GB2217719A - Flame retardant coating compositions - Google Patents
Flame retardant coating compositions Download PDFInfo
- Publication number
- GB2217719A GB2217719A GB8909009A GB8909009A GB2217719A GB 2217719 A GB2217719 A GB 2217719A GB 8909009 A GB8909009 A GB 8909009A GB 8909009 A GB8909009 A GB 8909009A GB 2217719 A GB2217719 A GB 2217719A
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- flame
- water
- substance
- retardant
- weight
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims description 46
- 239000003063 flame retardant Substances 0.000 title claims description 45
- 239000008199 coating composition Substances 0.000 title claims 2
- 239000011347 resin Substances 0.000 claims description 67
- 229920005989 resin Polymers 0.000 claims description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- 239000000126 substance Substances 0.000 claims description 46
- 238000000576 coating method Methods 0.000 claims description 34
- 239000011248 coating agent Substances 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 26
- 230000015572 biosynthetic process Effects 0.000 claims description 19
- 239000000945 filler Substances 0.000 claims description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 238000004804 winding Methods 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 14
- 230000008030 elimination Effects 0.000 claims description 10
- 238000003379 elimination reaction Methods 0.000 claims description 10
- 239000004020 conductor Substances 0.000 claims description 9
- 230000018044 dehydration Effects 0.000 claims description 9
- 238000006297 dehydration reaction Methods 0.000 claims description 9
- 150000004684 trihydrates Chemical class 0.000 claims description 9
- 230000004580 weight loss Effects 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 7
- 238000005259 measurement Methods 0.000 claims description 7
- 230000008859 change Effects 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 230000001627 detrimental effect Effects 0.000 claims description 4
- 238000010616 electrical installation Methods 0.000 claims description 4
- 230000002035 prolonged effect Effects 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 2
- 208000005156 Dehydration Diseases 0.000 claims 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 71
- 239000000377 silicon dioxide Substances 0.000 description 35
- 235000012239 silicon dioxide Nutrition 0.000 description 32
- 229910052681 coesite Inorganic materials 0.000 description 31
- 229910052906 cristobalite Inorganic materials 0.000 description 31
- 229910052682 stishovite Inorganic materials 0.000 description 31
- 229910052905 tridymite Inorganic materials 0.000 description 31
- 238000005755 formation reaction Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 12
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000002485 combustion reaction Methods 0.000 description 8
- 239000004848 polyfunctional curative Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 230000006870 function Effects 0.000 description 6
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 6
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 5
- 229910001679 gibbsite Inorganic materials 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000002671 adjuvant Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000013021 overheating Methods 0.000 description 3
- 230000000930 thermomechanical effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000892 gravimetry Methods 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- 229910018626 Al(OH) Inorganic materials 0.000 description 1
- 229920003319 Araldite® Polymers 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical class C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 102100023055 Neurofilament medium polypeptide Human genes 0.000 description 1
- 101710109612 Neurofilament medium polypeptide Proteins 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000000538 analytical sample Substances 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- 238000007707 calorimetry Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000011491 glass wool Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000006194 liquid suspension Substances 0.000 description 1
- -1 magnesia dihydrate Chemical class 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/40—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes epoxy resins
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
- Organic Insulating Materials (AREA)
- Insulating Of Coils (AREA)
- Paints Or Removers (AREA)
- Coils Of Transformers For General Uses (AREA)
- Epoxy Resins (AREA)
- Housings And Mounting Of Transformers (AREA)
Description
DRY TRANSFORMER WITH COATED WINDINGS, SIMILAR
ELECTRICAL CONDUCTqRS OR INSTALLATIONS,
AND PROCESS FOR THE PREPARATION OF
THEIR COATING RESIN.
The invention relates to the improvement in the fire behaviour of coated electrical conductors which operate hot.
It applies in particular to dry power or dis- tribution transformers, whose working temperatures habitually exceed the ambient temperature by more than a hundred degrees centigrade (working temperature generally of the order of 140-150"C). Accordingly, and solely for reasons of convenience, reference will be made to the example of the abovementioned transformers in the remainder of the description.
In transformers of this type, which are usually selected for a voltage range extending from 3 to 36 kV, the coil winding is embedded in an insulating synthetic resin with dielectric properties and with a thickness of several millimetres (e.g. from 2 to 5 mm). It is recalled that, in addition to its electrical insulating role, the resin plays a part in protection against moisture and dust, which could lower the breakdown voltage. It also protects the electrical coil windings against an environment contaminated by corrosive chemical agents and plays a major part in mechanical behaviour by ensuring the immobilization of the turns relative to one another in the coil winding.
Nevertheless, it is known that in accidental extreme conditions of utilization, or following an anomaly, transformers can burn. A study of their fire behaviour has made it possible to realize that, when the coating resin burns, it often continues to burn, even if the fire which caused it has ceased, because the resin becomes flammable in air above a critical temperature which is specific to it.
At this stage, a few reminders concerning the constitution of these resins may be found useful in what follows.
Present coatings for dry transformers are heatcurable resins obtained by heating an initial mixture composed of a liquid resin (generally an epoxide) and a hardener such as a anhydride. A classical example is provided by bisphenol A diglycidyl ether derivatives, more commonly called BADGE, and formed by reaction between bisphenol A and epichlorohydrin (see, e.g. USP 3,202,947). These resins are in most cases crosslinked and made infusible and insoluble by addition of amines and of polysulphides of low molecular mass (for example Aralditee resin). Other examples are to be found among heat-curable polyesters. The proportions by weight are usually 50 % in the case of the resin and 50 % in the case of the hardener.
Filled resins are generally employed: before the hardener is added, the initial liquid resin receives a filler, often inorganic, for example quartz (silica) flour, or glass wool, in proportions by weight which are of the order of 3 of filler per 1 of resin. In the initial mixture there will then be, for example, 20 % of resin, 60 % of silica and 20 % of hardener.
The function of this filler is to improve the thermomechanical behaviour and to absorb already some of the heat of polymerization of the resin, which makes it possible to avoid the formation of cracks. Another of its functions is mechanical reinforcement, because unfilled resin remains soft in consistency at the transformers' operating temperature.
From another aspect, elastomers, such as silicone resins or polyester resins which are thermoplastics, are more likely to be employed particularly in the case of coating of cables or of wires, so as -to permit a degree of flexibility therein. An example is provided by polyesters such as the polyterephthalate of ethylene glycol or of butylene glycol.
The invention does not discriminate according to the resin type (heat-curable, thermoplastic or elastomeric), insofar as this resin is an insulating material intended to be employed "hot" and therefore consequently has good thermomechanical behaviour at the elevated working temperatures indicated earlier. Accordingly, for convenience of language, the names "coating resin" or "filled resin" will be applied indiscriminately to the material constituting the final insulating coating formed by the mixture of: polymerizable resin proper, reinforcing filler (where applicable), and possible hardener (including usual adjuvants such as accelerator, flexibility promoters, and the like).
The purpose of the invention is to improve the fire behaviour of coated electrical conductors, especially the windings of dry transformers, by increasing the heat stability of the flame-retardant coating resin employed, at their service temperature.
To this end, the subject matter of the invention is an electrical conductor or winding coated with a filled insulating resin containing a substance which is flame-retardant due to water formation when the temperature rises, such as alumina hydrate, characterized in that a proportion of the filler equal to at least 20 % of the total weight of the coating resin consists of the said flame-retardant substance which has been previously partially dehydrated in such quantity that it does not cause an untimely formation of water in the resin while the coated conductor is in service in its normal temperature conditions.
Another subject of the invention is a process for the preparation of a filled insulating resin of this type for coating dry transformer windings, according to which there is added to the initial liquid resin a filler, a proportion of which, equal to at least 20 % of the total weight of the coating resin, consists of a substance having flame-retarding properties due to formation of water when the temperature rises, such as alumina hydrate, but this being done after the flame-retardant substance has been previously partially dehydrated, preferably by heating, in order that there may be no untimely formation of water within the resin, capable of being detrimental to its quality during the use of the transformer at its nominal operating temperature.
A further subject of the invention is a coated dry transformer in which at least one electrical winding is coated with a bulk of flame-retardant insulating resin in accordance with that obtained by the process specified above.
The flame-retarding role of alumina trihydrate, as an adjuvant in coating resins for electrical cables or for transformers, is already known, for example from document USP 3,202,947, referred to already (and the teaching of which is incorporated here by reference).
However, so far as the inventors are aware, it has never hitherto been possible to bring to light the advantage which could be paradoxically expected of a better heat stability of the resin by partially dehydrating an adjuvant of this kind beforehand, whereas it acts as a flame-retardant precisely by forming water.
The invention will be properly understood and other aspects and advantages will appear more clearly in the light of the detailed description which follows, given with reference: - to Tables I, II and III, presented in the body of the text and expressing the good fire behaviour of a coating resin according to the invention; - to table IV, also presented in the body of the de
scription, and giving the main characteristics of the
profile of the loss of water with the rise in tempera
ture for a number of flame-retardant substances; - to Figures 1 and 2, showing the change with time of the
loss in weight of various flame-retardant substances
which can be employed, due to the formation and removal
of water resulting from their "hot" instability when
they are heated at a constant temperature.
The two essential characteristics of the invention, stated earlier, are considered in succession: 1) ADDITION OF A SUFFICIENT OUANTITY OF A SUBSTANCE WHICH
IS FLAME-RETARDANT DUE TO WATER FORMATION DUE TO
INSTABILITY WHEN HOT.
The flame-retardant substance which is added may be alumina hydrate Al2O3.nH2O with n = 1, 2 or 3, magnesia dihydrate, zinc borate, or any other substance known for its self-extinguishing capacity properties due to elimination of water and additionally preferably capable of reinforcing the resin, just like silica. Preference may be given to alumina trihydrate, which has been found to be the most effective flame-retardant and which, in addition, gives off little or no smoke.
The water formation reaction can be written:
The rate of this reaction increases in the direction of the arrow with temperature, and its endothermicity delays, or even prevents, the ignition point of the resin from being reached.
It will be seen later that this rate does not change linearly with temperature, but that an intense water loss peak is formed, which is characteristic of the substance and whose decisive advantage is that it appears at temperatures which lie precisely in the overheating range at risk, and therefore below the critical ignition temperature of the coating resin.
The A1(OH)3 can be easily mixed with the starting inorganic filler, since both are in the form of powdered or finely granular solid matter.
Instead of 60 % by weight of SiO2 in the final resin, a major part thereof is substituted by the flameretardant substance. For example, a mixture representing 50 % of A1(OH)3 and only 10 % of SiO2 is thus produced.
However, experience has shown that the quantity of
A1(OH)3 could be lowered as far as 25 % (and thus 35 % of
SiO2) without significant detriment to the good fire behaviour qualities of the coating, which are due to the presence of the flame-retardant substance.
These values, established for an initial loading of 60 % by weight can, of course, be modified if this proportion varies.
Tables, I, II and III below provide indications and numerical results of tests carried out in the laboratory on a dry transformer, showing the effect of flameretardant substances (in this case A1(OH)3 and zinc borate) on the values of parameters which are recognized as representing the fire behaviour of materials, and in particular of coating resins for dry transformer windings, namely the Oxygen Index, the Rate of Combustion and the Upper Heating Power.
TABLE 1:Oxygen index (@ @)
measurement temperature 20 C 80 C 150 C 200 C minimal Oxygen Index 30 27 23.5 21 ALUMINA TRI-HYDRATE
70% of SiO2 # 30 # 28 # 24 # 19 FILLER LOAD@ 20% of SiO@ + # 39 # 37 # 32 # 31 70 % 50% of Al (OH)3 60% of SiO2 # 26 / / / 50% of SiO2 + # 25 / / / 10% of Al (OH)3 40% of SiO2 + # 27 / / / 20% of Al (OH)3 35% of SiO2 + # 30 # 28 # 25 # 20 FILLER 25% of Al (OH)3 LOAD@ 60 % 25% of SiO2 + 28-31 28-31 24-27 19-22 35% of Al (OH)3 20% of SiO2 + 30-33 29-33 25-28 23-24 40% of Al (OH)3 10% of SiO2 + 32-35 30-32 27-29 24-26 50% of Al (OH)3 ZINC BORATE
FILLER 10% de SiO2 et # 32.5 LOAD@65% 55% de Borate pas de valeurs FILLER 10% de SiO2 et # 30.3 LOAD@ 50% de Borate pas de valeurs 60 % 60% de Borate # 33.6 pas de valeurs The coating material was prepared in the follow Lng manner: after having been mixed with a suitable
quantity of the flame-retardant substance, the inorganic
filler (here, silica) was blended, one half with the
liquid resin (epoxide resin marketed by the Swiss firm
Ciba-Geigy under the name "Araldite CY 225"), and the
other half with the hardener, also in the liquid state
(an anhydride marketed by the abovementioned firm under
the name "Hardener HY 227"). The two mixtures were then
combined and the whole was blended and then placed in an
oven (80 to 1500C) for setting.
The methods of measurement in these tests were in
accordance with UTE Standard NF T51-071 at 200C and EDF
Standard HN20 M40 at 80, 150 and 2000C.
Note - The ranges of valves reflect the
fact that the measured O.I. depended in
this case on the source of the commercial
alumina employed.
- The boxes marked with a "/" reflect
measurements deemed to be useless. The
corresponding values, bearing in mind that
obtained at 20"C, are wholly unacceptable,
being too far below the stipulated minimum O.I.
It is immediately apparent that in the case of a
total loading of 60 * the minimum content of Al(OH)3 to
be conformed to is 20-25 %. Below this, the stipulated
minimum values of the 02 index are no longer ensured effectively. Additional measurements, not reported here,
have made it possible to demonstrate that with an overall
loading of 70 % by weight (lust part of the table), the
threshold value of Al(OH)3 drops to 20 %. It is also seen
that in the case of zinc borate the minimum threshold is much higher: at least 50 % by weight, which reflects a
greater effectiveness of alumina trihydrate, as was
known.
The Rates of Combustion reported in Table II
below were measured in the apparatus employed for the
determination of the Oxygen Indices on test specimens in the shape of small elongate plaques 100 mm in length, 6.5 mm in width and 4 mm in thickness. The test specimens incorporate two marks following each other along the length, the first being situated at 10 mm from one end, the second at 60 mm. The combustion time of the test specimen between the two marks is noted at ambient.
temperature and the mean Rate of Combustion (in mm/s) is deduced from this as a function of the proportion of oxygen in a combustive mixture of oxygen and nitrogen. 7 TABLE II: Rate of Combustion
I Oxygen per cent 1 35% , 40% : 45% : 50% 1 60% max. Combustion rate autorised (10m/s) 0.15 0.30 0.45 0.6 0.9 ALUMINA ARI-HYDRATE
70% of SiO2 0.28 0.37 0.47 0.58 1.05 FILLER LOAD @ 20% of SiO2 + 0.06 0.10 0.13 0.19 0.25 70 % 50% ofAl (OH)3 60% of SiO2 ~0.35 ~0.50 ~0.60 ~0.75 #1.0 50% of SiO2 + ~0.35 ~0.45 ~0.60 ~0.75 #1.0 10% of Al(OH)3 40% of SiO2 + ~0.20 ~0.35 ~0.45 ~0.55 #1.0 20% of Al (OH)3 35% of SiO2 + ~0.18 ~0.28 ~0.38 ~0.49 ~0.95 FILLER 25% of Al(OH)@ LOAD @ 60 % 25% de SiO2 + 0.14 0.20 0.27 0.34 0.56 35% d' Al (OH)3 0.17 0.23 0.30 0.37 0.59 20% de SiO2 + 0.13 0.19 0.24 0.30 0.48 40% d'Al (OH)3 0.16 0.20 0.27 0.35 0.56 10% de SiO2 + 0.07 0.14 0.20 0.26 0.37 50% d'Al (OH)3 0.10 0.16 0.23 0.29 0.40 I ZINC BORATE
FILLER 10% de SiO2 + ~0.16 ~0.21 ~0.30 ~0.8 LOAD65% 55% de Borate FILLER 10% de SiO2 + ~0.25 ~0.43 ~0.65 ~0.98 LOAD " 50% de Borate 60 % 60% de Borate ~0.25 ~0.31 ~0.52 ~0.96 Note: The meaning of pairs of values, where
shown, is the same as in the preceding
Table.
As can be easily concluded, the values given in
Table II corroborate those of Table I in showing that, in respect of the "Rate of Combustion" criterion as well, the "bottom" value to which the quantity of A1(OH)3 in the starting mixture should conform is substantially 25 % by weight (a little below 50 % in the case of the borate).
These conclusions remain wholly valied in the light of Table III below, showing the results of the series of tests carried out on the third parameter selected, the Upper Heating Power (U.H.P.). As can be seen, the maximum permitted value of 11 MJ per kg of material is never exceeded.
TABLE III: Upper Heating Power (Test method: adiabatic calorimetry according to UTE
Standard NF M 03-005.)
Filler Load : Filler Load : 60% 70% ALUMINA ART-HYDRATE
70%SiO2 20%SiO2 60% SiO2 40%SiO2 35% SiO2 25%SiO2 10% SiO2 + + + + + 50% Al. 10% Al. 25% Al. 35% Al. 50% Al.
~ 8 ~ 7 ~ 11 ~ 11 ~ 11 ~ 11 ~ 11 ZINC BORATE
10%SiO@+55%Bor. 10% SiO@ + 50% of Borate 60% of Borate ~ 10 ~ 11 ~ 11 These tables clearly show, therefore, the influence on the fire behaviour when a material which is flame-retardant due to water formation and elimination is added in suitable proportions to the initial resin, in accordance with the invention.
These results reflect a high release of water by the coating resin when the latter reaches abnormally high temperatures. A phenomenon of this kind acts as a selfcontrolled heat absorber which retards and has a braking action on the combustion of filled resin and endows the latter with the required characteristic of self-extinguishability.
Of course, an abundant formation of water molecules actually within the mass is not without consequences for the quality of the coating resin. The latter decomposes in the course of a process of this kind and, in general, can no longer be reemployed subsequently. The transformer must then be replaced or reconditioned.
The loss in weight of the flame-retardant substance with the rise in temperature is a good guide to its water-forming capacity. It will be noted, as shown by the suppliers' specifications, that in the case of Al(OH)3 the loss in weight is already close to 30 % at 3000C. Furthermore, it takes place practically solely at this temperature, in the form of a peak which is narrow and of high amplitude, which bears witness to the energy and the intensity of the phenomenon when this temperature level, characteristic of the flame-retardant agent employed, is reached.
This is verified, whatever the variety of commercial alumina trihydrate employed, as is shown more accurately by Table IV below.
This table of values is given merely by way of information, on the basis of data from suppliers of
A1(OH)3 sold under the name "Alcoa" in varieties whose commercial references are repeated for identification in the columns of the table.
TABLE IV: Analysis of endothermic water formation Peaks
(The temperature increases were performed from
25 to 6000C at a constant rate of 10 C/min.)
M15 S65/40 C31 M6 M15S S65/150 MEDIUM SODA Temp. peak 196 205 216 180 195 188 197 start ( C) Temp. peak 372 385 353 382 355 370 353 end ( C) top temp. of 316 312 314 314 311 309 312 peak ( C) #H of peak 1.03 1.01 1.07 1.06 1.03 1.0 1.02 (in kJ/g) For the effects expected for the type of flameretardant substance recommended by the invention to be fully satisfactory @ it is not only necessary that the intense water loss peak should be developed at suitable temperatures, that is to say between the normal hot operating point and that where the coating can ignite, but also that a formation of water should actually take place only in the case of abnormal overheating.In other words, it is appropriate to avoid any risk of premature decomposition of the coating resin, which could be caused by an untimely formation of water between the ambient temperature and that of the normal hot operation of the transformer.
It is this difficulty which is resolved by the second main characteristic of the invention, namely a moderate preaging of the resin, as will be seen in detail below: 2) PARTIAL PRELIMINARY DEHYDRATION OF THE OUANTITY OF
THE FLAME-RETARDANT SUBSTANCE WHICH IS ADDED.
This involves causing a preliminary dehydration in order to avoid its being produced subsequently in the transformer. However, this dehydration must be only partial, since it is required otherwise at a high temperature, when the transformer heats abnormally and when there is a danger that ignition may take place.
This dehydration can advantageously be performed by heating the A1(OH)3 beforehand. The objective to be attained is 'not a complete elimination of the water capable of being formed in a temperature range from the ambient to the "hot" operating temperature of the transformer (and which will be colourfully referred to as "volatile water" to emphasize that it must be released at low temperature), but a sufficient elimination in order that the residual "volatile" water may be present in too small a quantity to give rise to a decomposition of the resin. It has been possible to observe, in fact, that when the alumina trihydrate had not been preheated before being added to the inorganic filler, bursting of the resin coating the electrical coil windings of test transformers occurred at the operating temperature, which made it necessary for them to be rejected.
A convenient way of successfully producing the partial dehydration of the flame-retardant substance by preheating is to consider its curve of weight loss as a function of time. In the case of a substance employed for the first time, this can be advantageously done in two steps:
- a first step, on an analytical sample intended for determining the quantity of water which is eliminated over a prolonged period at a constant temperature which is that (or close to that) of the normal hot operation of the transformer;
- a second step, this time of treating all the material, consisting in heating it to a relatively high temperature in order to attain quickly - and hence under industrial conditions - a loss in weight corresponding to the water elimination value determined in the preceding stage.
This second step will obviously be repeated at each preparation of resin, whereas the first is actually required only once, to characterize a type of flameretardant substance which had never been employed previously.
The curves of Figures 1 and 2 clearly illustrate this first stage of investigation of samples, showing, at certain values of temperature, the rate of change in the loss in weight as a function of time for certain values of the temperature. The curves correspond to some of the varieties of "Alcoa" alumina trihydrate of Table IV, indicated by their commercial references at the righthand end of each curve. Three temperature values have been considered: 140, 160 and 180 OC, so as to cover properly the usual "hot" running conditions of the transformers. To avoid unnecessary overloads, the three corresponding groups of curves have been separated in the two figures: Figure 1 shows together the groups at 1400C (broken lines)-and 1600C (solid line); Figure 2 shows only the group at 1800C, using a solid line.
As can be seen, all these curves are advantageously generally logarithmic in form, with a very fast increase at the beginning, followed by a plateau which is slightly inclined to the horizontal, this plateau being reached proportionately earlier, the higher the working temperature. Thus, at 1800C (Fig. 2), most of the "volatile" water (approximately 80 %) has already formed after only 140 h, out of more than 700 h of the total test period. The loss in weight then ranges approximately between 5.3 % and 2.5 %, depending on the type of alumina.
The existence and the stability of the plateaux is verified by testing aluminas which have been preheated to a higher temperature. Tests have thus been carried out on two samples of the "M15" variety, one of which was kept at 180at and the other at 200 C, for 18 h. The results appear in Fig. 1 in the form of two straight lines (A) and (B) whose original ordinates are 1.6 % and 4.2 % of weight loss in the case of 180 and 200 C respectively. They can be seen to be virtually horizontal, which clearly reflects the insensitivity of the samples to a second heating to a lower temperature, as a result of the fact that virtually all of their "volatile water" at 1400 or at 1600C has effectively been eliminated during the first heating.
Furthermore, in Fig. 2 it can be seen that after 18 h at-180 C, an "M15" sample is barely midway along its curve of rapid increase in weight loss due to elimination of water.
It will immediately be understood that these curves have a characteristic favourable form which enables the degree of preliminary partial dehydration which must be achieved to be very easily deduced. Thus, for instance, the beginning of the plateau can be chosen as a criterion and the value given by the ordinate at this beginning of the plateau can be taken as the proportion of "volatile" water to be eliminated.
Thus, the figures show that, in the case of the "S65/40" variety, 2.5 % of weight loss can be taken, for a transformer operating temperature of 1400C, 4 % at 1600C and 5.5 % at 1800C.
Similarly, the "M15" variety will put up with a preliminary weight loss of 2 % for a transformer operation at 1600C and 3.5 % at 1800C.
At 14 OOC, the curve for this variety is less typical in form. It will be noted, however, that the value of 0.7 % obtained after approximately 500 h will be perfectly suitable.
To make the concept more concrete, it can therefore be said in general that the preliminary weight loss to be aimed at ranges approximately between 0.5 % and
10 % for all the flame-retardant substances selected for implementing the invention.
The subsequent conversion to the industrial stage consists merely in consequently dehydrating the bulk of flame-retardant substance using methods of fast heating in an oven, with monitoring of the loss in weight, for example by gravimetry with the aid of an automatic balance whose pan is placed in the oven enclosure.
By way of information, in the case of aluminas of the "Ml5" type, it has been possible to obtain the loss in weight of 3.5 %, required for a transformer operation at 1800C, after only 6 hours' heating at 2000C.
This heating operation will, of course, be proportionately faster, the higher the heating temperature. However, for obvious reasons of maintaining a high water formation capacity, necessary in the event of abnormal overheating, care will be taken not to greatly exceed, and preferably to remain below, the onset temperature of the peak of the intense water elimination which is characteristic for the flame-retardant substance employed and some values of which are given in Table IV above.
If the need to operate using gravimetry is undesirable, especially because of excessively large quantities of material which it might be necessary to process1 it will be advantageous to proceed via an intermediate step which makes it possible to convert the loss in weight which is aimed at into a heating time.
This can be done with the aid of a second sample for measuring the flame-retardant substance in question, for which the weight proportion of water to be eliminated is known and which is subjected to a fast heating at a specified high temperature. This heating will be carried out with continuous weighing of the sample to make it possible to measure the time needed to arrive at a weight loss corresponding to the known proportion of water to be eliminated. The measured value defines the duration of the heating operation at a temperature which is strictly identical with that of the above intermediate operation, to which the bulk of the flame-retardant substance to be processed will be subjected.
If need be, the correct performance of the operation may be confirmed by gravimetric determination at a high temperature of, for example, 1200"C, of the residual water content of a sample taken for this purpose from the;bulk of the flame-retardant substance which is processed. By comparing with the total initial water content (usually approximately of the order of 20 to 35 % by weight) which will have been determined previously in a similar manner on a reference sample, it can be deduced therefrom that the quantity of "volatile" water actually eliminated is well in accordance with that aimed at.
It will be noted that the heating time is not completely independent . of the particle size of the material. In the course of tests it has been possible to observe that a coarse particle size resulted in a greater loss in weight than a fine particle size, for a given heating time.
It will also be observed that the weight loss values determined above by reading curves for tests carried out on samples do not in any way represent an upper limit not to be exceeded. Only, as these values correspond to the beginning of the plateau, there is in principle no point in prolonging the heating in order to gain a few tenths of a per cent which, in any case, are probably too insignificant to produce a water release capable of damaging the quality of the coating resin.
It will certainly have been understood that these curves, which apply to the normal operating temperatures of the transformer when hot, reflect the behaviour of so-called "volatile" water at ' these temperatures. At higher temperatures the plateaux are situated at higher levels and are reached more quickly, especially at the peak temperature characterizing the flame-retardant substance employed, which, as we have seen, is situated in the neighbourhood of 300"C for all the Al(OH)3 varieties investigated.
Pretreated in this manner, the flame-retardant substance becomes ready for use. It remains to complete the preparation of the coating resin in the usual manner: the inorganic filler, after having being intimately mixed with a suitable quantity of partially predehydrated flame-retardant substance, is divided into two equal parts. One is then introduced into the bath of pure resin and the other into the hardener, also in the liquid state. The two mixtures are blended separately to form two solid-liquid suspensions, and are then combined into a single mixture which is in its turn blended to ensure good homogeneity. The resulting pulp is then poured into a mould in which the electrical coil winding of the transformer which it is intended to coat has been -arranged beforehand. After pouring, the mould is placed in an oven for the resin to solidify.After removal from the oven and cooling, the block of resin incorporating the coil winding is demoulded and can then be fitted into the transformer intended to receive it.
It is obvious that the invention could not be limited to the examples described above, but extends to many alternative forms or equivalents, so long as the characteristics listed in the claims which follow are observed.
In particular, the invention is not limited to transformers as such. This term, as employed here, should be understood, in fact, to mean more broadly all the inductive electrical apparatus or equipment capable of operating at relatively high temperatures, from 100 to 200"C as we have seen, and whose electrical windings can be encased in a block of insulating resin.
Similarly, although the invention was originally conceived for applications of heat-curable resins (coating of inductive coil windings, particularly in transformers), it relates, in fact, to all dielectric coating materials. It offers an especially marked advantage in the case of electrical installations which nominally function for long periods at an elevated or moderately elevated temperature. This means that it will be particularly advantageous to employ it for coating resins which are already capable of good thermomechanical behaviour.
Claims (14)
- I. Coated dry transformer, or a similar electrical installation, in which at least one winding is coated with a filled insulating resin containing a substance which is flame-retardant due to water formation when the temperature rises, characterized in that a proportion of the filler equal to at least 20 % of the total weight of the coating resin consists of the said flame-retardant substance which has been previously partially dehydrated in such quantity that it does not cause an untimely formation of water in the coating resin capable of being detrimental to the quality of the latter, while the transformer is employed in its normal temperature conditions.
- 2. Electrical conductor coated with a filled insulating resin containing a substance which is flameretardant due to water formation when the temperature rises, characterized in that a proportion of the filler equal to at least 20 % of the total weight of the coating resin consists of the said flame-retardant substance which has been previously partially dehydrated in such quantity that it does not cause an untimely formation of water in the coating resin capable of being detrimental to the quality of the latter, while the conductor is employed in its normal temperature conditions.
- 3. Dry transformer or conductor coated,according to Claim 1, or according to Claim 2, characterized in that the said flame-retardant substance exhibits a loss in weight approximately from 0.5 to 10 % relative to its initial undehydrated state.
- 4. Dry transformer or conductor coated,according to Claim 1, or according to Claim 2, characterized in that the flame-retardant substance is alumina trihydrate.
- 5. Process for the preparation of a filled insulating resin for coating electrical conductors or windings, of coated dry transformers, or of other similar electrical installations, according to which there is added to the initial liquid resin, in addition to the filler, a substance which is flame-retardant due to water formation when the temperature rises, which process is characterized in that the said substance 'is added in a proportion of at least 20 % of the total weight of the coating resin and in that before the said substance has been partially dehydrated in such quantity that there is no untimely formation of water capable of being detrimental to the behaviour of the coating resin, while the electrical installation remains in service at its nominal operating temperature.
- 6. Process according to Claim 5, characterized in that the flame-retardant substance is subjected to a preliminary partial dehydration treatment until it exhibits a loss in weight of approximately between 0.5 to 10 % of its initial weight.
- 7. Process according to Claims 5 and 6, characterized in that alumina trihydrate is employed as the flame-retardant substance.
- 8. Process according to Claim 5, characterized in that the degree of preliminary partial dehydration of the flame-retardant substance which is employed for the first time is determined by taking a measurement sample which is subjected to a prolonged heating at a constant temperature lower than that of the peak of elimination of water belonging to the flame-retardant substance employed and by considering the rate of change in the loss in weight of the said sample with time.
- 9. Process according to Claim 5 or 8, characterized in that the preliminary partial dehydration of the flame-retardant substance is performed by subjecting it to a rapid heating until its loss in weight corresponds to the quantity of water to be eliminated according to a proportion determined beforehand on a measurement sample whose change in the loss in weight has been followed as a function of time during a prolonged heating at a temperature below that of the peak of elimination of water belonging to the flame-retardant substance employed.
- 10. Process according to Claim 9, characterized in that the said rapid heating is performed for a period which has been predetermined by a heating operation conducted at an identical temperature and performed with weighing of a sample of the flame-resistant substance employed until this sample exhibits a weight loss corresponding to the quantity of water which it is desired to eliminate.
- 11. Process according to Claim 10, characterized in that the said quantity of water to be eliminated has been determined beforehand by following the change with time of the loss in weight of a measurement sample which has been subjected to a prolonged heating at a constant temperature which is lower than that of the peak of elimination of water belonging to the flame-retardant substance employed.
- 12. A coated dry transformer, substantially as herein described.
- 13. A process for the preparation of a coating resin, substantially as herein described.
- 14. An electrical winding coated with a flame-retardant coating composition prepared by a process substantially as herein described.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8805641A FR2630578B1 (en) | 1988-04-22 | 1988-04-22 | DRY COATED TRANSFORMER WITH IMPROVED FIRE BEHAVIOR AND PROCESS FOR PREPARING ITS COATING RESIN |
Publications (3)
Publication Number | Publication Date |
---|---|
GB8909009D0 GB8909009D0 (en) | 1989-06-07 |
GB2217719A true GB2217719A (en) | 1989-11-01 |
GB2217719B GB2217719B (en) | 1991-12-11 |
Family
ID=9365755
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB8909009A Expired - Lifetime GB2217719B (en) | 1988-04-22 | 1989-04-20 | Dry transformer with coated windings,similar electrical conductors or installations,and process for the preparation of their coating resin |
Country Status (16)
Country | Link |
---|---|
JP (1) | JP2722405B2 (en) |
AT (1) | AT402242B (en) |
BE (1) | BE1006158A4 (en) |
CA (1) | CA1325072C (en) |
CH (1) | CH678988A5 (en) |
DE (1) | DE3912874C2 (en) |
DK (1) | DK192089A (en) |
ES (1) | ES2010928A6 (en) |
FR (1) | FR2630578B1 (en) |
GB (1) | GB2217719B (en) |
IE (1) | IE64367B1 (en) |
IT (1) | IT1234438B (en) |
LU (1) | LU87494A1 (en) |
NL (1) | NL8900954A (en) |
PT (1) | PT90346B (en) |
SE (1) | SE508250C2 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AT402242B (en) * | 1988-04-22 | 1997-03-25 | France Transfo Sa | DRY TRANSFORMER WITH SHEATHED WINDINGS AND SHEATHED LADDER AND METHOD FOR PRODUCING THE RESIN FOR SHEATHING |
US6638567B1 (en) * | 1999-03-16 | 2003-10-28 | Vantico, Inc. | Hardenable composition with a particular combination of characteristics |
CN111623884A (en) * | 2020-05-28 | 2020-09-04 | 山东大学 | Transformer hot spot temperature identification method and system based on improved heat network model |
EP3848946A4 (en) * | 2018-09-03 | 2022-09-07 | Sumitomo Seika Chemicals Co., Ltd. | Laminate of conductor and insulating film, coil, rotating electrical machine, insulating coating, and insulating film |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6567797B1 (en) * | 2018-09-03 | 2019-08-28 | 住友精化株式会社 | Laminated body of conductor and insulating film, coil, rotating electric machine, insulating paint, and insulating film |
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- 1989-04-04 CH CH1231/89A patent/CH678988A5/fr not_active IP Right Cessation
- 1989-04-06 LU LU87494A patent/LU87494A1/en unknown
- 1989-04-14 IT IT8909403A patent/IT1234438B/en active
- 1989-04-14 BE BE8900417A patent/BE1006158A4/en not_active IP Right Cessation
- 1989-04-14 ES ES8901315A patent/ES2010928A6/en not_active Expired
- 1989-04-17 NL NL8900954A patent/NL8900954A/en not_active Application Discontinuation
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- 1989-04-18 CA CA000597015A patent/CA1325072C/en not_active Expired - Fee Related
- 1989-04-19 DE DE3912874A patent/DE3912874C2/en not_active Expired - Fee Related
- 1989-04-20 DK DK192089A patent/DK192089A/en unknown
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- 1989-04-20 GB GB8909009A patent/GB2217719B/en not_active Expired - Lifetime
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AT402242B (en) * | 1988-04-22 | 1997-03-25 | France Transfo Sa | DRY TRANSFORMER WITH SHEATHED WINDINGS AND SHEATHED LADDER AND METHOD FOR PRODUCING THE RESIN FOR SHEATHING |
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CN111623884A (en) * | 2020-05-28 | 2020-09-04 | 山东大学 | Transformer hot spot temperature identification method and system based on improved heat network model |
CN111623884B (en) * | 2020-05-28 | 2021-05-18 | 山东大学 | Transformer hot spot temperature identification method and system based on improved heat network model |
Also Published As
Publication number | Publication date |
---|---|
ATA94689A (en) | 1996-07-15 |
SE8901148L (en) | 1989-10-23 |
JP2722405B2 (en) | 1998-03-04 |
NL8900954A (en) | 1989-11-16 |
CH678988A5 (en) | 1991-11-29 |
AT402242B (en) | 1997-03-25 |
DK192089D0 (en) | 1989-04-20 |
FR2630578B1 (en) | 1990-07-27 |
LU87494A1 (en) | 1989-09-12 |
FR2630578A1 (en) | 1989-10-27 |
DE3912874C2 (en) | 1996-12-12 |
IE891229L (en) | 1989-10-22 |
DK192089A (en) | 1989-10-23 |
BE1006158A4 (en) | 1994-05-31 |
IT8909403A0 (en) | 1989-04-14 |
ES2010928A6 (en) | 1989-12-01 |
CA1325072C (en) | 1993-12-07 |
IT1234438B (en) | 1992-05-18 |
DE3912874A1 (en) | 1989-11-09 |
GB2217719B (en) | 1991-12-11 |
SE508250C2 (en) | 1998-09-21 |
SE8901148D0 (en) | 1989-04-03 |
PT90346B (en) | 1994-04-29 |
GB8909009D0 (en) | 1989-06-07 |
IE64367B1 (en) | 1995-07-26 |
PT90346A (en) | 1989-11-10 |
JPH0212904A (en) | 1990-01-17 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
PE20 | Patent expired after termination of 20 years |
Expiry date: 20090419 |