L. Montagne*, L. Delevoye, F. Mar, G. Tricot J.P. Amoureux, O. - - PowerPoint PPT Presentation

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L. Montagne*, L. Delevoye, F. Mar, G. Tricot J.P. Amoureux, O. - - PowerPoint PPT Presentation

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Verres et vitrocramiques de phosphates L. Montagne*, L. Delevoye, F. Mar, G. Tricot J.P. Amoureux, O. Lafon, J. Trebosc, P. Rajbandhari, T. Lemesle, N. Forler, F. Vasconcelos Unit de Catalyse et Chimie du Solide Equipe Verres et RMN

slide-1
SLIDE 1

Verres et vitrocéramiques de phosphates

  • L. Montagne*, L. Delevoye, F. Méar, G. Tricot

J.P. Amoureux, O. Lafon, J. Trebosc,

  • P. Rajbandhari, T. Lemesle, N. Forler, F. Vasconcelos

Unité de Catalyse et Chimie du Solide Equipe Verres et RMN Université de Lille

slide-2
SLIDE 2

Verres de phosphates ? Applications des verres et vitrocéramiques de phosphates :

bilbiographie (et contributions de l’UCCS)

Verres pour l’optique Verres de confinement de déchets nucléaires Verres pour applications biologiques

2

slide-3
SLIDE 3

Verres de phosphates: caractéristiques structurales Verres de phosphates: caractéristiques structurales Verres de phosphates: caractéristiques structurales Verres de phosphates: caractéristiques structurales

  • P [Ne] 3s2 3p3 => hydridation sp3
  • P5+, Si4+, B3+
  • Coordinence tétraèdrique : présence d’électrons π
  • P=O d=0,145nm, P-O-P d=0,15 à 0,16 nm
  • Délocalisation des électron π
  • Conséquence structurale :
  • silicates : Q0 à Q4, phosphates Q0 à Q3
  • P5+ très peu compatible avec Si4+, mais très compatible avec Al3+ ou B3+

=> Verres de phosphates « à réseaux mixtes »

9

Videau, Le Flem (2010)

slide-4
SLIDE 4

Phosphate glasses: compositions

Invert silicate glasses Q2 Q2 Q2 Q1 Q1 Q1 Q0 Q0 Q0 Q3 Q3 Q3 Silicate glasses Q4 Q

Oligophosphates polyphosphate pyrophosphate

  • rthophosphate

O/P P 2O 5 PO 3

  • P2O 7

4-

PO 4

3-

3.5 4 Oxyphosphates Ultraphosphates 2.5 3 Oligophosphates polyphosphate pyrophosphate

  • rthophosphate

O/P P 2O 5 PO 3

  • P2O 7

4-

PO 4

3-

3.5 4 Oxyphosphates Ultraphosphates 2.5 3 polyphosphate pyrophosphate

  • rthophosphate

… … … … … …

O/P P 2O 5 PO 3

  • P2O 7

4-

PO 4

3-

3.5 4 Oxyphosphates Ultraphosphates 2.5 3 … … … … … …

Phosphate glasses Mixed network phosphate glasses (Alumino-, Boro-, Vanado-, …)

slide-5
SLIDE 5

Conséquences sur les propriétés Conséquences sur les propriétés Conséquences sur les propriétés Conséquences sur les propriétés

  • Q0 à Q3 => Réseau moins polymérisé que silicates
  • Liaisons P-O-M labiles
  • => Tg basse
  • Valeur typique 300 à 400°C
  • => Coefficients de dilatation élevés (10 à 25.10-6K-1)
  • => faible durabilité chimique

11

slide-6
SLIDE 6

Verres de phosphates: caractéristiques Verres de phosphates: caractéristiques Verres de phosphates: caractéristiques Verres de phosphates: caractéristiques chimiques chimiques chimiques chimiques

Conséquence chimique : z/a2 très élevé, donc oxyde très

acide

P : 2,16.1020 m-2 Si: 1,54.1020 m-2 B: 1,39.1020 m-2 P2O5 + O2- 2PO3

  • Très fort pouvoir dissociant (perles de fluoX)

Accepte quasiment tous les oxydes, en grande quantité :

zones de vitrifications très étendues (verres à réseaux mixtes)

Verres « réducteurs » (cas du Cr uniquement en Cr3+)

12

slide-7
SLIDE 7

Verres à réseau mixte: aluminophosphates Verres à réseau mixte: aluminophosphates Verres à réseau mixte: aluminophosphates Verres à réseau mixte: aluminophosphates

13

Brow JNCS (1990) Van Wullen ss-nmr (2007) 27Al NMR

slide-8
SLIDE 8

Al(4) modificateur et Al(6) formateur ? Al(4) modificateur et Al(6) formateur ? Al(4) modificateur et Al(6) formateur ? Al(4) modificateur et Al(6) formateur ?

14

slide-9
SLIDE 9

Les niobiophosphates Les niobiophosphates Les niobiophosphates Les niobiophosphates

15

Flambard JNCS (2008) Hoppe PCCP (submitted)

slide-10
SLIDE 10

Les borophosphates Les borophosphates Les borophosphates Les borophosphates

16

Ducel Phys Chem Glass (1997) Raguenet SSI (2012) 11B NMR

slide-11
SLIDE 11

Et aussi… Et aussi… Et aussi… Et aussi…

Les vanadophosphates (Tricot 2011) Les phosphates de Zinc ? Ex: verre 2ZnO-P2O5 Les silicophosphates ?

Si(VI) modificateur (si faible qq de SiO2 dans un verre de

phosphate)

Incompatibilité due à l’instabilité de la liaison P-O-Si Séparations de phase, ségrégation des cations autour des

phosphates

Compatibilité si présence de Al2O3 et/ou B2O3

  • Connexions via P-O-Al ou P-O-B

17

slide-12
SLIDE 12
  • 50
  • 30
  • 10

10 30 (ppm)

Na3PO4 (ortho-) Na4P2O7 (pyro-) Na5P3O10 (tripoly-) ( ultraphosphate de sodium Q0 Q1 Q2 Q3 NaPO3 chaînes

31 31 31 31P NMR: Q

P NMR: Q P NMR: Q P NMR: Qn

n n n sites

sites sites sites

Q2 Q3 Q1 Q0

slide-13
SLIDE 13

Qn sites: chemical shifts depends on efs (z/a2)

AlPO4 0.99

Ca3(PO4)2 0.36 Na3PO4 0.18

  • 45
  • 40
  • 35
  • 30
  • 25
  • 20
  • 15
  • 10
  • 5

5 10 15 20 25 (ppm)

31 31 31 31P NMR: second neighbors

P NMR: second neighbors P NMR: second neighbors P NMR: second neighbors

slide-14
SLIDE 14
  • 30
  • 20
  • 10
  • 30
  • 20
  • 10
  • 10
  • 20
  • 30
  • 30
  • 20
  • 10
  • 20
  • 40
  • 60
  • 30
  • 20
  • 10
  • 20
  • 40
  • 60
  • 30
  • 20
  • 10
  • 20
  • 40
  • 60
  • 30
  • 20
  • 10
  • 20
  • 40
  • 60

Devitrified Na2O-Al2O3-P2O5 glass

2D homo 2D homo 2D homo 2D homo-

  • nuclear connectivity (

nuclear connectivity ( nuclear connectivity ( nuclear connectivity (31

31 31 31P/

P/ P/ P/ 31

31 31 31P)

P) P) P)

  • Through space (RFDR)
  • Through bonds (INADEQUATE)
  • 4 phases
  • 1 of the phases, « Y » contains 3 sites
  • This « Y »phase contains P-O-P
slide-15
SLIDE 15
  • 30
  • 25
  • 20
  • 15
  • 10
  • 05
  • 20
  • 15
  • 10
  • 5

⇒ Several aluminophosphate phases ⇒The phase « Y » contains P-O-Al bonds dimension 31P (ppm) dimension haute résolution 27Al (ppm)

2D hetero 2D hetero 2D hetero 2D hetero-

  • nuclear connectivity (

nuclear connectivity ( nuclear connectivity ( nuclear connectivity (31

31 31 31P/

P/ P/ P/ 27

27 27 27Al)

Al) Al) Al)

Devitrified Na2O-Al2O3-P2O5 glass

MQ-CP-Hetcor

31P NMR 27Al NMR

slide-16
SLIDE 16

Qn

m, AlOx

31P {27Al} CP-HETCOR 31P {27Al} REAPDOR 31P J-RESolved

(a) (b) (c)

KAlP_10

2D NMR « strategy » 2D NMR « strategy » 2D NMR « strategy » 2D NMR « strategy »

slide-17
SLIDE 17
  • ppm
  • 15
  • 10
  • 5

10 5 ppm 6 8 10 12 14 16 18 20

  • °
  • !"# $"

"! %& '! "(# !$'") * +!, #")( (!$!"-'-

2D hetero 2D hetero 2D hetero 2D hetero-

  • nuclear connectivity (

nuclear connectivity ( nuclear connectivity ( nuclear connectivity (31

31 31 31P/

P/ P/ P/ 1

1 1 1H)

H) H) H)

slide-18
SLIDE 18

NMR can NMR can NMR can NMR can quantify quantify quantify quantify amorphous / crystalline parts amorphous / crystalline parts amorphous / crystalline parts amorphous / crystalline parts

  • 50.0
  • 40.0
  • 30.0
  • 20.0
  • 10.0
0.0 10.0 20.0 (ppm) 0.00 100.00 200.00
  • Ortho Pyro meta

31P NMR

Ecole thématique « Nucléation-cristallisation » Mai 2013

slide-19
SLIDE 19

HT NMR of phosphate glasses: in situ study of HT NMR of phosphate glasses: in situ study of HT NMR of phosphate glasses: in situ study of HT NMR of phosphate glasses: in situ study of crystallization, dynamics crystallization, dynamics crystallization, dynamics crystallization, dynamics

31

Van Wüllen J. Phys Chem (2007) Wegner J. Phys Chem (2009) 31P NMR 27Al NMR

slide-20
SLIDE 20

Quelques exemples d’applications Quelques exemples d’applications Quelques exemples d’applications Quelques exemples d’applications

32

slide-21
SLIDE 21

Phosphate glasses: applications

  • Water softening (Calgon)
  • biomaterials
  • sealing glasses
  • Photonic glasses, laser glasses
  • Electrolyte glass
  • Anti-oxidation coatings
  • Nuclear waste vitrification

Phosphate glasses Mixed network phosphate glasses

slide-22
SLIDE 22

Laser Glass Development at SCHOTT – 2011

Development of continuous melting of phosphate laser glass

Artist Rendition of National Ignition Facility (NIF) Laser

slide-23
SLIDE 23

Laser Glass Development at SCHOTT – 2011

Beamlet eighteen liter rare earth doped phosphate glass amplifier slab

  • The NIF laser alone required 3000

slabs (150 metric ton) with the following specifications:

  • Index uniformity to <0.000001
  • Free of inclusions and bubbles

larger than 100um

  • Residual hydroxyl content

<100ppmw

  • Platinum particle free
  • Free of all detectable striae
  • Low 1054nm absorption of

<.19% per cm thickness

slide-24
SLIDE 24

Laser Glass Development at SCHOTT – 2011

Damage grows with successive shots above the damage threshold

  • Redeposited

platinum vapor of spatial size >0.3µm can damage on the next shot

  • Below 0.3µm,

the heat is conducted into the glass

  • Laser glass parts

became unusable after only a few high power shots

slide-25
SLIDE 25

Laser Glass Development at SCHOTT – 2011

The key to solving the Pt particle problem was to dissolve the particles into the glass structure as ionic Pt4+

  • Platinum particles appear

to be created at the start of the melt cycle

  • Dissolution is limited by

diffusion of platinum away from the particle surface

  • Care must be taken to

avoid the late arrival of Pt particles into the melt from condensed vapors

slide-26
SLIDE 26

Laser Glass Development at SCHOTT – 2011

Meeting the laser glass requirements in terms of cost, quality, and rate of delivery for NIF

Melt and Form

  • 7. Annealing Lehr

Batching Lab Samples Continuous Monitoring All Properties

  • 2. Melter 3.Conditioner
  • 4. Refiner
  • 5. Homogenizer
  • 6. Forming

Exhaust Process Control

  • 1. Raw

Material To Scrubber

  • 8. Cut /

Inspect

Melt and Form

  • 7. Annealing Lehr

Batching Lab Samples Continuous Monitoring All Properties

  • 2. Melter 3.Conditioner
  • 4. Refiner
  • 5. Homogenizer
  • 6. Forming

Exhaust Process Control

  • 1. Raw

Material To Scrubber

  • 8. Cut /

Inspect

Over 1400 laser slabs were first produced by the new continuous melting process

slide-27
SLIDE 27

High power lasers: >3000 neodynium-doped phosphate glass slabs (NIF LLNL USA, Megajoule Bordeaux, HPL Indore India)

Laser phosphate glasses Laser phosphate glasses Laser phosphate glasses Laser phosphate glasses Second harmonic generation: optical switchs

slide-28
SLIDE 28

Glass compositions: xNb2O5-(100-x)(95NaPO3-5Na2B4O7)

0.0 5.0x10

3

1.0x10

4

1.5x10

4

2.0x10

4

0.0 2.0x10

  • 19

4.0x10

  • 19

6.0x10

  • 19

8.0x10

  • 19

n=1.96 n=1.89 n=1.84 n=1.58 n=1.72 n=1.61

x=0 x=0.37 x=0.22 x=0.4 x=0.11 x=0.43 n2SiO

2=0.6 10

  • 19 m

2/W

Non-libear index n2 (m

2/W)

Nb Concentration (mol/m

3)

Large increase of n2 : Nb-O-P, Nb-O-Nb ? => 31P, 93Nb, 17O NMR

Niobiophosphate Niobiophosphate Niobiophosphate Niobiophosphate glasses show large glasses show large glasses show large glasses show large increase increase increase increase of n

  • f n
  • f n
  • f n2

2 2 2

index index index index with with with with Nb Nb Nb Nb2

2 2 2O

O O O5

5 5 5 content

content content content

  • M. Dussauze, E. Fargin, J. Phys. Chem. (2007)
  • C. Rivero, E. Fargin, T. Cardinal, Ceram. Transaction (2006)
slide-29
SLIDE 29

20 40 60 80 100 3 3.5 4 4.5 5 5.5 6 6.5 10 20 30 40 x Nb2O5 O/P % Qn Q2 Q1 Q0 Q0exp Q1exp Q2exp 20 40 60 80 100 3 3.5 4 4.5 5 5.5 6 6.5 10 20 30 40 x Nb2O5 O/P % Qn 20 40 60 80 100 3 3.5 4 4.5 5 5.5 6 6.5 10 20 30 40 x Nb2O5 20 40 60 80 100 3 3.5 4 4.5 5 5.5 6 6.5 20 40 60 80 100 3 3.5 4 4.5 5 5.5 6 6.5 10 20 30 40 x Nb2O5 10 20 30 40 x Nb2O5 O/P % Qn Q2 Q1 Q0 Q0exp Q1exp Q2exp

Nb2O5 dissociation is not complete: assumes Nb-O-Nb bonds

31 31 31 31P NMR:

P NMR: P NMR: P NMR: Q Q Q Qn

n n n site quantification in glasses

site quantification in glasses site quantification in glasses site quantification in glasses

  • A. Flambard, L. Montagne, L. Delevoye, G. Palavit, J.P Amoureux, J.J. Videau JNCS (2004)
slide-30
SLIDE 30

2000 1000

  • 2000
  • 1000

Chemical Shift (ppm) 2000 1000

  • 2000
  • 1000

2000 1000

  • 2000
  • 1000

Chemical Shift (ppm)

40Nb2O5-60NaPO3

(18.8T)

P-O-Na P-O-Nb

40Nb2O5-60NaPO3 (9.4T)

P-O-Nb Nb -O-Nb Nb -O-Nb

17O chemical shift (ppm)

Nb-O-Nb P-O-Na P-O-P P-O-Nb

140 200 80 260 320 380 440 500 560 620

17O chemical shift (ppm)

Nb-O-Nb P-O-Na P-O-P P-O-Nb

140 200 80 260 320 380 440 500 560 620 6Nb2O5-94NaPO3

P-O-Na P-O-P

NbONb PONa (NBO) NbONb PONa (NBO) NbONb PONa (NBO) NbONb PONa (NBO)

P-O-Nb P-O-P P-O-Na Nb -O-Nb Nb-O-Nb

17 17 17 17O NMR: chemical shift assignments

O NMR: chemical shift assignments O NMR: chemical shift assignments O NMR: chemical shift assignments

slide-31
SLIDE 31

% Nb2O5 % Oxygène

P-O-(Na,Nb) P-O-Na P-O-Nb P-O-P Nb-O-Nb 10 20 30 40 50 60 70 80 10 20 30 40 50

% Nb2O5 % Oxygène

P-O-(Na,Nb) P-O-Na P-O-Nb P-O-P Nb-O-Nb

RMN 31P RMN 17O

Oxygen Oxygen Oxygen Oxygen sites sites sites sites in niobiophosphate glasses in niobiophosphate glasses in niobiophosphate glasses in niobiophosphate glasses

Nb-O-Nb are confirmed by 17O NMR

slide-32
SLIDE 32

? ? ? ?

(ppm)

  • 2500
  • 1500
  • 500

500 (ppm)

  • 2500
  • 1500
  • 500

500

6 12 20 30 40 x

Chemical shift / ppm

  • 2500
  • 1500
  • 500

500

18.8T – 33KHz

./012 )( *3$ ,' , $,"($4$"

93 93 93 93Nb NMR

Nb NMR Nb NMR Nb NMR

93Nb chemical shift assignment ?

We need crystalline reference compounds

slide-33
SLIDE 33 Nb7 Nb7 Nb1 Nb1 Nb1 Nb1 Nb3 Nb3

Nb1 Nb1

Nb2 Nb2 Nb1 Nb1 Nb2 Nb2 Nb3 Nb3 Nb1 Nb1

Nb2 Nb2 Nb4 Nb4 Nb3 Nb3

Nb2 Nb2 Nb1 Nb1
  • 900
  • 1000
  • 1100
  • 1200
  • 1300
  • 1400
  • 1500
  • 1600

NaNbO3 NaBa2Nb5O15 H-Nb2O5 Na3.04Nb7P4O29 Cs4Nb11O30 Nb3(NbO)2(PO4)7 NbPO5 PNb9O25 Na4Nb8P4O32 NaBa2Nb5O15 PNb9O25 Na4Nb8P4O32

  • 900
  • 1000
  • 1100
  • 1200
  • 1300
  • 1400
  • 1500
  • 1600

NaNbO3 NaBa2Nb5O15 H-Nb2O5 Na3.04Nb7P4O29 Cs4Nb11O30 Nb3(NbO)2(PO4)7 NbPO5 PNb9O25 Na4Nb8P4O32 NaBa2Nb5O15 PNb9O25 Na4Nb8P4O32

O.B. Lapina ss-nmr 28 (2005) 204–224

  • A. Flambard, L. Montagne, L. Delevoye, S. Steuernagel

Solid-State NMR (2007)

Crystalline references for Crystalline references for Crystalline references for Crystalline references for 93

93 93 93Nb chemical

Nb chemical Nb chemical Nb chemical shift assignment shift assignment shift assignment shift assignment

  • 1700
  • 1600
  • 1500
  • 1400
  • 1300
  • 1200
  • 1100

1 2 3 4 5 6

x Chemical shift (ppm)

NbO6 Nb(OP)n

slide-34
SLIDE 34

? ? ? ?

(ppm)

  • 2500
  • 1500
  • 500

500 (ppm)

  • 2500
  • 1500
  • 500

500

6 12 20 30 40 x

Chemical shift / ppm

  • 2500
  • 1500
  • 500

500

./012 )( *3$ ,' , $,"($4$"

Nb(OP)6-x(ONb)x Nb(ONb)6 => Clusters

93Nb sites are assigned from crystalline references, but uncertainty remains,

DFT calculations are needed.

slide-35
SLIDE 35

Nb+5 P+5 Na+1 O-2 Nb+5 P+5 Na+1 O-2 Nb+5 P+5 Na+1 O-2

0 < x < 20

Nb+5 P+5 Na+1 O-2 Nb+5 P+5 Na+1 O-2 Nb+5 P+5 Na+1 O-2 Nb+5 P+5 Na+1 O-2

20 ≤ x < 30

Nb+5 P+5 Na+1 O-2 Nb+5 P+5 Na+1 O-2 Nb+5 P+5 Na+1 O-2

x ≥ 30 Q2 + Q1, Nb(OP)6 Q2, Q1 + Q0

Nb(OP)6-x(ONb)x

Q1 + Q0, NbO6 clusters

0.0 5.0x10

3

1.0x10

4

1.5x10

4

2.0x10

4

0.0 2.0x10

  • 19

4.0x10

  • 19

6.0x10

  • 19

8.0x10

  • 19

n=1.96 n=1.89 n=1.84 n=1.58 n=1.72 n=1.61

x=0 x=0.37 x=0.22 x=0.4 x=0.11 x=0.43 n2SiO

2=0.6 10
  • 19 m

2/W

Non-libear index n

2 (m 2/W)

Nb Concentration (mol/m

3)

0.0 5.0x10

3

1.0x10

4

1.5x10

4

2.0x10

4

0.0 2.0x10

  • 19

4.0x10

  • 19

6.0x10

  • 19

8.0x10

  • 19

n=1.96 n=1.89 n=1.84 n=1.58 n=1.72 n=1.61

x=0 x=0.37 x=0.22 x=0.4 x=0.11 x=0.43 n2SiO

2=0.6 10
  • 19 m

2/W

Non-libear index n

2 (m 2/W)

Nb Concentration (mol/m

3)

Property vs. structure Property vs. structure Property vs. structure Property vs. structure

slide-36
SLIDE 36

Phosphate glasses and nuclear waste vitrification Phosphate glasses and nuclear waste vitrification Phosphate glasses and nuclear waste vitrification Phosphate glasses and nuclear waste vitrification

56

slide-37
SLIDE 37

Phosphate glasses and nuclear Phosphate glasses and nuclear Phosphate glasses and nuclear Phosphate glasses and nuclear waste vitrification waste vitrification waste vitrification waste vitrification

Alternative solution to borosilicate glasses for special wastes

High load Larger solubility of chromium, molybdenum Lower melting T : less volatilization of sulfur, iodine

70’ : USSR: Mamoshin: aluminophosphate glasses 80’: USA: Sales and Boatner : Pb-Fe phosphate glasses 90’: USA: Day : Fe phosphate glasses

57

slide-38
SLIDE 38

58

slide-39
SLIDE 39

iron iron iron iron phosphate glass phosphate glass phosphate glass phosphate glass

  • Contains 26 wt% of the Hanford AZ-102 LAW
  • Targets high sulfate (4.3 wt%) and high Na2O (20 wt%)
  • Approximately 3x greater waste loading than typical borosilicate glass
  • Recommended processing temperature of 1000 - 1050°C
  • High retention of Cs, Re, and SO3 in laboratory melts
  • Meets PCT and VHT durability requirements for Hanford LAW

disposal (regardless of thermal history)

  • Melt viscosity and electrical conductivity within acceptable ranges

for JHM and CCIM processing

  • Compatible with Inconel 693/690 and K-3 refractory

60

C.-W. Kim, D.E. Day JNCS (2010)

Open questions: Chemical durability (long term) Devitrification resistance Corrosiveness

+-,(! 5!('#( $ (!$-(! !67$"5 $"('"--,'!"

slide-40
SLIDE 40

Immobilization of Radioactive iodine in phosphate Immobilization of Radioactive iodine in phosphate Immobilization of Radioactive iodine in phosphate Immobilization of Radioactive iodine in phosphate glasses glasses glasses glasses

  • T. Lemesle1,2, F.O. Méar1, L. Campayo2, O. Pinet2, L. Montagne1

1 Unité de Catalyse et Chimie du Solide - UMR-CNRS 8181 -

Université Lille Nord de France, F-59652 Villeneuve d’Ascq, France

2DEN/DTCD/SECM/LDMC, CEA Marcoule, BP 17171,

30207 Bagnols sur Cèze, France

slide-41
SLIDE 41

Why Iodine? Why Iodine? Why Iodine? Why Iodine?

  • 0.2$ "'!8"!"9!$'! ,$!$"'")!

,'($),(

3 ,-'!8!#5!5!("()

  • "4(!#!"("'8$"-!

+!$"! '#!"8"(!(:!"°

  • +(8$"!(

;"5-(! '"$"$!"$!)"$.

slide-42
SLIDE 42

Influence of the incorporation of AgI on the Influence of the incorporation of AgI on the Influence of the incorporation of AgI on the Influence of the incorporation of AgI on the structure as a function of Ag/P by structure as a function of Ag/P by structure as a function of Ag/P by structure as a function of Ag/P by 31

31 31 31P NMR

P NMR P NMR P NMR

Addition of AgI for different ratios of Ag/P changes the chemical shift: modification of angles and bond length in phosphate network

(ppm)

  • 35
  • 30
  • 25
  • 20
  • 15
  • 10
  • 5

5 10 15 20 25 30 35

AgPO3

Q2 Q1

AgPO3-AgI Ag5P3O10 Ag5P3O10-AgI Ag4P2O7 Ag4P2O7-AgI

slide-43
SLIDE 43

Ajout de Al Ajout de Al Ajout de Al Ajout de Al2

2 2 2O

O O O3

3 3 3 : réseau aluminophosphate

: réseau aluminophosphate : réseau aluminophosphate : réseau aluminophosphate

70

(a)

31P chemical shift / ppm

  • 40
  • 30
  • 20
  • 10

10

31P chemical shift / ppm

  • 40
  • 30
  • 20
  • 10

10 (b)

{27Al} - 31P

31P 31P

{27Al} - 31P

slide-44
SLIDE 44

109 109 109 109Ag NMR

Ag NMR Ag NMR Ag NMR

Broad signal of P-O-Ag : distribution of ionic bonds No signal of AgI : no cluster Average signal of silver in AgI-AgPO3-Al2O3 glasses : confirms no clustering since all Ag+ are bonded both to Iodine and phosphates

(1)Multi-nuclear,

Solid Stz Nuclear Magnetic Resonance, KK Olsen, 123-132 (1995)

(2)Mustarelli et al.,

1998

(3)Kawamura and

al., 2002

(4)Kawamura and

al., 2002

(ppm)

  • 350
  • 300
  • 250
  • 200
  • 150
  • 100
  • 50

50 100 150 200 250 300 350 400 450 500 550 600 650 700

AgPO3 AgI-AgPO3 (1% vol) AgPO3-3Al AgI –AgPO3-3Al (1% vol) AgI –AgPO3-5Al (1% vol)

AgPO3 430 ppm

24 ppm 334 ppm

(1)

AgI **: 728, 710, 680 ppm

(2)

AgPO3 AgPO3-AgI AgPO3-Al2O3 AgPO3-3Al2O3-AgI AgPO3-5Al2O3-AgI AgI AgPO3

slide-45
SLIDE 45

75

Q1

31P Chemical shift / ppm

  • 20
  • 10

10 20

Q1

1

Q20 Q2

0-Q2

Q10-Q20 Q1

0-Q1 1

Q1

1-Q2

Q10-Q10

(a) (b) (d) (e) (f) (c)

  • 10

20 10 ppm

  • 20

(a) (b) (d) (e) (f)

31P Chemical shift / ppm

Q10 Q11 Q20 Q2

0-Q2

Q10-Q20 Q1

0-Q1 1

Q10-Q10 Q11-Q20

(c)

Without AgI With AgI

31P-1P DQ-NMR

slide-46
SLIDE 46

Sealing glasses Sealing glasses Sealing glasses Sealing glasses

Wilder et al. Brow et al. (Sandia) Morena et al. (Corning) Low Tg High CTE for sealing to Al alloys Sn phosphate glass Zn phosphate glass F phosphate glass : extension to

Glass-polymer blends (Tischendorf)

98

slide-47
SLIDE 47

Phosphate glasses as biomaterials Phosphate glasses as biomaterials Phosphate glasses as biomaterials Phosphate glasses as biomaterials

100

slide-48
SLIDE 48
  • Bone : apatite = calcium phosphate
  • Hench’s bioglasses : silicophosphates
  • Vogel et al : Ca, Fe, Na phosphate glass-ceramics (machineable)
  • Knowles : Na, Ca, Ti phosphate
  • Good biocompatibility
  • Control of dissolution rate is a key issue

Phosphate glasses as biomaterials Phosphate glasses as biomaterials Phosphate glasses as biomaterials Phosphate glasses as biomaterials

101

Knowles Acta Biomaterialia (2012)

slide-49
SLIDE 49

Phosphate glass fibers as biomaterials Phosphate glass fibers as biomaterials Phosphate glass fibers as biomaterials Phosphate glass fibers as biomaterials

102

  • C. Vitale Mat. Sc & Eng.(2011)
slide-50
SLIDE 50

Phosphate glass Phosphate glass Phosphate glass Phosphate glass-

  • ceramics as biomaterials

ceramics as biomaterials ceramics as biomaterials ceramics as biomaterials

  • Abe et al. (Nagoya)
  • Ca(PO3)2 sub-Tg crystallization
  • NaCaTi(PO4)2 NASICON porous glass-ceramics impregnated with

Ag+ : bactericide bioceramics

103

Kasuga ACERS (1997) Abe et al Nature (1989)

slide-51
SLIDE 51

Phosphate glass bio Phosphate glass bio Phosphate glass bio Phosphate glass bio-

  • enamels

enamels enamels enamels

Na,Ca, Fe phosphate glasses + TiO2 (CTE matching) Enamels on Alumina hip prothesis cup In-vivo tests and push-out evaluation (Hopital Lariboisière Paris) Showed good bioactivity (apatite formation, osteocells) However, alumina diffusion through coating inhibited bone

mineralization

104

4 mm

Montagne et al. GTB (1998)

slide-52
SLIDE 52

Phosphate glass fertilizers Phosphate glass fertilizers Phosphate glass fertilizers Phosphate glass fertilizers

Slow release of oligo-elements (Mn, Cu)

105

Ivandelko Völkenrode (2007)

slide-53
SLIDE 53

NaPO NaPO NaPO NaPO3

3 3 3 Hydration (Calgon)

Hydration (Calgon) Hydration (Calgon) Hydration (Calgon)

  • 17O NMR @18.8T
slide-54
SLIDE 54

ppm 60 80 100 ppm 70 80 90 100 110 17O MAS 17O HR 17O 3Q-SPAM-MAS ppm

  • 10
  • 5

ppm 70 80 90 100 110 31P MAS 17O/31P 3Q-SPAM-

INEPT

ppm

  • 10
  • 5

31P MAS 31P/17O HMQC

Q0 Q1

Na2H2P2O7 NaH2PO4 NaH2PO4,H2O

17O-31P Heteronuclear correlations

slide-55
SLIDE 55

Identification & Quantification of NaPO3 hydration products through spectra simulations.

!"#$%#$ !"###$& !"#$% !"###$& "#$% "#$%#$ "###$&

17O 3QMAS NMR at 18.8T

112

  • Weathering leads to monomers and short phosphate chains.
  • Modelisation enables quantification (kinetic study)

(Coll. T. Charpentier, CEA Saclay)

slide-56
SLIDE 56

Phosphate glasses: applications

  • Water softening
  • biomaterials
  • sealing glasses
  • Photonic glasses, laser glasses
  • Electrolyte glass
  • Anti-oxidation coatings
  • Nuclear waste vitrification

Phosphate glasses Mixed network phosphate glasses

slide-57
SLIDE 57
slide-58
SLIDE 58

Acknowledgements Acknowledgements Acknowledgements Acknowledgements

IFCPAR for project funding #4008-1 The glass & NMR group

  • EC and French institutions for NMR and projects fundings