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Metal soaps in oil paintStructure, mechanisms and dynamicsHermans, J.J.

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Citation for published version (APA):Hermans, J. J. (2017). Metal soaps in oil paint: Structure, mechanisms and dynamics.

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Download date: 22 Mar 2021

3The crystallisation of metal soaps and

fatty acids in linseed oil

This chapter is based on:J. J. Hermans, K. Keune, A. van Loon and P. D. Iedema,

Physical Chemistry Chemical Physics 18, 2016, 10896-10905

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−

−

0 20 40 60 80

heat

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(end

o up

)

2 W/g

0.10

0.82

0.71

0.630.500.390.280.15

1.00

a

a0 20 40 60 80

2 W/g

0.10

0.82

0.71

0.630.500.390.280.15

1.00

b

40 60 80 100 120

heat

tran

sfer

(end

o up

)

60 70 80 90 100

0.18

0.82

0.78

0.66

0.550.380.280.23

1.00

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0.04

0.04

0.06

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0.18

2 W/g

1 W/g

c

40 60 80 100 120

2 W/g 0.18

0.82

0.78

0.66

0.55

0.38

0.28

0.23

1.00

0.06

0.12

0.04d

40 60 80 100 120 140T (°C)

heat

tran

sfer

(end

o up

)

80 90 100 110 120

0.5 W/g

0.05

0.07

0.14

0.04 W/g0.14

0.89

0.75

0.650.520.350.280.22

1.00

0.050.07

e

40 60 80 100 120T (°C)

0.14

0.89

0.75

0.65

0.52

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0.22

1.00

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0.5 W/g

f

mol fraction HPa

T (°C

)

00 0.2 0.4 0.6 0.8 1

0

10

20

30

40

50

60

20

40

60

80

100

120

ΔHm

elt (kJ/mol H

Pa)

±

○

= ○ ( − )

○○

± ±

± ± ±± ± ± ⋅± ± ± ⋅

0 5 10 15 20heating rate (K/min)

0

10

20

30

40

50

60

70

hyst

eres

is (°C

)

0

20

40

60

80

100

ΔHm

elt (kJ/mol)

HPaPbPaZnPa

///

0 0.2 0.4 0.6 0.8 1mol fraction PbPa

0

20

40

60

80

100

T (°C

)

0

20

40

60

80

100

120

140

160

ΔHm

elt (kJ/mol PbPa)

±

±

⋅ −

0 0.2 0.4 0.6 0.8 1mol fraction ZnPa

0

20

40

60

80

100

120

T (°C

)

0

20

40

60

80

100

120

140

160

180

ΔHm

elt (kJ/mol ZnPa)

⋅ −

± ±○

0 0.2 0.4 0.6 0.8 1mol fraction ZnPa

0 0.2 0.4 0.6 0.8 1mol fraction PbPa

0 0.2 0.4 0.6 0.8 1mol fraction HPa

0

20

40

60

80

100

ΔHm

elt (k

J/m

ol m

ixtu

re)

a b c

= +

=

0 20 40 60 80 100 120curing time (min)

0

10

20

30

40

50te

mpe

ratu

re (°

C)

-50

-40

-30

-20

-10

0

ΔHcrys (kJ/m

ol HPa)

a

0 10 20 30 40 50 60curing time (min)

0

20

40

60

80

100

tem

pera

ture

(°C)

-80

-60

-40

-20

0ΔH

crys (kJ/mol ZnPa)

c

0 50 100 150curing time (min)

0

20

40

60

80

tem

pera

ture

(°C)

-100

-80

-60

-40

-20

0

ΔHcrys (kJ/m

ol PbPa)

b

80010001200140016001800wavenumber (cm-1)

abso

rban

ce

ZnPa-LO

PbPa-LO

unheated

3h at 150 °C

25d at RT

unheated

3h at 150 °C

25d at RT

ZnPa

PbPa

0 50 100 150time (min)

0.14

0.16

0.18

0.20

3010

cm

-1 b

and

inte

nsity

HPa-LOPbPa-LOZnPa-LO

a b

−−−−

− − −−

−

−

− −

−− −

−− −−−− −

− −

a

f

dc

e

C15H31COOH

Pb(C6H13COO)2

Zn(C7H15COO)2

b

− −

− −

8001000120014001600wavenumber (cm-1)

abso

rban

ce

30 °C

110 °C

150 °C

PbPaa

8001000120014001600wavenumber (cm-1)

abso

rban

ce

30 °C

115 °C

160 °C

ZnPab