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Home , Cif, Fluorine, Fluorine compounds, Monel, Monofluoride, Oxygen difluoride

Elemental

Contents

1 Introduction...... 4

2.1 Technical Application of Fluorine...... 5

2.2 Electronic Application of Fluorine...... 7

2.3 Fluorine On-Site ...... 8

3 Specifications...... 9

4 Safety...... 10

4.1 Maintenance of the F2 system...... 12

4.2 First Aid...... 13

5.1 Chemical Properties...... 14

5.2 Physical Data...... 15

6 Toxicity...... 18

7 Shipping and Transport...... 20

8 Environment...... 22

8.1 Product Stewardship for F2...... 22

8.2 Solvay Way...... 23

9 Solvay – The Specialists for ...... 24

10 Bibliography...... 26

Solvay Special Chemicals Elemental Fluorine 3 1 Introduction

The element fluorine (: F) In the field of organic fluorine chemistry belongs to the . The name the development of new products con- “fluorine” derives from the “fluor- tinues. Fluorine containing polymers are spar”. highly valued for their remarkable prop- Fluorine is the most reactive element in erties. The most known examples are the . This is why fluorine oc- polytetrafluorethylene (PTFE) and polyvi- curs in nature only in chemically bonded nylidene (PVDF). Fluorinated or- form as fluoride. ganic compounds are also used as:  in Lithium ion batteries Fluorspar (CaF2) was added to the to lower their and thus  Solvents make them more fluid (hence the name,  from the Latin = fluere, “to flow”). Among the , fluorine is the element that  Pharmaceuticals occurs most abundantly in nature. Solvay  Pesticides owns two fluorspar mines in Namibia and  Lubricants Bulgaria to secure the raw material for its fluorine production sites in Europe and  Blood substitutes Asia.  The manufacture of fluorine, together with  Starting material for organic synthesis its inorganic and organic compounds has And many more. given remarkable new to fluorine chemistry. Typical areas of application Today the main industrial applications for ­include , aluminum electroly- elemental fluorine are fuel tank fluorination sis, the manufacture and processing of for cars and cleaning of CVD tools during , abrasives, electroplating process- the production of semiconductors. es, ­ceramics, electrical engineering, elec- trochemical elements, energy storage, nuclear technology, flat panel production, photovoltaic production and semiconduc- tor production.

Fig. 01: The raw material: fluorspar crystal from the Solvay mine in Okorusu, Namibia.

4 Elemental Fluorine Solvay Special Chemicals 2.1 Technical Application of Fluorine

Fluorine is widely used in applications for the direct reaction with organic sub­ stances. The reaction between the pure fluorine and the organic substance results in the formation of the thermodynamically more stable end products CF4 and HF:

CnH2n + 2 + (3n + 1) F2 -> – E nCF4 + (2n + 2)HF

This entails that the aim in all methods of fluorine treatment is to minimize the for- mation of by-products or waste products as far as possible. At the same time it is essential to maximize the yield of the tar- get compound. An optimum reaction is achieved through control of the process parameters:  Concentration of reagent blow moulding process (in-line treatment)  Reaction temperature so that only the inner walls are treated. Fig. 02: Fluorinated plastics for high ­performance applications.  Reaction time. Off-line fluorination, carried out when blow-moulding is completed, is a discon- In simplified terms, the various processes tinuous process. Fluorination may be con- used may be divided into two categories: fined to the inner walls of the container;  Single- fluorination alternatively, both inner and outer walls  Two-phase fluorination. may be treated. In another process, plas- tic surfaces are treated with elemental flu- In the single-phase method, the sub - orine i.e. in solution with inert solvents or stance to be fluorinated and the fluori- solvent mixtures. nating agent (F2 diluted with an inert ) are present in one and the same phase. Plastic Processing A number of different variants have been The finishing of plastic surfaces is of great developed for both the gaseous-phase significance in the foil industry. For the and liquid-phase fluorination technique. production processes of gluing, coating, In the case of two-phase fluorination the laminating, painting and printing good ad- compound to be fluorinated and the fluori- hesion is absolutely essential. nating agent are present in different phas- During the nineteen eighties a continuous es. As early as 1954, Rudge filed a patent fluorinating process was developed for application in which the fluorination of pol- the treatment of foils. With this method the yethylene surfaces by means of a fluorine/ surfaces of foils can be activated, on one inert gas mixture was described. A whole or both sides, independent of the size and series of processes specifically designed length of the rolls, in a continuous process for direct fluorination of plastic surfaces from roll to roll. The fluorination of almost have subsequently been developed, some all types of foils consistently results in a of them differing in terms of the steps in- significant increase in surface energy. volved. Foam sheeting can be treated in a continuous fluorination process. Selective fluorination of hollow plastic containers can now be carried out during the actual

Solvay Special Chemicals Elemental Fluorine 5 Fluorination of Tanks For this reason the automobile indus - try performs the fluorination process to , the plastic employed for the reduce the permeability of fuel through production of fuel tanks and containers petrol tanks walls. A layer of CF will be for different chemicals, has often the dis- 2 formed. The permeation of fuel through advantage of being relatively permeable to polyethylene fuel-container walls can be the stored vapour. This undesirable prop- dramatically reduced by the chemical erty to permeate to the extent of a process of forming a layer which is almost few grams per day from a PE container. impermeable.

[CF2]n 100% < 1 %

Untreated Tank Fluorinated Tank

Fig. 03: Permeation in plastic fuel tanks.

inner wall

outer wall ~ 10 µm

~ 3 mm

Fig. 04: Cross-Section of a container wall with a fluorinated inner layer.

6 Elemental Fluorine Solvay Special Chemicals 2.2 Electronic Application of Fluorine

Solvay is producing F2 electronic grade in two in and South Korea. This is unique in the world so far and ena- bles the highest possible supply security among all F2 high purity manufactures. As fluorine is the most reactive element, it is obvious that it is a strong oxidizer. This ability is useful for the removal of - (SiO2) and Siliconnitride (Si3N4). This process is done in a CVD Tool (Chemical Vapour Deposition) and the residues of these compounds are deposited at the chamber walls of these tools. After remov- ing the wafer, the tool has to be cleaned with fluorine containing like NF3, SF6, CF4, C2F6 and others. These gases however have . An environmental friendly alternative Fig. 05: Chamber cleaning in the semiconduc- tor industry with F mixtures. to these cleaning gases are F2/N2 or Ar, Kr as mixtures are used. The radiation 2 F2/N2/Ar mixtures. Fluorine reacts spon- of these gas mixtures is reflecting the min- taneously already at ambient temperature imum size of the structure. with deposits of silicon and all its com- F2 Mixtures as pounds to generate SiF4, which is gase- ous and can be therefore easily removed Replacement for Other Cleaning from the chamber to be cleaned. In order Gases to have the reaction better controlled fluo- F2 in dilution with nitrogen at 20 % is a rine is diluted with nitrogen. very competitive cleaning gas for cleaning CVD tools. Tests at the Fraunhofer Insti- F /N Mixtures 2 2 tute in Munich have proven the full com- Within the production process of semi- patibility of the F2 mixtures on the AMAT P conductors, one process step is the etch- 5000 tool. It has been demonstrated that ing process. Within this step a structure it is possible to reduce the cleaning time is etched into the semiconductors. The of SiO2 and Si3N4 up to 44 % vs. CF4 and step takes place in a so called etcher. up to 21% vs. NF3 based on the cleaning The etched material is as well deposited recipes. on the wall of the etching tool. Therefore The fluorine gas consumption has also a separate process to clean this tool is re- been drastically reduced compared to quired. In most of the cases it is cleaned both NF3 (49%) and CF4 (in this case 1 kg with NF3, but there are etchers on the F2 can substitute 35 kg of CF4). market using F2/N2 mixtures with high pu- In addition to the savings, the applied F2 rity. ­Solvay is producing this F2/N2 mixture process will reduce the environmental im- with high purity. A basic specification can pact enormously, because the GWP of F be seen on page 9. 2 is ZERO, compared to the values of 7,390 F2 Gas mixtures for CF4 and 17,200 for NF3. /1/ Within the production of semiconduc- tors, the lithographic process is one of the most important ones, because here the structure of the wafer is created. In the higher technology nodes below 128 nm wavelength with F2 and Ne,

Solvay Special Chemicals Elemental Fluorine 7 2.3 Fluorine On-Site Plant

The development of the F2 on-site con- cept for the production of fluorine by of hydrogenfluoride in an on- site production-unit is based on existing Solvay F2 production-technology. The onsite plant concept was developed for high fluorine demands as for example photovoltaic and flat panel manufacturers. The concept is based on a skid mounted F2 on-site production plant. This F2 elec- tronic grade onsite modular approach in- cludes the scale-down of common tech- nology parts and process improvements. It allows a safe and reliable production of F2 e-grade on-site, delivered over-the- fence to the customer on demand. The unit is designed for connection to stand- ard utilities on customer site. Base case is a module with 100 to/a F2 capacity. Detailed safety studies were performed on the F2 skid-mounted concept. Invento- ries of HF and F2 in the unit are limited and pressures for HF and F2 are low. Gas de- tection sensors for HF and F2 are installed

Fig. 06: F2 onsite plant. and the skids are ventilated with connec- tion to the emergency response scrub- ber system. Additionally, scrubbers for HF abatement and F2 off-spec destruction are included in the concept. A new concept for HF supply as raw ma- terial for the process and handling is real- ized via transportable HF tanks à 2 to HF per tank. Analysis equipment is installed to monitor the impurities in the fluorine, like HF, CF4 and others.

Fig. 07: Solar panels.

8 Elemental Fluorine Solvay Special Chemicals 3 Specifications

Specifications for T-grade Fluorine (Technical Grade)

Characteristics Unit Specification

F2 v o l % ≥ 99.0 HF v o l % ≤ 0.2

Specifications for T-grade Fluorine (20) / Nitrogen (80)

Characteristics Unit Specification

F2 content v o l % 19 . 5 – 2 0 . 5

N2 content v o l % 7 9 . 5 – 8 0 . 5 HF v o l % ≤ 0.05

Specifications for T-grade Fluorine (10) / Nitrogen (90)

Characteristics Unit Specification

F2 content v o l % 9 . 5 – 10 . 5

N2 content v o l % 8 9 . 5 – 9 0 . 5 HF v o l % ≤ 0.05

Specifications for E-grade Fluorine (20) / Nitrogen (80) (Electronic Grade)

Characteristics Unit Specification

F2 content v o l % 19 . 5 – 2 0 . 5

N2 content v o l % 7 9 . 5 – 8 0 . 5 HF vppm ≤ 500

CF4 vppm ≤ 160 There are other F2/N2 mixtures and ­ F mixtures available upon O vppm ≤ 400 2 2 ­r e q u e s t .

Vol. % 10 0 %

9 0 %

8 0 %

70 % N2 6 0 % 8 0 % N2 F2 112 b a r 9 0 % 5 0 % 10 0 % 13 5 b a r 2 8 b a r 4 0 %

3 0 %

2 0 % F2 10 % 2 0 % F2 10 % 2 8 b a r 15 b a r 0 %

Fig. 08: Pressure of the components.

Solvay Special Chemicals Elemental Fluorine 9 4 Safety

When handling fluorine it is essential to The size of side adapters are regulated by Basic needs for : parts have observe the rules and regulations laid national and international standards. Cyl- to be cleaned carefully, parts must be oil down by the government of the respec- inders, bundles and tube trailers are de- and grease free and dry, system must be tive country. “Technical Regulations for signed for safest handling. e.g. bundles proven free of leakages and all parts must Hazardous Materials” define the latest are equipped with pneumatic for be carefully passivated. government safety standards relating to remote controlling the gas flow. Workplace and Personnel all aspects on the use and handling of Leakage Check hazardous industrial materials including Fluorine should be handled only by technical advice, occupational medicine, Already small leakages are technically de- ­qualified, well-trained personnel! hygiene and transport. The extreme reac- tectable. Leakages can be detected by When working on components or ­systems tivity of fluorine makes special safety pre- gas monitors. Fluorine can be recognized that contain fluorine! by F odor at ~ 0.1 ppm (TLV level 1 ppm). cautions essential. To ensure safe han- 2 1. Safety goggles must be worn at all dling of this product, we recommend an An easy method to check connections times! extended safety code, based on industrial can be done by using a iodide 2. Heavy duty clean neoprene (or leather) recommendations and government regu- paper. In the case of existing small fluorine gloves must be worn at all times! lations. releases the paper will change color from Due to the reduced oxidizing behavior, to black (this relates to a concen- 3. Protective helmets with visors made fluorine mixtures (mixed with inert gas- tration of approx. less 1 ppmw). of a chemically resistant material must be worn if fluorine valves need to be es) with lower F2 concentrations than Passivation 30 % show some difference in handling ­manipulated manually! Fluorine reacts with all materials, depend- and material use compared to elemental 4. Personnel must refrain from eating, ing on temperature or other properties. ­fluorine (F ~ 100 %). drinking, smoking and the use of 2 This reaction could be very fast or slow. ­inhalants while handling fluorine. Handling of F2 100 % and To prepare metal parts for fluorine trans- ­Mixtures Thereof port these materials need to be passivat- 5. Adequate ventilation must be provided ed beforehand. Therefore a smooth fluori- in all enclosed spaces where fluorine Fluorine, as the most electronegative el- nation under regulated fluorine conditions is handled or processed. ement in the periodic system, is a highly is necessary. Passivation will result in a reactive substance. The extreme reactivity 6. Emergency showers and eye wash metal fluoride containing surface prevent- of fluorine makes special safety precau- stations should be installed at easily ing raw metal surfaces against fast oxida- tions essential. accessible places within the working tion of fluorine and fluorine burning. New area. Fluorine can be transported in com - passivation investigations conclude that pressed form in an approved gas cylinder 7. Personnel working on a fluorine con- post heating to ~ 200 °C will increase the at 30 bar (435 psi) following the interna- taining system must always work in solidity of the passivation layer. /2/ tional rules for transport. Gas cylinders for pairs. Everyone should remain within F2 need a recurrent approval every five sight and calling distance at all time. years by a surveyor. Checks of valves, connections and the condition of cylinder surfaces need to be carried out at every filling.

Fluorine 100% Fluorine Mixture < 20 % F2

Metal burn can occur in case of In clean tubes metal burns of ­impingement or increased flow rate F2 mixtures are very unlikely Only Ni ­alloyed recommended is recommended for use for ­higher temperatures at higher temperature applications

Flow rate must be limited No flow rate limitation necessary

185 ppm (or ml/m3 = LC50) 925 ppm (or ml/m3 = LC50) (LC = Lethal Concentration) calculated Fig. 09: Safe handling comparison./3/

10 Elemental Fluorine Solvay Special Chemicals Pressure regulator  Higher concentrated F2 mixtures need to be scrubbed using a wet scrub-  regulators with special sealing ber with ~ 20% KOH solution, or for work with 100 % fluorine are avail- materials (e.g. Al O ), which react with able from the market 2 3 F2 in a compatible way. In some cases  Monel regulator is recommended OF2 will be generated – this can be for fluorine nitrogen gas mixtures avoided by using oxidative substanc- > 20 % F2 es.  Stainless steel can be used for fluorine Sealing compounds mixtures < 20 % F2 up to 200 bars For fluorine and fluorine mixtures in inert Pressure Determination gas at concentrations equal to or below  Special edition­ for fluorine – 20 % of fluorine, Monel, , or Monel gauge stainless steel systems can be used. Scrubber PTFE is used, out of the flow path for sys- tems of fluorine and fluorine mixtures, The handling of scrubbers needs to be such as for valve packing, gasket mate- split in two applications of fluorine use. rial and pipe thread sealant. PTFE may be  CaCO3 solid absorber can be used used up to 10% F2 concentration. if fluorine concentration is between 1–2% in the application (eg. the use of fluorine in the online fluorination of petrol tanks). In­ order to use CaCO3 scrubbers properly, the waste gas stream should be humidified.

Fig. 10: Material compatability. /3/

Material F2 Concentration Application

Monel and Nickel > 4 bar F2 100 % Piping

Stainless steel < 4 bar F2 100 % Piping (up to 30 bar F2 systems with additional safe guard)

Stainless steel < 4 bar F2 in mixtures with Piping for 20 % F2 up to 150 bar inert gases

Carbon steel > 1 bar or less F2 100 % Piping (gas cylinder up to 30 bar)

Brass < 4 bar F2 100 % Valve material (caution, as they are suscepti- ble to de-zincification)

Copper < 4 bar F2 100 % Seals and washer

Aluminium and Aluminium Alloys < 4 bar F2 100 % Tests at Solvay showed good resistance and ductibility for use as Al gaskets up to 200 °C

PTFE < 10 % F2 Piping

Filled PTFE < 10 % F2 Regulator valve seat

Solvay Special Chemicals Elemental Fluorine 11 4.1 Maintenance of the F2 system

During maintenance any contamination Install blank flanges, pipe caps etc., not use magnets or slings to lift gas cylin- and exposure to moisture must be avoid- on any open ports of a F2 system. ders. Do not use the valve protection cap ed. Moisture can not only be a possible Piping systems that use fluorine mixtures to lift a gas cylinder. It is necessary to take source of F2 ignition but also can hydro- will become contaminated with a pow- precautions to prevent gas cylinders be- lyze the passivation layer and result in the dery residue over time. This material is ing dropped or striking each other or other formation of . The hydro- composed of metal fluorides and should objects. Dropping or striking may damage gen fluoride can to accelerated cor- be handled with caution since the materi- the cylinder valve, which could turn the cyl- rosion in the system. It is not advisable to al may contain hydro­fluoric acid. It should inder into a dangerous torpedo with the use a vacuum pump or fan to allow air to also be assumed that any li­quids or mois- potential to destroy property and/or injure be sucked into a fluorine system. To mini- ture found in these fluorine systems would personnel. mize air infiltration when a system must contain hydrofluoric acid. This material is Gas cylinders should be properly secured be momentarily opened, consider the use very corrosive to many other materials of at all times to prevent tipping, falling or roll- of low flow inert gas purge as protection construction. ing. They can be secured with straps or against moist air infiltration. If the system is exposed to at- chains connected to a wall bracket or other mosphere for extended periods fixed surface, or by using a cylinder stand. ­re-drying and re-passivation is Store cylinders in a cool, dry, well- ­recommended as a safeguard prior ventilated, -resistant area in to re-introducing F2 at full operat- ­accordance with local regulations. ing pressure. A cylinder storage area should be located Storage in an area where the cylinders will not be Storage conditions should always be in knocked over or damaged by falling ob- line with the local fire department regula- jects. tions. According to pressure vessel regula- When a cylinder is not being used, the tions, compressed gases are substances valve should be closed and the valve pro- whose vapour pressure at 50 °C is above tector secured in place. 3 bar. In line with the regulations governing Inspection pressure vessels these gases may only be transferred to approved and labelled gas- Gas cylinders should be visually tight gas cylinders or containers. Wherever ­inspected to ensure that they are these containers are handeld, there must in a safe condition. be no open or heat sources (e.g. If necessary, a cylinder can be tested ul- Fig. 11: Twelve cylinders building a bundle. hot metallic surfaces) or reactive products. trasonically for hidden defects. Leaking An important precondition is strict adher- and malfunctioning regulators, cylinder ence to the threshold limit value (TLV). valves or other equipment should be tak- Handling en out of service. A cylinder’s contents should be identified at all times. Cylinder Be sure to close all cylinder valves status should also be identified; for exam- when not in use. The valves of emp- ple, whether the cylinder is full, empty or ty cylinders should also be closed. in service. Ensure that gas cylinders are transported so that they do not tip, fall or roll. Gas cyl- SDS inders should be secured to the cylinder Consult the appropriate SDS for trucks or carts. Regulators should be re- ­detailed information on the chemical moved and valve protection caps should contained in the gas cylinder. be secured in place before moving cyl- inders. Also, cylinder valves should be Specific chemical handling and storage closed before moving cylinders. Appropri- precautions will be outlined in the SDS. ate lifting devices, such as cradles or nets, The SDS will also have specifications for must be used when using a crane, hoist appropriate personal protective equipment or derrick to transport gas cylinders. Do for worker protection.

12 Elemental Fluorine Solvay Special Chemicals 4.2 First Aid

Rescue Eyes: First protect yourself and afterwards bring  Rinse with fresh water or better cal- injured people out of the hazardous area. cium gluconate 1% solution in physi- Place injured people in quiet, uncontami- ological serum. nated and well ventilated area. Skin: Contaminated Bodyparts  Remove contaminated clothes im- mediately, under shower if necessary. Inhalation: Wash the affected skin with running  Give fresh air immediately, or water. Immediately apply glu- cardiopulmonary resuscitation if nec- conate gel 2.5 % and massage into essary. affected area using rubber gloves;  Keep insured people warm (blanket). continue to massage while repeatedly  If possible perform therapy with (inhal- applying gel until 15 minutes after pain able corticoid) e.g. Auxiloson™. is relieved.  In all cases consult with a physician –  Keep insured people warm (blanket). take insured people to hospital.  In all cases consult with a physician – take insured people to hospital.  If possible use O2 portable cylinder nebulizer during emergency transport. If daily work with fluorine is your business, Corrugated tubing and mask; 500 cc. an informative precaution meeting with of a 2.5 % nebuliz- the next hospital should take place, be- ing solution. fore an accident happens. /4/

Fig. 12: First Aid set.

Solvay Special Chemicals Elemental Fluorine 13 5.1 Chemical Properties

Fluorine is an almost colourless gas. ln Reaction with water Reaction with other non-metals dense concentrations and in the liquid Fluorine reacts with water to form oxygen, , silicon, , sulphur, sele- state it is seen to have a pale greenish­ and fluoride. nium and tellurium all react with fluorine yellow colour. lt has a characteristic odour, Small quantities of ozone and hydrogen to cause and the formation of similar to a mixture of ozone and . peroxide may also be formed. Passing fluorides of the highest valency. Normal- As the most reactive of all the elements fluorine through dilute ly, oxygen and nitrogen do not react with and the most powerful known oxidizing or potassium hydroxide is the standard fluorine, but reactions may occur under agent, fluorine is able to react with almost method for preparing oxygen difluoride. special conditions, such as dark electrical all elements and compounds, with the ex- Mixtures of fluorine and water vapour are discharges, plasma arcs, etc. Of the noble ception of lighter, noble gases and fluo- potentially explosive. gases, and react readily with rides of the highest valency. Fluorine re- fluorine while reacts only under acts with many substances even at room Reaction with halogens special conditions. temperatures, sometimes explosively, and lf fluorine is combined with any of the oth- often accompanied by combustion. er elements in Group VII of the periodic Reactions with organic compounds­ Reaction with hydrogen table, it leads into an highly exothermic re- action, from which a series of All organic compounds react with fluorine. Fluorine and hydrogen react with extreme compounds are formed (CIF, CIF3, CIF5, lgnition usually occurs, and under certain violence, in a highly exothermic reaction BrF, BrF3, BrF5, IF, IF3, IF5, IF7). Halogen circumstances the reaction may be ex- [∆ H° HF (g) 25°C = – 271.7 kJ/mol]. Even fluorides are also widely used as fluorinat- plosive. The end product of the reaction at very low temperatures (solid fluorine, ing agents. is invariably tetrafluoride. Under liquid hydrogen) a violent reaction is pro- suitable reaction conditions, organic com- duced. Reaction with carbon pounds may be partially or completely Reaction with silicium Carbon reacts variously with fluorine, de- fluorinated with elemental fluorine, without pending on its structure and surface con- Fluorine reacts significantly with silicon at causing destruction of the . figuration. Active carbon may ignite at 120 °C to SiF . Simultaneously a chemi- With the exception of , 4 room temperature in presence of fluorine; luminescence can be observed. The re- all fully halogenated carbon compounds the resulting reaction produces CF4, C2F6 action with silicon is increasing with in- also react with fluorine. ln many cases, and small quantities of higher perfluori- creasing partial pressure of fluorine, at the however, this reaction proceeds so slowly nated . lf the mixture does not ig- same time the intensity of the chemilumi- that some of these materials, such as pol- nite, the fluorine is absorbed and carbon nescence is reduced. An increase of the ytetrafluoroethylene, can be used as con- (CF)x formed. This may de - fluorine reaction rate with silicon can be struction materials or sealants, providing compose explosively at higher tempera- achieved by increasing the temperature to that certain reaction ­conditions are main- tures to form carbon and 600 °C, but less relevant compared to the tained. compounds. When combined with graph- partial pressure increase of fluorine. ite, fluorine forms graphite fluorides, which Reaction with metals are likewise liable to decompose violently Fluorine attacks metals at room tempera- SiF2(chemisorbed) + F2 ↔ [SiF2·F2] at higher temperatures. ture, but some metals and alloys form a [SiF ·F ] SiF + F SiF 2 2 surf → 2 2 (chem.) → x At temperatures below 500°C, or in the protective layer of fluoride that effectively (x > 2) presence of metal fluorides, fluorine re- prevents further attack. When deliberately SiF2 + F 2 → SiF3* + F → SiF3 + F acts smoothly with carbon to form CF4 induced, the process is known as passi- and higher perfluorinated alkanes or cy- SiF3 * → SiF3 + hv vation. Treated in this way, some metals cloalkanes. and alloys (Mg, Al, Fe, Ni, Cu, Cr, etc.) be- SiF3* + F2 → SiF3 + F2 /5/ come valuable materials for the handling of elemental fluorine.

14 Elemental Fluorine Solvay Special Chemicals 5.2 Physical Data

Parameter Value Unit Bibliography 37.9 97 g/mol /6/ Transition point – 227.61 °C /6/ Melting point – 219.62 °C /6/ – 188.14 °C /6/ Critical temperature – 129.16 °C /7/ Critical pressure 55.715 bar /8/ Critical densitiy 573.76 g/l /9/ (liquid at boiling point) 1.513 g/cm3 /10/ Density (gas, 0°C, 1.013 bar)

F2 100% 1.695 g/l /11/

F2 10% | N2 90% 1.294 g/l /11/

F2 20% | N2 80% 1.339 g/l /11/

F2 20% | N2 70% | Ar 10% 1.392 g/l /11/

F2 20% | N2 40% | Ar 40% 1.552 g/l /11/ bp Refractive index (nD , liquid) 1.20 /12/ 0 Refractive index (nD at 1.013 bar) 1.000214 /12/ Molar refractivity 3.22 cm3/mol /12/ Heat of transition 728.09 J/mol /6/ Heat of fusion 510.79 J/mol /6/ Heat of vapourization (at boiling point) 6548 J/mol /6/ Kirchhoff formula log p = 7.08718 – (357.258/T)– ((1.3155 ·10-13 )/ T8) /6/ (temperature range: – 219.6 to –183 °C) (p: Torr, T:K) Entropy of transition (–227.61°C) 15.99 J/mol K /6/ Entropy of fusion (– 219.62°C) 9.55 J/mol K /6/ Entropy of vapourization (at boiling point) 76.6 J/mol K /6/

Standard entropy S°298 203.09 J/mol K /13/ (at boiling point) 13.6 · 10 -5 N/cm /10/ Eötvös constant 2.1 /10/ (liquid at boling point) 0.24 mPa · s /14/ Viscosity (Gas, 0°C, 1.013 bar) 0.0218 mPa · s /15/ (Gas, 0°C, 1.013 bar) 2.48 · 10-4 W/cmK /16/ Coefficient of self-diffusion (Gas, 0°C, 1.013 bar) 0.170 cm2/s /15/ Impulse diameter 0.37 · 10-8 cm /15/ Internuclear distance 1.435 · 10 -8 cm /17/ Dissociation energy (0°C) 156.6 kJ/mol /18/ of atoms 340 kJ/mol /18/ Fig. 13: Table of Physical Data.

Solvay Special Chemicals Elemental Fluorine 15 Fig. 14: Best etch rates found for selected materials at 150°C. F2 20 sccm + Ar 300 sccm

Ar / NF3 100 sccm 500 Etch rate [nm/Min] rate Etch 400

300

200

100

SiOxNy SiOxNy TaN W A r / F2 N2 / F2 TiN SiO2 0 Material

Fig. 15: Best etch ratio of 20 sccm

F2 in Ar compared to 20 sccm NF3 best

known method. [%]

3 100

80

fluorine content equivalent

60 mass equivalent Etch rate ratio rate Etch compared NF to 40

20

SiOxNy SiOxNy TaN W A r / F2 N2 / F2 TiN SiO2 0 Material F2-Ar etching rates

16 Elemental Fluorine Solvay Special Chemicals Fig. 16: Dissociaton degree of the ­halogens /18/. 1.0

F2 2 F 0.8 Dissociaton degree Dissociaton l2 2 l 0.6

Br2 2 Br 0.4

0.2

0 500 750 1,000 1,250 1,500 1,750 Temperature (°C)

Fig. 17: Rite report etching comparison of 30,000 different gases. /19/. m i n ) / (Å

25,000 F2

20,000

15,000 NF3

10,000

C3F8 COF2 C2F6 5,000

C3F6 0 0 % 2 0 % 4 0 % 6 0 % 8 0 % 10 0 % ( v o l %)

Solvay Special Chemicals Elemental Fluorine 17 6 Toxicity

Fluorine gas is classified as a highly toxic gas for handling, use and transport. The es - tablished maximum limits of fluorine exposure reflects this. Please refer to the governing agency in the country where the fluorine is being used.

Threshold Limit Value (TLV) 1.0 ppm

Short Time Exposure Limit (STEL) 2.0 ppm

Permissible Exposure Limit (PEL) 0.1 ppm Fig. 18: Common established maximum limits Workplace Exposure Limits (WEL) 1.0 ppm of fluorine exposure. TLVs or WELs are the maximum average airborne concentrations of a hazardous ma- terial to which healthy adult workers can be exposed during an 8-hour workday and 40-hour work week – over a working lifetime – without experiencing significant adverse health effects. Under emergency conditions, the following maximum exposure limits are established.

Emergency Exposure Level (EEL) . 25 ppm for 5 min Fig. 19: Maximum limits of fluorine exposure Immediately Dangerous to Life and Health (IDLH) 25 ppm (NIOSH) under emergency conditions.

Established LC50 (lethal concentration 50%) values

LC50 (1h, rat) pure fluorine 185 ppm

LC50 (1h, rat) for 20% fluorine in nitrogen 925 ppm (calculated)

LC50 (1h, rat) for 10% fluorine in nitrogen 1,850 ppm (calculated) Fig. 20: Established LC50 values. Reference: ISO 10298 Determination of gas or gas mixture toxicity.

The Destructive Effects on Human­ Body Tissue are due to three Causes  The immediate oxidizing effect of the It is unlike other acids because it cannot fluorine be rapidly neutralized and can destroy  The termic damage resulting from the tissue for several days after exposure to heat generated when fluorine reacts skin. The fluoride ion readily penetrates with the tissue the skin, causing destruction to deep tis- sue layers including bone.  Poisoning of the tissue by hydrogen Since fluorine , even in small concentra- fluoride – this is formed when fluorine tions, is already detectable by its pungent reacts with water in the tissue. odor, cases of poisoning are relatively ra- The effect to the human body resembles re. The gas is detectable by human smell that of . Hydrogen fluo- at concentrations starting at 0.1ppm. ride is a deep-acting protoplasmic poison.

18 Elemental Fluorine Solvay Special Chemicals Routes of Exposure a risk of shock due to the reduction of free available calcium () following Inhalation the extent of the lesions. Symptoms after Inhalation of vapours is irritating to the skin contact could be skin irritation, red- respiratory system and may cause throat ness, swelling of tissue and burn. pain and cough. Aspiration may cause Eye contact pulmonary oedema and pneumonitis. There is a risk of hypocalcemia with nerv- Eye contact may cause permanent eye ous problems (tetany) and cardiac ar- injury up to blindness and intoxication rhythmia. Symptoms after inhalation could hazards by simultaneous inhalation of be: breathing difficulties, sore throat, nose the product. Symptoms after eye contact bleeding. Repeated exposure could result could be: lachrymation, redness, swelling in chronic bronchitis. of tissue and burn. /20/ Skin contact Skin contact with fluorine causes severe burns and intoxication hazards by simul- taneous inhalation of the product. There is

Fig. 21: Labeling ­according to the ­Global CAS-No.: 7782-41-4 ­Harmonized System Fluorine EC-No.: 231-954-8 for Index-No.: 009-001-00-0 from Wimpfen plant, Germany. Signal Word: Danger

Hazard statements H270: May cause or intensify fi re, oxidiser. H280: Contains gas under pressure, may explode if heated. H330: Fatal if inhaled. H314: Causes severe skin burns and eye damage.

Precautionary statements Prevention P220: Keep/Store away from clothing/fl ammable/ combustible materials. P260: Do not breathe dust/fume/gas/mist/vapours/spray. P280: Wear protective gloves/protective clothing/ eye protection/face protection.

Response P303+P361+P353: IF ON SKIN (or hair): Take off immediately all contaminated clothing. Rinse skin with water/shower. P305+P351+P338: IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. P310: Immediately call a POISON CENTER or doctor/physician.

Made in Germany Solvay Fluor GmbH Plant Bad Wimpfen Hans-Böckler-Allee 20 Carl-Ulrich-Straße 34 Emergency Tel. 30173 Hannover 74206 Bad Wimpfen a. N. Tel. +49 511 857-0 Tel. +49 70 63 / 51-0 +44(0)1235 239 670 Germany Germany

Solvay Special Chemicals Elemental Fluorine 19 7 Shipping and Transport

Elemental fluorine is shipped by Solvay as Land transport compressed gas either pure or as a mix- Compressed fluorine and fluorine mix- ture with nitrogen (other gases for mixture tures in inert gases are authorized for on request). The product is available in shipment in containers with the appropri- individual cylinders, in stacks, bundle- or ate service pressure. However, the LC50 tube trailer. Fluorine cylinders are fitted of the mixture is used to determine the UN with specially designed valves. The valve Number and the proper shipping name of plug closure must be gas-tight and firmly the gas or gas mixtures. Certain shipping attached to the valve (chain). Fluorine cyl- restrictions are linked to the UN numbers inders should never be emptied to the according to International transport regu- point where an internal vacuum is created, lations, namely; since this could cause other gases to be  Pure 100 % fluorine is transported un- sucked inside. After emptying the cylinder der UN1045 Fluorine, compressed. its valve should be closed immediately. The transport is not authorized in Please return empty cylinders for refilling. tubes or pressure drums. The filling pressure is limited to 30 bar and the quantity of fluorine to a maximum of 5 kg in a single vessel.

Fig. 22: Bundle trailer.

Fig. 23: Packaging forms of fluorine gas.

20 Elemental Fluorine Solvay Special Chemicals  Mixtures containing fluorine with a Air Transport 3 LC50 of less than 200 ml/m (e.g. IATA (International Air Transport Associa- 92.5 % or more of F2 in N2) are trans- tion) prohibits the shipment of dangerous ported under UN3306, compressed goods identified by UN3306 and UN1045. gas, toxic, oxidizing, corrosive, N.O.S. Sea Transport The transport is not authorized in tubes Compressed fluorine and fluorine mix- or pressure drums. Bundles contain- tures of all concentrations are permitted ing fluorine and fluorine mixtures may for sea shipment following provisions de- be divided into assemblies (groups) of tailed in IMDG (International Maritime Dan- cylinders not exceeding 150 litres total gerous Goods) Code. water capacity.  Mixtures containing fluorine with a 3 LC50 of between 200 ml/m and 5,000 ml/m3 (e.g. between 3.7% and 92.5% of F2 in N 2) are transported under UN3306, compressed gas, toxic, oxi- dizing, corrosive, N.O.S. but are au- thorized to be transported in tubes and pressure drums. /21/

Fig. 24: Fluorine cylinders are fitted with ­specially designed valves.

Fig. 25: Container volume.

Cylinder Bundle Bundle Trailer* Tube Trailer Volume (water) l 50 50 50 47 600 600 600 3,600 12,000

F2 Concentra- % 10 20 100 20 10 20 100 20 20 tion Pressure bar 150 140 28 75 150 140 28 140 140

F2 Capacity kg 1.19 2.22 2.22 1.12 14.28 26.64 26.64 160 634 Volume (gas) l 7,50 0 7,000 1,400 3,525 90,000 84,000 16,800 504,000 1,680,000

* Bundle trailers are available from 6 (here calculated) to 24 bundles per trailer.

Fig. 26: Valve connector specification for tech- nical and electronical grade Fluorine.

Technical grade (Brass)* Electronic grade (Stainless steel) DIN 477 No.8 CGA 679 CGA-DISS 728 JIS () pneumatic manual pneumatic manual pneumatic manual pneumatic manual Asia       Europe     USA    

* Stainless steel available on request.

Solvay Special Chemicals Elemental Fluorine 21 8 Environment

As Fluorine is a highly toxic gas every As fluorine reacts with the moisture from ­effort must be made to avoid contact with ambient air and is transferred to hydrogen personnel and environmental releases. fluorine, F2 has no ozone depleting (ODP) For more detailed information, please see and no global warming potential (GWP). the safety data sheet (SDS). Therefore it is an ideal replacement gas Because fluorine reacts with moisture, in the semiconductor industry to susti- any release will form hydrogen fluoride tude high global warming gases like NF3 and this should be taken into account in (17,200 GWP) or PFC’s like CF4 ( 7,3 9 0 the control measures adopted. GWP) and C2F6 (12,200 GWP).

8.1 Product Stewardship for F2 Solvay is a well known manufacturer and In addition to the above mentioned sup- a global supplier of Fluorine and Fluorine port, Solvay offers to its customers tech- gas mixtures. nical training including emergency behav- Since Fluorine and its mixtures with other ior before the first delivery starts. gases are toxic, Solvay has established a Customers are highly recommended to detailed product stewardship program for take advantage of the support offered these products. by Solvay within its product stewardship Within this product stewardship program program to minimize risks on their end Solvay supports its customers e.g. in the due to failures in installation or false hand- safe handling, transport and application of ling. Fluorine and its mixtures with other gases. Fluorine users shall have an Emergency In principle, for the three kinds of available Rescue Coffin Vehicle (ERCV) available supply packaging for these products, the on hand. following safety requirements are manda- tory at the customer location:

Fig. 27: Fluorine user safety requirements.

Packaging Fluorine user safety requirements Fluorine user safety requirements for the packaging for gas destruction

Cylinder ERCV (Emergency Rescue Coffin Vehicle) CaCO3 point of use gas scrubber

Bundle Gas cabinet Al2O3 point of use gas scrubber Bundle trailer/ISO-container Sprinkler, ventilation Central gas scrubber (wet or dry for high volumes)

22 Elemental Fluorine Solvay Special Chemicals 8.2 Solvay Way

We believe that better chemical solutions sumption or low energy road lighting, are need not come at the expense of the en- designed to contribute to the quality of vironment and have to respect people’s life and meet stakeholders’ expectations lives. regarding sustainable development. As We strive to offer employees a safe and a supplier to thousands of industries, we secure working environment that en- continually look at ways to further reduce courages professional development, and our impact on the environment, asking maintain a regular dialogue with them in chemistry to do more with less. an atmosphere of trust. This exchange is Because we commit to progress towards particularly important as they are the key our stakeholders, in 2013 we launched players in our responsible performance. Solvay Way, our sustainable development Our products, such as solutions keeping policy that provides a framework to guide clothes clean, water purification, home and measure our success at meeting our heating solutions that reduce energy con- objectives.

Fig. 28: More information www.solvay.com –> Sustainability –> Solvay Way

Solvay Special Chemicals Elemental Fluorine 23 9 Solvay – The Specialists for Fluorides

Solvay Special Chemicals end applications such as heat exchangers and Li-ion batteries. The Global Business Solvay Special Chemicals is active in a Unit (GBU) has a global presence: more range of markets: Energy Conservation than 35 sites, HQ in Seoul and 2,300 em- and Storage, Semicon/Electronics, Agro ployees spread across four continents. & Food, and Performance Materials. It is a world leader in Fluorine Chemistry and Professional Fluorochemistry maintains this position through innovation, Solvay Special Chemicals stands for a utilising its distinct knowledge for high- professional team of experienced chem- ists and a sales staff committed to taking on any challenge and to solving problems in close co-operation with our clients. With our state-of-the-art application technolo- gies we offer a full range of fluorochemi- cals, using fluorspar produced in-house. In line with our commitment to manag - ing challenges we further focus our Fluor business on high ­value-added specialty products to bring value to our customers.

Fig. 29 Plant Bad Wimpfen, Germany.

Fig. 30 Plant Onsan, South Korea.

24 Elemental Fluorine Solvay Special Chemicals Product range of from GBU Special Chemicals Product Range HF and Inorganic Fluorides Fluorine Specialties

Hydrofluoroalkanes  Ammonium hydrogenfluoride  Elemental Fluorine (F2)  SOLKANE® 227 pharma  Ammonium hydrogenfluoride Elemental Fluorine (F2), SOLKANE® 134a pharma electronic grade electronic grade

 SOLKAFLAM® 227   Fluorine Nitrogen Mixtures (F2/N2)

 SOLKANE® 134 a  Fluorine Nitrogen Mixtures (F2/N2), electronic grade SOLKANE® 143 a  , synth powder  pentafluoride (IF ) SOLKANE® 227 tech  5  Sulphur (SF ) SOLKANE® 365 / 227  Hydrofluoric acid 6 Sulphur Hexafluoride (SF ), SOLKANE® 365mfc  Hydrogen fluoride 6 electronic grade SOLKANE® 404A  Hydrogen fluoride electronic grade Materials for Lithium SOLKANE® 407A  Lithium cryolite Ion Batteries SOLKANE® 407C   Potassium cryolite Monofluoroethylene carbonate (F1EC) SOLKANE® 410  Potassium fluoroaluminate Organic Intermediates SOLKANE® 507  solution  CF : SOLKANE® 22L 3  Potassium fluoroborate 4-Ethoxy-1,1,1-trifluoro-3-buten-2-one SOLKANE® 22M (ETFBO)  Potassium hydrogenfluoride SOLKANE® 141b (TFA)  Sodium hydrogenfluoride  SOLKATHERM® SES24 Trifluoroacetylchloride (TFAC) SOLKATHERM® SES30 Aluminium Trifluoroacetic anhydride (TFAH) SOLKATHERM® SES36 Fluxing Agents Trifluoroacetic acid ethylester (TFAEt)  NOCOLOK® Flux  SOLVOKANE® 1,1,1-Trifluoroacetone (TFK) NOCOLOK® Flux Drystatic SOLVOKANE® S Trifluoroacetic acid methylester NOCOLOK® Sil Flux SOLVOKANE® E1. 5 (TFAMe) NOCOLOK® CB Flux Trifluoroacetic acid isopropylester Brominated Polyols ® NOCOLOK Cs Flux (TFAiP)  IXOL® B 251 ® NOCOLOK Zn Flux  CF Molecules: IXOL® M125 2 ® NOCOLOK Li Flux 1H-Pyrazole-4-carboxylic- NOCOLOK® Li Flux Drystatic 3-(difluoromethyl)-1-methyl-ethylester (DFMMP) Aluminium Brazing Supporting Products  NOCOLOK® Flux plus binder mixture NOCOLOK® Sil Flux plus binder NOCOLOK® Binder NOCOLOK® Thickener NOCOLOK® Precoating NOCOLOK® Flux Paste

Solvay Special Chemicals Elemental Fluorine 25 10 Bibliography

/1/ /11/ February 2009 edition of SOLID STATE TECH- Solvay – Berechnet mit der thermischen­ NOLOGY Zustandsgleichung idealer Gase mit Copyright 2009 by PennWell Corporation R=8,314462 J/mol*K /2/ /12/ IEEE Transaction of Semiconductor Manufac- Franck, E.U.; turing Vol. 3, No. 1, Feb. 1990 “Eine Neubestimmung der Brechzahl /3/ gasförmigen Fluors”; EIGA Doc_140_11 Code of good practice Naturwiss. 41 (1954), 37 compressed fluorine and mixtures with innert /13/ gases. Cole, L.G.; Farber, M. u. Elverum, G.W.; /4/ “Thermodynamic Properties of the Management of hydrogen fluoride injury – Fluorine Atom and Molecule and of Notes for health professionals (third edition), Hydrogen Fluoride at 5000 K”; Eurofluor (CTEF, European Technical Commit- J. Chem. Phys. 20 (1952), 586 tee for Fluorine) /14/ /5/ Elverum, G.W. und Doescher, R.N.; The Journal of Physical Chemistry, “Physical Properties of Liquid Fluorine”; Vol. 85, No. 23, 1981 J. Chem. Phys. 20 (1952), 1834 /6/ /15/ Hu, I.-H.; White, D. u. Johnston, H. L.; Franck, E.U. u. Stöber, W.; “Condensed Gas Calorimetry. V. Heat Capaci- “Zähigkeit und molekularer Wirkungs- ties, Latent Heat and Entropies of Fluorine durchmesser des Fluors”; from 13 to 85 K; Heats of Transition, Z. Naturforsch. 7a (1952), 822 Fusion, Vaporization and Vapor Pressures of /16/ the Liquid”; Franck, E.U. u. Wicke, E.; J. Amer. Chem. Soc. 75 (1953), 5642 “Über die Wärmeleitfähigkeit und die /7/ ­Dissoziation des Fluors”; Strennenberg, R.K. u. Vogel, R.C.; Z. Elektrochem. 55 (1951), 643 Reactor Handbook II, 3d Ed., 258 /17/ Interscience Publ. Inc. N.Y. 1961 Rogers, M.; Schomaker, V. u. Stevenson, D.P.; /8/ “The Internuclear Distance in the Fluorine Cady, G.H. u. Hildebrand, J.H.; ­Molecule”; “The Vapor Pressure and Critical J. Amer. Chem. Soc. 63 (1941), 2610 Temperature of Fluorine”; /18/ J. Amer. Chem. Soc. 52 (1930), 3839 Wicke, E. und Franck, E.U.; /9/ “Physikalisch-chemische Eigenschaften des Prydz, R. u. Straty, G.C. Fluors”; „The Thermodynamic Properties of Com- Angew. Chem. 66 (1954), 701 pressed Gaseous and Liquid Fluorine“ /19/ National Bureau of Standards, Ref. 19.03.2003 RITE Report in Japanese Technical Note 392, Washington 1973 (website) /10/ /20/ White, D.; Hu, I.-H. u. Johnston, H.L.; F2 Safety Data Sheet, Solvay “The Density and Surface Tension of /21/ Liquid Fluorine between 66 and 80 k”; Seite 20 ADR/RID, UNECE J. Amer. Chem. Soc. 76 (1954), 2584

26 Elemental Fluorine Solvay Special Chemicals www.ahlersheinel.de All statements, information and data given herein are believed to be accurate and reliable but are presented without guarantee, warranty or responsibility of any kind, express or implied. Statements or or Statements implied. or express kind, any of required. be not may measures The other patent. responsibility any that or or to infringe indicated, are warranty recommendations not are measures and guarantee, safety all that infringement, without of patent is free assume use not such any that should presented user or warranty are but representation reliable without made are and products of our use accurate possible be to concerning believed are suggestions herein given data and information statements, All www.solvay.com Fax Phone Germany Hannover 30002 220 Postfach GmbH Fluor Solvay 817338 511 +49 857-2444 511 +49 Fax Phone Korea South 120-140 Seoul Soedaemun-gu Bukahyun-ro 150, Center R&I EWAH-Solvay Ltd. Co., Korea Solvay +82 2 2125 5380 22125 +82 5306 22125 +82

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