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A1_105_2010

CIGRE 2010

Formaldehyde emissions in large rotating electrical machines root cause analysis, background and prevention
1

I. BERGMANN1, R. DRAPER2, F. RAMSAUER1, G. LEMESCH1 2 ANDRITZ Hydro GmbH ANDRITZ Hydro Lte./Ltd Austria Canada

SUMMARY
Odours have been generated during commissioning and first time operation of large rotating electrical machines. These emissions were observed in machines from several manufacturers. Subsequent investigations indicated that formaldehyde was present. The main source of the emissions was located in the insulation varnish of the sheets of the stator core. In core sheet varnishes, formaldehyde containing precursors are often used as crosslinking agents. Energy input during the curing process, determines the extent of reversibly bonded formaldehyde after the cure. Weakly bonded formaldehyde is released when the coated sheets are heated during the early operation of the generator. The influence of the curing conditions on the formaldehyde emissions of stator core sheets was investigated in laboratory experiments. Experiments showed a decrease in formaldehyde emissions by increasing the energy input during the curing process. Even if the energy input was high enough to achieve the required mechanical (e.g. cross cut test), chemical (e.g. rubbing alcohol test) and electrical properties (e.g. surface resistivity), the formaldehyde release could still be reduced by further increase of the energy input. Appropriate material properties do not correlate with the amount of releasable formaldehyde in the varnish. This gives an opportunity to modify the curing to reduce or eliminate the emissions without negatively impacting the insulating properties. The influence of the chemistry of the varnishes on the formaldehyde release was also studied. Varnishes based on phenolic and melamine resins give the highest emissions, while the polyester based varnishes showed no emissions. The temperature dependence and the kinetics of the formaldehyde release of stator core sheets are investigated in model tests. The laboratory experiments on the kinetics of the emissions showed, that at a certain temperatures the majority of formaldehyde is emitted over a short time. Later emissions approach zero with continued thermal exposure. Temperature tests on stator core sheets in the range of 30C to 100C showed, that at 30C, small amounts of formaldehyde are released. Interestingly the formaldehyde emission does not increase linearly with increasing temperature, it shows a first maximum at about 60C and a second maximum at about 100C. This implies chemical reactions associated with definite activation energies are required for splitting off the formaldehyde.

irmgard.bergmann@andritz-hydro.com

Measures can be taken, during lamination processing, to avoid improper formaldehyde emission in large rotating electrical machines (safety measures and venting in existing machines, optimization of the curing process, development of formaldehyde free coatings for stator core laminations).

KEYWORDS
formaldehyde, emissions, large rotating machines, insulation varnish, stator core laminations

Introduction
In recent years an unpleasant odour was observed during commissioning and start of normal operation of large rotating electrical machines. These observations were made independently on machines from several manufacturers. In the subsequent extensive investigations, formaldehyde turned out to be the substance that caused the odour and the irritation of eyes and throat of site personnel. Formaldehyde is a colourless gas with a strong pungent odour. The odour threshold is between 0,5 and 1,0 ppm. It may cause allergic reactions, skin, respiratory system and eye irritations. The maximum occupational exposure limits (OEL), short term exposure limits (STEL) and Ceiling Exposure Limit (CEL) of selected countries are shown in table 1 [1,2]. This table shows clearly the strong differences in the regulations.
Table 1 : Current and scheduled regulated OELs, STELs and CELs for formaldehyde [1,2]:

Country OELi (ppm) STELii (ppm) CELiii (ppm) Australia 1,0 2,0 Austria 0,5 Brazil 1,6 China 0,5 Canada-Alberta 0,75 2,0 Canada-Ontario 0,3 France 0,5 1,0 iv Germany 0,5 (0,3 ) 0,6 1,0 Japan 0,5 Netherlands 1,0 1,5 Norway 0,5 1,5 1,0 United Kingdom 2,0 2,0 USA-OSHAv 0,75 2,0 USA-NIOSHvi recommendation 0,016 0,1 Switzerland 0,3 0,6 i

OEL (or equivalent): concentration of a substance in air which may not be exceeded over a normal 8 hour work period. STEL (or equivalent): concentration of a substance in air which may not be exceeded over any 15 minute period, limited to no more than 4 such periods in an 8 hour work shift with at least one hour between any 2 successive 15 minute excursion periods. iii Ceiling (or equivalent): concentration of a substance in air which may not be exceeded at any time during the work period. iv Scheduled value v OSHA: Occupational Safety & Health Administration vi NIOSH: National Institute for Occupational Safety and Health
ii

The source of the emissions was located in the insulation of the sheets of the stator core. The varnishes used for this application are C6-varnishes (according to ASTM 967-3) which are characterized by excellent insulation properties, a high temperature resistance and a high filler content of approximately 50 wt%. In C6-core sheet varnishes, formaldehyde containing precursors based on melamine or phenolic resins are generally used as crosslinking agents. Fast curing, good elastic properties, good corrosion resistance and good adhesion at a moderate cost level are the reasons for the long term success of these crosslinking agents in this application. From the chemistry side they are condensation resins, that means that they split off volatile monomers during the crosslinking reaction. In the case of melamine and/or phenolic resins the monomers which are split off are water and/or alcohols and formaldehyde. Further, methylene ether bridges are converted to methylene bridges and release formaldehyde under the influence of temperature. The condensation- and crosslinking reactions of melamine resins are shown in table 2. Table 2 shows that 4 out of 12 possible reactions lead to an emission of formaldehyde (H2C=O). The reactions of phenolic resins are similar to the shown reactions of melamine resins, but generally they split even more formaldehyde during crosslinking. The amount

of formaldehyde, which can be emitted from melamine and/or phenolic resins depends on the type of resin as well as on the curing conditions.
Table 2 : Reactions of partially methylated melamine formaldehyde resins [3]. 1 x-NCH2OCH3 + ROH NCH2OR +CH3OH 2 x2 -NCH2OCH3 + H2O -NCH2N- + H2C=O + 2 CH3OH 3 x-NCH2OCH3 + -NH -NCH2N- + CH3OH 4 x2 -NCH2OCH3 -NCH2N- + CH3OCH2OCH3 5 x-NCH2OCH3 + -NCH2OH -NCH2OCH2N- + CH3OH 6 x-NCH2OCH3 + H2O -NCH2OH + CH3OH 7 x-NCH2OH -NH + H2C=O 8 x-NCH2OH + -NH -NCH2N- + H2O 9 x2 -NCH2OH -NCH2N- + H2C=O + H2O 10 x-NCH2OH + ROH NCH2OR + H2O 11 x2 -NCH2OH -NCH2OCH2N- + H2O 12 - -NCH2OCH2N- -NCH2N- + H2C=O

For large rotating machines that means, that depending on the energy input during the curing process the melamine and phenolic resins can still contain reversibly bonded formaldehyde after the cure. This weakly bonded formaldehyde is then released when the coated sheets are heated again during the time of early operation of the generator. Our observations showed that depending on the type of generator (size, temperature of the stator core in operation, etc.), the structural environment (enclosure, caverns, power house, etc.) and the operating conditions the emissions last between a few weks up to a few months and longer. In laboratory experiments, the influence of the curing conditions of the varnish on the formaldehyde emissions of the stator core sheets was explored. Further studies were made using different, recently developed, varnishes which promised to be formaldehyde-free or show only very low formaldehyde emissions. Due to the instability of formaldehyde in water the most widely used methods for the determination of the concentration of formaldehyde require the formation of a derivative for separation and detection. For the detection of formaldehyde in ambient air absorption methods in aqueous solutions containing derivatisation reagents (aqueous DNPH solution) or on reactive surfaces (Draeger detector tubes) are well established, but also online methods based on spectroscopy and electrochemical oxidation are possible, if the detection limits are low enough and the presence of other substances that interfere can be excluded.

Materials and Methods

Determination of formaldehyde emissions of stator core sheets by Draeger detector tubes. The set-up for the determination of formaldehyde emissions of stator core sheets uses Draeger detector tubes is shown in figure 1 (left side). The sample under test was comprised of 10 sheets (300mm x 300mm) with spacers between for airflow. Each sample was placed into a pre-heated convection oven, with respect to a very quick transfer in order not to cool down the oven. After 30 minutes at 80C the Draeger tube was inserted into a small duct and the actual formaldehyde concentration was measured.

T = 80C

air flow = const.

T = 80C

convection oven

convection oven

gas analyser

Figure 1 : left side: set-up for determination of formaldehyde emissions of stator core sheets by Draeger detector tubes, right side: set-up for determination of formaldehyde emissions of stator core sheets by the gas analyzer.

Determination of formaldehyde emissions of stator core sheets by the gas analyzer. The set-up for the determination of formaldehyde emissions of stator core sheets by a gas analyzer is shown in figure 1, right side. The gas analyzer (Innova 1302, Fa. Lumasense, DK) uses a measurement system based on the photoacoustic infrared detection method. Gas selectivity is achieved through the use of optical filters. For these measurements, a filter with transmissibility at a wavenumber of 2730cm-1 was chosen. The detection limit for formaldehyde for this filter is specified with 0,12 ppm. Nevertheless, interferences with other volatile substances emitted from the stator core laminations cannot be excluded. So this measurement method allows a semi-quantitative determination of the formaldehyde emissions only. Similar to the measurements with the Draeger tubes for each measurement also 10 pieces of stator core laminations (with spacers in between, to let the air flow between the sheets) of a size of 300 x 300 mm were put into the pre-heated convection oven, with respect to a very quick transfer in order not to cool down the oven. A predefined constant air flow through the oven was applied in order to get a semi-quantitative calculation of the formaldehyde emissions coming from the stator core laminations. The correct working of the setup was tested with paraformaldehyde.

Results and Discussion Time dependence of the emissions The gas analyzer based on the photoacoustic infrared detection method is an excellent method for monitoring the time dependence of the formaldehyde emissions of stator core sheets. The characteristic progress of the emissions under laboratory conditions is shown in figure 2.

formaldehyde emissions [mg/m stator core laminate].. .

0,50 0,40 0,30 0,20 0,10 0,00

0 50 0 00 00 00 00 00 00 35 10 15 20 25 30 40 00
0,4 0,3 0,2 0,1 0,0
10 20 30 0 40 50 60

time at 80C [min]

Figure 2 : Characteristics of emissions of formaldehyde from stator core sheets in a laboratory experiment.

Figure 2 shows the emission of the stator core laminations at 80C under laboratory conditions. During heating of the laminations, the emissions peak occurs after about 20-30 minutes. After the peak, the emissions die out relative quickly and converge toward zero slowly. After 4000 minutes the emissions approach zero. This result confirms to our observations in generators. As described above, in generators we noticed high emission levels at the beginning of operation which die out relative quickly to a certain level and approach zero after continued operation. The rate of decay of the emissions was different for each machine.

Temperature dependence of the emissions Beside the time dependence, a temperature dependence of the emissions was also expected. Therefore the temperature dependence of the emissions under laboratory conditions was studied. A pack of stator core laminations was heated from 20C to 100C within 10 hours, where the temperature was raised every 60 minutes by 10 centigrade. The result of the experiment is shown in figure 3.

Formaldehyde [mg/m]...

0,25 0,20 0,15 0,10 0,05 0,00

0

20C 30C 40C 50C 60C 70C 80C 90C 100C

60

-6

0 42

12

18

time [min]

Figure 3 : Formaldehyde emissions of stator core laminations under laboratory conditions: The temperature was raised every 60 minutes for 10 centigrade, starting from 20C up to 100C.

Figure 3 shows that emissions start at 30C. Interestingly, the formaldehyde emissions do not increase linearly with the temperature. This implies that the emissions are not solely sourced from physically bonded formaldehyde. Temperature dependent chemical reactions with defined activation energies seem to be the reason for the emissions. As discussed above, the transformation reaction of methylene ether bridges to methylene bridges under emission of formaldehyde (table 2, reaction 12) as well as the elimination of formaldehyde from unreacted methylol-groups (table 2, reaction 3) can be the origin of the emissions.

Dependence of the formaldehyde emissions on the curing conditions Since formaldehyde is a normal bi-product of curing, it is assumed that lamination processing parameters have an impact on later machine emissions. In figure 4 and figure 5 the influence of the energy input during curing at constant curing speed is shown. The measurements as described before were done by Draeger tubes (figure 4) and also by gas-monitor measurements (figure 5, left side). Energy inputs of 85%, 75% and 65% (varied by changing temperature)of the maximum energy input of the curing process were selected and additionally stator core laminations processed with 65% energy input were post baked at 230C for 30 min. The figures show clearly the dependence of the formaldehyde emissions and the good correlation between the Draeger tubes measurements and the gas-monitor measurements (figure 5, right side). The 65% energy input level was too low and the stator core sheets did not pass the standard control after the curing process, but 75% and 85% energy input were sufficient to pass all the standard controls regarding the crosslinking of the varnish. This

24

30

36

48

shows clearly that also within the standard production range the formaldehyde emissions of the stator core laminations can vary strongly. The post baked stator core laminations did not show any significant emissions as expected. This result is very important for short and medium term actions to reduce the formaldehyde emissions of machines which are already in production.
18 16 14 12 10 8 6 4 2 0 0 2 4 6 Formaldehyde Draeger-tubes [ppm]

4 3 2 1 0 65+post baking 85 75 65

energy input [%]

Figure 4 :Left side: Influence of the energy input during curing on the formaldehyde emissions of stator core laminations Measurement by Draeger tubes. Right side: Correlation between Measurement by Draeger tubes and gas-monitor measurements (integration of emissions over the first 60 min).

Formaldehyde [mg/m] xxx

0,6 0,5 0,4 0,3 0,2 0,1 0,0 0 20

85% 75% 65% 65%+post baking

Formaldehyde [mg/m] xxx

0,7

0,30 0,25 0,20 0,15 0,10 0,05 0,00

0 10 20 30 40

Formaldehyde 60 min Gas-Monitor [mg/m] xxx

5 Formaldehyde [ppm]

100% 75% 62% 50%

40 time [min]

60

50

time [min]

Figure 5 : Left side: Influence of the energy input during curing on the formaldehyde emissions of stator core laminations Gas monitor measurements. Right side: Influence of throughput speed (% of max. speed) on the formaldehyde emissions of stator core laminations.

Further processing investigations focused on the influence of the throughput speed of the curing process on the formaldehyde emissions. A set of stator core sheets were insulated with 100%, 75%, 62% and 50% of the maximum curing speed of the process. We measured the emissions of the stator core sheets by using the gas-monitor system. Again as expected we found a clear dependence of the formaldehyde emissions on the curing speed of the coating process (figure 5, right side). So beside the energy input the curing speed is the second potential for immediate actions regarding formaldehyde reduction of machines in production.

Conclusion The investigations on the formaldehyde emissions of stator core sheets in the laboratory provided a better understanding of the emissions in large rotating machines. A series of measures can be taken to avoid improper formaldehyde concentrations in large rotating electrical machines.

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Recommended, short term measures for machines which are already in operation, include implementing safety instructions when the formaldehyde level in the machine exceeds the national exposure limits, and an entering of the machine is required, e. g. personal protective equipment is obligatory. Additionally an air exchange between cooling and ambient air or the usage of filter systems can reduce the formaldehyde level in large rotating machines. Medium term measures for emission improvement focus on the adaptation of the curing of the stator core laminations. Optimization of the curing process regarding energy input provides a significant reduction of formaldehyde emission in large rotating electrical machines. Lab measurements showed, that a reduction of the curing speed or a second heat treatment can reduce the formaldehyde emissions of the stator core laminations significantly up to more than 80%. For further reduction of formaldehyde emissions and for formaldehyde-free machines cooperation with manufacturers of varnishes and stator core sheets are essential. New generations of varnishes are available from the core sheet varnish producers, that are formaldehyde-free or show significantly reduced formaldehyde release in the cured varnishes. Such varnishes have been tested and give promising results. ANDRITZ Hydro takes the formaldehyde emissions in large rotating machines very seriously and takes all possible measures to overcome the problem.

BIBLIOGRAPHY
[1] [2] [3 ] www.worksafebc.com/regulation_and_policy/.../formaldehyde.pdf Formaldehyde, 2-Butoxyethanol and 1-tert-Butoxypropan-2-ol, IARC Monographs on the Evaluation of Carcinogenic Risks to Humans 88, Lyon, France: International Agency for Research on Cancer, 2006, pp. 39325, ISBN 92-832-1288-6, http://monographs.iarc.fr/ENG/Monographs/vol88/mono88-6.pdf. D. R. Bauer Progress in Organic Coatings, 14: 193-218, 1986