nitrided (oxynitride) glasses...nitrided (oxynitride) glasses spring school gdr verres, cargèse...

Nitrided (oxynitride) glasses

Spring School GDR Verres, Cargèse 2017

Francisco MuñozCeramics and Glass Institute (CSIC), Madrid (Spain)

[email protected]

The origin and concept of nitrided glassesMethods of preparation. Silicates vs PhosphatesStructure of oxynitride networksEffect of N on physical and chemical propertiesApplications and current developments

First experiments by Hans-Otto Mulfinger:Studied dissolution of N through bubbling N2, H2/N2 or NH3 in silicate and borate melts: < 1 wt. % N

(Mulfinger, J. Am. Ceram. Soc. 49 (1966) 462)

Origin of nitrided glasses

Importance of nitrogen in glasses:Hot pressing of nitrogen containing ceramics to produce SiAlON phasesand formation of a glassy phase at grain boundaries

(Jack, J. Mat. Sci. 11 (1976) 1135)Incorporation of nitrogen in phosphate glassesThermal ammonolysis of the phosphate melt

(Marchand, CR Acad Sc Paris 294 (1982) 91,Marchand, J. Non-Cryst. Solids 56 (1983) 173)

Synthesis of oxynitride glasses

• Silicate glasses: melting with metallic nitrides

Si3N4, AlN, Li3N, Ca3N2, Mg3N2 (Hampshire, J. Eur. Ceram. Soc. 28 (2008) 1475Sharafat, Ceram. Int. 41 (2015) 3345)

La + SiO2 + Si3N4 (Hakeem, Adv. Mat. 17 (2005) 2214)

• Phosphate glasses: thermal ammonolysis of phosphate melts

Melting of phosphate glass+

Thermal treatment in NH3 flow at T < 800ºC

Liquid-gas chemical reaction: MPO3 + xNH3 → MPO3-3x/2Nx + 3x/2H2O

— O — P — N —

O-

O-

— O — P O —

N

O-

— O — P — N —

O-

N

— O — P — O —

O

O-

Metaphosphate glassnetwork

Exception to one of Zachariasen’s rules:“Anions should not bind more than 2 central atoms”Þ Higher degree of interconnected network

PO3N

PO2N2

Improves the chemical resistanceIncreases the electrical conductivityIncreases viscosity Þ Higher resistance to devitrification

NH3

Substitution of nitrogen for oxygen in phosphates

TNH3

N2N2

Tt

t

Phosphateglassmelting+

ThermaltreatmentinNH3 atT

N/Pra

tio

N/P=KT·Öt

N/Pa T

F.Muñozetal.,Phys.Chem.Glasses 43C(2002)113;FMuñoz52(4)(2011)181

Kinetics inLiNaPbPO3-3x/2Nx glasses


SubstitutionrulesbyMarchand:Nt =3/2B

Nd =NBO+1/2BO


2PO4+NH3 PO3N-PO3N

PO4+PO3N+NH3 PO2N2-PO3N

Systemof2pseudo-firstorderconsecutivereactions

F.Muñozetal.,Phys.Chem.Glasses 43C(2002)113;FMuñoz52(4)(2011)181

200 300 400 500 600 700 800 900 1000 1100 12000

2

4

6

8

10

12 NaPO3 LiPO3 Ba(PO3)2 Sr(PO3)2 Ca(PO3)2 Zn(PO3)2 Mg(PO3)2 VFT

log h

(dP

a.s)

T (ºC)

NaPO3LiPO3

LiNaPO3LiZnPO3

Alkali+akaline-earth


Muñoz-Senovilla et al., J. Non-Cryst. Solids 385 (2014) 9-14

0.4 0.6 0.8 1.0 1.2 1.4 1.6

log ( in dPa.s)

0.0

0.1

0.2

0.3

0.4

0.5

0.6

N/P

ratio

h h

Na-Pb-P-O-NLi-Pb-P-O-N

Li-Na-Pb-P-O-N

Parameters controlling nitrogen incorporation:Viscosity of the phosphate melt at the temperature of ammonolysisIonic Field Strength (z/r2)of the modifier cations


• Metals:Dependence on their reduction EºPrecipitation of Cu, Ag, AuSn4+ ® Sn2+Pb2+ ® Pb possible in PbPO3

• Volatiles: S2-, F-, SO42- (reduced)

• Former elements:SiO2 and Al2O3 increase reaction TB2O3 lowers the N content, may form BN

0 2 4 6 8 10

% B2O3

0.2

0.4

0.6

0.8

wt.

% N

2

N2 in (50-x)Li2O.xB2O3.P2O5 700ºC, 0.5 h

Li+ + e− ® Li(s)Na+ + e− ® Na(s)Ba2+ + 2 e− ® Ba(s)Ca2+ + 2 e− ® Ca(s)La3+ + 3 e− ® La(s)Ti3+ + 3 e− ® Ti(s)Zn2+ + 2 e− ® Zn(s)Pb2+ + 2 e− ® Pb(s)

Cu+ + e− ® Cu(s)Ag+ + e− ® Ag(s)Au3+ + 3 e− ® Au(s)Sn4+ + 2 e− ® Sn2+

E°(V)−3.0401

−2.71−2.912−2.868−2.379−1.21

−0.7618−0.13

+0.520+0.7996

+1.52+0.15

• Alkali and alkaline-earth elements:No problem provided the melt viscosity is low


100 nm

PbPO3

Structure of oxynitride glasses

29Si NMR

Y15Si15Al10O4515N15

Y12.3Si18.5Al7.1O54.215N7.9

-47, -52, -60, -70, -81 ppm:

Koroglu et al., Phys. Chem. Glasses 52 (2011) 175

SiN4 (impurities from melting)SiN3OSiN2O2SiNO3SiO4


15N NMR (I=-1/2, 0,37%,4.10-6), needing enrichment in 15N

Y15Si15Al10O4515N15

Y12,3Si18,5Al7,1O54,215N7,9

Y15,2Si14,6Al8,7O54,715N6,9

%N

-268 ppm: NSi2

-300 ppm: NSi3

Si-N=Si

Si-N

-40-30-20-1001020Chemical shift 31P (ppm)

Inte

nsity

(a.u

.)

N/P = 0.10

N/P = 0.12

N/P = 0.22

N/P = 0.25

N/P=0.46

N/P=0.68

31P MAS NMR9.4 T, 10 kHz

Structural groups distribution in NaPO3-3x/2Nx glasses

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7

N/P ratio

0

20

40

60

80

100

% P

(O,N

) 4 g

roup

s

PO4PO3N

PO2N2

1. PO3N formed2. PO2N2 from PO3N-PO4 regions

PO4

PO3NPO2N2


-50-40-30-20-10010Chemical shift 31P (ppm)

N/P = 0.05

N/P = 0.10

N/P = 0.18

N/P = 0.42

N/P = 0.45

N/P = 0.63

Inte

nsity

(a.u

.)31P MAS NMR9.4 T, 10 kHz

PO4

PO3N

PO2N2

Structural groups distribution in LiPO3-3x/2Nx glasses

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7

N/P ratio

0

20

40

60

80

100

% P

(O,N

) 4 g

roup

s

PO4PO3NPO2N2

Much lower content of PO3N groupsIs nitrogen segregated in regions of PO2N2 ?


LiPO3-3x/2Nx

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7

N/P ratio

0

20

40

60

80

100

% P

(O,N

) 4 g

roup

s

PO4PO3N + PO2N2

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7

N/P ratio

0

20

40

60

80

100

% P

(O,N

) 4 g

roup

s

PO4PO3N + PO2N2

NaPO3-3x/2Nx


Correlations

PO4-PO4

PO4-PO3N

PO3N-PO2N2

Q1-Q1 (Pyrophosphate)

Homogeneous distributionof oxynitride microdomains

Double Q

uantumdim

ension, w1 (ppm

)

MAS dimension, w2 (ppm)

A: Q2(-20.5 ppm)

C: PO2N2(-3.1 ppm)

Q1(+4.1 ppm)

A-A

A-B

B-CQ1-Q1

B: PO3N(-7.6 ppm)31P DQ MAS NMR

9.4 T, 10 kHzN/P = 0.69

B-A

C-B

31P DQ MAS NMR in Li0.25Na0.25Pb0.25PO3-3x/2Nx


F. Muñoz et al., J. Non-Cryst. Solids 324 (2003) 142-149

N1s XPS

Intensity (a.u.)

Binding energy (eV)

401 399 397 395

Nt (-N

3QMAS 17O9.4 T

-461-230023046117O frequency shift (ppm)

NaPO3

9.4 T

BO

NBO

— O — P — O —

O

O-


In a metaphosphate glass:

17O NMR9.4 T

170 60708090100110120130140150160

diso/ppm (17O)

BO

NBO1

NBO2

3Q-MAS 17O

Inte

nsity

(a. u

.)

25507510012515017O frequency shift (ppm)

NaP17O3

NaP17ON-1

NaP17ON-2

NaP17ON-3

NaP17ON-4

Inte

nsity

(a.u

.)

18.8 T108.48 MHz20 kHz3.2 mm

BO

NBO


Down-field shift of 17O resonance in PON of imidophosphates(J. Am. Chem. Soc. 105 (1983) 6475)

Sample dCS % PON

NaP17ON 8.0 (4.0) 0

NaP17ON-1 14.9 (5.2) 20

NaP17ON-2 14.2 (7.1) 41

NaP17ON-3 12.2 (8.3) 53

NaP17ON-4 15.8 (8.8) 81

— O — P — N <

O

O-

PO3N: BO/NBO = 0.25

-O — P — N <

N

O-

PO2N2: BO/NBO = 0 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7N/P ratio

0

10

20

30

40

50

60

70

80

90

100

% P

ON

calculated

17O NMR

% PON = [100×(xPO3N + xPO2N2)]/[ xPO4 + xPO3N + xPO2N2]


— O — P — O —

O

O-PO4: BO/NBO = 0.5

Properties and applications

Oxynitride phosphate glasses: thermal and chemical stability

0 40 80 120 160 200

tiempo (h)

0

2

4

6

8

10

12

m/S

(mg

cm-2

)D

N/P=0

N/P=0,03

N/P=0,05

N/P=0,22

Weight loss vstimeat55ºCInLiNaPbPON glasses

T=55ºC

Time(h)

0.0 0.1 0.2 0.3 0.4 0.5 0.6

N/P

240

260

280

300

320

340

360

T g (º

C)

NaPbPONLiNaPbPONLiPbPON

0.0 0.1 0.2 0.3 0.4 0.5 0.6

N/P

10

12

14

16

18

20

22

(30-

225

ºC) x

106

(K-1

)

a

NaPbPONLiNaPbPONLiPbPON

F. Muñoz et al, Phys. Chem. Glasses 43C (2002) 39

Nitrogen variable content allows for the adjustment of thesoftening temperatures as well as the coefficients of thermal expansion

Properties of Li2O-Na2O-PbO-P2O5 sealing glasses

Low temperature sealing glasses

Control of the dissolution rate:• CaO/Na2O ratio• Content of nitrogen in the glass

Q. Riguidel et al. Acta Biomaterialia 7 (2011) 2631

Biocompatible/resorbable materials

Oxynitride phosphate glasses: stability against crystallization in LiPON

0 100 200 300 400 500 600 700 800

Temperature (ºC)

-80

-60

-40

-20

0

20

40

DTA

( V

)

AN2-80

-60

-40

-20

0

20

40

60A

0 100 200 300 400 500 600 700 800

-80

-60

-40

-20

0

20

40

DTA ( V)AN3

-80

-60

-40

-20

0

20

40

60AN1

µµ

Tg Tg

TgTg

Increase ofthermal stability

N/P=0 N/P=0.05

N/P=0.15 N/P=0.22

Bates et al., Solid State Ionics 135 (2000) 33

RF magnetron sputtering

Li3PO4 N2

LiPON (Li~2.8PO~3.5Nx) amorphous

s (25ºC) ~ 2·10-6 S cm-1, Ea = 0.55 eV

Yu et al., J. Electrochem Soc. 144(2) (1997) 524

„I learned that adding nitrogen to sodiummetaphosphate glasses improves their durabilityin contact with air and water vapor. So we decided tosputter the lithium orthophosphate in nitrogen ratherthan the standard gas mixture of argon and oxygen.… the presence of this small amount of nitrogen greatlyimproves the performance of the electrolyte.“

J. B. Bates

Development of phosphate and oxynitride phosphate glasses

Solid electrolytes for lithium batteries

Wang et al., J. Non-Cryst. Solids, 183 (1995) 297-306

• Higher s in the glassy material than in the crystalline counterpart• Increase in s with increasing nitrogen content• Increase in the thermal and mechanical stability of the electrolyte• The oxynitride may act as a protecting barrier for Li-metal


0.0 0.1 0.2 0.3

N/P ratio

0.60

0.65

0.70

0.75

E a (e

V)

Li1.22PO3.11-3x/2Nx

0.00 0.05 0.10 0.15 0.20 0.25 0.30

N/P ratio

-9.0

-8.5

-8.0

-7.5

-7.0

log

( in

S c

m-1

), 25

ºCs

LiPO3-3x/2Nx

Li1.22PO3.11-3x/2Nx

Li1.35PO3.18-3x/2Nx


N. Mascaraque et al. Solid State Ionics 233 (2013) 73-79

XPSO1s


ratio

N. Mascaraque et al. Solid State Ionics 233 (2013) 73-79

The change inBO/NBOratioafter nitridation decreases wtih Li2OThe higher the BO/NBOchange,the higher the increase ins

N/P=0.25


1st melting: 55Li2O.45P2O5 + NH3 Li-P-O-N

2nd melting: Li-P-O-N + LiF Li-P-O-F-N

Synthesis of (55-x/2)Li2O.xLiF.(45-x/2)P2O5 glasses

0 1 2 3 4

mol % F2

280

290

300

310

320

330

340

350

T g (º

C)

Non-nitrided glasses

Oxynitride glasses 4 mol % N2

0.0 0.5 1.0 1.5 2.0 2.5 3.0

mol % F2

-9

-8

-7

-6

Log

( in

S.c

m-1

), 25

ºCs

Oxynitride glasses 4 mol % N2

Non-nitrided glasses

Mascaraque et al. Solid State Ionics 254 (2014) 40

N2


Log s LiPON = -7.8Log s LiPOSN = -6.6

Æ=10 mm

Ar in out

Silica tube

Silica cap

Vitreous carboncrucible

Sample

Silicon rubber

1 mol Li1.22PO2.66N0.3 + 0.2 mol Li2S

Melted @ 650ºC for 30 min in Ar flowusing vitreous carbon crucible

Mascaraque et al. J. Non-Cryst. Solids405 (2014) 159


Nd-doped luminiscent oxynitride glasses

Optical properties ofnitridedglasses

15Na2O-15K2O-20BaO-50P2O5+0.5wt.%Nd2O3

0.0 0.1 0.2 0.3

N/P ratio

300

305

310

315

320

325

330

T g (º

C)

Na0.3K0.3Ba0.2PO3-3x/2Nx


0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2Time (ms)

-7.0-6.0-5.0-4.0-3.0-2.0-1.00.01.02.0

Inte

nsity

(arb

. uni

ts)

4F3/2 lexc= 800 nm

P13P13N1P13N2P13N3P13N4P13N5

Transition: 4F3/2→4I11/2

1010 1030 1050 1070 1090 1110 1130 1150Wavelength (nm)

0.00

0.03

0.06In

tens

ity (a

rb. u

nits

)

P13

P13N2P13N3P13N4P13N5

P13N14F3/2®4I11/2

0.0 0.1 0.2 0.3

N/P ratio

75

100

125

150

175

200

225

250

275

300

(ms)

t


15002000250030003500400045005000

wave number (cm-1)

0

25

50

75

100

Tran

smitt

ance

(%)

N/P=0.13 after ammonolysis

N/P=0.13 + N2 at 800ºC, 3 hN/P=0.13 + N2 at 750ºC, 3 h

150020002500300035004000450050005500

wave number (cm-1)

0

25

50

75

100

Tran

smitt

ance

(%)

N/P=0

N/P=0.14N/P=0.13

N/P=0.27N/P=0.17 N-H and O-H bonds may contribute to

The non-radiative decay of the Nd3+Fluorescence and make decrease theAverage lifetime

Thermal annealing at temperaturesAbove the ammonolysis T can reduceThe water content in the glasses andImprove their optical quality

• Nitrogen increases the glass-forming range

• Improves thermal and chemical stability

• Modifies diffusion depending properties

• Allows application of phosphates below Tg

Conclusions

Thank you for your attention

Francisco MuñozCeramics and Glass Institute (CSIC), Madrid (Spain)

[email protected]

1988. Richard Brow & Mary Reidmeyer: NaPON, LiPONN substitution without preference for BO and NBO oxygens

2000. André Le Sauze & Roger Marchand: LiNaPONRandom distribution of N, growing of oxynitride regionsat the expense of the oxide regions

Nt = 3/2 BO, Nd = NBO + 1/2BO

2003. F. Muñoz, L. Pascual, A. Durán, L. Montagne & Roger MarchandMechanism of nitridation based on the preference for the oxygensnear Pb2+ in LiNaPbPON

2006. F. Muñoz, L. Pascual, A., R. Berjoan & Roger Marchand: LiNaPbPONXPS O1s results on the N for O substitution following Marchand’s rules

2013. F. Muñoz, L. Montagne, L. Delevoye, T. CharpentierDistinction between BO and NBO in P(O,N)4 tetrahedra[J. Non-Cryst. Solids 363 (2013) 134]

PO3N PO2N2PO3N

0.0 0.1 0.2 0.3

N/P ratio

-9.0

-8.5

-8.0

-7.5

-7.0

log

(

in S

cm

-1),

25ºC

s LiPO3-3x/2Nx

Li1.22PO3.11-3x/2Nx

Li1.35PO3.18-3x/2Nx

s

Increaseofnon-bridgingoxygensÞ s

strengthofLi-O

Þ counteracts s

F. Muñoz et al., Solid State Ionics 179 (2008) 574

Oxynitride phosphate glasses: conductivity in LiPON glasses

PCl5 + 4H2O* ® H3PO*4 + 5HCl

H3PO*4 + Na2CO3 ® NaH2PO*4 + CO2 + H2O ® NaPO*3

Phosphate glasses in biodegradable composite materials• Congruent dissolution in aqueous media• Control of the dissolution rate• Glass formulation with bio-compatible elements

ApplicationsReinforcement with polymers and calcium phosphate cementsPhosphate glass fibersDrugs release; Antibacterial effect, antimicrobial (Ga, Cu, Ag)Fluorine release for reparation in odontology

Knowles J.C. et al., J. Mater. Chem. 13 (2003) 2395Valappil S.P. et al., Adv. Func. Mater. 18 (2008) 732

Abou Neel E.A. et al., J. Mater. Chem. 19 (2009) 690Lin S.T. et al., Biomaterials 15(13) (1994) 1057

Increase of chemical durability ® + Fe, Al

Biocompatible/resorbable materials

TV solder glasses: BaO-PbO-ZnO-B2O3-SiO2PbO must be substituted : Low softening T and high CTE

source: SCHOTT technical handbook

Low temperature sealing glasses

1. Sealing temperature T < Tm melting temperature2. Viscosity: Log h = 3 – 53. Adjust coefficient of thermal expansion

Da = am - ag = 0.5 – 1.10-6 K-15. Minimize residual tensions5. High chemical durability at the same time6. Low thermal expansion7. High electrical resistance

nitrided (oxynitride) glasses...nitrided (oxynitride) glasses spring school gdr verres, cargèse...

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