BTG Mütek GmbH

Operation manual
PCD 03/ PCD 03 pH
Particle Charge Detector

Mütek WET ® Lab

Copyright© 2003 BTG Mütek GmbH
All rights reserved. No part of this manual may be copied, photocopied,
published, reproduced, translated or converted into electronic or machine-
readable form without written permission of BTG Mütek GmbH.

Subject to technical modifications

BTG Mütek GmbH, December 2003
Printed in Germany
 List of contents

List of contents

Chapter Paragraph Title Page

I. Basic safety 1.1 Manufacturer’s liability . . . . . . . . . . . . . . . . . . . . . . . 5

instructions 1.2 Intended application of the PCD 03/ PCD 03 pH . . 6
1.3 Non-legitimated usage . . . . . . . . . . . . . . . . . . . . . . 6
1.4 Qualification of personnel . . . . . . . . . . . . . . . . . . . . 6
1.5 General safety directions. . . . . . . . . . . . . . . . . . . . . 7
1.6 Informal safety measures . . . . . . . . . . . . . . . . . . . . 7
1.7 Expendable and spare parts . . . . . . . . . . . . . . . . . . 7
1.8 Symbols. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.9 Packaging & transport . . . . . . . . . . . . . . . . . . . . . . . 8

II. Product description 2.1 General . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

2.1.1 Fundamentals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.1.2 Measuring principle . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.1.3 Calculation of charge demand. . . . . . . . . . . . . . . . . 10
2.1.4 Determination of the isoelectric point . . . . . . . . . . . 10
2.1.5 Determination of optimum dispersant dosages . . . . 11
2.2 Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.3 Designation of the PCD 03/ PCD 03 pH . . . . . . . . . 12
2.4 Technical data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.5 Scope of delivery . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.5.1 PCD 03 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.5.2 PCD 03 pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

III. Layout and function 3.1 Description of PCD 03/ PCD 03 pH. . . . . . . . . . . . . 15
3.1.1 Measuring cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
3.1.2 pH-Electrode . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18

IV. Installation 4.1 Safety rules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

4.2 Personnel requirements . . . . . . . . . . . . . . . . . . . . . 19
4.3 Preparations on-site . . . . . . . . . . . . . . . . . . . . . . . . 19
4.4 Installation environment . . . . . . . . . . . . . . . . . . . . . 19
4.4.1 Installation point . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
4.4.2 Power connection . . . . . . . . . . . . . . . . . . . . . . . . . . 19
4.4.3 Sample specification . . . . . . . . . . . . . . . . . . . . . . . . 21
4.5 Start up procedure. . . . . . . . . . . . . . . . . . . . . . . . . . 23
4.5.1 Prepare electrical connections . . . . . . . . . . . . . . . . 23
4.5.2 Automatic titration . . . . . . . . . . . . . . . . . . . . . . . . . . 23
4.5.2.1 PCD-Two titrator . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
4.5.2.2 PCD 03 pH with Metrohm Titrino 702/ 716 . . . . . . . 25
4.5.2.3 Manual operation. . . . . . . . . . . . . . . . . . . . . . . . . . . 26
4.5.3 Calibration of pH-electrode of the PCD 03 pH. . . . . 26
4.5.4 Titrant solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
4.5.5 Acids/bases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
4.5.6 Cleaning solution . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
4.5.7 Buffer solutions for pH calibration . . . . . . . . . . . . . . 27

PCD 03/ PCD 03 pH Operation manual 3

© BTG Mütek GmbH, December 2003
List of contents

Chapter Paragraph Title Page

V. Operation 5.1 Safety rules. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29

5.2 Personnel requirements . . . . . . . . . . . . . . . . . . . . . 29
5.3 Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
5.4 Sample preparation . . . . . . . . . . . . . . . . . . . . . . . . 29
5.4.1 Filtration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
5.4.2 Centrifugation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
5.4.3 Screening . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
5.4.4 Back titration. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
5.4.4.1 Example of back titration . . . . . . . . . . . . . . . . . . . . 30
5.5 Measuring with the PCD 03/ PCD 03 pH . . . . . . . . 31
5.6 Titration curves . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
5.6.1 Colloidally dissolved particles. . . . . . . . . . . . . . . . . 32
5.6.2 Solid particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
5.6.3 Heterogeneous stock systems . . . . . . . . . . . . . . . . 32
5.6.4 Selection of titration rate. . . . . . . . . . . . . . . . . . . . . 33

VI. Diagnostics and 6.1 Safety rules. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35

troubleshooting 6.2 Personnel requirements . . . . . . . . . . . . . . . . . . . . . 35
6.3 Tables of system faults. . . . . . . . . . . . . . . . . . . . . . 35

VII. Maintenance 7.1 Personnel requirements . . . . . . . . . . . . . . . . . . . . . 37

7.2 Cleaning the measuring cell . . . . . . . . . . . . . . . . . . 37
7.3 Functional test . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
7.3.1 Basic test of PCD without cell. . . . . . . . . . . . . . . . . 37
7.3.2 Standard titration . . . . . . . . . . . . . . . . . . . . . . . . . . 37
7.3.3 Check of streaming current . . . . . . . . . . . . . . . . . . 37
7.3.4 Electrostatic charging of the cell. . . . . . . . . . . . . . . 38
7.3.5 Functional test of pH-electrode. . . . . . . . . . . . . . . . 38

VIII. Shutting down the 8.1 Safety rules. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39

system, storage and 8.2 Personnel requirements . . . . . . . . . . . . . . . . . . . . . 39
disposal 8.3 Shutting down the system . . . . . . . . . . . . . . . . . . . 39
8.4 Storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
8.5 Disposal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
8.5.1 Official regulations . . . . . . . . . . . . . . . . . . . . . . . . . 39

IX. Part lists 9.1 Components . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41

9.2 Consumable goods. . . . . . . . . . . . . . . . . . . . . . . . . 42
9.3 Work safety. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42

4 PCD 03/ PCD 03 pH Operation manual

© BTG Mütek GmbH, December 2003

I. Basic safety instructions
1.1 Manufacturer’s liability
Notices in the operation manual
- Operators of the PCD 03/ PCD 03 pH have to
strictly adhere to the basic safety instructions
and the safety rules in order to ensure safe
handling and reliable operation of the PCD 03/
PCD 03 pH
- This operation manual contains the basic safety
instructions and the safety rules in order to
ensure safe handling and reliable operation of
the PCD 03/ PCD 03 pH
- All persons operating the PCD 03/ PCD 03 pH
must observe this operation manual, and in parti-
cular the safety directions
- In addition, all applicable accident prevention
regulations have to be met for the specific loca-
tion
Obligations of the user
The warranty and service quality pledges are only
applicable subject to the following conditions:
- The PCD 03/ PCD 03 pH may be operated only
by persons who have to be thoroughly trained
and authorized by BTG Mütek GmbH
- All instructions by BTG Mütek GmbH regarding
operation and maintenance of the PCD 03/ PCD
03 pH must be observed
- Storage and maintenance of the instrument must
be carried out in accordance with BTG Mütek
GmbH’s instructions
- Use of any parts other than the original BTG
Mütek GmbH replacement and spare parts will
cause instant termination of service quality and
guarantee claims
- Failures which affect safe operation of the sys-
tem have to be repaired immediately
- When the system is obviously damaged or parts
in the inside are loose or the system does not
work, operation with the PCD 03/ PCD 03 pH
has to be stopped
PCD 03/ PCD 03 pH Operation manual
© BTG Mütek GmbH, December 2003
I. Basic safety instructions
Hazards involved in handling the PCD 03/ PCD 03
pH
The PCD 03/ PCD 03 pH has been built to reflect
state-of-the-art techniques and to meet recognized
safety rules. However, its operation may entail the
risk of accidents for users or third parties or of
damage to the PCD 03/ PCD 03 pH or other pro-
perty. The PCD 03/ PCD 03 pH shall only be opera-
ted
- For the applications outlined in these operation
manual
- In a condition meeting all safety rules
Users are obliged to immediately eliminate without
delay any faults that may afffect operational safety.
Warranty and liability
This instrument was built and tested in accordance
with EG guidelines EN50081, EN50082 and
EN61010 and complied with all safety regulations at
the time of leaving our factory. To maintain this con-
dition and ensure safe operation, the user must
observe the safety instructions and warning notes
contained in this operation manual. It is the responsi-
bility of the owner and user to make sure that all
safety devices and requirements concerning the
location of the instrument are adequately provided
for. Basically, the General Terms and Conditions of
BTG Mütek GmbH will apply and are available to the
operator of the PCD 03/ PCD 03 pH at the latest on
the day the sales contract is concluded. BTG Mütek
GmbH shall not be liable for any warranty or liability
claims for personal injury or property damage that
may be consequential to one or several of the follo-
wing causes:
- Non-legitimated use of the PCD 03/ PCD 03 pH
- Opening of the instrument or removing the seal
of the holding down bolt on the rear of the sys-
tem
- Inexpert installation/assembly, commissioning,
operation and servicing of the PCD 03/ PCD 03
pH
- Operation of the PCD 03/ PCD 03 pH although
its safety devices and protection facilities are
defective, inexpertly mounted or malfunctioning
- Failure of the user/operator to adhere to the
instructions given in this operation manual regar-
ding transport, storage, assembly, commissio-
ning, operation and maintenance of the PCD 03/
PCD 03 pH
5
I. Basic safety instructions
- Modifications made to the PCD 03/ PCD 03 pH
without the prior approval of BTG Mütek GmbH
- Inadequate routine checks of PCD 03/ PCD 03
pH parts/assemblies that are subject to wear
- Inexpert repairs
- Catastrophes caused by the effects of foreign
objects or by acts of God
Trouble-free and safe operation of the instrument is
possible only subject to correct transport, correct sto-
rage, installation and assembly and to careful hand-
ling and maintenance.
If the PCD 03/ PCD 03 pH is sent in for repair the
whole system has to be sent in.
The guarantee for the PCD 03/ PCD 03 pH is one
year starting with the date of delivery.
For defects included in the guarantee, BTG Mütek
GmbH shall not be liable for any damages higher
than the cost price.
For defects included in the guarantee, BTG Mütek
GmbH has the right to decide whether damaged
parts are exchanged or repaired (provided that all
parts have been returned to an authorized retailer in
time).
This guarantee does not include parts which have
been commissioned or altered without prior written
permission by an authorized BTG Mütek GmbH-
retailer.
Neither does BTG Mütek GmbH take any obligations
in connection with the sale of the measuring instru-
ment nor has BTG Mütek GmbH instructed any other
person to take on such an obligation.
Exclusion of liability
BTG Mütek GmbH has checked the contents of the
printed manual for consistency with the hardware
described. However, deviations cannot be entirely
excluded, so that BTG Mütek GmbH will not accept
responsibility for absolute consistency. The contents
of this manual are regularly revised, and any correc-
tions which may be necessary will be included in
later issues.
The right is reserved to make technical alterations.
6 PCD 03/ PCD 03 pH Operation manual
© BTG Mütek GmbH, December 2003
1.2 Intended application of the PCD 03/
PCD 03 pH
The instrument may only be used for the purposes
defined in this operation manual and in the technical
description, and only in conjunction with external
instruments and components recommended or
approved by BTG Mütek GmbH.
The BTG Mütek GmbH Particle Charge Detector
PCD 03/ PCD 03 pH is to be solely used for charge
identification of aqueous samples and for identifying
the isoelectric point.
Any other or further-reaching application is not legiti-
mate. BTG Mütek GmbH will not be held liable for
damage resulting from such use. An integral part of
legitimate use is also:
- To follow all the instructions in this operation
manual, and
- To perform the inspection and maintenance work
as specified
1.3 Non-legitimated usage
Non-legitimated usage (misuse) is defined as fol-
lows:
- Any usage other than the legitimate usage defi-
ned above, or extending beyond the designated
usage
- Failure to follow the instructions given in this
operation manual
- Failure to observe the safety directions
- Failure to immediate correction, prior to continu-
ing work with the instrument, any defect which
might endanger safety (operation of the instru-
ment in a condition which does not meet techni-
cal and safety requirements)
- Any unauthorized modification of the instrument
1.4 Qualification of personnel
The instrument may be commissioned and operated
only by qualified personnel. Qualified personnel as
definded by the safety instructions in these operation
manual are persons trained and instructed by BTG
Mütek GmbH.
 I. Basic safety instructions

1.5 General safety directions 1.8 Symbols

For all installation, operation, maintenance and
repair work performed on the PCD 03/ PCD 03 pH, it
is essential that the directions given below be follo-
wed:
- Installation and operation has to be performed by
trained personnel
- Inspection tasks due on a daily basis must be
performed by trained personnel
- Maintenance and repair work not described in
this manual should not be performed without first
consulting the manufacturer or an authorized
service agent
- When working on electrical and electronic parts,
the instrument must be switched off at the main
switch and the plug disconnected from the power
supply
- When replacing defective parts, use only original
spare parts
- When handling dangerous materials, please
observe the directions for protective equipment,
industrial hygiene and proper disposal
The following symbols and notices are used in this
operation manual to designate hazards or to provide
special information:
Information
"Information" means tips for operators and useful
information.
It helps you make optimum use of all functions of the
PCD 03/ PCD 03 pH.
Hint
"Hint" refers to expert handling and operation of the
PCD 03/ PCD 03 pH.
Non-adherence to these hints may lead to operatio-
nal failures of the PCD 03/ PCD 03 pH or to trouble in
its surroundings.
Caution
"Caution" refers to a potentially dangerous situation.
Failure to observe this information may result in slight
personal injury or in damage to equipment.

1.6 Informal safety measures Warning

"Warning" refers to potential hazards.
Take care to keep this operation manual on the
Failure to observe this information may result in
PCD 03/ PCD 03 pH. In addition, make sure that severe injury to health.
documentation on general and local accident preven-
tion and environmental protection standards is near
at hand and strictly adhered to. Keep all safety
instructions and warnings on the PCD 03/ PCD 03
pH in a legible condition and renew, if necessary.

1.7 Expendable and spare parts

Use original expandable and spare parts only to
ensure operational safety of the PCD 03/ PCD 03 pH
and to safeguard your guarantee claims. Spare parts
are available from your local authorized representa-
tive of BTG Mütek GmbH.

PCD 03/ PCD 03 pH Operation manual 7

© BTG Mütek GmbH, December 2003
I. Basic safety instructions

1.9 Packaging & transport

The BTG Mütek GmbH PCD 03/ PCD 03 pH is a
compact and sturdy unit which is easy to transport for
onsite measurements.

Hint
The aluminium case does not stand up to rough
handling in transit.

Hint
The aluminium case is unsuitable for rail forwarding
or postal delivery of the unit.
- To avoid damage in transit to the precision can-
tact pins do not keep any small components in
the measuring chamber. Before transport, take
the measuring cell off the dovetailed guide.
- At outdoor temperatures below +15°C [59°F], it
is recommended to let the unit adjust to ambient
temperature after transport before putting it into
operation.
Hint
If the PCD 03/ PCD 03 pH is exposed to very low
temperatures for a protracted period of time, the
electronics may be damaged. Take care to remove
the device from the trunk of your car in cold weather.

8 PCD 03/ PCD 03 pH Operation manual

© BTG Mütek GmbH, December 2003
 II. Product description

II. Product description

2.1 General
In aqueous systems, such as dispersions or emulsi-
ons, the charges play a crucial role, because they
are responsible for reaction mechanisms between
colloidal particles.
Applying polyelectrolyte titration, the PCD 03/ PCD
03 pH Particle Charge Detector continuously moni-
tors the total surface charges of all dissolved and
undissolved substances present in an aqueous
sample.
2.1.1 Fundamentals
Streaming current
Practically all colloidally dissolved substances and
solid particles in water carry electric charges. This
leads to a concentration of oppositely charged ions,
the so-called counter-ions, on the colloids surfaces. If
these counter-ions are separated from, or sheared
off, the dissociated macromolecule or particle, a stre-
aming current can be measured in mV. A streaming
current of zero mV denotes the point of zero charge,
i.e. all existing charges in the sample are neutralized.
If the measured potential is unequal to zero, the sign
of the measured value merely indicates whether the
charge is positive (cationic) or negative (anionic).
The potential itself is a relative parameter that
depends on different influential factors, such as
- Electrical conductivity of the sample dispersion
- Sample viscosity
- Molecular weight and particle sizes of the
sample
- Dimensions of the measuring cell
- Temperature
- Cleaning of the measuring cell
- Chemical properties of the sample
2.1.2 Measuring principle
Streaming current measurements with the PCD 03/
PCD 03 pH are based on the following principle (Fig.
2-1 Schematic of test setup): the central element is a
plastic measuring cell (4) with a fitted displacement
piston (5).
If an aqueous sample is filled into the measuring cell,
colloidally dissolved molecules will adsorb at the
plastic surface of the piston and on the cell walls
under the action of van der Waal forces. The coun-
ter-ions remain comparatively free. A defined narrow
gap is provided between cell wall and piston.
Driven by a motor (6), the piston (5) oscillates in the
measuring cell (4) and creates an intensive liquid
flow which entrains the free counter-ions, thus sepa-
rating them from the adsorbed sample material.
At the built-in electrodes (3), the counter-ions induce
a current which is rectified and amplified electroni-
cally (2).
The streaming current is shown on the display (1)
with the appropriate sign.
6
1
5
4
2
3

Fig. 2-1 Schematic of test setup

Designations
1 Display 4 Plastic measuring cell
2 Electronics 5 Displacement piston
3 Electrodes 6 Motor

PCD 03/ PCD 03 pH Operation manual 9

© BTG Mütek GmbH, December 2003
II. Product description

2.1.3 Calculation of charge demand

Polyelectrolyte titration
For quantitative charge measurements of the
sample, a polyelectrolyte titration has to be conduc-
ted which uses the streaming current to identify the
point of zero charge (0 mV). To this end, an opposi-
tely charged polyelectrolyte of known charge density
is added to the sample as a titrant.
The titrant charges neutralize existing charges of the
sample. Titration is discontinued as soon as the point
of zero charge (0 mV) is reached.
Titrant consumption in ml is the actual measured
value which forms the basis for further calculations.
If several identical samples are to be compared, the
charge quantity q does not have to be calculated pro-
vided the samples are titrated under identical conditi-
ons, i.e. at the same sample solids and titrant
concentrations. In this case, the measured volume of
consumed titrant in ml may be directly used and the
values obtained are directly comparable. In this con-
text, the terms anionic and cationic demand of a
sample are in common use.
2.1.4 Determination of the isoelectric point

Calculation Acid/base titration

The specific charge quantity q [eq/g] is calculated Apart from charge density measurements, the PCD
according to the following formula: 03/ PCD 03 pH lends itself to identifying the isoelec-
tric point (IEP) of dispersions.
V*c
The IEP is the pH-dependent point of zero charge of
q=
a particle. In this context, existing layers of specifi-
m
cally adsorbed charge carriers are taken into
account.
V: consumed titrant volume [l] By dropwise addition of a titrant (acid/base), the
sample pH’s are shifted until the point of zero charge
c: titrant concentration [eq/l]
(streaming current = 0 mV) is reached.
m: solids of the sample or its active substance [g]
Cationic samples are titrated with a base and anionic
q: specific charge quantity [eq/g] samples with an acid up to the point of 0 mV.
The pH value is detected parallel to the streaming
Example: When measuring an 0.1 % Ti02 suspen- potential.
sion, a 10 ml sample contains 0.01 g solids,
m = 0.01 g.
Consumption of cationic polyelectrolyte
until point of zero charge 2.5 ml.
Titrant concentration was 0.001 N.
0.0025 [l] * 0.001 [eq/l]
= 250 * 10-6 [eq/g]
0.01 [g]

By multiplying the specific charge quantity in eq/g by

the Faraday’s constant F = 96485 C/eq, the total
charge quantity in C/g will be obtained.

Fig. 2-2 Isoelectric point

10 PCD 03/ PCD 03 pH Operation manual

© BTG Mütek GmbH, December 2003
 II. Product description

2.1.5 Determination of optimum dispersant 2.2 Applications

dosages
Paper making
Optimum dispersant additons are conveniently iden-
tified by titrating a particle suspension of a defined - Improved machine running through optimized
solids content with the dispersant solution. For this elimination of anionic trash
purpose it will be sufficient to obtain a concentration- - Enhanced retention
dependent potential characteristic without an end- - Increased chemical performance
point titration to zero mV being required. Short-chai- - Good runnability
ned inorganic dispersants and longer-chained orga- - Chemical savings
nic additives give clearly different graphs. In both
cases, optimum dispersant dosages can be derived Effluent treatment
from the potential characteristics obtained from the - Chemical savings by controlled flocculant dosa-
PCD and the results can be readily transferred to the ges
technological process concerned. The PCD 03/ PCD - Increased dry content of sludges through impro-
03 pH thus lends itself very well to an assessment of ved dewatering
particle/ additive interactions, overall stability and - Precise identification of the demulsification point
optimized chemical additions. of emulsions and cooling lubricants
- Optimized selection of flocculants
Filler/pigment processing
- Determination of the optimum dispersed condi-
tion and of dispersant amounts.
PCD-potential U [mV]

organic
dispersant - Identification of the isoelectric point permits
selective particle flocculation.
inorganic
dispersant

optimum
dosage

Dispersant V [ml]

Fig. 2-3 Stability maxima

PCD 03/ PCD 03 pH Operation manual 11

© BTG Mütek GmbH, December 2003
II. Product description

2.3 Designation of the PCD 03/ PCD 03

pH
In the following, the designationof the PCD 03/ PCD
03 pH is shown.

Hint
The label should be easily visible and legible. Make
sure to exchange damaged or illegible plate/label
before placing the PCD 03/ PCD 03 pH in service.

Type plate PCD 03/ PCD 03 pH

The following type plate is located on the back of the
PCD 03/ PCD 03 pH.
The voltage given on the type plate refers to a power
supply of 230VAC or 115 VAC.

Caution
This instrument is only to be operated if the voltage
stated on the type plate is identical to the line voltage
at the place of operation.

Fig. 2-4 Type plate, PCD 03

Fig. 2-5 Type plate, PCD 03 pH

12 PCD 03/ PCD 03 pH Operation manual

© BTG Mütek GmbH, December 2003
 II. Product description

2.4 Technical data

Measure - Wide: 160 mm [6.3 in.]

- Deep: 200 mm [7.9 in.]
- High: 340 mm [13.4 in.]

Weight Approximately 10 kg [22 lb.]

Power Supply - Input voltage: 230VAC/ 115VAC

- Frequency: 50 Hz/ 60Hz
- Consumption: mMaximum 460 W
- Fuses of the device: 2 x 315 mA slow-blowat 230 VAC
2 x 630 mA slow-blow at 115
VAC

Conditions of service - Ambient temperature: +5°C to +60°C [41°F - 140°F];

no condensation
- Storage/ transport temperature: -30°C to +60°C [-22°F - 140°F]

Measured variables - Streaming current in mV

- Anionic & cationic demand of a sample

Result - Charge level of polyelectrolyte additives in µeq/g, C/g or µeq/l, C/l

- pH of the isoelectric point (only for PCD 03 pH)
- pH-charge profile (only for PCD 03 pH)

Sample volume - Standard cell type 1: 10 ... 30 ml

- Precision cell type 2: 10 ... 60 ml

Measuring values - Streaming current

Output signals - Streaming current display and titrator: +/- 2000 mV

- LED showing the charge sign
- pH‘s indicated on display, for titrator and recorder
(only for PCD 03 pH)

Operating modes - Manual: hand pipette

- Automatic: BTG Mütek GmbH PCD titrator
or any other titration system

Reproducibility Up to a standard deviation of s (x) = 0.01 %

Detection limit Up to 1 ppm depending on sample specification

EU-Specifications - EN 50081
- EN 50082
- EN 61010

Safety and protection class - Safety class I

PCD 03/ PCD 03 pH Operation manual 13

© BTG Mütek GmbH, December 2003
II. Product description

2.5 Scope of delivery

2.5.1 PCD 03 2.5.2 PCD 03 pH

Pieces Description Pieces Description

1 PCD 03 main unit
1 Standard measuring cell
1 Displacement piston, 0.1 mm
1 Teflon ring
1 Mains cable
1 Piston brush
1 0.001 N PES-Na (100 ml, anionic polye-
lectrolyte)
1 0.001 N PolyDadmac (100 ml, cationic
polyelectrolyte)
1 Screen for filtrating fiber suspension
1 Application tips for using polyelectrolytes
1 Test printout of standard titration
1 Operation manual
1 Recommended Test Procedure
Optional
Pieces Description
Optional
1 Displacement piston, 0.5 mm
1 Precision measuring cell
1 Precision displacement piston
1 Piston-operated pipetter 2 - 10 ml
1 Transportation case
1 PCD 03 pH main unit
1 Precision measuring cell
1 Precision displacement piston
1 pH-electrode
1 Mains cable
1 Piston brush
1 0.001 N PES-Na (100 ml, anionic polye-
lectrolyte)
1 0.001 N PolyDadmac (100 ml, cationic
polyelectrolyte)
2 Buffer solution pH = 4.01 (20 ml)
2 Buffer solution pH = 7.00 (20 ml)
1 Screen for filtrating fiber suspension
1 Application tips for using polyelectrolytes
1 Test printout of standard titration
1 Operation manual
1 Recommended Test Procedure
Pieces Description
1 Standard measuring cell
1 Displacement piston, 0.1 mm
1 Displacement piston, 0.5 mm
1 Miniature measuring cell
1 Miniature displacement piston
1 Piston-operated pipetter 2 - 10 ml
1 Transportation case

14 PCD 03/ PCD 03 pH Operation manual

© BTG Mütek GmbH, December 2003
 III. Layout and function

III. Layout and function

3.1 Description of PCD 03/ PCD 03 pH

On its facing side, the front panel (15) features a digi- Designations
tal display (14) indicating the potential in mV. A digi- 1 LED cationic
tal pH display (13) is located below (only for PCD 03 2 Switch for piston drive
pH). 3 LED anionic
Arranged in the middle are a cationic LED (1) and an 4 Switch for pH measurement (PCD 03 pH)
anionic LED (3). Vertically arranged are a motor
5 Burette tip holder
switch (2) for the piston drive. A switch (4) for pH
6 Contact pins
measurement is located below (only for PCD 03 pH).
7 Guide for measuring cell
A power LED (12) is located at bottom right of the
8 Measuring chamber
panel (15). The measuring chamber (8) accommoda-
9 Measuring cell
tes the burette tip holder (5), the measuring cell (9)
with contact pins (6) and guide (7) for the measuring 10 Displacement piston
cell (9). The displacment piston (10) is mounted in 11 Piston suspension
the PCD on suspension (11). 12 Power LED
13 pH display (PCD 03 pH)
14 Potential mV display
15 Front panel
1 Potential (mV) 15
on
cationic
2 Motor -15 79 14
anionic
off
3
on

4 pH 5.6 8 13
off
pH
Mütek PCD 03 pH
Particle Charge Detector
Power 12

11

10
5

Fig. 3-1 Front view of PCD 03/ PCD 03 pH

PCD 03/ PCD 03 pH Operation manual 15

© BTG Mütek GmbH, December 2003
III. Layout and function

Arranged on the rear panel of the chassis are the

power module connection with a window showing the
set voltage (6), a fuse latch (7), the power switch (8)
and a power cord socket (9). The output signal jack
(12) is located at the right. The BNC connector (12)
for the streaming current output optionally serves for
connection of the titrator or of a recorder. The CE
symbol (11) denotes that the instrument conforms to
the CE Directives of the EU.

PCD 03 pH 1 pH Potential (mV)

13
For PCD 03 pH only, a DIN connector (1) and a BNC
connector (2) for the pH-electrode are located on the 2 12
In/Out 1 In/Out 2 Rec. Out Out
left side. Both connectors may also be used to con-
nect the titrator and to transmit the pH signal. In
C 11
cases where no BTG Mütek Titrator (including soft- 40 60
ware) is used, a recorder may be connected to the 20 80
10
recorder output (13) to plot pH’s during titration. 3 0 100 9
Temperature compensation of the built-in pH electro- 8
nics is not automatic but has to be manually adjusted
7
with temperature switch (3). The two adjustment con- 4
trols (4 and 5) serve to set the drift (zero point) ∆pH 5 6
(5) and the line inclination mV/pH (4) of the pH-elec- D pH mV/pH

trode via buffer solutions.

Fig. 3-2 Back view of PCD 03/ PCD 03 pH

Designations
1 DIN connector for pH-electrode (PCD 03 pH)
2 BNC connector for pH-electrode (PCD 03 pH)
3 Temperature compensation switch for pH
measuring (PCD 03 pH)
4 Inclination of pH line (PCD 03 pH)
5 Drift of pH measurement (PCD 03 pH)
6 Set voltage/ fuses
7 Latch
8 Power switch
9 Power socket
10 Type plate
11 CE symbol
12 Output signal jack +/- 2000 mV
13 Cinch jacks/ recorder output (PCD 03 pH)

16 PCD 03/ PCD 03 pH Operation manual

© BTG Mütek GmbH, December 2003
 III. Layout and function

3.1.1 Measuring cells

4 3
1 1

2 3 2

Fig. 3-3 Standard measuring cell type 1 with piston Fig. 3-4 Precision measuring cell type 2 for highly
type 1 sedimating samples

Designations Designations
1 Standard measuring cell type 1 1 Precision measuring cell type 2
2 Gold electrodes 2 Platinum electrodes
3 Teflon ring 3 Precision piston type 2 for optimum sample
4 Piston type 1 mixing

The PCD 03 is standard-equipped with a measuring

cell type 1 and a piston type 1. A piston with deep
grooves providing for a larger clearance is available
for highly viscous and shear-sensitive samples.
Alternatively, the precision measuring cell type 2 with
precision piston type 2 may be employed. This option
is particularly suitable for highly sedimenting particles
and larger sample volumes (< 60 ml).
For PCD 03 pH both measuring cells are suitable.
Depending on the application the ideal measuring
cell according to the above mentioned criteria shall
be selected.
The enlarged measuring chamber of the precision
measuring cell is rated for commercial pH-electrodes
measuring up to 10 mm in diameter.

PCD 03/ PCD 03 pH Operation manual 17

© BTG Mütek GmbH, December 2003
III. Layout and function

3.1.2 pH-Electrode
The PCD 03 pH is standard-equipped with a pH-mini-
electrode which equally goes with the standard
measuring cell type 1 and the precision measuring
cell type 2.

1 3

Fig. 3-5 pH-electrode

Designations
1 Plexiglass shaft
2 Ceramic diaphragm
3 Support

18 PCD 03/ PCD 03 pH Operation manual

© BTG Mütek GmbH, December 2003

IV. Installation
This chapter covers the installation of the PCD 03/
PCD 03 pH and the necessary preparations. In the
course of installation, settings should be made as
required.
4.1 Safety rules
Please adhere to the applicable safety rules during
preparatory work and when commissioning the sys-
tem.
4.2 Personnel requirements
On-site preparations should be made by qualified
and skilled personnel. For installation of the PCD 03/
PCD 03 pH, call in a technician of BTG Mütek GmbH
or an authorized agent.
4.3 Preparations on-site
Prior to installation of the PCD 03/ PCD 03 pH, all
preparations mentioned under chapter 4.4 "Installa-
tion environment" must be made and the ambient
conditions met.
Allow the PCD 03/ PCD 03 pH to adapt to ambient
temperature before commissioning the system.
PCD 03/ PCD 03 pH Operation manual
© BTG Mütek GmbH, December 2003
IV. Installation
4.4 Installation environment
4.4.1 Installation point
Hint
In order to guarantee safe handling and reliable ope-
ration of the PCD 03/ PCD 03 pH, check the follo-
wing requirements before starting to use the device:
❑ Ambient temperature
- +15°C to +45 °C [59°F to 113°F]
❑ The device needs to be placed on an even and
stable ground
❑ The room where the PCD 03/ PCD 03 pH is used
has to be dry and clean
❑ Do not use the device while it is exposed to
direct sunlight
❑ Do not use the device when it is or was exposed
to water
❑ Do not use the device in explosion prone rooms
❑ Do not use the device when it is or was exposed
to aggressive chemical substances
❑ If there is condensed water either after storage
or transportation of the device, allow at least two
hours before switching on the device
❑ If outdoor temperatures are below +15°C [59°F],
wait until the device has adjusted to ambient
temperature in the laboratory
4.4.2 Power connection
Hint
Before setting the device to work check whether the
voltage shown on the measuring unit is the same as
locally used.
❑ Input voltage
- 230 VAC
- 115 VAC
❑ Frequency
- 50 Hz / 60 Hz
❑ The electrical instalation in the room where the
PCD 03/ PCD 03 pH is set up must conform to
VDE 0107
❑ Do only use the device with shockproof sockets
❑ Do not undo any earthing contacts inside or out-
side the device
❑ The BTG Mütek GmbH guarantee expires if the
device is used with an inappropriate voltage
❑ The PCD 03/ PCD 03 pH is rated for overvoltage
category III to IEC 664
19
IV. Installation

Voltage selection
The PCD 03/ PCD 03 pH is rated for two different
voltages: 230 VAC and 115 VAC Fig. 4-1.

Hint
BTG Mütek GmbH does not assume any guarantee if
the voltage is wrongly selected.
Use the voltage selector (3) to set the device to the
local power voltage.
• Insert a small screwdriver and depress latch (5)
to unlock.
• Remove fuse holder (1).
• Remove voltage selector (3), rotate through 180°
and reinsert.
• Withdraw fuses (2) from holder (1) and insert the
fuses required for the set voltage:
- 230 V: 2 x 315 mA/slow-blow
- 115 V: 2 x 630 mA/slow-blow
• Reinsert holder (1) with fuses (2) into enclosure
(4) until latch (5) clicks into position.
• Check if the proper voltage appears in the win-
dow in fuse holder (1).
Hint
Make sure that only replacement fuses of the speci-
fied type and amperage are used. It is not allowed to
use repaired fuses or to short-circuit the fuse holder.

Fig. 4-1 Power entry module

Designations
1 Fuse holder
2 Fuses
3 Voltage selector
4 Enclosure
5 Latch

20 PCD 03/ PCD 03 pH Operation manual

© BTG Mütek GmbH, December 2003

4.4.3 Sample specification
General
Basically, nearly every aqueous sample - including
original concentrations - can be measured. The
measurability of a sample is verified in the PCD itself.
To this end, fill the sample into the measuring cell,
install the cell together with the piston in the PCD
and turn on the motor. If the motor runs smoothly and
silently and if the signal is comparatively stable
(about 50 mV), the sample can be readily measured.
The limit values indicated in this chapter are not
absolute values, but are merely indicative of sample
characteristics that might lead to measuring pro-
blems.
If there are doubts about whether or not a substance
can be measured, a test measurement should be
conducted and the sample be suitably prepared, if
necessary.
Solvents
Charges can only be measured after functional
groups are dissociated. As this dissociation can only
take place in aqueous solutions, the substance to be
tested must be available in this form or be dispersed
in water.
If required, the test substance may also be dissolved
in lower alcohols (methanol, ethanol, isopropanol)
and then diluted with de-ionized water for subse-
quent titration.
The proportion of organic solvents depends on the
sample and should be determined in pretests. To
begin with, a blank reading should be obtained for
the solvent concerned. For this purpose, fill 10 ml of
the solvent (de-ionized water or a water/alcohol mix-
ture) into the measuring cell and titrate up to the
point of zero charge.
Even if the cell is filled with de-ionized water only, the
streaming current will not be at 0 mV as might be
expected, but shows a comparatively high anionic
signal. This signal drops to zero as soon as a mini-
mum amount of cationic titrant is added.
If de-ionized water is titrated, approx. 0.02 ml poly-
DADMAC is normally required.
The blank value thus obtained is to be deducted from
the results of all further titrations.
PCD 03/ PCD 03 pH Operation manual
© BTG Mütek GmbH, December 2003
IV. Installation
Particle sizes
If the standard piston or the precision piston are
employed, solid particle sizes in the sample should
not exceed 300 µm. On the other hand, measure-
ments of fibres of a length more than 1 mm are rea-
dily possible. For larger particles measuring up to 1
mm, the special piston with deeper grooves should
be used.
The lower limit amounts to 10 nm.
Viscosity
The standard piston type 1 is suitable for use with
samples of a viscosity below 300 mPa*s.
For samples of higher viscosities up to 6000 mPa*s,
the special piston type 1 with deeper grooves has
been developed.
Viscosities exceeding the above values impede the
oscillating movement of the piston in the cell. Moreo-
ver, the flocculation effect typically occurring towards
the end of titration will change viscosities, too.
Samples with a viscosity exceeding 6000 mPa*s
should be diluted with de-ionized water.
If highly viscous samples are to be titrated, mixing of
the titrant with the sample will take longer than with
low-viscosity samples. Accordingly, a lower titration
rate should be selected.
Molecular weight
The minimum molecular weight of the polyelectroly-
tes to be studied should be approximately 300 g/mol.
If the molecules are smaller, their adsorption on the
cell wall by van der Waal forces cannot be ensured.
No ions present in the sample will be measured.
At the upper end of the scale, there is no limiting
molecular weight of colloidally dissolved substances.
21
IV. Installation

Conductivity
The conductivity of the sample decisively impacts the
streaming current: the higher the conductivity the
lower the electrical resistance in the sample will be
and the more the streaming current will decrease wit-
hout, however, influencing the titration results.

-2000
0,05 mS/cm
1,86 mS/cm
3,45 mS/cm
5.97 mS/cm
10,80 mS/cm

-1000
mV

0
0 2 4 6 8 10
titrant ml

Fig. 4-2 Conductivity vs. streaming current

In Fig. 4-2, various proportions of NaCl were added

to PES-Na 0.001 N and the samples were titrated
with poly-DADMAC 0.001 N.
If conductivities are excessively high (20 mS/cm to
50 mS/cm), the streaming current may fluctuate bet-
ween anionic and cationic so that an end-point
detection and thus titration is no longer possible. In
these cases, the conductivity can be reduced by dilu-
ting the sample with de-ionized water.

Information
Samples that do not meet the above specifications
may be prepared as outlined under chapter 5.4
"Sample preparation", page 29.

22 PCD 03/ PCD 03 pH Operation manual

© BTG Mütek GmbH, December 2003
 IV. Installation

4.5 Start up procedure

4.5.1 Prepare electrical connections

The PCD 03/ PCD 03 pH is rated for automatic or PCD 03
manual titration.
PCD-Two Titrator
4.5.2 Automatic titration
RS-232-C Centronics IN pH
Computer Balance Printer

BTG Mütek GmbH recommends the use of an auto- IN mV

matic titrator, because it gives results of maximum Titrator/ Printer

Centronic
reproducibility. In addition, the titration curve can be Potential (mV) Keyboard Fill Start
Keys
Power ON/OFF

recorded via a printer. Generally, every automatic Out

titrator can be connected to the PCD. PCD 03/ PCD-Two-Titrator

Streaming potential [mV]

4.5.2.1 PCD-Two titrator

The PCD-Two titrator was specially developed for
use in combination with the PCD 03/ PCD 03 pH for PCD 03

polyelectrolyte titrations.
Fig. 4-4 Cabling of PCD 03 with PCD-Two titrator
Automatic titration with the PCD 03/ PCD 03 pH is
and printer
simplest and cheapest with the PCD-Two titrator.

Printer PCD-Two Titrator PCD 03/ PCD 03 pH

Connecting cable
RS232 interface PCD with titrator

Fig. 4-3 PCD 03/ PCD 03 pH configuration with

PCD-Two titrator and printer

Fig. 4-5 Printout of PCD-Two titrator connected with

PCD 03/ PCD 03 pH

PCD 03/ PCD 03 pH Operation manual 23

© BTG Mütek GmbH, December 2003
IV. Installation

PCD 03 pH (IEP)

PCD-Two Titrator mV/ml

RS-232-C Centronics IN pH
sample ident
pH-electrode

Computer Balance Printer

IN mV

pH Potential (mV) Keyboard Fill Start Power ON/OFF

Keys

In/Out 1 In/Out 2 Rec. Out Out

40
C
60
PCD 03 pH/ PCD-Two Titrator
20 80 Streaming current (mV)
0 100

Printer

PCD 03 pH
D pH mV/pH

Fig. 4-6 Cabling of PCD 03 pH with PCD-Two titrator

and printer

When working with the PCD 03 pH and the PCD-Two

titrator the streaming current, the titrant (acid/ base)
consumption and the pH value (IEP) is recorded.
After the measurement a three page result will be pH/ml
printed out automatically. It shows the streaming
potential mV versus pH, streaming potential mV ver-
sample ident

sus consumption ml and the pH value versus titrant

consumption ml.
On the first page the results of consumption at 0 mV
and pH value at 0 mV are listed.

mV/pH
***************** MUETEK PCD Titrator two *****************
Method number: 8
Method name: pH iep >2ml

Sample ident: TI02 1% 2

Titration start: 14:53:40 11.09.02

Titration end: 15:05:08 11.09.02

Active substance: 1.00000 g

Titrant: Conc. Titrant: 1.000000 (mol/l)

Stop pH: pH= 2.000

Stop ml: 20.0 ml

Start value: pH= 7.839 -2005.000mV

End point 0.0 mV IEP: pH= 2.813 0.386 ml

Fig. 4-7 Printout of PCD-Two titrator connected with

PCD 03 pH

24 PCD 03/ PCD 03 pH Operation manual

© BTG Mütek GmbH, December 2003
 IV. Installation

4.5.2.2 PCD 03 pH with Metrohm Titrino 702/ 716

This configuration is eminently suitable for determi- Mütek GmbH titration software which has been spe-
ning the isoelectric point and optimum dispersant cifically tailored to the PCD 03 pH allows a juxta-
dosages. Besides, it renders valuable service in the position of streaming currents and pH’s.
research and development area. Controlling the Titrino device, this software allows
Stability maxima may be derived from the streaming streaming currents, pH’s and consumption levels to
current characteristics optained.The use of BTG be evaluated in parallel.
Printer PC Titrino PCD 03 pH
1 2 3

Potential (mV)
on
cationic
Motor
anionic
-15 79
off

on

pH 10.6 8
off
pH
Mütek PCD 03 pH
Particle Charge Detector
Power

Fig. 4-8 Configuration of PCD 03 pH/ Titrino 702

Designations
1 Parallel interface 3 pH-electrode
2 RS232 interface 4 Connecting cable PCD 03 pH/ Titrino

PCD 03 pH

Connecting cable
Titrino PCD/ Titrino for
mV signal
adapter E - F
IND 2 connector
RS232 female/ RS232 female

pH Potential (mV)
pH-electrode

In/Out 1 In/Out 2 Rec. Out Out

Titrino/ PC

°C
40 60
20 80

0 100

Connecting cable Mütek Analytic GmbH S-Nr. 42-2001

IND 2 connector
D-82211 Herrsching
Fax: (0049) 8152 4374 U: 220/240 V~

PCD/ Titrino for I: 250 mA

Muetek Analytic Inc . U: 110/117 V~

adapter E - F
USA-Marietta, GA 30067
Fax: (001) 770 955 2383 I: 500 mA

pH value
f: 50/60 Hz
Made in German y S: 30 VA

D pH mV/pH

PC/ printer

PC parallel interface Printer

Fig. 4-9 Rear view of configuration PCD 03 pH/ Titrino 702

PCD 03/ PCD 03 pH Operation manual 25

© BTG Mütek GmbH, December 2003
IV. Installation

4.5.2.3 Manual operation 4.5.3 Calibration of pH-electrode of the PCD 03

To operate the PCD 03/ PCD 03 pH manually, use a pH
measuring pipette to add the titrant dropwise into the Two buffer solutions are needed for calibration: one
measuring cell. The point of zero charge is attained if of about pH 7 and another one in the acid or alkaline
the streaming current is at 0 mV, which is indicated range, such as pH 4 or pH 9. The buffers used for
by the LED. In the majority of cases, titration will be calibration should correspond to the pH range of the
fast at the beginning and slow down towards the end. samples.
• Set temperature compensation switch (3, Fig. 3-
2) to the measuring temperature.
• Immerse pH-electrode (Fig. 3-5) in pH 7 buffer.
Potential (mV)
on
• Wait until signal on pH display (13, Fig. 3-1) sta-
cationic
bilizes.
Motor - 15 79
off
anionic
• Turn ∆pH control (5, Fig. 3-2) to adjust display to
1
pH 7.
• Rinse pH-electrode (Fig. 3-5) with deionized
water and immerse in pH 4 buffer.
Mütek PCD 03 • Wait until signal on pH display (13, Fig. 3-2) sta-
Particle Charge Detector
Power
bilizes. Turn mV/pH control (4, Fig. 3-2) to adjust
to pH 4.
• Check calibration with suitable buffer solutions
and repeat the calibration routine, if necessary.
Hint
If the PCD 03 pH is operated with the Titrino plus
software (see 4.5.2.2, page 25), both the Titrino and
the PCD 03 pH have to be calibrated. (Please refer
to the Instruction Manual for the Titrino).

Fig. 4-10 Manual operation

Designation
1 Measuring pipette

Titrant consumption can be read off the measuring

pipette.
In case of polyelectrolyte titration this information is
required to calculate the charge quantity.
If an acid/ base titration is performed with the PCD
03 pH, the pH display indicates the isoelectric point
(at 0 mV streaming current).
Manual operation is particularly convenient for quick
pretests or onsite measurements.

26 PCD 03/ PCD 03 pH Operation manual

© BTG Mütek GmbH, December 2003
 IV. Installation

4.5.4 Titrant solutions 4.5.6 Cleaning solution

Titrants must always carry the opposite charge of the
Warning
sample. Optimum sample concentration should be
selected (dilution) to keep titrant consumption bet- Acetone and cleaning solution are highly flammable.
ween 0.2 and 10 ml. Warning
Polyelectrolytes Pay particular attention to the safety rules in chapter
BTG Mütek GmbH recommends the use of Pes-Na 1.5 "General safety directions".
and poly-DADMAC as standard reagents, because
their charge densities are practically pH-indepen- The cleaning solution for manual cleaning is produ-
dent. ced from 50 parts sodium bromide (NaBr) and 50
parts acetone plus 125 parts water.
Pes-Na
• Prepare the above proportions.
Pes-Na (polyethene sodium sulfonate) is an anionic • Fill water into a suitable vessel.
polyelectrolyte. It serves as a calibrating substance • Add sodium bromide and dissolve.
to determine the content of other titrants.
Hint
Poly-Dadmac
Take care that sodium bromide is dissolved comple-
Polydimethyl diallyl ammonium chloride is a cationic tely.
polyelectrolyte with molecular weight of 107000 g/
• Add acetone and mix carefully.
mol.
For technical reasons, the activity of poly-DADMAC Information
is subject to minor variation between the individual Selection of an optimum detergent depends on the
batches. Before using a fresh solution, use Pes-Na sample concerned.
to conduct a factor determination. For 10 ml Pes-Na
0.001 N, the poly-DADMAC 0.001 N consumption is 4.5.7 Buffer solutions for pH calibration
usually between 9.5 and 10 ml.
Commercial buffer solutions may be used for pH cali-
Other polyelectrolytes bration.
The following additional titrants are in frequent use
today:
- Cationic: methyl glycol chitosane (MGCH)
‘Hymin’
- Anionic: potassium polyvinyl sulfate (KPVS)
dodecyl sulfate sodium salt (SDS)

4.5.5 Acids/bases
For anionic samples, diluted acids are used as a
titrant and diluted bases for cationic samples. Hydro-
chloric acid, sulfuric acid and sodium hydroxide solu-
tion have proven useful in this context and are
normally applied in concentrations of 0.1 - 0.01 mol/l.

PCD 03/ PCD 03 pH Operation manual 27

© BTG Mütek GmbH, December 2003
IV. Installation

28 PCD 03/ PCD 03 pH Operation manual

© BTG Mütek GmbH, December 2003
 V. Operation

V. Operation

5.1 Safety rules

Make sure to follow the "Basic safety instructions", 5.4.2 Centrifugation
page 5, before commissioning the PCD 03/ PCD 03 It is very important that centrifuging times are identi-
pH. cal for all samples.

5.2 Personnel requirements 5.4.3 Screening

On-site preparations may be made by qualified and
skilled personnel. For installation of the PCD 03/
PCD 03 pH, call in a technician of BTG Mütek GmbH
or an authorized agent.
5.3 Preparation
• Setting up the connections in accordance with
"Installation environment", page 19
• Clean the measuring cell in accordance with
"Cleaning the measuring cell", page 37
In the majority of cases, it will be sufficient to sepa-
rate long fibres and larger particles by a coarse nylon
screen. However, the formation of a filter cake should
be avoided.
Quick and reproducible sampling is achieved in the
following way: replace the bottom of a plastic cup by
a nylon screen. Immerse the cup into the sample and
remove the screened supernatant liquid with a
pipette.

5.4 Sample preparation

For stock systems including both colloidally dissolved
material and solid particles, different ways of sample
preparation will give different data on the charge con-
ditions prevailing in a sample Fig. 4-2, page 22.
Generally speaking, results are only directly compa-
rable if the samples are prepared in an identical man-
ner. Test results obtained for samples of the same
kind but which were treated by different methods
may yield additional information about, e.g., the
charge conditions of solids.
In each case, quantitative sampling must be ensured
which gives reproducible values. 3

5.4.1 Filtration
1
To separate larger solid particles from the sample,
2
samples are usually filtered with a whiteband filter.
This may falsify results because polyelectrolytes tend
to be adsorbed at the filter paper. We therefore stron-
Fig. 5-1 Screening of samples
gly advise against using paper filters.
Ceramic filters do not normally cause any problems.
Designations
1 BTG Mütek screen for filtrating fiber suspension
(e.g. nylon screen of 300 µm mesh)
2 Original sample e.g. thick stock, coating broke
3 Rising measurable sample

PCD 03/ PCD 03 pH Operation manual 29

© BTG Mütek GmbH, December 2003
V. Operation

5.4.4 Back titration

This method of sample preparation suggests itself in Result V1: Consumed Pes-Na 4.83 ml
the following cases:
- Due to their structure, the samples cannot be In addition, titrate 10 ml of fresh poly-DADMAC solu-
placed into the cell directly, such as if the charge tion with Pes-Na up to the point of zero charge.
level of larger chemical pulp fibres is to be quan-
Result V2: Consumed Pes-Na 10.68 ml
titatively determined
- Reaction of test substance with the titrant is too
slow so that direct titration would be useless Calculation of charge amount q:
(V2 - V1) * c
5.4.4.1 Example of back titration

Type of sample m
The total charge of an anionic solid sample contai- V2 - V1: Difference between the charges of the
ning a large number of long fibres and other solid fresh poly-DADMAC and the reacted poly-
particles is to be determined. In view of the high DADMAC indicates the charge amount
solids content or excessive particle sizes, direct neutralized in the sample.
measurement in the cell is not feasible. This is where c: Concentration of the titrant, i.e. here 0.001
back titration is recommended. eq/l.
m: 2 g of the original sample were used for tit-
Procedure ration. (20 g were filled up to 100 g, of
Take 20 g of the anionic sample to be measured and which 10 g were used for titration).
fill up to 100 g with poly-DADMAC 0.001 N. Stir this
mixture for approx. 2 hours with a magnetic stirrer. (0.01068 - 0.00483) [l] * 0.001 [eq/l]
During this period, the cationic poly-DADMAC will q=
neutralize all anionic charges of the sample. Since 2 [g]
there is an excess amount of poly-DAMAC, a resi-
dual cationic charge will remain in the sample. After q = 2.925 * 10-6 [eq/g]
the reaction period, screen out the solids of the mix-
ture. Decant 10 ml of the solution into the measuring Result: the charge level of the sample under test is
cell and titrate up to the point of zero charge with 2.925 µeq/g.
Pes-Na 0.001 N.

Method SCREENING CENTRIFUGING BACK TITRATION

Sample preparation If possible, the complete
sample is measured or the
long fibre fraction is separa-
ted by screening, e.g
Separation of the solids in
the sample by centrifuging
An excessive amount of
polyelektrolyte is added to
the sample. After a defined
period the solids are separa-
ted by centrifuging

Sample type Total stock, very fine fibers Colloidally dissolved system Colloidally dissolved system
fillers, long fibers

Result Total charge (fines, fillers Charge of the colloidally Fibre charge and charge of
colloidally, dissolved matter) dissolved system the colloidally dissolved
(= anionic trash) system

Fig. 5-2 Sample preparation methods

30 PCD 03/ PCD 03 pH Operation manual

© BTG Mütek GmbH, December 2003
 V. Operation

5.5 Measuring with the PCD 03/ PCD 03 pH

• Fill a sample into the measuring cell (8, Fig. 3-1). • Insert the burette tip into the opening of the tip
holder (4, Fig. 3-1) and fasten with the bolt.
Information
Take care to keep both gold electrodes (2, Fig. 3-3) Hint
covered with liquid. The minimum sample volume Take care to ensure that every single drop of the
should be 10 ml. To precisely dose the sample quan- titrant reaches the sample. The burette tip may come
tity for charge quantity calculation, weigh in the into contact with the interior wall of the measuring
sample or use a measuring pipette. cell, but do not touch the piston or the electrodes with
Good reproducibility of results can only be achieved the burette tip, because this may result in strong
if the sample is appropriately homogenized for quan- potential fluctuation.
titative sampling. To exactly position the burette tip, carefully bend the
• Position piston ring (3, Fig. 3-3) on the piston (4, holder into a suitable position.
Fig. 3-3) of the type 1 standard mesuring cell. • Start titration (manual or automatic with titrator
system)
Information
The piston ring prevents spurting of the sample
material. Position the ring as far down as possible. A
slurping noise during measurement indicates that air
enters the narrow gap. This may lead to considerable
signal variation and to spurting of sample material.
Push the piston ring further down to eliminate the
problem.
Should the ring fit too loosely, adjust by bending it
slightly.
• Insert piston (4, Fig. 3-3) into the measuring cell
(1, Fig. 3-3).
• Displace measuring cell (8, Fig. 3-1) along the
guide (6, Fig. 3-1) to the rear up to the stop.
- The electrodes should face towards the rear
• Pull piston (9, Fig. 3-1) upward and turn clock-
wise to lock it in the bayonet catch (10, Fig. 3-1).
- The measuring cell is correctly positioned if
the piston can be hooked in the bayonet
catch easily and without canting
Only for PCD 03 pH:
• Insert pH-electrode
Hint
Position the pH-electrode in such a manner that
titrant dripping from the burette does not come
into direct contact with the electrode.
• Turn on the motor (2, Fig. 3-1).
- The streaming current will be indicated in the
display (12, Fig. 3-1)
- LEDs (1 and 3, Fig. 3-1) indicate the signs of
the charges
• Wait for about 30 seconds until the potential sig-
nal has stabilized.
- Precise titration is only possible if the strea-
ming current is stable

PCD 03/ PCD 03 pH Operation manual 31

© BTG Mütek GmbH, December 2003
V. Operation

5.6 Titration curves

If a titrator with printer is used in PCD 03/ PCD 03 pH 5.6.2 Solid particles
measurements, a titration curve may be printed out. Titration curve for solid particles suspended in water.
This curve gives valuable information on the kind of
The titration curve is nearly straight, because all solid
response of the stock system under test.
particles make a contribution to the streaming cur-
Low-concentration solutions are most likely to yield a rent.
titration curve that is easily interpreted.
Optionally, three different kinds of sample can be 2000
measured:

5.6.1 Colloidally dissolved particles

1000
Titration curve for a colloidally dissolved sample. At
the beginning of the titration process, the streaming
current remains practically unchanged, because non-

mV
adsorbed colloids are neutralized which do not cont- 0
ribute to the streaming current.
Subsequently, the curve shows a sharp drop, which
is indicative of adsorbed charge carriers being elimi-
nated in the course of titration. -1000
0 2 4 6 8 10
titrant ml
2000
Fig. 5-4 Titration curve of a solid particle

1000 5.6.3 Heterogeneous stock systems

Titration curve for heterogeneous systems (colloids,
dissolved substances, solid particles, fibres, etc.).
mV

0 The curve drops sharply, but flattens out towards the

end of titration.
Levelling-off around the point of zero charge may be
caused by titrant penetrating into the fibres.
-1000
0 2 4 6 8 10
2000
titrant ml

Fig. 5-3 Titration curve of a colloidally dissolved par-

ticle 1000
mV

-1000
0 2 4 6 8 10
titrant ml

Fig. 5-5 Titration curve of a heterogeneous stock

system

32 PCD 03/ PCD 03 pH Operation manual

© BTG Mütek GmbH, December 2003
 V. Operation

5.6.4 Selection of titration rate

The titration rate may influence measuring results
and should in each case be selected according to the
reaction time between titrant and sample.
If the two substances are very slow to react, the
potential will decrease drastically as titrant is added.
The observer may gain the impression that the point
of zero charge is reached. The potential rises again
when reaction actually takes place.
If pure polyelectrolyte solutions are titrated, titrant
dosages should not exceed some 300 µl per minute.
If the sample includes layered structures or porous
particles (e.g. clay, ion exchangers etc.), the ideal tit-
ration rate will be far lower: the usually large molecu-
les of the titrant have to penetrate the layers of the
sample material before they effect charge neutraliza-
tion.
An excessive titration rate is reflected in an irregular
curve and a drop in potential after titration is finished.
If an end-point titrator is used, dynamic titration can
be realized. In this case, the titrator matches additi-
ons and addition rates to the changes in potential,
thus taking the peculiarities of the sample into
account.
If pH-dependent potential characteristics are to be
studied, a response time of the pH-electrode has to
be taken into account which is at least 10 seconds.
If the results of several titrations are to be compared,
it will be indispensable to use an identical titration
rate and configuration of the automatic titrator for all
tests.

Information
Excessive titration periods may cause changes to
fresh production samples.

PCD 03/ PCD 03 pH Operation manual 33

© BTG Mütek GmbH, December 2003
V. Operation

34 PCD 03/ PCD 03 pH Operation manual

© BTG Mütek GmbH, December 2003
 VI. Diagnostics and troubleshooting

VI. Diagnostics and troubleshooting

6.1 Safety rules 6.2 Personnel requirements

In the case of errors not listed in the table below, dis- Troubleshooting may only be performed by qualified
connect the PCD 03/ PCD 03 pH and mark as and skilled personnel.
"defective". Contact BTG Mütek GmbH to ensure
quick remedial action.

6.3 Tables of system faults

Symptom
Heavy fluctuations of strea-
ming current after sample is
filled in
Potential reverses after rea-
ching the end point
At the start of titration,
potential increases instead
of decreasing
Potential remains essenti-
ally unchanged during titra-
tion
Sign of indicated potential
not in conformity with
sample specification
pH-electrode can not be
calibrated
Probable cause
- Excessive electrical conductivity
of the sample
- Sample amount in the cell too
small
- High solids in the sample
- Piston ring incorrectly positioned
- Very slow reaction between titrant
and sample
- Wrong titrant
- Sample concentration too high,
titrant concentration too low
- Concentration of sample very high
- Sample charge depends on pH
- Excessive viscosity
- Soiled or defective
Corrective action
• Dilute the sample.
• Weigh in once again or use
pipette.
• Dilute the sample or
• Centrifuge screen to remove
coarse particles.
• Push piston ring further down.
• Titrate more slowly or
• Perform back titration.
• Check sample for homogeneity.
• Select titrant with opposite charge
to that of sample.
• Dilute the sample.
• Dilute the sample or
• Use a higher strength titrant.
• Check pH dependence of sample.
• Dilute the sample.
• Clean or replace pH-electrode.

PCD 03/ PCD 03 pH Operation manual 35

© BTG Mütek GmbH, December 2003
VI. Diagnostics and troubleshooting

36 PCD 03/ PCD 03 pH Operation manual

© BTG Mütek GmbH, December 2003

VII. Maintenance
7.1 Personnel requirements
Maintenance shall exclusively be carried out by qua-
lified and skilled personnel.
7.2 Cleaning the measuring cell
The measuring cell has to be always cleaned with
water and cleaning solution.
After each measurement, go through the following
cleaning routine:
• Empty the measuring cell (9, Fig. 3-1).
• Rinse the measuring cell with tap water.
• Clean the measuring cell (9, Fig. 3-1) and the
piston (10, Fig. 3-1) with cleaning brush and
cleaning solution.
• Rinse both with de-ionized water.
• Empty the measuring cell.
• Dry with clean paper cloth on the outside of the
measuring cell but not the piston.
Hint
Failure to clean the cell after each measurement will
lead to measuring errors and prevent reproducibility
of results.
Hint
To avoid deposits in the measuring cell and at the
piston, fill the cell with cleaning solution and leave
overnight.
Caution
A measuring cell filled with solvent must be removed
from the measuring chamber of the PCD, since
otherwise the drive might be damaged.
Warning
Before each measurement, clean measuring cell and
piston with water as described above, since solvent
residues will falsify measured results.
If different samples are measured and maximum
measuring precision is required, rinse with cleaning
solution first before going through the above cleaning
routine.
PCD 03/ PCD 03 pH Operation manual
© BTG Mütek GmbH, December 2003
VII. Maintenance
7.3 Functional test
To avoid measuring errors that are caused by faulty
operation of the unit or soiling of the cell, functional
testing can be performed by different methods.
7.3.1 Basic test of PCD without cell
• Turn on power switch (8, Fig. 3-2).
- LED power (12, Fig. 3-1) will come on
• Switch on piston drive (2, Fig. 3-1).
- Digital display (14, Fig. 3-1) streaming current
will indicate 0 mV
- Depending on the sign of the streaming cur-
rent signal, LED cationic (1, Fig. 3-1) or LED
anionic (3, Fig. 3-1) will come on
7.3.2 Standard titration
Fill 10 ml of the anionic standard Pes-Na into the cell
and titrate with poly-DADMAC 0.001 N up to the
point of zero charge. If the result obtained deviates
from the expected value (9.6 ml - 10.0 ml), clean the
cell thoroughly once more (see chapter 7.2, "Clea-
ning the measuring cell").
Information
This check should be performed at least once a
week. The polyelectrolyte concentration should be
continuously monitored.
7.3.3 Check of streaming current
If a freshly cleaned cell is filled with 10 ml of anionic
standard Pes-Na 0.001 N repeatedly in succession,
the streaming current values measured should be
roughly identical. Depending on the equipment, the
potential is generally in the range of -1000 to -1600
mV. If the cell is used very frequently, this value will
diminish over time due to wear. This does not, howe-
ver, affect titration results. If the streaming current is
suddenly measured to be some 100 mV below the
previous result, the cell is presumably soiled. To
avoid measuring errors, clean the cell thoroughly
once again (see chapter 7.2, "Cleaning the measu-
ring cell").
37
VII. Maintenance

7.3.4 Electrostatic charging of the cell

If it is doubtful if the PCD receives a signal from the
measuring cell, such as when the signal remains stri-
kingly stable during the titration process, the function
should be verified as follows: switch on the motor
and rub your hand quickly up and down on the out-
side of the cell. This will cause the signal to bounce.
If no such reaction is observed although the motor is
running, there is probably an electronics failure. In
this case please contact the BTG Mütek GmbH ser-
vice or your local BTG Mütek GmbH agency.

7.3.5 Functional test of pH-electrode

Before starting a test series, measure a buffer solu-
tion with the pH-electrode.
The electrode should respond within 10 - 30
seconds. If measuring performance is inadequate
and cannot be improved by cleaning and repeated
calibration, replace the electrode.

38 PCD 03/ PCD 03 pH Operation manual

© BTG Mütek GmbH, December 2003
 VIII. Shutting down the system, storage and disposal

VIII. Shutting down the system, storage and disposal

8.1 Safety rules 8.4 Storage

Please adhere to applicable safety rules when put- The PCD 03/ PCD 03 pH should be stored in a pro-
ting the system out of operation. tected place inside a building. Do not keep outdoors.

8.2 Personnel requirements 8.5 Disposal

The system should only be put out of operation by
8.5.1 Official regulations
qualified and skilled personnel.
Be sure to meet the local regulations governing the
disposal fo the PCD 03/ PCD 03 pH.
8.3 Shutting down the system
To shut down the PCD 03/ PCD 03 pH, proceed as
follows:
• Switch off the PCD 03/ PCD 03 pH.
• Disconnect the PCD 03/ PCD 03 pH from its
main supply.
• Disconnect the PCD 03/ PCD 03 pH from PCD-
two titrator.
• Clean the measuring cell in accordance with
chapter 7.2, "Cleaning the measuring cell", page
37.
For PCD 03 pH only:
• Clean the pH-electrode with 3 M KCl solution.
• The diaphragm of the pH-electrode (2, Fig. 3-5)
must not get dry. Fill the cover of the pH-elec-
trode with 3 M KCl solution and keep the pH-
electrode in this cover in times of no usage.

PCD 03/ PCD 03 pH Operation manual 39

© BTG Mütek GmbH, December 2003
VIII. Shutting down the system, storage and disposal

40 PCD 03/ PCD 03 pH Operation manual

© BTG Mütek GmbH, December 2003
 IX. Part lists

IX. Part lists

9.1 Components

Pos. Designation Part-No.

1 Aluminium carrying case, suitable for air transport 400 - 09077
2 Standard measuring cell type 1 with gold electrodes for routine measure- 400 - 10318
ments; sample volume min. 10 ml / max. 30 ml
3 Standard piston type 1 with 0.1 mm deep grooves for samples of normal vis- 400 - 09120
cosity
4 Special piston type 1 with 0.5 mm deep grooves for high-solids and highly vis- 400 - 09122
cous samples
5 Teflon ring for piston type 1 400 - 10133
6 Precision measuring cell type 2 with platinum electrodes giving high reprodu- 400 - 09119
cibility of the mV signal, such as for zeta potential assessments and for critical
samples with high conductivity, highly sedimenting particles;
sample volume min. 10 ml / maximum 60 ml
7 Precision piston type 2 400 - 09121
8 Connecting cable between PCD and titrator (BNC/A2) for transmission of 570 - 02484
streaming current and pH
9 Cable BNC and banana plug connecting recorder and PCD 420 - 02485
10 Burette tip holder 410 - 09117
11 Piston brush for cleaning of measuring cells, 20 mm dia. 400 - 10158
12 100 ml plastic bottles with caps 400 - 10161
13 Screen for filtrating fiber suspensions with 300 µm mesh 400 - 18977
14 Precision pipette, 2 - 10 ml 552 - 18772
15 Plastic tips for precision pipette, 2 - 10 ml 552 - 18773
16 pH-electrode, plexiglass shaft, ceramic diaphragm, gel filling, holder 420 - 09115
17 pH-electrode glass shaft, glass section diaphragm, gel filling holder 420 - 09133

PCD 03/ PCD 03 pH Operation manual 41

© BTG Mütek GmbH, December 2003
IX. Part lists

9.2 Consumable goods

Pos. Designation Remarks Part-No.

1 Polyelectrolyte anionic, 0.001 N, Standard solution, ready for use 811 - 10216
1000 ml, PES-Na
2 Polyelectrolyte cationic, 0.001 N, Standard solution, ready for use 811 - 10217
1000 ml, poly-DADMAC
3 Polyelectrolyte anionic, PES-Na, Reagent-grade, approximately 99.5 % 812 - 10219
powder dry content, MW 19100 g/mol
4 Polyelectrolyte concentrated, anio- Approximately 51 % solids, 821 - 10220
nic, PES-Na, liquid MW 21800 g/mol
5 Polyelectrolyte concentrated, catio- Approximately 41 % solids, 812 - 10218
nic, poly-DADMAC, liquid MW 107000 g/mol
6 Acetone Commercial quality
7 Sodium bromide (NaBr) Commercial quality
8 3 M KCl-solution Commercial quality
9 Cleaning solution for manual clea- To be prepared (see 4.5.6 "Cleaning
ning solution")

9.3 Work safety

Pos. Designation Disposal Hazard

3/4 Goggles Keep away from open wounds (anticoagulant), Incineration n.a.
rinse thoroughly with water after contact with open
wounds
5 Gloves, gog- Rinse thoroughly with water after contact with skin Landfilling or n.a.
gles or eyes incineration
6 Gloves, gog- Rinse with water after skin contact. In case of eye Special waste easily flam-
gles contact rinse with water immediately and consult mable
an oculist
7 Gloves, gog- Rinse thoroughly with water after contact with skin Special waste n.a.
gles or eyes
8 Gloves, gog- Rinse with water after skin contact. In case of eye Special waste easily flam-
gles contact rinse with water immediately and consult mable
an oculist
Chapter 9.3 is an excerpt from DIN Safety Sheets.
Cons. Nos. 3, 4, 5, 6, 7, 8 above refer to the con-
sumables listed under chapter 9.2 above.

42 PCD 03/ PCD 03 pH Operation manual

© BTG Mütek GmbH, December 2003
BTG Mütek GmbH
Arzbergerstrasse 10
D-82211 Herrsching
phone +49 8152 9312-0
fax +49 8152 4374
email info-muetek@btg-group.com
Internet www.wetendtechnology.com