite that was irradiated with gamma ray at dose 0.1 to 10 kGy and investigated by ESR. The peak to peak intensity shows in table 1 and Fig 5 show the effect of the radiation dose of bulk QS-HAp irradiated with  radiation at various dose. From this figure showed that the intensity ESR signal of carbonate radical was increased with increasing radiation dose.
Fig.5 Effect of the radiation dose of bulk QS-HAp irradiated with  radiation at various dose
Electron spin resonance spectroscopy 14

15. Irradiation dose (kGy) Dose from calibration curve
Results & discussion (cont.)
Dose response of hydroxyapatite
Part 2-2 : Bulk QS-HAp (linear function.)
Table 4. Comparison of radiation dose of bulk QS-HAp
Irradiation dose (kGy)
Dose from calibration curve
(kGy)
%error
0.1
-0.657 -
0.2
-0.322
0.4
0.051
87.118
0.8
0.983
22.901
1.0
1.117
11.650
2.0
2.877
43.858
4.0
5.005
25.127
8.0
8.090
1.130
10.0
9.356
6.441
in this slide show dose response curve of bulk QS-HAp irradiated with gamma radiation at dose kGy. The relation between radiation dose and intensity of ESR was plotted and show in Fig. 6. The dose response curve was tried to fit by a linear function. The results show that the percentage errors of powder hydroxyapatite was about 87%
that low accuracy. As a result, dose respond from 0.1 to 10 kGy of Hap is inappropriate to calibration curve. So, the dose response was reconsidered and tried to fit by polynomial function as show in the next slide.
Fig.6 Dose response curve of bulk QS-HAp irradiated with  radiation at room temperature (linear function) 15

16. Irradiation dose (kGy) Dose from calibration curve
Results & discussion (cont.)
Dose response of hydroxyapatite
Part 2-2 : Bulk QS-HAp (polynomial function.)
Table 5. Comparison of radiation dose of bulk QS-HAp
Irradiation dose (kGy)
Dose from calibration curve
(kGy)
%error
0.1
-0.073 -
0.2
0.190
5.181
0.4
0.493
23.162
0.8
1.301
62.585
1.0
1.424
42.353
2.0
3.299
64.937
4.0
7.800
94.998
8.0
10.0
From polynomial function we can calculate new radiation dose from calibration curve and compare with Fricke solution dose and show results in table 5. The results show that the percentage errors of dose about 95% that is terrible (เทอระเบิล) and inappropriate to calibration curve.
Fig.7 Dose response curve of bulk QS-HAp irradiated with  radiation at room temperature (polynomial function) 16

17. Results & discussion (cont.)
Dose response of hydroxyapatite
Part 2-2 : Bulk QS-HAp (polynomial function.)
Table.6 Intensity of ESR signal on QS-HAp dose range kGy
kGy
0.1 – 2 kGy
Dose (kGy)
Intensity (a.u.)
0.1
0.2
0.4
0.8
1.0
2.0
4.0
8.0
10.0
So, we separated curve into small range from kGy show in Figure 8. The dose response curve obtained in case of gamma irradiation was tried to fit by a polynomial function.
%error = 94.99%
Fig.7 Dose response curve of bulk QS-HAp irradiated with  radiation at dose kGy
Fig.8 Dose response curve of bulk QS-HAp irradiated with  radiation at dose kGy 17

18. Irradiation dose (kGy) Dose from calibration curve
Results & discussion (cont.)
Dose response of hydroxyapatite
Part 2-2 : Bulk QS-HAp (polynomial function.)
Table 7. Comparison of radiation dose of QS-HAp
Irradiation dose (kGy)
Dose from calibration curve
(kGy)
%error
0.2
0.198
0.940
0.4
0.351
12.290
0.8
0.751
6.134
1.0
0.811
18.926
2.0
1.679
16.028
From polynomial function we can calculate new radiation dose from calibration curve and compare with Fricke solution dose and show results in table 7. The results show that all of dose from 0.2 – 2 kGy have the percentage errors less than 20% and less than powder hydroxyapatite.
Fig.8 Dose response curve of bulk QS-HAp irradiated with  radiation at dose 0.1 – 2 kGy 18

19. Results & discussion (cont.)
Dose response of hydroxyapatite
Conclusions
Samples
Type
Optimum range (kGy)
Function
Equation R2
Maximum
error
QS-HAp
powder
0.1 – 10.0
linear
y = x
0.9933
28.92%
bulk
0.2 – 2.0
polynomial
y = x x
0.9956
18.93%
From the experiment can conclusion the powder and bulk hydroxyapatite can use the dosimeter for routine dosimeter in range 0.1 to 10.0 and 0.2 to 2.0 kGy, respectively. 19

20. Results & discussion (cont.)
Fading on hydroxyapatite
Part 3-3 : QS-HAp
Bulk hydroxyapatite
Powder hydroxyapatite
Bulk hydroxyapatite
Powder hydroxyapatite
Fading time and percentage of ESR intensity of hydroxyapatite after irradiated from 1 to 60 days was calculated and shown in Fig. 9 and 10, respectively. The results show that the intensity of ESR signal was decreased with increasing time. The ESR intensity of powder hydroxyapatite was decreased about 22% after left for 60 days that less than bulk. The bulk hydroxyapatite is easier to handle, although fading time is decrease more than powder.
Fig.9 Fading of ESR signal intensity of (a) powder and (b) bulk hydroxyapatite irradiated at 1 kGy
Fig.10 Percentage ESR signal intensity as a function of storage time for (a) powder and (b) bulk hydroxyapatite irradiated at 1 kGy 20

21. Conclusions
Gamma radiation induced carbonate radicals with a center g-factor of and indicated that hydroxyapatite from quail eggshell has characteristic and properties similar to hydroxyapatite in bone or tooth human.
Powder and bulk hydroxyapatite from quail eggshell could be used the best dosimeter in the range of 0.1 – 10.0 kGy and 0.2 – 2.0 kGy, respectively.
Hydroxyapatite from quail eggshell can use to be a dosimeter for routine dosimetry.
Next part is about conclusions of this study. The fisrt 21

22. References
Negron-Mendoza, A., Uribe M., R., Ramos-Bernal, S., Camargo-Raya, C., Gomez-Vidales, V. and Kobayashi, K., (2015), “Calcium carbonate as a possible dosimeter for high irradiation doses”, Applied Radiation and Isotopes, Vol.100, pp
Rokhmistrov,D.V., Nikolov, O.T., Gorobchenko, O.A. and Loza, K.I., 2012, “Study of structure of calcium phosphate materials by means of electron spin resonance”, Applied Radiation and Isotopes, Vol.70, pp
Da Costa, Z.M., Pomtuschka, W.M., Ludwig, V., Giehl, J.M., Da Costa, C.R. and Duarte, E.L., 2007, “A Study based on ESR, XRD and SEM of Signal Induced by Gamma Irradiation in Eggshell”, Radiation Measurements, Vol.42, pp
Engin, B. and Demirtas. H., 2004, “The Use of ESR Spectroscopy for the Investigation of Dosimetric Properties of Egg Shells”, Radiation Physics and Chemistry, Vol.71, pp
Da Costa, Z.M., Pomtuschka, W.M. and Campos, L.L., 2004, “Study of the ESR Signal of Gamma Irradiated Hydroxyapatite for Dose Assessment” Nuclear Instruments and Methods in Physics Research B, Vol.218, pp 22

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