産業技術総合研究所

高エネルギー物質研究グループ

発熱分解エネルギー測定の標準化

熱分析結果

tert-Butyl peroxide - Toluene

C8H18O2 – C6H5CH3

CH3

TBP - Toluene

CH3

H3C

O

CH3

H3C

CH3

O

H3C

ARC device: New ARC (TIAX, LLC)
Material of Bomb: Ti, Hastelloy C
Waiting & Searching Time: 15 min, 30 min
TBP Concentration: 10%, 20%, 30%
Date: 2008/12, 2009/6
Operator: Y. S.

a) Material of Bomb: Hastelloy C
Waiting & Searching Time: 30 min
TBP Concentration: 20%

5000

250

Temperature
Pressure

4000

150

3000

100

2000

50

1000

0
0

200

400

600

800

Time / minTime vs. Temperature and Pressure

1000

0
1200

Pressure / kPa

Temperature / ℃

200

103

before correction
after correction
Self heating rate/ K min-1

102

101

100

10-1

10-2
100

120

140

160

180

200

220

240

260

Temperature/ ℃ (Plotted as 1/T K)
Temperature vs. Self heating rate

240

before correction
after correction

Temperature/ ℃

220

200

180

160

140

120

100
10-4

10-3

10-2

10-1

100

TMR/ min
TMR vs. Temperature

101

102

103

1.E+02-1

0.00260.00250.00240.00230.00220.00210.002

1.E+000.00180.0019Heat Rate/ K min

1.E+01

1.E-01-1.7020E+04x

y = 5.2406E+17e
R2 = 9.9980E-01

1.E-02Temperature/ K-1

Temperature vs. Self heating rate (approximate calculation)
1.E+03

1.E+02

TMR/ miny = 4.0404E-16e1.5789E+04x
R2 = 9.9960E-01

1.E+01

1.E+000.00180.00190.002

0.00210.00220.00230.0024

1.E-01
Temperature/ K-1

Temperature vs. TMR (approximate calculation)

0.00250.00262

1

0.00260.00250.00240.00230.002200.002

0.0021

-1

-1

-3

-4

-5

-6

y = -1.8703E+04x + 4.0200E+01
R2 = 9.9994E-01

-7

-8

-9
Temperature/ K-1

Arrhenius equation (approximate calculation)b) Material of Bomb: Ti
Waiting & Searching Time: 30 min
TBP Concentration: 20%

250

5000

Temperature
Pressure

4000

150

3000

100

2000

50

1000

0
0

200

400

600

800

Time/minTime vs. Temperature and Pressure

1000

0
1200

Pressure/kPa

Temperature/℃

200

ln k*/ min

-2

103

before correction
after correction
Self heating rate/ K min-1

102

101

100

10-1

10-2
100

120

140

160

180

200

220

240

Temperature/ ℃ (Plotted as 1/T K)
Temperature vs. Self heating rate

240

before correction
after correction

220

Temperature/ ℃

200

180

160

140

120

100
10-3

10-2

10-1

100

TMR/ min
TMR vs. Temperature

101

102

103

1.E+02-1

0.00260.00250.00240.00230.00220.00210.002

1.E+000.0019Heat Rate/ K min

1.E+01

1.E-01-1.6767E+04x

y = 2.6624E+17e2
R = 9.9983E-01

1.E-02Temperature/ K-1

Temperature vs. Self heating rate (approximate calculation)
1.E+03
1.5845E+04x

y = 3.7577E-16e
2
R = 9.9981E-01

1.E+010.00270.00260.00250.00240.00230.00220.00210.002

1.E+000.0019

1.E-01
Temperature/ K-1

Temperature vs. TMR (approximate calculation)

TMR/ min

1.E+02

2.00E+00

0.00270.00260.00250.00240.00230.00220.0021

0.00E+00
0.002-1-4.00E+00-6.00E+00

y = -1.8624E+04x + 4.0074E+01
2
R = 9.9994E-01-8.00E+00-1.00E+01
Temperature/ K-1

Arrhenius equation (approximate calculation)c) Material of Bomb: Ti
Waiting & Searching Time: 15 min
TBP Concentration: 20%

250

4000

Temperature
Pressure
200

150
2000
100

1000
50

0

0
0

200

400

600

Time/minTime vs. Temperature and Pressure

800

Pressure/kPa

Temperature/℃

3000

ln k*/ min-2.00E+00

103

before correction
after correction
Self heating rate/ K min-1

102

101

100

10-1

10-2
100

120

140

160

180

200

220

240

260

Temperature/ ℃ (Plotted as 1/T K)
Temperature vs. Self heating rate

240

before correction
after correction

220

Temperature/ ℃

200

180

160

140

120

100
10-3

10-2

10-1

100

TMR/ min
TMR vs. Temperature

101

102

103

1.E+02-1

0.00260.00250.00240.00230.00220.0021

0.002

0.0019

1.E+000.0018Heat Rate/ K min

1.E+01y = 3.1798E+17e-1.6832E+04x
R2 = 9.9981E-01
1.E-01

1.E-02Temperature/ K-1

Temperature vs. Self heating rate (approximate calculation)
1.E+03y = 6.2870E-16e1.5630E+04x
R2 = 9.9967E-01

1.E+010.00260.00250.00240.00230.00220.00210.002

1.E+000.0019

1.E-01
Temperature/ K-1

Temperature vs. TMR (approximate calculation)

TMR/ min

1.E+02

2

10.00260.00250.00240.00230.002200.002

0.0021

-1

-1

-3

-4

-5

-6

y = -1.8914E+04x + 4.0804E+01
R2 = 9.9990E-01
-7

-8

-9
Temperature/ K-1

Arrhenius equation (approximate calculation)d) Material of Bomb: Hastelloy C
Waiting & Searching Time: 15 min
TBP Concentration: 20%

250
4000

Temperature
Pressure
3000

150

2000
100

1000
50

0
0

200

400

600

Time/minTime vs. Temperature and Pressure

800

0
1000

Pressure/kPa

Temperature/℃

200

ln k*/ min

-2

103

before correction
after correction
Self heating rate/ K min-1

102

101

100

10-1

10-2
100

120

140

160

180

200

220

240

260

Temperature/ ℃ (Plotted as 1/T K)
Temperature vs. Self heating rate

240

before correction
after correction

Temperature/ ℃

220

200

180

160

140

120

100
10-4

10-3

10-2

10-1

100

TMR/ min
TMR vs. Temperature

101

102

103

1.E+02-1

0.00260.00250.00240.00230.00220.00210.002

1.E+000.0019Heat Rate/ K min

1.E+01-1.7072E+04x

y = 5.9330E+17e
R2 = 9.9978E-01
1.E-01

1.E-02Temperature/ K-1

Temperature vs. Self heating rate (approximate calculation)
1.E+03

1.5840E+04x

y = 3.5717E-16e
R2 = 9.9959E-01

1.E+010.00260.00250.00240.00230.00220.00210.002

1.E+000.0019

1.E-01
Temperature/ K-1

Temperature vs. TMR (approximate calculation)

TMR/ min

1.E+02

2

10.00260.00250.00240.00230.002200.002

0.0021

-1

-1

-3

-4

-5

-6

y = -1.8767E+04x + 4.0352E+01
R2 = 9.9999E-01
-7

-8

-9
Temperature/ K-1

Arrhenius equation (approximate calculation)e) Material of Bomb: Hastelloy C
Waiting & Searching Time: 15 min
TBP Concentration: 10%

250
1400

Temperature
Pressure
1200
1000

150
800
600

100

400

50
200
0

0
0

200

400

600

800

1000

Time/ minTime vs. Temperature and Pressure

1200

1400

Pressure/ kPa

Temperature/ oC

200

ln k*/ min

-2

101

Self heating rate/ K min-1

before correction
after correction

100

10-1

10-2
120

130

140

150

160

170

180

190

o

Temperature/ C (Plotted as 1/T K)
Temperature vs. Self heating rate

before correction
after correction

170oTemperature/ C

160

150

140

130

120

10-1

100

101

TMR/ min
TMR vs. Temperature

102

103

0.00255

0.00250.002450.00240.00235

0.00230.00225

0.00220.0021510.0021

0.1

y = 6.8809E+15e-1.5566E+04x
R2 = 9.9907E-01

Self heating rate/K min-1

0.00260.01
Temperature/K-1

Temperature vs. Self heating rate (approximate calculation)
1000

TMR/min100

y = 2.1450E-14e1.4525E+04x
R2 = 9.9998E-01

100.00260.00255

0.00250.002450.0024Temperature/K-1

0.00235

0.0023Temperature vs. TMR (approximate calculation)

0.002251
0.0022

0.0026

0.00255

0.00250.002450.002400.00230.00235

-1

-2

-4

-5

-6

-7
y = -18730x + 40.307
R2 = 0.9998-8
Temperature/ K-1

Arrhenius equation (approximate calculation)f) Material of Bomb: Hastelloy C
Waiting & Searching Time: 15 min
TBP Concentration: 30%

20000

300

Temperature
Pressure
15000

200
10000

150

100
5000

50

0

0
0

200

400

600

800

1000

Time/ minTime vs. Temperature and Pressure

1200

1400

Pressure/ kPa

Temperature/ oC

250

ln k*/ min-1-3

before correction
after correction

Self heating rate/ K min

-1

103

102

101

100

10-1

10-2
100

120

140

160

180

200 220 240 260 280 300oTemperature/ C (Plotted as 1/T K)
Temperature vs. Self heating rate

280
260

before correction
after correction

240oTemperature/ C

220
200
180
160
140
120
100
10-4

10-3

10-2

10-1

100

TMR/ min
TMR vs. Temperature

101

102

0.0027

0.00250.00230.002110.00170.0019Self heating rate/K min-1

10

0.1-1.7743E+04x

y = 4.7811E+18e
2
R = 9.9971E-01

0.01
Temperature/K-1

Temperature vs. Self heating rate (approximate calculation)
1000

y = 1.9182E-17e1.6834E+04x
R2 = 9.9996E-01

TMR/min100

100.00270.00260.00250.00240.00230.0022Temperature/K-1

0.0021

0.002

Temperature vs. TMR (approximate calculation)

0.001910.0018

0.0027

0.00260.00250.00240.00230.00220.00210.002

00.0019
-1

-2

-4

-5
y = -19029x + 41.167
2
R = 0.9999
-6

-7

-8

-9
Temperature/ K-1

Arrhenius equation (approximate calculation)a) Material of Bomb: Hastelloy C
Waiting & Searching Time: 30 min
TBP Concentration: 20%
Date

2008/12/2

Measuring

ARC device

NewARC (TIAX, LLC)

conditions

Operating Institute

AIST

Operator

Y. S.

Material of Bomb

Hastelloy C

Weight of Bomb (g)14.7934

Volume of Bomb (mL)about 9Weight of sample (g)6.0039Weight of residue (g)

－
-1

-1

0.419

-1

-1

Specific heat of sample (J K g )2.093

φ facotr

1.493

Start temperature (℃)

80

End temperature (℃)

220

Temperature increment (K)5Waiting time (min)30

Specific heat of Bomb (J K g )ln k*/ min-1-3

Searching time (min)15-1

Exothermic threshold (K min )0.02

Logging intervals (℃)

0.15 ℃

Pressure limit (kPa)

7000

AtmosphereAir, atmospheric pressure

To, Exothermic temperature (℃)

115.65

Self heating rate at To (K min-1)

0.033

Pressure at To (kPa)249.53Temperature at maximum self heating

195.46rate (℃)
Maximum self heating rate (K min-1)

15.014Pressure at maximum self heating rate

3001.3(kPa)
Pressure rising rate at maximum self
Results

925.60-1

heating rate (kPa min )Maximum pressure (kPa)

3966.1-1

Maximum pressure rising rate (kPa min )940.36

Temperature at maximum pressure rising197.23rate (℃)
Time to maximum rate (min)284.14

Maximum temperature (℃)

206.47

Adiabatic temperature rise (℃)

90.82

-1

Corrected
results

Activation energy (kJ mol )155

Heat of decomposition (J g-1)

284

TARC, Exothermic temperature (℃)

107.50Time of maximum rate at TARC (min)417.39Self heating rate at TARC (K min-1)

0.02
-1

Maximum self heating rate (K min )527.33

Maximum temperature (℃)

251.25

Adiabatic temperature rise (℃)

143.75-1

Heat of decomposition (J g )301b) Material of Bomb: Ti
Waiting & Searching Time: 30 min
TBP Concentration: 20%
Date

2008/12/8

ARC device

NewARC (TIAX, LLC)

Operating Institute

AIST

Operator

Y. S.

Material of Bomb

Ti

Weight of Bomb (g)6.4039Volume of Bomb (mL)about 9Weight of sample (g)6.0012

Weight of residue (g)

－
-1

-1

Specific heat of Bomb (J K g )0.544

MeasuringSpecific heat of sample (J K-1 g-1)

2.093

conditions

φ facotr

1.277

Start temperature (℃)

80

End temperature (℃)

220

Temperature increment (K)5Waiting time (min)30

Searching time (min)15-1Results

Exothermic threshold (K min )0.02

Logging intervals (℃)

0.15

Pressure limit (kPa)

7000

AtmosphereAir, atmospheric pressure
110.40To, Exothermic temperature (℃)-1

Self heating rate at To (K min )0.022

Pressure at To (kPa)

220.59Temperature at maximum self heating

199.59rate (℃)
Maximum self heating rate (K min-1)

23.156

Pressure at maximum self heating rate

2872.4(kPa)
Pressure rising rate at maximum self

1637.1

heating rate (kPa min-1)
Maximum pressure (kPa)

4251.7-1

Maximum pressure rising rate (kPa min )1713.1

Temperature at maximum pressure rising200.84rate (℃)
Time to maximum rate (min)439.13

Maximum temperature (℃)

211.21

Adiabatic temperature rise (℃)

100.81

Activation energy (kJ mol-1)

155

-1

Heat of decomposition (J g )269

TARC, Exothermic temperature (℃)

107.67

Time of maximum rate at TARC (min)441.43-1

Corrected
results

Self heating rate at TARC (K min )

0.02
-1

Maximum self heating rate (K min )310.54

Maximum temperature (℃)

239.52

Adiabatic temperature rise (℃)

131.85Heat of decomposition (J g-1)

276c) Material of Bomb: Ti
Waiting & Searching Time: 15 min
TBP Concentration: 20%
Date

2008/12/12

Measuring

ARC device

NewARC (TIAX, LLC)

conditions

Operating Institute

AIST

Operator

Y. S.

Material of Bomb

Ti

Weight of Bomb (g)6.3646

Volume of Bomb (mL)about 9Weight of sample (g)6.0010Weight of residue (g)

－
-1

-1

Specific heat of Bomb (J K g )0.544

Specific heat of sample (J K-1 g-1)

2.093

φ facotr

1.276

Start temperature (℃)

80

End temperature (℃)

220

Temperature increment (K)5Waiting time (min)15

Searching time (min)15-1

Exothermic threshold (K min )0.02

Logging intervals (℃)

0.15

Pressure limit (kPa)

7000

AtmosphereAir, atmospheric pressure
115.31

To, Exothermic temperature (℃)-1

Self heating rate at To (K min )0.037

Pressure at To (kPa)214.40Temperature at maximum self heating200.34rate (℃)
Maximum self heating rate (K min-1)

28.984Pressure at maximum self heating rate

2695.9(kPa)
Pressure rising rate at maximum self
Results

1838.8-1

heating rate (kPa min )Maximum pressure (kPa)

3616.7-1

Maximum pressure rising rate (kPa min )1875.3Temperature at maximum pressure rising202.27rate (℃)
Time to maximum rate (min)255.61

Maximum temperature (℃)

211.65

Adiabatic temperature rise (℃)

96.34

Activation energy (kJ mol-1)

157

-1

Heat of decomposition (J g )257

TARC, Exothermic temperature (℃)

107.55Time of maximum rate at TARC (min)425.42-1

Corrected
results

Self heating rate at TARC (K min )

0.02
-1

Maximum self heating rate (K min )272.58Maximum temperature (℃)

240.39Adiabatic temperature rise (℃)

132.84Heat of decomposition (J g-1)

278d) Material of Bomb: Hastelloy C
Waiting & Searching Time: 15 min
TBP Concentration: 20%
Date

2008/12/17

Measuring

ARC device

NewARC (TIAX, LLC)

conditions

Operating Institute

AIST

Operator

Y. S.

Material of Bomb

Hastelloy C

Weight of Bomb (g)14.7859

Volume of Bomb (mL)about 9Weight of sample (g)6.0062

Weight of residue (g)－Specific heat of Bomb (J K-1 g-1)
-1

Results-1

0.419

Specific heat of sample (J K g )2.093

φ facotr

1.493

Start temperature (℃)

80

End temperature (℃)

220

Temperature increment (K)5Waiting time (min)15

Searching time (min)15

Exothermic threshold (K min-1)

0.02

Logging intervals (℃)

0.15

Pressure limit (kPa)

7000

AtmosphereAir, atmospheric pressure

To, Exothermic temperature (℃)

115.14

Self heating rate at To (K min-1)

0.031

Pressure at To (kPa)

267.66

Temperature at maximum self heating

194.15rate (℃)
Maximum self heating rate (K min-1)

14.802Pressure at maximum self heating rate

2617.3(kPa)
Pressure rising rate at maximum self

884.67-1

heating rate (kPa min )Maximum pressure (kPa)

3871.9Maximum pressure rising rate (kPa min-1)

978.81

Temperature at maximum pressure rising196.19rate (℃)
Time to maximum rate (min)302.37

Maximum temperature (℃)

206.34

Adiabatic temperature rise (℃)

91.20

-1

Activation energy (kJ mol )156

Corrected
results

Heat of decomposition (J g-1)

285

TARC, Exothermic temperature (℃)

107.61Time of maximum rate at TARC (min)416.83Self heating rate at TARC (K min-1)

0.02
-1

Maximum self heating rate (K min )513.02

Maximum temperature (℃)

251.15

Adiabatic temperature rise (℃)

143.54-1

Heat of decomposition (J g )300e) Material of Bomb: Ti
Waiting & Searching Time: 15 min
TBP Concentration: 10%
Date

2009/6/22

ARC device

NewARC (TIAX, LLC)

Operating Institute

AIST

Operator

Y. S.

Material of Bomb

Hastelloy C

Weight of Bomb (g)10.1658

Volume of Bomb (mL)about 9Weight of sample (g)6.0114Weight of residue (g)－Specific heat of Bomb (J K-1 g-1)
-1

-1

0.544

MeasuringSpecific heat of sample (J K g )2.093

conditions

φ facotr

1.440

Start temperature (℃)

80

End temperature (℃)

220

Temperature increment (K)5Waiting time (min)15

Searching time (min)15

Exothermic threshold (K min-1)

0.02

Logging intervals (℃)

0.15

Pressure limit (kPa)

20000

AtmosphereAir, atmospheric pressure

To, Exothermic temperature (℃)

120.22

Self heating rate at To (K min-1)

0.032

Pressure at To (kPa)275.16

ResultsTemperature at maximum self heating

155.80rate (℃)
Maximum self heating rate (K min-1)

0.3563Pressure at maximum self heating rate

1068.3(kPa)
Pressure rising rate at maximum self

5.1217-1

heating rate (kPa min )Maximum pressure (kPa)

1077.0-1

Maximum pressure rising rate (kPa min )6.8837

Temperature at maximum pressure rising

152.96rate (℃)
Time to maximum rate (min)434.22

Maximum temperature (℃)

165.70Adiabatic temperature rise (℃)

45.48

-1

Corrected
results

Activation energy (kJ mol )156

Heat of decomposition (J g-1)

137

TARC, Exothermic temperature (℃)

112.34

Time of maximum rate at TARC (min)495.84

Self heating rate at TARC (K min-1)

0.02
-1

Maximum self heating rate (K min )2.472

Maximum temperature (℃)

185.64

Adiabatic temperature rise (℃)

73.3

-1

Heat of decomposition (J g )153f) Material of Bomb: Ti
Waiting & Searching Time: 15 min
TBP Concentration: 30%
Date

2009/6/26

Measuring

ARC device

NewARC (TIAX, LLC)

conditions

Operating Institute

AIST

Operator

Y. S.

Material of Bomb

Ti

Weight of Bomb (g)10.1759

Volume of Bomb (mL)about 9Weight of sample (g)6.0169Weight of residue (g)－Specific heat of Bomb (J K-1 g-1)
-1

-1

0.544

Specific heat of sample (J K g )2.093

φ facotr

1.440

Start temperature (℃)

80

End temperature (℃)

300

Temperature increment (K)5Waiting time (min)15

Searching time (min)15

Exothermic threshold (K min-1)

0.02

Logging intervals (℃)

0.15

Pressure limit (kPa)

20000

AtmosphereAir, atmospheric pressure

To, Exothermic temperature (℃)-1

110.14

Self heating rate at To (K min )0.025

Pressure at To (kPa)

209.89Temperature at maximum self heating

206.95rate (℃)
Maximum self heating rate (K min-1)

122.33Pressure at maximum self heating rate

8278.5(kPa)
Pressure rising rate at maximum self
Results

122.33

heating rate (kPa min-1)
Maximum pressure (kPa)8280.3

Maximum pressure rising rate (kPa min-1)

38816

Temperature at maximum pressure rising

191.41rate (℃)
Time to maximum rate (min)345.93

Maximum temperature (℃)

233.76

Adiabatic temperature rise (℃)

123.62-1

Activation energy (kJ mol )

158

-1

Heat of decomposition (J g )373

Corrected

TARC, Exothermic temperature (℃)

104.98results

Time of maximum rate at TARC (min)414.32-1

Self heating rate at TARC (K min )0.02

Maximum self heating rate (K min-1)

4727.4

Maximum temperature (℃)

290.04

Adiabatic temperature rise (℃)-1Heat of decomposition (J g )185.06387