The Conclave Reports
90 The first conclave report, that of 11 August 2008, relevantly reads as follows:
'2. Points of Agreement:
2.1 Blistering in Narellan Pools
2.1.1 There is a high incidence of blistering in pools where Hetron 942 has been used in the tie layer.
2.1.2 Blisters occur in the tie layer close to (within ~100µm) but not including the gelcoat (shown by microscopic examination of the pool cutouts taken around the blister)
2.1.3 Blisters form where there are glass fibres present in the tie layer
2.1.4 Blisters in a tie layer may form when there are water soluble materials (either present initially or formed by the action of water) and/or poorly bonded fibres
2.1.5 There is no evidence for blisters deep in the tie layer or in the structural laminate of any pool sections examined
2.1.6 The blisters examined are on the order of 1 cm in diameter.
2.1.7 The nature of the blistering is similar for all pool samples examined (ie. not dependent on gelcoat composition).
2.1.8 There is evidence that there is a layer of vinyl ester resin and wet-out glass fibres against the gelcoat in a region of tie layer away from the blisters.
2.2 Composition of tie layer in pools fabricated with Hetron 942
2.2.1 The tie layer of a blistered Narellan pool analyzed by Ashlands and independently by Prof George, by infra-red micro-spectrophotometry, exhibited a peak which gave evidence for the presence of a terephthalate resin as well as a vinyl ester resin within the tie layer.
2.2.2 This has been confirmed by spectral comparison with a spectrum of the known terephthalate resin in the structural layer.
2.2.3 Spectral subtraction has shown that this terephthalate resin was present in the tie layer of blistered pool 8036, made with Hetron 942 resin, and not pool 8031 which was not made with Hetron 942 resin.
2.2.4 The origin of the terephthalate resin in the tie layer is unknown.
2.2.5 Measurement of the relative amount of terephthalate compared to vinyl ester resin shows that within error the amount appears constant across the tie layer.
2.3 Specification and composition of Hetron 942 resin delivered to Narellan Pools
2.3.1 The composition of Hetron 942 resin, batch 05310911, is uncertain because of an amount of 400 to 450 kg that cannot be accounted for in the production (run) sheet.
2.3.2 Examination of several run sheets has indicated to us that it was normal practice to record only the final test data in the last column.
2.3.3 This practice appears to have been followed in the case of batch 053109001 of 26-Feb-01 so that the amount of 400 to 450 kg extra resin and/or styrene cannot be accounted for as the necessary extra material to achieve specification.
2.3.4 Examination of the production sheet shows that the gel time was probably not measured after the final addition of three drums of Hetron 914, but it is not possible to determine whether this is significant.
2.3.5 The gel time specification is agreed to be 30 to 40 min.
2.3.6 The resin supplied in the second delivery was out of specification for viscosity (both cone and plate, and Brookfield).
2.3.7 There is no significant difference between the incidences of failure (37 %) for the second delivery compared with the first delivery (35 %) of Hetron 942 resin.
2.3.8 Extra additives were included in the production (possibly after the addition of one drum and then two drums of Hetron resins, based on the proportion of additives added) to allow for the accelerator and stabiliser components.
2.3.9 The production batch of 26-Feb-01 differed in composition from the trial batch of 17-Nov-00, because of the extra resin and additives.
2.3.10 The thixotrope level in the production batch of 26-Feb-01, following addition of extra resin, approached the value in the trial batch of 17-Nov-00.
2.2.11 The differences in styrene concentration between the trial and production batches are not believed to be a factor in the formation of blisters.
2.4 Fabrication procedure for Pools at Narellan Pools
2.4.1 From separate site visits conducted by both experts, the pool fabrication procedure was such as to avoid incorrect resin application and/or contamination by having a separate work station for each layer of the pool construction process.
2.4.2 Spraying of resin and glass fibres and consolidation of resin and glass fibres was in accordance with expectations. Resin thickness was intermittently checked with a depth gauge.
2.4.3 The production records show an apparent wide difference between time of fabrication for different pools that could be construed as an indication of excessive time between depositing successive layers. However there is no correlation between these figures and incidence of failure.
2.4.4 We have been advised that the time taken between depositing the gelcoat and tie layer is less than 24 hours, but this is not recorded on the production sheets.
3. Points of disagreement
In the following section, the points of disagreement are presented as separate position statements which give each expert's opinion on the evidence and any moderation of the points of agreement in Section 2 which is felt to be appropriate.
3.1 Position of Professor George.
The evidence is presented in more detail in my Reports of 12 July 2004, 28 March, 2007 and 14 April, 2008. The important points and interpretation of the evidence from these reports are summarized below.
3.1.1 The statistics of failure of pools fabricated by Narellan Pools with Huntsman Hetron 942 resin Batch 053109001 point to a fundamental problem with the resin as supplied in the two deliveries of March and November 2001. The failure rate of these pools was 34% compared to an industry accepted standard achieved by Narellan of <1 % when using resin other than this batch of Hetron 942.
3.1.2 Three units (pools or spas) were fabricated with a Trial batch of 197 kg of Hetron 942 (Batch 238-034) manufactured by Huntsman in November 2000 and none of these have failed. In contrast, 77 units were manufactured with tie layer resin containing (either totally or partially) Hetron 942 resin of Batch 053109001 of 6830 kg. Of these, 28 units or 36% have failed by blistering of the tie layer.
3.1.3 Examination of production and Quality Assurance (QA) records for this batch of resin (053109001) point to it differing significantly from the trial batch of resin (238-034) in composition and compliance with the Huntsman specification for this resin.
3.1.4 The production sheet for Batch 053109001 shows that what was originally intended to be a batch of 4770 kg had become a batch of 6830kg through addition of extra resin and styrene because the resin could not readily be brought into viscosity specification. This may be linked to the contaminant discussed in 3.1.5 below, but was exacerbated by the fact that the Manufacturing Instruction No 53584 for batch 053109001 had a level of thixotrope (Aerosil 202) viscosity modifier that was 36% higher than used in the trial batch. The attempts to bring the resin into specification resulted in the addition of extra resin so the ratio of Hetron 922 to Hetron 914 changed as did the content of stabilizers, accelerator etc. (In spite of the addition of further additives, these were still ≥20% below what had been used in the trial batch).
3.1.5 Further, there is an amount of 400 to 450 kg of unknown material that has been added as part of this process of adjustment or was an unknown contaminant at the beginning of the batch. There is strong evidence that the Hetron 942 resin in the tie layers of pools fabricated by Narellan contains a contaminant which is a terephthalate resin. This is manufactured by Huntsman as a laminating resin and it may be the unknown extra material in 2.2.2 above. The fact that it is seen in uniform concentration through the tie layer of all pools analyzed by IR micro-spectrophotometry suggests that it has not arisen due to interpenetration from the laminate during fabrication, but was originally present in Batch 053109001. In addition, the levels of contaminant in all pools examined appears to be similar.
3.1.6 Inspection of the factory of Narellan Pools has shown that it is not possible for laminating resin to contaminate the tie layer resin. The Hazcons delivering the resin are sealed and tapped into directly. The work stations and spray equipment for the tie layer are separated and not used for laminating.
3.1.7 The QA records of Huntsman show that the resin as supplied by Huntsman to Narellan in the second delivery in November 2001 was outside viscosity specification and no adjustment had been made by them prior to delivery. Further, Huntsman advised Narellan that it was in specification and provided a QA sheet from the original production and not the QA data that had been generated on the resin actually delivered.
3.1.8 By using the Huntsman QA data for viscosity as measured on the resin batch 053109001 at manufacture and during storage, it may be determined that it drifted quite quickly out of specification such that it is likely to have been at the upper limit of, or just outside viscosity specification at the time that Narellan fabricated the first pools with this batch in March 2001.
3.1.9 The sum of these composition and performance differences between the trial batch 238-034 and the production batch 053109001 would have been to provide a material with different microscopic wetout properties when used to make pools by Narellan in the usual way. Further the contaminant will have compromised the integrity of the vinyl ester resin and its inherent resistance to hydrolysis (since a terephthalate resin has inherently lower hydrolytic resistance than a vinyl ester resin).
3.1.10 For the above reasons, the Hetron 942 resin batch 053109001 when used as a tie layer by Narellan Pools did not have the necessary quality or performance characterisitics [sic] to provide pools with resistance to osmotic blistering.
3.2. Position of Professor Shanks
My observations, testing and interpretation is presented in my reports of 6 October 2004 and 15 July 2008. Information from these reports is included in the points of agreement and some further points are raised in this section.
3.2.1 Hetron 942 was a special low styrene content vinyl ester resin based on Ashland Hetron 942/35. Cone-plate and Brookfield viscosity measurements, performed by Huntsman Chemicals, aim to predict the performance in a spray gun and upon subsequent consolidation. The behaviour of Hetron 942 in spray application, with glass fibres, may be different from the behaviour of other vinyl ester or unsaturated polyester resins.
3.2.2 No comparable low styrene content vinyl ester resin is known to me to be available from Huntsman Chemicals or their competitors. I am not aware of Narellan Pools, previously or at the time of using Hetron 942, using an alternative low styrene content resin.
3.2.3 The trial batch was submitted to the normal quality control tests. I am unaware of any more rigorous performance testing being carried out by Huntsman Chemicals or Narellan. The basis on which the trial batch was accepted and upon which Narellan decided to proceed with order of a production batch has not been revealed.
3.2.4 The trial batch was used in preparation of three pools. There was no reported blistering. On the basis of the overall incidence of blistering of 36 % this would suggest that one pool of the three prepared from the trial batch should blister. The sample size of three pools, however, is insufficient to attribute significance to the observations of the three pools.
3.2.5 The gel coat and tie layer of sampled failed pools were readily separated, mainly along the interface. This indicates poor fibre wet-out by the resin or incomplete consolidation of the resin-fibre glass mixture in the vicinity of the gel coat-tie layer interface.
3.2.6 Incomplete cure of the Hetron 942 in the tie layer, prior to spraying the structural layer, was not supported by inspection nor observed in tests such as Barcol Hardness.
3.2.7 The source of contamination by terephthalate is unknown. The normal procedures of Huntsman Chemicals and Narellan Pools would avoid such contamination. The resin batch prepared prior to Hetron 942 PAS was Aropol 6433PAS that consists of Hetron FR992H, a vinyl ester resin, and an ortho-phthalate resin (Annex 7). Terephthalate resin was not present in the prior batch. Further, it is unknown whether an impurity of terephthalate would lead to blistering.'
(Emphasis added)
91 What is significant about the first conclave report is that what appears under the heading 'Points of disagreement', are not points on which Professors George and Shanks necessarily disagree at all. For example, Professor George's conclusion at 3.1.10 is not put in issue by Professor Shanks and nothing in his evidence in chief or in cross-examination suggests otherwise. Again, what Professors Shanks says at 3.2.7 concerning the respective normal procedures of Huntsman and Narellan avoiding contamination, is not a point of disagreement; on the contrary, so far as Narellan is concerned, it is totally consistent with the Point of Agreement at 2.4.1. I raised this observation with Professor Shanks when I asked him:
'You seem to be like two ships passing in the night?'
To which he replied:
'Yes, I see that too, your Honour, and I suppose, in reaching the points of agreement, we made a list of things where we tried to divide the issues into as many specific items as possible, but in recording points of disagreement, we went away and did those independently, and we didn't, sort of, come back together and look at the disagreements, and maybe another iteration might have said what you are saying.'
I then said:
'So the label, Points of
Disagreement, is really not a correct description?'
To which he replied:
'Yes, well …'
92 There is no doubt that Professor Shanks' explanation as to what he and Professor George did after they had identified their points of agreement, that is, go off and independently write their own comments without any reference to what the other was writing and lump them under the head 'Points of disagreement', has led to the predicament that I raised with him.
93 There was a concession by Professor Shanks that there may be some disagreement between him on the one side and Professor George on the other, but he never attempted to identify what that disagreement was even though I gave him the opportunity to do so.
94 I have to say that in assessing the respective comments of the two experts under the head 'Points of disagreement', and I hasten to add that in saying what I am about to say is not a criticism of Professor Shanks nor the evidence he gave, but the evidence of Professor George was directed or fashioned in a way which was more utile to the task of resolution of the issues in dispute between the parties. Neither in his points of disagreement in the first conclave report nor in his oral evidence, in chief and in cross-examination, did Professor Shanks challenge or take issue with Professor George's conclusion at 3.1.10, nor the process of reasoning by which he got there.
95 The second conclave report, that of 3 March 2009, relevantly reads as follows:
'2. Points of Agreement:
2.1 Identification of materials used in batch 053109001 of Hetron 942 resin produced by Huntsman Chemical Company on 26 February 2001.
2.1.1 The Production Sheet (No 105 of Applicants' Bundle of Documents) for the batch 053109001 of Hetron 942 does not reflect the final composition of the resin as analyzed in failed Narellan pools.
2.1.2 Infrared (FT-IR) analysis of the tie layer of the retained samples of pools fabricated by Narellan from batch 053109001 of Hetron 942 shows that it contains a component that is not consistent with the materials listed in the Production Sheet.
2.1.3 This analysis has been performed by Ashland Chemicals as well as separately by Professors Shanks and George and Shows a prominent signature at 730 cm-1 that is not present in vinyl ester resins (eg Hetron 922) manufactured by Huntsman Chemical Company or other suppliers of vinyl ester resins (eg Dow Chemical Company, manufacturer of Derakane resins).
2.1.4 Infrared analysis of the tie layer of pools fabricated by Narellan using Derakane resins (see Appendix 1) does not show this signature and this may be used to differentiate pools that have been manufactured using Derakane resin from those using Hetron 942 resin of batch 053109001.
2.1.5 The identification of the contaminant material with the infrared signature band of 730 cm-1 is uncertain. If it is assumed to be a terephthalate (which has a band in that position) the amount of terephthalate present would exceed the known level of contaminant (which has been previously agreed to be no greater than 450 kg). The estimated level of contaminant, if it is assumed to be a terephthalate resin, is around 30% which would be over 2000 kg.
2.1.6 If the contaminant originated during manufacture by Huntsman then the Production Sheet would have to be in gross error to the extent of mis-recording the addition of one major component such as Hetron 922 resin (which has no batch number recorded in the Production Sheet) and replacing it with a terephthalate resin.
2.1.7 The presence of the band at 732 cm-1 in Hetron 942 resin has also been detected in a test laminate (284-083-4) prepared by Huntsman for analysis by the Analytical Services and Technology section of Ashland Inc and shown in the report of July 24, 2008, page 31.
2.1.8 A question considered by the experts is whether the contaminant may be unambiguously identified as a terephthalate resin. A band at 731 cm-1 is also present in the infrared spectrum of one of the major starting materials in Hetron 922, bisphenol A. No batch number for the Hetron 922 was recorded in the production sheet for batch 053109001 of Hetron 942, so the details of the production of this batch of Hetron 922 resin are not known. A further example is that the resin Hetron 992H (which was in the batch preceding the production of batch 053109001) has a band at 738 cm-1 and is spectrally very similar to the Hetron 942 resin. However, consideration of the possible levels of contamination from either of these routes renders them extremely unlikely.
2.1.9 A component of the resin in the production sheet that has no batch number recorded against it is the hydrophobic thixotrope, Aerosil 202. In spite of a draft report of Professor Shanks that referred to this thixotrope being replaced with a hydrophilic thixotrope Wacker N20, there is no evidence that this was the case. The change of thixotrope from the hydrophobic Aerosil 202 to the hydrophilic Wacker N20 by Huntsman Chemical Company did not occur until 2002, after the date of manufacture of this batch of resin (affidavit of Dr G Durrant of 2 March 2009).
2.2 Sources of contamination of Hetron 942 resin
2.2.1 The experts considered further the possibility that the contamination could arise by infiltration of terephthalate resin from the structural layer due to incomplete cure of the tie layer before commencement of lay-up of the structural layer. This is not considered likely for the following reasons:
• The amount of terephthalate that is required to migrate would result in secondary effects, in particular swelling of the tie layer and rendering of the boundary between the tie layer and structural layer diffuse, which was not seen.
• It would be evident to the operator that the vinyl ester had not fully reacted. For interdiffusion of the amount of resin found in the tie layer (around 30%), this would require gelling of the tie layer to be severely delayed such that the operator could not walk on the structure to apply the laminate.
• There is evidence that the concentration across the tie layer is approximately uniform (Experts' Joint Report of 11 August 2008, point 2.2.5) which would not be expected if there was diffusion of the terephthalate resin into the uncured tie layer.
2.2.2 Narellan has procedures in place to ensure that contamination cannot occur. These are dedicated workstations and pump-lines from the resin Hazcon containers. It is understood that these procedures were in place at the time of manufacture of the pools in question.
2.2.3 It is understood that Huntsman has procedures in place that isolate the reactor from all materials other than those being used in the resin manufacture so reducing the risk of contamination.
2.3 Role of contamination in blister formation
2.3.1 There can be other substances from the resin synthesis and formulation that are present in the Hetron 942 that lead to an osmotic cell provided certain conditions are met. This is widely accepted as a normal occurrence in osmotic blistering.
2.3.2 The primary process for osmotic cell formation requires a poorly wetted region of glass fibres that allows firstly condensation of moisture and secondly hydrolysis of the poly(ethylene-vinyl acetate) (EVA) sizing on the poorly wetted glass fibres to form acetic acid.
2.3.3 The subsequent process of black spot formation may involve physical and/or chemical processes which lead to the rupture of the gelcoat and release of cobalt salts.
2.3.4 There has been no analysis of blister fluids to determine if the terephthalate resin (which is suggested from our study as being present in the tie layer) has hydrolysed and so contributed to osmotic cell formation.
3. Position of Professor George
3.1 Appendix I summarizes the results of the infrared analysis of the tie layers of pools fabricated by Narellan. The number of pools analyzed now totals 17 and the analysis shows that:
• the Hetron 942 resin was not a pure vinyl ester resin and contained an impurity which, while not unambiguously identified, is consistent with a terephthalate resin (Points of agreement 2.l .1 to 2.1.8) .
• several of the pools recorded in the Narellan production sheets as containing a Derakane resin from FGI were in fact fabricated using batch 053109001 of Hetron 942 (Point of agreement 2.1.4).
• all pools analyzed as containing this impurity have shown blistering (Particulars of failure provided by Marsden's Law Group, 20 February, 2009).
3.2 It is noted that batch 053109001 as produced by Huntsman Chemical Company on 26 February 2001 specifically for Narellan Pools differed substantially from the test batch No 238¬034 manufactured on 17 November 2000 that had been trialled by Narellan prior to the first order for Hetron 942.
3.3 None of the three units units fabricated with the test batch 238-034 have failed but the number of units fabricated with batch 053109001 that have shown blistering (based on the above particulars provided by Marsden's Law Group prior to this further conclave) is 35 which is a failure rate of greater than 40%. This failure rate has increased from the previous Conclave due to the report of a further 6 pools that have blistered.
3.4 The subjective nature of reporting of pool failures is such that the first date of blistering can never be unambiguously determined and statistics of the number of failed pools reflect only the minimum number that have failed. The failure rate expected in the pool industry is less than 1%.
3.5 Examination of the cross-section of blistered pools has confirmed the point of blistering to be in the tie layer within about 0.1mm of the gel coat, ie the region containing Hetron 942 resin and fibreglass. Microscopic examination is required to determine this and reports of Ashland Analytical Services and Prof Shanks that have reported failure "at the interface between the gelcoat and tie layer" have been inaccurate because they did not examine the failure region at high magnification.
3.6 The report of Ashland Analytical Services of July 24, 2008 (made available by Huntsman on 22 December, 2008) contains useful analytical information but the "Comments on Blisters" (Section 11, p3) suggest a lack of experience with osmotic blistering. In particular the view is put that the resin degradation observed may be related to "penetration of swimming pool chemicals". In osmotic blistering there is no penetration of any external agents, other than migration and condensation of water, and all chemical action is generated from within the resin/glass composite.
3.6 Retained samples of the pools in question (skimmer box cutouts) have been made available for examination and analysis. Delamination of the tie layer from the gelcoat in an unblistered region requires considerable force (impact cleavage with a blade) and microscopic examination of the fracture surface reveals that it always contains fibres that have pulled out of the tie layer resin and sections of gelcoat adhering to the tie layer, both of which indicate strong bonding between the two layers. This suggests that, in the absence of water exposure, the structure is sound which is consistent with appropriate manufacturing processes and the impurity or impurities are not interfering with the initial adhesion between the gelcoat and tie layer and between the fibreglass and resin in the tie layer.
3.7 Blistered regions have undergone debonding between the resin and fiberglass due to the chemical action of the blister fluids and it is impossible to determine either the strength of the original laminate or the extent of bonding between the fibers and resin by examination and testing of a blistered region alone.
3.8 It is important to note that the tie layer is the "corrosion barrier" that is designed to prevent blistering of the pool. For this reason premium grade resins such as pure vinyl esters are employed and the layer is richer in resin than the structural laminate that follows.
3.9 The substitution of a part of the vinyl ester resin with a terephthalate resin would render the system less resistant to hydrolytic attack by the acetic acid present in blister fluids. From the poor performance of the pools fabricated with a Hetron 942 tie layer in which blistering has occurred rapidly (within the first year of use as a pool in some cases) then the tie layer has failed in its purpose. This is consistent with a gross defect in the resin system as formulated.
3.10 The analysis of the production record for batch 053109001 and the Quality Assurance data performed immediately before the two separate deliveries of this batch, reveal that this material was possibly out of specification from the outset. It certainly contained foreign material not in the formulation; it had a viscosity profile close to the upper limit and was very different in composition from the material first trialled by Narellan.
3.11 Conclusion: The further studies and analysis since the first conclave have assisted in determining the true nature of the resin that was used in the tie layer of pools manufactured over the period when Hetron 942 had been purchased from Huntsman. Pools manufactured with Hetron 942 batch 053109001 all have an infrared signature that is consistent with a terephthalate impurity level of around 30% and this has enabled the resin to be distinguished from FGI (Derakane) resins that were used by Narellan when Hetron 942 was not used (eg between the two resin deliveries and between production runs). Blistering at a rate of over 40% of pools produced has occurred only from pools fabricated with Hetron 942 batch 053109001. When pools were made in the same way over the same period but using other tie layer resins (eg. Derakane resins from FGI) there have been no reports of blistering. The Hetron 942 resin batch 0531109001 was not fit for the purpose intended ie. a corrosion-resistant tie layer for fiberglass swimming pools.
4. Position of Professor Shanks
4.1 Hetron 942 was a special low styrene content vinyl ester resin based on Ashland Hetron 942/35. The production batch of Hetron 942/35 was used by Narellan in the manufacture of 82 pools; some pools were manufactured with a mixture of resin types, Hetron and Derakane, as containers were exchanged. Pools manufactured with Hetron were found to exhibit an extraneous peak in the infrared spectrum at 732 wavenumbers. This was identified by Ashland as being characteristic of a terephthalate resin. The source of the terephthalate contaminant was proposed by Prof. George to be due to an amount of 400-450 kg of material that was not recorded on the production sheet. This would amount to 6.7 % of the Hetron. The size of the peak at 732 wavenumbers relative to other peaks in the Hetron spectrum and by comparison with a spectrum of a terephthalate resin of the structural layer of failed pool test pieces looked to be much greater than 6.7 %. I used infrared spectroscopy to measure and calculate the content of terephthalate by several methods and an average of about 30 % was found.
4.2 A level of 30 % terephthalate in Hetron 942 will change the properties of the Hetron by more than expected of a low styrene content resin. The styrene content will not be as low as expected since the terephthalate resin will have a normal styrene content of 48-50 %, thereby increasing the styrene content of Hetron 942 to greater than the intended 32 %. The mixture of resins is likely to have unexpected application and structural properties. The likely application and structural properties are speculative since I do not know of any resin produced with this composition.
Both terephthalate and vinyl ester resins are soluble in styrene so a homogeneous solution is expected. Some likely consequences of a mixture of vinyl ester and terephthalate resins are:
(a) Spray viscosity different from expected,
(b) Different cure rates between vinyl ester and terephthalate components,
(c) Uneven solidification (as the resin passes from a liquid to a solid),
(d) Cure can still be complete since all components can cure with the catalyst system used. Incomplete cure of the tie layer is not supported by observation prior to spraying structural layer, nor by a test such as Barcol Hardness.
4.3 The consistent location of blisters, near the gel coat-tie layer interface, the relatively small size of blisters (≤1 cm), and the distribution of pool failures over the period from manufacture until now, is consistent with intermittent defects (meaning poor fibre wet-out by the resin and incomplete consolidation of the resin-glass fibre composite) in the resin structure in the region of blistering. Some limited tests on removal of the gel coat from laminate samples showed that the gel coat readily separated from the tie layer. Measurement of the strength could not be performed.
4.4 Blisters were not formed deeper in the tie layer, indicating that the barrier properties of the tie-layer (also often called a barrier layer) were not compromised. The position of blisters and distribution of failures in the years between 2002-2006 are consistent with the description proposed in 2.3.3, rather than terephthalate hydrolysis which, being a chemical reaction involving a particular concentration of terephthalate, would be expected to continue evenly with increasing hydrolysis over time.
4.5 The formation of a blister occurs when water migrates into the laminate and condenses in a void. Soluble substances typically found in a resin (catalyst from resin manufacture - amine salts, accelerators - dimethylaniline, cobalt salts, peroxide catalyst residues, solvents for the additives) dissolve in the water and create an osmotic pressure. Poly(ethylene-co-vinyl acetate) (EVA) size coating from the glass fibres is hydrolysed by the water to give water-soluble acetic acid (vinegar) that can be smelled in blister fluids (though such fluids were not able to be collected from the blisters examined). The osmotic pressure created by dissolved substances in the condensed water causes physical rupture of the laminate giving an external bulge on the pool surface. When stretching of the resin structure exceeds its limiting strain, a crack is formed to the surface to relieve the pressure. Dissolved cobalt in the blister fluid is emitted from the crack and upon meeting the less acidic environment of the pool water forms black cobalt oxide, giving a black spot at the location of the blister. These are the necessary and sufficient factors for causing blister formation.
Resin hydrolysis occurs progressively over a longer time due to continued presence of water and acidic (acetic acid) conditions in the blister region. Since the resin is a polymer, two adjacent hydrolysis reactions are required to form a small molecule, capable of being dissolved, from the polymer chain.
4.6 Conclusion: Formation of blisters is the result of intermittent defects in the structure promoted by an impurity of terephthalate resin. Terephthalate resins are manufactured by Huntsman. Narellen [sic] uses terephthalate resins in the structural layers of its pools. The source of the terephthalate resin impurity is not known.
APPENDIX 1: Composition of tie layers of pools based on infrared analysis. The presence of a band at 730 cm-1 is common to pools fabricated with Hetron 942 resin batch 053109001 and may be used to distinguish them from those containing Derakane resin supplied by FGI, which do not contain this band.
Pool Number Composition of tie layer Pool blistered or black spot reported (Yes/No)
from IR analysis
8018 Derakane No
8020 Derakane No
8034 Hetron 942 Yes
8036 Hetron 942 Yes
8037 Hetron 942 Yes
8074 Derakane No
8075 Derakane No
8281 Derakane No
8753 Hetron 942 Yes
8914 Derakane No
8978 Hetron 942 Yes
8980 Hetron 942# Yes
8999 Hetron 942# Yes
9002 Hetron 942 Yes
9008 Hetron 942# Yes
9009 Hetron 942# Yes
9031 Derakane No