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 hydroperoxide
H3C

C4H10O2

TBHP

CH3OH

H3CO

ARC device: New ARC (TIAX, LLC)
Date: 2009/12
Operator: Y. S.

a) Weight: 0.233 g

200
800

Temperature
Pressure

180

700
160

120

500

100
400
80
300
60
40200

20
100
00200

400

600

800

1000

Time/ minTime vs. Temperature and Pressure

1200

1400

Pressure/ kPa

Temperature/ oC

600
140

1010

before correction
after correction

Self heating rate/ K min-1

108106

104

102

100

10-2100

200

300

400500oTemperature/ C (Plotted as 1/T K)
Temperature vs. Self heating rate

before correction
after correction

500

Temperature/ oC

400300

200

100

10-12

10-10

10-8

10-6

10-4

TMR/ min
TMR vs. Temperature

10-2

100102

1.E+06

1.E+05

1.E+03

1.E+02

Self heating rate/K min-1

1.E+04

1.E+01y = 1.6831E+23e-2.0201E+04x
R2 = 9.9989E-01

0.00260.00240.00220.002

0.00180.00160.0014

1.E+000.0012

1.E-01
Temperature/K-1

Temperature vs. Self heating rate (approximate calculation)
1.E+02

1.E+01y = 5.8192E-22e1.9200E+04x2R = 9.9982E-01

0.00240.00220.002

0.00180.00160.0014

1.E+000.0012

1.E-01
TMR/min0.0026

1.E-02

1.E-03

1.E-04

1.E-05Temperature/K-1

Temperature vs. TMR (approximate calculation)

0.0027

0.00268

0.00266

0.002640.00262

0.00260.0025800.00254

0.00256-1-2-4-5
y = -20405x + 48.091
R2 = 0.9935-6-7-8Temperature/ K-1

Arrhenius equation (approximate calculation)b) Weight: 0.495 g

3500
250

Temperature
Pressure
3000

2500

150
20001500
1001000
5050000500

1000

1500

Time/ minTime vs. Temperature and Pressure

02000

Pressure/ kPa

Temperature/ oC

200

ln k*/ min-1-3

1010

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

108

106

104

102

100

10-2
100

200

300

400

500 600 700oTemperature/ C (Plotted as 1/T K)
Temperature vs. Self heating rate

600

before correction
after correction

Temperature/ oC

500

400

300

200

100

10-10

10-8

10-6

10-4

10-2

TMR/ min
TMR vs. Temperature

100102

1.E+07

1.E+06

1.E+04

1.E+03

1.E+02

Self heating rate/K min-1

1.E+05

1.E+01y = 2.5545E+19e-1.7001E+04x
R2 = 9.9989E-01

0.00280.00260.00240.00220.002

0.00180.00160.00140.0012

1.E+000.001

1.E-01
Temperature/K-1

Temperature vs. Self heating rate (approximate calculation)
1.E+02

1.E+01y = 3.2695E-18e1.6150E+04x
R2 = 9.9995E-01

0.00250.00230.00210.00190.00170.00150.0013

1.E+000.0011

1.E-01

1.E-02

1.E-03

1.E-04

1.E-05

1.E-06
Temperature/K-1

Temperature vs. TMR (approximate calculation)

TMR/min0.0027

0.00275

0.00270.00265

0.00260.00255

0.002500.00240.00245-1-2-4-5-6
y = -17719x + 40.2
R2 = 0.9928-7-8-9Temperature/ K-1

Arrhenius equation (approximate calculation)c) Weight: 0.750 g

5000

Temperature
Pressure

200

4000

150

3000

100

2000

50

1000

000200

400

600

800

1000

1200

Time/ minTime vs. Temperature and Pressure

1400

1600

Pressure/ kPa

Temperature/ oC

250

ln k*/ min-1

-3

108

before correction
after correction

107

Self heating rate/ K min-1106105104103102
101
100
10-1
10-2100200300

400500 600 700oTemperature/ C (Plotted as 1/T K)
Temperature vs. Self heating rate

600

before correction
after correction

Temperature/ oC

500400300

200

100

0
10-8

10-7

10-6

10-5

10-4

10-3

10-2

10-1

TMR/ min
TMR vs. Temperature

100101102

1.E+05

1.E+04

1.E+02

Self heating rate/K min-1

1.E+03

1.E+01y = 1.5271E+15e-1.3128E+04x
R2 = 9.9992E-01

0.00270.00250.00230.00210.00190.00170.00150.0013

1.E+000.0011

1.E-01
Temperature/K-1

Temperature vs. Self heating rate (approximate calculation)
1.E+02

1.E+01
1.2195E+04x

y = 8.7531E-14e
R2 = 9.9985E-01

0.00260.00240.00220.002

0.00180.00160.0014

1.E+000.0012
TMR/min0.0028

1.E-01

1.E-02

1.E-03Temperature/K-1

Temperature vs. TMR (approximate calculation)

0.0028

0.00270.00260.00250.002400.00220.0023-1-2-4-5-6-7
y = -13651x + 30.073
R2 = 0.9985-8-9
Temperature/ K-1

Arrhenius equation (approximate calculation)d) Weight: 1.017 g

6000
250

Temperature
Pressure
5000

4000
150
3000
100
2000501000

00200400600

800

1000

Time/ minTime vs. Temperature and Pressure

1200

0
1400

Pressure/ kPa

Temperature/ oC

200

ln k*/ min-1-3

108

before correction
after correction

Self heating rate/ K min-1

107106105
104
103
102
101
100
10-1
10-2
100

200

300

400

500 600oTemperature/ C (Plotted as 1/T K)
Temperature vs. Self heating rate

before correction
after correction

500

Temperature/ oC

400

300

200

100

10-8

10-710-610-510-4

10-3

10-2

TMR/ min
TMR vs. Temperature

10-1100101102

1.E+04

1.E+02

1.E+01

Self heating rate/K min-1

1.E+03y = 7.0115E+16e-1.4534E+04x
R2 = 9.9978E-01

0.00270.00250.00230.00210.00190.00170.00150.0013

1.E+000.0011

1.E-01
Temperature/K-1

Temperature vs. Self heating rate (approximate calculation)
1.E+02

1.E+011.3550E+04x

y = 1.9541E-15e
R2 = 9.9972E-01

0.00260.00240.00220.002

0.00180.00160.0014

1.E+000.0012
TMR/min0.0028

1.E-01

1.E-02

1.E-03Temperature/K-1

Temperature vs. TMR (approximate calculation)

0.0028

0.00270.00260.00250.00240.002300.00210.0022-1-2-4-5-6-7
y = -14895x + 33.56
R2 = 0.9976-8-9
Temperature/ K-1

Arrhenius equation (approximate calculation)e) Weight: 1.314 g

8000
250

Temperature
Pressure

7000

6000

5000
150
4000

3000
100
2000
50
1000

000200

400

600

800

1000

Time/ minTime vs. Temperature and Pressure

1200

1400

Pressure/ kPa

Temperature/ oC200ln k*/ min-1-3

108

before correction
after correction

Self heating rate/ K min-1

107106105104103102
101
100
10-1
10-2
100

200

300

400500 600

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

500

before correction
after correction
Temperature/ oC

400

300

200

100

0
10-8

10-7

10-6

10-5

10-4

10-3

10-2

10-1

TMR/ min
TMR vs. Temperature100

101102

1.E+05

1.E+04

1.E+02

1.E+01y = 9.4854E+16e-1.4710E+04x
R2 = 9.9870E-01

0.00290.00270.00250.00230.00210.0019

0.00170.00150.0013Self heating rate/K min-1

1.E+03

1.E+000.0011

1.E-01

1.E-02Temperature/K-1

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

1.E+02

1.E+010.00280.00260.00240.00220.002

0.00180.00160.0014

1.E+000.0012

1.E-01

1.E-02

1.E-03

1.E-04Temperature/K-1

Temperature vs. TMR (approximate calculation)

TMR/miny = 4.5768E-16e1.4178E+04x
R2 = 9.9925E-01

20.0029

0.00280.00270.00260.00250.00240.002300.00210.0022-4-6
y = -16097x + 36.594
R2 = 0.9891-8-10
Temperature/ K-1

Arrhenius equation (approximate calculation)f) Weight: 0.733 g
Heating rate: 0.04 K/min

3500
200

Temperature
Pressure

3000

2000

100
1500

1000
50
500

0010002000

3000

Time/ minTime vs. Temperature and Pressure

04000

Pressure/ kPa

Temperature/ oC

2500
150

ln k*/ min-1-2

108

before correction
after correction

107

Self heating rate/ K min-1

106
105
104
103
102
101
100
10-1
10-2
100

200

300

400500 600oTemperature/ C (Plotted as 1/T K)
Temperature vs. Self heating rate

500

before correction
after correction

Temperature/ oC

400

300

200

100

10-8

10-7

10-6

10-5

10-4

10-3

10-2

TMR/ min
TMR vs. Temperature

10-1

100

101102

1.E+05

1.E+04

1.E+02

Self heating rate/K min-1

1.E+03

1.E+01-1.4465E+04x

y = 4.8266E+16e
R2 = 9.9914E-01

0.00270.00250.00230.00210.00190.00170.00150.0013

1.E+000.0011

1.E-01
Temperature/K-1

Temperature vs. Self heating rate (approximate calculation)
1.E+02

1.E+01
1.3380E+04x

y = 3.5342E-15e
R2 = 9.9932E-01

0.00260.00240.00220.002

0.00180.00160.0014

1.E+000.0012

1.E-01

1.E-02

1.E-03

1.E-04Temperature/K-1

Temperature vs. TMR (approximate calculation)

TMR/min0.0028

0.0028

0.00275

0.00270.00265

0.00260.00255

0.00250.002450.002400.00235-1-2-4-5
y = -14777x + 33.173
R2 = 0.9969-6-7-8Temperature/ K-1

Arrhenius equation (approximate calculation)a) Weight: 0.233 g
Date

2009/12/17

Measuring

ARC device

NewARC (TIAX, LLC)

conditions

Operating Institute

AIST

Operator

Y. S.

Material of Bomb

Hastelloy C

Weight of Bomb (g)20.4096

Volume of Bomb (mL)about 9Weight of sample (g)0.2327Weight of residue (g)－-1-1Specific heat of Bomb (J K g )0.419

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

2.093

φ facotr

18.56

Start temperature (℃)

50

End temperature (℃)

192

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

Searching time (min)15-1

Exothermic threshold (K min )0.02

ln k*/ min-1-3

Logging time (℃)

0.5 minPressure limit (kPa)

20000

AtmosphereAir, atmospheric pressure

To, Exothermic temperature (℃)

100.27

Self heating rate at To (K min-1)

0.027

Pressure at To (kPa)

269.13Temperature at maximum self heating

115.78rate (℃)
Maximum self heating rate (K min-1)

0.085

Pressure at maximum self heating rate

503.38(kPa)
Pressure rising rate at maximum self
Results

0.9551-1

heating rate (kPa min )Maximum pressure (kPa)

566.28Maximum pressure rising rate (kPa min-1)1.0784

Temperature at maximum pressure rising

108.88rate (℃)

Correctedresults

Time to maximum rate (min)271.44

Maximum temperature (℃)

122.66

Adiabatic temperature rise (℃)

22.39

-1

Activation energy (kJ mol )

169.6

-1

Heat of decomposition (J g )869.8

TARC, Exothermic temperature (℃)

78.83

Time of maximum rate at TARC (min)285.26

Self heating rate at TARC (K min-1)

0.02
-1

Maximum self heating rate (K min )6.7425×1010

Maximum temperature (℃)

515.35

Adiabatic temperature rise (℃)

436.52-1

Heat of decomposition (J g )913.6b) Weight: 0.495 g
Date

2009/12/11

Measuring

ARC device

NewARC (TIAX, LLC)

conditions

Operating Institute

AISTOperator

Y. S.

Material of Bomb

Hastelloy C

Weight of Bomb (g)20.4096

Volume of Bomb (mL)about 9Weight of sample (g)0.4948Weight of residue (g)

－-1

-1

0.419

-1-1

Specific heat of sample (J K g )2.093

φ facotr

9.258

Start temperature (℃)

50

End temperature (℃)

250

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

Specific heat of Bomb (J K g )Searching time (min)15-1

Results

Exothermic threshold (K min )0.02

Logging time (℃)

0.5 minPressure limit (kPa)

20000

AtmosphereAir, atmospheric pressure

To, Exothermic temperature (℃)

95.25

Self heating rate at To (K min-1)

0.026

Pressure at To (kPa)

264.42Temperature at maximum self heating

141.84rate (℃)
Maximum self heating rate (K min-1)

1.0552Pressure at maximum self heating rate

1091.3(kPa)
Pressure rising rate at maximum self

19.812-1

heating rate (kPa min )Maximum pressure (kPa)1415.2-1Maximum pressure rising rate (kPa min )19.848Temperature at maximum pressure rising142.01rate (℃)
Time to maximum rate (min)429.96

Maximum temperature (℃)

155.02

Adiabatic temperature rise (℃)

59.77

-1

Activation energy (kJ mol )147.3

Heat of decomposition (J g-1)

1158

TARC, Exothermic temperature (℃)

76.67

Time of maximum rate at TARC (min)366.68-1

Correctedresults

Self heating rate at TARC (K min )0.02

Maximum self heating rate (K min-1)

1.2535×1010

Maximum temperature (℃)

647.06

Adiabatic temperature rise (℃)

570.39Heat of decomposition (J g-1)

1194c) Weight: 0.750 g
Date

2009/12/10

ARC device

NewARC (TIAX, LLC)

Operating Institute

AISTOperator

Y. S.

Material of Bomb

Hastelloy C

Weight of Bomb (g)20.4096

Volume of Bomb (mL)about 9Weight of sample (g)0.7496Weight of residue (g)－-1-1Specific heat of Bomb (J K g )0.419

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

2.093

conditions

φ facotr

6.451

Start temperature (℃)

50

End temperature (℃)

250

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

Searching time (min)15-1

Results

Exothermic threshold (K min )0.02

Logging time (℃)

0.5 minPressure limit (kPa)

20000

AtmosphereAir, atmospheric pressure

To, Exothermic temperature (℃)
-1

85.25

Self heating rate at To (K min )0.028

Pressure at To (kPa)

236.71

Temperature at maximum self heating

148.99

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

2.5137

Pressure at maximum self heating rate

1430.4(kPa)
Pressure rising rate at maximum self

50.992-1

heating rate (kPa min )Maximum pressure (kPa)

2111.1-1

Maximum pressure rising rate (kPa min )54.440Temperature at maximum pressure rising

151.76rate (℃)
Time to maximum rate (min)423.91

Maximum temperature (℃)

169.05

Adiabatic temperature rise (℃)

83.80

-1

Corrected
results

Activation energy (kJ mol )113.5

Heat of decomposition (J g-1)

1131

TARC, Exothermic temperature (℃)

64.55

Time of maximum rate at TARC (min)422.02

Self heating rate at TARC (K min-1)

0.02
-1

Maximum self heating rate (K min )4.6017×107

Maximum temperature (℃)

624.29Adiabatic temperature rise (℃)

559.74-1

Heat of decomposition (J g )1171d) Weight: 1.017 g
Date

2009/12/7

Measuring

ARC device

NewARC (TIAX, LLC)

conditions

Operating Institute

AISTOperator

Y. S.

Material of Bomb

Hastelloy C

Weight of Bomb (g)20.5174

Volume of Bomb (mL)about 9Weight of sample (g)1.0170Weight of residue (g)

－-1-1

0.419

-1-1

2.093

Specific heat of Bomb (J K g )Specific heat of sample (J K g )φ facotr

5.039

Start temperature (℃)

50

End temperature (℃)

250Temperature increment (K)5Waiting time (min)15

Searching time (min)15-1

Exothermic threshold (K min )0.02

Logging time (℃)

0.5 minPressure limit (kPa)

20000

AtmosphereAir, atmospheric pressure
85.29

To, Exothermic temperature (℃)-1

Self heating rate at To (K min )0.031

Pressure at To (kPa)

246.45Temperature at maximum self heating

165.28rate (℃)
Maximum self heating rate (K min-1)

18.655Pressure at maximum self heating rate1867.0(kPa)
Pressure rising rate at maximum self
Results

396.55-1

heating rate (kPa min )Maximum pressure (kPa)

3000.9-1

Maximum pressure rising rate (kPa min )420.09Temperature at maximum pressure rising

168.82rate (℃)
Time to maximum rate (min)302.39Maximum temperature (℃)

186.19Adiabatic temperature rise (℃)

100.9

Activation energy (kJ mol-1)

123.8

-1

Heat of decomposition (J g )1064

Corrected

TARC, Exothermic temperature (℃)

67.22

results

Time of maximum rate at TARC (min)380.34-1

Self heating rate at TARC (K min )0.02

Maximum self heating rate (K min-1)

1.3213×108

Maximum temperature (℃)

592.97

Adiabatic temperature rise (℃)

525.75Heat of decomposition (J g-1)

1100e) Weight: 1.314 g
Date

2009/12/16

ARC device

NewARC (TIAX, LLC)

Operating Institute

AISTOperator

Y. S.

Material of Bomb

Hastelloy C

Weight of Bomb (g)20.3064

Volume of Bomb (mL)about 9Weight of sample (g)1.3142

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

0.419

MeasuringSpecific heat of sample (J K g )2.093

conditions

φ facotr

4.093

Start temperature (℃)

50

End temperature (℃)

253

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

Searching time (min)15

Exothermic threshold (K min-1)

0.02

Logging time (℃)

0.5 minPressure limit (kPa)

20000

AtmosphereAir, atmospheric pressure

To, Exothermic temperature (℃)

80.18

Self heating rate at To (K min-1)

0.025

Pressure at To (kPa)241.18Temperature at maximum self heating

167.15Resultsrate (℃)
Maximum self heating rate (K min-1)

51.685Pressure at maximum self heating rate

2159.3(kPa)
Pressure rising rate at maximum self

1343.0-1

heating rate (kPa min )Maximum pressure (kPa)3933.9

Maximum pressure rising rate (kPa min-1)

1553.8Temperature at maximum pressure rising

185.77rate (℃)
Time to maximum rate (min)596.12

Maximum temperature (℃)

198.00Adiabatic temperature rise (℃)

117.82-1

Activation energy (kJ mol )133.8

Heat of decomposition (J g-1)

1009

TARC, Exothermic temperature (℃)

68.92

Time of maximum rate at TARC (min)458.34-1

Corrected
results

Self heating rate at TARC (K min )

0.02
-1

Maximum self heating rate (K min )1.3866×108

Maximum temperature (℃)

562.41

Adiabatic temperature rise (℃)

493.49-1

Heat of decomposition (J g )1033

f) Weight: 0.733 g
Heating rate: 0.04 K/min
Date

2009/12/21

Measuring

ARC device

NewARC (TIAX, LLC)

conditions

Operating Institute

AISTOperator

Y. S.

Material of Bomb

Hastelloy C

Weight of Bomb (g)20.3064

Volume of Bomb (mL)about 9Weight of sample (g)0.7326Weight of residue (g)

－-1

-1

0.419

-1-1

Specific heat of sample (J K g )2.093

φ facotr

6.549

Start temperature (℃)

45End temperature (℃)

202

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

Searching time (min)30

Specific heat of Bomb (J K g )Exothermic threshold (K min-1)

0.02

Logging time (℃)

0.5 minPressure limit (kPa)

20000

AtmosphereAir, atmospheric pressure
92.00

To, Exothermic temperature (℃)-1

Self heating rate at To (K min )0.037

Pressure at To (kPa)

373.61

Temperature at maximum self heating

146.82rate (℃)
Maximum self heating rate (K min-1)

1.8888Pressure at maximum self heating rate1329.9(kPa)
Pressure rising rate at maximum self
Results

35.362-1

heating rate (kPa min )Maximum pressure (kPa)

1684.9-1

Maximum pressure rising rate (kPa min )36.004Temperature at maximum pressure rising148.63rate (℃)
Time to maximum rate (min)248.82

Maximum temperature (℃)

162.70Adiabatic temperature rise (℃)

70.70

-1

Activation energy (kJ mol )122.9

Heat of decomposition (J g-1)

969.1

TARC, Exothermic temperature (℃)

68.59

Time of maximum rate at TARC (min)356.48-1

Correctedresults

Self heating rate at TARC (K min )

0.02
-1

Maximum self heating rate (K min )7.1875×107

Maximum temperature (℃)

577.06

Adiabatic temperature rise (℃)

508.47-1

Heat of decomposition (J g )1064