EMAC ’05 Lyon 26-29th October 2005

METHODOLOGICAL ASPECTS OF SANS AND TOF NEUTRON DIFFRACTION MEASUREMENTS ON POTTERY. THE CASE OF MISENO AND CUMA

A.Botti, A. Sodo, M. A. Ricci

G. De Rossi

W. Kockelmann

Length scalesLength scales

| |-Si-O-Si-

| |

~10 µ 100-200 nm 10-20 nm < 1nm

EMAC ’05 Lyon 26-29th October 2005

Some questionsSome questions

Is it possible to use neutron instruments for investigating pottery ?

-Multiple scattering effects ⇔ sample thickness-Non destructivity vs. micro destructivity-Activation

The application of neutron techniques to an actual case gives information?

-The case of Miseno and Cuma

Which are the firing parameters neutrons are sensitive to?

-Maximum firing temperature-Composition-Heating rate

Which are the prospects opened by this approach?

EMAC ’05 Lyon 26-29th October 2005

Forschungszentrum jülich

EMAC ’05 Lyon 26-29th October 2005

KWS I - KWS II - KWS III - DKD reactor

PAXE - PAXY reactor

ROTAX – VESUVIO - INES spallation

Laboratoire Léon Brillouin

Rutherford Appleton Lanbortory

FacilitiesFacilities

SANSSANS

D ~ 1x10-1 – 2x103 Å

guide

collimation

Up to 20 m

detectors

D

D

sample

DD

)2

sin(4 ϑλπ

== qq r

ϑ

iik λ

π2=

fk q

Velocity selector

EMAC ’05 Lyon 26-29th October 2005

EMAC ’05 Lyon 26-29th October 2005

SANSSANS

100-200 nm

| |-Si-O-Si-

| |

< 1nm10-20 nm~10 µ

10-3 10-2 10-110-1

100

101

102

103

104

105

106I

q

Rg

d

NDND

EMAC ’05 Lyon 26-29th October 2005

nλ = 2d sinθ

The Bragg’s law

EMAC ’05 Lyon 26-29th October 2005

NDND

100-200 nm

| |-Si-O-Si-

| |

10-20 nm < 1nm~10 µ

10-3 10-2 10-110-1

100

101

102

103

104

105

106I

q1 10

0

8

16

24

32

40

48

56

920

850

800

750

700

650

I [a.

u.]

d-spacing

ThicknessThickness

Is it possible to use neutron instruments for investigating pottery ?

-Multiple scattering effects ⇔ sample thickness-Non destructivity vs. micro destructivity-Activation

The different thicknesses:

d ~ 3 [mm] chips ~ 0.5 [mm] powderd ~ 6 [mm]

EMAC ’05 Lyon 26-29th October 2005

http://images.google.it/imgres?imgurl=www.menteglocale.it/equochocolate/foto/cacao/Polvere.jpg&imgrefurl=http://www.menteglocale.it/equochocolate/cacao.htm&h=278&w=261&prev=/images%3Fq%3Dpolvere%26start%3D20%26svnum%3D10%26hl%3Dit%26lr%3D%26ie%3DUTF-8%26oe%3DUTF-8%26sa%3DN

EMAC ’05 Lyon 26-29th October 2005

ThicknessThickness

10-3 10-2 10-110-4

10-3

10-2

10-1

100

101

102

White

I(Q) [

a.u.

]

Q [Å-1]10-3 10-2 10-1 100

Red

10-3 10-2 10-110-5

10-4

10-3

10-2

10-1

100

101

BA

Q [Å-1]

I(Q) [

a.u.

]

10-3 10-2 10-1 100

1

2

The thinner is the sample the more reliable is the measurement. If possible, a micro-destructive sampling is the best solution.

The use of high energy neutrons lowers multiple scattering effects.

It is possible to apply numerical corrections.

Firing parametersFiring parameters

Which are the firing parameters neutrons are sensitive to?

-Maximum firing temperature-Composition-Heating rate

The different firing conditions:

The maximum firing temperature: 650 [°C], 700 [°C], 750 [°C], 800 [°C], 850 [°C], 920 [°C]

The heating rate: a fast and a slow rate

The composition: ‘Terraglia Bianca’ and ‘Terraglia Rossa’

EMAC ’05 Lyon 26-29th October 2005

EMAC ’05 Lyon 26-29th October 2005

Firing parametersFiring parameters

Between the maximum firing temperature and the parameter d there is a linear dependence.

d does not show any extra dependence (or it is not detectable) on the heating rate.

600 650 700 750 800 850 900 950100

200

300

400

500

600

700

800

Rg [

Å]

T [°C]

600 650 700 750 800 850 900 9503.0

3.2

3.4

3.6

3.8

4.0

d

T [°C]

?The dimension of the voids/aggregates seems to

have a linear dependence on the maximum firing temperature but there is incertitude on the result.

Firing parametersFiring parameters

∑−

=

⎪⎩

⎪⎨⎧

Historical BackgroundHistorical Background

During the Roman Age, the harbour of Miseno was the biggest military harbour of the Mediterranean.

conversion into a commercial harbour. It kept its activity until the casting off by the Duchy of Naples in favour of the Aghlabids Arabs from Sicily.

abandoned in the second half of the IX century A.D.

Early typology tends to disappear during the VIII century A.D.; while, other typologies continue until the IX century A.D. and are actually known as "broad line ceramic“.

EMAC ’05 Lyon 26-29th October 2005

Archaeological BackgroundArchaeological Background

The samples have been foundin the same site, called "Località Cudemo", where two kilns have been discovered. The two kilns were never operative at the same time, nevertheless the finds belong to the same typology. The second kiln was indeed constructed on top of the first one after its voluntary burial. In that area, there is no evidence of other facilities after the 9th century A.D.

EMAC ’05 Lyon 26-29th October 2005

anphora VI-VIII 3 Manphora VI-VIII 4 Manphora VI-VIII 6 Mcommon VII-VIII 7 Mcommon VII-VIII 8 Mcommon VII-VIII 10Mcommon XI-XIII 11Mcommon XI-XIII 12M

Miseno

common VIII-XI 1 Ccommon VII-VIII 2 Ccommon VII-VIII 3 Ccommon VIII-XI 4 Ccommon VII-VIII 5 Ccommon VII-VIII 8 Ccommon VII-VIII 11Camphora VI-VIII 12Camphora VI-VIII 15Camphora VI-VIII 17C

Cuma

Medieval Medieval sherdssherds

EMAC ’05 Lyon 26-29th October 2005

Samples from Miseno have a homogeneous composition

Samples from Cuma are more dispersed

Samples from Cuma and Miseno have a composition similar to that of the red reference samples.

EMAC ’05 Lyon 26-29th October 2005

Medieval Medieval sherdssherds

-5 0 5 10 15 20

-8 -4 0 4 8 12 16 20 24 28

distance

A

B

distance

CumaMiseno

White

Miseno

Red

Cuma

6 7 8 9 10 11 12 133.0

3.1

3.2

3.3

3.4

3.5

3.6

3.7

3.8

3.9

4.0

d

century

Medieval Medieval sherdssherds

600 650 700 750 800 850 900 950

3.2

3.4

3.6

d

T [°C]

The maximum firing temperature lowers moving from the 7th to the 12th century.

This feature is shared by the samples of Miseno and Cuma.

EMAC ’05 Lyon 26-29th October 2005

A working hypothesisA working hypothesis

The application of neutron techniques to an actual case gives information?

-The case of Miseno and Cuma

VI sec. AD XII sec. AD

Arc

hae

olo

gy

TIME

HISTORY

Romans abandonmentAghlabids Arabs

ROUGHNESS

Arc

hae

om

etry

TEMPERATURE

900-1000 °C 700-800 °C

EMAC ’05 Lyon 26-29th October 2005

EMAC ’05 Lyon 26-29th October 2005

OutlookOutlook

Study on the firing environment: oxidizing and reducing

Better define the mesoscopic structures

Sampling of a wider geographical area

Other typologies of materials

EMAC ’05 Lyon 26-29th October 2005

Microscopic structuresMicroscopic structures

600°C 950°C

600 650 700 750 800 850 900 9503.0

3.2

3.4

3.6

3.8

4.0

d

T [°C]

0 500 1000 1500 20000

0.5

1

1.5

2

2.5

3

3.5

4x 10

-3

size

frequ

ency

10-5 10-4 10-3 10-2 10-110-810-710-6

1x10-51x10-4

10-310-210-1100101102103

I

q

SANS

USANS

EMAC ’05 Lyon 26-29th October 2005

OutlookOutlook

Study on the firing environment: oxidizing and reducing

Better define the mesoscopic structures

Sampling of a wider geographical area

Other typologies of materials

CantiereCantiere ““MitelloMitello”” near near OtrantoOtranto (IT)(IT)

On the Adriatic coast of the south of Italy, the “CantiereMitello”, close to Otranto in the Apulian region of Salento, is one of the few Mediterranean production centres which can be attributed to the early Middle Ages.

In the site two kind of artefacts can be recognized: the transport amphorae and a series of objects such as pots, saucepans, basins, lids and small pitchers which belong to the domestic life.

EMAC ’05 Lyon 26-29th October 2005