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Measurement of water sorption isotherms of materials using combined real-time humidity and microwave resonance measurements

Richard Dockree

Background
Material surface and bulk moisture content affect: Mechanical properties numerous materials such as concrete, paper, powders processing Growth/inhibition of bacteria foods, agriculture, conservation Chemical activity - pharmaceutical shelf life and potency, corrosion Thermal properties - insulations, combustion and much else. A range of techniques exist for measuring the water/moisture content of materials but the majority are time consuming/destructive. Certified reference materials (CRMs) exist for water content which can be used to calibrate/check moisture measurement instrumentation.

Water Sorption Measurement


Water sorption characteristics are determined for many materials normally by studying weight changes after a sample has been exposed to salt solutions of established relative humidities (e.g. COST 90 procedure). An established technique (dynamic vapour sorption (DVS)) uses a microbalance and controlled gas flow to measure water sorption.

Measurement Summary
The use of a microwave resonance technique has been adapted to provide non-destructive, realtime measurements of moisture transients when the material under test is subjected to flowing air of well-defined humidities. Initial exploratory work had shown that the sample holder used with the instrument could be adapted to allow flow of air through the test material.

Figure 1. Study of moisture sorption (DVS)


(Source: Surface Measurement Systems)

Figure 2. An example of a typical sorption isotherm

(source: http://www.fst.ohio-state.edu/olympiad/Laboratories/ Olymp/Lab%201_WaterActivity.htm)

The water content of a material can be plotted against its water activity or the relative humidity it was exposed to producing a sorption isotherm. Hysteresis is often observed due to different adsorption/desorption characteristics of the material.

In this project the technique was progressed, refined and used to investigate the water sorption characteristics of materials.

Measurement Principle
The instrument operates in the frequency region between 2 GHz and 3 GHz, and detects shifts in resonant frequency of the order of a megahertz when the microwave field is perturbed by water within a sample.
Microwave excitation input

Progress
Achieving minimal background water content contribution of the sample holder whilst maintaining functionality was an evolutionary process.
Gas of a known dew point in

Figure 3. Schematic diagram of microwave resonance moisture analyser

Test of MW moisture reading with varying relative humidity in different container designs
Empty container design d)

0.8 8 0.8 0.6 0.4 . 0.2 0 0 5 10

0.0085

83 73

= Filter = Sample

0.0075 0.0065 0.0055 0.0045 0.0035


Foam filter and plug in container design c) Foam filter and plug in container design d)

MW moisture MBWE rh

63 53 43 33 23 13

Resonance signal Microwave generator and signal processor Resonator


Gas out to dew point hygrometer a) Standard sample holder b) Adapted with push-fit fittings to allow air flow through material c) Inlet pushfit replaced by PTFE tubing d) Outlet pushfit replaced by PTFE swagelok connection

0.0025 17/08/2011 17/08/2011 17/08/2011 18/08/2011 18/08/2011 18/08/2011 11:02 15:50 20:38 01:26 06:14 11:02 Date and time

Figure 5. Evolution from standard container to current design

Figure 6. Effect of improving container design and moisture absorption characteristics of foam filter.

Figure 4. Effect of inserting moist material into resonator on microwave signal


(Source: Sartorius)

Changing from setup b) to c) allowed analysis of smaller sample sizes and greatly reduced moisture equilibration time following humidity changes. Changing to hygrophobic materials used in the fittings connecting the flowing air to the container, c) to d), greatly reduced the background effect that the container had on material moisture measurements.

BCR-302 CRM Water Content Measurements


BCR-302 is a microcrystalline cellulose with certified water content values when exposed to specific humidities.
14
COST 90 certified NPL COST 90

Water Sorption Isotherm Measurement with Microwave Instrument


10% relative humidity changes were applied in the range 15%rh to 85%rh at four hour intervals.
Test of MW moisture reading with varying relative humidity in PTFE design d) with BCR-302 cellulose
0.016

Conclusions
The microwave resonance technique has demonstrated to provide the following advances in water sorption measurement 1. Much faster equilibration times- typically 10 to 100 times faster than traditional experimental approaches (COST 90) and similar to those of DVS technique 2. High precision and sensitivitysample sizes less than 15 mg can be readily studied. 3. Full automation- removes labour intensive nature of sorption measurements.

Mean hysterisis shown in steped profile test of BCR-302 in PTFE join design d)
Mean values absorption Mean values desorption

Water content (% by mass)

12 10 8 6 4 2 0

Evolved vapour analysis

0.016
Microwave moisture

83
Microwave moisture

0.014 0.012 0.01 0.008 0.006 0.004 19/08/2011 17:45 MW moisture MBWE rh

63 53 43 33 23 20/08/2011 05:45 20/08/2011 21/08/2011 17:45 05:45 Date and time 21/08/2011 17:45 13 22/08/2011 05:45

Relative Humidity / %

73

0.014 0.012 0.01 0.008 0.006 10 20

30

40

50 60 MBWE %rh

70

80

90

0.2

0.4

0.6

0.8

Figure 7. Comparison of water content measurement through evolved vapour analysis compared with certified values determined through the COST 90 procedure.

www.npl.co.uk

Queens Printer and Controller of HMSO, 2011. 9760/0911

Nominal Water Activity (aw)

Figure 8. Microwave moisture value of BCR-302 reference material with stepped RH profile.

Figure 9. Typical hysteresis shown by the BCR-302 material

Relative Humidity / %

Microwave moisture (arb units)

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