Measurement Process

Figure 4.17: The Experimental Setup screen. Fill in identifying information on

the experiment.

Name is the identifying name of the measurement, used to help locate the
specific experiment later.
User is the person conducting the measurement.
Date records the time and date for future reference. It cannot be altered.

By selecting a Resonator (a quartz crystal) all of the required fields are

automatically filled. If a new Resonator is added fill in the relevant data about
it into the Database so as to avoid having to fill them in manually each time
an experiment is run. Information in the Liquid/Gas and the Addition fields
are for use when analysing the data as well as for reference.

Once all of the required information is filled out press Start to continue.

4.3.3 Software Control of the Measurement

When the Experimental Setup has been completed, two windows will open,
the Measurement Controls window and the Sweep Graph window. The
Sweep Graph plots impedance and phase against frequency, and once the
experiment is begun a Graph of frequency change against time will open on
top of it. If harmonics are selected they will all be shown on separate graphs.
The Measurement Controls window controls the measurement chamber,
how it resonates and what data is sent back to the computer. In most cases
very little needs to be done in this screen except choosing all of the harmonics
and pressing Start.

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QCM-Z500 Manual

Figure 4.18: The Measurement Controls screen. Select measurement setup

and press Start to begin an experiment.

There is only one measuring Method to choose from by default. This method,
Automatic, sets the parameters for the measurements (that is, the Resonator,
Search and Sweep Parameters) to fixed values that have been found to
work in most cases for measurements involving a gas, a liquid of either high
or low density or soft films.

The Resonator, Search and Sweep Parameters cannot be changed when

using the Automatic method. To change the parameters of the experiment
create a new Method and fill in the parameters as wanted in the Database.
From the Edit menu select Database to access it, please see section 5.2 Edit
Database for details.

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 Measurement Process

What must be determined before the measurement are the Recording

Options and the Included harmonics (overtones). The harmonics are
selected by checking the respective box, the measurement data will be more
complete and easier to analyse with more harmonics so it is advisable that
they are all chosen.

The Measurement Time should be longer than the experiment is expected to

last so that all of the interesting phenomenon will be recorded. With
AutoSave checked the data will automatically be recorded, if unchecked
begin and end recording with the Rec On and Rec Off butons. The Rec
buttons will only be active if AutoSave is not selected.

The software side of beginning the experiment is complete, it is now time to

ready the chamber for the experiment if this has not yet been finished.

4.3.4 The Measurement Process

Check now that all of the steps in 4.2 Preliminaries have been completed.
This means checking that

 All of the cables are connected and the electronics unit is on.
 If a temperature control unit is present make sure that it is connected to
the measuring chamber and to the computer directly (and not to the
main electronics unit).
 The outlet tubes have a waste beaker under them so that the waste
liquid is collected and can be disposed of appropriately.
 The temperature loop is filled with the background liquid, and if a
Temperature Control Unit is available then it is set to the target
temperature.
When ready begin the experiment by pressing Start. The Sweep Graph
should now activate and scan for the capacitance of each harmonic
separately. Once that is finished the Sweep Graph is replaced by the normal
Graph which by default shows change in frequency against time.

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QCM-Z500 Manual

Figure 4.19: Graph of change in frequency against time for all harmonics.

Once the frequencies have stabilised it is time to introduce the actual sample
into the chamber. Follow these steps to do so

 Empty the reservoir and open the Bypass. Let the bypass drain the
background liquid.

 Pour the sample liquid into the reservoir. When a few milliliters of the
sample have come out from the bypass outlet switch the valve to Stop
and wait a few minutes to ensure thermal equilibrium.

 Turn the valve to Chamber. Allow a few milliliters to pass through the
chamber to flush it and then put the valve on Stop.

 Again wait for the frequencies to stabilise. Flush with the background
liquid another time or introduce the next sample according to what is
being measured. Press Stop when finished, obtaining data for the
measurement is now complete.

The measurement can be stopped at any time before the chosen

Measurement Time has been reached by pressing Stop. This action will
bring up a query of whether to keep the experiment data or not. If the
measurement data collected so far should be stored in the database for
further analysis press Yes, but if the measurement data is not useful (for

44
 Measurement Process

example if waiting for frequencies to stabilse before the actual experiment)

then press No.

4.3.5 Useful Tips

Whenever operating the valve the some key points about the working of the
tubing should be kept in mind. When the sample is a liquid, it is important that
no air bubbles reach the chamber. Thus whenever something is to be
introduced to the chamber it must run through the bypass loop first. Also
whenever anything is flowing out of the reservoir to either the chamber or the
bypass checks should be kept on the level of the liquid. It should always have
a few milliliters in reserve.

When changing liquids first empty the reservoir, set the valve to Bypass and
allow it to empty. Then flush the bypass loop with the new liquid by filling the
reservoir and allowing the liquid to flow down the bypass for several milliliters.
It might be necessary to allow more liquid to flow down to clean the tubing.

Whenever changing from the Bypass to the Chamber position or visa versa
always go by Stop.

The volume of liquid in the bypass loop is slightly above 2 ml, so by careful
liquid handling it is possible to exchange the liquid in the actual measuring
chamber with 2 ml of the sample liquid. This can be done by letting a small
amount of air into the bypass loop and replacing the actual sample liquid with
a less expensive liquid like water, and then with the help of measuring the
amount of this substitute water make sure that the air bubble between the
actual sample liquid and the substitute water never reaches the actual
measuring chamber. This method however requires careful measuring and
concentration to be successful.

The Sample Interval in the Recording options box can be reduced to 0.2
seconds i.e. 5 data points can be collected per second. However, this will
increase the noise level of the measured signal and should not be used if
there is not a real need for fast measurements.

To check that everything is working correctly before starting an actual

measurement it is possible to check the status of the QCM. Start a new
experiment but do not let any liquid into the chamber, and check what
resistance is measured across the crystal. The standard 5 MHz gold plated
quartz crystal when clean and dry has a resistance of about 20 Ohm. Let
water into the chamber and check the change in frequency. The change from
air to water should be about -700 Hz. If either of these figures are off then
there might be a problem with the cleanliness of the crystal, the water or some
part of the QCM.

To view other graphs during the measurement choose different parameters

for the x- and y-axis from the drop-down menu at the top of the Graph
window. An additional curve can be plotted on the same graph by choosing a
y2-axis parameter, click on the respective button to change the scale.

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QCM-Z500 Manual

46
4.4. Window Measurement Chamber - Overview
The window measurement chamber is an alternative to the axial flow
measurement chamber. The principal concept of the window measurement
chamber is the same as that of the axial flow one, that is the sample flows
through a chamber where the crystal is housed. However, the liquid flow in
the window measurement chamber is parallel flow, while the standard
measuring chamber has a axial flow with a stagnant point. The advantages of
the window measurement chamber are the smaller size, which means that
smaller sample volumes are required, and a window directly to the chamber
which allows the user to view what is actually happening in the measuring
chamber. It is also possible to use a microscope to observe the microscopic
changes as a sample is introduced.

Image 1: The window measurement chamber.

4.5. Window Chamber - Physical Description

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QCM-Z500 Manual

The window measurement chamber has two modules. The upper module
contains the main body of the measurement chamber, the chamber itself, and
the valve for controlling the flow direction of the sample whilst the lower
module consists of the support platform for the measurement chamber, the
temperature control assembly with peltier, heat sink and fan, and the
electronics with connecting electrodes.

Image 2: The upper module of the window measurement chamber.

1) Chamber outlet 5) Finger screw for cover

attachment
2) Temperature loop outlet 6) Crystal holder / Measuring
chamber
3) 3-way valve for liquid flow 7) Upper module cover
direction control
4) Sample inlet

The quartz crystal is placed in the measuring chamber by turning the upper
module up-side-down having the 3-way valve in the lower right hand corner,
then placing a small O-ring in the crystal holder/measuring chamber, where
after the crystal is placed in the crystal holder/measuring chamber so that the
larger electrode is downwards while the smaller keyhole electrode is upwards
and points in the opposite direction than the chamber outlet tubing i.e. so that
the straight cut of the crystal is oriented against the front edge of the upper

48
 Window Chamber Introduction

module. This is of utmost importance as the larger electrode which is in

contact with the sample liquid phase has to be grounded and only this
orientation of the crystal will ensure this, otherwise the measurement
can not be performed. Hereafter, the measuring chamber is sealed from the
crystal side by using a spring loaded bajonett locking piece so that the two
holes for the lower module contacting pins is aligned horizontally.

Image 3: Placing the quartz crystal into the upper module of the window
measurement chamber.

1) Small O-ring 2) Quartz crystal

3) Spring loaded bajonett locking
piece

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QCM-Z500 Manual

Image 4: The lower module of the window measurement chamber.

1) Connection to main electronics 6) Fan with heat sink

unit (3-pin D-connector)
2) Contacting pins for crystal
electrodes
3) Grounding connection for
electrochemical measurements
4) Socket for temperature control
5) Socket for fan connection from
temperature control unit
7) Peltier element for temperature
control
8) Guiding positioning poles for
upper module
9) Metal body for heat transfer and
electronics

The upper and lower modules of the window measuring chamber is attached
to each other with a finger screw in order to ensure a tight connection
between the modules for optimum temperature control of the whole window
chamber measuring module. The measuring chamber is sealed to form an
enclosed measuring chamber by placing a large O-ring in the groove of the
crystal holder/measuring chamber, placing the window to seal the chamber,
and tightening the fastening nut to keep the quartz/plastic window in place.

50
 Window Chamber Introduction

Image 5: The assembled window measuring chamber.

1) O-ring 2) Quartz/plastic window

3) Fastening nut to keep window in 4) Finger screw for attaching
place modules

The upper module and its components can easily be disassembled for
example for more through cleaning (e.g. sterilization or ultrasound bath) of the
viton tubings and the titanium crystal holder/measuring chamber. The main
body of the upper module is made of aluminum to maximize heat transfer, and
this is attached to the cover with 4 finger screws. By removing these 4 finger
screws the main body of the upper module can be removed from the cover in
order to access and release the viton tubings and crystal holder/measuring
chamber. While cleaning please check that any sample or cleaning solution
does not react with Viton from section 9. Appendix A - Chemical
Compatibility of Viton, if necessary alternative substances are available.

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QCM-Z500 Manual

Image 6:The upper module with the cover plate removed exposing the viton
tubings and titanium crystal holder/measuring chamber.

1) Finger screws for cover

2) Viton tubings
attachment
3) Titanium crystal
4) 3-position valve
holder/measuring chamber

4.5.1 The Valve

The sample fluid flows through the 3-position valve into the measurement
chamber via a viton tube. The viton tube loops around in the aluminium main
body of the upper module to ensure that the liquid is appropriately
thermostated before entering above the crystal in the measuring chamber. By
using the Bypass loop there is also a possibility to exchange sample liquid
and pre-temperaturize this without interfering or mixing with the sample liquid

52
 Window Chamber Introduction

in the measuring chamber before introducing a new sample liquid into the
measuring chamber. The flow direction of the sample liquid from the sample
reservoir is controlled by the 3-position valve, connecting the sample
reservoir, the bypass loop and the measuring chamber. Which parts are
connected are defined by the position of the valve marker, and are detailed
below.

BP Sample liquid flow through the Bypass (Temperature) loop from

the sample reservoir
CH Sample liquid flow into the Measuring chamber from the Bypass
(Temperature) loop
STOP No flow of sample liquid

The recommended procedure in operating the valve either for filling the
chamber with a sample is to have the valve in the STOP position before filling
the reservoir. Fill the reservoir and then turn the marker to the BP position.
Allow a few drops to come out of the outlet of the Bypass, then turn the valve
anti-clockwise through the STOP position to the CH position. Again allow a
few drops to come out from the outlet of the measuring chamber and turn the
valve to the STOP position again.

To clean the tubing, set the 3-position valve to BP or CH position and pour the
cleaning solution into the sample reservoir. The cleaning solution will then
flow either through the Bypass or the Measuring chamber, be sure to do so
above a sink or so that the chamber and the bypass outlets are above a
beaker.

4.5.2 Temperature Control

A Peltier element connects the main aluminum body of the lower module to
the heat sink, and it can be used to control the temperature of the
measurement chamber if an optional Temperature Control Unit is available.
Plug the power cable of the TCU to a mains supply and connect the red cable
from the TCU to the side of the lower module in order to measure and control
the temperature, and the black cable from the TCU to the back of the lower
module in order to activate the fan for the heat sink for optimum performance
of the whole temperature control assembly.

Whenever using temperature control in an experiment allow enough time for

the measurement chamber to reach an equilibrium temperature before
starting a new measurement. About 30 minutes should be sufficient in most
cases.

53
4.6 Cleaning the Window Measurement
Chamber
4.6.1 Disassembly

The first step in cleaning the window measurement chamber is to separate

the upper module from the lower module by removing the finger screw holding
the modules together (see Image 5, Section 9.2.). Remove the crystal and
small O-ring by releasing the spring loaded bajonett locking piece (See Image
3, Section 9.2.) and pick out the quartz crystal and small O-ring with tweezers.
Then, remove the quartz/plastic window and large O-ring by removing the
fastening nut on the upper module (see Image 5, Section 9.2.) and turn the
upper module up-side-down so that the quartz/plastic window falls out. If the
quartz/plastic window does not fall out, then use the tweezers to gently press
the window from the quartz crystal side (be careful not to scratch the window).

The disassembly is now complete, the following parts should have been taken
away from the upper module for cleaning:

1) Small O-ring
2) Quartz crystal
3) Large O-ring
4) Quartz/plastic window

4.6.2 Cleaning

Clean the removed parts from the upper module with a cleaning and then a
rinsing solution. Often by flushing thoroughly with pure ethanol and then
copious amount of ion-exchanged water is sufficient. Be especially attentive
with parts that will be in direct contact with the sample and the crystal, e.g. the
o-rings and the glass plate. Dry the parts by blowing with Nitrogen or leave
them drying by their own in the ambient air protected by a clean glassware for
dust. Depending on the application where the crystal has been used it might
not be possible to clean it and a new crystal is needed. The new crystal
should be cleaned as described in Section 4; Measurement Preliminaries.

Clean the Viton tubings and crystal holder/measurement chamber of the

upper module by first filling the sample reservoir with cleaning solution and
flush thoroughly through both the BP and CH liquid flow directions. Hereafter,
flush the crystal holder/measurement chamber with the same cleaning
solution. Repeat this cleaning procedure by using a rinsing solution. Repeat
the whole flushing procedure with a cleaning and rinsing solution as
appropriate. Often it is sufficient to use pure ethanol and ion-exchanged water
as the cleaning and rinsing solutions, respectively. Dry the Viton tubings and
the crystal holder/measuring chamber by blowing with Nitrogen or use an
aspirator to remove excess liquid from the tubings and the crystal
holder/measuring chamber.

54
 Window Chamber Cleaning

4.6.3 Assembly

Assemble the window measuring chamber as is described in Section 9.2.

55
4.7 Measurement Procedure
4.7.1 Overview

The software procedure with the window measurement chamber is exactly the
same as with the axial flow measurement chamber. Follow the steps in
section 3. Installation for details on setting up the computer and the
connection between the computer and the QCM. Add the window
measurement chamber to the database by selecting Edit > Database and
from there open the tab Measurement Chambers and click on the Add icon.
Type the name of the chamber, "Window," and the name of the file that will be
created to store the calibration information, for example WindowCal.txt. See
section 6. The Database for details.

4.7.2 Calibration

During the calibration of the window chamber the calibration tool is placed on
the lower module in a short circuit position, with no calibration tool and in the
known resistance position. The calibration software of the QCM-Z500 will
guide the user through these steps.

Open the Calibration Controls window and select Window as the

measurement chamber, see section 3.3 Calibration for details. Click
Calibrate. When instructed to do so place the calibration tool on the lower
module so that the short circuit position is in line with the electrodes. Push the
tool down gently to set it in place. Remove the tool when instructed to do so.
When instructed to do so place the calibration tool back on the lower module,
this time with the known resistance in line with the electrodes, and push down
gently.

56
 Window Chamber Measurement

1) Short circuit position of 2) Known resistance position of

calibration tool calibration tool
3) Spring loaded bajonett locking
piece

4.7.3 Measurement

Follow the instructions in section 4.3 Measurement Process on making a

measurement. Be sure to select the appropriate chamber in the Experimental
Setup screen i.e. Window in order to use the correct calibration file for the
window chamber.

57
5. Data Analysis and Reduction
5.1 Overview
Handling the data obtained by QCM-Z500 microbalance measurements is all
done with the separate Browse Experiments program. Use it to review data,
print reports, view and manipulate graphs or to export data to another
application. A separate Analysis program exists within the Browse
Experiments screen, the use of which is described in section 5.5 Analysis.

Figure 5.1: Use the Browse Experiments screen to locate and analyse
experiments.

5.2 Browse QCM Measurements

Open the QCM Brows Experiments by clicking on the icon on the desktop or
selecting Start > All Programs > QCM > QCMBrowse from the Start menu.

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 Data Analysis

It can also be found from the installation folder, open My Computer and
select C:\Program Files\KSV\QcmBrowse.exe

The main window is split into four boxes. The Experiments box lists all of the
experiments that are on the database and fit the search criteria inserted in the
Find Experiment box. The data sent by the QCM of the selected experiment is
shown in the Original Data box, and if an analysis is run of the experiment
then the results will be shown in the Sampled Data box.

The menu bar includes these options.

File
 Delete Experiment: deletes highlighted experiment in the Experiments
box.
 Delete Record: deletes highlighted data point in the Original Data or
Sampled Data box.
 Copy Data to Clipboard: copies the data of the highlighted experiment to
the clipboard for pasting in another program.
 Print: Opens a Print Preview screen of a report of the experiment
containing all of the vital information.
 Export/Delete data: exports or deletes selected data into a format only
recognised by QCM software. Used mainly for backup or transferring
data.
 Import data: Imports the exported data.
 Exit: Closes the Browse Experiments window

View
 Experimental Setup: Opens the Experimental Setup window of the
highlighted experiment for viewing and editing purposes.
 Graph: Opens the latest graph viewed, will be blank until some data
has been graphed.

The icons have the most commonly used functions readily available.

Print a report of the highlighted experiment.

Copy the Data of the highlighted experiment to the clipboard for
pasting in another program.
View Experimental Setup window of the highlighted experiment for
viewing and editing purposes.
View the latest Graph opened.

The axis of the graph can be chosen directly from the top of the Browse
Experiments screen using the x- and y-axis selectors. Next item down is the
Find Experiment box with search parameters that can be filled as far as
necessary. The search fields limit the experiments visible in the Experiments
box, select an experiment either by clicking on it or by scrolling with the
arrows. Once an experiment is selected the Original Data box will show the
following information about the measurement.

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QCM-Z500 Manual

Time [s]: Time at which the data point was taken.

Harmonic: The overtone number of the frequency at which the data point was
taken. 1 signifies the fundamental frequency; 3, 5 etc the 3rd, 5th etc
harmonic frequency.
Frequency: The measured frequency at the time the data point was taken.
Q: The measured Q-value at the time the data point was taken.
D: The measured dissipation value at the time the data point was taken.
R: The measured resistance value at the time the data point was taken.
Cnd: The measured conductivity value at the time the data point was taken.
X: The measured
L: The measured induction value at the time the data point was taken.
C: The measured capacitance value at the time the data point was taken.
Cp:The measured parasitic capacitance value at the time the data point was
taken.
T: The measured temperature at the time the data point was taken.

5.3 Data Graphing

The graphs of the Browse Experiments program are very versatile. The
same graph can show simultaneously two separate variables plotted against a
third variable for any number of experiments. To view the basic graph, right-
click on an experiment in the Experiments box and select Graph >
Fundamental or Graph > Nth harmonic where N is replaced by the number
of the harmonic.

Figure 5.2: Graph of change of frequency against time for the third harmonic.

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 Data Analysis

This is the same graph as is open during an experiment, plotting the change
in frequency against time. To view the frequency change of another
experiment on the same graph right-click on the experiment and select Add
to Graph > Fundamental. To view the frequency changes of all of the
harmonics of an experiment at the same time select Graph > All. To change
the variable of an axis select a new one from the top of the Browse
Experiments screen, right-click on an experiment and select Graph. Below is
an example of all of the harmonics for an experiment.

Figure 5.3: Graph of change of frequency against time for the all harmonics.

To alter the data visible the Data Manipulation menu gives the possibility to
ignore selected data points. The options are to hide data before a selected
point, after a selected point or between two selected points. Hidden data is
not considered when running an Analysis. The Data Manipulation menu is
also used to select sampled data, this is explained below. To select a point
double-click on it.

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QCM-Z500 Manual

Figure 5.4: Removing data spikes from view to simplify analysis.

After hiding all of the irrelevant spikes (caused by operating the valve) the
graph looks like this.

62