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Sulfur Hexafluoride

A Unique Dielectric Fredi Jakob Ph.D. and Nicholas Perjanik M.B.A. Analytical ChemTech International, Inc.

I.

INTRODUCTION

Fluids, either gases or liquids, that are used as dielectrics in electrical equipment must possess certain basic properties. The selected fluid must provide thermal conductivity in order to dissipate heat generated within the equipment. It must have excellent insulating properties and must be able to quench arcs. Additional desirable physical and chemical properties that are important include low viscosity, chemical stability and low toxicity. Sulfur hexafluoride, SF6, is a unique gas that meets all of the stated requirements. Physical properties of SF6 are summarized in Table 1. This very high molecular weight gas has a density five times that of air. Even though the gas is non-toxic it will displace air and precautions are required before entering a closed compartment filled with SF6. One must flush a compartment filled with SF6 in order to physically displace the gas and to replace it with air. A recent article1 describes a potential environmental problem with SF6 . The article notes that SF6 is a very stable gas, lasting 3500 years in the atmosphere and that it is a very potent greenhouse gas. There is also mounting concern that SF6, like freons, diminishes the ozone layer in the atmosphere. ASTM and IEC specifications for SF6 are detailed in Table 2. The carbon tetrafluoride, CF4, that may be found initially in SF6 is a by-product that is generated during the manufacturing process. As will be shown later CF4 levels can be used as a tool in diagnostic interpretation of decomposition products found in SF6. Sulfur hexafluoride should be as dry as possible, even though small amounts of dissolved water have a minimal effect on the dielectric breakdown voltage. However, even small amounts of moisture that condense may result in flashover. Water also interferes with the "self healing" properties of SF6. Sulfur hexafluoride should be free of oil since traces of oil, mixed with oxygen, can result in explosive mixtures. Oil vapor will also be absorbed by the desiccant and destroy the desiccants ability to absorb moisture and SF6 decomposition products. Table 1. PHYSICAL PROPERTIES OF SF6 Property Molecular Weight Dielectric Strength Density Color Odor Flammability Value 146.06 2.3 Five times that of air Colorless Odorless Non-flammable

Table 2. SULFUR HEXAFLUORIDE SPECIFICATIONS SPECIFICATION Water content, at max. dew point, oC Water content in ppm, volume, max. Acidity, as HF, max. ppm weight Air, as nitrogen, max. wt. percent CF4 , max. wt. percent Oil, max. ppm weight SF6 , min. wt. percent Toxicity IEC (1) -40 105 0.3 .05 .05 10 not specified non toxic ASTM (2) -62 8 0.3 .05 .05 not specified 99.9 non toxic

(1) IEC- International Electrotechnical Commission (2) ASTM- American Society for Testing and Materials, ASTM Spec D2472-92 Heat transfer properties of SF6 are shown in Figure 1. The two primary factors that determine the ability of a gas to conduct heat are its thermal conductivity and its specific heat.. Thermal conductivity of a gas is inversely proportional to molecular weight. Thus hydrogen, molecular weight =2, has the highest thermal conductivity of any gas. Based on molecular weight alone one would predict that the very heavy SF6 molecules would be poor thermal conductors. But this is more than compensated for by its high specific heat. Thus, SF6 has heat transfer properties that are better than that of hydrogen, helium or air.

H e a t t r a n s f e r w a t t s

50 40 30 20

SF 6 H2 He Air

10

5.0 4.0 3.0 2.0

1.0

0.5 0.4 0.3 0.2

10

20

30

40 50

100

200
oC

300 400

1000

Temperature,

Heat transfer by free convection and radiation SF 6 vs other gases.

Figure 1. Heat transfer properties of SF6

High dielectric strength is an essential property of any insulating fluid. Dielectric strengths of insulating gases are directly proportional to pressure, as shown in Figure 2. The dielectric strength of SF6, 2.3, is higher than that of nitrogen (air), 1.0. The high dielectric strength of SF6

B r e a k d o w n V o l t a g e K V

800

770

SF
700 600 500 400

675 578 482 383

F i e l d S t r e n g t h V o lts per m il

N
300 200 100

290 193 97

25

50

75

100

125

150

175

P r e s s u r e , p s ig

F ig u r e 2 . B re a k d o w n v o lta g e a n d fie ld s tre n g th v s p re s s u re

permits manufacturers to build equipment with close tolerances designed for very high voltages. It is important to maintain the recommended gas pressures in SF6 filled equipment in order to meet the dielectric properties required by the manufacturer. Under certain combinations of gas pressure and temperature, as shown in Figure 3, SF6 is present as a liquid rather than as a gas. In colder climates one must consider the possibility of liquification. If liquification occurs the remaining gas will be present at lower than the desired pressure. Two remedies exist to prevent liquification, one is to use an auxiliary heater, the other is to add nitrogen, which acts as an anti-freeze. The addition of nitrogen to pure SF6 does lower the dielectric strength of the mixture, but fortunately the decrease in dielectric strength is not linear with respect to the amount of nitrogen added. For example, a 25% nitrogen content results in only a 10% reduction in dielectric strength.

Sulfur Hexafluoride
1000 900 800 700 600 500

Critical Point Liquid

P r e s s u r e p s i g

400 300 200

100 90 80 70 60 50 40 30 20
Temperature 32 70 114.17
o

Vapor

F Pressure, psig 167.26 298.43 530.50

10 -60 -40 -20 0 20 40 60


o

80

100

120

140

160

Temperature,

Figure 3. Vapor Pressure vs. Temperature for SF6

100% SF 6
100

C u r r e n t, rms, amp

75

50% SF6 -Air Mixture


50

25

100% Air

0 0 30 60 90 120 150 180

Pressure, psig Arc quenching ability of SF6 vs Air

Figure 4. Arc quenching ability of SF6 vs Air

The arc quenching ability of SF6 is shown in Figure 4. In order to quench arcs the insulating fluid must capture charge carriers (electrons), absorb the electron energy and lower the arc temperature. The very high cross sectional area of SF6 molecules and the high electron affinity of the fluorine atoms are the fundamental reasons that SF6 is such an effective arc quenching gas. The reactions that occur in SF6 when an arc is quenched are:

SF6

e dissociation Recombination

SF5- + F

A very unique property of SF6 is its ability to "self heal." The absorption and deceleration of electrons generated by the arcing process cause partial decomposition of the SF6. Unlike other insulators such as oil or cellulose, which are irreversibly decomposed in an arc, most of the SF6 decomposition products recombine to regenerate SF6. This unique ability to self heal is a major reason for the widespread utilization of SF6 as an insulating gas.

II. WHY TEST SF6? Some of the reasons that one would consider laboratory analysis of SF6 samples from electrical equipment are summarized in Table 3. Impurities that can be found in SF6 include moisture, oxygen and freons. Moisture and oxygen, which are present in the atmosphere, enter equipment that is not completely sealed. Carbon tetrafluoride may be present as a manufacturing byproduct, or be formed as a result of internal arcing. Freons are often used for leak detection and traces of residual gas have been found in laboratory samples from breakers that were previously tested for leaks. The use of Freon to detect leaks is not necessary since leak detectors will respond to the SF6 itself. Table 3.

Why Test Sulfur Hexafluoride ?


Detection of Impurities
Moisture Oxygen Freons Determination of Nitrogen / SF Ratio 6 Detection of Decomposition Products Safety Diagnostic Evaluation

Regeneration of SF6 from decomposition products, as is the case with most organic chemical reactions, is less than 100 percent complete. This observation can be used to help determine the condition of equipment in which the SF6 is being used as an insulator. Applying methods similar to those used when determining the decomposition products of insulating liquids, such as Dissolved Gas Analysis (DGA)2,3, to the analysis of SF6 decomposition products may allow one to ascertain the condition of gas insulated equipment. Some of the compounds that may be present after an arc in SF6 are: SO2, SOF2, SO2F2, CF4, COS, SOF4, and WF6. These gases and their relative compositions in the SF6 matrix may allow one to determine the operating history of gas insulated equipment. Table 4 is a compilation of all of the gases, impurities and decomposition products, that one might find in a sample of SF6 from gas filled equipment. The well known success of DGA for locating incipient faults in oil filled transformers and load tap changers suggests that similar concepts can be applied to SF6 insulated equipment. Since arcing occurs in a circuit breaker every time it operates, a certain level of decomposition gases is always produced. If a desicant is used on the equipment then some of the decomposition products will be absorbed. To distinguish the "normal" concentrations of decomposition products and the elevated levels that indicate an incipient fault sufficient data must be acquired. Gas filled buses and current transformers are not normally subjected to arcing and any amount of decomposition products may indicate a potential problem. It is hoped that laboratory analysis of SF6 decomposition products will provide a powerful diagnostic tool for the evaluation of gas insulated equipment.

TABLE 4 TLV* ppmv N/A N/A 1000 3 2 0.5 ? 0.1 0.025 1 5 0.5 0.1 0.6 10 N/A 50

GASES FOUND IN SF6

GAS Air (80%N2 ,20%O2 ) Moisture Carbon Tetrafluoride Hydrofluoric Acid Sulfur Dioxide Sulfur Monofluoride Sulfur Difluoride Sulfur Tetrafluoride Disulfur Decafluoride Thionyl Fluoride(1) Sulfuryl Fluoride Thionyl tetrafluoride Tungsten Hexafluoride Silicon Tetrafluoride Carbon Disulfide Carbon Dioxide Carbon Monoxide

FORMULA N2 , O2 H 2O CF4 HF SO2 S2F2 SF2 SF4 S2F10 SOF2 SO2F2 SOF4` WF6 SiF4 CS2 CO2 CO

SOURCE Leaks Leaks Production by-product, arc tip erosion, any carbon containing component, oil, grease Produced in SF6 when arcs occur Produced when SOF2 reacts with water Will not be present due to high reactivity Reactive Intermediate Very reactive intermediate Very toxic, presence in SF6 questionable Will be present if arcing occurs and water is present Will be present if arcing occurs and water is present Occurs if arcing takes place and oxygen is present Contact Erosion Arcing in the presence of silicon Arcing in the presence of silicon From carbon containing compounds From carbon containing compounds

(1) The Thionyl fluoride smells like "rotten eggs" and is often mistaken for hydrogen sulfide. * Threshold Limiting Value. The Threshold Limiting Value (TLV) is the concentration, in ppm vol, that an unprotected worker can tolerate for forty hours per week without any significant health hazard.

III. THE CHEMISTRY OF SF6 DECOMPOSITION Mastroianni and Jackson5 presented an excellent review, at the April 1980 Doble Client Conference, of the decomposition reactions that occur in SF6 subjected to arcing or corona. They reported that several studies showed that the initial decomposition products formed when arcing or corona occurs included fluorine, metal fluorides, sulfur tetrafluoride (SF4 ) and sulfur monofluoride (S2F2). Both SF4 and S2F2 are very reactive gases and react within minutes with water and/or oxygen to form sulfur oxyfluorides. The sequence of reactions in which the sulfur oxyfluorides are formed are shown in Figure 5 and Figure 6. Metal fluorides, in the presence of water, can undergo hydrolysis reactions. The hydrolysis reactions of the metal fluorides and other possible reactions taking place in an arc are listed in Figure 7. The white powder often observed in circuit breakers is aluminum trifluoride, AlF3 . Faulted breakers can contain large amounts of AlF3 which must be removed with appropriate safety precautions. AlF3 is not toxic but it is easily hydrolyzed in the presence of moisture and the resulting acid is a skin irritant. Aluminum trifluoride is an inhalation hazard because of its small particle size. Since moisture and oxygen are invariably present in gas insulated equipment the sulfur- containing gases that one would expect to find in the SF6, after an arc or corona has occurred, include SOF2, SOF4, SO2F2

and SO2 . Hydrofluoric acid (HF) will not be found because it is so reactive. The presence of tungsten hexafluoride (WF6) would indicate erosion of tungsten contacts. The presence of any carbon containing compounds (CO2 , CO, COS, CF4 ) would indicate that the arc involved carbon-containing materials such as Teflon, epoxies, oil or grease. Freons such as dichlorodifluoromethane (R-12) are often used to test breakers for leaks, and if the test gas is not completely removed it appears as a detectable component in the SF6 . Scrubbers containing molecular sieves or activated alumina are widely used to remove moisture and gas decomposition products from SF6. Removal of arc or corona generated decomposition products makes it difficult to ascertain the number of normal circuit breaker operations by determination of the concentrations of the decomposition products in the gas. However, if a fault occurs in a breaker, the quantity of decomposition products that are formed exceeds the capacity of the scrubbers and relatively high concentrations of SF6 decomposition products will be found. Maintenance of the scrubbers and clean up of the SF6 will be required eventually, even if no fault occurs, and certainly after a fault is sustained. Arcing does not normally occur in buses so the presence of any SF6 decomposition products indicates a problem condition. IV. CASE HISTORY Samples were analyzed from a breaker which was cleared for pullrod replacement. SF6 was sequentially removed from poles 1, 2 and 3, and the breaker modifications were completed prior to refilling the breaker with SF6. The breaker was returned to service after all three poles had been modified. Two weeks later the breaker was once again removed from service in order to modify the control valves. Subsequently the breaker timing was thoroughly checked. The breaker was operated several times and a complete set of timing pictures were produced. The breaker was then returned to service, but after only 20 minutes in service, the breaker failed. The internal fault lasted for three cycles at a current of 30,000 amps. Laboratory results for samples from each pole are summarized in Table 5.

TABLE 5. 500 KV BREAKER FAILURE

Date Collected Report Number

5/24/95 10535

5/24/95 10536

5/24/95 10534

Gas Sulfur Hexafluoride (SF6) Oxygen (O2) Nitrogen (N2) Carbon Tetrafluoride (CF4) Dichlorodifluoromethane R-12 (CCL2F2) Sulfuryl Fluoride (SO2F2) Carbon Dioxide (CO2) Sulfur Dioxide (SO2) Carbonyl Sulfide (COS) Thionyl Fluoride (SOF2) Thionyl Tetrafluoride (SOF4) Tungsten Hexafluoride (WF6) TOTAL GAS OTHER THAN SF6 Total Gas

Pole 1 (PPM) 996300 300 1680 80 1280 0 60 0 0 0 300 0 3700 1000000

Pole 2 (PPM) 996160 1070 2280 20 460 0 10 0 0 0 0 0 3840 1000000

Pole 3 (PPM) 996370 1220 2360 20 20 0 10 0 0 0 0 0 3630 1000000

Moisture (PPM) Dielectric (KV)

25 12.1

40 12.4

35 12.5

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The highlighted results in Table 5 are worthy of discussion. The elevated level of CF4 found in pole 1 may be due to arc tip corrosion or decomposition of organic material such as oil or grease in the presence of an arc. The breaker that failed, pole #1, was inspected after the fault and a loose washer was discovered. Signs of arcing on the breaker tank wall indicated that a second loose washer might have been the cause of the failure. The first washer was coated with grease. A reasonable assumption would be that the second washer was also coated with grease. The elevated level of carbon dioxide in pole the #1 sample may be due to the decomposition of the grease in the presence of an arc. The R-12 Freon is probably residual Freon that was used for leak testing and remained in the gas cart. The order of gas removal from the breaker poles was #1, #2 then #3. The SF6 was removed from the breaker with the gas cart and then returned to the respective pole. The sequential decrease in Freon concentrations supports the hypothesis that the Freon contamination originated in the gas cart. It is significant to note that the SF6 in the failed breaker was the only sample that contained thionyl tetrafluoride, which is an expected SF6 decomposition product. The lower concentrations of both oxygen and moisture in the faulted breaker could be due to the participation of these two compounds in the SF6 degradation process described in Figures 5 and 6. It is abundantly clear that analysis of the gas in a faulted breaker shows detectable levels of decomposition products. V. CONCLUSION Analysis of the decomposition products in samples of SF6 obtained from gas insulated electrical equipment has potential as a diagnostic tool for the location of incipient faults in the equipment. It remains to be seen if the analytical results allow one to distinguish between normal and abnormal fault gas levels.

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References 1. 2. 3. P. Irvin, Electric Light and Power, November 1995 T.J. Haupert, F. Jakob, NETA World, Winter 1986, pp. 4-5, 20 T.J. Haupert, F. Jakob, Electrical Insulating Oils, STP998, American Society for Testing and Materials, 1988, pp. 108-115 Figures 1,2,3 and 4 used with permission Allied Signal, Inc., AccuDri SF6 Sulfur Hexafluoride, 1995 Allied Signal, Inc., 97-0103.4m.595m Mastroianni, M.J. and Jackson, R.B., Minutes of the Forty Seventh Annual International Conference of Doble Clients, 1980, Sec. 10-101

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