Analysis of Alternatives for the Use of Trichloroethylene As an Extraction

ANALYSIS OF ALTERNATIVES

Analysis of Alternatives for the use of trichloroethylene as an extraction solvent for removal of process oil and formation of the porous structure in polyethylene based separators used in lead-acid batteries

Legal name of applicant(s): ENTEK International Limited Mylord Crescent Camperdown Industrial Estate Killingworth, Newcastle upon Tyne NE12 5XG, UK

Submitted by: ENTEK International Limited

Substance: Trichloroethylene, CAS 79-01-6; EC 201-167-4 Use title: Use of trichloroethylene as an extraction solvent for removal of process oil and formation of the porous structure in polyethylene based separators used in lead-acid batteries Use number: USE 1

CONTENTS

SUMMARY ...... 7

ACTIONS AND TIMEFRAME FOR IDENTIFICATION AND DEVELOPMENT OF A SUITABLE AND AVAILABLE ALTERNATIVE...... 15

2. ANALYSIS OF SUBSTANCE FUNCTION ...... 17

2.1 OVERVIEW AND BACKGROUND ...... 17

2.2 MANUFACTURE OF POLYETHYLENE-BASED SEPARATORS - PROCESS DESCRIPTION ...... 20

2.3 CONSIDERATION OF OBSTACLES OR DIFFICULTIES IDENTIFIED OR EXPECTED IN RELATION TO FINDING AN ALTERNATIVE FULFILLING OR REPLACING THE EQUIVALENT FUNCTION OF TRI. 24

3 ANNUAL TONNAGE ...... 30

4 IDENTIFICATION OF POSSIBLE ALTERNATIVES ...... 31

4.1 LIST OF POSSIBLE ALTERNATIVES ...... 31

4.2 DESCRIPTION OF EFFORTS MADE TO IDENTIFY POSSIBLE ALTERNATIVES...... 41

4.2.1 Research and Development ...... 42

4.2.1.1 Solvent Alternatives ...... 42

4.2.2 Manufacturing Alternatives ...... 55

4.2.3 Consultations ...... 65

5. SUITABILITY AND AVAILABILITY OF POSSIBLE ALTERNATIVES ...... 67

5.1 INTRODUCTION ...... 67

5.2 N- HEXANE ...... 67

5.2.1 Substance ID and properties ...... 67

5.2.2 Technical feasibility ...... 69

5.2.3 Reduction of overall risk due to transition to the alternative ...... 75

5.2.4 Economic feasibility ...... 78

5.2.5 Availability ...... 83

5.2.6 Conclusion on suitability and availability for n-hexane ...... 83

5.3 DICHLOROMETHANE ...... 85

5.3.1 Substance ID and properties ...... 85

5.3.2 Technical feasibility ...... 87

5.3.3 Reduction of overall risk due to transition to the alternative ...... 87

5.3.4 Economic feasibility...... 92

5.3.5 Availability ...... 93

5.3.6 Conclusion on suitability and availability for dichloromethane ...... 93

5.4 TETRACHLOROETHYLENE ...... 95

5.4.1 Substance ID and properties ...... 95

5.4.2 Technical feasibility ...... 97

5.4.3 Reduction of overall risk due to transition to the alternative ...... 97

5.4.4 Economic feasibility ...... 102

5.4.5 Availability ...... 103

5.4.6 Conclusion on suitability and availability for tetrachloroethylene ...... 103

5.5 VERTREL® SDG ...... 105

5.5.1 Substance ID and properties ...... 105

5.5.2 Technical feasibility ...... 108

5.5.3 Reduction of overall risk due to transition to the alternative ...... 108

5.5.4 Economic feasibility ...... 116

5.5.5 Availability ...... 117

5.5.6 Conclusion on suitability and availability for Vertrel® SDG ...... 117

5.6 HFE-72DE...... 119

5.6.1 Substance ID and properties ...... 119

5.6.2 Technical feasibility ...... 120

5.6.3 Reduction of overall risk due to transition to the alternative ...... 121

5.6.4 Economic feasibility...... 124

5.6.5 Availability ...... 125

5.6.6 Conclusion on suitability and availability for HFE-72DE ...... 125

5.7 N-PROPYL BROMIDE ...... 126

5.7.1 Substance ID and properties ...... 126

5.7.2 Technical feasibility ...... 127

5.7.3 Reduction of overall risk due to transition to the alternative ...... 128

5.7.4 Economic feasibility...... 131

5.7.5 Availability ...... 132

5.7.6 Conclusion on suitability and availability for n-propyl bromide ...... 132

5.8 D-LIMONENE ...... 133

5.8.1 Substance ID and properties ...... 133

5.8.2 Technical feasibility ...... 135

5.8.3 Reduction of overall risk due to transition to the alternative ...... 135

5.8.4 Economic feasibility...... 138

5.8.5 Availability ...... 139

5.8.6 Conclusion on suitability and availability for D-limonene ...... 139

5.9 ACETONE ...... 140

5.9.1 Substance ID and properties ...... 140

5.9.2 Technical feasibility ...... 141

5.9.3 Reduction of overall risk due to transition to the alternative ...... 141

5.9.4 Economic feasibility...... 145

5.9.5 Availability ...... 146

5.9.6 Conclusion on suitability and availability for Acetone ...... 146

5.10 ASSESSMENT OF TECHNICAL ALTERNATIVES ...... 146

5.10.1 Lead Acid Battery Classifications ...... 146

5.10.2 Alternative separator products ...... 147

6 OVERALL CONCLUSIONS ON SUITABILITYAND AVAILABILITY OF POSSIBLE ALTERNATIVES FOR USE OF TRICHLOROETHYLENE AS AN EXTRACTION SOLVENT FOR REMOVAL OF PROCESS OIL AND FORMATION OF THE POROUS STRUCTURE IN POLYETHYLENE BASED SEPARATORS USED IN LEAD-ACID BATTERIES ...... 150

6.1 OVERALL CONCLUSION...... 150

6.2 ACTIONS AND TIMEFRAME FOR IDENTIFICATION AND DEVELOPMENT OF A SUITABLE AND AVAILABLE ALTERNATIVE...... 154

ANNEX I – JUSTIFICATION FOR CONFIDENTIALITY CLAIMS ...... 160

REFERENCES ...... 163

WEB REFERENCES ...... 165

List of Abbreviations AoA Analysis of Alternatives C&L Classification & Labelling CAS Chemical Abstracts Service CEFIC The European Chemical Industry Council CLP Classification, Labelling and Packaging CMR Carcinogen, mutagen or reproductive toxin (as defined in Article 57 of REACH) CSR Chemical Safety Report DCM Dichloromethane (methylene chloride) ECHA European Chemicals Agency EEA European Economic Area eSDS extended Safety Data Sheet ESR Existing Substances Regulation EU European Union GHG Greenhouse gas LABS Lead acid battery separator NPV Net present value PBT Persistent, Bioaccumulative, and Toxic (as defined in Article 57 and Annex XIII of REACH) PEC Predicted environmental concentration PNEC Predicted no effect concentration RAR Risk Assessment Report RMM Risk Management Measure SEA Socio Economic Analysis SEAC Socio Economic Analysis Committee SLI Starting, lighting, and ignition SVHC Substance of Very High Concern TCE or Tri-CE or Trichloroethylene TRI UHMWPE Ultra high molecular weight polyethylene

USE OF TRICHLOROETHYLENE AS AN EXTRACTION SOLVENT FOR REMOVAL OF PROCESS OIL AND FORMATION OF THE POROUS STRUCTURE IN POLYETHYLENE BASED SEPARATORS USED IN LEAD-ACID BATTERIES

SUMMARY

Entek International Ltd. is a producer of lead acid battery separators. The function of a battery separator is to prevent the positive and negative electrodes of the lead-acid battery from touching and short-circuiting, whilst allowing the electrodes to communicate via ion transport through the electrolyte (i.e. sulphuric acid). Battery separators have 50 to 60% porosity with a mean pore diameter of approximately 0.1 micron: these pores are large enough for ion transport through the separator thickness, but small enough to ensure that dendrites do not grow through the separator and cause a short circuit. The battery separator is formulated to retain structural and electrical integrity for multiple years whilst submerged in sulphuric acid solution, challenged by the vibration and jarring that a battery is subjected to under the bonnet of an automobile and with exposure to temperature extremes.

Battery separators are a specialty product with very specific technical qualities and there are only a few manufacturers, especially as compared to the complete battery. The manufacturing process for battery separators requires a large capital investment and a high degree of technical skill in order to meet quality and cost targets. Because the product is essential to the modern, sealed flooded lead-acid battery – the most cost- effective and reliable Starting, Lighting and Ignition (SLI) power source available for automobiles – major battery makers seek to ensure their uninterrupted supply and consistent performance of the material by requiring contractual commitments for supply and severe limitations on the separator producer’s ability to change materials, process or product specifications.

During the manufacture of ENTEK’s polyethylene separators, precipitated silica and UltraHigh Molecular Weight PolyEthylene (UHMWPE) are combined with a process oil and various minor ingredients to form a mixture that is extruded at elevated temperature to form an oil-filled sheet. The oil-filled sheet is calendered (rolled out) to the desired thickness, and the majority of the process oil is extracted with TRI. The sheet is then passed through a dryer and hot air oven to remove the TRI, leaving behind a microporous structure in the separator sheet. Finally, the sheet is cut at multiple positions to form rolls of separator sheet that have the appropriate profile for customers’ battery designs. The term “profile” refers to the width, backweb thickness, number of ribs, rib height, and shoulder design of the separator as shown in Figure 1.2.

The conclusion of the analysis of alternatives is that there are currently no alternatives that are both suitable and available to the applicant for the replacement of the Annex XIV substance function. A number of

possible solvent alternatives have been tested at laboratory scale or otherwise analysed by ENTEK. Although it was found that for one or two of the substances there is potential for the replacement of TRI, a considerable amount of further research is required to determine the commercial feasibility of these substances.

It is very important to note that all of the described alternatives are still at a very early stage of investigation and none can be considered commercially feasible without extensive further research and development. It is important to make a distinction between technical feasibility and commercial feasibility. As used herein, the criteria for technical feasibility in the early stages of the Stage-Gate Research and Development process (see Figure 4.11) are simply to show that a porous material can be produced which is chemically compatible with sulphuric acid (i.e., the electrolyte in a lead-acid battery). Even if technical feasibility can be demonstrated in the laboratory, commercial feasibility can only be confirmed after economic scale-up of the manufacturing process and customer qualification of lead-acid batteries containing any battery separator produced with an alternative solvent.

If ENTEK is able through further research to determine that an alternative substance is commercially feasible, ENTEK would have to demonstrate to its customers that it can produce separators that consistently meet customer requirements. Battery manufacturers sell products with multi-year warranties, making them extremely adverse to risks that could result in higher warranty claims. In addition, battery manufacturers that produce batteries for original equipment manufacturers are held to very strict standards and any major product change needs to be approved by these end customers. As a result, it is common for battery manufacturers to contractually bind battery separator suppliers not to change raw materials, process or product specifications without prior approval and verification of product performance via extensive lab testing, field testing, process validation and product validation; the battery manufacturers are similarly bound by their customers. ENTEK is subject to these restrictions.

Given the long-term promise of battery performance reflected in battery warranties, the logic of ENTEK’s customers in severely curtailing ENTEK’s ability to make changes in material, process and product is sound. The performance of a battery separator is derived from the raw materials used to make it, the equipment the separator was made on, and the operating conditions under which the equipment was run. Given the number of raw materials and the complexity of a battery separator line, the possible combinations of material, equipment, and process settings is immense. Prototyping a new process in the lab, engineering and constructing the commercial solution, finding the correct process conditions and validating the finished separator product is a lengthy and complex undertaking.

ENTEK is fully aligned with the goal of REACH to reduce the use of substances of concern in the European Union and research into the possible replacement of TRI is already underway. We recognize that finding a safe and satisfactory substitute for TRI in our battery separator process is a desirable outcome for all stakeholders. We do not have that substitute in hand today and it will take a highly skilled research,

engineering and production team to find and implement that substitute. ENTEK believes that it has the right team and will continue to invest in the reduction and ultimate potential replacement of TRI.

ENTEK requests a 12-year authorization period to allow continuing with the development of the materials, process, and products required to satisfy customers and safeguard the well-being of associates, local community, and the EU at large. In the 12 years requested ENTEK will continue to invest in research to find a suitable alternative to TRI that will both satisfy the customers’ demands and improve on the human and environmental safety in the production of battery separators.

Table 1.1 Summary of essential criteria for substance function

Essential criterion for substance Justification/explanation function 1. Task performed by Annex XIV TRI is used to remove (extract) naphthenic process oil from substance polyethylene/silica sheet during the manufacture of battery separators for onward use in lead acid batteries in automobiles. The use of TRI maintains fire and explosion safety in ENTEK’s continuous manufacturing process. It also enables effective recovery and reuse of TRI by distillation or carbon adsorption/desorption. Lead acid battery separators are primarily composed of UHMWPE, precipitated silica and oil. UHMWPE is a unique polymer that requires a large percentage of process oil to be extruded in sheet form. This polymer imparts the necessary mechanical properties for handling in the manufacturing process. It also imparts high puncture strength demanded by customers. There is significantly less oil in the finished product than the amount of oil required for manufacturing separators; therefore, a solvent is required to remove the majority of the oil from the extruded sheet. After removal of the required amount of oil, the solvent must then be evaporated from the sheet. This step leaves behind the required amount of porosity to enable ion transport in a battery. The solvent must be highly miscible with the process oil and nonflammable in the ENTEK continuous separator manufacturing process. After removal of the process oil the oil/solvent mixture must be distilled into its separate components for reuse in the manufacturing process. The solvent is also recaptured after evaporation from the separator sheet in both vapour and liquid form. The vapour is recovered through adsorption/desorption in a carbon bed system and the liquid is phase separated from the condensed steam/solvent mixture formed in the dryer. 2. What critical properties and quality criteria must the substance fulfill? Non-flammability A non-flammable solvent is critical to worker and equipment safety. Additionally, this characteristic makes it compatible with the ENTEK continuous manufacturing process. A high degree of solvency with process The solvent must have a high degree of solvency for the oil process oil so that the oil can be extracted efficiently. Reasonable vapour pressure for effective The vapour pressure determines the ability of the solvent to evaporation be evaporated and recovered from the continuous process, enabling recycling of the substance. Condensable in a steam atmosphere The recovery processes require a solvent that can be A reversible recovery of solvent using condensed in a steam atmosphere and that can be captured on distillation and high surface area carbon carbon and subsequently released and recovered. 3. Function conditions

Ambient/room temperature processing Effective extraction of oil from the sheet in closed solvent baths allows efficient use of energy and control and capture of solvent vapour. The recovery of process oil is accomplished through distillation of the oil TRI mixture removed from the extractors.

Recovery of process solvent and process TRI is recovered in both vapour and liquid form at different oil points in the manufacturing process. Liquid TRI is recovered via distillation of the oil/TRI mixture and from phase separation of the water/TRI mixture condensed during the drying stage. Finally, TRI vapour is recovered through adsorption/desorption in the carbon beds. The recovered TRI is then reused in the ENTEK continuous separator manufacturing process. 4. Process and performance constraints Product Upon evaporation of the solvent, the finished separator must have sufficient porosity and wettability to provide low electrical (ionic) resistance. Performance of the separator in lead acid It is essential that the separator provides mechanical integrity batteries and acceptance of product by so that the separator can be enveloped at high speeds and to customers. prevent grid wire puncture during battery assembly or operation. It is also essential that any trace amount of the solvent left in the separator will not negatively affect the electrochemical performance of the lead acid batteries.

Compatibility with the process equipment TRI is stable and nonreactive with the grade of Stainless for making polyethylene separators. Steel used throughout the ENTEK plant for equipment that handles solvent (e.g. piping, valves, fittings, carbon beds, extractor and dryer). 5. Is the function associated with another There are two main processes involving TRI: process that could be altered so that the 1) The extraction of process oil from the separator sheet use of the substance is limited or to reduce the oil content from about 65% by weight eliminated? to about 15% by weight in the finished product. 2) The recovery and recycling of the TRI that allows reuse of the solvent with a high degree of efficiency. Both processes allow battery separators to be manufactured efficiently in a continuous process with good control of releases. Both processes are interdependent and specifically designed for the use of TRI. The possibilities for using an alternative substance are analysed and the associated process changes considered in this document. It is found that it is not currently possible for the applicant to use an alternative. Research concludes that it will be at least 12 years before an alternative could be commercially acceptable. 6. What customer requirements affect the use of the substance in this use? Key separator characteristics The lead-acid storage battery includes positive and negative

electrodes that are separated from each other by a porous battery separator. There are five major requirements for the battery separator, it must: 1) be an electrical insulator to prevent shorting between the electrodes; 2) be composed of materials that can provide chemical and oxidation resistance; 3) be porous to allow for ionic conduction through the separator as the battery is discharged; 4) provide the correct mechanical spacing and electrolyte volume between the electrodes; and 5) run effectively through the separator enveloping line during battery manufacture. TRI enables the above key separator characteristics by:  controlled quantitative removal of process oil from the extruded separator sheet;  evaporation of solvent from the separator sheet to leave behind the required pore size distribution and percent porosity;  not negatively impacting battery performance even if trace amounts of residual solvent remain in the finished product; and  closed loop recycling allows for safe reuse of the solvent in the manufacturing process and delivery of the separator to the customer at a competitive price. Security of supply Separators are a critical component in lead acid batteries used throughout Europe. Security of supply is of critical importance for battery manufacturers. Each supply location plays a critical role in the security of supply for the battery manufacturers. Each supplier is expected to have robust processes to ensure timely delivery of this critical component. For example, annual analysis and reporting on risks to continuous operation and mitigation efforts for these risks, for example, fire safety, may be contractually required. 7. Are there particular industry sector Battery Council International (BCI), Society of Automotive requirements or legal requirements for Engineers (SAE), and European Norm (EN) specifications technical acceptability that must be met must be met for both separators and lead-acid batteries. and that the function must deliver?

Table 1.2 (Table 5.1 in the main report) presents a summary of the solvents that were researched for their potential to replace TRI in the ENTEK process. Each substance is evaluated against the criteria of technical feasibility, economic feasibility, risk and availability.

Table 1.2 Summary of findings of the analysis of potential alternatives for substance

Substance Technical feasibility Economic feasibility Similar or additional risk? Availability n-Hexane Possible on basis of lab trials. No – complete change of processing plant Highly flammable. Neurotoxin and reproductive toxin. Yes (CAS 110-54-3) Presents difficulties due to high required. Need for compliance with major Likely to come under further regulatory pressure in volatility. accident hazard regulations and need to future. relocate plant. Presents control difficulties due to high volatility. Dichloromethane Possible on basis of lab trials. Possible. Suspect Carcinogen. Yes (methylene chloride) Considerable time and investment needed to Likely to come under further regulatory pressure in (CAS 75-09-2) convert, high business risk on basis of future. hazard/risk profile. Tetrachloroethylene Possible on basis of lab trials Possible. Suspect Carcinogen. Yes (perchloroetheylene) Considerable time and investment needed to Likely to come under further regulatory pressure in (CAS 127-18-4) convert, high business risk on basis of future. hazard/risk profile. Vertrel® SDG Possible on basis of lab trials. Likely Considerable time and investment needed to No - (Poor availability of data on the whole substance, Yes to be problems with solvent recovery convert. which has not been fully assessed. A constituent is and recycling. Product is 30x more expensive than TRI. classified as flammable, harmful by inhalation and for the environment.) HFE 72DE 1,2- Possible on basis of lab trials. Considerable time and investment needed to No - (Poor availability of data on the whole substance, Yes trans-1,2- Recovery could be problematic. convert. which has not been fully assessed. A constituent is dichloroethylene Product is 30x more expensive than TRI classified as flammable, harmful by inhalation and for the environment.) n-Propyl bromide (1- Possible on basis of lab trials Considerable time and investment needed to SVHC1 (repro. toxin). Flammable Yes bromopropane) convert, high business risk on basis of (CAS 106-94-5) hazard/risk profile. D-Limonene Possible on basis of lab trials. Large costs of energy associated with Flammable. Yes (CAS 5989-27-5) Likely to be problems with solvent potential use Dangerous to the environment. recovery and recycling. Acetone (67-64-1) No – does not perform function to Not assessed. Flammable Yes remove process oil effectively.

1 Substance of very high concern (SVHC)

Solvent substances that showed some promise in ‘bench-scale’ trials are also under some regulatory scrutiny in the EU and elsewhere. In recent years, TRI has changed classification as a Cat. 2 carcinogen to a Cat 1B carcinogen and only very recently has it been decided by ECHA that TRI should be considered to be a non- threshold carcinogen (for the purposes of authorisation application as least). n-Hexane is a neurotoxin and a reproductive toxin and tetrachloroethylene and methylene chloride are both currently classified as carcinogens (Category 2, H351), and are subject to evaluation under CoRAP (now concluded) and restrictions, respectively. It is therefore unlikely to be sustainable in terms of business planning to invest in substances with these risk profiles that (based on their properties) would present similar challenges for emission/release control as TRI. The implementation of a solvent alternative must therefore take account of possible regulatory changes that would have a severe impact on the use of the substance in the future. It is clear that for substances that show the possibility for being an alternative to TRI in the ENTEK process, tetrachloroethylene and methylene chloride, that the regulatory and risk profile of these substances now and in the future rule them out as likely options. n-Hexane, while used by an ENTEK competitor in France, is ruled out as it is not compatible with the ENTEK continuous separator manufacturing process due to its flammability and volatility in addition to its properties as a neurotoxin and a reproductive toxin.

Confidential

ACTIONS AND TIMEFRAME FOR IDENTIFICATION AND DEVELOPMENT OF A SUITABLE AND AVAILABLE ALTERNATIVE.

There are a number of technical barriers to the use of an alternative solvent in the ENTEK continuous separator manufacturing process. Even with no alternative currently technically feasible, however, we consider how an industrial-scale trial of a solvent could be implemented and describe that in terms of actions and associated timescales. First ENTEK must analyse interaction between the alternative solvent and its equipment and likely retrofit its equipment to adapt the metallurgy to the specific solvent and develop any appropriate solvent recovery systems. ENTEK must then gain customer approval of its process and resulting separator products made with the alternative solvent. To gain such approval, ENTEK must make a significant quantity of samples for its various customers to test in the production of batteries. For the customer qualification of the process, the samples must be made on the production equipment that will be used to manufacture separators on an ongoing commercial basis. To avoid cross-contamination with TRI, these samples can only be run during a temporary plant shutdown period using the existing plant infrastructure. Concurrently, ENTEK would undertake the engineering study to design the converted plant and the trial results would feed into that engineering work. A 78 week programme is estimated for the time needed to get feedback on each trial from customers. ENTEK would be required to conduct at least three separate trials to gain broad customer approval. In order to continue to meet current customer demand, plant shutdowns of a sufficient duration are only scheduled in the month of December. The total elapsed time in this plan is estimated to be a minimum of nine years. This time frame would not be adequate if ENTEK received any negative feedback from customers or if customers delay in their willingness to participate in the trials. It is noted that no replacement solvent is currently commercially feasible and possible candidate replacement solvents each pose similar or greater risks than TRI.

If ENTEK is unable to identify an alternative solvent for use in the ENTEK continuous separator manufacturing process, ENTEK would then analyse whether a change to its process would make an alternative solvent technically feasible. Such a change would be more significant than the process outlined above and take significantly more engineering, procurement and construction. A temporary plant shutdown alone as outlined above may not accommodate a commercial scale trial as required by the customers. Depending on the process change, a longer shut down or complete plant reconstruction would be required

resulting in the longer term shutdown of the plant. If an alternative solvent requiring something less than complete reconstruction of the plant could be identified, ENTEK would need at minimum of twelve years to implement such process changes in addition to the trials required for customer approvals set forth above. Any difficulties in implementation or negative customer reactions would result in a longer implementation timeline.

Confidential

2. ANALYSIS OF SUBSTANCE FUNCTION

2.1 OVERVIEW AND BACKGROUND

Entek International Ltd. is a producer of lead acid battery separators that are made of polyethylene, precipitated silica and a process oil. Most flooded lead acid batteries use these separators. This type of battery is used in motor vehicles to provide power for starting, lighting and ignition (SLI). Polyethylene separators are microporous and require large amounts of precipitated silica to be sufficiently acid-wettable (i.e., to fill the pore space in the separator and present a continuous volume of acid through the separator to the lead plates in the battery). The volume fraction of precipitated silica and its distribution in the separator control electrical properties, while the volume fraction and orientation of polyethylene in the separator control mechanical properties. The porosity range for commercial polyethylene separators is 50-60%.

During the manufacture of ENTEK’s polyethylene separators, precipitated silica and ultrahigh molecular weight polyethylene (UHMWPE) are combined with a process oil and various minor ingredients to form a mixture that is extruded at elevated temperature to form an oil-filled sheet. The oil-filled sheet is calendered (rolled out) to the desired thickness, and the majority of the process oil is extracted with TRI. The sheet is then passed through a dryer and hot air oven to remove the TRI, leaving behind a microporous structure in the separator sheet. Finally, the sheet is cut at multiple positions to form rolls of separator sheet that have the appropriate profile for customers’ battery designs. The term “profile” refers to the width, backweb thickness, number of ribs, rib height, and shoulder design of the separator as shown in Figure 2.1.

Figure 2.1. Schematic drawing of a lead-acid battery separator.

Shoulder Shoulder Region Ribs Region

Backweb Backweb The polyethylene separator sheet is typically delivered to lead acid battery manufacturers in roll form.

The separator provides mechanical integrity for high speed enveloping and prevents sharp grid wires or plates from shorting the battery during assembly. The separator is fed to a machine that forms ‘envelopes’ by cutting the separator material, inserting an electrode, and sealing its edges (see Figure 2.2). The electrode is either a positive or negative grid that is pasted with electrochemically active material. Together with the separator envelope, it forms an electrode package. The electrode package is then alternated with the other electrode (positive or negative) type to form a stack in which the separator acts as a physical spacer and an electronic insulator between the grids (i.e., electrodes). After making series and parallel connections between the grids, an electrolyte (i.e., sulphuric acid) is then introduced into the assembled battery to facilitate ionic conduction within the battery. The battery then goes through an electrochemical formation step prior to final inspection and shipment.

Figure 2.2. Schematic drawing of a lead-acid battery and the depiction of a separator envelope surrounding an electrode.

Battery manufactures require a microporous polyethylene separators with a material composition that provides good puncture resistance, high oxidation resistance and low electrical resistance. These characteristics are critical for the separator to function properly both during and after formation of the battery. UHMWPE is the material widely chosen for lead-acid battery separators because it can impart excellent mechanical properties while serving as a “binder” for the large quantities of precipitated silica necessary to provide wettability.

The repeat unit of polyethylene is shown below:

(-CH2CH2-)x where x represents the average number of repeat units in an individual polymer chain. In the case of polyethylene used in many film and molded part applications, x equals about 103-104 whereas for UHMWPE x equals about 105. This difference in the number of repeat units is responsible for the higher degree of chain entanglement and the unique properties of UHMWPE.

A specific desired property is the ability of UHMWPE to resist material flow even when heated above its crystalline melting point (135°C). This phenomenon is a result of the long relaxation times required for individual chains to slip past one another, and therefore, UHMWPE is not a true thermoplastic. It requires a plasticizer such as a naphthenic process oil (as explained below) to assist in solubilizing and disentangling the polymer chains under the high temperature and shear conditions inside a twin screw extruder. After the extrudate passes through the die and between the calender rolls that emboss a rib pattern, the sheet is cooled so that the oil phase separates from the polymer to form regions that will eventually become pores after removal of the oil. There is always a controlled amount of oil left in the finished separator because it has a positive impact upon the oxidation resistance of the separator. The residual oil is believed to reside within the UHMWPE fibrils that are dispersed throughout the separator. In this case, the oil serves as a reactive species for scavenging oxygen and other oxidizing agents that can attack the long polymer chains and cause embrittlement of the separator.

The primary purpose of the hydrophilic silica is to increase the acid wettability of the separator, thereby lowering its electrical (ionic) resistivity. In the absence of silica, the sulphuric acid would not wet the hydrophobic polyethylene fibrils and ion transport would not occur, resulting in an inoperable battery. Consequently, the silica component of the separator typically accounts for between 55% and 70% by weight of the separator. Figure 2.3 shows the typical structure of a microporous separator.

Figure 2.3. Scanning electron micrograph showing the morphology of an ENTEK Pb-acid battery separator.

2.2 MANUFACTURE OF POLYETHYLENE-BASED SEPARATORS - PROCESS DESCRIPTION

An overview of the ENTEK separator manufacturing process to make polyethylene separators is illustrated in Figure 2.4. This represents a very simple schematic of a single production line. For a more comprehensive description of ENTEK’s separator manufacturing process, including the solvent extraction and recovery process, refer to Figure 2.5.

Mix preparation Extrusion Filler- silcia Calendering Extraction (formation of sheet) polyethylene (formation of sheet) (of oil with TRI) Process oil

Drying (steam) Hot air oven (removal of TRI) (removal of TRI)

Winding and slitting (finished separator rolls)

Figure 2.4. Simple schematic of the ENTEK separator manufacturing process, showing a single processing line.

Figure 2.5. Comprehensive schematic of the ENTEK separator manufacturing process, showing solvent extraction and recovery loops.

A critical step in the manufacturing process is the extraction of a controlled amount of process oil from the sheet and subsequent removal of the extraction solvent to form a microporous separator. ENTEK uses the Annex XIV substance TRI as its extraction solvent. The purpose and function of the TRI in this use is to perform the extraction of process oil by displacing the majority of the oil in the sheet. This is followed by evaporation of the TRI to leave behind interconnected pores in the finished separator.

There are seven critical requirements for an extraction solvent (as fulfilled by TRI) in the ENTEK manufacturing process: 1. Non-flammability. 2. Miscibility with a process oil that is a plasticizer for UHMWPE. 3. Recoverable in high purity via distillation of oil/solvent mixtures. 4. High affinity for activated carbon to promote vapour recovery. 5. Minimal solubility in water. 6. A low health and safety risk when exposure is managed within accepted limits. 7. Chemical stability under the conditions used for extraction, drying and recovery.

In the ENTEK process, TRI is recovered by distillation of the oil-TRI mixture that results from extraction of the sheet. Trichloroethylene is also recovered during the drying step, as both a liquid that has been condensed from the steam-TRI mixture in the dryer and as a vapour that is adsorbed in a carbon bed recovery system (see Figure 2.5). Based on the critical requirements for an extraction solvent as set forth above, the following selection criteria were developed to analyze potential alternatives.

Following are the primary selection criteria for an extraction solvent in the ENTEK process: 1. Hazard rating: non-flammable. 2. High degree of solvency for the process oil. 3. Reasonable vapour pressure for effective evaporation. 4. Low surface tension to prevent pore collapse due to capillary forces exerted during evaporation of the solvent from the sheet. 5. Condensable in a steam atmosphere. 6. Minimal solubility in water. 7. Reversible recovery of high purity solvent using distillation and vapour adsorption/desorption onto activated carbon in a continuous process. 8. Low environmental, health, and safety risk when exposure is managed within acceptable limits. 9. Chemical stability under the conditions used for extraction, drying, and recovery. 10. Available in required quantity at reasonable cost. 11. A finished separator that meets customer requirements for battery production and performance.

These selection criteria have guided ENTEK’s choice of TRI as its extraction solvent. First and foremost, ENTEK believes that it is prudent to use a non-flammable solvent to ensure the safety of its workforce and capital investment. The use of any flammable solvent is not compatible with ENTEK’s continuous separator manufacturing process (raw materials to finished separator rolls). The requirement for a non-flammable solvent quickly consolidates the potential solvent options.

A high degree of solvency for the ENTEK process oil is important because it ultimately determines the residence time that is required in the extractor. The solvent also needs to have a vapour pressure that is compatible with recovery in distillation and drying steps.

In the ENTEK process, the TRI is evaporated from the sheet with steam in the dryer. The ability to utilize steam is beneficial because a condensable atmosphere can be created such that cooling coils at the bottom of the dryer can be utilized to condense a large portion of the TRI as a liquid mixed with water. The phase separation of the TRI/water mixture is readily accomplished, and a reduced amount of TRI vapour is sent to carbon beds for recovery. This is a much less energy intensive option as compared to using hot air to evaporate the TRI from the separator sheet and then sending 100% of it to the carbon beds in vapour form.

Finally, solvent cost and availability are important to ensure that the ENTEK separator manufacturing process remains profitable.

2.3 CONSIDERATION OF OBSTACLES OR DIFFICULTIES IDENTIFIED OR EXPECTED IN RELATION TO FINDING AN ALTERNATIVE FULFILLING OR REPLACING THE EQUIVALENT FUNCTION OF TRI.

The guidance in the analysis of alternative template document from ECHA requests the applicant to “Present the list of essential criteria for fulfilling the substance function that served as the basis for the assessment of the alternatives. Justify why these criteria are the most relevant for the selection of the possible alternatives by linking the criteria to the function, tasks and conditions under which the substance is used in the specific use applied for”. The functions of TRI as a process solvent for the extraction of process oil from polyethylene sheet are set out above. Table 2.1 below is a summary of the essential criteria with a short explanation/comment to justify why that is the case; however, the detailed arguments are set out in the subsequent sections. The table also takes account of the checklist for Annex XIV Substance Function suggested in the ECHA Guidance on Authorisation Applications.

Table 2.1 Summary of essential criteria for substance function

Essential criterion for Justification/explanation substance function 1. Task performed by Annex TRI is used to remove (extract) naphthenic process oil from polyethylene/silica sheet during the manufacture of battery XIV substance separators for onward use in lead acid batteries in automobiles. The use of TRI maintains fire and explosion safety in ENTEK’s continuous manufacturing process. It also enables effective recovery and reuse of TRI by distillation or carbon adsorption/desorption. Lead acid battery separators are primarily composed of UHMWPE, precipitated silica and oil. UHMWPE is a unique polymer that requires a large percentage of process oil to be extruded in sheet form. This polymer imparts the necessary mechanical properties for handling in the manufacturing process. It also imparts high puncture strength demanded by customers. There is significantly less oil in the finished product than the amount of oil required for manufacturing separators; therefore, a solvent is required to remove the majority of the oil from the extruded sheet. After removal of the required amount of oil, the solvent must then be evaporated from the sheet. This step leaves behind the required amount of porosity to enable ion transport in a battery. The solvent must be highly miscible with the process oil and nonflammable in the ENTEK continuous separator manufacturing process. After removal of the process oil the oil/solvent mixture must be distilled into its separate components for reuse in the manufacturing process. The solvent is also recaptured after evaporation from the separator sheet in both vapour and liquid form. The vapour is recovered through adsorption/desorption in a carbon bed system and the liquid is phase separated from the condensed steam/solvent mixture formed in the dryer. 2. What critical properties and quality criteria must the substance fulfill? A non-flammable solvent is critical to worker and equipment safety. Additionally, this characteristic makes it Non-flammability compatible with the ENTEK continuous manufacturing process.

A high degree of solvency The solvent must have a high degree of solvency for the process oil so that the oil can be extracted efficiently. with process oil Reasonable vapour pressure The vapour pressure determines the ability of the solvent to be evaporated and recovered from the continuous process, for effective evaporation enabling recycling of the substance.

Condensable in a steam The recovery processes require a solvent that can be condensed in a steam atmosphere and that can be captured on atmosphere carbon and subsequently released and recovered. A reversible recovery of solvent using distillation and high surface area carbon 3. Function conditions Ambient/room temperature Effective extraction of oil from the sheet in closed solvent baths allows efficient use of energy and control and capture of processing solvent vapour. The recovery of process oil is accomplished through distillation of the oil TRI mixture removed from the extractors.

Recovery of process solvent TRI is recovered in both vapour and liquid form at different points in the manufacturing process. Liquid TRI is and process oil recovered via distillation of the oil/TRI mixture and from phase separation of the water/TRI mixture condensed during the drying stage. Finally, TRI vapour is recovered through adsorption/desorption in the carbon beds. The recovered TRI is then reused in the ENTEK continuous separator manufacturing process. 4. Process and performance constraints Upon evaporation of the solvent, the finished separator must have sufficient porosity and wettability to provide low Product electrical (ionic) resistance.

Performance of the separator It is essential that the separator provides mechanical integrity so that the separator can be enveloped at high speeds and to in lead acid batteries and prevent grid wire puncture during battery assembly or operation. It is also essential that any trace amount of the solvent acceptance of product by left in the separator will not negatively affect the electrochemical performance of the lead acid batteries. customers.

Compatibility with the TRI is stable and nonreactive with the grade of Stainless Steel used throughout the ENTEK plant for equipment that process equipment for handles solvent (e.g. piping, valves, fittings, carbon beds, extractor and dryer). making polyethylene separators.

5. Is the function associated There are two main processes involving TRI: with another process that 3) The extraction of process oil from the separator sheet to reduce the oil content from about 65% by weight to could be altered so that the about 15% by weight in the finished product. use of the substance is limited or eliminated? 4) The recovery and recycling of the TRI that allows reuse of the solvent with a high degree of efficiency. Both processes allow battery separators to be manufactured efficiently in a continuous process with good control of releases. Both processes are interdependent and specifically designed for the use of TRI. The possibilities for using an alternative substance are analysed and the associated process changes considered in this document. It is found that it is not currently possible for the applicant to use an alternative. Research concludes that it will be at least 12 years before an alternative could be commercially acceptable. 6. What customer requirements affect the use of the substance in this use? The lead-acid storage battery includes positive and negative electrodes that are separated from each other by a porous Key separator characteristics battery separator. There are five major requirements for the battery separator, it must: 1) be an electrical insulator to prevent shorting between the electrodes; 2) be composed of materials that can provide chemical and oxidation resistance; 3) be porous to allow for ionic conduction through the separator as the battery is discharged; 4) provide the correct mechanical spacing and electrolyte volume between the electrodes; and 5) run effectively through the separator enveloping line during battery manufacture. TRI enables the above key separator characteristics by:  controlled quantitative removal of process oil from the extruded separator sheet;  evaporation of solvent from the separator sheet to leave behind the required pore size distribution and percent porosity;  not negatively impacting battery performance even if trace amounts of residual solvent remain in the finished product; and  closed loop recycling allows for safe reuse of the solvent in the manufacturing process and delivery of the separator to the customer at a competitive price.

Security of supply Separators are a critical component in lead acid batteries used throughout Europe. Security of supply is of critical importance for battery manufacturers. Each supply location plays a critical role in the security of supply for the battery manufacturers. Each supplier is expected to have robust processes to ensure timely delivery of this critical component. For example, annual analysis and reporting on risks to continuous operation and mitigation efforts for these risks, for example, fire safety, may be contractually required. 7. Are there particular Battery Council International (BCI), Society of Automotive Engineers (SAE), and European Norm (EN) specifications industry sector requirements must be met for both separators and lead-acid batteries. or legal requirements for technical acceptability that must be met and that the function must deliver?

Section 4 below sets out the research, development, and engineering undertaken by ENTEK to identify and investigate potential alternatives. Section 6 considers the steps needed to phase in potential alternatives including the technical and commercial barriers that must be overcome.

3 ANNUAL TONNAGE The applied for tonnage is within the tonnage band 10-100 tonnes per year.

4 IDENTIFICATION OF POSSIBLE ALTERNATIVES

4.1 LIST OF POSSIBLE ALTERNATIVES

As described in Section 2, the function of the Annex XIV substance (TRI or TCE) in the manufacture of polyethylene separators for lead-acid batteries is as a solvent to extract process oil from the sheet in required to impart specific qualities to the sheet. In addition, the choice of solvent allows effective extraction recovery and recycling of solvent. This identification of possible alternatives therefore focuses on possible solvents that could be suitable for replacement of TRI and their compatibility with the ENTEK continuous separator manufacturing process and end-product. There are other separator technologies available that are currently available (i.e., it is possible to use separators in lead acid batteries that are not polyethylene based, see section 4.2.2). While the substance function does not direct the investigation of these technical alternatives, the need for consideration of them is acknowledged, as this analysis should be in line with the non-use scenario set out in the Socio Economic Analysis (SEA), which considers what the response would be should polyethylene separators made using TRI not be available.

ENTEK scientists and engineers with detailed knowledge of the ENTEK continuous separator manufacturing process have investigated possible alternatives to TRI. The list of possible substance alternatives was identified as follows: 1. n-Hexane 2. Dichloromethane (methylene chloride) 3. Tetrachloroethylene (perchloroethylene) 4. Vertrel® SDG - an engineered mixture of non-flammable hydrofluorocarbons (HFCs) and trans-1,2- dichloroethylene (t-DCE). 5. HFE 72DE trans-1,2-dichloroethylene CAS 156-60-5 (68 – 72%); ethyl nonafluoroisobutyl ether CAS 163702-06-5 (4 – 16%); ethyl nonafluorobutyl ether CAS 163702-05-4 (4 – 16%); methyl nonafluoroisobutyl ether CAS 163702-08-7 (2 – 8%); methyl nonafluorobutyl ether CAS 163702- 07-6 (2 – 8%) 6. n-Propyl bromide (1-bromopropane) 7. D-Limonene 8. Acetone

Other solvents (such as 1,2–dichloroethylene, alcohols (e.g. propan-2-ol and n-butanol) and siloxanes (such as octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5)) and approaches to extraction were considered, but eliminated because of chemical or equipment incompatibilities. For example, water

cannot be used as the extraction solvent since it is not miscible with the process oil. Additionally, while supercritical carbon dioxide can be used as an extraction solvent for certain applications (e.g., decaffeination of coffee beans), it requires a closed pressure vessel and is not a viable option in the ENTEK separator manufacturing process because it is not possible to use this in a continuous process.

Table 4.1 below sets out a list of possible substance alternatives, which was a starting point for research on possible replacement substances in the ENTEK continuous separator manufacturing process. Key physicochemical properties as well as classification and labelling requirements in the EU are key considerations for technical feasibility and hazards profile. In addition, consideration is given to the status of substances under the REACH Regulation to give an initial indication of availability and regulatory status.

Table 4.1 Possible TRI alternatives in the ENTEK continuous separator manufacturing process (based on information from ENTEK and other sources), TRI data is presented for reference.

Substance name CAS Boiling Heat of Flash Flamma Classification Regulatory Comments and risk phrases/hazard Point Vaporisation Point bility (EU dangerous Status (EU) statements (oC) (kJ/kg) /auto limits substances ignitio (%) directive and n temp CLP/GHS)1 (oC)

Trichloroethylene 79-01-6 87 263 N/A/ 8 / 12.5 Carc. Cat. 2; R45 Registered Current solvent. Subject to EU risk assessment 420 - Muta. Cat. 3; under under ESR, Reach Registration done by Dow R68 - R67 - REACH LR. Possible placing on Carcinogens and Xi; R36/38 - phase 1 Mutagens Directive (with bOEL), current iOEL R52-53 10ppm (8hr TWA) GHS Skin Irrit. 2 H315 H315 Causes skin irritation Eye Irrit. 2 H319 H319 Causes serious eye irritation STOT SE 3 H336 H336 May cause drowsiness or dizziness Muta. 2 H341 H341 Suspected of causing genetic defects Carc. 1B H350 H350 May cause cancer Aquatic Chronic H412 Harmful to aquatic life with long lasting 3 H412 effects n-Hexane 110-54-3 68 335 -23/224 1.2 / 7.7 F; R11 - Registered + R11 : Highly flammable. under Repr. Cat. 3; R62 + R48/20 : Harmful: danger of serious damage REACH - Xn; R65-48/20 to health by prolonged exposure through phase 1 - Xi; R38 - inhalation. R67 - N; R51- Being + R62 : Possible risk of impaired fertility. 53 considered under the + R51/53 : Toxic to aquatic organisms, may GHS CoRAP cause long-term adverse effects in the aquatic Flam. Liq. 2 (2012 – on environment. H225 going) H225 – Highly flammable liquid and vapour Asp. Tox. 1 H304 grounds for

Skin Irrit. 2 H315 concern: H304 May be fatal if swallowed and enters Human airways. STOT SE 3 H336 health/CMR H315 Causes skin irritation Repr. 2 H361f and neurotoxicity H336 May cause drowsiness or dizziness STOT RE 2 H373 ; H361f Suspected of damaging fertility Aquatic Chronic Exposure/Wi 2 H411 de dispersive H373 May cause damage to organs use, high aggregated Affected organs: nervous system tonnage Route of exposure: Inhalation H411 Toxic to aquatic life with long lasting effects

Methylene 75-09-2 40 329 N/A 12 / 23 Carc. Cat. 3; R40 Registered + R40 : Limited evidence of a carcinogenic chloride /556 under effect. GHS (dichloromethane REACH H351: Suspected of causing cancer. ) Carc. 2 H351 phase 1. Self-classification: Self- classification: H315: Causes skin irritation. H319: Causes serious eye irritation. Skin Irrit. 2 H315. H336: May cause drowsiness or dizziness. Eye Irrit. 2 H319: Affected organs: central nervous system STOT Single Route of exposure: Inhalation Exp. 3 H336:

Tetrachloroethyle 127-18-4 121 209 N/A/N/ N/A/N/A Carc. Cat. 3; R40 Registered + R40 : Limited evidence of a carcinogenic ne A - N; R51-53 under effect. (perchloroethylen REACH GHS: + R51/53 : Toxic to aquatic organisms, may e) phase 1.

Carc. 2 H351 Considered cause long-term adverse effects in the aquatic under the environment. Aquatic Chronic CoRAP 2 H411 H351: Suspected of causing cancer. (2013 – on Self- going) H411: Toxic to aquatic life with long lasting classification: grounds for effects. Skin Irrit. 2 H315 concern: CoRAP completed with final decision provided Human in July 2014: no further data needs identified. Eye Irrit. 2 H319: health/CMR; ‘Concern clarified; No need of further risk Skin Sens. 1B Environment management measures’ H317. /Suspected PBT; STOT Single Exposure/Wi Self-classification: Exp. 3 H336: de dispersive H315: Causes skin irritation. use; Aggregated H319: Causes serious eye irritation. tonnage: H317: May cause an allergic skin reaction.

H336: May cause drowsiness or dizziness. Affected organs: central nervous system Route of exposure: Inhalation Vertrel® SDG N/A 43 N/A no 7 / 14 No harmonised Constituent For trans-dichloroethylene CAS 156-60-5: flashpo classification is CAS + R11 : Highly flammable int / available for the 138495-42-8 N/A mixture. The (5-25%) has + R20: Harmful by inhalation constituent trans- been + R52/53 : Harmful to aquatic organisms, may dichloroethylene registered cause long-term adverse effects in the aquatic CAS 156-60-5 under environment. (65-90%) has the REACH following phase not H225: Highly flammable liquid and vapour harmonised determined. H332: Harmful if inhaled classification: Constituent H411: Harmful to aquatic life with long lasting

F; R11 - Xn; CAS 15290- effects. 77-4 (5- R20 - R52/53 15%) has a GHS NONS Flam. Liq. 2 - registration H225 as a polymer Acute Tox 4 - H332, Aquatic Chronic 3 – H412 HFE 72DE trans- N/A 45 N/A N/A / 6.7 / 13.7 No harmonised Constituent For trans-dichloroethylene, CAS 156-60-5: 1,2- 396 classification is CAS + R11 : Highly flammable dichloroethylene available for the 138495-42-8 mixture. The (5-25%) has + R20: Harmful by inhalation constituent trans- been + R52/53 : Harmful to aquatic organisms, may dichloroethylene registered cause long-term adverse effects in the aquatic CAS 156-60-5 under environment. (65-90%) has the REACH following phase not H225: Highly flammable liquid and vapour harmonised determined. H332: Harmful if inhaled classification: H411: Harmful to aquatic life with long lasting F; R11 - Xn; effects. R20 - R52/53

GHS Flam. Liq. 2 - H225 Acute Tox 4 - H332 Aquatic Chronic 3 – H412 n-Propyl Bromide 106-94-5 71 243 22/490 4.6 / - F; R11 - Repr. Registered New data indicating have been published

(1- Cat. 2; R60 - under indicating neurotoxic effects in workers exposed bromopropane) Repr. Cat. 3; R63 REACH to low levels on nPB—ACGIH decreased the - Xn; R48/20 - phase 1. TLV to 0.1 ppm in response; OSHA issued an Xi; R36/37/38 - alert. Substance of R67 very high + R60 : May impair fertility. GHS concern + R11 : Highly flammable. (SVHC) on Flam. Liq. 2 the basis of + R36/37/38 : Irritating to eyes, respiratory H225 toxicity to system and skin. Skin Irrit. 2 H315 reproduction + R48/20 : Harmful: danger of serious damage Eye Irrit. 2 H319 and listed on to health by prolonged exposure through the REACH inhalation. STOT SE 3 H335 Candidate + R63 : Possible risk of harm to the unborn STOT SE 3 H336 list for Authorisatio child. Repr. 1B H360FD n H225 – Highly flammable liquid and vapour STOT RE 2 H373 H315 Causes skin irritation

H319 Causes serious eye irritation H335 May cause respiratory irritation H336 May cause drowsiness or dizziness H360FD. May damage fertility. May damage the unborn child. H373 May cause damage to organs (R)-p-mentha- 5989-27- R10 Registered R10 – Flammable 1,8-diene 5 under Xi; R38 R38 – Irritating to skin REACH D-Limonene R43 phase 1. R43 – May cause sensitization by skin contact N; R50-53 R50-53 – Very toxic to aquatic organism, may cause long term adverse effects in the aquatic GHS

Flam. Liq. 3 environment. H226 H226 – Flammable liquid and vapour Skin Irrit. 2 H315 H315 Causes skin irritation Skin Sens. 1 H317 May cause and allergic skin reaction H317 H400 – Very toxic to aquatic life Aquatic Acute 1 H400 H410 – Very toxic to aquatic life with long lasting effects. Aquatic Chronic 1 H410 Acetone 67-64-1 57 525 -20/465 2.5 / 12.8 F; R11 - Xi; Registered + R11 : Highly flammable. R36 - R66 - under (representative of + R36 : Irritating to eyes. R67 REACH various ketones) phase 1. + R66: Repeated exposure may cause skin GHS dryness or cracking Flam. Liq. 2 + R67: Vapours may cause drowsiness and H225 diziness Eye Irrit. 2 H319

STOT SE 3 H336 H225 – Highly flammable liquid and vapour

H319 Causes serious eye irritation H336 May cause drowsiness or dizziness 1,2- 540-59-0 60.1 305.4 2/ 460 5.6/12/8 F; R11 - Xn; Not yet + R11 : Highly flammable. Dichloroethylene R20 - R52-53 registered + R20 : Harmful by inhalation. under Flam. Liq. 2 REACH + R52/53 : Harmful to aquatic organisms, may H225 cause long-term adverse effects in the aquatic Acute Tox. 4* environment. H332 H225 – Highly flammable liquid and vapour Aquatic Chronic H332 – Harmful if inhaled

3 H412 H412 Harmful to aquatic life with long lasting effects Examples of alcohols

Propan-2-ol 67-63-0 82 45.39 12/399 2.0/12.7 F; R11 - Xi; Registered + R11 : Highly flammable. R36 - R67 under + R36 : Irritating to eyes. REACH GHS phase 1. + R67: Vapours may cause drowsiness and Flam. Liq. 2 H225 diziness Eye Irrit. 2 H319 H225 – Highly flammable liquid and vapour STOT SE 3 H336 H319 – Causes serious eye irritation H336 – May cause drowsiness or dizziness n-Butanol 71-36-3 117.7 52.35 37/343 1.4 / 11.2 R10 – Xn; R22 – Registered + R10 : Flammable. Xi; R37/38-41 – under + R22: Harmful if swallowed R67 REACH phase 1. + R37/38 : Irritating to respiratory system and GHS skin. Flam. Liq. 3 + R41: Risk of serious damage to eyes Acute Tox – 4 + R67: Vapours may cause drowsiness and Skin irrit. 2 diziness Eye Dam. 1 H226 – Flammable liquid and vapour STOT SE 3 H335 H302 – Harmful if swallowed STOT SE 3 H336 H315 – Causes skin irritation H318 – Causes serious eye damage H335 – May cause respiratory irritation H336 – May cause serious drowsiness or dizziness

Octamethylcyclot 556-67-2 175 N/A 51-55 / 0.75 / 7.4 Repr. Cat. 3; R62 Registered R53 : May cause long-term adverse effects in etrasiloxane (D4) N/A - R53 under the aquatic environment. REACH GHS + R62 : Possible risk of impaired fertility. phase 1 Repr. 2 H361f Aquatic Chronic 4 H361f Suspected of damaging fertility H413 H413 May cause long lasting harmful effects to aquatic life. Decamethylcyclo 541-02-6 210 N/A 51-55/ 0.45 / GHS (not Registered H413 May cause long lasting harmful effects to pentasiloxane N/A 13.21 harmonised, under aquatic life. (D5) summary of all REACH H319 – Causes serious eye irritation proposals) phase 1 H341 – Toxic if inhaled Aquatic Chronic 4 H413 H315 – Causes skin irritation Eye Irrit. 2 H319 H335 – May cause respiratory irritation Acute Tox. 3 H331 Skin Irrit. 2 H315 STOT SE 3 H335

Notes: 1 Classifications are harmonized unless indicated otherwise.

4.2 DESCRIPTION OF EFFORTS MADE TO IDENTIFY POSSIBLE ALTERNATIVES

The alternative solvents listed above (see Table 3.1 below) were evaluated in the ENTEK R&D laboratory as noted. Initial experiments involved collecting an oil-filled precursor polyethylene sheet from an ENTEK production line. The oil-filled sheet was then cut into ~ 160 mm x ~160 mm pieces that were individually placed in the alternative solvents for various time periods to evaluate extraction rates and efficiency. The solvent-laden sheets were then dried in air and the resultant separator properties were evaluated. The major characterization data that were collected from these laboratory experiments included:

 Solubility of ENTEK process oil in each alternative solvent

 Rate of process oil extraction for each alternative solvent

 Shrinkage of solvent-laden separator upon drying

 Impact of trace solvent in the separator on lead acid electrochemistry

 Separator porosity

 Separator electrical (ionic) resistance

 Separator mechanical properties

In the case of dichloromethane (DCM), additional work was done on rolls of oil-filled precursor sheet that were passed through a portable extractor-dryer unit to more closely mimic the ENTEK separator manufacturing process. The DCM-dried separator was then compared to separator dried from TRI using the same portable extractor-dryer unit.

It should be noted that in all cases, the laboratory and portable extractor-dryer experiments only give a partial answer in regard to the feasibility of an alternative solvent. Full scale production trials are required before any definitive decision can be made regarding the commercial feasibility of an alternative solvent. This is necessary to ensure that expected throughputs can be met on existing equipment and that the final separator properties and roll characteristics meet specification. Furthermore, closed loop recovery of any alternative solvent must be demonstrated via distillation and vapour adsorption/desorption in carbon beds. Such large scale trials would also be required by battery manufacturers attempting to qualify any new separator or change to the separator manufacturing process with their OEM (original equipment manufacturer) customers (see Section 5).

It is difficult to perform such trials at the ENTEK plant because the carbon bed, oil recirculation, and water recovery systems for the four production lines are coupled together forming a highly integrated continuous

process system. Isolating a single production line to carry out a scaled production trial with an alternative solvent would reduce the capacity of the plant serving current customers and require the duplication of solvent and oil recovery systems in addition to specifying, ordering and installing specialty equipment. As such, due to existing separator demand from the ENTEK plant, the only opportunity for such experiments to be performed is during the annual shutdown period that takes place two weeks in December (see Section 5 for the REACH Solvent Conversion Plan).

4.2.1 Research and Development

Confidential

4.2.1.1 Solvent Alternatives

Table 4.2 lists the physico-chemical properties of TRI and other alternative solvents that have been investigated by ENTEK. The human health and environmental classifications for each solvent are addressed individually in a later portion of this analysis report.

Table 4.2 Key physicochemical properties of possible alternatives in comparison to TRI

Solvent CAS Boiling Density Vapour Viscosity at Surface Heat of Flash Solubility Initially point (g/ml) Pressure 25oC (cps) Tension, 25oC vaporisatio Point in water tested by (oC) at 25oC (dynes/cm) n (cal/g) closed cup (25oC) ENTEK (mm Hg) (oC) (g/100cc) Trichloroethylene 79-01-6 87 1.44 74 0.54 32.3 56.4 None 0.11 Yes n-Hexane 110-54-3 69 0.65 150 0.32 17.9 79.9 -22 0.00095 Yes

Dichloromethane 75-09-2 40 1.33 350 0.44 28.1 75.3 None 1.3 Yes (DCM)

Tetrachloroethyle 127-18-4 121 1.62 18 0.75 29.5 50.1 None 0.015 Yes ne

Vertrel SDG 43 1.29 388 0.59 21.2 67.1 None 0.95 Yes

HFE 72DE 43 1.28 350 0.45 19 52 None 0.001 Yes n-Propyl bromide 106-94-5 71 1.35 150 0.49 25.9 58.8 21 0.23 Yes

D-Limonene 5989-27- 176 0.84 1.4 1.28 25 84.3 48 0.00138 Yes 5

Acetone 67-64-1 56 0.78 230 0.4 23.7 120 -20 infinite Yes

1,2 156-59-2 60.2 1.28 200 0.48 0.0028 305.4 2.2-3.9 3.5- No Dichloroethylene 6.4E+03

Propan-2-ol 67-63-0 82 0.76 45.4 2.04 20.9 45.39 12 soluble No n-Butanol 71-36-3 117 0.81 7.0 2.5 24.9 52.35 37 soluble No

D4 (siloxane) 556-67-2 175 0.95 1.18 2.4-2.7 N/A N/A 51-55 300000 No

D5 (siloxane) 541-02-6 210 0.96 0.174 3.5 N/A N/A 82.7 0.017 No

Solvency and Extraction Rate

The solubility of the alternative solvents with process oil (as used in the ENTEK separator manufacturing process) was first estimated using Hansen solubility parameters from the literature. It should be noted that no values were available for Vertrel® SDG.

‘Hansen Solubility Parameters’ (HSPs) are a set of parameters devised by Charles M. Hansen that determine if any two compounds will dissolve into each other. The first parameter is δD which is a measure of dispersion or Van Der Waals forces. The second parameter is δP which measures the energy related to polar interactions and finally δH is a measure of energy resulting from hydrogen bonds. This allows a calculation of whether two solvents will dissolve. These three parameters combined with the interaction radius of the species being dissolved can determine whether a solvent will dissolve the compound in question.

The Hansen solubility parameters for the solvents were calculated based upon their thermodynamic properties as defined below:

Ra2 = 4(δD1 – δD2)² + (δP1 – δP2)² + (δH1 – δH2)²

δ: partial/Hansen solubility parameter

D, P, H: dispersion, polar, and hydrogen bonding components of the solubility parameter

1 denotes solvent, 2 denotes oil

Ra: solubility parameter distance in the Hansen solubility space

Minimization of Ra is desired

RED = Ra/R0

R0: Solubility sphere of the oil, centred at (δD2, δP2, δH2)

R0 is determined experimentally

Solubility occurs when the distance Ra lies within the sphere: RED number <1

Solvency of oil in a solvent is higher as R0 approaches zero.

The Hansen solubility parameters for the naphthenic process oil used in the ENTEK continuous separator manufacturing process were estimated from the work of Levin and Redelius (Energy & Fuels 2008; vol. 22, issue 5, pp. 3395-3401).

Table 4.2 lists the relevant Hansen solubility parameters and the RED value that was calculated for each alternative solvent and its interaction with a naphthenic process oil. In the case of acetone, the RED value is greater than 1, indicating that it is a relatively poor solvent for the oil. All other solvents show strong interaction with oil.

Table 4.2 Comparative Hansen solubility parameters

0.5 0.5 0.5 2 Solvent δ D(MPa) δ p(MPa) δ H(MPa) Ra Ra RED n- Hexane 14.9 0 0 18.8 4.3 0.4 HFE 72 de 16.3 6.9 2.5 52.3 7.2 0.7 Dichloromethane 18.2 6.3 6.1 70.7 8.4 0.8 Trichloroethylene 18 3.1 5.3 34.1 5.8 0.6 n-Propylbromide 16.4 7.9 4.8 65.5 8.1 0.8 Tetrachloroethylene 18.3 5.7 0 78.5 8.9 0.9 D-Limonene 16.6 0.6 0 21.2 4.9 0.5 Acetone 15.5 10.4 7 116.6 10.8 1.1

In addition to the above calculations, ENTEK also performed laboratory experiments to evaluate the extraction rate using the alternative solvents. These experiments were performed on oil-filled precursor sheets obtained from a separator production line. The extraction was performed at room temperature with an excess amount of solvent under agitation in a large beaker. Samples were removed after certain time periods, dried, and then weighed to determine the amount of oil that had been extracted. The experiment was repeated three different times for each solvent.

Figure 4.1 shows the results of the extraction experiment. The dashed line represents a residual oil value of 15 wt. % which is the target value for ENTEK separator production. It is clear from the data that acetone cannot be used as the extraction solvent as was predicted from the Hansen solubility calculations. Compared to TRI, samples extracted with tetrachloroethylene or D-limonene have higher residual oil contents for a given extraction time. These data indicate that both solvents are less efficient at oil extraction than TRI. While they still might be viable in a production process, ENTEK would be forced to slow down its production lines, increase the length of its extractors, or heat the alternative solvent to an elevated temperature in its extractors.

Although Hansen solubility parameters were not available for Vertrel® SDG, the extraction data show that both it and hexane actually exhibit faster extraction rates than TRI. Based upon the extraction rate data,

diffusion coefficients were calculated from the slope of the lines shown in Figure 3.2 for each alternative solvent. A relative diffusion coefficient ratio was then calculated from the slope for each solvent divided by the TRI slope. Table 3.3 shows that n-hexane, Vertrel® SDG, HFE 72 DE, and dichloromethane would all provide faster oil extraction compared to TRI. Significantly longer extraction times were exhibited by n- propyl bromide, tetrachloroethylene and D-limonene. Finally, acetone can be eliminated as a potential alternative solvent based upon its slow extraction rate for naphthenic process oil.

Oil Filled Flatsheet Extraction: Room Temperature DCM Acetone n-Hexane Tetra-CE nPB HFE 72DE D-Limonene Vertrel SDG Tri-CE 70%

60%

50%

40%

30%

20% Residual Oil Content Oil Residual

10%

0% 0 10 20 30 40 50 60 70 80 90 100 Time (sec.)

Figure 4.1. Residual oil content vs. time for various extraction solvents. Oil Filled Flatsheet Extraction: Room Temperature DCM Acetone n-Hexane Tetra-CE nPB HFE 72DE D-Limonene Vertrel SDG Tri-CE

1.000 0

0.100

0.010 Dimensionless Concentration, C/C Concentration, Dimensionless

0.001 0 10 20 30 40 50 60 70 80 90 100 Time (sec.)

Figure 4.2. Dimensionless concentration vs time for various extraction solvents.

Table 4.3 Rates of oil extraction compared to TRI

Slope of ln(C/C0) Relative Diffusion Viscosity, 25°C Solvent vs. Time Coefficient Ratio vs. TCE (cps) RED n-Hexane 0.1170 0.67 0.32 0.4 Vertrel SDG 0.0962 0.82 0.59 NA HFE 72DE 0.0877 0.90 0.45 0.7 Dichloromethane (DCM) 0.0866 0.91 0.44 0.8 Trichloroethylene (Tri-CE) 0.0789 1.00 0.54 0.6 n-propylbromide (nPB) 0.0748 1.05 0.49 0.8 Tetrachloroethylene (Tetra-CE) 0.0525 1.50 0.75 0.9 R-(+)-Limonene (D-Limonene) 0.0452 1.75 1.28 0.5 Acetone 0.0105 7.51 0.40 1.1

Drying

Once the oil has been extracted to its target level, the solvent-laden sheet then passes into the dryer. In the ENTEK drying process, steam is used to evaporate the solvent from the sheet. In the laboratory experiments, the solvent-laden sheets were simply dried in an oven to determine the amount of shrinkage in all three dimensions. As the solvent is evaporated from the sheet, capillary forces are exerted on the pore walls. The capillary force depends upon surface tension of the solvent, the contact angle, and the pore radius as shown in the following equation:

Pc = (- 2 LV cos  ) / r where Pc equals capillary pressure, LV is surface tension at the liquid-vapour interface,  is the contact angle, and r equals pore radius. Such capillary forces can lead to the collapse or compaction of the pores, resulting in dimensional shrinkage and smaller pore size distribution in the finished separator. The capillary force is governed by the surface tension of the extraction solvent – the higher the surface tension, the higher the capillary force, and thus the higher the separator shrinkage.

Table 4.4 shows the surface tension of the alternative solvents along with the measured separator shrinkage.

Table 4.4 Shrinkage of polyethylene sheet on drying compared to TRI

Surface Tension, MD Shrinkage CMD Shrinkage Thickness Relative Volume Solvent 25°C (dynes/cm) (%) (%) Shrinkage (%) after Shrinkage n-Hexane 17.9 6.9 2.7 1.0 0.90 Vertrel SDG 21.2 6.8 2.5 1.5 0.89 HFE 72DE 19 6.8 2.2 0.5 0.91 Dichloromethane (DCM) 28.1 7.7 3.8 1.7 0.87 Trichloroethylene (Tri-CE) 32.3 11.0 5.7 5.0 0.80 n-propylbromide (nPB) 25.9 9.8 4.5 2.2 0.84 Tetrachloroethylene (Tetra-CE) 29.5 14.4 8.1 3.9 0.76 R-(+)-Limonene (D-Limonene) 25 16.8 8.2 6.3 0.72 Acetone 23.7 12.5 6.3 5.0 0.78

Separator shrinkage is important because it affects the final separator properties such as porosity, pore size distribution, and also enables ENTEK to determine if the same calender rolls (that impart the rib pattern to the oil-filled sheet) can be utilized to achieve the same final separator profile. From the data, it is clear that solvents such as n-hexane, Vertrel® SDG, HFE 72DE, and dichloromethane result in less separator shrinkage than when the drying is done from TRI. While this would result in higher porosity that may be beneficial to separator electrical resistance, it means that the final separator profile (rib spacing, shoulder width, thickness) would be out of specification using the existing calender rolls. The costs and timelines associated with a change in calendar rolls are assessed in the following section. ENTEK has over 40 different calender/profile rolls at its UK plant that would need to be re-machined or replaced if any of the alternative solvents are used. While acetone gives nearly the same shrinkage as TRI, it is not a viable choice because of its slow extraction rate.

Electrochemical Compatibility

Residual solvent in the final separator can have a potential impact on the performance and life of a Pb-acid battery. As such, we evaluated the electrochemical compatibility (ECC) of leachates from separator samples that were extracted and dried from the alternative solvents to a residual oil content of 14%. In this test, a 7 gram sample from each separator type was leached in sulphuric acid (sp. gr. = 1.21) for 7 days at 60 °C. A cyclic voltammogram was performed on pure sulphuric acid (sp. gr. = 1.21) and then on the same acid with 10 ml of leachate. The 3-electrode apparatus for performing the cyclic voltammograms is shown in Figure 4.3. The cathodic and anodic scans for a TRI-extracted separator are shown in Figures 4.4 and 4.5, respectively.

Lead (Pb) rotating disk working electrode (WE)

Lead (Pb) counter Electrode (CE) Hg/HgSO4 Referenceelectrode (RE)

stopcock

Figure 4.3.Schematic diagram of the electrochemical cell used for ECC testing.

120601 TCE-extracted - Cathodic Scan

2.0

1.5 Hydrogen evolution current

1.0

Charge peak

0.5 Current (mA) Current 0.0

Discharge peak -0.5

blank leachate -1.0 -1.8 -1.6 -1.4 -1.2 -1.0 -0.8 Voltage vs. Ref.

Figure 4.4. Cathodic scan for TRI-extracted separator shows only a small increase in hydrogen overpotential with little change in the charge or discharge peaks.

120606 TCE-extracted - Anodic Scan

6.0 5.0 Discharge peak 4.0 3.0 2.0 1.0 0.0 blank -1.0 leachate

Current (ma) Current -2.0 -3.0 Charge peak -4.0 -5.0 -6.0 Oxygen evolution currennt -7.0 0.8 1.0 1.2 1.4 1.6 1.8 Voltage vs. Reference

Figure 4.5. Anodic scan for TRI-extracted separator shows no change in oxygen evolution, or in the charge and discharge peaks.

ENTEK performed ECC tests on separators extracted from each of the alternative solvents. Leachates from all of the separators had a minimal impact upon the behavior of either the negative (cathodic scan) or positive (anodic scan) lead electrode. Leachates from separators extracted with the alternative solvents had a larger increase in the hydrogen over-potential (> 50 mV at 1 mA) as compared to the TRI-extracted separator. The increase in hydrogen overpotential could actually lead to some beneficial results in a lead- acid battery (e.g., reduced water loss). As such, all of the alternative solvents appear viable based upon ECC testing.

Separator Properties

The two most important battery separator properties are electrical (ionic) resistance and mechanical strength, in particular puncture strength. Battery separators, extracted to 14% residual oil with the alternative solvents, were tested in accordance with Battery Council International (BCI) test procedure #03B3 to measure electrical resistance. In this test, the separators were first boiled in water for 10 minutes and then soaked in sulphuric acid (sp.gr = 1.28) for 20 minutes prior to measuring their electrical (ionic) resistance in a Palico Low Resistance Measuring System unit. The Palico measures the resistance drop between carbon electrodes while the separator covers an open orifice that allows current to travel through it. The resistance drop is then multiplied by the open orifice area to give units of mohm-cm2. Electrical resistivity (mohm-cm) was obtained for each separator type by dividing the electrical resistance (mohm-cm2) by the backweb thickness (cm).

As shown in Figures 4.6 and 4.7, the electrical resistance and electrical resistivity of the separators is independent of the extraction solvent, even though differences in shrinkage were observed during drying from the alternative solvents. This result would indicate that some of the porosity in separators that shrank the least is not being filled with acid and thus not contributing to ionic conduction. As used in these figures TCE means TRI.

Alternative TCE Solvents: Boiled ER 14% Residual Oil, 2.3:1 120

100

Electrical(mΩ-cm²) Resistance 20

0 Tri-CE DCM Vertrel SDG n-Hexane Tetra-CE n-PB HFE 72DE D-Limonene

Figure 4.6. Electrical resistance (mohm-cm2) of battery separators extracted with various solvents to a 14% residual oil content.

Alternative TCE Solvents Study: Boiled ER 14% Residual Oil, 2.3:1 3500

3000

2500

2000

1500

1000 Electrical(mΩ-cm) Resistivity 500

0 Tri-CE DCM Vertrel SDG n-Hexane Tetra-CE n-PB HFE 72DE D- Limonene

Figure 4.7. Electrical resistivity (mohm-cm) of battery separators extracted with various solvents to a 14% residual oil content.

The tensile strength of the separators was measured in an Instron machine in both the machine direction (MD) and cross-machine direction (CMD) at a cross-head speed of 500 mm/min. The puncture strength of the separators was measured in accordance with BCI test procedure # 03B11 using a 1.9 mm diameter flathead pin. The absolute puncture strength was then divided by the backweb thickness to provide a comparison of the separators produced from different extraction solvents.

As shown in Figures 4.7 and 4.8, there is no statistical difference in the MD and CMD tensile strength for any of the separators. Figure 4.9 shows that puncture strength, normalized for backweb thickness, is also nearly the same for all separator types. The slight increase in puncture strength (~ 5%) for the separator extracted with D-limonene is considered insignificant.

Alternative TCE Solvents Study: MD Tensile 14% Residual Oil, 2.3:1 14.0

12.0

10.0

8.0

6.0

4.0 PeakStress (MPa) MD -

2.0

0.0 Tri-CE DCM Vertrel SDG n-Hexane Tetra-CE n-PB HFE 72DE D-Limonene

Figure 4.8. Machine-direction (MD) tensile strength for separators extracted and dried from alternative solvents.

Alternative TCE Solvents Study: XMD Tensile 14% Residual Oil, 2.3:1 8.0

7.0

6.0

5.0

4.0

3.0

PeakStress (MPa) XMD - 2.0

1.0

0.0 Tri-CE DCM Vertrel SDG n-Hexane Tetra-CE n-PB HFE 72DE D-Limonene

Figure 4.9. Cross machine direction (CMD) tensile strength for separators extracted and dried from alternative solvents.

Alternative TCE Solvents Study: BW Puncture 14% Residual Oil, 2.3:1 45

Backweb Puncture (N/mm) Puncture Backweb 10

0 Tri-CE DCM Vertrel SDG n-Hexane Tetra-CE n-PB HFE 72DE D-Limonene

Figure 4.10. Normalized puncture strength (N/mm) for separators extracted and dried from alternative solvents.

In conclusion, the electrical and mechanical properties of the separators extracted and dried from the alternative solvents are similar to the control separator produced from TRI. Conclusions on the trials of possible solvent alternatives The ‘bench scale’ trail on the substances that may be possible alternatives is summarised in Table 4.5.

Table 4.5 Summary of solvent trials on polyethylene sheet compared to TRI

Solvent Hansen Residual oil Sheet properties – (compare with TRI (predicted extraction extracted) solvation time Shrinkage Electrochemical Stength and with oil - (compare properties puncture lower is with TRI better) extracted) n-Hexane 0.4 faster lower similar similar Dichloromethane 0.8 faster lower similar similar (DCM) Tetrachloroethylene 0.9 slower higher similar similar Vertrel SDG N/A faster lower similar similar HFE 72DE 0.7 faster lower similar similar n-Propyl bromide 0.8 slower similar similar similar D-Limonene 0.5 slower higher similar similar Acetone 1.1 fail similar similar similar

It is stressed that the above trial will only give an indication of the potential for other solvents to perform the oil extraction function of TRI. As indicated in Table 2.1 there are a number of other critical functions of TRI that would also need to be fulfilled in order for TRI to be replaced. A key property is the compatibility with the solvent capture and recycling system that allows recovery and reuse of the solvent in the ENTEK process. It is not a surprise that n-hexane is an effective solvent for extraction of oil from PE separator sheet, since it is known that n-hexane is used for this purpose in the production of PE separators. However, a critical consideration for the selection of possible alternatives is the hazard/risk profile of the substance and this is considered in depth in Section 5.

4.2.2 Manufacturing Alternatives

Confidential

4.2.2 Data searches ENTEK is aware of the solvent substitution work that has been done in the pharmaceutical industry (www.acs.org/gcipharmaroundtable) and at the Toxics Use Reduction Institute (TURI) of the University of Massachusetts-Lowell (www.turi.org). A review of the work done at these organizations reveals that there are no clear alternatives to TRI for battery separator applications.

4.2.3 Consultations

ENTEK is working directly with Dow Chemical and Safechem regarding the continued use of TRI in battery separator production. In addition, ENTEK has hired Peter Fisk Associates to serve as Project Manager to coordinate the multiple aspects of our authorization application. ENTEK has also consulted with Professor James Hutchinson, who heads up the Green Chemistry program at the University of Oregon, which is located near the ENTEK-US manufacturing plant.

ENTEK is also working with several battery separator customers to better understand the costs and timeline for original equipment manufacture’s (OEM) approval of batteries that would be built with separators from a new or modified separator manufacturing process. Details of these consultations are in the SEA report.

5. SUITABILITY AND AVAILABILITY OF POSSIBLE ALTERNATIVES

5.1 INTRODUCTION

As detailed in Section 3.2 a research programme was initiated to identify possible viable substance alternatives. Confidential

In all cases however, none of these possible alternatives is either suitable or presently available to ENTEK and thus the application for authorisation is made on the basis that no alternative can be used to replace TRI in the ENTEK process for some years.

5.2 N- HEXANE

5.2.1 Substance ID and properties

Chemical Name(s): hexane

Other names: Methyl pentane, n-Hexane, Hexyl hydride

Trade Name(s): Skellysolve B; n-C6H14; Esani; Heksan; Hexanen; Hexyl hydride; Gettysolve-B; NCI- C60571; NSC 68472

CAS Number: 110-54-3

EC Number: 203-777-6

Molecular Formula: C6H14

Molecular weight: 86.18

Classification and Labelling

The harmonised classifications according to the CLP regulation no. 1272/2008 and according to the Dangerous Substances Directive 67/548/EEC are presented in the tables below.

Classification CLP - according to Regulation No Dangerous Substance Directive – area 1272/2008 Annex VI according to Directive 67/548/EEC Physicochemical Flam. Liq. 2 F; R11

Health Asp. Tox. 1 Repr. Cat. 3; R62

Skin Irrit. 2 Xn; R65-48/20

STOT SE 3 Xi; R38

Repr. 2 R67

STOT RE 2

Environmental Aquatic Chronic 2 N; R51-53

Hazard H225: Highly flammable liquid and vapour 11: Highly flammable Statements

H304: May be fatal if swallowed and enters 65-48/20: Harmful: danger of serious airways damage to health, may cause lung damage if swallowed

H315: Causes skin irritation 38: Irritating to skin

H336: May cause drowsiness or dizziness 67: Vapours may cause drowsiness and dizziness

H361f: Suspected of damaging fertility 62: Possible risk of impaired fertility

H373: May cause damage to organs through prolonged or repeated exposure

H411: Toxic to aquatic life with long 51-53: Toxic to aquatic organisms, may lasting effects cause long-term adverse effects in the aquatic environment

Hexane is a highly volatile hydrocarbon that is a major component of gasoline. A summary of the physicochemical properties are presented in Table 5.1. The human health and environmental classifications for hexane are listed above.

Table 5.1 Physico-Chemical Properties of hexane

Properties Characteristics of Chemical Source(s) of Information

Flammability Highly flammable HSDB, 2013

Vapour pressure 20 kPa at 25°C HSDB, 2013

Boiling point 68.73°C HSDB, 2013

Properties Characteristics of Chemical Source(s) of Information

Melting point -95.35°C HSDB, 2013

Water solubility 9.5 mg/L at 25 °C HSDB, 2013

Log Kow 3.90 HSDB, 2013

5.2.2 Technical feasibility

As discussed in Section 4.2.1, n-hexane is an effective solvent for naphthenic process oils and the laboratory scale experiments showed that separators treated with hexane have properties that are similar to the TRI- extracted separators. ENTEK knows that one of its separator competitors uses hexane as an extraction solvent at its plant in France (and also at their US plant in Owensboro, Kentucky), but it must be recognized that this competitor does not use a continuous process for the manufacture of battery separators. In the n- hexane process, oil-filled sheet is manufactured in very large rolls that are subsequently unwound and passed through a shallow pan extractor filled with hexane. The extraction equipment is located outside the main building, and the operators monitor the operation behind an explosion-proof wall.

It is believed that this multistep, staged process (in contrast to the ENTEK continuous separator manufacturing process) is used by a competitor to partially isolate the explosion and fire risk associated with the extraction and drying of the oil filled sheet. In their case, the extrusion and calendering part of the process and the final slitting process for converting jumbo rolls into finished slit rolls with the appropriate width for enveloping are isolated from the highest risk step of extraction and drying with n-hexane. In a continuous separator manufacturing process, the risk cannot be decoupled from the extrusion, calendering and slitting operations in order to result in a product that is usable by the battery manufacturer in its enveloping process. Further consideration of the feasibility of replacement of TRI with n-hexane is considered in detail below.

Substituting n-hexane for TRI at ENTEK International LTD

The three major concerns for substituting hexane for TRI in the ENTEK battery separator plant in Newcastle, UK are: 1. Flammability of n-hexane and lack of possibilities in the current ENTEK plant design for handling

an R11 substance in the process.

2. Capital equipment and operational modifications unrelated to flammability – for example in the

processes for oil extraction and solvent recovery - required to allow substitution.

3. Customer acceptance of the substitution.

The high flammability of n-hexane is the foremost concern. Comparing n-hexane to TRI:

Hexane Trichloroethylene Flash Point -22°C - Auto-Ignition Temperature 225°C 414°C Lower Flammability Limit 1.1 vol. % 12.0 vol. % Upper Flammability Limit 7.5 vol. % 40.0 vol. % Boiling Point 68.5°C 87.6°C Vapour Pressure in mm Hg @ 20°C 121 60 R Phrases for Flammability R11 -

Trichloroethylene’s auto-ignition temperature is quite high and its flammability limits are above the range that would be measured around process equipment under any foreseeable process scenario. Trichloroethylene is classed by most sources as non-flammable, for example by the European Chlorinated Solvent Association. These factors make the use of TRI a negligible risk for fire or explosion in the battery separator process.

In contrast to TRI, hexane has the R11 risk phrase ‘highly flammable’, a significantly lower auto-ignition temperature and flammability limits that could be reached during normal process operations. Hexane is approximately twice as volatile as TRI at room temperature: the combination of high volatility and low flammability limits makes the possibility of fire quite high in a process not specifically designed for the use of hexane.

Mitigating the risk of fire and explosion in the use of hexane for making battery separators will require extensive engineering design, equipment and facilities modifications, and changes to operational practices.

Engineering Design Changes for Hexane Use Processing highly flammable liquids in an industrial process requires careful attention to sources of ignition. Electric motors, electrically powered instruments, lighting, electrical panels, junction boxes, rotating equipment and any item capable of carrying a static charge are all areas of concern. Battery separator sheet in both the oil-filled (~65% oil by weight) and finished state (~15% oil by weight) can carry a high static charge. In a battery separator process using hexane all of these ignition sources pose a serious hazard to human health and capital investment. Mitigating the risks posed by these ignition sources would be both prudent and legally mandated.

The analysis of risk begins by defining the areas within the production process that are at risk of fire and explosion due to the presence of the flammable compound. There are three zones to be considered:

1. Zone 0: Explosive gas-air mixture is continuously present or present for long periods 2. Zone 1: Area in which an explosive gas-air mixture is likely to occur for short periods in normal operation 3. Zone 2: Area in which an explosive gas-air mixture is not likely to occur and, if it does occur, will only exist for a short time due to abnormal process conditions.

An ATEX2 notified body must certify equipment rated for and used within zones 0 and 1. Manufacturers can self-certify equipment for use in zone 2.

Broadly speaking, the following engineering analysis and changes in ENTEK capital equipment would be required:

2 Directive 94/9/EC of the European Parliament and the Council of 23 March 1994 on the approximation of the laws of the Member States concerning equipment and protective systems intended for use in potentially explosive atmospheres.

If a conformity assessment procedure under the Directive calls for third-party intervention, this is then undertaken by so-called "Notified Bodies", who are appointed by the Member States because they have the relevant expertise and facilities to undertake the required procedures.

This might include a "Type Examination", which involves an assessment made of the product against the EHSRs of the Directive, or even (amongst others) a report of the manufacturer's quality assurance procedures to ensure that the "type" will continue to comply with the requirements.

Whilst these Bodies are given a number and are listed in the NANDO Information System prior to their operation, the activities of Notified Bodies are a matter for Member States, as they are appointed under their authority.

In addition, whilst the Notified Body has various responsibilities under the Directive, the manufacturer (or authorised representative) always remains responsible for the compliance of the equipment.

1. Analyse for and define the zone classification for hexane-air mixtures in the battery separator process. 2. In any locations defined as zone 0 or 1, replace all equipment not specifically certified for use in zones 0 or 1 with properly rated equipment. a. At minimum, the following items would need to be replaced: electric motors, electrically powered instruments, electrical devices, electrical enclosures and most/all electrical wiring. b. ENTEK’s affiliate ENTEK Manufacturing LLC, designs and builds capital equipment for making battery separator. Some or all of this equipment would be within zone 0 or zone 1 classified locations. Whether this equipment could be certified ex post is unknown at this time; it is possible that some or all of the existing process equipment would have to be re- engineered, built, certified and installed according to ATEX requirements to satisfy the regulator’s requirements. 3. In locations defined as zone 2, equipment can be self-certified by the manufacturer. This fact would not relieve ENTEK of the legal and moral obligation to provide a safe workplace.

Hexane Process Areas Likely To Be Classified Zone 0, 1 or 2 A provisional analysis of ATEX classifications for the processes where hexane would be present in making battery separators was undertaken to judge the scope and cost of the conversion from TRI to hexane. The results of that analysis are shown in the table on the next page.

Flammable mixtures of hexane and air would or could be present within and/or around all battery separator processes starting with the oil extraction step through the sheet finishing operation at the winder.

Further, the distillation equipment that would be used to separate hexane from oil could be expected to have flammable hexane and air mixtures around the equipment under upset conditions.

The carbon beds used to recover the oil-extracting solvent could have explosive mixtures within the carbon beds under normal operating conditions; explosive mixtures could be present outside the carbon beds and their associated condensers, decanters, and storage tanks under upset conditions.

All hexane storage tanks could contain explosive mixtures of hexane and air; under upset conditions there could be explosive mixtures outside the tanks.

ENTEK’s provisional analysis of likely ATEX zone classifications for a battery separator process using hexane indicates extensive areas of zone 0, 1 and 2 classification. All equipment in zones 0 and 1 would need to be ATEX certified. This zone would likely include the extractors, dryers, ovens, sheet finishing, carbon beds and hexane storage tanks. Most of this equipment is currently built internally by ENTEK utilizing our proprietary knowledge of battery separator manufacturing to afford the company a competitive

advantage in the battery separator market. The equipment in these areas currently installed in ENTEK’s Newcastle facility was not designed for use with a flammable solvent like hexane. It is likely that this equipment would need to be re-designed, built, and installed to obtain the legally mandated ATEX certification for using hexane.

Physical Isolation of Processes Using Hexane

One of the most effective safety measures for processes classified as zone 0 or zone 1 is physical isolation. Isolation entails housing the process in an unmanned room separated from the zone 3 and unclassified process areas by walls. High ventilation rates within the enclosed space insure that flammable gases do not build up to dangerous levels. The isolated room is equipped with fire suppression equipment and explosion- relief venting. Isolating the zone 0 or zone 1 processes serves as a reminder to personnel who occasionally work in these areas that special precautions are required to work in the classified area.

Unfortunately, the ENTEK process was designed in 1988 to be a continuous process using a non-flammable liquid solvent for oil extraction. There was no provision in the design for isolating any part of the process and no extra room was planned into the production facility to house such a process. These facts mean that physical isolation would be very difficult to implement at ENTEK’s facility.

5.2.3 Reduction of overall risk due to transition to the alternative

Hexane is subject to a SCOEL recommendation for an occupational exposure limit for the protection of workers at EU level8. The iOEL is summarised as follows:

8 hour TWA: 20 ppm [72 mg/m3] STEL (15 min): No STEL or "skin" notation was considered to be necessary-

Table 5.2 below summarises further information on the hazard profile of the substance.

8 Recommendation from the Scientific Committee on Occupational Exposure Limits on Tetrachloroethylene (perchloroethylene) SCOEL/SUM/133, June 2009

Table 5.2 hazard profile of n-hexane

Human Health Hazards

Acute Toxicity Acute toxicity Hexane has low acute toxicity with inhalation LC50 value of >5000 ppm. SUM 1995 Acute inhalation exposure of humans to high levels of hexane causes mild CNS depression. US EPA 2000 CNS effects include dizziness, giddiness, slight nausea, and headache in humans. Acute exposure to hexane vapours may cause dermatitis and irritation of the eyes and throat in humans.

Skin or eye Hexane is classified as a skin irritant, however it is not classified as an eye irritant. ECHA 2013 corrosion/irritation Inhalation can cause respiratory irritation.

Respiratory or skin n-hexane is not considered to be a sensitizing agent. ECHA 2013 sensitisation Chronic toxicity Carcinogenicity EPA has classified hexane as a Group D, not classifiable as to human carcinogenicity, based on US EPA 2000 a lack of data concerning carcinogenicity in humans and animals. It is not classified by IARC.

Long term toxicity The main effect of repeated exposure to hexane in laboratory animals and in humans is SCOEL 1995 characterized by neurotoxicity. The clinical signs of neurotoxicity from hexane include limb weakness progressing to paralysis. In humans repeated exposure to inhaled hexane resulted in sensorimotor polyneuropathy, with US EPA 2000 numbness in the extremities, muscular weakness, blurred vision, headache, and fatigue observed.

Reproductive and Testicular damage has been observed in male rats exposed to hexane via inhalation. SCOEL 1995 developmental toxicity Rats exposed chronically exposed to hexane via inhalation showed CNS effects and decreased body weight at concentrations at which maternal toxicity was also observed (1500 ppm or 5370 mg/m3).

Mutagenicity Hexane is considered a weak mutagen in the absence of metabolic activation. ECHA 2013

Endocrine disruption No information Neurotoxicity Neurotoxic effects to both the peripheral and the central nervous systems of humans may occur HSDB, 2013 after exposure to n-hexane. Immune system No information toxicity Systemic toxicity yes, effects to the peripheral and central nervous system. Cardiotoxicity Sub-cutaneous exposure of rats to 0.1 ml n-hexane for 30 days resulted in cardiotoxicity. ECHA 2013 90 days subcutaneous exposure to 0.1 ml of hexane resulted in lowered ventricular fibrillation threshold and lowered levels of magnesium, potassium, and zinc in rats. Toxic metabolites The main metabolite of hexane is 2-5,hexanedione, a neurotoxic agent. SCOEL 1995 Environmental effects/toxicity Degradation 100% degradation has been achieved after 4 weeks in a Japanese MITI test. HSDB, 2013

Bioaccumulation The calculated BCF is 501.87. It does not meet the criteria for B in PBT. ECHA 2013

However the log Kow is greater than 3, therefore the substance has potential for bioaccumulation. Acute/chronic There are no aquatic toxicity data with n-hexane in the disseminated dossier, however the ECHA 2013 aquatic toxicity substance is classified as Aquatic Chronic 2 under CLP. Fish toxicity LC50 values have been reported as low as 2.5 mg/l with Pimephales promelas. An HSDB 2013 3 invertebrate EC50 value of 45 mmol/m has been reported with Daphnia magna and an algal 3 EC50 value of 94 mmol/m has been derived with Chlamydomonas angulosa (green algae).

Greenhouse gas Hexane is not identified as a greenhouse gas. formation potential Ozone-depletion Hexane is not classed as an ozone depleting substance. Regulation (EC) No 2037/2000 potential

n-Hexane is metabolised to 2-5,hexanedione, a neurotoxic agent. Acute exposure to hexane can cause respiratory and skin irritation, and effects to the central and peripheral nervous systems (such as dizziness), which may result in damage to peripheral nerves. The substance is in fact classified for acute effects under CLP as an Aspiration Toxicant 1, Skin Irritant 2 and STOT SE 3, with the associated hazard statements, amongst others, H335 and H336 (may cause respiratory irritation and may cause drowsiness or dizziness).

The main effect of repeated exposure to hexane is neurotoxicity, which may progress to paralysis. It may also cause testicular damage and maternal toxicity. It is classified under CLP as a Reproductive toxicant 2 and STOT RE 3. It is therefore not considered to be a safe substance from a human health point of view.

In addition, hexane has the potential to bioaccumulate in the environment (log Kow >3), even though it does not meet the criteria for B in PBT due to its bioaccumulation factor being below the threshold value for B (501.9 against the cut-off value of 2000 L/kg) and it is toxic to fish in short-term toxicity studies with the lowest LC50 value of 2.4 mg/L (no long-term aquatic toxicity data are available). Hexane is classified under CLP as Aquatic Chronic 2.

PBT and CMR As a reproductive toxicant category 2, hexane would be considered to meet the toxicity (T) criterion for PBT, but not the reproductive toxicity (R) criterion for CMR, thus it is not has been proposed as a substance of very high concern (SVHC). Hexane is being assessed in the REACH CoRAP program due to concerns for human health/CMR and neurotoxicity; exposure/wide dispersive use and high aggregated tonnage.

5.2.4 Economic feasibility

Cost Estimate to Change ENTEK’s UK Facility to n-hexane n-Hexane is not a “drop-in” solvent replacement for TRI as noted above. It would mean the replacing large parts (if not completely) the existing production process and equipment. As per the ECHA SEA guidance, the lost (book) value of existing equipment is considered a ‘sunk cost’ and therefore not considered in the analysis. The additional capital and operating costs of making PE SLI battery separators is however relevant to the assessment of economic feasibility.

Changing the ENTEK facility over to use hexane as an oil-extracting fluid in place of TRI would require a long-term engineering effort, engagement of ATEX authorities, permitting, and capital equipment design, build, install and start-up efforts. At this time, it is not known whether the existing facility could be re- engineered and re-built to safely use hexane. These facts make any cost estimate for the change from TRI to n- hexane subject to large uncertainty. In order to model this uncertainty:

 Scenario 1 considers the economic feasibility of retrofitting the existing equipment to be able to use hexane; and

 Scenario 2 considers the economic feasibility of new equipment to use hexane.

Scenario 1

Scenario 1 is the least expensive conversion scenario in terms of time and capital investment as it assumes it is possible to convert the existing equipment and certify it per ATEX requirements to use hexane. An extensive engineering study and consultation with an ATEX notified body would be needed to determine if this option is feasible. Assuming this approach is found to be feasible, a first-pass estimate of the timeline and cost is estimated below at €9.98 million over 45 months (3.75 years). This time excludes qualification time required by battery manufacturers (minimum 2 years of 24 months – See SEA section 3.2).

Hexane Conversion Time and Cost: Modify Equipment

Preliminary Engineering Analysis Months Cost (ϵ) Engage ATEX consulting resource 1 € 37,619 Classify Existing Processes into ATEX Zones 4 € 149,048 Identify Opportunities to Re-Classify 3 € 106,429 Determine Feasibility of Conversion 3 € 106,429 Draft Conversion Plan 1 € 35,476 Total for ATEX-Related Activities 12 € 435,000

Prototyping and Design Data Acquisition

Extraction, Drying, Oven, Distillation, Carbon Recovery 12 € 869,643

Design/Build Design Equipment 9 € 790,089 Build Equipment 9 € 2,928,214 Install Equipment 3 € 4,925,536 Total For Design/Build Activities 21 € 8,643,839

Grand Total 45 € 9,948,482

Table 5.3 shows that the minimum cost to ENTEK is ~ €55million net present value (NPV). It is considered a minimum costs as it excludes some additional costs like redundancy (over the period 2016-2019) and assumes post 2019, ENTEK can make equivalent profits. This assumption is however highly unlikely since the new battery separator would (i) still need to be qualified by customers (up to 2 years) given the significant changes in the production process, (ii) assumes ENTEK would not have lost any market share due to no sales after the sunset date (April 2016) to 2019, and (iii) assumes profit margins would be similar compared to using TRI (which is highly unlikely given no new plants across the world has chosen hexane over TRI).

Table 5.3 Minimum economic costs to ENTEK of switching to hexane (scenario 1)

COSTS TO ENTEK (€ million) 2016 2017 2018 2019 Total NPV Capex costs € 0.44 € 0.87 € 1.77 € 6.88 € 9.95 € 7.85 Best estimates of lost profit (until new production using n-Hexane is online) € 10.14 € 15.21 € 15.21 € 15.21 € 55.78 € 46.79 Total cost € 10.58 € 16.08 € 16.98 € 22.09 € 65.73 € 54.64 Notes:

1. Based on a discount rate of 7% and a base period of 2016

2. Lost profit figures have been taken from the SEA (See SEA Section 4.2.1) – lost profit is lower in 2016 as it assumes continued production (and therefore profits from sales) with TCE up until the sunset date.

When comparing the minimum cost of switching to hexane is at least €54.6m with the cost of building additional production lines at the existing US site (in Oregon) which is €48m (see Section 4.2.2 of the SEA); which enables ENTEK to avoid any production/sales disruption (i.e. can provide battery separators to the existing markets after the sunset date), it is clear that switching to hexane is not economically feasible.

Factoring in the additional time (2 years) for product qualification, this increases lost profit beyond 2019 (i.e. up to 2021), resulting in a total cost to ENTEK of €76 million (NPV). If it is also assumed that it takes a further 5 years for ENTEK to recover their market share (i.e. 80% of lost profit in 2022, declining linearly to 0% in 2026) then the net cost to ENTEK is €93 milion (NPV). This further reinforce the conclusion that hexane is not economically feasible.

Scenario 2

The Scenario 1 estimate (€93 million) assumes that the existing equipment can be modified to use hexane in place of TRI despite the substantial differences in physical properties and processing characteristics of the two substances. This assumption is unlikely to be satisfied for at least some of the existing equipment and quite possibly all of it, which is modelled below as Scenario 2. It will only be clear at the end of the “Prototyping and Design Data Acquisition” phase of the project if all new equipment is required.

The most time-consuming and costly option for conversion to hexane is the need to replace all existing equipment in ATEX zones 0 and 1. A first-pass estimate of the time and cost to accomplish the conversion is estimated below at €43.86million over 84 months (7 years). This time excludes qualification time required by battery manufacturers (minimum 2 years of 24 months – See SEA section 3.2).:

Hexane Conversion Time and Cost: New Equipment

Prototyping and Design Data Acquisition

Extraction, Drying, Oven, Distillation, Carbon Recovery 12 € 869,643

Design/Build Design Equipment 24 € 3,054,286 Build Equipment 24 € 29,945,714 Install Equipment 12 € 9,552,143 Total For Design/Build Activities 60 € 42,552,143

Grand Total 84 € 43,856,786

Table 5.4 shows that the minimum cost to ENTEK under scenario 2 is ~ €107 million (NPV). Similarly to scenario 1, it is considered a minimum costs as it excludes some additional costs like redundancy (over the period 2016-2022) and assumes post 2022, ENTEK can make equivalent profits. This assumption is however highly unlikely since the new battery separator would (i) still need to be qualified by customers (up to 2 years) given the significant changes in the production process, (ii) assumes ENTEK would not have lost any market share due to no sales after the sunset date (April 2016) to 2022, and (iii) assumes profit margins would be similar compared to using TRI (which is highly unlikely given no new plants across the world has chosen hexane over TRI).

Table 5.4 Minimum economic costs to ENTEK of switching to hexane (scenario 2)

COSTS TO ENTEK (€ million) Total costs 2016-2022 NPV Capex costs € 44 € 30 Best estimates of lost profit (until new production using n- Hexane is online) € 101 € 77 Total cost € 145 € 107 Notes:

1. Based on a discount rate of 7% and a base period of 2016

When comparing the minimum cost of switching to hexane is at least €107m with the cost of building additional production lines at the existing US site (in Oregon) which is €48m (see Section 4.2.2 of the SEA); which enables ENTEK to avoid any production/sales disruption (i.e. can provide battery separators to the existing markets after the sunset date), it is clear that switching to hexane is not economically feasible under scenario 1 or 2.

Factoring in the additional time (2 years) for product qualification, this increases lost profit beyond 2022 (i.e. up to 2024), resulting in a total cost to ENTEK of €114 million (NPV). If it is also assumed that it takes a further 5 years for ENTEK to recover their market share (i.e. 80% of lost profit in 2024, declining linearly to 0% in 2028) then the net cost to ENTEK is €139 million (NPV). This further reinforces the conclusion that hexane is not economically feasible under scenario 1 or 2.

Practicality of Hexane Conversion at the Newcastle Facility Given that more than half of the major equipment in the Newcastle facility would at minimum need to be re- designed - and more likely be replaced - to convert the facility to hexane and comply with ATEX requirements, the feasibility of conversion is called into question. The existing plant does not have the required space to duplicate all of the equipment installations to allow uninterrupted operation of the facility during the conversion process.

For example, the plant must have a carbon bed system in-place and operational on an uninterrupted 24/7 basis to comply with legally mandated air discharge requirements imposed by the UK Environmental Authority. The existing carbon beds were not designed for use with a flammable solvent and this equipment will likely have an ATEX zone 0 classification inside and around the carbon beds if the Newcastle facility converts to hexane. Assuming it is possible to modify the existing beds to meet ATEX zone 0 requirements, all required modifications would need to be accomplished in 2 weeks or less to avoid interrupting battery separator supply to ENTEK’s customers.

If a re-build and re-installation of new beds is required, the old carbon beds would need to be removed and the new carbon beds installed to effect the conversion to hexane. This too would need to be accomplished in 2 weeks or less to avoid interrupting battery separator supply.

Now, consider the entire conversion process from TRI to hexane. The ENTEK Newcastle facility does not have the infrastructure to run TRI and hexane processes in parallel, nor does it have enough space to install a second process using hexane in parallel with the existing TRI process. Extensive removal of the equipment designed for TRI, installation of the new hexane-using equipment, and re-wiring to ATEX zone 0 through 2 standards would have to be performed to bring the facility into compliance for hexane use. The plant outage to accomplish this much work would take up to 12 months, an undertaking that would remove a substantial amount of battery separator supply from the EU market. ENTEK would break contractual supply commitments to customers and likely deal its business a commercial blow from which it would never recover.

5.2.5 Availability

The substance has been registered under REACH at a 10,000 to 100,000 tonnes per annum band, therefore it can be considered to be readily available.

5.2.6 Conclusion on suitability and availability for n-hexane n-Hexane is not a technically feasible alternative because the extraction and drying steps are an integral part of the continuous process that ENTEK uses to manufacture battery separators. The potential consequence of a fire or explosion with over ~34,000 litres of hexane being circulated in a closed loop process at the UK plant would be catastrophic. The extraction and drying steps could not be isolated without a complete retrofit of the ENTEK manufacturing process and the plant infrastructure. The large cost to switch to hexane compared to the costs of building additional production lines in the US, means this alternative is also not economically feasible. Even if such a project were completed at great capital expense, the human health risks associated with hexane are substantial and would not justify a change from the current extraction solvent.

As mentioned in Section 4, n-hexane is known to be used for the production of PE separators, but there are key technological reasons why ENTEK (and others) has opted for a continuous closed loop process using TRI. Interestingly, the competitor that uses n-hexane in France and one of its US operations, has elected to use TRI at its other three manufacturing locations (Thailand, China, USA) which have been more recently acquired or built. This fact indicates that this competitor views TRI as a better choice for the production of separators as compared to n-hexane.

As well as the technological disadvantages of the use of n-hexane there are clear risk indicators for not switching to n-hexane, due to its flammability and its toxicity. As indicated in this section below, n-hexane is currently classified as a reproductive toxin (albeit as a suspected reproductive toxin - Cat 3.) and it is also indicated to have specific target organ toxicity affecting the nervous system (STOT RE 2, H373). Although the substance is not currently an SVHC it is on the CoRAP list.

Given the volatility of n-hexane and its low DNEL (long term DNEL for neurotoxicity for workers is 75 mg/m3 (~21 ppm)) (the SCOEL iOEL (1995) is 72 mg/m3 (20 ppm)) 8 hour TWA), the problems associated with control of this substance are similar to TRI and the impacts to health, whilst not cancer, can cause long- term illness. The conclusion from a hazard and risk management point of view is that there is no advantage in use of n-hexane over TRI, the only advantage is that n-hexane is not designated as a SVHC today, although the indications are that it could well be subject to further restrictions on use in the future.

The toxicological profile and the continued regulatory pressure on dangerous substances like n-hexane, mean that the considerable investment to switch from TRI to n-hexane cannot be easily justified.

5.3 DICHLOROMETHANE

5.3.1 Substance ID and properties

Chemical Name(s): dichloromethane

Other names: Methylene chloride, methylene dichloride

Trade Name(s): Solmethine, Narkotil, Solaesthin, Di-clo, Freon 30, R-30, DCM, UN 1593, MDC

CAS Number: 75-09-2

EC Number: 200-838-9

Molecular Formula: CH2Cl2

Molecular Weight: 84.93

Classification and Labelling

The classifications according to the CLP regulation no. 1272/2008 and according to the Dangerous Substances Directive 67/548/EEC are presented in the tables below. Both the harmonised classification and the self-classification provided by the REACH disseminated dossier registrants are presented.CLP - according to Regulation No 1272/2008 Annex VI

Classification Harmonised Self-classification area Phsyicochemical Not classified Not classified

Health Carc. 2 Carc. 2

Skin Irrit. 2

Eye Irrit. 2

STOT SE 3. Affected organs: central nervous system Route of exposure: inhalation

Environmental Not classified Not classified

Hazard H351: Suspected of causing cancer H351: Suspected of causing cancer

Classification Harmonised Self-classification area Statements

H315: Causes skin irritation

H319: Causes serious eye irritation

H336: May cause drowsiness or dizziness

Dangerous Substance Directive – according to Directive 67/548/EEC

Classification Harmonised Self-classification area Health hazards Carc. Cat. 3; R40 Carc. Cat. 3; R40

Xi; R36/38

Risk Phrases R40: Limited evidence of a R40: Limited evidence of a carcinogenic effect carcinogenic effect

R36/38: Irritating to eyes and skin

R67: vapours may cause drowsiness and dizziness

Dichloromethane is a clear, colourless, highly volatile, non-flammable liquid with penetrating ether like odour. The odour threshold is ≥540 mg/m3. It has a boiling point of 40°C and a melting point of -95.1°C. It has a solubility in water of 13 g/L at 20°C and a vapour pressure of 47.4 kPa at 20°C. Pure methylene chloride vapour is denser than air.

Pure, dry dichloromethane is relatively stable but in the presence of water and light it slowly decomposes to produce small quantities of hydrogen chloride.

Commercial grades of dichloromethane normally contain between 0.005 and 0.02% of a stabiliser (such as methanol, ethanol, amylene, cyclohexane, phenolic compounds or tertiary butyl amine) to prevent acidification and corrosion1.

1 Recommendation from the Scientific Committee on Occupational Exposure Limits for methylene chloride (dichloromethane) SCOEL/SUM/130 June 2009

Table 5.5 Physico-Chemical Properties of dichloromethane

Properties Characteristics of Chemical Source(s) of Information

Flammability non-flammable SCOEL, 2009

Vapour pressure 47.4 kPa at 20°C SCOEL, 2009

Boiling point 40°C SCOEL, 2009

Melting point -95.1°C SCOEL, 2009

Water solubility 13 g/L at 20°C SCOEL, 2009

Log Kow 1.25 HSDB, 2010

5.3.2 Technical feasibility

From the research as described in Section 3.2 of this document it appears that dichloromethane may have the potential to be a technically feasible alternative to TRI as a process solvent for the manufacture of polyethylene battery separators. However, as indicated in that examination there is a considerable amount of further research that is required in order to understand if dichloromethane could be used at a commercial scale and would be compatible with full scale processing plant as well as meeting customer product quality criteria. The possible steps that may be needed to determine if an alternative solvent is technically feasible are described in Section 6.2

5.3.3 Reduction of overall risk due to transition to the alternative

Whilst dichloromethane does not meet the criteria for a substance of very high concern (SVHC), it is subject to a restriction under REACH and listed on Annex XVII of the regulation accordingly2. The restriction limits the use of the substance in products used as paint strippers in order to control the risk to workers health from the substance. The substance is classified as a category 3 carcinogen (under the Dangerous Substance Directive) and subject to a SCOEL recommendation for an indicative occupational exposure limit (iOEL) for the protection of workers at EU level3. The iOEL is summarised as follows:

8 hour TWA (time weighted average): 100 ppm [353 mg/m3]

2 COMMISSION REGULATION (EU) No 276/2010 of 31 March 2010 amending Regulation (EC) No 1907/2006 of the European Parliament and of the Council on the Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH) as regards Annex XVII (dichloromethane, lamp oils and grill lighter fluids and organostannic compounds)

3 Recommendation from the Scientific Committee on Occupational Exposure Limits for methylene chloride (dichloromethane) SCOEL/SUM/130, June 2009

STEL 15 min (short term exposure limit): 200 ppm [706 mg/m3]

BLVs (biological limit value): 4 % COHb4

0.3 mg dichloromethane / l urine

1 mg dichloromethane / l blood

Notation: ‘Skin’

SCOEL carcinogen group: C (genotoxic carcinogen for which a practical threshold is supported and a health –based OEL is proposed).

The UK Work Exposure Limit (WEL) has set the same TWA, but a higher STEL 300 ppm (1060 mg/m3).

Based on the production of carbon monoxide as a metabolite in the blood, the IPCS (1996) has set an exposure limit of 177 mg/m3.

Table 5.6 below summarises further information on the hazard profile of the substance.

4 A relevant toxic metabolite of methylene chloride is carbon monoxide. For carbon monoxide SCOEL has recommended an OEL of 20 ppm, compatible with a biological limit (BLV) of 4% COHb (SCOEL/SUM/57D). [COHb = Carboxyhaemoglobin]

Table 5.6 hazard profile of dichloromethane

Chemical Properties Characteristics of Chemical Source(s) of Information

Human Health Hazards

Acute toxicity Low oral and dermal toxicity (>2000 mg/kg) and low inhalation toxicity (calculated 4 ECHA, 2013 h LC50 86 mg/L).

The acute toxicity of methylene chloride is low. The predominant effects in humans IPCS, 1996 are Central Nervous System (CNS) depression and elevated blood carboxyhaemoglobin (CO-Hb) levels. These acute effects are reversible. Other target organs include the liver and, occasionally, the kidney.

Skin or eye corrosion/irritation Dermal contact causes a burning sensation, numbness, coldness and pain. Heath Protection Agency IM sheet, 2011 Eye contact with vapour can cause irritation. Contact with liquid methylene chloride may cause corneal burns.

Methylene chloride has been self-classified as a skin and eye irritant. ECHA, 2013

Respiratory or skin Not sensitizing SIAP, 2011 and ECHA, 2013 sensitization

Chronic toxicity Carcinogenicity Carcinogenicity studies in rodents have shown an increase in liver and lung cancer ATSDR, 1998 IPCS, 1996 and HSDB, (when exposed to7100 and 14 100 mg/m3) and benign mammary gland tumors 2010 following inhalation exposure to methylene chloride. ECHA, 2013 The relevance of the animal findings in humans is uncertain. From epidemiological studies methylene chloride is not expected to be a human carcinogen.

Long term toxicity The predominant effects following repeated or long-term exposure to methylene IPCS, 1996 chloride are the same as for acute exposure. Mostly reversible symptoms of CNS depression are seen in several species, including humans. Liver effects have also been ECHA, 2013 reported in animals following exposures as low as 25 ppm [88 mgm-3] (continuous exposure). The chronic NOAEL from an inhalation rat bioassay was 200 ppm (695

Chemical Properties Characteristics of Chemical Source(s) of Information

mg/m3) based on histopathological lesions in the liver and mammary tissue.

Mutagenicity Overall, the substance is not considered to be mutagenic in vivo. SIAP 2011

Methylene chloride was positive in two strains of bacteria with and without metabolic ECHA, 2013 activation, and was found to cause chromosomal aberrations in mammalian cells in vitro at concentrations causing cytotoxicity. The substance has not been classified as a mutagen. Neurotoxicity Effects on the CNS have been observed in both animals and humans. IPCS, 1996 Immune system toxicity Guideline inhalation study on rats indicated NOAEL >5187 ppm for immunotoxicity parameters. ECHA, 2013 Systemic toxicity The lowest NOAEL for neurotoxic effects in rats from chronic inhalation is 200 ppm. ACGIH, 2001 Toxic metabolites Biological activation of methylene chloride to toxic metabolites. The major oxidative SCOEL, 2009 (saturable) pathway leads to carbon monoxide. A minor reductive (glutathione- dependent) pathway leads to potentially reactive metabolites, such as formaldehyde. Reproductive/developmental No studies were located regarding developmental or reproductive effects in humans ATSDR, 1998 from inhalation or oral exposure. ECHA, 2013 Animal studies have demonstrated that methylene chloride does not affect HSDB, 1993 reproduction (fertility) parameters; it crosses the placental barrier, and minor skeletal variations and lowered fetal body weights have been noted in the presence of maternal toxicity. Environmental Hazards General Dichloromethane is naturally formed at levels exceeding industrial production Baker, et al., 2001.

Acute/chronic aquatic toxicity Dichloromethane is acutely toxic to aquatic invertebrates in the range 10 and 100 SIAP 2011 mg/L. Bioaccumulation Methylene chloride is not expected to bioaccumulate SIAP 2011

Persistence Dichloromethane is not readily biodegradable. However, biological degradation IPCS, 1996 processes have been identified capable of mineralizing methylene chloride in a few days. Main route of elimination is hydrolysis in the atmosphere. Greenhouse gas formation Methylene chloride is degraded to carbon dioxide and hydrogen chloride as major IPCS, 1996 potential breakdown products. Therefore some contribution to greenhouse gas is expected.

Chemical Properties Characteristics of Chemical Source(s) of Information

Ozone-depletion potential Methylene chloride is not classified as an ozone depleting substance. Regulation (EC) No 2037/2000

Monitoring - has the substance In ambient air in rural and remote areas, background levels of 0.07-0.29 µg/m3 have IPCS, 1996 been found in human or been measured. In suburban and urban areas levels up to 2 and 15 µg/m3 have been environmental samples? found.

Concentrations have been reported in the range below 10 µg/L in the surface water of rivers in industrialized areas and up to 200 mg/L in industrial effluents, outfalls of municipal water treatment plants and leachates of landfills. Monitoring data typically fails to discriminate natural Dichloromethane from industrial.

Dichloromethane is of low short term toxicity to humans, however short-term effects as a result of inhalatory exposure to dichloromethane vapours may cause CNS depression manifested through dizziness and drowsiness. The substance has been self-classified as STOT SE 3 under CLP with the associated hazard statement H316: may cause drowsiness or dizziness. Its vapours may cause eye irritation and skin contact may also cause irritation and has been classified under CLP.

When heated to decomposition dichloromethane will produce phosgene, hydrogen chloride gas, and chlorine gas which are toxic. In addition, it is metabolised to carbon monoxide, carbon dioxide and inorganic chloride (HSDB 2010) in the body, which can result in secondary poisoning. Animal data suggests that the substance may cause liver and lung cancer, while epidemiological data do not support a link of these effects in humans. However the substance has been classified as Carcinogenic Category 3 under CLP. The SCOEL concluded that taking together the current knowledge on the potential of human metabolic activation of dichloromethane, it appears unlikely that this compound poses a practical carcinogenic risk to humans, under conditions of current occupational exposures. In consequence, SCOEL has decided to assign dichloromethane to the SCOEL carcinogen group C with a “practical” threshold (Bolt and Huici-Montagud 2008) and to derive an OEL based on non-cancer endpoints5.

5.3.4 Economic feasibility

Dichloromethane is not a “drop-in” solvent replacement for TRI as noted above. It would mean the replacing large parts (if not completely) the existing production process and equipment. As per the ECHA SEA guidance, the lost (book) value of existing equipment is considered a ‘sunk cost’ and therefore not considered in the analysis. The additional capital and operating costs of making PE SLI battery separators is however relevant to the assessment of economic feasibility.

A major consideration is the reengineering of processes in order to accommodate the alternative even if it were technically feasible. This would need to include consideration of solvent recycling and emission capture. This has not been estimated given the significant technical (feasibility) difficulties. As set out in Section 6.2, it would take a minimum of 12 years to make a possible alternative solvent suitable. When comparing the minimum cost of lost profit for 12 years of €116 million NPV (see SEA section 4.2.1 for details on lost profits, but using a discount rate of 7% rather than 4% in the SEA) with the cost of building additional production lines at the existing US site (in Oregon) which is €48 million (see Section 4.2.2 of the SEA); which enables ENTEK to avoid any production/sales disruption (i.e. can provide battery separators to the existing markets after the sunset date), it is clear that switching to dichloromethane is not economically feasible.

The €116 million is considered a minimum costs as it excludes any capital costs as well as some additional costs like redundancy (over the period 2016-2027) and assumes post 2027, ENTEK can make equivalent profits. This assumption is however highly unlikely since (i) it assumes ENTEK would not have lost any market share due to no sales after the sunset date (April 2016) to 2027, and (ii) assumes profit margins would be similar compared to using TRI. Optimistically factoring in that it would only takes a further 5 years for ENTEK to recover their market share (i.e. 80% of lost profit in 2024, declining linearly to 0% in 2031) then the net cost to ENTEK is €125 million (NPV). This further reinforces the conclusion that dichloromethane is not economically feasible.

5.3.5 Availability

Dichloromethane is registered under REACH at the 1,000 tonnes per annum level (Phase 1) and thus can be assumed to be available to be supplied in the volumes required.

5.3.6 Conclusion on suitability and availability for dichloromethane

As described in Section 3 the R&D process identified that dichloromethane as a potential alternative for TRI. While initial laboratory and pilot scale trials have been promising, however, there are numerous technical and economic challenges that need to be evaluated before a final decision can be made on the suitability of dichloromethane in the ENTEK separator manufacturing process. The large expected capital cost to switch and loss in profits compared to the costs of building additional production lines in the US, means this alternative is also not economically feasible.

From an engineering and operations standpoint, the high solubility of dichloromethane in water, its lower adsorption affinity for activated carbon, and its potential degradation to hydrogen chloride in the presence of steam are problematic. For example, manufacturers of carbon beds for TRI recovery – a system in which the solvent routinely contacts steam and water at high temperatures – often recommend stainless steel grade 316L as a material of construction. Carbon bed manufacturers for dichloromethane recovery do not recommend using 316L Stainless Steel, specifying a more expensive material such as Hastelloy for this application. The ENTEK-UK plant utilizes 316L Stainless Steel for most of its piping and vessels in which the extraction solvent becomes in contact with water and steam. Currently, the infrastructure would be at risk of highly accelerated corrosion and subsequent failure with the use of dichloromethane. Failure of the structure would pose a significant hazard to human health and the environment in the event of a major release of dichloromethane.

5 Recommendation from the Scientific Committee on Occupational Exposure Limits for methylene chloride (dichloromethane) SCOEL/SUM/130, June 2009

In addition to the technical challenges it can be seen from Section 4.3.3, that dichloromethane is a hazardous substance and is classified as such. Although dichloromethane is not a substance of very high concern (SVHC) it is a suspected carcinogen and subject to an indicative OEL (iOEL) at EU level as well as a restriction under REACH. The substance would probably represent a reduction in risk, but since there are concerns for the substance in terms of long term health risks this would have to be taken into consideration in the further research being done to identify this substance as an alternative along with other substances that may have a more favourable hazard and risk profile.

5.4 TETRACHLOROETHYLENE

5.4.1 Substance ID and properties

Chemical Name(s): tetrachloroethylene

Other names: tetrachloroethene, perchloroethylene, commonly abbreviated to PCE or Perc, 1,1,2,2- tetrachloroethylene, ethylene tetrachloride, tetrachloro-, Perchloroethene, Per

Trade Name(s): Perstabil®, Ankilostin®, Didakene®,Perclene®, Dowper®,Perklone®

CAS Number: 127-18-4

EC Number: 204-825-9

Molecular Formula: C2Cl4

Molecular weight: 165.85

Classification and Labelling

The classifications according to the CLP regulation no. 1272/2008 and according to the Dangerous Substances Directive 67/548/EEC are presented in the tables below. Both the harmonised classification and the self-classification as presented in the REACH disseminated dossier registrants are provided.

CLP - according to Regulation No 1272/2008 Annex VI

Classification Harmonised Self-classification area Physicochemical Not classified Not classified

Health Carc. 2 Carc. 2

Skin Irrit. 2

Skin Sens. 1B

STOT Single Exp. 3. Affected organs: central nervous system Route of exposure: inhalation

Environmental Aquatic Chronic 2 Aquatic Chronic 2

Hazard H351: Suspected of causing cancer H351: Suspected of causing cancer Statements

Classification Harmonised Self-classification area H315: Causes skin irritation

H317: May cause an allergic skin reaction

H336: May cause drowsiness or dizziness

H411: Toxic to aquatic life with long H411: Toxic to aquatic life with long lasting lasting effects effects

Dangerous Substance Directive – according to Directive 67/548/EEC

Classification Harmonised Self-classification area Health hazards Carc. Cat. 3; R40 Carc. Cat. 3; R40

R38

Environmental R51-53 R51/53 hazards

Risk Phrases R40: limited evidence of a R40: Limited evidence of a carcinogenic effect carcinogenic effect

R38: Irritating to skin

R51/53: Toxic to aquatic organisms, R51/53: Toxic to aquatic organisms, may cause may cause long-term adverse effects long-term adverse effects in the aquatic in the aquatic environment. environment.

Tetrachloroethylene is a colourless, relatively volatile, non-flammable liquid, it is not considered to have explosive properties and is not subject to auto-ignition. The physicochemical properties of tertrachloroethylene are summarised in Table 5.7.

Table 5.7 Physico-Chemical Properties of tetrachloroethylene

Properties Characteristics of Chemical Source(s) of Information

Flammability non-flammable EU RAR 2005

Vapour pressure 1.9 kPa at 20°C EU RAR 2005

Boiling point 121.2°C EU RAR 2005

Melting point -22°C EU RAR 2005

Water solubility 149 mg/L EU RAR 2005

Properties Characteristics of Chemical Source(s) of Information

Log Kow 2.53 EU RAR 2005 6

5.4.2 Technical feasibility

From the research described in Section 3.2 of this document, it appears that tetrachloroethylene may be a technically feasible alternative to TRI as a process solvent for the manufacture of polyethylene battery separators. Although it exhibits a slower extraction rate compared to TRI, this property could potentially be adjusted with temperature of the extraction bath. Further research is required to understand if tetrachloroethylene could be used at a commercial scale, and to understand whether it would be compatible with all manufacturing and recovery processes such that the resultant separator meets all customer requirements. The possible steps to qualify an alternative solvent are described in Section 6.2.

5.4.3 Reduction of overall risk due to transition to the alternative

Tetracholoroethylene is classified as a category 2 carcinogen and subject to a SCOEL recommendation for and occupational exposure limit for the protection of workers at EU level7. The iOEL is summarised as follows:

8 hour TWA: 20 ppm [138 mg/m3]

STEL (15 min): 40 ppm [275 mg/m3]

BLVs (biological limit value): 0.4 mg tetrachloroethylene/l blood

3 ppm [0.435 mg/m3] tetrachloroethylene in end-exhaled air

SCOEL carcinogen group: D (non-genotoxic carcinogen with threshold)

Notation: ‘skin’

Table 5.8 below summarises further information on the hazard profile of the substance.

6 European Union Risk Assessment Report. Tetrachloroethylene, Part I – Environment, CAS No: 127-18-4, EINECS No: 204-825-9 European Chemicals Bureau, 1st Priority List, volume 57. EUR 21680 EN. Final Report 2005, United Kingdom

7 Recommendation from the Scientific Committee on Occupational Exposure Limits on Tetrachloroethylene (perchloroethylene) SCOEL/SUM/133, June 2009

Table 5.8 hazard profile of tetrachloroethylene

Chemical Properties Characteristics of Chemical Source(s) of Information

Human Health Hazards Acute toxicity Acute toxicity in humans resulting from ingestion or inhalation resulted in ATSDR (1997) neurological effects such as dizziness, fatigue, coma, some deaths (concentration unknown), kidney dysfunction, reversible liver damage. IRIS (2012)

Irritation of the respiratory tract following inhalation has also been observed. WHO (2006) Acute toxicity in animals is low, effects are only reported at high concentrations ATSDR (1997) of oral or inhalation exposure to tetrachloroethylene. Effects include depression of Central Nervous System (CNS), effects on liver, kidneys, and spleen; lung IRIS (2012) hemorrhages were also observed in deceased rats. ECHA (2013) Skin or eye Tetrachloroethylene was highly irritating to the eyes of humans following acute corrosion/irritation exposure to a high dose of the vapours (930 ppm). While burning or stinging of the eyes occurred at doses of 600 or 280 ppm, at 216 or 106 ppm the substance was only very mildly irritating to a few volunteers. SCOEL (2009) Dry cleaning workers exposed to 20 ppm on average for 8 hours complained of irritation.

Tetrachloroethylene is a skin irritant in humans, causing reddening and SCOEL (2009) blistering. Effects may persist for months after severe exposure has occurred. Respiratory or skin Tetrachloroethylene has been demonstrated to be a weak dermal sensitizer in ECHA, 2013 sensitization animals, and is self-classified as a skin sensitiser. NEG-DECOS (2003) describe SCOEL (2009) two case reports of tetrachloroethylene skin sensitisation in humans.

Chronic toxicity

Carcinogenicity Occupational exposure studies with dry cleaning workers show associations IRIS, 2012 between exposure to dry cleaning solvents and certain types of cancer, in WHO (2006) particular: bladder, multiple myeloma, kidney, oesophagus, cervix, breast, and

Chemical Properties Characteristics of Chemical Source(s) of Information

non-Hodgkin’s lymphoma. However some of the cancer associations with tetrachloroethylene are weak and the studies are confounded as the workers were exposed to multiple solvents. In addition, the exposure concentrations and initial health status were not clear. In animals there is clear evidence that tetrachloroethylene is carcinogenic. IRIS (2012) Inhalation exposure to rats caused leukaemia and kidney tumours, while WHO (2006) inhalation exposure to mice caused liver tumours. Oral exposure to mice caused liver tumours.

Long term toxicity The main effects on humans and animals from long-term exposure to WHO (2006) tetrachloroethylene are neurotoxicological effects. IRIS (2012) Occupational exposure levels for tetrachloroethylene have been typically around SCOEL (2009) 100 ppm, although currently lower. The target organs are the CNS, liver, and kidneys.

Generally, no clear effects on the kidney or the liver of humans were seen at concentrations below 50 ppm.

Mutagenicity Overall, tetrachloroethylene is not considered to be mutagenic. EU RAR (2005) The majority of the in vitro studies conducted with liquid and vapour phase WHO (2006) tetrachloroethylene conclude that tetrachloroethylene is not genotoxic. SCOEL (2009)

Neurotoxicity A large number of studies and epidemiological data are available assessing the IRIS, 2012 neurotoxicological and behavioural effects of tetrachloroethylene on humans and rats.

In humans, long-term inhalation of tetrachloroethylene caused neurological effects such as sensory symptoms (headaches, dizziness) and impairment of cognitive and neurobehavioural functioning and colour visions decreases. Immune system toxicity Mild microcytic anemia and bone marrow and immune function changes Germolec et al., 1989 occurred in mice exposed via drinking water to tetrachloroethylene plus 24 other groundwater contaminants Systemic toxicity Chronic inhalation exposure to 100 ppm resulted in kidney and lung effects in NTP, 1986 mice. ATSDR, 1997

Chemical Properties Characteristics of Chemical Source(s) of Information

Toxic metabolites In humans, the substance is mainly exhaled as tetrachloroethylene (95%), and WHO (2006) and SCOEL (2009) the remainder excreted in the urine as trichloroacetic acid. Certain toxic metabolites were not detectible during metabolism of tetrachloroethylene in humans. In animals, excess tetrachloroethylene can lead to the formation of cytotoxic and genotoxic metabolites.

Reproductive/developmental There are limited data from studies with significant confounders (e.g, no/limited SCOEL (2009) exposure information; lack of consideration of recognized risk factors) describing relatively weak associations between occupational exposure to ECHA, 2013 tetrachloroethylene and spontaneous abortions and disruption of menstrual IRIS (2012) cycle. Based on a guideline 2-generation inhalation rat study, tetrachloroethylene is not considered a fertility or reproductive toxicant, as maternal toxicity likely affected the fertility parameters (reductions in litter size and pup survival at 1000 ppm, and pup body weight at 1000 and 300 ppm). The maternal NOAEL of 250 ppm from a guideline inhalation developmental toxicity study in rats corresponded with the developmental NOAEL; slight reductions in fetal weight and some fetal variations were within historical control values. Drinking water contaminated with tetrachloroethylene and other chlorinated IRIS (2012) hydrocarbons has been associated with birth defects, however the exposure was to a mixture of chemicals, therefore a direct link to tetrachloroethylene cannot SCOEL (2009) be drawn.

Environmental Hazards Acute aquatic toxicity In short-term toxicity studies on three trophic levels with tetrachloroethylene ECHA 2013 effects have been found in the range 1-10 mg/L, with algae being the most sensitive.

Chronic aquatic toxicity In long-term toxicity studies on three trophic levels with tetrachloroethylene the ECHA 2013 most sensitive species was Daphnia magna with a 28 day NOEC 0.51 mg/L based on reproduction. Terrestrial toxicity Tetrachloroethylene has been tested with various terrestrial organisms, however ECHA 2013 due to volatilisation of the substance maintaining exposure concentrations was considered to be difficult. Studies where a lack of effect took place may be due to the substance evaporating from test medium.

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Chemical Properties Characteristics of Chemical Source(s) of Information

Effects have been reported in the range of a NOEC <0.1 mg/kg based on nitrification with loam to 14 day LC50 945 mg/kg with earthworms. Bioaccumulation Tetrachloroethylene has a low potential for bioaccumulation based on a ECHA 2013 measured BCF in fish of 40-50 l/kg w. wt. and low log Kow. Persistence Tetrachloroethylene is not readily biodegradable (0% degradation in 21 days). ECHA (2013), EU RAR (2005) However the substance is subject to anaerobic degradation, through reductive dechlorination. Its degradation products are TRI, dichloroethylene, vinyl chloride, ethene and ethane. Tetrachloroethylene will evaporate from moist mediums. In soil and sediment, the substance’s adsorption potential (high Koc 665) indicates that some EU RAR (2005) persistence is possible. Greenhouse gas formation Tetrachloroethylene is not expected to significantly contribute to global EU RAR (2005) potential warming. Ozone-depletion potential Tetrachloroethylene will degrade to substance which may enter the stratosphere, EU RAR (2005) carbon tetrachloride is the only known ozone depleting degradation product, however the contribution of carbon tetrachloride from degradation of tetrachloroethylene is considered negligible.

Overall the substance is not considered to have ozone depleting potential. Tetrachloroethylene is not classed as an ozone depleting substance. Regulation (EC) No 2037/2000

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The main form of toxicity of the tetrachloroethylee is expressed through inhalation of its vapours, where the substance can produce irritating effects to the eyes, lungs and at high enough concentrations dysfunction of the Central Nervous System (CNS) in humans. It has been self-classified under CLP as Skin Irritant 2, as a Skin Sensitiser 1B and as STOT SE 3, affecting the CNS through inhalation.

Overall, the SCOEL states that there are no clear repeated dose toxicity effects in humans exposed up to 25 ppm (173 mg/m3) tetrachloroethylene.

Tetrachloroethylene is classified as a possible carcinogen. The human evidence of its carcinogencity is limited due to the presence of other solvents in exposure to humans data. However the substance is positively carcinogenic in animal studies. It is classified as Carcinogenic 2 in the CLP. The NTP classified the substance as “reasonably anticipated to be a human carcinogen”, while the SCOEL carcinogen group is D (non-genotoxic carcinogen with threshold).

Tetrachloroethylene is toxic to aquatic and terrestrial organisms, with long-term effects reported with Daphnia magna, 21-d NOEC 0.51 µg/L, and nitrification effects observed with Loam, a NOEC of ≤1 mg/kg wwt has been derived. Tetrachloroethylene is classified under CLP as Aquatic Chronic 2.

PBT and CMR

Tetrachloroethylene does not fulfil the PBT criteria, because it does not fulfil the B and T criteria. It does however fulfill the T criterion based on its classification as Carcinogenic 2 under CLP.

The substance is considered a CMR because it is classified as Carcinogenic 2.

Tetrachloroethylene is being assessed in the CoRAP program because it is a CMR agent, a suspected PBT, it has wide and dispersive use with a high risk of exposure in the workplace, and a high aggregated tonnage in the EU.

5.4.4 Economic feasibility

Tetrachloroethylene is not a “drop-in” solvent replacement for TRI as noted above. It would mean the replacing large parts (if not completely) the existing production process and equipment. As per the ECHA SEA guidance, the lost (book) value of existing equipment is considered a ‘sunk cost’ and therefore not considered in the analysis. The additional capital and operating costs of making PE SLI battery separators is however relevant to the assessment of economic feasibility.

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comparing the minimum cost of lost profit for 12 years of €116 million NPV (see SEA section 4.2.1 for details on lost profits, but using a discount rate of 7% rather than 4% in the SEA) with the cost of building additional production lines at the existing US site (in Oregon) which is €48 million (see Section 4.2.2 of the SEA); which enables ENTEK to avoid any production/sales disruption (i.e. can provide battery separators to the existing markets after the sunset date), it is clear that switching to tetrachloroethylene is not economically feasible.

5.4.5 Availability

Tetrachloroethylene is registered under REACH at a tonnage band of 100,000 to 1,000,000 tonnes per annum level and thus can be assumed to be available to be supplied in the volumes required.

5.4.6 Conclusion on suitability and availability for tetrachloroethylene

As described in Section 3 the R&D process identified that tetracholoroethylene could be a potential alternative for TRI. While initial laboratory trials show promise, there are numerous technical and economic challenges that need to be evaluated before a final decision can be made; on the suitability of tetrachloroethylene in the ENTEK separator manufacturing process. Further detail of the possible steps that would need to be taken and the timing associated with those steps is described in section 5.

The large expected capital cost to switch and loss in profits compared to the costs of building additional production lines in the US, means this alternative is also not economically feasible.

From an engineering and operations standpoint, the exceedingly low solubility of tetrachloroethylene in water and its low vapour pressure could be advantageous in the areas of solvent containment and worker exposure. The lower oil extraction rate of tetrachloroethylene can potentially be addressed by heating the solvent. Nevertheless, further work is required to determine the impact of the higher extraction temperature and boiling point on energy costs for separator manufacturing and solvent recovery.

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In addition to the technical challenges it can be seen from Section 4.4.3 above that tetrachloroethylene is a hazardous substance and is classified as such. Although tetrachloroethylene is not a substance of very high concern it is a suspected carcinogen and subject to an indicative OEL (iOEL) at EU level. The substance was evaluated under REACH in the Community Rolling Action Plan (CoRAP) due to concerns for human health/CMR; environment/suspected PBT; exposure/wide dispersive use and aggregated tonnage (although no further action to control risks was indicated). The substance would probably represent a reduction in risk in respect of emissions control, but since there are concerns for the substance in terms of long term health hazards this would have to be taken into consideration in the further research being done to identify this substance as an alternative, along with other substances that may have a more favourable hazard and risk profile.

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5.5 VERTREL® SDG

Vertrel® SDG is the trade name of a chemical produced by DuPont. It has not been registered in the EU and there is generally little information available on the substance outside of the information given in the two Material Safety Data Sheets available online. Vertrel® SDG is a mixture and additional information is available on its constituents (see Table 4.13).

5.5.1 Substance ID and properties

Vertrel® SDG is a mixture of non-flammable hydrofluorocarbons (HFCs) and trans-1,2-dichloroethylene (t- DCE). Summary data for Vertrel® SDG is set out in Table 5.9 below.

Table 5.9 Composition of Vertrel® SDG.

Substance name CAS # Concentration trans-dichloroethylene 156-60-5 65 - 90 %

1,1,1,2,2,3,4,5,5,5-decafluoropentane 138495-42-8 5 - 25 %

1,1,2,2,3,3,4-heptafluorocyclopentane 15290-77-4 5 - 15 %

The compositional information has been taken from the most recent available MSDS sheet, dated 2012.

Classification and Labelling A classification and labelling for the substance mixture is not available. The human health and environmental harmonised classifications for the constituents in Vertrel® SDG according to the CLP regulation no. 1272/2008 and to the Dangerous Substances Directive 67/548/EEC are presented in the tables below, where available. Trans-dichloroethylene, CAS 156-60-5

Classification area CLP - according to Regulation No Dangerous Substance Directive – 1272/2008 Annex VI according to Directive 67/548/EEC Physicochemical Flam. Liq. 2 F; R11

Health Acute Tox 4 Xn; 20

Environmental Aquatic Chronic 3 R52/53

Hazard Statements H225: Highly flammable liquid and 11: Highly flammable vapour

H332: harmful if inhaled 20: Harmful by inhalation

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Classification area CLP - according to Regulation No Dangerous Substance Directive – 1272/2008 Annex VI according to Directive 67/548/EEC H412: harmful to aquatic life with long 52/53: Harmful to aquatic organisms, may lasting effects cause long-term adverse effects in the aquatic environment.

1,1,1,2,2,3,4,5,5,5-Decafluoropentane, CAS 138495-42-8 No harmonized classification and labelling exists for decafluoropentane. The classification and labelling reported in the ECHA disseminated dossier have been presented instead.

Classification area CLP - according to 1272/2008 Annex Dangerous Substance Directive – VI – disseminated dossier according to Directive 67/548/EEC – disseminated dossier Physicochemical Not classified Not classified

Health Aquatic Chronic 3 R52/53

Environmental Not classified Not classified

Hazard Statements H412: harmful to aquatic life with long R52/53: Harmful to aquatic organisms, lasting effect may cause long-term adverse effects in the aquatic environment.

1,1,2,2,3,3,4-Heptafluorocyclopentane, CAS 15290-77-4

Classification area CLP - according to Regulation No Dangerous Substance Directive – 1272/2008 Annex VI according to Directive 67/548/EEC Physicochemical Not classified Not classified

Health Not classified Not classified

Environmental Aquatic Chronic 3 R52/53

Hazard Statements H412: harmful to aquatic life with long 52/53: Harmful to aquatic organisms, may lasting effects cause long-term adverse effects in the aquatic environment.

The physico-chemical properties of Vertrel® SDG were previously listed in Table 4.3 and compared to TRI and other alternatives that have been investigated by ENTEK.

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Table 5.10 Physico-Chemical Properties of Vertrel® SDG Properties Characteristics of Chemical Source(s) of Information

Flammability Does not flash. No flash point was obtained, but DuPont, MSDS 2012 the product may release flammable vapour. Vapour pressure 51.7 kPa at 25˚C DuPont, MSDS 2012 Boiling point 43°C DuPont, MSDS 2012 Melting point N/A Water solubility Slightly soluble DuPont, MSDS 2007

Log Kow N/A

Vertrel® SDG is a clear liquid with a slightly ether-like odour. It is slightly soluble in water (not quantified) and is very volatile. The vapours are said to be heavier than air. [DuPont, MSDS 2012]

Table 5.11 Physico-Chemical Properties of the constituents of Vertrel® SDG

Properties trans-Dichloroethylene (CAS 1,1,1,2,2,3,4,5,5,5- 1,1,2,2,3,3,4- 156-60-5) Decafluoropentane Heptafluorocyclopentane (CAS 138495-42-8) (CAS 15290-77-4) EC Number 205-860-2 420-640-8 430-710-1

Molecular C2H2Cl2 C5H2F10 N/A Formula Molecular Weight 96.94 g/ml 252.05 N/A [MSDS 2013, Sigma-Aldrich] Flammability Highly flammable Not flammable, based on Not flammable, based on Flash Flash point >70˚C point ≥82.5˚C [NTP 2002] [ECHA 2013] [ECHA 2013] Vapour pressure 44 kPa at 25˚C 31.3 kPa at 25˚C 1.6 kPa at 20˚C

[HSDB 2012] [ECHA 2013*] [ECHA 2013] Boiling point 48.4˚C 53.2-54.2°C 82.5°C

[NTP 2002] [ECHA 2013*] [ECHA 2013] Melting point -50˚C -84°C 20.5°C

[NTP 2002] [ECHA 2013*] [ECHA 2013] Water solubility 630 mg/L 126 ± 33 mg/L 717 mg/L

[NTP 2002] [ECHA 2013*] [ECHA 2013]

Log Kow 2.06 2.7 2.4

[NTP 2002] [ECHA 2013*] [ECHA 2013] * The data are for the substance: Reaction mass of (3R,4R)-1,1,1,2,2,3,4,5,5,5-decafluoropentane and (3S,4S)- 1,1,1,2,2,3,4,5,5,5- decafluoropentane, CAS 138495-42-8, EC 420-640-8

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5.5.2 Technical feasibility

As discussed in Section 3.2.1, Vertrel® SDG appears to be an effective solvent for naphthenic process oils and the resultant separators have properties that are similar to the TRI-extracted separators. There are however major obstacles to the use of Vertrel® SDG as an alternative solvent in the ENTEK continuous separator manufacturing process. Vertrel® SDG is highly volatile with a boiling point of only 43°C. As such, ENTEK would need to efficiently contain and recover this solvent in its separator manufacturing operation. The ability to adsorb and desorb the Vertrel° SDG chemical components from a carbon bed is unknown. This solvent is often used in degreasing applications with the vapours released to the atmosphere. As such, there has been little work on the efficient recovery of this solvent. In addition, due to the volatility and vapour pressure of this substance there are likely to be much more evaporative losses (compared to TRI). This would mean re-assessment and reengineering of emission capture and recycling in order to recycle the substance and to control releases.

While initial laboratory trials showed promise, there are numerous technical challenges that need to be evaluated before a decision could be made on the suitability of Vertrel® SDG in the ENTEK continuous separator manufacturing process. From engineering and operations standpoints, the significantly higher vapour pressure, the high solubility of Vertrel® SDG in water, its unknown adsorption affinity for activated carbon, and potential degradation of its chemical components in the presence of steam are problematic.

5.5.3 Reduction of overall risk due to transition to the alternative

Table 5.12 below summarises further information on the hazard profile of the substance. Tables 5.13 to 5.15 summarise the available data on the hazard properties of Vertrel® SDG constituents. These have been presented because the data for the mixture is poor and because from a risk point of view, once the substance is released into the environment the properties of its individual constituents will determine the fate.

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Table 5.12 Hazard profile of Vertrel® SDG

Chemical Properties Characteristics of Chemical Source(s) of Information

Human Health Hazards Acute toxicity Inhalation of high doses may cause cardiac arrhythmia, Central Nervous System DuPont, MSDS 2012 (CNS) effects and convulsions. Effects may include tiredness or drowsiness. Ingestion may cause pulmonary edema (body fluid in the lungs) and respiratory DuPont, MSDS 2007 distress. Ingestion may also cause pathological changes in the liver and CNS depression. [Information taken from the DuPont, MSDS sheet dated 2007; which is not presented in the 2012 MSDS sheet.]

Skin or eye corrosion/irritation Skin contact may cause severe irritation with burning, redness, swelling, pain or rash. DuPont, MSDS 2007 Eye contact may cause severe eye irritation with tearing, pain or blurred vision.

Carcinogenicity No data available, however none of the constituents are classified as carcinogens. DuPont, MSDS 2007

Environmental Hazards Greenhouse gas formation Low global warming potential. DuPont, Technical sheet 2008 potential No further information on its degradation products is available. Ozone-depletion potential Zero ozone depletion potential. DuPont, Technical sheet 2008

The substance has not been classified as an ozone depleting substance. Regulation (EC) No 2037/2000

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Table 5.13 Hazard profile of trans-dichloroethylene – constituent (65-90% of total)

Chemical Properties Characteristics of Chemical Source(s) of Information

Human Health Hazards

Acute Toxicity Acute toxicity Inhalation 4 h LC50: 96.4 mg/l in rat, CNS effects observed. DuPont, MSDS 2012 Inhalation (duration unspecified) LC50: 2.2*105 mg/m3. NTP 2002 Not acutely toxic via oral or dermal administration DuPont, MSDS 2012 Skin or eye corrosion/irritation Skin irritant and mild eye irritant in rabbits. DuPont, MSDS 2012 1,2-Dichloroethylene can cause eye and skin irritation. However it is not classified as a skin or eye irritant under CLP. HSDB, 2012 Respiratory or skin Cardiac sensitisation threshold limit: 7.9*105 mg/m3 DuPont, MSDS 2012 sensitization However it is not classified as a sensitising agent under CLP. Chronic Toxicity

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Chemical Properties Characteristics of Chemical Source(s) of Information

Long term toxicity Oral – rat 90 d study: No toxicologically significant effects were found. DuPont, MSDS 2012 Inhalation – rat. 90 d study: No toxicologically significant effects were found. No further details are available. Generally, little toxicity is observed with ingestion of microencapsulated trans-1,2- NTP, 2002 dichloroethylene. Reproductive/developmental Animal testing showed no reproductive or developmental toxicity. No further details DuPont, MSDS 2012 are available. Toxicity to the dams was not observed at concentrations below maternal toxicity NTP, 2002 (6000 ppm). Mutagenicity Not genotoxic in vitro and in vivo DuPont, MSDS 2012 and NTP, 2002 Neurotoxicity trans-1,2-Dichloroethylene has been shown to cause central nervous system effects in NTP, 2002 humans, characterized by dizziness, drowsiness, vertigo, and increased intracranial pressure (ATSDR, 1990). CND depression has not been observed in chronic toxicity studies with rats and mice. Immune system toxicity Suppression in humoral immune status and decreased macrophage induction NTP, 2002 Environmental Hazards

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Chemical Properties Characteristics of Chemical Source(s) of Information

Acute/chronic aquatic toxicity Acute fish and Daphnia toxicity: 10-100 mg/l, algae >100 mg/l DuPont, MSDS 2012

Bioaccumulation Bioaccumulation potential is low DuPont, MSDS 2012 and HSBD, 2012

Persistence Readily biodegradable DuPont, MSDS 2012

Not readily biodegradable. However 73% of the substance was lost in 6 months under HSDB, 2012 anaerobic conditions, forming vinyl dichloride. Vapour-phase trans-1,2-dichloroethylene will degrade in the atmosphere by reaction HSDB, 2012 with photochemically-produced hydroxyl radicals; the half-life in air is estimated to be 6.9 days. Ozone depleting potential The vapour-phase trans-dichloroethylene has an atmospheric half-life of about 320 HSDB, 2012 days at an atmospheric concentration of 7*1011 ozone molecules per cu cm. Monitoring - has the substance 1,2-Dichloroethylene has been detected in groundwater at concentrations up to 3 NTP, 2002 and HSBD, 2012 been found in human or 900 μg/L and in drinking water at concentrations from none to 2 277 μg/L. environmental samples?

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Table 5.14 Hazard profile of 1,1,1,2,2,3,4,5,5,5-decafluoropentane – constituent (5-25% of total)

Chemical Properties Characteristics of Chemical Source(s) of Information

Human Health Hazards Acute toxicity Oral LD50 >5000 mg/kg bw ECHA, 2013

Inhalation 4 h LC50 114 428 mg/m3 (11 100 ppm)

Dermal LD50 >5000 mg/kg bw

Inhalation 4 h LC50 114 mg/l , rat. Central nervous system effects. Convulsions DuPont, MSDS 2012

Not acutely toxic via oral or dermal administration

Skin or eye corrosion/irritation Not a skin or eye irritant. DuPont, MSDS 2012 and ECHA, 2013

Long term toxicity In an inhalation toxicity study with rats (duration unknown), no toxicologically DuPont, MSDS 2012 significant effects were found. ECHA, 2013 14 week NOAEL with rats: 500 ppm based on clinical signs of central nervous system toxicity.

Mutagenicity No genotoxicity found in vitro and in vivo DuPont, MSDS 2012

Respiratory or skin Did not cause sensitisation in guinea pig. DuPont, MSDS 2012 sensitization The substance has not been classified as a sensitising agent. ECHA, 2013

Neurotoxicity The NOAEL for CNS effects in rats has been determined at 15 463 mg/m3. ECHA, 2013

Reproductive/developmental Animal testing showed no reproductive or developmental toxicity. DuPont, MSDS 2012 No further information provided.

The NOAEL for reproduction was ≥3500 ppm (36081 mg/m3) in rats exposed for 90 ECHA, 2013 days.

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Chemical Properties Characteristics of Chemical Source(s) of Information

The NOAEL for developmental toxicity was determined at 2000 ppm (20 618 mg/m3), based on litter weight effects.

Environmental Hazards Acute/chronic aquatic toxicity Fish and Daphnia acute: 10-100 mg/l, algae >100 mg/l DuPont, MSDS 2012 and ECHA, 2013 Chronic daphnia: 1.72 mg/l

Bioaccumulation Bioaccumulation is unlikely for decafluoropentane. DuPont, MSDS 2012 Persistence Not biodegradable. DuPont, MSDS 2012 and ECHA, 2013

The atmospheric half-life has been determined at 23 years, through reaction with OH. ECHA, 2013 Greenhouse gas formation The 100 year Global Warming Potential is 1640 (compared to a GWP of 34 for ECHA, 2013 potential methane). Ozone-depletion potential The substance has not been classified as an ozone depleting substance. Regulation (EC) No 2037/2000

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Table 5.15 Hazard profile of 1,1,2,2,3,3,4-heptafluorocyclopentane – constituent (5-15% of total)

Chemical Properties Characteristics of Chemical Source(s) of Information

Human Health Hazards

Acute toxicity Inhalation 4 h LC50 ca. 115 mg/l, rat DuPont, MSDS 2012 and ECHA, 2013

Oral and dermal: non toxic Skin or eye corrosion/irritation Skin irritation: non-irritant, Eye irritation: non-irritant DuPont, MSDS 2012 and ECHA, 2013

Long term toxicity Oral, rat: No toxicologically significant effects were found. DuPont, MSDS 2012 Inhalation, rat: No toxicologically significant effects were found.

Oral NOAEL 1000 mg/kg bw/day, NOEL <15 mg/kg bw/day ECHA, 2013 Inhalation NOAEL 2.85 mg/L air, NOEC <2.85 mg/L air Mutagenicity Not genotoxic in vitro DuPont, MSDS 2012

Respiratory or skin Not sensitising DuPont, MSDS 2012 and ECHA, 2013 sensitization

Cardiac sensitization was investigated in dogs, however results are not available. ECHA 2013

Environmental Hazards

Acute/chronic aquatic toxicity Fish, daphnia and algae acute: 10-100 mg/l DuPont, MSDS 2012 Algal 72 h NOEC: 25 mg/L and ECHA, 2013

Bioaccumulation No data DuPont, MSDS 2012

Persistence 0% degradation in 28 d ECHA, 2013

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Limited information is available on the hazard profile of Vertrel® SDG. Upon combustion the substance can degrade to toxic substance such as hydrogen fluoride, fluorinated hydrocarbons, carbonyl fluoride, carbon oxides and hydrogen chloride. The DuPont, MSDS (2012) sheet indicates that vapours are heavier than air and can cause suffocation by reducing oxygen available for breathing.

The short-term exposure to high levels of Vertrel® SDG may cause effects to the central nervous system (CNS) with symptoms including tiredness and drowsiness, changes to the heartbeat frequency and regularity and convulsions. The substance itself does not have a harmonised classification and labelling nor is it classified in its MSDS, however one of its constituents, trans-dichloroethyle (CAS 156-60-5, 65-90% of total substance) is classified as Acute Toxicity 4. For this constituent effects to the CNS have been been observed in rats. Effects to the CNS have also been observed in acute inhalation studies with the 1,1,1,2,2,3,4,5,5,5- decafluoropentane (5-25% of total substance).

The substance is said to cause severe eye and skin irritation upon contact, and its constituents are described as mild irritants.

The substance and some of its constituents cause cardiac sensitisation however neither are classified as such.

Data available on the constituents of Vertrel® SDG, indicate that they are not considered as readily biodegradable substances and in short-term ecotox studies effects are reported in the range 10-100 mg/l. In fact, where classification is reported, they are classified as Aquatic Chronic 3 under CLP.

5.5.4 Economic feasibility

It is understood that this material is currently some 40-50 times the cost of TRI. This is prohibitively expensive. In addition, based upon laboratory testing results, Vertrel° SDG would result in less separator shrinkage than occurs with TRI. This difference would result in all calender tools needing to be re-cut with a new groove pattern to end up with a final separator having the desired profile. ENTEK has 43 calender/profile rolls (also known as tools) at its UK plant that would need to be re-machined. The time period to convert all of these tools would be at least two years at an estimated cost of € 1.2 million. Furthermore, a major consideration is the reengineering of processes in order to accommodate the alternative even if it were technically feasible. This would need to include consideration of solvent recycling and emission capture since the volatility of the substance is quite different from TRI.

Vertrel® SDG is not a “drop-in” solvent replacement for TRI, as noted above. It would mean the replacing large parts (if not completely) the existing production process and equipment. As per the ECHA SEA guidance, the lost (book) value of existing equipment is considered a ‘sunk cost’ and therefore not considered in the analysis. The additional capital and operating costs of making PE SLI battery separators is however relevant to the assessment of economic feasibility.

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5.5.5 Availability

The product that is a substance mixture is commercially available.

5.5.6 Conclusion on suitability and availability for Vertrel® SDG

As described in Section 4.2 the R&D process identified that Vertrel® SDG is a potential alternative for TRI. While initial laboratory trials show promise, there are numerous technical and economic challenges that need to be evaluated before a decision can be made on the suitability of Vertrel® SDG in the ENTEK separator manufacturing process.

The large expected capital cost to switch and loss in profits compared to the costs of building additional production lines in the US, means this alternative is also not economically feasible.

From an engineering and operations standpoint, a significantly higher vapour pressure, the high solubility of Vertrel® SDG in water, its unknown adsorption affinity for activated carbon, and potential degradation of its chemical components in the presence of steam are problematic. From a hazard point of view, there is very

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limited information on the substance, however. based on the available information it seems likely that the substance will possess similar hazard properties to other solvents, since effects to the CNS and some irritation potential have been observed. Extensive further testing would be required to ensure that the use Vertrel® SDG would not pose similar hazard and risk levels compared to the continued use of TRI.

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5.6 HFE-72DE

5.6.1 Substance ID and properties

HFE-72DE is a mixture of 1,2-trans-dichloroethylene, ethyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether and methyl nonafluorobutyl ether, produced by 3M™ Novec™.

Table 5.16 Composition of HFE-72DE.

Substance name CAS # Concentration trans-dichloroethylene 156-60-5 68-72% ethyl nonafluoroisobutyl ether 163702-06-5 4-16% ethyl nonafluorobutyl ether 163702-05-4 4-16% methyl nonafluoroisobutyl ether 163702-08-7 2-8% methyl nonafluorobutyl ether 163702-07-6 2-8%

The compositional information has been taken from the most recent available MSDS sheet, dated 2007.

Classification and Labelling A classification and labelling for the substance mixture is not available, A harmonised classification for trans-dichloroethylene is available and has been reported in Table 4.1. No other harmonisation classifications for the other constituents of HFE-72DE are available.

Based on the information reported on the ECHA pages, only notified classifications and labelling (3 aggregated) according to the CLP regulation no. 1272/2008 are available for the ethyl nonafluorobutyl constituent of HFE-72DE (no notifications are available relating to classification according to the Dangerous Substances Directive 67/548/EEC):

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Ethyl nonafluoroisobutyl ether, CAS 163702-06-5

Classification area CLP - according to Regulation No 1272/2008 Annex VI Phsyicochemica Not classified

Health Eye Irrit. 2

Environmental Aquatic Chronic 4

Hazard Statements H319: causes serious eye irritation

H412: may cause long lasting harmful effects to aquatic organisms

Table 5.17 Physico-Chemical Properties of HFE-72DE

Properties Characteristics of Chemical Source(s) of Information

Flammability LEL 6.7% 3M, MSDS 2007 UEL 13.7%

Vapour pressure 44kPa at 25 ºC 3M, MSDS 2007

Volatility Very volatile 3M, MSDS 2007

Boiling point 45˚C 3M, MSDS 2007

Melting point Not applicable 3M, MSDS 2007

Water solubility Negligible 3M, MSDS 2007

HFE-72DE is described as a clear, colourless liquid with a slight odour. Its use is intended as an industrial only cleaning and coating solvent.

5.6.2 Technical feasibility

As discussed in Section 3.2.1, HFE-72DE is an effective solvent for naphthenic process oils and the resultant separators have properties that are similar to the TRI-extracted separators. There are major obstacles to the use of HFE-72DE as an alternative solvent in the ENTEK separator manufacturing process:

HFE-72DE is expensive and highly volatile with a boiling point of only 43 °C. As such, ENTEK would want to efficiently contain and recover this solvent in its separator manufacturing operation. The ability to adsorb and desorb the HFE-72DE chemical components from a large scale carbon bed system has not been demonstrated. This solvent is often used in degreasing applications with the vapours released to the atmosphere. As such, there has been little work on the efficient recovery of this solvent.

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While initial laboratory trials showed promise, there are numerous technical challenges that need to be evaluated before a decision could be made on the suitability of HFE-72DE in the ENTEK separator manufacturing process. From engineering and operations standpoints, a significantly higher vapour pressure, the high solubility of HFE-72DE in water, its unknown adsorption affinity for activated carbon, and potential degradation of its chemical components in the presence of steam are problematic.

5.6.3 Reduction of overall risk due to transition to the alternative

Table 5.18 below summarises further information on the hazard profile of the substance as the whole substance or of the constituents where available. The hazard profile of trans-dichloroethylene is presented in Table 5.13.

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Table 5.18 hazard profile of HFE-72DE

Human Health Hazards

Acute toxicity HFE-72DE is considered non-toxic by inhalation based on a 4-hour inhalation MSDS (2007) – all

study in rats (4-hour LC50 greater than 20 mg/L).

If thermal decomposition occurs: May be harmful if inhaled. May be absorbed following inhalation and cause target organ effects. Skin or eye corrosion/irritation Moderate Eye Irritation MSDS (2007) Moderate Skin irritation

Respiratory Tract Irritation: Signs/symptoms may include cough, sneezing, nasal discharge, headache, hoarseness, and nose and throat pain. Carcinogenicity No data Target Organ toxicity May cause target organ toxicity. Central Nervous System (CNS) Depression: MSDS (2007) Signs/symptoms may include headache, dizziness, drowsiness, incoordination, nausea, slowed reaction time, slurred speech, giddiness, and unconsciousness. Neurotoxicity Yes, see above Respiratory or skin Cardiac Sensitization: Signs/symptoms may include irregular heartbeat (arrhythmia), MSDS (2007) sensitization faintness, chest pain, and may be fatal. Toxic metabolites? N.A. but at elevated temperatures – extreme conditions of heat, the substance may MSDS (2007) decompose into the following hazardous by-products:

Hydrogen chloride Hydrogen fluoride Perfluoroisobutylene (PFIB)

Environmental Hazards

Acute/chronic aquatic toxicity Testing results indicate that ethyl nonafluoroisobutyl ether, ethyl nonafluorobutyl MSDS (2007) ether, methyl nonafluoroisobutyl ether and methyl nonafluorobutyl ether have insignificant toxicity to aquatic organisms at their saturation point (Lowest LC50,

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EC50, or IC50 >substance water solubility). MSDS (2007) Bioaccumulation The majority of the constituents ares said to be unlikely to bioaccumulate based on MSDS (2007) their volatilization properties. Persistence No data on biodegradation. However they state: These compounds are highly volatile MSDS (2007) and have high Henry's Law constants and are thus expected to move rapidly through vaporization from solution in an aquatic compartment or from a soil surface in a terrestrial compartment to the atmosphere. Greenhouse gas formation Global Warming Potential (GWP): 320 (100 year ITH, WMO 1998 method) for MSDS (2007) potential methyl nonafluoroisobutyl ether and methyl nonafluorobutyl ether; 55 (100-yr ITH) for ethyl nonafluoroisobutyl ether and ethyl nonafluorobutyl ether using the calculation method outlined in Climate Change 2001; and essentially zero for 1,2- trans-dichloroethylene.

GWP of product as formulated: approximately 43 (100-yr ITH). Ozone-depletion potential The substance has not been classified as an ozone depleting substance. The MSDS Regulation (EC) No 2037/2000 sheet indicates that the substance has zero ozone depleting potential. and MSDS (2007)

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Limited information is available on the hazard profile of HFE-72DE. Upon combustion the substance can degrade to toxic substance such as hydrogen fluoride, hydrogen chloride and perfluoroisobutylene.

The short-term exposure to high levels of HFE-72DE may cause effects to the central nervous system (CNS) with symptoms including dizziness, drowsiness, slowed reaction times and unconsciousness. The substance itself does not have a harmonised classification and labelling nor is it classified in its MSDS, however one of its constituents, trans-dichloroethylene (CAS 156-60-5, 68-72% of total substance) is classified as Acute Toxicity 4. For this constituent effects to the CNS have been also been observed with rats.

HFE-72DE is said to cause mild eye and skin irritation upon contact, and its constituents are described as mild irritants. The substance is also said to potentially cause irregular heartbeats and chest pain although it is not classified as a respiratory sensitising agent.

The fluoro based constituents are said to not be toxic in short-term aquatic toxicity tests up to their limit of solubility.

5.6.4 Economic feasibility

It is understood that this material is currently some 40-50 times the cost of TRI. In addition, based upon laboratory testing results, HFE-72DE would result in less separator shrinkage than occurs with TRI. This difference would result in all calender tools needing to be re-cut with a new groove pattern to end up with a final separator having the desired profile. ENTEK has 43 calender/profile rolls (also known as tools) at its UK plant that would need to be re-machined. The time period to convert all of these tools would be ~ 1 year at an estimated cost of € 1.2 million. Furthermore a major consideration is the reengineering of processes in order to accommodate the alternative even if it were technically feasible. This would need to include consideration of solvent recycling and emission capture since the volatility of the substance is quite different from TRI.

HFE-72DE is not a “drop-in” solvent replacement for TRI as noted above. It would mean the replacing large parts (if not completely) the existing production process and equipment. As per the ECHA SEA guidance, the lost (book) value of existing equipment is considered a ‘sunk cost’ and therefore not considered in the analysis. The additional capital and operating costs of making PE SLI battery separators is however relevant to the assessment of economic feasibility.

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for details on lost profits, but using a discount rate of 7% rather than 4% in the SEA) with the cost of building additional production lines at the existing US site (in Oregon) which is €48 million (see Section 4.2.2 of the SEA); which enables ENTEK to avoid any production/sales disruption (i.e. can provide battery separators to the existing markets after the sunset date), it is clear that switching to HFE-72DE is not economically feasible.

5.6.5 Availability

The substance mixture is commercially available.

5.6.6 Conclusion on suitability and availability for HFE-72DE

As described in Section 4 the R&D process identified that HFE-72DE is a potential alternative for TRI. While initial laboratory trials indicate possibilities , there are numerous technical and economic challenges that need to be evaluated before a final decision can be made on the suitability of HFE-72DE in the ENTEK separator manufacturing process.

The large expected capital cost to switch and loss in profits compared to the costs of building additional production lines in the US, means this alternative is also not economically feasible.

From an engineering and operations standpoint, a significantly higher vapour pressure, limited data for recovery from activated carbon and potential degradation of its chemical components in the presence of steam are problematic. The substance had a much higher cost compared to TRI (x 40-50 ). From a hazard point of view, there is very limited information on the substance, however. based on the available information it seems likely that the substance will possess similar hazard properties to other solvents, since effects to the CNS and some irritation potential have been observed. Extensive further testing would be required to ensure that the use HFE-72DE would not pose a similar level of hazard and risk compared to the continued use of TRI.

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5.7 N-PROPYL BROMIDE

The substance n-propyl bromide is a brominated hydrocarbon. Vapours may form explosive mixtures with air, and the vapours may travel to source of ignition and flash back. Its vapours are heavier than air, so they will spread along ground and collect in low confined areas.

N-Propyl bromide is a substance of very high concern (SVHC) under REACH on the basis of its reproductive toxicity and it is therefore listed on the Candidate List for substance that can be recommended for placing on Annex XIV.

5.7.1 Substance ID and properties Chemical Name(s): n-propyl bromide Other names: 1-bromopropane, 1-propyl bromide, n-bromopropane CAS Number: 106-94-5 EC Number: 203-445-0

Molecular Formula: C3H7Br

Molecular Weight: 123

Classification and Labelling

The harmonised classifications according to the CLP regulation no. 1272/2008 and to the Dangerous Substances Directive 67/548/EEC are presented in the tables below.

Classification CLP - according to Regulation No Dangerous Substance Directive –according to area 1272/2008 Annex VI Directive 67/548/EEC Physicochemical Flam. Liq. 2 F; R11

Health Skin Irrit. 2 Repr. Cat. 3; R62

Eye Irrit. 2 Repr. Cat. 2; R60

STOT SE 3 (H335) Xn; R48/20

STOT SE 3 (H336) Xi; R36/37/38

Repr. 1B R67

STOT RE 2 (H373)

Environmental Not classified Not classified

Hazard H225: Highly flammable liquid and R11: Highly flammable

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Classification CLP - according to Regulation No Dangerous Substance Directive –according to area 1272/2008 Annex VI Directive 67/548/EEC Statements vapour

H315: Causes skin irritation R60: May impair fertility

H319: Causes serious eye irritation R36/37/38: Irritating to eyes, respiratory system and skin

H335: May cause respiratory R62: Possible risk of impaired fertility irritation

H336: May cause drowsiness or R67: Vapours may cause drowsiness and dizziness dizziness

H360FD: May damage fertility. May R48/20: Harmful: Danger of serious damage to damage the unborn child health by prolonged exposure through inhalation

H373: May cause damage to organs R63: Possible risk of harm to the unborn child through prolonged or repeated exposure

The physico-chemical properties of n-propyl bromide are set out in table 5.19, below.

Table 5.19 Physico-Chemical Properties of n-propyl bromide

Properties Characteristics of Chemical Source(s) of Information

Flammability highly flammable vapours HSDB 2009

Vapour pressure 14.8 kPa at 20 ˚C ECHA 2013

Boiling point 71 ˚C ECHA 2013

Melting point -110 ˚C ECHA 2013

Water solubility 2450 mg/L at 20 ˚C HSDB 2009

Log Kow 2.16 ECHA 2013

5.7.2 Technical feasibility

From the research described in Section 3.2 of this document, it appears that n-propyl bromide may be a technically feasible alternative to TRI as a process solvent for the manufacture of polyethylene battery separators. While n-propyl bromide exhibits nearly the same oil extraction rate as TRI, its low flashpoint, higher water solubility, and potential degradation in a high temperature steam environment are of concern. However, the substance is disregarded as an alternative on the basis of risk, since it is an SVHC, flammable and decomposition could lead to the formation of hydrogen bromide.

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Furthermore, the extraction step is an integral part of the continuous process that ENTEK uses to manufacture battery separators. The potential consequence of a fire or explosion with over 34,000 litres of n-propyl bromide being circulated in a closed loop process at the UK plant would be catastrophic. The arguments set out for n-hexane in terms of the capital and operational costs of converting a separator plant for use of a highly flammable substance apply here also (see section 5.2.4).

5.7.3 Reduction of overall risk due to transition to the alternative

Table 5.20 below summarises further information on the hazard profile of the substance.

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Table 5.20 Hazard profile of n-propyl Bromide

Chemical Properties Characteristics of Chemical Source(s) of Information

Human Health Hazards

Acute toxicity n-Propyl bromide is of low acute toxicity to animals (LD50 values in excess of >2500 ECHA 2013 mg/kg bw or LC50 35 000 mg/m3 air). The target organ is said to be the lungs.

Acute exposure to anesthetic levels on n-propyl bromide may result in lung and liver HSDB 2009 injury.

Overexposure has resulted in effects to the Central Nervous System (CNS) resulting CDC, 2008 in confusion, dysarthria, dizziness, paresthesias, and ataxia; unusual fatigue and headaches, development of arthralgias, visual disturbances (difficulty focusing), paresthesias, and muscular twitching. Symptoms may persist over one year after exposure.

Skin or eye corrosion/irritation The substance is irritating to the eyes and the respiratory tract. ECHA 2013 Respiratory or skin Not sensitising ECHA, 2013 sensitization Carcinogenicity In animal studies n-propyl bromide caused tumours in the intestine, skin and lungs of NTP, 2013 rats and mice.

Long term toxicity n-Propyl bromide is described as a neurotoxic and hepatoxic agent. HSDB 2009

Exposure to 400 ppm n-propyl bromide for 28 days caused histopathological lesions to the CNS. A NOAEL of 200 ppm based on no effects on the liver has been reported for rats exposed to n-propyl bromide for 13 weeks. Mutagenicity n-Propyl nromide has shown mutagenic activity in a mouse lymphoma assay. ECHA 2013 However it is not mutagenic in vivo.

There is limited evidence that n-propyl bromide causes DNA damage in vivo. NTP 2013

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Chemical Properties Characteristics of Chemical Source(s) of Information Endocrine disruption No information Reproductive/developmental Rats exposed to n-propyl bromide showed effects in viability, sexual maturation and ECHA, 2013 body weight of offspring when exposed to doses above 100 ppm. Maternal toxicity and feotoxicity was also observed in another study with rats exposed to doses in excess of 100 ppm. The substance is classified as a reprotoxic substance (CLP classification Repro 1B). Neurotoxicity n-Propyl bromide is a neurotoxic agent and acts by damaging the nerves in the arms, Cal/OSHA (undated) legs, and body, and there is evidence suggesting this brain damage may also occur HSDB 2009 after exposure to n-propyl bromide. Immune system toxicity Rats exposed to n-propyl bromide have experienced immunological effects. NTP 2013 Systemic toxicity No information Toxic metabolites n-Propyl bromide may produce propylene oxide upon metabolisation. NTP 2013 Environmental Hazards

Acute/chronic aquatic toxicity n-Propyl bromide is of low acute toxicity to aquatic organisms, LC50 and EC50 ECHA 2013 values have been reported in the range 72 to 203 mg/L. An algal NOEC of 12.4 mg/L is available. Bioaccumulation n-Propyl bromide is considered to have a low bioaccumulation potential and does not ECHA 2013 fulfil the B in the PBT criteria. The BCF has been calculated to be 11.29 L/Kg wwt (Log BCF 1.05). Owing to this and its low log Kow. Persistence n-Propyl bromide is not readily biodegradable. ECHA 2013 Greenhouse gas formation n-Propyl bromide does not form greenhouses gases upon degradation. potential Ozone-depletion potential The substance has been proposed as a replacement for ozone depleting solvents and it HSDB 2009 and Regulation (EC) No is not classified as ozone depleting substance. 2037/2000

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n-Propyl bromide is considered a highly toxic substance due to its long lasting effects to the CNS following repeated exposure and its reproductive toxicity. It is classified as a skin and eye irritant category 2, STOT SE 3, with the associated hazard phrase H335 (may cause respiratory irritation), STOT SE 3 with the associated hazard phrase H336 (may cause drowsiness or dizziness) and STOT RE 2, with the associated hazard phrase H373 (may cause damage to organs through prolonged or repeated exposure) and as a reproductive toxicant category 1B under CLP. In addition, rats and mice exposed to n-propyl bromide have developed tumours in the intestine, skin and lungs.

In short-term aquatic toxicity data the substance is not very toxic (with the lowest EC/LC50 being 72 mg/L).

Overall the hazard properties of n-propyl bromide do not make it a potential candidate for the substitution of TRI.

PBT and CMR n-Propyl bromide has been placed on ECHA’s candidate list as a substance of very high concern because of its classification as reproductive toxin. n-Propyl bromide does not fulfil the B criteria in the PBT assessment (see Table 5.8), therefore it is not considered to be a candidate PBT or vPvB substance.

5.7.4 Economic feasibility n-Propyl bromide is not a “drop-in” solvent replacement for TRI as noted above. It would mean the replacing large parts (if not completely) the existing production process and equipment. As per the ECHA SEA guidance, the lost (book) value of existing equipment is considered a ‘sunk cost’ and therefore not considered in the analysis. The additional capital and operating costs of making PE SLI battery separators is however relevant to the assessment of economic feasibility.

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5.7.5 Availability

The substance has been registered under REACH phase I at 1 000 to 10 000 tonnes per annum level. Therefore it is considered to be sufficiently available.

5.7.6 Conclusion on suitability and availability for n-propyl bromide

The substance is classified as a reproductive toxin and is a CMR. As a result of this it is being considered as an SVHC substance. In addition it may cause damage to the Central Nervous System.

On the basis of the substance leading to equal or greater risk it is not considered to be a possible alternative.

The large expected capital cost to switch and loss in profits compared to the costs of building additional production lines in the US, means this alternative is also not economically feasible.

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5.8 D-LIMONENE

Limonene is a naturally occurring terpene, found in citrus and other plants. It exists in two isomeric forms: D- and L-limonene, and the racemic mixture diptene. The available data does not always distinguish between two forms, in which case the substance is referred to as limonene. Commercial D-limonene generally has a purity of 90-98%.

5.8.1 Substance ID and properties

Chemical Name(s): 1-methyl-4-(1-methylethenyl)-cyclohexene

Other names: 4-isopropenyl-1-methylcyclohexene, p-menth-1,8-diene, Racemic: DL-limonene; Dipentene

Trade Name(s): not available

CAS Number: 5989-27-5

EC Number: 227-813-5

Molecular Formula: C10H16

Molecular Weight: 136.24

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Classification and Labelling The harmonised classifications according to the CLP regulation no. 1272/2008 and according to the Dangerous Substances Directive 67/548/EEC are presented in the tables below.

Classification CLP - according to Regulation Dangerous Substance Directive –according to area No 1272/2008 Annex VI Directive 67/548/EEC Physicochemical Flam. Liq. 3 R10

Health Skin Irrit. 2 Xi; R38

Skin Sens. 1 R43

Environmental Aquatic Acute 1 N; R50-53

Aquatic Chronic 1

Hazard H315: Causes skin irritation R10: Flammable Statements

H226: Flammable liquid and R38: Irritating to skin vapour

H317: May cause an allergic R43: May cause sensitization by skin contact skin reaction

H400: Very toxic to aquatic life R50/53: Very toxic to aquatic organisms, may cause long-term adverse effects in the aquatic environment.

H410: Very toxic to aquatic life with long lasting effects

Table 5.21 Physico-Chemical Properties of D-limonene

Properties Characteristics of Chemical Source(s) of Information

10 Flammability Flammable HBSD 2006 Vapour pressure 200 Pa at 16°C ECHA 2013

Boiling point 175-178°C ECHA 2013

Melting point -75°C ECHA 2013 Water solubility 13.8 mg/l at 25°C ECHA 2013

11 Log Kow 4.4 at 37°C ECHA 2013

10 HSDB 2006 for d-limonene, CAS 5989-27-5, accessed November 2013

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D-Limonene is a slightly yellow liquid at room temperature, classified as a flammable liquid (Fla. Liq. 3 according to CLP and R10 according to DSD). The substance has a boiling point of 175-178°C and a melting point of -75°C. It has a water solubility of 14 mg/1, a vapour pressure of 200 Pa at 16°C and a log Kow of 4.4 at 37°C.

D-Limonene has a flashpoint of 51°C above which explosive vapour/air mixtures may be formed (HSDB 2006). It is said to react violently with a mixture of iodine pentafluoride and tetrafluoroethylene, causing fire and becoming an explosion hazard, and it may also react with oxidants. [ECHA 2013 and HSDB 2006].

D-Limonene is not an oxidising agent and is stable at ambient temperatures

5.8.2 Technical feasibility

From the research described in Section 3.2 of this document, it appears that D-limonene may be a technically feasible alternative to TRI as a process solvent for the manufacture of polyethylene battery separators. Although it exhibits a slower extraction rate compared to TRI, this property could potentially be adjusted with temperature of the extraction bath. While the low solubility of D-limonene in water is potentially advantageous, its high boiling point and high heat of vaporization would add significant costs to the solvent recovery process. Further research is required to understand if D-limonene could be used at a commercial scale, and whether it would be compatible with all manufacturing and recovery processes such that the resultant separator meets all customer requirements.

5.8.3 Reduction of overall risk due to transition to the alternative

Table 5.22 below summarises further information on the hazard profile of the substance.

11 ECHA disseminated dossier on d-limonene, CAS 5989-27-5, accessed November 2013

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Table 5.22 hazard profile of D-limonene

Chemical Properties Characteristics of Chemical Source(s) of Information

Human Health Hazards

Acute toxicity D-Limonene is not acutely toxic to animals, the oral and dermal LD50s are in excess ECHA 2013 of 2000 mg/kg

Skin or eye corrosion/irritation Limonene is a skin irritant in humans and in experimental animals. WHO 1998 HSDB 2006 In rabbits, D-limonene was found to be an eye irritant.

Respiratory or skin The substance itself is not a sensitizer, but air oxidized D-limonene induced contact HSDB 2006 sensitization allergy in guinea pigs.

Carcinogenicity D-Limonene increases the incidence of renal tubular tumours in male rats, but the IARC 1999 mechanism of tumour formation in rats is not relevant to humans. Long term toxicity D-Limonene is a nephrotoxic agent in rats. The critical organ in animals (except for HSDB 2006 male rats) following peroral or interperitoneal administration is the liver. There are insufficient data to determine the critical organ in humans.

Exposure to limonene affects the amount and activity of liver enzymes and liver WHO 1998 weight.

Reproductive/developmental Oral exposure to high levels of D-limonene has resulted in delayed maternal growth IARC 1999 and skeletal abnormalities have been observed in foetuses of laboratory animals. WHO 1998

Mutagenicity D-Limonene is not genotoxic in vitro and in vivo studies. HSDB 2006

Endocrine disruption No data Neurotoxicity Decreased motor activity has been observed in mice administered D-limonene, HSDB 2006 however it was difficult to ascertain whether this was due to direct effects of the WHO 1998 chemical or general intoxication. Immune system toxicity Some immune responses such as suppressed primary and secondary anti-keyhole HSDB 2006 limpet hemocyanin and increased antibody and mitogen-induced proliferative WHO 1998 responses have been observed in a study with mice. However the purity of D-

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Chemical Properties Characteristics of Chemical Source(s) of Information limonene was not established and it is possible that the effects seen were a response to the oxidation products rather than the substance itself.

Toxic metabolites Toxic metabolites are not formed during the metabolisation of D-limonene. HSDB 2006

Environmental Hazards Acute/chronic aquatic toxicity Short-term toxicity effects have been reported with fish and invertebrates below ECHA 2013 1 mg/L (LC50 and EC50 values of 0.38 and 0.72 mg/l respectively). A long-term toxicity study with invertebrates from a surrogate substance indicates a 21 d NOEC with Daphnia below 1 mg/l (0.27 mg/l).

Terrestrial toxicity D-Limonene is used as an insecticide HSDB 2006

Bioaccumulation The calculated BCF is 360.5 to 1022 L/kg wet/wet (BCFBAF and OASIS ECHA 2013 respectively).

The estimated BCF of 660 suggests that bioaccumulation potential is high. HSDB 2006

Persistence D-Limonene is readily biodegradable (biodegradation in activated sludge is > 60% ECHA 2013 ThOD). HSDB 2006 Vapor-phase limonene is rapidly degraded in the atmosphere by reaction with photochemically-produced hydroxyl radicals, nitrate radicals and ozone. Greenhouse gas formation The degradation of the substance does not produce greenhouse gases. potential Ozone-depletion potential The oxidation of D-limonene can lead to the formation of hydrogen peroxide and WHO 1998 and organic peroxides, however it is not indicated as an ozone depleting substance in Regulation (EC) No 2037/2000. Regulation (EC) No 2037/2000, probably due to its rapid degrading in the atmosphere.

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D-Limonene, a terpene, is increasingly being used a solvent and is also used in food manufacturing and some medicines. Therefore even though the substance is classified as a skin irritant category 2 and as a skin sensitiser, the hazard properties of the substance to humans are considered sufficiently low to allow some level of exposure to it.

D-Limonene is highly toxic to aquatic organisms in short- and long-term studies, and it is classified under CLP as such: Aquatic Acute and Chronic category 1. D-Limonene is an active ingredient in biocidal products, it is used as a repellent and as an insecticide. Therefore releases to the environment would need to be monitored.

PBT and CMR

D-Limonene does not fulfil the PBT criteria, because it does not fulfil the P criteria based on rapid biodegradation.

The substance is not considered as a CMR agent as it is not classified as a carcinogen, mutagenic or reproductive agent.

5.8.4 Economic feasibility

The substance is disregarded on the basis of its flammability and in addition due to its heat of vaporization - the energy costs required compared to TRI would be ~ 50% higher. D-Limonene is not a “drop-in” solvent replacement for TRI as noted above. It would mean the replacing large parts (if not completely) the existing production process and equipment. As per the ECHA SEA guidance, the lost (book) value of existing equipment is considered a ‘sunk cost’ and therefore not considered in the analysis. The additional capital and operating costs of making PE SLI battery separators is however relevant to the assessment of economic feasibility.

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5.8.5 Availability

The substance has been registered under REACH at a 10,000 to 100,000 tonnes per annum band, therefore it can be considered to be readily available.

5.8.6 Conclusion on suitability and availability for D-limonene

As described in Section 3 the R&D process identified that D-limonene could be a potential alternative for TRI. While initial laboratory scale evaluation shows promise, D-limonene is eliminated as a possible alternative to TRI because it is flammable and based on its heat of vaporization the energy costs required compared to TRI would be ~ 50% higher.

The large expected capital cost to switch and loss in profits compared to the costs of building additional production lines in the US, means this alternative is also not economically feasible.

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5.9 ACETONE

Acetone is an organic compound naturally found in the body. It occurs as a metabolic by-product of animals and plants and is emitted by volcanoes and during forest fires. Its main use is as a solvent to dissolve paints, varnishes, oils, resins etc.

5.9.1 Substance ID and properties

Chemical Name(s): acetone, 2-propanone

Other names: propan-2-one, dimethyl ketone, dimethyl formaldehyde, dimethylketal, β-ketopropane, ketone propane, ketone methyl, propanone, 2-propanone, pyroacetic acid, pyroacetic ether, pyroacetic spirit (archaic)

CAS Number: 67-64-1

EC Number: 200-662-2

Molecular Formula: C3H6O

Molecular Weight: 58.08

Classification and Labelling

The harmonised classifications according to the CLP regulation no. 1272/2008 and according to the Dangerous Substances Directive 67/548/EEC are presented in the tables below.

Classification CLP - according to Regulation Dangerous Substance Directive –according to area No 1272/2008 Annex VI Directive 67/548/EEC Physicochemical Flam. Liq. 2 F; R11

Health Eye Irrit. 2 Xi; R36

STOT SE 3 R66 Affected organs: narcotic effect Route of exposure: inhalation

R67

Environmental No classification No classification

Hazard H225: Highly flammable liquid and 11: Highly flammable Statements vapour

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H319: Causes serious eye irritation 36: Irritating to eyes

H336: May cause drowsiness or 66: Repeated exposure may cause skin dryness or dizziness cracking

EUH066: Repeated exposure may 67: Vapours may cause drowsiness and dizziness cause skin dryness or cracking.

Table 5.23 Physico-Chemical Properties of Acetone Properties Characteristics of Chemical Source(s) of Information

Flammability Highly flammable (flash point below 20˚C) ECHA 2013

Vapour pressure 24.3 kPa at 20˚C OECD 1999

Boiling point 56.1˚C ECHA 2013

Melting point -94.8˚C ECHA 2013

Water solubility Soluble ECHA 2013

Log Kow -0.24 OECD 1999

Acetone is a colourless liquid at room temperature with a mildly pungent and somewhat aromatic odour. Acetone is flammable, owing to its low flash point (below 20˚C). The vapour/air mixtures are explosive and heating will cause a rise in pressure with the risk of bursting.

5.9.2 Technical feasibility

As discussed in Section 4.2.1, acetone is a poor solvent and not fully miscible with naphthenic process oils. While other ketones such a methyl ethyl ketone (MEK) and methyl iso-butyl ketone (MIBK) would be expected to have a higher degree of solvency for the process oil, all of these compounds have high flammability. As such, acetone and other ketones are not viable in the ENTEK separator manufacturing process. As for n-hexane this leads to considerable difficulties and costs which are set out in section 5.2.4.

5.9.3 Reduction of overall risk due to transition to the alternative

Acetone is generally of low toxicity, however it is subject to a SCOEL recommendation for an occupational exposure limit for the protection of workers at EU level12. The iOEL is summarised as follows:

8 hour TWA: 500 ppm [1210 mg/m3]

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STEL (15 min): 1000 ppm [2420 mg/m3]

Notation: none

The UK’s Health and Safety Executive (HSE) has issued a long term work exposure limit (WEL) of (8h) 500 ppm (1210 mg/m3), and a short term WEL of (15min) 1500 ppm (3620 mg/m3).

Table 5.24 below summarises further information on the hazard profile of the substance.

12 Recommendation from the Scientific Committee on Occupational Exposure Limits on Acetone SEG/SUM/74, March 1997

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Table 5.24 Hazard profile of Acetone

Chemical Properties Characteristics of Chemical Source(s) of Information

Human Health Hazards

Acute Toxicity Acute toxicity Very low acute toxicity via oral, dermal and inhalation exposure (LD/LC50 values are >5000 ECHA 2013 mg/kg bw and 50 000 mg/m3) in experimental animals. Exposure at high levels could cause lowering of consciousness. ICSC 2009

Skin or eye corrosion/irritation Acetone has been shown to be an eye irritant in animal studies. ECHA 2013 Respiratory or skin In animal studies, acetone has been found not to be a sensitising agent. ECHA 2013 and OECD 1999 sensitization Chronic Toxicity Long term toxicity The NOELs in the drinking water study were 1% for male rats (900 mg/kg/d) and male mice OECD 1999 (2258 mg/kg/d), 2% for female mice (5945 mg/kg/d), and 5% for female rats (3100 mg/kg/d). The main findings were reduction in spleen weight and an increase in liver weight in mice.

Reproductive/developmental Acetone has shown to be of low reproductive and developmental toxicity when exposed by OECD 1999 inhalation or via the drinking water. The NOEL for developmental toxicity was 5220 mg/m3 for both rats and mice. The NOEL for teratogenic effects were in rats and mice was ≥26,110 and ≥15,665 mg/m3, respectively.

In mice a NOAEL of 2200 ppm has been determined for developmental toxicity based on NTP 1988 reduction in foetal weight and an increase in late resorption.

Carcinogenicity There are no studies available on the carcinogenicity of acetone , however acetone has been EHC 1998 used as a solvent vehicle in skin carcinogenicity studies.

Topical treatment of mice with 0.1 and 0.2 ml acetone once or twice per week did not induce an incidence of tumours above the background levels. OECD 1999

Mutagenicity Acetone has been generally proven to be non-mutagenic ECHA 2013 SUM 1997

Neurotoxicity Acute exposure to acetone has been found to alter performance in neurobehavioural tests in EHC 1998

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Chemical Properties Characteristics of Chemical Source(s) of Information laboratory animals at concentrations greater than 7765 mg/m3 (>3270 ppm).

Acute exposures to acetone have been reported to alter performance in neurobehavioural tests in humans at 595 mg/m3 (250 ppm).

Immune system toxicity The T cells response capacity was measured respond in mice treated with up to 1144 mg/kg EHC 1998 bw and was found to be unaltered.

Systemic toxicity Acetone is moderately toxic to the liver and has some haematological effects. The mechanism EHC 1998 of these effects is unknown. The renal toxicity may be due to the formation of known nephrotoxic agent, formate, which is excreted by the kidneys (Hallier et al., 1981).

Toxic metabolites None EHC 1998 Environmental Hazards Acute/chronic aquatic toxicity Acetone is virtually non-toxic in short-term and long-term aquatic toxicity tests (EC/LC50 OECD 1999 values in the range 2100 to 15000 mg/L and NOECs >1000 mg/L).

Terrestrial toxicity Acetone is of low toxicity to terrestrial organisms with NOECs of >80 mg/L in plants and OECD 1999 >40 000 mg/kg in avian toxicity studies. Bioaccumulation Bioaccumulation is not of concern for this substance due to its low log Kow (calculated BCF = ECHA 2013 3) and low persistence in the environment. Persistence Acetone is considered as readily biodegradable (ca. 90% biodegradation after 28, 10-d ECHA 2013 window criteria fulfilled) Greenhouse gas formation None found potential Ozone-depletion potential Acetone is not indicated as an ozone depleting substance in Regulation (EC) No 2037/2000. Regulation (EC) No 2037/2000 Acetone degrades in the atmosphere by reacting with OH* radicals. The reactions with ozone EHC 1998 (OD) or NOx are considered to be too slow to be important under tropospheric conditions.

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Acetone does not have a high toxicity profile. Exposure to high levels of acetone can cause depression of the Central Nervous System (CNS) and it is classified as such under CLP (STOT SE3). It is also an eye irritant in animals. No other significant hazards have been found for human health and the environment.

PBT/CMR and any other regulatory actions Acetone does not fulfil any of the criteria for PBT and is not classified as a CMR agent. No regulatory action is currently being taken with this substance.

5.9.4 Economic feasibility

The substance is disregarded on the basis of not being technically feasible. Acetone is not a “drop-in” solvent replacement for TRI as noted above. It would mean the replacing large parts (if not completely) the existing production process and equipment. As per the ECHA SEA guidance, the lost (book) value of existing equipment is considered a ‘sunk cost’ and therefore not considered in the analysis. The additional capital and operating costs of making PE SLI battery separators is however relevant to the assessment of economic feasibility.

then the net cost to ENTEK is €125 million (NPV). This further reinforces the conclusion that acetone is not economically feasible.

5.9.5 Availability

Acetone is widely used and available. In the EU it is distributed at 1*105 to 1*106 tonnes per annum range.

5.9.6 Conclusion on suitability and availability for Acetone

Acetone is not a viable alternative because of its poor miscibility with the naphthenic process oils. The potentially large expected capital cost to switch and loss in profits compared to the costs of building additional production lines in the US, means this alternative is also not economically feasible.

5.10 ASSESSMENT OF TECHNICAL ALTERNATIVES

This section is addresses the possible alternatives to PE battery separators, i.e. separators that can be used in lead-acid batteries that are not produced with TRI. The focus of this analysis of alternatives is on replacement of the function of TRI, that is finding a way of extracting oil from PE separators without using TRI. However, since the analysis of alternatives should be in-line with the non-use scenario the possible alternatives to PE separators are discussed here. Some understanding of lead-acid batteries is set out first so that the possibilities of use for other types of is clear, before considering the possible alternatives.

5.10.1 Lead Acid Battery Classifications

Lead acid batteries are often classified into the following categories based on their application and use: 1. SLI (Starter, Lighting, and Ignition) --- used in automobiles 2. Start-Stop --- designed to operate in automobiles where internal combustion engine shuts off during stops to reduce CO2 emissions; 3. Stationary --- used for back-up power supply for telecommunication, electric utility, or computer systems. 4. Motive Power --- industrial batteries used to power forklifts, floor scrubbers, etc. 5. Special Purpose --- military equipment, submarines, etc. In terms of maintenance, lead acid batteries are classified as follows:

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1. Flooded --- require water addition because grid alloys with high antimony (Sb) content catalyze hydrogen and oxygen loss 2. Maintenance Free --- contain lead/tin/calcium grids for the positive plates and lead/calcium grids for the negative plates 3. Valve Regulated (VRLA) --- utilize lead/tin/calcium grids and absorptive glass mat (AGM) separators. As mentioned in the SEA report, lead-acid polyethylene separator starting lighting and ignition (PE SLI) batteries compete to some extent with absorbed glass mat (AGM) separators that are used within valve regulated lead acid (VRLA) batteries. As vehicles become more advanced, including more electrical devices and features, the demands of the battery supplying the power to these devices are increasing. These new electronic and technological advancements need batteries to power them along with greater cycling (charging and discharging) capabilities. VRLA batteries are marketed as providing this enhanced power source for electronic features. The advancement of the VRLA market could lead to erosion of PE SLI lead acid batteries’ market share. As mentioned in Section 3, the applicant does not participate in this alternative separator technology and has determined that this is not a market in which they can compete successfully.

5.10.2 Alternative separator products

Currently, there is a separator available in the marketplace for lead acid batteries that ENTEK does not manufacture. Absorptive glass mat (AGM) separators are used in Valve Regulated Lead Acid (VRLA) batteries. These separators have extremely high porosity (>90%) and are composed of interconnected micron-sized glass fibres as shown in Figure 5.13.

Figure 5.13 Scanning electron micrograph of an AGM separator.

As mentioned in the SEA report, lead-acid polyethylene separator starting lighting and ignition (PE SLI) batteries compete to some extent with absorbed glass mat (AGM) separators that are used within valve regulated lead acid (VRLA) batteries.

As shown in Figure 5.14 , an AGM separator is white and has smooth parallel faces, whereas polyethylene separators are grey with ribs of different heights across the face of one side. Table 5.25 shows some key separator characteristics and the distinct differences between these two types of separators. It is clear from these differences that one separator type cannot simply be substituted for the other in the same battery design.

Figure 5.14 Photograph shows AGM separator and polyethylene separator made by ENTEK

One advantage of the AGM separator is that it can immobilize the required amount of sulphuric acid between the positive and negative electrodes, such that a lead acid battery can operate in different orientations without the risk of an acid spill. A disadvantage of the AGM separator is its weak mechanical properties result in a lower production rate for VRLA batteries. In general, VRLA batteries are approximately 2.5-3 times more expensive than conventional flooded SLI batteries. Table 5.25 shows a comparison of key separator characteristics for the two most common separators used in lead acid batteries.

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Table 5.25 Key separator characteristics for the two most common separators used in lead acid batteries

Attribute Polyethylene Separator Absorptive Glass Mat Backweb Thickness (mm) 0.15-0.25 1.5

Overall Thickness (mm) 0.6-1.9 1.5

Porosity (%) 55-60 93

Puncture Strength (N) 5-10 1

Electrical Resistance (mΩ- cm²) 80-105 40

VRLA batteries are widely used in large portable electrical devices, off-grid power systems and similar roles, where large amounts of storage are needed at a lower cost than other low- maintenance technologies such as lithium-ion. VRLA batteries are also used in ‘start-stop’ vehicle applications because of their excellent cycle life and low susceptibility to acid stratification. The higher cost of VRLA batteries limits their adoption to only luxury vehicles, whereas an Extended Flooded Battery (EFB) design which uses a polyethylene separator is used in more modest vehicles with fewer electrical loads. There exists a growing market for EFB for new vehicles, but also a significant market for battery replacement in existing automobiles (the so-called ‘car park’). Although, it might be possible in some cases, for a VLRA battery to be used for battery replacement, the much greater cost without the added benefit would not be justified. In addition it is known that VRLA batteries are limited to specific sizes (indicated by DIN number specification), so that the selection of a VRLA for replacement would be limited. A more comprehensive analysis of the market for battery types and the after sales (battery replacement) market for EFB in the European car park is presented in the SEA.

6.1 OVERALL CONCLUSION

The conclusion of this analysis of alternatives is that there are no alternatives that are suitable and available to the applicant for the replacement of the Annex XIV substance function. A number of possible solvent alternatives have been tested at laboratory scale by ENTEK. Although it was found that for one or two of the alternatives (see Table 6.1 below) there was some potential for the replacement of TRI, a considerable amount of further research would be required to determine the technical feasibility of these substances at a commercial scale. In addition, the customer acceptability of the products manufactured using an alternative would also have to be ensured.

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Table 6.1 below presents a summary of the solvents that were researched for their potential to replace TRI in the ENTEK process. Each substance is evaluated against the criteria of technical feasibility, economic feasibility, risk and availability. It should be noted that:

1. The assessment of economic feasibility can be complex and is not simply a case of comparison of the cost of the possible alternative with the Annex XIV substance. 2. In some cases where the possible alternative has already be shown as not technically feasible or will lead to equal or greater risk than the Annex XIV substance, there is little point in the assessment of economic feasibility, because that becomes irrelevant.

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Table 6.1 Summary of findings of the analysis of alternatives for substances

Substance Technical feasibility Economic feasibility Similar or additional risk? Availability n-hexane Possible on basis of lab trials. No - The large expected capital cost to Highly flammable. Neurotoxin and Yes switch and loss in profits compared to the reproductive toxin. Presents difficulties due to high costs of building additional production Likely to come under further regulatory volatility and very high flammability. lines in the US, means this alternative is pressure in future. also not economically feasible. Presents control difficulties due to high Is not possible to use for a continuous volatility. process. Dichloro- Possible on basis of lab trials. No - The large expected capital cost to Suspect Carcinogen. Yes methane Not technically feasible without switch and loss in profits compared to the Likely to come under further regulatory (methylene considerable further research and costs of building additional production pressure in future. chloride) commercial testing for customer lines in the US, means this alternative is acceptability of the product. also not economically feasible.

Tetrachloro- Possible on basis of lab trials. No - The large expected capital cost to Suspect Carcinogen. Yes ethylene Not technically feasible without switch and loss in profits compared to the Likely to come under further regulatory (perchloroet considerable further research and costs of building additional production pressure in future. heylene) commercial testing for customer lines in the US, means this alternative is acceptability of the product. also not economically feasible.

Vertrel® Possible on basis of lab trials. No - The large expected capital cost to No. However, little data available. Yes SDG Recovery could be problematic. switch and loss in profits compared to the Not technically feasible without costs of building additional production considerable further research and lines in the US, means this alternative is commercial testing for customer also not economically feasible. acceptability of the product.

HFE 72DE Possible on basis of lab trials. No - The large expected capital cost to No. However, little data available.. Yes 1,2- Recovery could be problematic. switch and loss in profits compared to the Not technically feasible without costs of building additional production

considerable further research and lines in the US, means this alternative is commercial testing for customer also not economically feasible. acceptability of the product. n-propyl Possible on basis of lab trials. No - The large expected capital cost to SVHC (repro. toxin). Flammable Yes bromide (1- Not technically feasible without switch and loss in profits compared to the bromopropa considerable further research and costs of building additional production ne) commercial testing for customer lines in the US, means this alternative is acceptability of the product. also not economically feasible.

D-Limonene Possible on basis of lab trials. No - The large expected capital cost to Flammable. Yes Likely to be problems with solvent switch and loss in profits compared to the Dangerous to the environment. recovery and recycling. costs of building additional production lines in the US, means this alternative is also not economically feasible. Acetone No – does not perform function to No - The large expected capital cost to No Yes remove process oil effectively. switch and loss in profits compared to the costs of building additional production lines in the US, means this alternative is also not economically feasible.

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As addressed in this Section, consideration of an alternative solvent should take into account the risks of using the substance in the specific process. A key consideration that is closely associated with this is the regulatory status and pressures on a potential alternative (since these are related to hazard and risk). The introduction of a potential alternative into a process requires considerable time and money to test the technical feasibility at a commercial scale and to ensure consumer approval of the final product. It would therefore be a considerable business risk for a firm to invest in process-change that would have a very limited life-span. In the case of some solvents, notably n-hexane, this could mean not only rebuilding of a facility but relocation of a plant all of which would come at considerable cost which is judged to make the possibility to convert to the use of n-hexane not economically feasible.

As indicated in Section 4, solvent substances that showed some promise in ‘bench-scale’ trials are also under some regulatory scrutiny in the EU and elsewhere. Although not perhaps meeting the current specific criteria for SVHC and therefore not potentially subject to the need for authorization today, this may change in the future, this could easily be the case for n- hexane which is a neurotoxin and a reproductive toxin. Indeed, recent years have seen TRI change from classification as a Cat. 2 carcinogen to a Cat. 1B carcinogen today the status of TRI as a non-threshold carcinogen has been adopted by ECHA for the purpose of assessing authorisations applications. Tetrachloroethylene and methylene chloride are both currently classified as carcinogens (Category 2, H351), and subject to evaluation under CoRAP (now concluded) and restrictions, respectively. It is therefore unlikely to be sustainable in terms of business planning to invest in substances with these risk profiles that (based on their properties) would present similar challenges for emission/release control as TRI. The implementation of a solvent alternative must therefore take account of possible regulatory changes that would have a severe impact on the use of the substance in the future. It is clear that for substance that showed the possibility for being alternatives to TRI in the ENTEK process, n-hexane, tetrachloroethylene and methylene chloride that the regulatory and risk profile of these substance now and in the future would rule them out as sensible options. In particular for n-hexane since it is a particular focus due to its known use for the process of making PE separators the financial implications of converting the facility or relocating the facility have been set out and it has been concluded that it would not be economically viable for ENTEK to convert or rebuild or relocate its UK plant to use n-hexane.

6.2 ACTIONS AND TIMEFRAME FOR IDENTIFICATION AND DEVELOPMENT OF A SUITABLE AND AVAILABLE ALTERNATIVE.

There are a number of technical barriers to the use of an alternative solvent in the ENTEK continuous separator manufacturing process. Even with no alternative currently technically feasible, we consider how an industrial-scale trial of a solvent could be implemented and describe that in terms of actions and associated timescales. First ENTEK must analyse interaction between the alternative solvent and its equipment and likely retrofit its equipment to adapt the metallurgy to the specific solvent and develop any appropriate solvent recovery systems. ENTEK must then gain customer approval of its process and resulting separator products made with the alternative solvent. To gain such approval, ENTEK must make a significant quantity of samples for its various customers to test in the production of batteries. For the customer qualification of the process, the samples must be made on the production equipment that will be used to manufacture separators on an ongoing commercial basis. To avoid cross-contamination with TRI, these samples can only be run during a temporary plant shutdown period using the existing plant infrastructure. Concurrently, ENTEK would undertake the engineering study to design the converted plant and the trial results would feed into that engineering work. A 78 week program is estimated for the time needed to get feedback on each trial from customers. ENTEK would be required to conduct at least three separate trials to gain broad customer approval. In order to continue to meet current customer demand, plant shutdowns of a sufficient duration are only scheduled in the month of December. The total elapsed time in this plan is estimated to be a minimum of nine years. This estimated time frame would not be adequate if ENTEK received any negative feedback from customers or if customers delay in their willingness to participate in the trials. It is noted that no replacement solvent is currently technically feasible without trials and extensive restructuring of the plant, and possible candidate replacement solvents each pose similar or greater risks than TRI.

A plan, to indicate the main actions and timescales that would be required in order to investigate the technical feasibility and commercial viability of two alternatives solvents, is set out below.

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Table 6.2 Solvent Conversion Plan ENTEK Newcastle Facility

Estimated Task Duration (weeks)

1.Lab-scale Research & Development 60 Initial Candidates: Dichloromethane, Tetrachlorooethylene Extraction Rate Drying with Steam

 Shrinkage

 Physical Properties

 Electrical Properties Drying Without Steam

 Shrinkage

 Physical Properties

 Electrical Properties Establish Screening Plan for Additional Candidates

2.Pilot Scale Extraction and Drying 78 With Steam

 Shrinkage

 Physical Properties

 Electrical Properties

 Samples to Customers for Preliminary Evaluation Without Steam

 Shrinkage

 Physical Properties

 Electrical Properties

 Samples to Customers for Preliminary Evaluation Preliminary Estimate of Parameters Needed for Tooling Design

3.Engineering Analysis - Plant Trial 52

Identify all Physical and Thermodynamic Properties Required for Detailed Design

 Evaluate Available Data and Fill in Database

 Estimate Properties, as needed

Identify all Current Unit Operations

Develop Mathematical Models for all Unit Operations

 Estimate Model Accuracy

 Identify Where Physical Testing is Needed

Develop Physical Testing Methods as Required

Identify Need for Upgraded/New Unit Operations

 Preliminary Design of Upgraded/New Unit Operations

 Preliminary Cost Estimate for Upgraded/New Unit Operations

Material Balance

Energy Balance

Production Scenario: Volumes and Yields

Economic Analysis of Alternatives

Implementation Plan for Conversion

4.Research and Development Confirmation of Engineering Design 20

Plant-Level Trial

Trial Plan

Design of Upgraded/New Unit Operations for Trial

Build/Procurement of Required Unit Operations and Equipment

 Installation

 Start-Up

 Run Trials

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Verify/Refine Tooling Design Parameters

5. 1st Roll Samples and Preliminary Qualification 4

Production Part Approval Process (PPAP) for Process and Products

Identify End-Users for PPAP Trials

Identify Starting-Lighting-and Ignition Profiles for PPAP

Identify Industrial Profiles for PPAP

Build Required Tooling

Build SLI Profiles

Build Industrial Profiles

Send Roll Samples and Process Capability Data to Customers

Obtain PPAP Qualification from Customers

Build Samples for Customers

Battery Trials: Bench and Field Testing 78

6. 2nd Roll Samples and Preliminary Qualification 8

Production Part Approval Process (PPAP) for Process and Products

Identify End-Users for PPAP Trials

Identify Starting-Lighting-and Ignition Profiles for PPAP

Identify Industrial Profiles for PPAP

Build Required Tooling

Build SLI Profiles

Build Industrial Profiles

Send Roll Samples and Process Capability Data to Customers

Battery Trials: Bench and Field Testing 78

7.Final Roll Samples and Full Product/Process Qualification 4

Production Part Approval Process (PPAP) for Process and Products

Identify End-Users for PPAP Trials

Identify Starting-Lighting-and Ignition Profiles for PPAP

Identify Industrial Profiles for PPAP

Build Required Tooling

Build SLI Profiles

Build Industrial Profiles

Send Roll Samples and Process Capability Data to Customers

Obtain PPAP Qualification from Customers

Build Samples for Customers 78

Battery Trials: Bench and Field Testing

SLI Product Approval from ENTEKs Customer's Customers

Industrial Product Approval from ENTEK's Customer's Customers

8.Engineering Analysis - Conversion 13

Identify all Physical and Thermodynamic Properties Required for Detailed Design

Identify Need for Upgraded\New Unit Operations

Preliminary Design of Upgraded/New Unit Operations

Preliminary Cost Estimate for Upgraded/New Unit Operations

 Material Balance

 Energy Balance

Production Scenario: Volumes and Yields

Economic Analysis of Alternatives

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Implementation Plan for Conversion

9.Conversion

Build/Procurement of Plant-Wide Required Unit Operations and Equipment 104

Installation 30

Start-Up 15

Qualification of Plant-Wide Process 15

Total Time 12.4 years

The conclusion from this table is that a minimum of 12 years would be required to convert to a substitute solvent. (It should be noted that the table above sets out the best case scenario and does not account for likely barriers such as regulatory compliance requirements such as permitting, etc.)

Confidential

APPENDIXES AND ANNEXES

(Include other information that you consider relevant for the Analysis of Alternatives, e.g., list of data sources, data collection approach, organisations consulted, summary of assumptions, etc.)

ANNEX I – JUSTIFICATION FOR CONFIDENTIALITY CLAIMS

Blanked out item Page Justification for blanking reference number

Text below table 14/15/16 Confidential R&D 1.2 See justification text below.

4.2.1 Research 44 Confidential R&D and Development See justification text below. 4.2.2 57-66 Confidential R&D Manufacturing Alternatives See justification text below.

6.1 second 146 Confidential R&D paragraph See justification text below.

Text below table 182 Confidential R&D 6.2 See justification text below.

Justification for Confidentiality

1. Demonstration of commercial interest ENTEK is expending material resources on the development of separator technologies and manufacturing processes. Each unique approach is not yet patent protected. The separator technologies and manufacturing processes for lead acid separators that are being investigated are entirely unique and whilst in the very early stages of development, ENTEK are confident that further research and development efforts could provide ENTEK with a distinct competitive advantage.

2. Demonstration of potential harm

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The exceptions referred to in Article 4 of regulation (EC) No 1049/2001 are relied upon by ENTEK in justifying the confidential treatment of information. Article 4 (2) specifically makes provision for ECHA to refuse access to information or documents where disclosure 'would undermine the protection of commercial interests of a natural or legal person, including intellectual property unless there is an overriding public interest in disclosure'.3

The information that is subject to the request is highly confidential business information relating to R&D activity that is not in the public domain. Disclosure of the information would damage ENTEK’s prospects of obtaining patent or other intellectual property protection for candidate processes in future by making it publicly known. Additionally, ENTEK has certain pending patents and any disclosure could result in a waiver of ENTEK’s intellectual property rights. This in turn would adversely affect ENTEK's return on its investment in R&D in new separator technologies and manufacturing processes. Publication of the relevant information would also damage ENTEK's commercial interests by disclosing its R&D strategy to the public, removing the potential competitive advantage that it represents. It is probable that ENTEK's actual and potential competitors would quickly gain access to this information through their routine market intelligence activity. They are likely then to use this information to 'free-ride' on ENTEK's investment by replicating its activity, or to disrupt the development of the new technology. Furthermore, the information in question is highly confidential and relates to ENTEK's future commercial strategy in the markets where it operates. It is therefore precisely the type of information that EU and national competition laws do not want companies disclosing to their actual or potential competitors, whether directly or via a third party such as ECHA, because of the risk that competition would be restricted or distorted as a result. More generally, because of the commercial and legal risks summarised above, ENTEK notes that any policy of publication by ECHA of non-public R&D information would be likely to have a chilling effect on innovation and competition in this sector over time. The incentives for applicants to invest in developing alternatives to their authorised substances will be significantly reduced going against one of the main objectives of REACH namely, to enhance competitiveness within the market place4. It is understood that in considering the justification for confidentiality the Agency will weigh up the private commercial interests of ENTEK against the general public interest in ensuring transparency of information, and the specific public interest guaranteed by REACH in ensuring a high level of protection of human

3 Regulation (EC) No 1049/2001 Of The European Parliament And Of The Council of 30 May 2001 regarding public access to European Parliament, Council and Commission documents. 4 Decision of the Chairman of the Board Of Appeal of the ECHA Joined cases A-011- 2013 to A015-2013;

health and the environment5. That being said it is essential that the agency take into consideration the fact that there is no public or consumer exposure to any of the separator technologies or manufacture processes that would justify an 'overriding public interest' in disclosure of ENTEK's R & D activity.

3. Limitation to validity of Claim Research and development are very much in the early stages with further work to be carried out around development, cost analysis and positive battery test results. ENTEK therefore request for all information concerning ‘Research and Development' to remain confidential until such time that the information is disclosed by ENTEK itself or published or otherwise becomes part of the public domain through no fault of ECHA but only after it becomes part of the public domain.

5 Decision of the Chairman of the Board Of Appeal of the ECHA Joined cases A-011- 2013 to A015-2013.

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