METTLER TOLEDO TItrators

Analysis of High Temperature

Superconductivity Materials
Application brochure 30
Editorial

Dear Reader,

The High Temperature Superconductors are interesting materials. Not too long ago their characteristics
have been theory and wishful thinking only.

The chemical analysis of these HTSC materials is as well interesting and a nice showpiece of the modern
titrimetric analysis.

All the methods presented have been developed in the early 90’s by Rolf Kucharkowski and Ilona Vogel
and applied to their daily research work at the Chemical Analysis Department of the IFW. They used 2
METTLER TOLEDO DL70 at those times to run all the samples and produce the results.

We have recently re-edited the methods using the actual version of the titrator DL70ES.

We thank Rolf and Ilona very much and are glad to share their experience with you, dear reader.

We wish you interesting titrations and good results.

Georg Reutemann Christian Walter

Region Market Manager Technical Support Specialist

Page 2/28 METTLER TOLEDO Analysis of High Temperature Superconductivity Materials

Introduction
The term superconductivity stands for the (almost complete) disappearance of the Ohm resistance of
materials and, thus, the (almost) loss-free transport of electric current. This effect of superconductivity
appears in some metals and intermetallic compounds at very low temperature. It appears suddenly at a
certain temperature which is a characteristic of the compound. The jump to superconductivity usually
occurs at temperatures below 25K (approx. -248°C) which is the range of liquid helium or hydrogen.

At the end of the 1980’s, oxidic ceramic materials have been found, which superconduct at tempera-
tures as high as 70 to 100K. This temperature range is within the liquid nitrogen. The new superconduc-
tors, called “High Temperature Superconductors HTSC”, have been thoroughly investigated and some
are in technical use already since then. The invention of the HTSC materials was awarded the Nobel
Prize later on.

Superconductivity at higher temperature is a prerequisite for its safe and efficient technical use in the
transport of strong electric currents, in the generation of strong magnetic fields or in microelectronics.

HTSC Materials
The ceramic HTSC compounds have a crystalline structure built of layers. The existence of CuO2 layers in
the lattice and the defined occurence of oxygen blank positions in the lattice are decisive for the super-
conductive properties.

Few of the most thoroughly investigated ceramic HTSC are of the following type:

- the Y-Ba-Cu-O type, e.g. Y1Ba2Cu3O7-x (0.05 < X < 0.5)

This is the classic compound, also called “1-2-3 Phase”

- the Bi-(Pb)-Sr-Ca-Cu-O type, e.g. Bi2Sr2CaCu2O8

The systematic research of superconductors needs to rely on the real and actual stoichiometric ratios of
the elements, e.g.: Y : Ba : Cu = 1.00 : 2.00 : 3.00 of the “1-2-3 Phase”. The evaluation of the stoichio-
metric ratio of the HTSC materials, to be used for research or for application, requires analytical methods
of suitable reliability.

The reliable and reproducible preparation and production of the starting powder materials, compact
sample, bands, wires, layers ect. asks for the exact characterisation, mainly the actual stoichiometric
ratio, of the starting compounds (e.g. Y2O2, BaCO3, CuO).

The Analysis of HTSC Materials

The usual and, thus, mostly applied spectroscopic methods of analysis (e.g. atomic emission or absorp-
tion spectroscopy, x-ray fluorescence analysis) cannot meet the requirements regarding accuracy and
precision. Chemical methods of analysis however do, of which titration is the most flexible and versatile

Analysis of High Temperature Superconductivity Materials METTLER TOLEDO Page 3/28

technique and can easily be performed in a fully automated manner.

Besides the elemental composition, the valencies (valency, oxidation, state) are highly important for the
characteristics of superconductors. The variable occupancy of the oxigen position of the crystalline lat-
tice causes variable valencies of the Cu ions in the lattice (ratio Cu2+ : Cu3+). Furthermore, the valency of
Bi of the Bi-Sr-Ca-Cu-O type HTSC may also vary. Also here, titration provides suitable methods for the
determination of the valency.

As a summary, titration is the unsurpassed technique of analysis of HTSC materials, because both sto-
ichiometric ratio and valency can be determined in high precision.

The Advantages of Titration

Basics of the precision and accuracy of titrimetric analyses are the stoichiometric course of reactions and
the calibration via exact primary standards. These standards are nowadays certified standard reference
materials (CSRM).

The titrators of the DL70 family of METTLER TOLEDO offer adequate conditions for the precise and accu-
rate content determinations and valency analysis of high temperature superconductors.

- exact dosing of titrant

- accurate and flexible titration control to follow the equilibrium of the reaction at the equivalence
point
- data storage and various data evaluations as equivalence point procedures, statistics
- easy access to method development and method storage as well as simple routine work
- open to various indication principles as potentiometric, photometric or voltametric
- control of several burette units within 1 method

The Methods
This Application Brochure is based on a collection of methods used at the IFW Dresden [1] for the
analysis of HTSC materials with a METTLER TOLEDO Titrator DL70. The methods can be transferred to all
titrators of the DL7x and DL5x families taking into account the various possibilities of automation and
use of the titrator in questions. The user has her/his full choice!

Most of the determinations are complexometric titrations with photometric indication.

Schematic reviews explain the sample preparation and the course of the analysis for the content determi-
nation of the Y-Ba-Cu-O and the Bi-Pb-Sr-Ca-Cu-O high temperature superconductor materials.

[1] Institut fuer Festkoerper - und Werkstoffforschung, POB, 01171 Dresden, Germany
Dr. R. Kucharkowski, Dr. I. Vogel

Page 4/28 METTLER TOLEDO Analysis of High Temperature Superconductivity Materials

 Schematic of the Chemical Analysis of HTSC Materials of the Y-Ba-Cu-O Type

Yttrium Copper Barium

* sample size approx. 70 mg * sample size approx. 80 mg

* dissolve in diluted nitric acid * dissolve in 0.12 M HCl
* fill to volume, aliquot * buffer to pH 5-6 with ammonium acetate
Aliquot * precipitation of Ba with 0.05 M K2Cr2O7

* mask Cu with NH2CSNH2 * mask Y with NaF * back titration of Cr2O72- with Fe2+

Analysis of High Temperature Superconductivity Materials

* buffer to pH 5-6 with ammonium acetate * titration with 0.05 M FAS
* titration with 0.01 M EDTA, photometric indication * potentiometric indication (redox)
* colour indicator : xylenol orange

chemical reaction

precipitation reaction
Y3+ + H2Y2- ----> YY- + 2H+ Cu2+ + H2Y2- ---->CuY2- + 2H+ 2Ba2+ + Cr2O72- + H2O ---->2BaCrO4 + 2H+
titration reaction
Cr2O72- + 6Fe2+ + 14H+ ----> 2Cr3+ + 6Fe3+ + 7H2O

precision (f = 20)

METTLER TOLEDO
s = 0.10% s = 0.15% s = 0.25%

Page 5/28
METTLER TOLEDO DL70 Customer Methods
M245 Determination of Yttrium in High Temperature Superconductors

Sample: solid material with 12-14% Y Standard: Y standard solution (eg. Merck)
eg. Y-Ba-Cu-O
Reagents: - buffer solution: 20% ammonium
Substance: Yttrium, Y acetate
M = 88.91 g/mol - thiourea p.a.
- Xylenol orange
Preparation: - dissolve approx. 70 mg sample in
diluted HNO3 Instruments: - Mettler-Toledo DL70ES
- fill to 100 mL in volumetric flask - Printer
- take aliquot (20 mL)
Accessories: beaker ME-101974
- buffer to pH 5.5 with NH4Ac
- mask Cu Indication: DP550 on Sensor 2 with DIN-
LEMO adapter ME-89600
Titrant: EDTA, c = 0.01 M

Results:
Yttm Yttrium photometric Date: 24-May-2001 9:57 am
24-May-2001 9:42 am Titrator: Engelchen II
SW Version 2.0 User: Vogel

Results

No. ID Sample Size Results

1/1 Y/HTSL 9/2 0.07056 g 2.268 mL consumption

14.287 % Y-content
1/2 Y/HTSL 9/3 0.07068 g 2.265 mL consumption
14.248 % Y-content
1/3 Y/HTSL 9/4 0.07049 g 2.250 mL consumption
14.189 % Y-content

Statistics
Number results R2 n = 3
Mean value X = 14.242 % Y-content
Standard diviation s = 0.0495 % Y-content
Rel. standard diviation srel = 0.348 %

Remarks:
In case of Y-Ba-Cu-O HTSC materials, Y and Cu are titrated in the sum unless Cu is masked by complex-
ation with thiourea.

Page 6/28 METTLER TOLEDO Analysis of High Temperature Superconductivity Materials

Method Calculation
Result name . . . . . . . . . Y-content
Method Ytfm Yttrium photometric Formula . . . . . . . . . . . R2=VEQ*c*C2/m
version 24-May-2001 9:42 am Constant . . . . . . . . . . . C2=5*M/(10*z)
Result unit . . . . . . . . . %
Title Decimal places . . . . . . . . 3
Method ID . . . . . . . . Ytfm Statistics
Title . . . . . . . . . . Yttrium photometric Ri (i=index) . . . . . . . . . R2
Date/time . . . . . . . . May/24/2001 9:42 am Standard deviation s . . . . . Yes
Sample Rel. standard deviation srel . Yes
Number samples . . . . . . 10 Record
Titration stand . . . . . Stand 1 Output unit . . . . . . . . . Printer+Computer
Entry type . . . . . . . . Weight m All results . . . . . . . . . Yes
Lower limit [g] . . . . 0.0
Upper limit [g] . . . . 2.0
ID1 . . . . . . . . . . . Y/HTSL
Molar mass M . . . . . . . 88.9059
Equivalent number z . . . 1 Titration Curve
Temperature sensor . . . . Manual
Measure
Sensor . . . . . . . . . . DP550
Unit of meas. . . . . . . mV
dE [mV] . . . . . . . . . 0.5
dt [s] . . . . . . . . . . 1.0
t(min) mode . . . . . . . Fix
t(min) [s] . . . . . . 3.0
t(max) [s] . . . . . . . . 30.0
Stir
Speed [%] . . . . . . . . 50
Time [s] . . . . . . . . . 10
Titration
Titrant . . . . . . . . . EDTA
Concentration [mol/L] . . 0.01
Sensor . . . . . . . . . . DP550
Unit of meas. . . . . . . mV
Titration mode . . . . . . EQP
Predispensing 1 . . . . mL
Volume [mL] . . . . 1.5
Titrant addition . . . DYN
dE(set) [mV] . . . . 4.0
Limits dV . . . . . Absolute
dV(min) [mL] . . 0.01
dV(max) [mL] . . 0.1
Measure mode . . . . . EQU
dE [mV] . . . . . . 0.2
dt [s] . . . . . . . 2.0
t(min) [s] . . . . . 4.0
t(max) [s] . . . . . 15.0
Threshold . . . . . . . 150.0
Maximum volume [mL] . . 3.0
Evaluation procedure . Standard
Steepest jump only . . Yes
Calculation
Result name . . . . . . . Consumption
Formula . . . . . . . . . R=VEQ
Constant . . . . . . . . . C=1
Result unit . . . . . . . mL
Decimal places . . . . . . 3

Analysis of High Temperature Superconductivity Materials METTLER TOLEDO Page 7/28

METTLER TOLEDO DL70 Customer Methods
M246 Determination of Barium in High Temperature Superconductors

Sample: solid material with approx. 40% Ba
eg. Y-Ba-Cu-O
Substance: Barium, Ba
M = 137.33 g/mol
Preparation: - dissolve approx. 100 mg in
0.12 M HCl
- buffer to pH 5.5
- precipitate Ba with K2Cr2O7
- fill to 100 mL in volumetric flask
- filtrate and take aliquot (20 mL)
Titrant: (NH4)2Fe(SO4)2, c = 0.05 M (FAS)
Standard: Ba standard solution, (e.g. Merck)
Reagents: - K2Cr2O7 solution, c = 0.05 M
- buffer solution:
20% ammonium acetate
- acid mixture: H3PO4 : H2SO4 (1:1)
Instruments: - Mettler-Toledo DL70ES
- Printer
Accessories: beaker ME-101974
Indication: DM140 on Sensor 2

Results:
BaPO Ba in YBaCu potentiometric Date: 24-May-2001 1:03 pm
24-May-2001 9:41 am Titrator: Engelchen II
SW Version 2.0 User: !!!!

Results

No. ID Sample Size Results

1/1 Sample 4 0.09345 g 5.599 mL Fe consumption

176.323 mg ZWE
40.357 % Ba-content
1/2 Sample 5 0.09091 g 5.898 mL Fe consumption
176.245 mg ZWE
40.340 % Ba-content
1/3 Sample 6 0.08566 g 6.562 mL Fe consumption
175.243 mg ZWE
40.110 % Ba-content

Statistics
Number results R3 n = 3
Mean value X = 40.269 % Ba-content
Standard diviation s = 0.1379 % Ba-content
Rel. standard diviation srel = 0.342 %

Remarks:
Let the sample stand several hours after precipitation, transfer to volumetric flask and fill to volume.
Principle: Ba is precipitated by a known excess amount of Cr2O72-:
2Ba2+ + Cr2O72- + H2O ----> 2BaCrO4 + 2H+
Then the excess of Cr2O72- is titrated back with Fe2+ as iron(II)-ammonium sulphate (FAS).
Page 8/28 METTLER TOLEDO Analysis of High Temperature Superconductivity Materials
 Calculation
Method Result name . . . . . . . . .
Formula . . . . . . . . . . . R1=VEQ
Method BaPO Ba in YBaCu potentiometric Constant . . . . . . . . . . . C=1
Version 24-May-2001 9:41 am Result unit . . . . . . . . . mL
Decimal places . . . . . . . . 3
Title Calculation
Method ID . . . . . . . . BaPO Result name . . . . . . . . . ZWE
Title . . . . . . . . . . Ba in YBaCu potentiometr. Formula . . . . . . . . . . . R2=(C2-VEQ*H1*H6)/m
Date/time . . . . . . . . May/24/2001 9:41 am Constant . . . . . . . . . . . C2=H2*H3
Instruction Result unit . . . . . . . . . mg
check values of H1 and H2 Decimal places . . . . . . . . 3
Sample Calculation
Number samples . . . . . . 2 Result name . . . . . . . . . Ba-Gehat
Titration stand . . . . . Stand 1 Formula . . . . . . . . . . . R3=C3*R2
Entry type . . . . . . . . Weight m Constant . . . . . . . . . . . C3=(2*M*c)/(z*10)
Lower limit [g] . . . . 0.05 Result unit . . . . . . . . . %
Upper limit [g] . . . . 0.1 Decimal places . . . . . . . . 3
ID1 . . . . . . . . . . . Sample Statistics
Molar mass M . . . . . . . 137.33 Ri (i=index) . . . . . . . . . R1
Equivalent number z . . . 6 Standard deviation s . . . . . Yes
Temperature sensor . . . . Manual Rel. standard deviation srel . Yes
Dispense Statistics
Titrant . . . . . . . . . acidmix Ri (i=index) . . . . . . . . . R3
Concentration [mol/L] . . 1.0 Standard deviation s . . . . . Yes
Volume [mL] . . . . . . . 6 Rel. standard deviation srel . Yes
Stir Record
Speed [%] . . . . . . . . 50 Output unit . . . . . . . . . Printer+Computer
Time [s] . . . . . . . . . 10 All results . . . . . . . . . Yes
Measure
Sensor . . . . . . . . . . DM140-SC
Unit of meas. . . . . . . mV
dE [mV] . . . . . . . . . 1.0
dt [s] . . . . . . . . . . 2.0
Auxiliary Values:
t(min) mode . . . . . . . Fix
t(min) [s] . . . . . . 3.0 H1 = Aliquot factor of sample
t(max) [s] . . . . . . . . 30.0
Titration H2 = Volume of K2Cr2O7
Titrant . . . . . . . . . (NH4)2Fe(SO4)2
Concentration [mol/L] . . 0.05
H3 = Titer of K2Cr2O7
Sensor . . . . . . . . . . DM140-SC H6 = Titer of FAS
Unit of meas. . . . . . . mV
Titration mode . . . . . . EQP
Predispensing 1 . . . . mL
Volume [mL] . . . . 1.0 Titration Curve:
Titrant addition . . . DYN
dE(set) [mV] . . . . 3.0
Limits dV . . . . . Absolute
dV(min) [mL] . . 0.01
dV(max) [mL] . . 0.05
Measure mode . . . . . EQU
dE [mV] . . . . . . 0.5
dt [s] . . . . . . . 1.0
t(min) [s] . . . . . 2.0
t(max) [s] . . . . . 20.0
Threshold . . . . . . . 50.0
Maximum volume [mL] . . 17.0
Termination at potential . Yes
Potential . . . . . . . 460
Evaluation procedure . . . Standard
Steepest jump only . . . . Yes

Analysis of High Temperature Superconductivity Materials METTLER TOLEDO Page 9/28

METTLER TOLEDO DL70 Customer Methods
M247 Determination of Copper in High Temperature Superconductors

Sample: solid material with 26-30% Cu Standard: Cu standard solution, (e.g. Merck)
e.g. Y-Ba-Cu-O
Reagents: - buffer solution:
Substance: Copper, Cu 20% ammonium acetate
M = 63.546 g/mol - sodium fluoride p.a.
- xylenol orange
Preparation: - dissolve approx. 70 mg in con-
centrated HNO3 Instruments: - Mettler-Toledo DL70ES
- fill to volume in 100 mL volumet- - Printer
ric flask
Accessories: beaker ME-101974
- take aliquot
- buffer to pH 5.5 Indication: - DP 550 on Sensor 2 with
- mask Y DIN-LEMO adapter ME-89600

Titrant: EDTA c = 0.01 M

Results:
CuMn Copper photom. after mask Date: 23-May-2001 5:20 pm
23-May-2001 3:13 pm Titrator: Engelchen I
SW Version 2.0 User: Vogel

Results

No. ID Sample Size Results

1/1 Cu 9/2 0.07056 g 4.694 mL consumption

28.182 % Cu-content
1/2 Cu 9/3 0.07068 g 4.715 mL consumption
28.260 % Cu-content
1/3 Cu 9/4 0.07049 g 4.706 mL consumption
28.281 % Cu-content

Statistics
Number results R2 n = 3
Mean value X = 28.241 % Cu-content
Standard diviation s = 0.0524 % Cu-content
Rel. standard diviation srel = 0.186 %

Remarks:
In case of Y-Ba-Cu-O HTSC, Y and Cu are titrated in the sum unless Y is masked by fluoride. Y forms
fluoride complexes and can, thus, no longer be titrated by EDTA.

Page 10/28 METTLER TOLEDO Analysis of High Temperature Superconductivity Materials

Method Calculation
Result name . . . . . . . . . Consumption
Formula . . . . . . . . . . . R=VEQ+VDISP
Method CuMa Copper photom. after mask
Constant . . . . . . . . . . . C=1
version 23-May-2001 3:13 pm
Result unit . . . . . . . . . mL
Decimal places . . . . . . . . 3
Title
Calculation
Method ID . . . . . . . . CuMa
Result name . . . . . . . . . Cu-content
Title . . . . . . . . . .
Formula . . . . . . . . . . . R2=(Q+QDISP)*C2/(15*m)
Date/time . . . . . . . . May/23/2001 3:13 pm
Constant . . . . . . . . . . . C2=M*10
Sample
Result unit . . . . . . . . . %
Number samples . . . . . . 2
Decimal places . . . . . . . . 3
Titration stand . . . . . Stand 1
Statistics
Entry type . . . . . . . . Weight m
Ri (i=index) . . . . . . . . . R2
Lower limit [g] . . . . 0.0
Standard deviation s . . . . . Yes
Upper limit [g] . . . . 2.0
Rel. standard deviation srel . Yes
ID1 . . . . . . . . . . . Cu
Record
Molar mass M . . . . . . . 63.546
Output unit . . . . . . . . . Printer+Computer
Equivalent number z . . . 1
All results . . . . . . . . . Yes
Temperature sensor . . . . Manual
Measure
Sensor . . . . . . . . . . DP550
Unit of meas. . . . . . . mV
dE [mV] . . . . . . . . . 0.5 Titration Curve
dt [s] . . . . . . . . . . 1.0
t(min) mode . . . . . . . Fix
t(min) [s] . . . . . . 3.0
t(max) [s] . . . . . . . . 30.0
Stir
Speed [%] . . . . . . . . 50
Time [s] . . . . . . . . . 10
Dispense
Titrant . . . . . . . . . EDTA
Concentration [mol/L] . . 0.01
Volume [mL] . . . . . . . 2
Stir
Speed [%] . . . . . . . . 50
Time [s] . . . . . . . . . 180
Titration
Titrant . . . . . . . . . EDTA
Concentration [mol/L] . . 0.01
Sensor . . . . . . . . . . DP550
Unit of meas. . . . . . . mV
Titration mode . . . . . . EQP
Predispensing 1 . . . . mL
Volume [mL] . . . . 0.2
Titrant addition . . . DYN
dE(set) [mV] . . . . 4.0
Limits dV . . . . . Absolute
dV(min) [mL] . . 0.01
dV(max) [mL] . . 0.1
Measure mode . . . . . EQU
dE [mV] . . . . . . 0.2
dt [s] . . . . . . . 2.0
t(min) [s] . . . . . 4.0
t(max) [s] . . . . . 15.0
Threshold . . . . . . . 100.0
Maximum volume [mL] . . 10.0
Evaluation procedure . Standard
Steepest jump only . . Yes

Analysis of High Temperature Superconductivity Materials METTLER TOLEDO Page 11/28

 Schematic of the Chemical Analysis of HTSC Materials of the Bi-Pb-Cu-Ca-Sr-O Type

Page 12/28
sample size 200 mg
dissolution

electrolytic separation

METTLER TOLEDO
Bi-Pb-Cu Ca-Sr

precipitate on electrodes dissolved in electrolyte

extraction precedure
anode cathode
Pb and x Bi as mixture of oxides Cu and (1-x) Bi as metals in alcoholic mixture

dissolve precipitate from anode dissolve precipitate from cathode as soluble nitrate as insoluble nitrate
titration of Bi and Pb titration of Bi and Cu - evaporate alcohol - evaporate alcohol

titration of Ca titration of Sr

All titrations are complexometric. pH depends on metal ion. Indication is photometric or voltametric.

Precision (real samples, f = 5)

Analysis of High Temperature Superconductivity Materials

Bi: s = 0.4% Pb: s = 0.3% Cu: s = 0.15% Ca: s = 0.25% Sr: s = 0.5%
METTLER TOLEDO DL70 Customer Methods
M248 Simultaneous Determination of Bismuth and Lead
in High Temperature Superconductors

Sample: solid material with approx. 40% Bi, Titrant: EDTA c = 0.01 M
<10% Pb, e.g. Bi-Pb-Cu-Ca-Sr-O
Standard: Bi standard solution, (e.g. Merck)
Substance: xBi and Pb Pb standard solution, (e.g. Merck)
M = 208.98 g/mol
Reagents: - xylenol orange 0.5%
M = 207.20 g/mol
- hexamethylene tetramine p.a.
Preparation: - dissolve 200 mg sample in 3 mL
Instruments: - Mettler-Toledo DL70ES
HNO3 conc.
- Printer
- electrolytic separation of Bi, Pb and
Cu Accessories: beaker ME-101974
- dissolve anodic precipitate with
Indication: - DP 550 on Sensor 2 with DIN-
HNO3/H2O2
LEMO adapter ME-89600
- take aliquot
- adjust to pH 1.0

Remarks:

• Pb and a part of Bi form the anodic precipitate of the electrolysis The precipitate is dissolved
and aliquoted.

• During the 1st titration Bi only is complexed and thus determined.

• EDTA can complex Pb only after the pH value is increased to pH 5.5 by hexamethylene
tetramine (2nd titration).

• The 1st titration is terminated at the maximum volume which is adjusted corresponding to
the ratio Bi : Pb.

• The content of Pb corresponds to the excess of the 1st titration VEX [1] plus the equivalence
volume of the 2nd titration VEQ [2].

Analysis of High Temperature Superconductivity Materials METTLER TOLEDO Page 13/28

Results:

METTLER DL70 Titrator IFS im IFW Dresden e.V.

Abt.Chem.Analytik

BiPb Bismut/Lead simultan Date: 24-May-2001 9:27 am

24-May-2001 9:55 am Titrator: Engelchen II
SW Version 2.0 User: ****

Results

No. ID Sample Size Results

1/1 HTSL 0.20124 g 6.212 mL cons. EDTA Bi

12.982 mg Bi of aliquot
0.788 mL excess
1.957 mL cons. EDTA Pb
4.055 mg Pb of aliquot
1.169 mL cons. of EQP2
1/2 HTSL 0.20124 g 6.223 mL cons. EDTA Bi
13.005 mg Bi of aliquot
0.777 mL excess
1.933 mL cons. EDTA Pb
4.006 mg Pb of aliquot
1.157 mL cons. of EQP2
1/3 HTSL 0.20124 g 6.236 mL cons. EDTA Bi
13.032 mg Bi of aliquot
0.764 mL excess
1.936 mL cons. EDTA Pb
4.011 mg Pb of aliquot
1.171 mL cons. of EQP2

Statistics
Number results R2 n = 3
Mean value X = 13.006 mgBi of aliquot
Standard diviation s = 0.0246 mgBi of aliquot
Rel. standard diviation srel = 0.189 %

Statistics
Number results R5 n = 3
Mean value X = 4.024 mg Pb of aliquot
Standard diviation s = 0.0269 mgPb of aliquot
Rel. standard diviation srel = 0.669 %

Page 14/28 METTLER TOLEDO Analysis of High Temperature Superconductivity Materials

Method
Method BiPb Bismut/Lead simultan
Version 24-May-2001 9:55 am
Title
Method ID . . . . . . . . . BiPb
Title . . . . . . . . . . . Bismut/Lead Simultan
Date/time . . . . . . . . . May/24/2001 9:55 am
Sample
Number samples . . . . . . . 3
Titration stand . . . . . . Stand 1
Entry type . . . . . . . . . Weight m
Lower limit [g] . . . . . 0.0
Upper limit [g] . . . . . 0.5
ID1 . . . . . . . . . . . . HTSL
Molar mass M . . . . . . . . 208.98
Equivalent number z . . . . 1
Temperature sensor . . . . . Manual
Stir
Speed [%] . . . . . . . . . 50
Time [s] . . . . . . . . . . 10
Measure
Sensor . . . . . . . . . . . DP550
Unit of meas. . . . . . . . mV
dE [mV] . . . . . . . . . . 0.5
dt [s] . . . . . . . . . . . 1.0
t(min) mode . . . . . . . . Fix
t(min) [s] . . . . . . . 3.0
t(max) [s] . . . . . . . . . 30.0
Titration
Titrant . . . . . . . . . . EDTA
Concentration [mol/L] . . . 0.01
Sensor . . . . . . . . . . . DP550
Unit of meas. . . . . . . . mV
Titration mode . . . . . . . EQP
Predispensing 1 . . . . . mL
Volume [mL] . . . . . 2.5
Titrant addition . . . . DYN
dE(set) [mV] . . . . . 10.0
Limits dV . . . . . . Absolute
dV(min) [mL] . . . 0.01
dV(max) [mL] . . . 0.1
Measure mode . . . . . . EQU
dE [mV] . . . . . . . 1.0
dt [s] . . . . . . . . 2.0
t(min) [s] . . . . . . 2.0
t(max) [s] . . . . . . 10.0
Threshold . . . . . . . . 500.0
Maximum volume [mL] . . . 7.0
Evaluation procedure . . Standard
Steepest jump only . . . Yes
Calculation
Result name . . . . . . . . cons. EDTA Bi
Formula . . . . . . . . . . R1=VEQ
Constant . . . . . . . . . . C=1
Result unit . . . . . . . . mL
Decimal places . . . . . . . 3
Calculation
Result name . . . . . . . . Bi of aliquot
Formula . . . . . . . . . . R2=VEQ*c*M
Constant . . . . . . . . . . C2=1
Result unit . . . . . . . . mg
Decimal places . . . . . . . 3
Calculation
Result name . . . . . . . . excess
Formula . . . . . . . . . . R3=VEX[1]
Constant . . . . . . . . . . C3=1
Analysis of High Temperature Superconductivity Materials
Result unit . . . . . . . . . mL
Decimal places . . . . . . . . 3
Instruction
Add hexamethylene tetramin until color
changes to red!
Stir
Speed [%] . . . . . . . . . . 50
Time [s] . . . . . . . . . . . 30
Measure
Sensor . . . . . . . . . . . . DP550
Unit of meas. . . . . . . . . mV
dE [mV] . . . . . . . . . . . 0.5
dt [s] . . . . . . . . . . . . 1.0
t(min) mode . . . . . . . . . Fix
t(min) [s] . . . . . . . . 3.0
t(max) [s] . . . . . . . . . . 30.0
Titration
Titrant . . . . . . . . . . . EDTA
Concentration [mol/L] . . . . 0.01
Sensor . . . . . . . . . . . . DP550
Unit of meas. . . . . . . . . mV
Titration mode . . . . . . . . EQP
Predispensing 1 . . . . . . mL
Volume [mL] . . . . . . 0.2
Titrant addition . . . . . DYN
dE(set) [mV] . . . . . . 10.0
Limits dV . . . . . . . Absolute
dV(min) [mL] . . . . 0.01
dV(max) [mL] . . . . 0.1
Measure mode . . . . . . . EQU
dE [mV] . . . . . . . . 1.0
dt [s] . . . . . . . . . 2.0
t(min) [s] . . . . . . . 2.0
t(max) [s] . . . . . . . 10.0
Threshold . . . . . . . . . 500.0
Maximum volume [mL] . . . . 8.0
Evaluation procedure . . . Standard
Steepest jump only . . . . Yes
Calculation
Result name . . . . . . . . . cons. EDTA Pb
Formula . . . . . . . . . . . R4=VEQ[2]+VEX[1]
Constant . . . . . . . . . . . C4=1
Result unit . . . . . . . . . mL
Decimal places . . . . . . . . 3
Calculation
Result name . . . . . . . . . Pb in aliquot
Formula . . . . . . . . . . . R5=R4*C5*c
Constant . . . . . . . . . . . C5=207.2
Result unit . . . . . . . . . mg
Decimal places . . . . . . . . 3
Calculation
Result name . . . . . . . . . cons. of EQP2
Formula . . . . . . . . . . . R6=VEQ[2]
Constant . . . . . . . . . . . C6=1
Result unit . . . . . . . . . mL
Decimal places . . . . . . . . 3
Statistics
Ri (i=index) . . . . . . . . . R2
Standard deviation s . . . . . Yes
Rel. standard deviation srel . Yes
Statistics
Ri (i=index) . . . . . . . . . R5
Standard deviation s . . . . . Yes
Rel. standard deviation srel . Yes
Record
Output unit . . . . . . . . . Printer
All results . . . . . . . . . Yes
METTLER TOLEDO Page 15/28
Titration Curve (Bi)

Titration Curve (Pb)

Page 16/28 METTLER TOLEDO Analysis of High Temperature Superconductivity Materials

METTLER TOLEDO DL70 Customer Methods
M249 Simultaneous Determination of (1-x) Bismuth and Copper
in High Temperature Superconductors

Sample: solid material with approx. 40% Bi, Titrant: EDTA c = 0.01 M
18% Cu, e.g. Bi-Pb-Cu-Ca-Sr-O
Standard: Bi standard solution, (e.g. Merck)
Substance: (1-x)Bi and Cu Cu standard solution, (e.g. Merck)
M = 208.98 g/mol
Reagents: - xylenol orange 0.5%
M = 63.546 g/mol
- hexamethylene tetramine p.a.
Preparation: - dissolve 200 mg sample in 3 mL
Instruments: - Mettler-Toledo DL70ES
HNO3 conc.
- Printer
- electrolytic separation of Bi, Pb and
Cu Accessories: beaker ME-101974
- dissolve cathodic precipitate with
Indication: - DP 550 on Sensor 2 wih DIN-
HNO3
LEMO adapter ME-89600
- take aliquot
- adjust to pH 1.0

Remarks:

• Cu and another part of Bi form the cathodic precipate of the electrolysis. The precipitate is
dissolved and aliquoted.

• During the 1st titration Bi is complexed only and thus determined. EDTA complexes with Cu
only after the pH is increased to pH 5.5 by hexamethylene tetramine (2nd titration).

• The 1st titration is terminated at a maximum volume only which is adjusted corresponding
to the ratio Bi : Cu.

• The content of Cu is equal to the excess of the 1st titration VEX [1] plus the consumption of
the 2nd titration VEQ[2].

• The overall total Bismuth is the sum of x Bi and (1-x) Bi and can be calculated after both
analysis procedures BiPb and BiCu have been performed.

Analysis of High Temperature Superconductivity Materials METTLER TOLEDO Page 17/28

Results:

METTLER DL70 Titrator IFS im IFW Dresden e.V.

Abt.Chem.Analytik

BiCu Bi/Cu simultan fotometr. Date: 24-May-2001 12:00 am

24-May-2001 10.01 am Titrator: Engelchen II
SW Version 2.0 User: ****

Results

No. ID Sample Size Results

1/1 HTSL 0.20124 g 2.371 mL cons. EDTA Bi

4.955 mg Bi of aliquot
3.629 ml excess
11.087 mL cons. EDTA Cu
7.045 mg Cu of aliquot
7.458 mL cons. of EQP2
1/2 HTSL 0.20124 g 2.352 mL cons. EDTA Bi
4.916 mg Bi of aliquot
3.648 ml excess
11.135 mL cons. EDTA Cu
7.076 mg Cu of aliquot
7.488 mL cons. of EQP2
1/3 HTSL 0.20124 g 2.370 mL cons. EDTA Bi
4.953 mg Bi of aliquot
3.630 m1 excess
11.073 mL cons. EDTA Cu
7.037 mg Cu of aliquot
7.443 mL cons. of EQP2

Statistics
Number results R2 n = 3
Mean value X = 4.941 mg Bi of aliquot
Standard diviation s = 0.0218 mg Bi of aliquot
Rel. standard diviation srel = 0.442 %

Statistics
Number results R5 n = 3
Mean value X = 7.053 mg Cu of aliquot
Standard diviation s = 0.0208 mg Cu of aliquot
Rel. standard diviation srel = 0.295 %

Page 18/28 METTLER TOLEDO Analysis of High Temperature Superconductivity Materials

Method
Method BiCu Bi/Cu simult. fotometr.
Version 24-May-2001 10:03 am
Title
Method ID . . . . . . . . . BiCu
Title . . . . . . . . . . . Bi/Cu simult. fotometr.
Date/time . . . . . . . . . May/24/2001 10:01 am
Sample
Number samples . . . . . . . 3
Titration stand . . . . . . Stand 1
Entry type . . . . . . . . . Weight m
Lower limit [g] . . . . . 0.0
Upper limit [g] . . . . . 1.0
ID1 . . . . . . . . . . . . HTSL
Molar mass M . . . . . . . . 208.98
Equivalent number z . . . . 1
Temperature sensor . . . . . Manual
Stir
Speed [%] . . . . . . . . . 50
Time [s] . . . . . . . . . . 10
Measure
Sensor . . . . . . . . . . . DP550
Unit of meas. . . . . . . . mV
dE [mV] . . . . . . . . . . 0.5
dt [s] . . . . . . . . . . . 1.0
t(min) mode . . . . . . . . Fix
t(min) [s] . . . . . . . 3.0
t(max) [s] . . . . . . . . . 30.0
Titration
Titrant . . . . . . . . . . EDTA
Concentration [mol/L] . . . 0.01
Sensor . . . . . . . . . . . DP550
Unit of meas. . . . . . . . mV
Titration mode . . . . . . . EQP
Predispensing 1 . . . . . mL
Volume [mL] . . . . . 0.5
Titrant addition . . . . DYN
dE(set) [mV] . . . . . 10.0
Limits dV . . . . . . Absolute
dV(min) [mL] . . . 0.01
dV(max) [mL] . . . 0.2
Measure mode . . . . . . EQU
dE [mV] . . . . . . . 1.0
dt [s] . . . . . . . . 2.0
t(min) [s] . . . . . . 2.0
t(max) [s] . . . . . . 10.0
Threshold . . . . . . . . 500.0
Maximum volume [mL] . . . 6.0
Evaluation procedure . . Standard
Steepest jump only . . . Yes
Calculation
Result name . . . . . . . . cons. EDTA Bi
Formula . . . . . . . . . . R1=VEQ
Constant . . . . . . . . . . C=1
Result unit . . . . . . . . mL
Decimal places . . . . . . . 3
Calculation
Result name . . . . . . . . Bi of aliquot
Formula . . . . . . . . . . R2=VEQ[1]*c*M
Constant . . . . . . . . . . C2=1
Result unit . . . . . . . . mg
Decimal places . . . . . . . 3
Calculation
Result name . . . . . . . . excess
Formula . . . . . . . . . . R3=VEX[1]
Constant . . . . . . . . . . C3=1
Analysis of High Temperature Superconductivity Materials
Result unit . . . . . . . . . mL
Decimal places . . . . . . . . 3
Instruction
Add Hexmethylene tetramin until color
changes to red.
Stir
Speed [%] . . . . . . . . . . 50
Time [s] . . . . . . . . . . . 30
Measure
Sensor . . . . . . . . . . . . DP550
Unit of meas. . . . . . . . . mV
dE [mV] . . . . . . . . . . . 0.5
dt [s] . . . . . . . . . . . . 1.0
t(min) mode . . . . . . . . . Fix
t(min) [s] . . . . . . . . 3.0
t(max) [s] . . . . . . . . . . 30.0
Titration
Titrant . . . . . . . . . . . EDTA
Concentration [mol/L] . . . . 0.01
Sensor . . . . . . . . . . . . DP550
Unit of meas. . . . . . . . . mV
Titration mode . . . . . . . . EQP
Predispensing 1 . . . . . . mL
Volume [mL] . . . . . . 1
Titrant addition . . . . . DYN
dE(set) [mV] . . . . . . 8.0
Limits dV . . . . . . . Absolute
dV(min) [mL] . . . . 0.01
dV(max) [mL] . . . . 0.2
Measure mode . . . . . . . EQU
dE [mV] . . . . . . . . 1.0
dt [s] . . . . . . . . . 2.0
t(min) [s] . . . . . . . 2.0
t(max) [s] . . . . . . . 10.0
Threshold . . . . . . . . . 100.0
Maximum volume [mL] . . . . 10.0
Evaluation procedure . . . Standard
Steepest jump only . . . . Yes
Calculation
Result name . . . . . . . . . cons. EDTA Cu
Formula . . . . . . . . . . . R4=VEQ[2]+VEX[1]
Constant . . . . . . . . . . . C4=1
Result unit . . . . . . . . . mL
Decimal places . . . . . . . . 3
Calculation
Result name . . . . . . . . . Cu of aliquot
Formula . . . . . . . . . . . R5=R4*C5*c
Constant . . . . . . . . . . . C5=63.546
Result unit . . . . . . . . . mg
Decimal places . . . . . . . . 3
Calculation
Result name . . . . . . . . . cons. of EQP2
Formula . . . . . . . . . . . R6=VEQ[2]
Constant . . . . . . . . . . . C6=1
Result unit . . . . . . . . . mL
Decimal places . . . . . . . . 3
Statistics
Ri (i=index) . . . . . . . . . R2
Standard deviation s . . . . . Yes
Rel. standard deviation srel . Yes
Statistics
Ri (i=index) . . . . . . . . . R5
Standard deviation s . . . . . Yes
Rel. standard deviation srel . Yes
Record
Output unit . . . . . . . . . Printer
All results . . . . . . . . . Yes
METTLER TOLEDO Page 19/28
Titration Curve (1-x) Bi

Titration Curve (Cu)

Page 20/28 METTLER TOLEDO Analysis of High Temperature Superconductivity Materials

METTLER TOLEDO DL70 Customer Methods
M250 Determination of Calcium in High Temperature Superconductors
after Separation from Strontium

Sample: solid material with approx.8% Ca, Titrant: EDTA c = 0.01 M

e.g. Bi-Pb-Cu-Ca-Sr-O
Standard: Ca standard solution, (e.g. Merck)
Substance: Calcium, Ca
Reagents: - Buffer solution NH3/NH4Cl
M = 40.08 g/mol
- 1 mL 10 mM Hg-EDTA / L buffer
Preparation: - dissolve 200 mg sample in 3 mL
Instruments: - Mettler-Toledo DL70ES
HNO3 conc.
- printer
- electrolytic separation of Bi, Pb and
- power supply unit
Cu
- amperometer
- separation of Ca and Sr in the elec-
- variable resistor
trolyte
- take aliquot Accessories: beaker ME-101974
- adjust to pH 10.0 Indication: Ag/AgHgx on Sensor 2

Remarks:

• Cu, Pb and Bi have to be removed first, then Ca and Sr are separated by alcoholic extraction.

• After extraction, the alcohol has to be evaporated completely.

• Complexometric titration of Ca. The indication is voltametric as explained in the figure. The
potential change of 2 electrodes under current is plotted against the titrant consumption.
Electrodes in use are a silver electrode and an amalgamated silver electrode.

Fig.: voltametric indication

Ag AgHgx
Analysis of High Temperature Superconductivity Materials METTLER TOLEDO Page 21/28
Method Calculation
Result name . . . . . . . . . Ca of aliquot
Formula . . . . . . . . . . . R2=Q*M
Method CaVt Calcium voltametric
Constant . . . . . . . . . . . C2=1
Version 23-May-2001 5:05 pm
Result unit . . . . . . . . . mg
Decimal places . . . . . . . . 3
Title
Statistics
Method ID . . . . . . . CaVt
Ri (i=index) . . . . . . . . . R2
Title . . . . . . . . . Calcium voltametric
Standard deviation s . . . . . Yes
Date/time . . . . . . . May/23/2001 5:05 pm
Rel. standard deviation srel . Yes
Sample
Record
Number samples . . . . . 2
Output unit . . . . . . . . . Printer+Computer
Titration stand . . . . Stand 1
All results . . . . . . . . . Yes
Entry type . . . . . . . Weight m
Lower limit [g] . . . 0.0
Upper limit [g] . . . 2.0
ID1 . . . . . . . . . . Ca
Molar mass M . . . . . . 40.08
Results
Equivalent number z . . 1
Temperature sensor . . . Manual CaVt Calcium Voltametric Date: 23-May-2001 5:37 pm
Measure
23-May-2001 5:05 pm Titrator: Engelchen II
Sensor . . . . . . . . . AgHgx
SW version 2.0 User: !!!!
Unit of meas. . . . . . mV
dE [mV] . . . . . . . . 1.0
dt [s] . . . . . . . . . 1.0 Results
t(min) mode . . . . . . Fix
t(min) [s] . . . . . 3.0 No ID sample size results
t(max) [s] . . . . . . . 30.0
Stir 1/1 Ca 0.0 g 5.226 mL consumption
Speed [%] . . . . . . . 50 2.093 mg Ca in aliquot
Time [s] . . . . . . . . 10 1/2 Ca 0.20124 g 5.207 mL consumption
Titration 2.087 mg Ca in aliquot
Titrant . . . . . . . . EDTA
1/3 Ca 0.20124 g 5.197 mL consumption
Concentration [mol/L] . 0.01
2.083 mg Ca in aliquot
Sensor . . . . . . . . . AgHgX
Unit of meas. . . . . . mV
Titration mode . . . . . EQP Statistics
Predispensing 1 . . . mL Number results R2 n = 3
Volume [mL] . . . 4.5
Mean value X = 2.088 mg Ca in aliquot
Titrant addition . . DYN
Standard deviation s = 0.0058 mg Ca in aliquot
dE(set) [mV] . . . 2.0
Limits dV . . . . Absolute Rel. standard deviation srel = 0.277 %
dV(min) [mL] . 0.02
dV(max) [mL] . 0.2
Measure mode . . . . EQU Titration Curve Bi/Pb
dE [mV] . . . . . 7.0
dt [s] . . . . . . 2.0
t(min) [s] . . . . 5.0
t(max) [s] . . . . 20.0
Threshold . . . . . . 100.0
Maximum volume [mL] . 7.0
Evaluation procedure. Standard
Steepest jump only . Yes
Calculation
Result name . . . . . . consumption
Formula . . . . . . . . R=VEQ
Constant . . . . . . . . C=1
Result unit . . . . . . mL
Decimal places . . . . . 3

Page 22/28 METTLER TOLEDO Analysis of High Temperature Superconductivity Materials

METTLER TOLEDO DL70 Customer Methods
M251 Determination of Strontium in High Temperature Superconductors
after Separation from Calcium

Sample: solid material with approx.17% Sr, Titrant: EDTA c = 0.01 M

e.g. Bi-Pb-Cu-Ca-Sr-O
Standard: Sr standard solution, (e.g. Merck)
Substance: Calcium, Ca
Reagents: - Buffer solution NH3/NH4Cl
M = 40.08 g/mol
- 1 mL 10 mM Hg-EDTA / L buffer
Preparation: - dissolve 200 mg sample in 3 mL
Instruments: - Mettler-Toledo DL70ES
HNO3 conc.
- printer
- electrolytic separation of Bi, Pb and
- power supply unit
Cu
- amperometer
- Separation of Ca and Sr in the elec-
- variable resistor
trolyte
- take aliquot Accessories: beaker ME-101974
- adjust to pH 10.0 Indication: Ag/AgHgx on Sensor 2

Remarks:

• Cu, Pb and Bi have to be removed first, then Ca and Sr are separated by alcoholic extraction.

• After extraction, the alcohol has to be evaporated completely.

• Complexometric titration of Sr. The indication is voltametric as explained in the figure. The
potential change of 2 electrodes under current is plotted against the titrant consumption.
Electrodes in use are a silver electrode and an amalgamated silver electrode.

Fig.: voltametric indication

Ag AgHgx
Analysis of High Temperature Superconductivity Materials METTLER TOLEDO Page 23/28
Method Calculation
Result name . . . . . . . . . Sr of aliquot
Formula . . . . . . . . . . . R2=Q*M
Constant . . . . . . . . . . . C2=1
Method SrVt Strontium voltametric
Result unit . . . . . . . . . mg
Version 23-May-2001 5:08 pm
Decimal places . . . . . . . . 3
Statistics
Title
Ri (i=index) . . . . . . . . . R2
Method ID . . . . . . . SrVt
Standard deviation s . . . . . Yes
Title . . . . . . . . . Stronltium voltmetric
Rel. standard deviation srel . Yes
Date/time . . . . . . . May/23/2001 5:08 pm
Record
Sample
Output unit . . . . . . . . . Printer+Computer
Number samples . . . . . 2
All results . . . . . . . . . Yes
Titration stand . . . . Stand 1
Entry type . . . . . . . Weight m
Lower limit [g] . . . 0.0
Upper limit [g] . . . 2.0
ID1 . . . . . . . . . . Sr
Molar mass M . . . . . . 87.62 Results
Equivalent number z . . 1
Temperature sensor . . . Manual SrVt Strontium Voltametric Date: 23-May-2001 7:20 pm
Measure 23-May-2001 5:08 pm Titrator: Engelchen II
Sensor . . . . . . . . . AgHgx SW version 2.0 User: !!!!
Unit of meas. . . . . . mV
dE [mV] . . . . . . . . 1.0 Results
dt [s] . . . . . . . . . 1.0
t(min) mode . . . . . . Fix
No ID sample size results
t(min) [s] . . . . . 3.0
t(max) [s] . . . . . . . 30.0 1/1 Sr 0.20124 g 4.752 mL consumption
Stir
4.164 mg Sr of aliquot
Speed [%] . . . . . . . 50
1/2 Sr 0.20124 g 4.743 mL consumption
Time [s] . . . . . . . . 10
Titration 4.156 mg Sr of aliquot
Titrant . . . . . . . . EDTA 1/3 Sr 0.20124 g 4.776 mL consumption
Concentration [mol/L] . 0.01 4.185 mg Sr of aliquot
Sensor . . . . . . . . . AgHgX
Unit of meas. . . . . . mV
Statistics
Titration mode . . . . . EQP
Predispensing 1 . . . mL Number results R2 n = 3
Volume [mL] . . . 3.3 Mean value X = 4.168 mg Sr of aliquot
Titrant addition . . DYN Standard deviation s = 0.0151 mg Sr of aliquot
dE(set) [mV] . . . 2.0 Rel. standard deviation srel = 0.363 %
Limits dV . . . . Absolute
dV(min) [mL] . 0.02
dV(max) [mL] . 0.2
Measure mode . . . . EQU
dE [mV] . . . . . 7.0
dt [s] . . . . . . 2.0
t(min) [s] . . . . 5.0
t(max) [s] . . . . 20.0
Threshold . . . . . . 100.0
Maximum volume [mL] . 8.0
Evaluation procedure. Standard
Steepest jump only . Yes
Calculation
Result name . . . . . . consumption
Formula . . . . . . . . R=VEQ
Constant . . . . . . . . C=1
Result unit . . . . . . mL
Decimal places . . . . . 3

Page 24/28 METTLER TOLEDO Analysis of High Temperature Superconductivity Materials

Notes

Analysis of High Temperature Superconductivity Materials METTLER TOLEDO Page 25/28

Notes

This application bulletin represents selected, possible application examples. These have been tested with
all possible care in our lab with the analytical instrument mentioned in the bulletin. The experiments were
conducted and the resulting data evaluated based on our current state of knowledge.

However, the application bulletin does not absolve you from personally testing its suitability for you in-
tended methods, instruments and purposes. As the use and transfer of an application example are beyond
our control, we cannot accept responsibility therefore.

Whe chemicals and solvents are used, the general safety rules and the directions of the producer must
be observed.

Page 26/28 METTLER TOLEDO Analysis of High Temperature Superconductivity Materials

Analysis of High Temperature Superconductivity Materials METTLER TOLEDO Page 27/28
Mettler-Toledo GmbH
Analytical
CH-8603 Schwerzenbach, Schweiz
Telefon (01) 806 77 11, Fax (01) 806 73 50
Internet: http://www.mt.com

AT Mettler-Toledo GmbH., A-1100 Wien

Tel. +43-1-604 19 80, Fax +43-1-604 28 80
AU Mettler-Toledo Ltd., Port Melbourne, Victoria 3207
Tel. +61-3-9644 5700, Fax +61-3-9645 3935
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Tel. +32-2-334 02 11, Fax +32-2-334 03 34
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Tel. +41-1-944 45 45, Fax +41-1-944 45 10
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Tel. +86-21-6485 0435, Fax +86-21-6485 3351
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Tel. +420-2-25 49 62, Fax +420-2-2424 7583
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Tel. +49-6-41 50 70, Fax +49-6-41 507 128
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Tel. +45-4327 0800, Fax +45-4327 0828
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Tel. +34-3-223 22 22, Fax +34-3-223 02 71
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Tel. +33-1-3097 1717, Fax +33-1-3097 1616
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Tel. +852-2744 1221, Fax +852-2744 6878
HR Mettler-Toledo, d.o.o., HR-10000 Zagreb
Tel. +385-1-230 41 47, Fax +385-1-233 63 17
HU Mettler-Toledo, KFT, H-1173 Budapest
Tel. +36-1-257 70 30, Fax +36-1-256 21 75
IT Mettler-Toledo S.p.A., I-20026 Novate Milanese
Tel. +39-2-333 321, Fax +39-2-356 29 73
JP Mettler-Toledo K.K., Osaka 540-6017
Tel. +81-6-949 59 01, Fax +81-6-949 59 45
KR Mettler-Toledo (Korea) Ltd., Seoul (135-090)
Tel. +82-2-518 20 04, Fax +82-2-518 08 13
KZ Mettler-Toledo CA, 480009 Almaty
Tel. +7- 3272-608 834, Fax +7-3272-608 835
MY Mettler-Toledo (M) Sdn. Bhd. 47301 Petaling Jaya
Tel. +60-3-703 27 73, Fax +60-3-703 17 72
MY Mettler-Toledo (S.E.A.), 47301 Petaling Jaya
Tel. +60-3-704 17 73, Fax +60-3-703 17 72
MX Mettler-Toledo S.A. de C.V., México C.P. 06430
Tel. +52-5-547 57 00, Fax +52-5-541 22 28
NL Mettler-Toledo B.V., NL-4000 HA Tiel
Tel. +31-3-4463 8363, Fax +31-3-4463 8390
PL Mettler-Toledo, Sp. z o.o., PL-02-929 Warszawa
Tel. +48-22-651 92 32, Fax +48-22-651 71 72
RU Mettler-Toledo C.I.S. AG, 10 1000 Moscow
Tel. +7-095-921 92 11, Fax +7-095-921 63 53
SE Mettler-Toledo AB, S-12008 Stockholm
Tel. +46-8-702 50 00, Fax +46-8-642 45 62
SG Mettler-Toledo (S) Pte. Ltd., Singapore 139944
Tel. +65-7786 779, Fax +65-7786 639
SK Mettler-Toledo, SK-82104 Bratislava
Tel. +421-7-4342 7496, Fax +421-7-4333 7190
SI Mettler-Toledo, d.o.o., SI-1236 Trzin
Tel. +386-61-162 18 01, Fax +386-61-162 17 89
TH Mettler-Toledo (Thailand) Ltd., Bangkok 10310
Tel. +66-2-719 64 80, Fax +66-2-719 64 79
TW Mettler-Toledo Pac Rim AG, Taipei
Tel. +886-2-2579 5955, Fax +886-2-2579 5977
UK Mettler-Toledo Ltd., Leicester, LE4 1AW
Tel. +44-116-235 70 70, Fax +44-116-236 63 99
US Mettler-Toledo, Inc., Columbus, OH 43240
Tel. +1-614-438 4511, Fax +1-614-438 4900

For all other countries: Subject to technical changes

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