Gun Powder Explosion Properties

Health and Safety Executive
Fire and explosion properties of nanopowders

Prepared by the Health and Safety Laboratory for the Health and Safety Executive 2010
RR782 Research Report

P Holbrow, M Wall, E Sanderson, D Bennett, W Rattigan, R Bettis & D Gregory Health and Safety Laboratory Harpur Hill Buxton Derbyshire SK17 9JN
Nanotechnology is a rapidly expanding technology in which existing and novel materials are engineered at the nanoscale, typically in the range of 1 to 100 nanometres. Engineered nanomaterials include uniquely manufactured products with unique shapes and enhanced physical and chemical properties, compared with conventional materials of the same composition. There is currently little available information on the explosion risks of these materials. The Health and Safety Executive therefore commissioned this project to investigate the potential fire and explosion hazards associated with nanopowders. Test equipment and procedures were developed to assess the key properties of a selected number of nanopowders. A specialised 2 litre test vessel was developed to determine the explosion characteristics and modified standard test apparatus was used to measure the minimum ignition energy of nanopowders. Resistivity and electrostatic charging characteristics were assessed using specially designed test apparatus. Key information including KSt, Pmax and MIE values were obtained for a range of metal and carbon nanopowders. Generally, the explosibility (maximum explosion pressure, rates of pressure rise and equivalent KSt) of nanopowders were found to be broadly similar to conventional micron-scale powders. However, the minimum ignition energies of some nanopowders were found to be lower than the equivalent material at micron-scale. It was demonstrated that with increasing relative humidity the resistivity of most nanopowders decreases. There was also a tendency for nanopowders to have higher resistivity values than conventional micron-scale powders. All the powders produced electrostatic charge. Generally, the charge developed by nanopowders was comparable with the micron-scale powders. This report and the work it describes were funded by the Health and Safety Executive (HSE). Its contents, including any opinions and/or conclusions expressed, are those of the authors alone and do not necessarily reflect HSE policy.
HSE Books
Crown copyright 2010 First published 2010 All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means (electronic, mechanical, photocopying, recording or otherwise) without the prior written permission of the copyright owner. Applications for reproduction should be made in writing to: Licensing Division, Her Majestys Stationery Office, St Clements House, 2-16 Colegate, Norwich NR3 1BQ or by e-mail to hmsolicensing@cabinet-office.x.gsi.gov.uk
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CONTENTS
1 2 INTRODUCTION......................................................................................... 1 LEGAL BACKGROUND............................................................................. 2
3 EXPLOSION SEVERITY............................................................................. 3 3.1 Standard test ........................................................................................... 3 3.2 Test vessel .............................................................................................. 4 3.3 Control and Instrumentation .................................................................... 7 3.4 Test procedure ........................................................................................ 8 4 MINIMUM IGNITION ENERGY ................................................................. 10 4.1 Test apparatus....................................................................................... 10 5 FIRE HAZARDS ....................................................................................... 13 5.1 Fire Hazards in nanopowders................................................................ 13 5.2 Practical Assessment of Fire Properties ................................................ 13 6 ELECTROSTATIC PROPERTIES ............................................................ 15 6.1 Electrostatic charge ............................................................................... 15 6.2 Charging test ......................................................................................... 16 6.3 Resistivity test........................................................................................ 17 7 TEST MATERIALS ................................................................................... 19
8 RESULTS ................................................................................................. 22 8.1 Commissioning tests explosion severity ............................................. 22 8.2 Explosion severity of nanopowders ....................................................... 28 8.3 Commissioning MIE test results ............................................................ 34 8.4 MIE test results nanopowders ............................................................ 35 8.5 Electrostatics ......................................................................................... 37 9 DISCUSSION............................................................................................ 54 9.1 Explosion test Equipment ...................................................................... 54 9.2 Explosion severity and MIE ................................................................... 54 9.3 Electrostatic issues ................................................................................ 58 10 11 12 CONCLUSIONS .................................................................................... 61 APPENDICES ....................................................................................... 63 REFERENCES ...................................................................................... 68
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EXECUTIVE SUMMARY
Objectives Nanotechnology is a rapidly expanding technology in which existing and novel materials are engineered at the nanoscale. However, there is currently little available information on the fire and explosion risks of nanoparticles. The objective of this project is to characterize the fire and explosion properties of a range of commercially available nanopowders.
Main Findings 1. A unique facility has been developed specifically to allow the safe handling and testing of nanopowders. The equipment comprises: i) ii) 2 litre explosion test apparatus for measuring the rate of pressure rise and the maximum explosion pressure. Minimum ignition energy test apparatus. The minimum ignition energy of nanopowders was measured using a modified Kuhner MIKE3 test apparatus modified to allow nanopowders to be safely handled within the test apparatus. Sealed systems that allow the safe handling of oxidized and non-oxidized nanopowders under inert atmospheres.
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2. Explosion properties of a range of nanopowders have been characterised including aluminium, iron, zinc, copper and several carbon nanomaterials. Generally, the explosibility (maximum explosion pressure, rates of pressure rise and equivalent KSt) of nanopowders are broadly similar to conventional micron-scale powders. The minimum ignition energies of some nanopowders have been lower than the equivalent material at micron-scale. This indicates that the nanopowders may be more susceptible to ignition but once ignited the explosion violence is no more severe than micron-scale powders. 3. Electrostatic properties of nanopowders have been considered. Dust layer resistivity measurements and charge tests have been made on a range of nanopowders.
Recommendations To build on the data already obtained, and develop further expertise and knowledge, further nanopowders should be obtained and characterised.
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INTRODUCTION
Nanotechnology is a rapidly expanding technology in which existing and novel materials are engineered at the nanoscale. Engineered nanomaterials include uniquely manufactured products with unique shapes and enhanced physical and chemical properties, compared with conventional materials of the same composition. The Health and Safety Executive has commissioned a project to investigate the potential hazards associated with nanopowders. The general method of approach is to use standard, and modified, fire and explosion characterization methods to assess the key properties of a selected number of nanopowders. As part of this project, a review (HSL report number XS/08/119) has been carried out to update a review done by HSL in 2003 and to ensure that all relevant new material in this fast changing area is incorporated. There is currently little available information on the explosion risks of nanoparticles. The little data that does exist is contradictory and suggests the explosion violence is less than that of larger particles, which goes against the expectation that smaller particles burn faster than larger ones due to the increased surface area. Fine powders are known to be an explosion risk, particularly organic and metallic powders. For fine particulates, there is standard test equipment available to determine the explosion and ignition characteristics for powders, but these typically require kilogram quantities of powder. Also, the powder is dispersed in the standard apparatus using compressed air. With nanopowders, their large surface to volume ratio means that many are spontaneously flammable on contact with air, or surface oxidation alters their properties. Hence equipment that avoids oxidation until the point of ignition has been developed. This project report describes the design, operation of test apparatus and results obtained relating to the explosion properties of nanopowders. Key information including explosion severity, minimum ignition energy and electrostatic properties is reported.
LEGAL BACKGROUND
The major legal regulations that could apply to nanopowders include the following: DSEAR Regulations It is the duty of employers to comply with the Dangerous Substances and Explosive Atmosphere Regulations 2002 (DSEAR) which seek to eliminate, reduce and control the fire and explosion risks from dangerous substances. Flammable nanopowders capable of fueling a dust explosion fall within the definition of a dangerous substance. Regulation 5 of these regulations requires that, where a dangerous substance is present at a workplace, the employer should make a suitable and sufficient assessment of the risks to their employees. Those risks should, where possible, be eliminated. Where it is not reasonably practicable to do this they should be reduced and controlled (Regulation 6). Measuring the fire explosion characteristics of nanopowders is an essential step in assessing the risk. CHIP Regulations The CHIP (Chemical Hazard Information and Packaging for Supply) Regulations 2009 have implications for nanopowders. Dangerous substances or preparations cannot be supplied unless they have been classified in accordance with the regulations. Classification requires a knowledge of the toxic and fire and explosion properties of the substance. In addition, suppliers are required to provide information about the hazards of the substances and to package and label them for safe transport. REACH Regulations REACH is a new European Union regulation concerning the Registration, Evaluation, Authorisation and restriction of CHemicals. It came into force on 1st June 2007 and replaces a number of European Directives and Regulations with a single system. A major part of REACH is the requirement for manufacturers or importers of substances to register them with a central European Chemicals Agency (ECHA). A registration package will be supported by a standard set of data on that substance. The amount of data required is proportionate to the amount of substance manufactured or supplied. The data requirement includes the fire and explosion properties of the substance.
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3.1 STANDARD TEST
EXPLOSION SEVERITY
The procedure for measuring the explosion severity of dust/air mixtures is described in a European standard available as BS EN 14034-1 (2004) and BS EN 14034-2 (2006). The standard test vessel for these determinations is the 1 m3 vessel. The peak maximum explosion pressure, Pmax, and the peak maximum rate of pressure rise, (dP/dt)max, are measured in this standard test procedure. The Pmax and (dP/dt)max are the highest values generated in an enclosed dust explosion. These characteristics are measured in a standard test at the optimum dust concentration and are obtained by testing the dust over a wide range of dust concentrations. The two peaks normally occur at different dust concentrations. The (dP/dt)max is used to calculate a dust specific explosibility characteristic called the KSt value. The KSt is given by: KSt = (dP/dt)maxV1/3 (2.1)
Where (dP/dt)max is the peak maximum rate of pressure rise (bar/s) and V is the total internal volume of the test vessel (m3). The units of KSt are bar m/s. Equation (2.1) is well known as the cubic law (Barton (2002)). The KSt is considered to be a constant for any dust, independent of vessel size and equation (2.1) acts as a simple scaling law. The KSt value is derived only from measurements in either a 20 litre sphere vessel or a 1 m3 vessel and if any other vessel is used to measure the KSt it must be calibrated against the 1 m3 or 20 litre standard test vessels. The ISO standard also allows the use of alternative vessels provided they give comparable results. The criterion for demonstrating conformity is given in the standard BS EN 14034-2 (2006); the standard has been prepared by CEN Technical Committee 305. This gives alternative test equipment procedures. It states that the maximum rate of pressure rise of dust clouds can be determined using alternative test equipment and/or test procedures. When using an alternative it shall be shown that at least for the following dusts that the method yields results within specific deviations. The dusts shall include at least two metal powders, two natural organic powders, two synthetic organic powders and two coal dusts. In the standard 1 m3 vessel the KSt value is equal to the maximum rate of pressure rise. The standard test apparatus typically requires kilogram quantities of powder and therefore a smaller scale test apparatus is required for nanopowders. Also, the powder is dispersed in the standard apparatus using compressed air. With nanopowders, their large surface to volume ratio means that many are spontaneously flammable on contact with air, or surface oxidation alters their properties. Hence equipment that avoids oxidation until the point of ignition is required. No commercial equipment is available to satisfy these requirements, so a specially designed test apparatus, to measure the explosion characteristics of nanopowders, has been developed in this project.
3.2
TEST VESSEL
An explosion test vessel with a volume of approximately 2 litres has been designed and manufactured specifically for testing nanopowders (Figure 1 - 3). The construction quality was specified to be similar to the existing standard 20 litre sphere apparatus at HSL but with specially treated internal surfaces. The vessel is constructed from stainless steel and designed for a maximum working pressure of 20 bar. It is fully certified and tested to British Standards and in accordance with the Pressure Systems Directive PD 5500: 2005. The shape of the internal test chamber is spherical since this will allow the dust to be dispersed as a homogeneous dust cloud and thus allow the burning material to expand uniformly towards the vessel wall. The internal volume of the spherical test chamber is 2 litres with an internal diameter of 156 mm. A twin-skinned wall to facilitate water-cooling as used in the 20 litre sphere apparatus was considered. This was rejected on the grounds that much of the vessel body will be congested with flanges and ports and the cooling would be ineffective. The vessel is therefore constructed with a single skin wall. The whole vessel assembly is capable of electrical isolation. Ports The test vessel incorporates a number of ports and flanged connections: 1. The main access into the vessel is via the top of the vessel. This access is sealed using a flanged plate that incorporates two holes to accept the ignition electrodes. The opening is sized to enable hand-access for cleaning and for installing the dispersion nozzle. 2. Two diametrically opposed flanges tapped with M14 threads for Kistler pressure transducers. 3. A port incorporating a glass viewing window with a diameter of 40 mm. 4. A dust injection port is located at the bottom of the vessel. 5. A pressure release valve and an evacuation port. Dust injection The dust is introduced into the vessel from an external dust container via a dust injection valve and solenoid system mounted on an intermediate flanged adapter at the base of the vessel and a dispersion nozzle. Dispersion nozzle A pepper-pot nozzle incorporating a rebound plate was selected for the test programme. The pepper-pot design with a circular deflector is designed to encourage a homogeneous dust distribution and is located into the base of the test chamber. Dust container A special dust container, designed for a working pressure of 20 bar, is attached to the dust injector. The container has a volume of approximately 0.06 litre. A inch BSP port is used for
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the attachment of a pressure hose and pressure gauge. The container was designed to allow remote loading of nanopowder under an inert atmosphere within a glovebox. Ignition Ignition of the dust cloud is achieved using an ignition source attached to two central electrodes. There are a number of possible ignition sources including: chemical igniters, electric fuse heads, spark and hot wire. A voltage is applied to the ignition source from the control system at the preset time delay following dust injection into the vessel.
Figure 1: Vessel general arrangement
Figure 2: Test vessel
Figure 3: Test vessel
The test vessel was located within a fume cupboard, that incorporated a HEPA filter system and a sink fitted with waste filters for cleaning the contaminated components. Located outside the fume cupboard and connected via a pass-through port were: vacuum pump, high pressure air supply, control system and data acquisition system and a glovebox fitted with an integral HEPA
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filter. To minimise operator contact with nanopowders, the materials were handled, weighed and loaded into the enclosed dust injection chamber within the glovebox (Figure 4). The glovebox also allowed the handling of nanopowders under an argon atmosphere, enabling powders to be transferred from the glovebox to the test apparatus under argon thus preventing premature oxidation of powders.
Figure 4: Glovebox 3.3 CONTROL AND INSTRUMENTATION
The control and instrumentation system is interfaced to a PC via custom control circuitry and commercial USB data acquisition and control hardware. The PC executes software providing control, data logging and analysis functions. The fume cupboard is fitted with safety interlocks to help ensure operator safety. The software has been developed using the National Instruments LabVIEW development environment. It is installed for use on the Microsoft Windows XP platform. In brief the test operates as follows. The sphere is sealed and evacuated. The powder under investigation is released into the sphere to form a cloud, driven by the in-rush of air from external pressure. The cloud is ignited, and the pressure rise in the sphere logged. This data is then analysed to determine the maximum rate of pressure rise and the peak pressure. The software controls the nanopowder release and ignition, logs the pressure data from the enclosure, and will analyse the data. Safety interlock status is monitored to prevent risk to personnel from unplanned attempts at powder release or ignition. The PC has two free USB 2.0 ports to allow interfacing to the USB data acquisition devices. The software provides appropriate interface signals via the interface hardware to control the apparatus. The software accepts appropriate interface signals to provide feedback for the control process and to log the required test data from two independent piezoelectric pressure sensors. The pressure transducers measure the pressure difference, not absolute pressure.
The software calculates dP/dt (the rate of pressure rise) and Pmax (maximum explosion overpressure) following each test. These are calculated for pressure sensor 1, for pressure sensor 2, and for the averaged readings of the two sensors. Kistler (type 701A) pressure transducers are used in the test apparatus and the details are shown in Table 1. Table 1: Pressure transducers Serial number Transducer location 128026 128027 L.H. port R.H. port
Laboratory instrument reference PT140
Channel 1 2
Charge amplifier sensitivity 152.1 154.1
3.4
TEST PROCEDURE
The following is a summary of the general operational procedure. Sample preparation 1. Remove container with nanopowder from the storage cupboard. Place in a secondary transport container to protect the nanopowder container from accidental breakage. Transport to the test facility. 2. Remove the nanopowder container from the transport container a place in the glove box. The balance will be located in the glovebox. 3. Weigh the required mass of nanopowder by carefully scooping the powder and placing on a stainless steel dish on the balance. Close the nanopowder container. 4. Pour the nanopowder into the dust injection vessel and seal the vessel. Transfer the vessel to the fume cupboard, fit to the dust injection vessel and connect the supply lines. 5. Non-oxidised nanopowder is handled under an inert atmosphere. Firing 1. Prepare the ignition source. 2. If a chemical igniter is used, connect to the electrodes inside the vessel and check the circuit continuity using an approved ohmmeter tester. 3. If spark electrodes are used, ensure that the gap is set and the correct discharge energy is selected. 4. Replace the vessel lid and ensure a full complement of screws are fitted and are tightened. 5. Close the vessel outlet valve, open the evacuation valve and open the dust injection isolation valve.
6. Partially evacuate the explosion vessel to the appropriate pressure, typically 0.4 bara. The gas mixture and pressure in the explosion vessel shall be adjusted so that at ignition the atmosphere is nominally atmospheric. 7. Pressurise the dust injection vessel with compressed air. The pressure and volume of the dust injection vessel is matched to the level and vacuum in the explosion vessel such that the pressure at ignition is at nominal atmospheric pressure. 8. Close the fume cupboard sash and initiate the test. 9. Display the pressure traces and save the data to hard disk for analysis. 10. Open the outlet valve and release the pressure.
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4.1
MINIMUM IGNITION ENERGY
TEST APPARATUS
The MIKE3 test apparatus, manufactured by Kuhner is normally used for the determination of minimum ignition energy (MIE) of micron-sized dusts (Figure 5). However, the risk assessment for handling nanopowders required improvements to the operating procedure for this apparatus. This equipment has therefore been modified to enable its use with nanopowders.
Figure 5: MIE test apparatus Dust dispersion chamber The dust dispersion chamber was modified to minimised operator contact with the powder and enable the safe handling, weighing of nanopowder and loading of the powder into the apparatus. This was achieved using a glovebox to weigh and transfer nanopowder to the MIKE3 apparatus. A two stage process was used to develop the modified dispersion chamber. Development Stage 1: An enclosed barrel shaped chamber was constructed to completely replace the Kuhner dispersion cup assembly (Figure 6).
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Figure 6: Dispersion chamber This comprised a stainless steel chamber split into three components, lower middle and top barrels that were screwed together to form the assembled chamber. Two aluminium bursting discs were sandwiched between the barrels to form a central chamber that held the nanopowder. The assembly method was as follows: Powder, dispersion chamber and balance were placed in a glovebox. The lower and middle barrels were assembled with the lower bursting disc inserted between the barrels. Powder was then deposited into the middle chamber, the second bursting disc is fitted and the top barrel is screwed into position. The assembly was removed from the glovebox and transferred and fitted to the MIKE3 apparatus. The compressed air line was connected to the lower chamber. This provided the blast of compressed air that, during the test, ruptured the bursting discs and dispersed the nanopowder into the glass tube. Following commissioning tests on the first design it became clear that the efficacy of the system was not acceptable in that it was not possible to obtain the established MIE of a standard test powder. This was likely to be the result of erratic rupturing of the bursting discs and the increased distance of the initial formation of the dust cloud to the ignition source. Development Stage 2: A second dispersion system was therefore developed utilising the existing Kuhner dispersion cup. A thin slide valve was manufactured and fitted to the top face of the dispersion cup (Figure 7). The close fitting of the slider and fixed slides provided sealed chamber once the valve was closed. This design had the benefit of utilizing the original dispersion cup, nozzle and geometric locations of the dispersion and ignition points.
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Figure 7: Slide valve dispersion chamber Test procedure: In common with the first design, the powder, dispersion chamber assembly and balance were placed in the glovebox. The air isolation valve was closed and the slide valve opened. Nanopowder was then weighed, placed in the dispersion cup and the powder was safely sealed within the cup by closing the slide valve. The assembly was removed from the glovebox, transferred and fitted to the MIKE3 apparatus and the compressed air line was connected to the lower chamber. The test procedure normally used in the operation of the Kuhner test apparatus was then followed in accordance with the general principles of BS EN 13821 (2002). Ignition energy levels used were 1 mJ, 3 mJ, 10 mJ, 30 mJ, 100 mJ, 300 mJ and 1000 mJ.
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5.1
FIRE HAZARDS
FIRE HAZARDS IN NANOPOWDERS
With highly mobile, easily dispersed materials it is difficult to draw boundaries between fire hazards, deflagration hazards and explosion hazards. Fire is normally understood to be the ignition and combustion of material in bulk - as layers or within packages. Limiting consideration to these circumstances, there are three major fire issues that might arise with nanopowders: New ignition routes due to the presence of bulk nanopowders e.g. the possibility of spontaneous combustion. The possibility of enhanced burning rates in bulk nanopowders compared with solids or larger particulates and powders. The potential for fire-induced air flows to lift bulk materials into a dispersed cloud while providing an ignition source for a nanopowder explosion.
The particular hazards in any fire situation are also threefold: heat, toxic gases and smoke that might lead to injury or death, heat and smoke that might cause property damage growth from a small, initial fire to a larger, more hazardous one.
At present, nanopowders other than carbon black are high value materials produced in relatively small quantities. Even large amounts in storage are limited to kilogram quantities or less. In terms of fire load, the amount of combustible material present, the packaging of many nanopowders (plastics, cardboard, shrinkwrap etc) and the storage infrastructure (pallets, equipment, cables, even paints) are likely to represent the main hazard to life and to property. If nanomaterial combustion is relatively slow, such small quantities will not release energy quickly enough to be an unusual fire threat. On the other hand, nanopowders may exhibit a much more rapid combustion than equivalent materials at larger particle sizes. This means that they might release energy at a much faster rate, tending asymptotically to the explosion scenario. It seems unlikely that the fire end of this range would cause significant harm with small amounts of nanopowders. 5.2 PRACTICAL ASSESSMENT OF FIRE PROPERTIES
Current nanopowders are typically highly mobile, requiring continuous containment to prevent losses even through diffusion into the air. This high mobility means that nanomaterials within process equipment would not be able to build up on surfaces without undergoing agglomeration or other physico-chemical changes, which would in turn - affect their fire properties. Unchanged nanopowders are unlikely to settle out even in still conditions, and much less so in
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any moving gas or air flows. Should nanomaterials escape from a process into a more open building (factory/storage) environment, the normal air movement present in large structures will help to reinforce their natural mobility and it is even less likely that any significant amount of nanomaterials could form a combustible mass or layer. The current high intrinsic value of almost all nanopowders means that there are also financial drivers on producers and handlers to minimise any losses again reducing the likelihood of a significant amount of material being allowed to build up in process or storage. To pose a fire risk, nanopowders need to be present in layers containing many grams, even kilograms, of material. For the present, at least, such quantities will only be present for materials in storage. Any fire assessment therefore needs to address nanomaterials in storage conditions. The important fire properties (rate of heat production, rate of fire spread and formation of toxic combustion products) all include processes that are scale dependent. For example, the effect of thermal radiation is important in the spread of fire but is dependent on the square of the distance. This means that small-scale testing does not reproduce the effects of a full-scale fire. Consequently, fire tests need to be carried out at a representative scale. Nanopowders that are likely to be important in the future are currently only available in limited quantities at relatively high cost. The health and environmental risks associated with nanomaterials have not been completely defined; despite considerable ongoing effort in the area of nanotoxicology, many unknowns remain and it is recommended that a precautionary approach is taken when handling nanomaterials in research and manufacturing workplaces (Seaton and Tran, 2009). The combination of high cost and potential risk means that only the minimum necessary amount of work should be undertaken with nanopowders. Given the current low risk of harm from nanomaterial fires simply as a result of the low quantities present in any given location, it is difficult to justify fire testing to further quantify that risk.
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6.1
ELECTROSTATIC PROPERTIES
ELECTROSTATIC CHARGE
The likelihood of accumulation of electrostatic charges and voltages in an industrial process increases with increasing electrical resistivity of powder (Eckhoff, 1997). With regard to dusts that penetrate into electrical and electronic equipment, the chance that they give rise to short circuits and equipment failure, increases as the dust resistivity decreases. In both situations the generation of ignition sources may result. BS EN 61241-2-2:1996 states that a dust with electrical resistivity equal to or less than 103 m is considered to be a conductive dust and a dust with electrical resistivity greater than 103 m is considered to be a non-conductive dust. The CCPS (2005) publication reports that resistivities above 108 m are indicative of the potential for significant electrostatic charging. Increased humidity in the atmosphere where powders are handled may help to reduce the potential for electrostatic discharges by increasing the conductivity of the powders. PD CLC/TR 50404 (2003) divides powders into 3 groups depending on their volume resistivity: a) low resistivity powders with volume resistivities up to about 106 m, b) medium resistivity powders in the range 106 m to 1010 m and c) high resistivity powders with resistivities of 1010 m and above. NFPA77 (2007) has a similar 3category classification for powder resistivity. They indicate that low resistivity powders with resisitivities of up to 108 m can become charged during flow. Powder resistivities within the range 108 to 1010 m are considered to be medium resistivity powders. High resistivity powders have resistivities greater than 1010 m. The significance of resistivity is discussed in NFPA 77, the main points being: a) Low resistivity powder can become charged during flow but rapidly dissipates when conveyed into a conductive grounded vessel. Powder conveyed into non-conductive container can result in an incendive spark. b) For medium resistivity powders coming to rest in bulk, the retained charge depends on the resistance between the powder and ground. Medium resistivity powders do not produce bulking brush discharges or sparks. c) High resistivity powders do not produce spark discharges themselves. However, they can produce corona, brush, bulking brush, and propagating brush discharges. Electrostatic charges are generated on solids during transport due to the rubbing of particles against particles or particles against equipment and the internal surfaces of pipes (CCPS, 2005). The charging of particles may take place independently of whether they are conductive or insulating materials. Equipment may also become charged by virtue of coming into contact with charged particles. However, an electrostatic charge by itself does not necessarily represent an ignition hazard this only exits when the charge is sufficiently high that a discharge occurs due to the breakdown of a high voltage electric field. The criteria described above relates to micron-scale powders. These parameters have been used to assess the potential for charge build-up in a range of nanopwders, and the chance of nanopowders becoming potential ignition sources. Two test rigs have been constructed to assess charging and resistivity.
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6.2
CHARGING TEST
In order to measure and demonstrate electrostatic charging of nanopowders in a realistic situation, a test apparatus has been constructed capable of generating particle movement and measuring the charge build-up. This incorporates a 25 mm diameter closed-loop continuous circulating PVC pipe incorporating a fan system to pneumatically circulate the powder. The overall length of the loop is approximately 1000 mm. A charge measuring station is incorporated into the pipe. Nanopowder was introduced through a valved port to be circulated within the loop. The aim is for any charge developed to be measured at an intermediate point in the loop. The system was developed, initially using four in-line fans, but later replaced with a centrifugal fan driven by a 55W single-phase motor (Figure 8).
Figure 8: charge test apparatus A number of techniques were employed to measure the deposition of charge at the measurement station during the commissioning of the test equipment. The technique that gave the most reliable results was to connect a capacitor between the measurement station and Earth; the voltage developed across the measurement capacitor is related to the charge accumulated on it. A number of measurement capacitor values were used during the tests, in each case the capacitance was accurately measured using a Wayne Kerr model 6425 LCR multi bridge. The voltage across the measurement capacitor was measured using a Keithley model 6514 electrometer. The data was captured using a PC running National Instruments Labview SignalExpress software and a National Instruments model USB-6221 data logger. The data logger captured data from the analogue output of the electrometer at a rate of 500Hz. Due to the high impedance of the electrometer it was necessary to provide an Earthed screen of wire mesh around the charging loop to control electrical noise. The relationship between the voltage across the capacitor and the supplied current is given by:
I =C
dV dt
Where I is the charging current (amps), dV/dt is the rate of change of voltage on the capacitor and C is the capacitance of the measurement capacitor (farad).
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The rate of change of voltage in the powder charging cycle can be determined from the graph of voltage against time. Hence the streaming current can be calculated. Each powder was tested using a new, clean set of pipes. Before the test equipment was loaded with powder the resistance between the measurement station and earthed casing of the fan was measured using a Robin model 3075DL insulation and continuity meter. In each case the resistance was found to be greater than 2000 M at 500V. The fan speed was set at the start of the tests and was not changed. The velocity of the air within the pipe was 28 m/s (measured using a TSI Airflow instrument) and is assumed to have been constant throughout the testing. The ambient environmental conditions were measured using a Rotronics Hygropalm 0 portable temperature and humidity meter. 6.3 RESISTIVITY TEST
Equipment has been designed and manufactured specifically to measure the bulk resisitivity of nanopowders in layers. The design is based on the equipment described in BS EN 61241-22:1996, but has been designed on a smaller scale to allow testing of small quantities of nanopowder. The equipment consists of a PTFE test cell (Figure 9) with two stainless steel bars. The bars have nominal cross sectional dimensions of 25 mm x 25 mm and are 25 mm long. These formed the electrodes and are located with a 10 mm long gap in a PTFE block. The block is 75 mm long x 90 mm wide with a channel in which the electrodes were located. Each electrode has a terminal connection for a calibrated resistance meter. Operator contact with nanopowders during these tests was minimised by locating the test cell in sealed test chamber within a glove box. Where necessary the atmosphere within the glovebox was inerted using argon. The humidity of the test chamber was adjusted using a desiccant and was monitored using a humidity meter. A weighed quantity of nanopowder was deposited within the cell and excess powder was removed by running a straight edge along the top of stainless steel electrodes. The bulk density of the sample was calculated by weighing the deposited sample. The electrodes were connected to the resistance meter and the resistance was measured over a range of humidity levels. The resistivity was calculated in accordance with the principles described in BS EN 61241-22:1996 and is described as follows. Where Ro is greater than 10 Rs, and the resistivity of the dust is calculated from the equation: = 0.001 Rs [H W/L] where is the resistivity in m Ro is the resistance of empty test cell in Rs is the resistance of the filled test cell in ; H is the height of the electrode in mm; W is the length of the electrode in mm; L is the space between electrodes in mm.
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A range of nanopowders was assessed and, for comparison purposes, a number of micron-scale powders were also tested.
Figure 9: Resistivity test cell
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TEST MATERIALS
Nanopowder test materials were obtained including metal powders and organic materials and are listed in Table 2. Micron-scale powders used in the tests are listed in Table 3. Initial tests were done using Lycopodium, a well-established micron-sized standard test powder. This was supplied by Fluka Reference 19108 (Explosion Safety Unit Sample No EC/026/08. Intrinsiq Materials Ltd (previously Qinetiq Nanomaterials Ltd) supplied a quantity of aluminium nanopowder from their early production runs in which some carbon contamination had occurred. The material was useful for early commissioning of the test apparatus. Intrinsiq Materials Ltd also supplied commercial grade aluminium nanopowder. This material is passivated during production by exposing the material to an oxygen/argon atmosphere. This produces a partially oxidised material such that it can be exposed to the atmosphere during experiments without the risk of rapid oxidation and burning.
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Table 2: Nanopowders
Material HSL Sample Number Supplier Suppliers Reference Information from supplier
Iron (passivated)
EC/147/07 Nanostructured & Amorphous 0266JY Materials, Inc. 16840 Clay Road, Suite 113, Houston, TX 77084, USA
Iron powder (Fe) (partially passivated) Purity: 99.5% (metal basis), APS: 25 nm SSA: 40 - 60 m2/g Color: black Morphology: spherical Bulk density: 0.10 - 0.25 g/cm3 True density: 7.87 g/cm3 Copper (Cu) (partially passivated) Purity: 99.8% (metal basis) APS: 25 nm SSA: 30 - 50 m2/g Color: black brown Morphology: spherical Bulk density: 0.15 - 0.35 g/cm3 True density: 8.94 g/cm3 Purity 97.5%; APS 45-55 nm; colour Grey white: Bulk Density 0.068 g/cm3; True density 3.22g/cm3; Morphology spherical; Specific surface area 70-90 m2/g
Copper (passivated)
EC/148/07 Nanostructured & Amorphous 0296JY Materials, Inc. 16840 Clay Road, Suite 113, Houston, TX 77084, USA
Silicon Carbide
EC/159/07 Nanostructured & Amorphous 4620KE Materials, Inc. 16840 Clay Road, Suite 113, Houston, TX 77084, USA
Zinc Oxide
EC/149/07 Nanostructured & Amorphous 5810MR Materials, Inc. 16840 Clay Road, Suite 113, Houston, TX 77084, USA
Zinc Oxide (ZnO) Purity 99.5%; APS: 20nm; SSA: 50 m2/g; Colour: milky white; Morphology: nearly spherical; Bulk density: 0.3-0.45 g/cm3; True density: 5.606 g/cm3
Iron Oxide
EC/150/07 Nanostructured & Amorphous 2652FY Materials, Inc. 16840 Clay Road, Suite 113, Houston, TX 77084, USA
Iron Oxide (Fe3O4); Purity 99.5%; APS 15-20 nm; Colour: black; Morphology : spherical; Bulk density : 0.8-0.9 g/cm3; True density 4.8-5.1 g/cm3
Zirconium Oxide
EC/151/07 Nanostructured & Amorphous 5930LQ Materials, Inc. 16840 Clay Road, Suite 113, Houston, TX 77084, USA
Zirconium Oxide (ZrO2); Purity 99.95%; APS: 29-68 nm; SSA: 15-35 m2/g; Colour: white; Morphology: spherical; Bulk density: 0.74 g/cm3; True density 5.89 g/cm3
Zinc
EC/152/07 Nanostructured & Amorphous 0303WF Materials, Inc. 16840 Clay Road, Suite 113, Houston, TX 77084, USA
Zinc (Zn); Purity 99.5%; APS : 130nm; SSA: 6.4 m2/g; Colour : Grey; Morphology: spherical; Bulk density: 0.70.85 g/cm3; True density 7.14 g/cm3
Multi-walled nanotubes
carbon EC/153/07 Nanostructured & Amorphous 1229YJ Materials, Inc. 16840 Clay Road, Suite 113, Houston, TX 77084, USA
MWNT Purity: > 95% ; Outside diameter: 20-30 nm; Inside diameter: 5-10 nm; Length: 10-30 um; SSA: ~ 110 m2/g; Colour: black; True density: ~2.1 g/cm3
Carbon nanofibres
EC/158/07 Nanostructured & Amorphous 1190JN Materials, Inc. 16840 Clay Road, Suite 113, Houston, TX 77084, USA
Carbon nanofibers; Purity 95%; Outside diameter: 80-200 nm; Core diameter: 1-10 nm; Length 0.5-20 um;BET: 2535 m2/g; Electronic Resistivity: 0.75-0.1 Omu.cm (20180MPa); Colour: black; Bulk density: 0.06-0.08 g/cm3; True density: 1.9 g/cm3
20
Table 2 (continued): Nanopowders

Carbon Nanofibre Carbon Nanofibre Carbon Nanofibre Aluminium EC/042/08 EC/116/08 EC/117/08 EC/104/08 Pyrograph Products Inc Applied Sciences Inc. Applied Sciences Inc Intrinsiq Materials Ltd PR-19-SLD PR-25-XTPS-AM PR-24-XTHHT-AM QNA 2607 Diameter 100-200 nm Length 30-100 micron Diameter 70-200 nm Length 2-5 micron Diameter 70-200 nm Length 2-10 micron Nominally 100nm Minimum 60% Al, remainder Aluminium oxide surface layer. Trace elements Fe, Na, Zn, Ga. Nominally 210 nm Minimum 60% Al, remainder Aluminium oxide surface layer. Trace elements Fe, Na, Zn, Ga. Estimated 73-109 nm 17 nm immediately after formation in the combustion process.
Aluminium
EC/011/09
Intrinsiq Materials Ltd
QNA 2798
Aluminium Carbon Black
EC/060/07 EC/076/07
Intrinsiq Materials Ltd Cabot
Ref: PQN301 Batch 17 Monarch 800
Table 3: Micron-scale powders

Material Aluminium Iron HSL Sample Number EC/085/08 EC/003/09 Supplier Alpoco Ronald Britton Ltd Suppliers Reference Batch 137X Code B10121 Batch 831302 96479 8Information from supplier Specification 99.7% Al, 8 micron. 100% <150 micron
Zinc oxide Copper Zirconium oxide Carbon Lycopodium Zinc Stearate Coal Toner
EC/112/08 EC/004/09 EC/111/08 EC/113/08 EC/026/08 EC/118/08 EC/120/08 EC/122/08
Fluka Ronald Briton Ltd Acros Organics Sigma Aldrich Fluka
100% < 75 micron 190522500 484164-50G 2-12 micron Sieved to 63 micron
21
8
8.1
RESULTS
COMMISSIONING TESTS EXPLOSION SEVERITY
Initial commissioning was done using micron-scale aluminium nanopowder and lycopodium powder shown in Table 4. The injection pressure was maintained at 20 barg. The variables were dispersion, dust concentration, ignition source, the valve timing, ignition delay, and vacuum pressure. The maximum rate of pressure rise and maximum explosion pressure were measured in the 2 litre sphere for each test powder over a range of conditions. The objective was to achieve a set of conditions that would produce a rate of pressure rise and maximum explosion pressure that could be related to the results obtained from the 20 litre sphere. Appendix 1 shows the range of test conditions used to explore this objective. Table 4: Commissioning powders Powder Lycopodium Aluminium nanopowder Sample Number EC/026/08 EC/060/07 Supplier Fluka Intrinsiq Comment Sieved to 63 micron Ref: PQN301 Batch 17 Estimated 73-109 nm
8.1.1
Ignition delay
The ignition delay is the difference between the time the control system initiates the opening of the dust injection valve and the time of the initiation of the ignition source. The ignition delay was varied within the range 60 110 ms. For the maximum rate of pressure rise, the optimum ignition delay was found to be 75 ms. 8.1.2 Ignition source
Chemical igniters manufactured by Sobbe GmbH were used in the test programme. Additionally, a low energy ignition source - an electric fuse head - was assessed. The strength of the ignition source will influence the rate of propagation of flame through the dust cloud and will therefore produce different explosion characteristics of the dust in an explosion severity test. For example a very strong ignition source may result in a much greater rate of pressure rise than that produced from a relatively weak ignition source. This is demonstrated by tests done using lycopodium powder in the 20 litre sphere (Table 5) where the rate of pressure rise was higher with correspondingly greater strength of ignition. The Pmax was relatively flat. The 10 kJ igniter is used in the standard 20 litre sphere test (BS EN 14034-1: 2004 and BS EN 14034-2: 2006) and clearly produces the highest rate of pressure rise. Without the presence of dust, the rate of pressure rise is approximately 100 bar/s with a peak pressure of approximately 1 bar.
22
Table 5: Ignition strength in the 20 litre sphere (lycopodium powder) Ignition source 42 J electric fuse head 1 kJ Sobbe 5 kJ Sobbe 10 kJ Sobbe Pmax (barg) 6.5 7.3 7.0 7.3 dP/dt (bar/s) 243 551 620 673 K (bar m/s) 66 150 168 183
A range of tests were performed in the 2 litre sphere with lycopodium (sample EC/026/08) and aluminium (sample EC/060/07) to assess the effect of the ignition strength on the rate of pressure rise and maximum explosion pressure (Table 6). As expected, the rate of pressure rise increased with increasing ignition strength. Table 4 shows that with an electric fuse head, the highest rate of pressure rise achieved with lycopodium was only 200 bar/s, and in some cases ignition was not achieved. At the other extreme, with a 5 kJ igniter both dusts tended to result in high rates of pressure rise and in the case of lycopodium the results were close to the 20 litre sphere but the aluminium far exceeded the 20 litre sphere results. The Pmax of the lycopodium was generally much greater than the 20 litre sphere tests whilst the aluminium was comparable. The 5 kJ igniter therefore had a tendency to over-drive the explosion such that an ignition source smaller than this value would be required for the nanopowder tests. Table 6: Effect of ignition strength on test dusts 2 litre vessel Ignition source Pmax (barg) dP/dt (bar/s)
Lycopodium ( sample EC/026/08) Electric fuse head 1 kJ Sobbe 5 kJ Sobbe 8.2 8.7 9.1 200 882 1500
Aluminium (sample EC/060/07) 1 kJ Sobbe 2 kJ Sobbe 5 kJ Sobbe 10.8 9.8 9.5 1450 1950 5000
Additionally, to assess the pressure development of the igniter itself, a number of igniters were tested in the 2 litre vessel, without the presence of a dust cloud. Table 7 shows the results of the tests with each of these igniters. The use of a 10 kJ Sobbe igniter in the 2 litre vessel would result in an over-driven ignition of the dust and was therefore not considered. The highest strength considered was a 5 kJ Sobbe igniter.
23
The 1 kJ Sobbe igniter selected for the nanopowder test programme since this would not overdrive the explosion. The igniter alone produced a pressure rise of 1.05 barg and a maximum rate of pressure rise of 75 bar/s. During nanopowder explosion tests, it is assumed that the effect of the 1 kJ igniter can be ignored after 1.05 barg, thus the rate of pressure rise of the nanopowder explosion is evaluated at pressures above this value.
Table 7: Ignition strength in the 2 litre vessel (without dust). Ignition source Electric fuse head 1 kJ Sobbe 2 x 1 kJ Sobbe 5 kJ Sobbe Pmax (barg) 0.2 1.05 1.5 4.2 dP/dt (bar/s) 3.3 75 154 250
8.1.3
Dp/dt, KSt value and Pmax
From the commissioning tests, a set of test conditions were established for main series of nanopowder tests. These are shown below are shown below: Dust injection pressure: 20 bar g Initial test chamber pressure: 0.1 - 0.4 bar a Dust injection valve open: 10 ms Dust injection valve closed: 65 ms Ignition ON: 83 ms Ignition OFF: 180 ms Igniter: 1 kJ Sobbe chemical igniter Logging rate 50 kHz The rates of pressure rise used to assess the explosion severity were lower than were needed for direct calculation using the cubic lawequation (2.1). This is mainly the result of flame impingement and quenching at the vessel wall. Consequently, it is not possible to calculate the KSt value directly using the 2 litre sphere. Table 8 and Figure 10 show the comparison of data from the 20 litre sphere and 2 litre sphere for a range of dusts using these test conditions. A scaling factor was established to relate the rate of pressure rise measured in the 2 litre sphere with the KSt value measured in the 20 litre sphere. To obtain the equivalent KSt value from the rate of pressure rise in the 2 litre sphere a scaling factor of 0.268 is applied. The expectation was for the maximum explosion pressure in the 2 litre sphere to be generally less than in the 20 litre sphere due to the greater cooling effects at the walls of the smaller test
24
chamber compared with the 20 litre chamber. However, Figure 10 shows that the maximum explosion pressures in the two vessels were broadly comparable. Table 8: Commissioning results Material 20 litre sphere results Rate of KSt pressure m/s) rise (bar/s) Lycopodium 673 EC/026/08 Aluminium EC/060/07 Zinc stearate EC/118/08 Coal EC/120/08 Toner EC/122/08 Carbon black EC/076/07 Aluminium EC/104/08 1200 1080 183 326 293 (bar Pmax (bar) 2 litre sphere results Rate of Pmax (bar) pressure rise (bar/s) 700 1450 1400 7.7 10.8 8.2
7.3 9.8 7.6
558 714 382
151 194 104
7.4 7.5 7.8
600 725 320
7.3 6.3 6.2
2368
643
12.0
2000
11.2
700
13
Kmax 20 litre sphere vessel (bar m/s)
600
12
500
20 litre vessel - Pmax (bar)

500 1000 1500 2000
11
400
10
300
200
100
6 5 6 7 8 9 10 11 12
Rate of pressure rise in 2 litre vessel (bar/s)
2 litre test vessel - Pmax (bar)
Figure 10: Comparison of 20 litre and 2 litre test apparatus
25
8.1.4
Pressure-time history
A typical pressure-time trace, taken from a 2 litre sphere test, is shown in Figures 11 and 12; the test material is aluminium nanopowder EC/104/08. Two pressure curves (red and blue) are logged from the two pressure transducers and an average value is displayed (green). The initial pressure rise is the injection of the dust into the test chamber which raises the pressure to atmospheric after which the ignition is initiated. This is followed by a rapid pressure rise due to the ignition of the dust. The pressures traces illustrate that the peak values of explosion pressure and rate of pressure rise can occur at different dust concentrations. In Figure 11, with a dust concentration of 3000 g/m3, the pressure rises to 11.2 bar g with a maximum rate of pressure rise of approximately 1625 bar/s. In Figure 12, with a dust concentration of 2500 g/m3, the maximum explosion pressure is 9.1 bar g with a maximum rate of pressure rise of 2000 bar/s.
Figure 11: Pressure time trace
Figure 12: Pressure-time trace
26
The tests on lycopodium (sample EC/026/08) are a good example of the scaling tests in the 2 litre and 20 litre spheres. Tests on lycopodium using the 20 litre sphere apparatus resulted in a rate of pressure rise of 673 bar/s, KSt of 183 bar m/s and a Pmax of 7.3 bar (Figure 13). Similar tests in the 2 litre sphere (Figure 14) resulted in a pressure rise of 700 bar/s and a Pmax of 7.7 bar. Application of the scaling factor to the rate of pressure rise results in a KSt value of 187 bar m/s.
Figure 13: Lycopodium - 20 litre sphere test
Sample number EC/026/08 Lycopodium powder Fluka 19108 2 litre sphere test
8.0 800
Sample Number EC/026/08 Lycopodium powder Fluka 19108 2 litre sphere test
7.5
700
Rate of pressure rise (bar/s)
Explosion pressure (barg)
600
7.0
500
6.5
400
6.0
300
5.5
200
5.0 200 400 600 800 1000 1200 1400
100 200 400 600 800 1000 1200 1400
Dust concentration (g/m3)
Figure 10: Lycopodium - 2 litre sphere test
27
8.2
EXPLOSION SEVERITY OF NANOPOWDERS
A range of nanopowders have been tested in the 2 litre sphere. The results are presented in Table 9 and plots of the individual test are shown in Figures 15 - 24. Table 9: Nanopowder test results in the 2 litre sphere results Sample number EC/011/09 Material Aluminium nanopowder (210 nm) EC/104/07 Aluminium nanopowder (100 nm) Iron nanopowder Zinc nanopowder Copper nanopowder Carbon nanofibre Carbon nanofibre Carbon nanofibre Carbon nanofibre Multi-walled carbon nanotubes 11.2 2000 536 Pmax (bar g) 12.5 dP/dt (bar/s) 1677 Equivalent KSt (bar m/s) 449
EC/147/07 EC/152/07 EC/148/07 EC/042/08 EC/158/07 EC/116/08 EC/117/08 EC/153/07
2.9 5.6 1.2 5.2 6.0 6.9 5.6 6.4
68 377 10 62.5 112 591 137 339
18 101 3 17 30 158 37 91
28
Sample number EC/011/09 Aluminium nanopowder Average particle size 210 nm Supplier: Intrinsiq
13
Sample number EC/011/09 Aluminium nanopowder Average particle size 210 nm Supplier: Intrinsiq
1800 1600
12

0 1000 2000 3000 4000 5000 6000 7000
Explosion pressure (bar g)
1400 1200 1000 800 600 400
11
10
200 0 1000 2000 3000 4000 5000 6000 7000
Figure 15: Aluminium nanopowder sample EC/011/09
Sample number EC/104/08 Aluminium nanopowder Average particle size 100 nm Supplier: Intrinsiq Batch: QNA 2607
12
2200
Sample number EC/104/08 Aluminium nanopowder Average particle size 100 nm Supplier: Intrinsiq Batch: QNA 2607
11
2000

500 1000 1500 2000 2500 3000 3500 4000
10
1800
1600
1400
1200
1000
800 500 1000 1500 2000 2500 3000 3500 4000
Figure 12: Aluminium nanopowder sample EC/104/08
29
Sample number EC/147/07 Iron nanopowder 25 nm Supplier: Nanostructured & Amorphous Matl
3.0
Sample number EC147/07 Iron nanopowder Average particle size 25 nm Supplier: Nanostructured & Amorphous Matls.
100
2.5
2.0

0 500 1000 1500 2000 2500 3000
80
60
1.5
40
1.0
20
0.5
500
1000
1500
2000
2500
3000
Figure 13: Iron nanopowder sample EC/147/07
Sample number EC/152/07 Zinc nanopowder APS 130 nm Supplier: Nanostructured & Amorphous Matl
6
400 350
Sample number EC/152/07 Zinc nanopowder APS 130 nm Supplier: Nanostructured & Amorphous Matls.
300 250 200 150 100 50 0
1 0 1000 2000 3000 4000 5000 6000 7000 8000
1000
2000
3000
4000
5000
6000
7000
8000

Concentration g/m3 vs Pmax bar

Concentration g/m3 vs dp/dt bar/s
Figure 14: Zinc nanopowder sample EC/152/07
30
Sample number EC/148/07 Copper nanopowder APS 25 nm Supplier: Nanostructured & Amorphous Matl
1.25
100
Sample number EC148/07 Copper nanopowder APS 25 nm Supplier: Nanostructured & Amorphous Matls.
1.20
1.15

0 500 1000 1500 2000 2500 3000 3500
80
60
1.10
1.05
40
1.00
20
0.95
0 0 500 1000 1500 2000 2500 3000
Figure 15: Copper nanopowder sample EC/148/07
Sample number EC/042/08 Carbon Nanofibre Supplier: Pyrograph Products Inc. PR-19-LD-PS
Sample Number EC/042/08 Carbon nanofibre Pupplier: Pyrograph Products Inc PR-19-LD-PS
5.5 5.0
70 60

0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200
4.5 4.0 3.5 3.0 2.5 2.0 1.5
50 40 30 20 10 0
200
400
600
800
1000 1200 1400 1600 1800 2000 2200
Figure 16: Carbon nanofibre sample EC/042/08
31
Sample number EC/158/07 Carbon nanofibre Supplier: Nanostructured & Amorphous Materials Inc Stock No 1190JN Lot No 1190-111907
6.5
120
Sample number EC/158/07 Carbon nanofibre Supplier: Nanostructured & Amorphous Materials Inc Stock No 1190JN Lot No 1190-111907
6.0
5.5
100
80
5.0
60
4.5
40
4.0
3.5 0 200 400 600 800 1000 1200 1400 1600
20 0 200 400 600 800 1000 1200 1400 1600
Figure 17: Carbon nanofibre sample EC/158/07
Sample number EC/116/08 Carbon Nanofibre Supplier: Applied Sciences Inc. PR-25-XT-PS-AM Batch 1323 Box5
Sample Number EC/116/08 Carbon nanofibre Supplier: Applied Sciences Inc PR-25-XT-PS-AM Batch 1323 Box5
700
7.0
600

0 500 1000 1500 2000 2500
6.5
500
6.0
400
5.5
300
200
5.0
100
4.5
0 0 500 1000 1500 2000 2500
Figure 18: Carbon nanotube sample EC/116/08
32
Sample number EC/117/08 Carbon nanofibre Supplier: Applied Sciences Inc. PR-24-XT-HHT-AM Batch 155 PS 1131 Box1
160
5.8
Sample Number EC/117/08 Carbon nanofibre Supplier: Applied Sciences Inc Batch 155 PS 1131
140
5.6 5.4
120
5.2 5.0 4.8 4.6 4.4 4.2 4.0 3.8 0 200 400 600 800 1000 1200 1400 1600
100
80
60
40
20 0 200 400 600 800 1000 1200 1400 1600
Figure 19: Carbon nanotube sample EC/117/08
Sample number EC/153/07 Multi walled carbon nanotubes Supplier: Nanostructured & Amorphous Materials Inc. Stock No 1229YJ Lot No 1229-101603
Sample number EC/153/07 Multi walled carbon nanotubes Supplier: Nanostructured & Amorphous Materials Inc. Stock No 1229YJ Lot No 1229-101603
400
7
350
300 250 200 150 100 50 0
0 0 200 400 600 800 1000 1200 1400 1600
200
400
600
800
1000
1200
1400
1600
Figure 20: Carbon nanotubes sample EC/153/07
33
8.3
COMMISSIONING MIE TEST RESULTS
To prove the efficacy of the modified MIE apparatus, initial tests were done using lycopodium powder, a well-established micron-sized test powder. The ignition circuit inductance was set at zero, L=0 mH. The purpose was to compare the performance with results using the conventional Kuhner test apparatus for the standard micron-sized test powder. Results for the conventional dispersion system are shown in Figure 25; the MIE for this powder is within the range 10 30 mJ. Barrel dispersion chamber The MIE obtained using the enclosed barrel dispersion chamber were 30 100 mJ. This result was greater than the conventional system and consequently the system was developed further and a slide valve dispersion chamber was manufactured. Slide valve dispersion chamber The MIE obtained using the slide valve dispersion chamber were equivalent to the conventional apparatus i.e. MIE = 10 30 mJ. This modified system was therefore used in subsequent tests. .
Figure 25: MIE test on lycopodium (File MO20813A.XYZ)
34
8.4
MIE TEST RESULTS NANOPOWDERS
Minimum ignition energies of nanopowders are presented in Table 10. Examples of tests shown in Figures 26 and 27 illustrate the different burning characteristics of two metal nanopowders. Iron nanopowder tended to produce many incandescent particles and less flame than zinc nanopowder which produced a very bright flame.
Table 10: Nanopowder minimum ignition energies Sample number Material Minimum Ignition Energy (mJ) < 1 mJ < 1 mJ >1000 mJ > 1000 mJ < 1 mJ 3 10 mJ > 1000 mJ
EC/104/08 EC/011/09 EC/153/07 EC/116/08 EC/147/07 EC/152/07 EC/148/07
Aluminium nanopowder Aluminium nanopowder Carbon nanotubes Carbon nanotubes Iron nanopowder Zinc nanopowder Copper nanopowder
35
Figure 26: Iron nanopowder
Figure 27: Zinc nanopowder

36
8.5 8.5.1 8.5.1.1
ELECTROSTATICS Resistivity test results Aluminium
Test data for aluminium nanopowder and micron-scale aluminium powder is presented in Table 11. and in Figure 28.
Table 11: Aluminium resistivity

Aluminium nanopowder EC/104/08 Relative Resistivity (.m) humidity (%) Resistance () 70.0 60.0 50.0 40.0 30.0 20.0 8.1 5.50E+07 9.48E+07 2.21E+08 7.01E+08 5.65E+10 3.86E+11 5.82E+12 3.44E+06 5.93E+06 1.38E+07 4.38E+07 3.53E+09 2.41E+10 3.64E+11 Aluminium standard powder EC/085/08 Relative Resistivity (.m) humidity (%) Resistance () 75.0 65.0 55.0 45.0 35.0 27.0 23.0 9.1 3.03E+03 2.89E+03 3.36E+03 3.97E+03 3.93E+03 3.71E+03 2.90E+03 2.94E+03 1.89E+02 1.81E+02 2.10E+02 2.48E+02 2.46E+02 2.32E+02 1.81E+02 1.84E+02
Bulk density 0.221 g/cm3
Bulk density 0.968 g/cm3
R e si st i v i t y v R e l a t i v e H u m i di t y f o r A l u m i ni um P owd e r s
Aluminium nanopow der EC/104/08

1.00E+ 12 1.00E+ 11 1.00E+ 10 1.00E+ 09 1.00E+ 08 1.00E+ 07 1.00E+ 06 1.00E+ 05 1.00E+ 04 1.00E+ 03 1.00E+ 02 1.00E+ 01 1.00E+ 00 0.0 10.0 20.0 30.0 40.0
Aluminium standard pow der EC/085/08
50.0
60.0
70.0
80.0
90.0
100.0
R e l a t i v e H umi di t y ( %)
Figure 28: Aluminium resistivity
37
8.5.1.2
Iron
Test data for iron oxide nanopowder, iron nanopowder and micron-scale iron powder is presented in Table 12. and in Figure 29. Table 12: Iron resistivity
Iron oxide nanopowder EC/150/07 Relative Resistance () Resistivity (.m) humidity (%) 75.0 3.85E+09 2.41E+08 65.0 3.87E+09 2.42E+08 55.0 3.96E+09 2.48E+08 45.0 4.17E+09 2.61E+08 35.0 4.46E+09 2.79E+08 25.0 5.44E+09 3.40E+08 16.6 7.63E+09 4.77E+08 7.7 5.51E+10 3.44E+09 Bulk density 1.108 g/cm3 Iron nanopowder EC/147/07D (inert atmosphere) Relative Resistivity (.m) humidity (%) Resistance () 7.8 1.45E+04 9.06E+02 Bulk density 0.606 g/cm3 Iron standard powder EC/003/09 Relative Resistivity (.m) humidity (%) Resistance () 65.0 51.5 3.22E+00 60.0 51.7 3.23E+00 55.0 51.8 3.24E+00 45.0 51.7 3.23E+00 35.0 51.8 3.24E+00 25.0 51.6 3.23E+00 5.0 51.2 3.20E+00 Bulk density 3.497 g/cm3
Resistivity v Relative Hum idity for Iron Pow ders Iron nanopow der EC/147/07D Iron oxide nanopow der EC/150/07
1.00E+10 1.00E+09 1.00E+08 1.00E+07 1.00E+06 1.00E+05 1.00E+04 1.00E+03 1.00E+02 1.00E+01 1.00E+00 0.0 10.0 20.0 30.0 40.0 50.0 60.0 70.0 80.0 90.0 100.0 R elat ive Humid i t y ( %)
Iron standard pow der EC/003/09
Figure 29: Iron resistivity
38
8.5.1.3
Zinc
Test data for zinc oxide nanopowder, zinc nanopowder and micron-scale zinc powder is presented in Table 13 and in Figure 30. Table 13: Zinc resistivity
Zinc oxide nanopowder EC/149/07 Relative Resistivity (.m) humidity (%) Resistance () 76.7 2.23E+06 1.39E+05 66.0 3.00E+06 1.88E+05 60.0 3.18E+06 1.99E+05 54.0 3.71E+06 2.32E+05 50.0 3.93E+06 2.46E+05 43.5 4.30E+06 2.69E+05 40.0 4.87E+06 3.04E+05 35.7 5.24E+06 3.28E+05 25.7 7.68E+06 4.80E+05 22.2 1.11E+07 6.95E+05 18.9 1.72E+07 1.07E+06 17.4 2.52E+07 1.58E+06 15.6 3.50E+07 2.19E+06 14.9 5.01E+07 3.13E+06 8.7 9.83E+10 6.14E+09 Bulk density 0.523 g/cm3 Zinc nanopowder EC/152/07 (inert atmosphere) Relative Resistivity (.m) humidity (%) Resistance () 5.7 6.00E+04 3.75E+03 Bulk density 1.220 g/cm3 Zinc oxide standard powder EC/112/08 Relative humidity (%) Resistance () Resistivity (.m) 90.0 1.93E+09 1.21E+08 85.0 1.77E+09 1.11E+08 78.1 1.93E+09 1.21E+08 70.0 2.13E+09 1.33E+08 63.2 2.44E+09 1.53E+08 52.3 3.52E+09 2.20E+08 44.9 5.42E+09 3.39E+08 40.2 7.61E+09 4.76E+08 28.8 2.48E+10 1.55E+09 23.5 6.10E+10 3.81E+09 19.9 1.14E+11 7.13E+09 16.6 2.29E+11 1.43E+10 14.6 4.68E+11 2.93E+10 8.5 1.82E+13 1.14E+12 Bulk density 0.690 g/cm3
Resistivity v Relative Humidity for Zinc Oxide powders

Zinc oxide nanopowder EC/149/07 Zinc oxide standard powder EC/112/08
1.00E+13 1.00E+12 1.00E+11 1.00E+10 1.00E+09 Resistivity (.m) 1.00E+08 1.00E+07 1.00E+06 1.00E+05 1.00E+04 1.00E+03 1.00E+02 1.00E+01 1.00E+00 0.0 10.0 20.0 30.0 40.0 50.0 60.0 70.0 80.0 90.0 100.0 Relative Humidity (%)
Figure 30: Zinc resistivity
39
8.5.1.4
Copper
Test data for copper nanopowder and micron-scale copper powder is presented in Table 14 and in Figure 31. Table 14: copper resistivity
Copper nanopowder EC/148/07A (inert atmosphere) Relative humidity (%) 6.6 Resistance () 3.75E+03 Resistivity (.m) 2.34E+02 Bulk density 0.523 g/cm3 Copper standard powder EC/004/09 Relative humidity (%) 70.0 60.0 50.0 45.0 40.0 30.0 25.0 10.0 Resistance () 121.9 120.7 119.8 116.3 115.9 115.4 114.7 113.6 Resistivity (.m) 7.62E+00 7.54E+00 7.49E+00 7.27E+00 7.24E+00 7.21E+00 7.17E+00 7.10E+00 Bulk density 2.742 g/cm3
Resistivity of Copper Pow ders versus Hum idity Copper nanopow der EC/148/07A
1.00E+05
Copper standard pow der EC/004/09
1.00E+04
1.00E+03
1.00E+02
1.00E+01
1.00E+00 0.0 10.0 20.0 30.0 40.0 50.0 60.0 70.0 80.0 90.0 100.0
R e l a t i v e H u m i di t y ( %)
Figure 31: Copper resistivity

40
8.5.1.5
Zirconium oxide
Test data for zirconium oxide nanopowder and micron-scale zirconium powder is presented in Table 15 and in Figure 32. Table 15: zirconium oxide
Zirconium oxide nanopowder EC/151/07D Relative humidity (%) 70.0 60.0 50.0 40.0 30.0 23.0 8.8 Resistance () 2.35E+07 2.58E+07 2.80E+07 3.34E+07 5.29E+07 1.64E+08 1.20E+09 Resistivity (.m) 1.47E+06 1.61E+06 1.75E+06 2.09E+06 3.31E+06 1.02E+07 7.51E+07 Bulk density 0.953 g/cm3
Zirconium oxide standard powder EC/111/08 Relative humidity (%) 75.0 70.0 65.0 60.0 50.0 40.0 28.3 22.5 18.3 16.9 7.5 Resistance () 1.85E+07 1.88E+07 1.93E+07 1.96E+07 2.05E+07 2.21E+07 2.64E+07 3.98E+07 5.08E+07 5.92E+07 3.95E+10 Resistivity (.m) 1.16E+06 1.17E+06 1.20E+06 1.23E+06 1.28E+06 1.38E+06 1.65E+06 2.49E+06 3.18E+06 3.70E+06 2.47E+09 Bulk density 1.716 g/m3
Resistivity v Relative Humidity For Zirconium Oxide Powders

Zirconium oxide nanopowder EC/151/07D Zirconium oxide standard powder EC/111/08
1.00E+10 1.00E+09 1.00E+08 1.00E+07 Resistivity (.m) 1.00E+06 1.00E+05 1.00E+04 1.00E+03 1.00E+02 1.00E+01 1.00E+00 0.0 10.0 20.0 30.0 40.0 50.0 60.0 70.0 80.0 90.0 100.0 Relative Humidity (%)
Figure 32: Zirconium oxide resistivity
41
8.5.1.6
Carbon
Test data for carbon nanomaterials and micron-scale carbon powder is presented in Table 16 and in Figure 33. Table 16: Carbon resistivity
Multi-walled carbon nanotubes EC/153/07C Relative humidity (%) 75.0 65.0 55.0 45.0 35.0 25.0 15.0 7.6 Resistance () 1.71E+02 1.64E+02 1.70E+02 1.69E+02 1.78E+02 4.64E+01 4.46E+01 4.44E+01 Resistivity (.m) 1.07E+01 1.03E+01 1.06E+01 1.06E+01 1.11E+01 2.90E+00 2.79E+00 2.78E+00 Bulk density 0.047 g/cm3 Carbon nanofibres EC/158/07A Relative humidity (%) 75.0 64.0 55.0 45.0 35.0 25.0 17.1 7.8 Resistance () 8.44E+02 7.98E+02 7.66E+02 7.52E+02 7.41E+02 7.40E+02 7.20E+02 3.05E+01 Resistivity (.m) 5.28E+01 4.99E+01 4.79E+01 4.70E+01 4.63E+01 4.63E+01 4.50E+01 1.91E+00 Bulk density 0.039 g/cm3 Pyrograf III nanofibres EC/042/08 Relative humidity (%) 75.0 65.0 55.0 45.0 33.0 25.0 19.6 9.8 Resistance () 8.36E+04 8.39E+04 8.58E+04 8.88E+04 8.73E+04 9.20E+04 9.23E+04 2.48E+04 Resistivity (.m) 5.23E+03 5.24E+03 5.36E+03 5.55E+03 5.46E+03 5.75E+03 5.77E+03 1.55E+03 Bulk density 0.105 g/cm3 Carbon micron powder EC/113/08 Relative humidity (%) 70.0 60.0 50.0 40.0 28.0 21.5 8.5 Resistance () 3.25 3.19 3.15 3.11 2.93 2.8 3.2 Resistivity (.m) 2.03E-01 1.99E-01 1.97E-01 1.94E-01 1.83E-01 1.75E-01 2.00E-01 Bulk density 0.577 g/cm3
42
Resistivity v Relative Hum idity for Carbon Pow ders Multi-w alled carbon nanotubes EC/153/07C Pyrograf III nanofibres EC/042/08
1.00E+04
Carbon nanofibres EC/158/07A Carbon micron pow der EC/113/08
1.00E+03
1.00E+02
1.00E+01
1.00E+00
1.00E-01 0.0
10.0
20.0
30.0
40.0
50.0
60.0
70.0
80.0
90.0
100.0
R el at i ve Humi d it y ( %)
Figure 33: Carbon resistivity
43
8.5.2 8.5.2.1
Charging test results Commissioning
Base-line test As part of the commissioning tests on this equipment, a base-line test with no powder was initially carried out; this was done regularly during the tests to ensure the instrumentation was functioning correctly. Although this test was performed with new, clean pipes, surface and air contaminants seem to have contributed to the occurrence of some charging. An example of the plot of voltage against time is shown in Figure 34 and the test data is shown in Table 17. The airflow was maintained at a velocity of 28 m/s for the test programme.
100m 50m 0 -50m - 100m - 150m - 200m - 250m - 300m - 350m - 400m - 450m - 500m - 550m - 600m - 650m - 700m - 750m - 800m - 850m - 900m - 950m -1 -1.05 -1.1 -1.15 -1.2 -1.25 0 50 100 150 2 00 250 300 350 4 00 45 0 Time (s) 500 550 600 65 0 700 750 800 8 50 88 0.2
Figure 34 : Base-line test without powder
Table 17 : Base-line test without powder

Rate of change of voltage (V/s) -6.29E-03 Capacitance (F) 1.02E-08 Current (A) -6.40E-11
Ambient environmental conditions: Humidity: 67.0%RH Temperature: 19.9C
44
Lycopodium (EC/026/08) To test the system, micron-scale lycopodium powder was tested. This was free flowing and did not aggregate or accumulate in any significant quantities. During testing a very fine layer of powder coated the inside wall of the pipes. Figure 35 shows the plot of voltage against time and Table 18 presents the test results. An initial period of high rate of change of voltage was noted in the first few seconds following the fan being started, the cause of this was not investigated. This was followed by a period of steady gradient.
11.5 11.25 11 10.75 10.5 10.25 10 9.75 9.5 9.25 9 8.75 8.5 8.25 8 7.75 7.5 7.25 7 6.75 6.5 6.25 6 5.75 5.5 5.25 5 4.75 4.5 4.25 4 3.75 3.5 3.25 3 2.75 2.5 2.25 2 1.75 1.5 1.25 1 750m 500m 250m 0 -250m 0 10 20 30 40 50 60 70 80 90 100 110 120 130 Time (s ) 14 0 150 160 170 18 0 190 200 210 220 230 240 250 255.7
Figure 35: Lycopodium (EC/026/08) Table 18: Lycopodium (EC/026/08)

Rate of change of voltage (V/s) 1.76E-01 Capacitance (F) 3.84E-09 Current (A) 6.77E-10
45
8.5.2.2
Charging tests
Micron-scale zinc oxide (EC/112/08) The micron scale zinc oxide powder was observed to be highly cohesive; small quantities could be compressed together to form a layer on the surface of a spatula. A mass of 0.1g of powder was tested. Charge was generated for less than 1.5 seconds. The powder quickly accumulated around any obstructions and rapidly removed the powder out of circulation; this was particularly apparent where the plastic pipe was connected onto a metal tube at the powder injection port. Some powder was also deposited on the inner wall of the pipes. The test results are shown in Table 19.
Table 19: Micron-scale Zinc Oxide (EC/112/08)

46
Zinc oxide nanopowder (EC/149/07) Zinc oxide nanopowder had a very fine consistency with very little cohesion under compression. A mass of 6g of powder was tested. Charging was observed for the whole duration of the test (Figure 36). A number of phases of charging each with different gradients are apparent from the data. There was little powder accumulation observed but a significant layer of powder formed at the inner walls of the pipe. A good proportion of the powder was observed resting in the bottom of the pipes following the test. The test results are shown in Table 20.
8 60m 8 40m 8 20m 8 00m 7 80m 7 60m 7 40m 7 20m 7 00m 6 80m 6 60m 6 40m 6 20m 6 00m 5 80m 5 60m 5 40m 5 20m 5 00m 4 80m 4 60m 4 40m 4 20m 4 00m 3 80m 3 60m 3 40m 3 20m 3 00m 2 80m 2 60m 2 40m 2 20m 2 00m 1 80m 1 60m 1 40m 1 20m 1 00m 80m 60m 40m 20m 0 -20m -40m 0 20 40 60 80 1 00 120 14 0 160 18 0 200 220 Time (s) 2 40 260 2 80 300 32 0 340 360 380 400 4 20 43 3.1
Figure 36: Zinc oxide nanopowder (EC/149/07)
Table 20: Zinc oxide nanopowder (EC/149/07)

47
8.5.2.3
Zirconium Oxide
Micron-scale zirconium oxide (EC/111/08) The powder had a very fine consistency with very little cohesion under compression. A mass of 1g of powder was tested. A rate of charging greater than anticipated was observed; the voltage across the capacitor rapidly increased to a value greater than could be measured. The powder was deposited in a thick layer on the inner wall of the pipe. Following the test the resistance between measuring station and the Earthed fan casing was measured as greater than 2000M. The test results are shown in Table 21. Table 21: Micron-scale zirconium oxide (EC/111/08)
Rate of change of voltage (V/s) 4.95E+00 Capacitance (F) 1.02E-08 Current (A) 5.04E-08
Zirconium oxide nanopowder (EC/151/07) The powder had a very fine consistency with very little cohesion under compression. A quantity of 1g of powder was tested. The powder accumulated at the pipe joints forming a significant build-up. Charging was recorded for approximately 2 seconds. There was little powder was deposited on the inner wall of the pipe. Further quantities of powder were added to try to overcome the problems of powder build and hence reduced powder circulation. A maximum of 6g of powder were used, these tests resulted in very similar behaviour and charging magnitudes. The test results are shown in Table 22.
Table 22: Zirconium oxide nanopowder (EC/151/07)

48
8.5.2.4
Carbon
Micron-scale carbon (EC/113/08) The powder was very cohesive; this was evident in the difficulty experienced in releasing the powder from the powder loading port. A quantity of 3g of powder was tested. The voltage across the capacitor rapidly increased to a value greater than could be measured. The powder was deposited in a significant layer on the inner wall of the pipe. A plot of the test is shown in Figure 37 and the test results are shown in Table 23. It was noted that the voltage on the capacitor returned to 0V within 1 second once the fan was stopped. The resistance between measuring station and the Earthed fan casing was measured as 0.50M. The carbon deposits on the inner walls of the pipe has significantly reduced the resistance to Earth.
10 .74 1 0.5 10 .25 10 9 .75 9.5 9 .25 9 8 .75 8.5 8 .25 8 7 .75 7.5 7 .25 7 6 .75 6.5 6 .25 6 5 .75 5.5 5 .25 5 4 .75 4.5 4 .25 4 3 .75 3.5 3 .25 3 2 .75 2.5 2 .25 2 1 .75 1.5 1 .25 1 75 0m 50 0m 25 0m 0 -263.4m 1 1:36:55.739 11:36:57.739 11:36 :59.739 11:37:01.739 11:37:03. 739 Time (s) 11:37:05.739 11:37:07.739 11:37:09.739 11:37:11.544
Figure 37: Micron Scale Carbon (EC/113/08)
Table 23: Micron Scale Carbon (EC/113/08)

Rate of change of voltage (V/s) 1.28E+01 Capacitance (F) 1.02E-08 Current (A) 1.31E-07
49
Carbon Pyrograf III nanofibres (EC/042/08) The powder was observed as being made up of mixed sized particles from fine dust to agglomerated particles of approximately 2mm in size. Powder could not be aggregated further when compressed. A quantity of 2g of powder was tested. A plot of the test is shown in Figure 38 and the test data is shown in Table 24. A continuous flow of powder was observed, there was no apparent powder accumulation. A significant layer of powder was deposited on the inner wall of the pipe. A quantity of mainly larger sized particles where present on the bottom of the pipe once the fan was stopped.
100m 50m 0 -50m -100m -150m -200m -250m -300m -350m -400m -450m -500m -550m -600m -650m -700m -750m -800m -850m -900m -950m -1 -1.05 -1. 1 -1.15 -1. 2 -1.25 -1. 3 -1.35 -1. 4 -1.45 -1. 5 -1.55 14: 00:36.256
14:01:26 .256
14:02:16.256
14:03:06.256
14:03:56.2 56 Time (s)
14:04:46.256
14:05: 36.256
14:06:26.25 6
14 :07:16.256
14:08 :11.156
Figure 38: Carbon Pyrograf III nanofibres (EC/042/08) Table 24: Carbon Pyrograf III nanofibres (EC/042/08)
50
Carbon nanofibres (EC/158/07) In common with sample EC/042/08, the powder was observed as being made up of mixed sized particles from fine dust to agglomerated particles of approximately 2mm in size. Powder could not be aggregated further when compressed. A quantity of 1g of powder was tested. During the test, a continuous flow of powder was observed but a layer of powder was deposited on the inner wall of the pipe. A quantity of mainly larger sized particles where present on the bottom of the pipe once the fan was stopped. The plot of the test is shown in Figure 39 and the test data is presented in Table 25. It was observed that the voltage across the capacitor dropped away rapid during the test. The resistance between measuring station and the Earthed fan casing was measured as 0.12M. The carbon deposits on the inner walls of the pipe has significantly reduced the resistance to Earth.
20m 0 -20m -40m -60m -80m -100m -120m -140m -160m -180m -200m -220m -240m -260m -280m -300m -320m -340m -360m -380m -400m -420m -440m -460m -480m -500m -520m -540m -560m -580m -600m -620m -640m -660m -680m -700m -720m -740m -760m -780m -800m -820m 0 10 20 30 40 50 60 70 80 90 100 110 120 1 30 140 Time (s ) 150 160 170 180 19 0 200 210 220 230 240 25 0 2 60 26 8.7
Figure 39: Carbon nanofibres (EC/158/07)
Table 25: Carbon nanofibres (EC/158/07)

51
Carbon multi-walled nanotubes (EC/153/07) The powder was observed as being made up of mixed sized particles from fine material of approximately 2mm in diameter. Powder could not be aggregated further when compressed. A quantity of 1g of powder was tested. A continuous flow of powder was observed. A significant layer of powder was deposited on the inner wall of the pipe and a quantity of mainly larger sized particles where present on the bottom of the pipe once the fan was stopped. During the test there was audible evidence of electrostatic discharges. However, there was no apparent visible evidence of discharges. Following the test the resistance between measuring station and the Earthed fan casing was measured as 0.15M. A plot of the test is shown in Figure 40 and the test data is presented in Table 26.
20m 0 -20m -40m -60m -80m -100m -120m -140m -160m -180m -200m -220m -240m -260m -280m -300m -320m -340m -360m -380m -400m -420m -440m -460m -480m -500m -520m -540m -560m -580m -600m -620m -640m -660m 16:23:15.287
16 :23:35.287
1 6:23:55.287
16:24:15.287
16:24:35.287
16:24:55.28 7
16:25:15.2 87
16:25:35. 287 Time (s)
16:25:55 .287
16:26:1 5.287
16:26 :35.287
16:2 6:55.287
16:27:15.287
16:27 :48.987
Figure 40: Carbon multi-walled nanotubes (EC/153/07)
Table 26: Carbon multi-walled nanotubes (EC/153/07)

52
8.5.2.5
Copper
Micron-scale copper (EC/004/09) The powder had a very fine consistency with very little cohesion under compression. A quantity of 5g of powder was tested. A continuous flow of powder was observed; there was no apparent powder accumulation. A very fine layer of powder was deposited on the inner wall of the pipe. The test data is presented in Table 27.
Table 27: Micron-scale copper (EC/004/09)

Copper nanopowder (EC/148/07) The powder was naturally aggregated into approximately 0.5mm material. The powder could not be aggregated further when compressed. A quantity of 2.5g of powder was tested. The powder was initially observed to flow reasonably well. The inner wall of the pipe was coated with a fine layer of powder shortly after starting the test. When the test was complete there was little evidence of any free powder remaining in the pipes. Following the test the resistance between measuring station and the Earthed fan casing was measured as greater than 2000M. The test data is presented in Table 28.
Table 28: Copper nanopowder (EC/148/07)

53
9
9.1
DISCUSSION
EXPLOSION TEST EQUIPMENT
A 2 litre explosion test facility has been established. Equipment has been manufactured and where necessary existing equipment has been modified and configured to allow the safe handling and testing of nanopowders. Sealed systems have been designed for use in conjunction with a glovebox that have allowed nanopowders to be weighed and handled under an inert atmosphere. This has enabled non-oxidised materials to be safely handled and held under inert conditions until the point of ignition. The 2 litre explosion test apparatus has been used to measure the explosion pressure and rates of pressure rise of nanopowders using a set of conditions established and calibrated against a range of dusts tested in both the 2 litre and 20 litre vessels. The small volume of the 2 litre vessel has reduced the quantity of test material required for the test procedure. Typically, 50 100 g of material is required for a series of tests covering a wide range of dust concentrations. This is approximately 10% of the material requirements for a standard 20 litre sphere test. The small volume of the test chamber was a concern in that quenching of the flame at the vessel wall was possible and could lead to lower combustion rates. This proved to be the case and the rates of pressure rise were lower than might be expected from a small vessel. However, a scaling factor has been obtained from the test data and equivalent KSt values have been obtained. The maximum explosion pressures were generally comparable with those measured in the 20 litre sphere. The minimum ignition energy of nanopowders was measured using a modified Kuhner MIKE3 test apparatus. The equipment was modified to allow nanopowder to be safely handled within the test apparatus. The modifications included enclosing the dispersion cup with a slide valve to fully contain the nanopowder and allow handling within a glovebox. Argon was used for inerting the material. The full test chamber assembly was configured such that it was removable as a complete sealed assembly for cleaning purposes.
9.2
EXPLOSION SEVERITY AND MIE
A comparison of the nanopowder data generated in this test programme with published micronscale powder data (BIA-Report 1997) is summarised in Table 29. Generally, the KSt values of nanopowders are similar to conventional micron-scale powders. The Pmax values are a little lower due to flame quenching effects at the vessel wall. Surprisingly, the large surface to volume ratio has not produced greater reactivity than the equivalent material at micron-scale. However, the minimum ignition energies of some nanopowders have been lower than the equivalent material at micron-scale. This may be explained by consideration of dispersion and agglomeration (Preining, 1998). Although powders are initially well dispersed in the 2 litre chamber, the rate of re-agglomeration may be such that nanopowders are dispersed only for a very short duration and rapidly begin to re-agglomerate. Thus, combustion may well take place initially with dispersed particles but some degree of re-agglomeration of the particles may take place before combustion has been completed. This hypothesis would need to be checked by sampling the dispersed dust cloud and measuring particle size using equipment that measures the size distribution and number concentration of fast dynamic aerosols. Equipment needed for measuring the particle size of the dispersed dust cloud was considered during this project. The current bench-mark instrument for measurement of nanoparticles in
54
their airborne state is considered to be the Scanning Mobility Particle Sizer (SMPS). This instrument measures a size and number distribution from around 5 nanometres up to 1 micron in diameter. The SMPS, comprises a Condensation Particle Counter (CPC) and a Differential Mobility Analyser (DMA). The latter component invariably employs a radioactive source to produce a known charge distribution on the sampled aerosol through ionisation of the sampled air. However, the SMPS cannot be used to obtain a particle size distribution in anything like realtime. Full particle size data is derived from a series of scans during which a varying voltage is applied to the selection electrode in the Differential Mobility Analyser. In general, instruments of the SMPS type require around three minutes to complete a full particle size scan. This means that the information gathered by the SMPS will be spurious if the concentration and size range of the aerosol being sampled are dynamic and not constant. This is particularly disadvantageous when measuring nanoparticles dispersed into the air during explosion testing. Under these circumstances, the distribution of sizes will be extremely transitory due to the tendency of the primary particles to rapidly agglomerate. Therefore the SMPS equipment could not be used for assessment of the particle size and agglomeration. An instrument is required that will capture the transient particle size distribution. The instrument identified for this work is a Fast Mobility Particle Sizer Spectrometer. A sample in near real-time is taken and is therefore an ideal tool to measure an aerosol composed of nanoparticles, either in the laboratory or in the field, under rapidly changing conditions. It is recommended that further work is done to assess the particle size/agglomeration of the dust cloud at the point of ignition using this instrument. In common with micron-scale powders the maximum rate of pressure rise and maximum explosion pressure of nanopowders sometimes occurred at different dust concentrations. The metal dusts tend to have relatively high optimum dust concentrations compared with carbon nanopowders, for example the optimum dust concentration for aluminium is within the range 2000 3000 g/m3 whereas carbon is typically within the range 400 1500 g/m3. 9.2.1 Aluminium
The aluminium nanopowders have demonstrated explosion properties comparable with the micron-scale powders. Published data (BIA, 1997) of micron-scale aluminium powders typically have KSt values within the range 300 700 bar m/s, and have maximum explosion pressures within the range 7 12 bar. KSt values of 449 bar m/s for 210 nm aluminium nanopowder and 536 bar m/s for 100 nm nanopowder powder are well within this range of values. As might be expected, the finer aluminium nanopowder had the higher KSt value. Other research workers (Nanosafe, 2008) have found the KSt of some aluminium nanpowders to decrease with decreasing particle size. This has been attributed to the thin oxide layer wrapping the passivated nanoparticles; this may make them less explosible than micron-scale aluminium nanopowders. The aluminium nanopowders are easily ignited, burning with a highly incandescent flame and are firmly in the St3 Dust Group. Aluminium nanopowders, as with micron-scale aluminium powders, have very severe explosion characteristics. The minimum ignition energies of aluminium nanopowders were comparable with micron-scale aluminium with MIE < 1 mJ. The aluminium nanopowders are therefore very sensitive to ignition by electrostatic discharge and extreme caution is required when handling these powders.
55
9.2.2
Zinc
Visually, zinc nanopowder burned in a similar manner to aluminium, producing a very bright flame. The maximum explosion pressure was 5.6 bar, the maximum rate of pressure rise was 377 bar/s resulting in an equivalent KSt value of 101 bar m/s. The nanopowder is thus classified as an St1 dust. The zinc nanopowder characteristics are typical of published micron-scale zinc powders (BIA 1997). The minimum ignition energy was 3 10 mJ and was considerably lower than published data for micron-scale zinc powder; 100-1000 mJ and 300-1000 mJ have been quoted. The ignitability of zinc nanopowder is therefore greater than conventional micron-scale zinc powder. 9.2.3 Iron
Iron nanopowder produced an explosion pressure of almost 3 bar and a rate of pressure rise of 68 bar m/s resulting in an equivalent KSt value of 18 bar m/s. This was lower than published data for micron-scale iron where explosion pressures 5.1 - 5.2 bar and KSt values of 41 - 50 bar m/s have been published. Iron nanopowder is clearly an St1 dust. The minimum ignition energy of iron nanopowder was less than 1 mJ. Although the explosion data is not as severe as micron-scale powder, the low MIE value is lower than micron-scale iron powder and demonstrates it is potentially a very ignitable nanopowder. 9.2.4 Copper
Copper nanopowder proved to have very low explosion characteristics to the extent that it is considered non-explosible. This is consistent with micron-scale copper powder; test data in the BIA database indicates micron-scale copper powder is non-explosible. 9.2.5 Carbon
The carbon nanopowders generally had a very agglomerated appearance and had poor handling characteristics in that they would not flow in the manner of free-flowing powders. KSt values were within the range 17-158 bar m/s and are therefore classified as St1 dusts and are weak to moderately explosible. The difference in the reactivity of the two extremes may be due to the length of the fibres. Sample EC/042/08 was the lowest rated carbon nanofibre and had relatively long fibres; 30-100 micron long with a diameter of 100-200 nm. The highest rated material was carbon nanofibre sample EC/116/08; this had a diameter of 70 200 nm but a significantly shorter length of 2-5 micron. Therefore, as might be expected, the shorter carbon nanofibres were more explosible than the longer fibres. The minimum ignition energies of these materials were greater than 1000 mJ and therefore the materials are not sensitive to ignition from electrostatic ignition sources.
56
Table 29: Comparison of nanopowders with micron-scale powders

Nanopowder Material Particle size Pmax (barg) Equivalent KSt(bar.m/s) 449 Micron-scale powder (typical range of data) Material Particle size Pmax (barg) 7-12 KSt (bar m/s) 300-700
Aluminium nanopowder (210 nm) Aluminium nanopowder (100 nm) Iron nanopowder
210 nm
12.5
Aluminium
Median <10-100m
100 nm
11.2
536
25 nm
2.9
18
Iron
Median 12m Median 32m
5.2 5.1 0.7 7.3 No ignition 8 7.1
50 41 2 176 No ignition 151 43
Zinc nanopowder
130 nm
5.6
101
Zinc
Median 160m Median 10m
Copper nanopowder Carbon nanofibre EC/42/08 Carbon nanofibre EC/158/07 Carbon nanofibre EC/116/08 Carbon nanofibre EC/117/08 Multi-walled carbon nanotubes EC/153/07
25 nm
1.2
Copper
Median 25 m
Dia 100-200 nm Length 30-100m
5.2
17
Carbon
100%<63m 100%<63 m
Dia 80-200 nm Length 0.5-20m Dia 70-200 nm Length 2-5m
6.0
30
6.9
158
Dia 70-200 nm Length 2-10 m
5.6
37
Dia 20-30 nm Length 10-30m
6.4
91
57
9.3 9.3.1
ELECTROSTATIC ISSUES Resistivity
The resistivity data demonstrates that with increasing relative humidity the resistivity of aluminium, zinc oxide and zirconium oxide nanopowders decreases. Carbon nanopowders tended to be relatively insensitive to changes in humidity. The effect of high relative humidity on reducing the resistivity of powders is a well-known characteristic in micron-scale powders. PD CLC/TR 50404 (2003) indicates that high relative humidity decreases the surface resistivity of many powders. But for this to be effective as a means of charge reduction, most materials need a relative humidity well in excess of 70 % and it is often impracticable to operate powder processing units at these high levels of humidity. NFPA 77 comments that at humidities of 65% and higher, the surface of most materials absorb enough moisture to ensure a surface conductivity that is sufficient to prevent accumulation of static electricity. Generally, nanopowders have greater resistivity values than conventional micron-scale powders. For example, the three carbon nanopowders all had greater resistivity values than the micron scale carbon powder. The test results have shown that nanopowders have lower packing densities than micron-scale powders, i.e. Table 16 shows densities of 0.047 g/cm3 to 0.105 g/cm3 for carbon nanopowders compared with 0.577 g/cm3 for micron-scale carbon. Since the low packing densities of nanopowders are accompanied by greater voids (air gaps) between the particles, when compared with micron-scale powders, this may be responsible for the higher resistivity values. Table 30 is a summary of the data over the range of humidity levels. Aluminium, iron oxide, and zinc oxide were medium resistivity powders but touched on high resistivity at low humidity levels. The individual materials are discussed in more detail below. Table 30: Summary of nanopowder resistivity
Powder Sample number Range of experimental resistivity values (m) 3.44E+06 to 3.64E+11 Comment
Aluminium nanopowder Iron nanopowder Iron oxide nanopowder Zinc nanopowder Zinc oxide nanopowder Copper nanopowder Zirconium oxide nanopowder Multi-walled carbon nanotubes Carbon nanofibres Carbon nanofibres
EC/104/08
Generally a medium resistivity powder.
EC/147/07 EC/150/07 EC/152/07 EC/149/07 EC/148/07 EC/151/07
9.06E+02 2.41E+08 to 3.44E+09 3.75E+03 1.39E+05 to 6.14E+09 2.34E+02 1.47E+06 to 7.51E+07
Conductive Medium resistivity powder Conductive Medium resistivity powder Conductive Medium resistivity powder
EC/153/07
2.78E+00 to 1.11E+01
Conductive
EC/158/07 EC042/08
1.91E+00 to 5.28E+01 1.55E+03 to 5.77E+03
Conductive Conductive
58
9.3.1.1
Aluminium
The resistivity of aluminium nanopowder was 3.64 x 1011 m at 8% RH drecreasing to 3.44 x 106 m at 70% RH. Micron-scale aluminium powder was insensitive to changes in humidity and had a relatively low resistivity in the order of 2 x 102 m. The aluminium nanopowder appears to be sensitive to changes in humidity and can be classified as medium resistivity for the medium RH levels. At low RH it can be classified as a low-resistivity powder and at high RH it can be classified as a high-resistivity powder. It was generally more resistive than micronscale aluminium powder. 9.3.1.2 Iron
Iron nanopowder had a resistivity of 9 x 102 m at 7.8% RH and was more resistive than the micron-scale iron powder. Iron nanopowder is considered to be a conductive powder. Iron oxide nanopowder had a resistivity of 3.44E+09 m at 7.7 % RH making this powder a medium resistivity powder. The micron-scale iron powder was insensitive to changes in humidity. 9.3.1.3 Zinc
Zinc nanopowder had relatively low resistivity with value of 3.75 x 103 m at a relative humidity of 5.7% and is classified as a conductive powder. The zinc oxide nanopowder had higher resistivity, decreasing with increasing humidity and is classified as a medium resistivity powder. 9.3.1.4 Copper
Copper nanopowder and micron-scale copper both had very low resistivity values (2.34 x 102 m and 7.1 m respectively) and are classified as conductive powders. The micron-scale powder was insensitive to humidity levels. 9.3.1.5 Zirconium oxide
Zirconium oxide nanopowder and micron-scale powder closely mirrored each other. At low humidity, both had similar resistivities, with the nanopowder having a resistivity of 7.51 x 107 m and the micron-scale powder 2.47 x 109 m. They are classified as medium resistivity powders. Both had decreasing resistivities with increasing humidity. 9.3.1.6 Carbon
Carbon nanofibres, nanotubes and micron-scale carbon powder all had low resistivities. Their resistivities appear to be relatively insensitive to changes in relative humidity. The resistivities were within the range 0.2 for micron-scale carbon to 5.7 x 103 m for the nanofibre sample. The samples were all considered to be a conductive powders. Should the conductive nanopowders penetrate into electric and electronic equipment, they could give rise to short-circuit problems and may lead to the generation of ignition sources. The possibility of nanopowders penetrating into electrical and electronic equipment may be greater due to their reduced particle size. 9.3.2 Charging
The results of the charging tests are presented in Table 31. The resistivity results for each powder are also shown in this table.
59
Powder Copper nanopowder Copper micron scale Carbon nanotubes Carbon nanofibres Carbon Pyrograf III nanofibres Carbon micron scale Zirconium Oxide nanopowder Zirconium Oxide micron scale Zinc Oxide nanopowder Zinc Oxide micron scale
Table 31: Charging tests Sample Number Resistivity (m) EC/148/07 EC/004/09 EC/153/07 EC/158/07 EC/042/08 EC/113/08 EC/151/07 EC/111/08 EC/149/07 EC/112/08 2.34E+03 7.49E+01 1.06E+01 4.79E+01 5.36E+03 1.97E-01 1.75E+06 1.23E+06 2.46E+05 1.53E+08
Current (A) -5.14E-08 5.93E-08 -2.63E-08 -1.22E-08 -3.59E-08 1.31E-07 -1.93E-07 5.04E-08 9.37E-09 8.26E-09
All the powders produced charge, indicated by the current in Table 31: some materials developed negative and some developed positive charge. Generally, the charge developed by nanopowders was comparable with the micron-scale powders. Various graphs of resistivity against current have been plotted but no relationship between these two properties can be identified from this data. The chargeability of powders is a notoriously complex subject with numerous factors (humidity, surface contaminants, particle size etc.) influencing a powders tendency to charge. The British standard BS5958-1:1991 refers to the charging characteristics of powders and states The charging characteristics are often determined at least as much by surface contamination of the particles as by the chemical composition of the powder itself and charge generation is usually difficult to predict. It is therefore likely that the charging characteristics of the nanopowders will be significantly influenced by their surface characteristics. BS5958-1:1991 indicates that the most important parameter in electrostatic phenomena in powders is the mass charge density of the powder (i.e. the charge to mass ratio). The tendency for many of the powders to accumulate around small obstructions, therefore reducing the net powder flowing in the system, meant that it wasnt possible to ensure that each test was performed with the same quantity of powder. This tendency for particle deposition also limited the duration of many tests, which meant it was difficult to identify whether a steady state of charge accumulation had been reached. BS5958-1:1991 provides details of suggested test apparatus for determining the mass charge density of a powder. This apparatus is not suitable for use with nanopowders given the potential risks from exposure and the small size of the particles. However, with further work and the experience gained in this test programme, the principles of this apparatus could be employed in new test apparatus designed specifically for work with nanopowders.
60
10
CONCLUSIONS
Equipment has been manufactured and where necessary existing equipment has been modified and configured to allow the safe handling and testing of nanopowders. The equipment comprises: 2 litre explosion test apparatus for measuring the rate of pressure rise and the maximum explosion pressure. Minimum ignition energy test apparatus. The minimum ignition energy of nanopowders was measured using a modified Kuhner MIKE3 test apparatus that allowed nanopowder to be safely handled within the test apparatus. Sealed systems that allow the safe handling of oxidized and non-oxidized nanopowders under inert atmospheres.
KSt , Pmax and MIE values have been obtained for a range of metal and carbon nanopowders. The KSt is an equivalent value scaled from the results obtained in the 2 litre vessel. Generally, the explosibility (maximum explosion pressure, rates of pressure rise and KSt) of nanopowders are broadly similar to conventional micron-scale powders. Surprisingly, their large surface to volume ratio has not produced greater explosion violence than the equivalent material at micron-scale. However, the minimum ignition energies of some nanopowders have been lower than the equivalent material at micron-scale. This indicates that the nanopowders may be more susceptible to ignition but once ignited the explosion violence is no more severe than micronscale powders. Resistivity measurements on nanopowders have demonstrated that with increasing relative humidity (RH) the resistivity of aluminium, zinc oxide and zirconium oxide decreases. Carbon nanopowders tended to be insensitive to changes in humidity and were classified as conductive powders. Aluminium, iron oxide, and zinc oxide were medium resistivity powders but touched on high resistivity at low humidity levels. There is a tendency for nanopowders to have higher resistivity values than conventional micron-scale powders. For example the three carbon nanopowders all had greater resistivity than the micron scale carbon powder. The lower packing densities of nanopowders and the accompanying voids between the particles may be responsible for the higher resistivity values. The conductive nanopowders, such as the carbon nanopowders, are not likely to be an electrostatic hazard but should these powders penetrate into electric and electronic equipment, they could give rise to short-circuit problems and may lead to the generation of ignition sources. The possibility of nanopowders penetrating into electrical and electronic equipment may be greater due to their reduced particle size. The following is recommended: a) Further nanopowders should be tested to broaden the body of knowledge relating to the explosion characteristics of nanopowders, and to develop further expertise and knowledge, particularly as new powders are developed. b) Although powders are initially well dispersed in the 2 litre explosion test chamber, the rate of re-agglomeration may be such that nanopowders are dispersed only for a very short duration and rapidly begin to re-agglomerate. Thus, combustion may well take place initially with dispersed particles but some degree of re-agglomeration of the particles may take place before combustion has been completed. This would need to be checked by sampling the dispersed dust cloud and measuring particle size using
61
equipment that measures the size distribution and number concentration of fast dynamic aerosols. It was not possible to assess the particle size/agglomeration of the dispersed dust cloud at the point of ignition using the SMPS equipment due to the transient nature of the dispersed dust cloud. An instrument is therefore required that will capture the transient particle size distribution. The instrument identified for this work is a Fast Mobility Particle Sizer Spectrometer. It is recommended that further work is done to assess the particle size/agglomeration of the dust cloud at the point of ignition using this instrument. c) In terms of fire characteristics, as nanopowders grow in use, balance of risk to benefit may change and further assessment of fire behaviour may be justified. The most important areas for study are then likely to be a) the potential for a fire to lead to a release of nanopowders that would subsequently form an explosion hazard of an environmental risk and b) the potential for nanopowders to form a source of ignition for a fire in more conventional materials. Perhaps the most important early tests should therefore be an examination of the effects of transient fires on nanopowder packaging is it possible to perforate storage materials without igniting the contents? Also, an examination of the potential for bulk nanopowders to react with air and form an ignition source through mechanisms analogous to the spontaneous combustion processes that can occur through oxidation in some other bulk materials.
62
11
APPENDICES
APPENDIX 1 : Commissioning data - Lycopodium sample number EC/026/08

Test run Dust concn. (g/m3) Igniter
t_open
(ms)
t_close
(ms)
t_ignition
(ms)
Vacuum (barg)
dP/dt (bar/s)
Pmax (barg)
Comments
1 2 3 4 4a 4b 4c 5 6 6a 7
500 500 500 500 500 500 500 500 No dust No dust 1500
Electric fuse head Electric fuse head Electric Electric fuse head Electric fuse head Electric fuse head Electric fuse head Electric fuse head 1kJ Sobbe Electric fuse head Electric fuse head Electric fuse head Electric fuse head 1kJ Sobbe 1kJ Sobbe
10 10 10 10 10 10 10 10 10 10 10
40 40 55 55 55 55 55 55 55 55 55
120 120 120 105 95 85 80 100 100 100 100
-0.65 -0.65 -0.65 -0.65 -0.65 -0.65 -0.65 -0.65 -0.65 -0.65 -0.65
100 170 40 20 166 -
7.9 8.2 7.7 4.5 3.6 7.5 0.9 0.05 Rebound nozzle. Dust not ignited Dust ignited Dust ignited not not
Dispersion nozzle fitted with deflector
8 8a 8b 8c
1500 1250 500 500
10 10 10 10
55 55 55 55
100 100 100 100
-0.65 -0.65 -0.65 -0.65
200 200
7.5 7.7 Misfire
250
63
Test run
Dust concn. (g/m3)
Igniter
t_open
(ms)
t_close
(ms)
t_ignition
(ms)
Vacuum (barg)
dP/dt (bar/s)
Pmax (barg)
Comments
9 9a 9b 9c 9d 9e 9f 10 10a 10b 10c 11 12 13 13a 13b 13c 13d 13e 13f
1000 1500 1500 1500 1500 1500 1500 500 1000 1000 1000
1kJ Sobbe 1kJ Sobbe 1kJ Sobbe Electric fuse head 1kJ Sobbe 1kJ Sobbe 1kJ Sobbe 1kJ Sobbe 1kJ Sobbe 1kJ Sobbe 1kJ Sobbe
10 10 10 10 10 10 10 10 10 10 10
55 55 65 65 65 65 65 65 65 60 60
100 100 100 90 80 75 75 75 75 75 70
-0.65 -0.65 -0.65 -0.65 -0.65 -0.65 -0.65 -0.65 -0.65 -0.65 -0.65
333 375 200 183 666 750 576 750 882 714
8.75 8.75 7.75 6.5 7.7 8.2 8.4 8.5 8.5 8.4 Misfires Misfires Misfired (3 attempts)
1000 1000 1500 800 400 555 300
5kJ Sobbe 5kJ Sobbe 5kJ Sobbe 5kJ Sobbe 5kJ Sobbe 5kJ Sobbe 5kJ Sobbe
10 10 10 10 10 10 10
60 60 60 60 60 60 60
75 75 75 75 75 75 75
-0.65 -0.65 -0.65 -0.65 -0.65 -0.65 -0.65
1300 888 1500 833 1500 944
9 9.1 Misfire
8.4 9.5 8.6
64
Test run
Dust concn. (g/m3)
Igniter
t_open
(ms)
t_close
(ms)
t_ignition
(ms)
Vacuum (barg)
dP/dt (bar/s)
Pmax (barg)
Comments
14 14a 14b 14c 14d 14e
360 400 625 700 550 550
5kJ Sobbe 5kJ Sobbe 5kJ Sobbe 5kJ Sobbe 5kJ Sobbe 5kJ Sobbe
10 10 10 10 10 10
60 60 60 60 60 60
75 75 75 78 78 78
-0.9 -0.9 -0.9 -0.9 -0.9 -0.9
666 1100 650 625 875 850
7.4 8.3 7.3 7.8 7.8 7.4
65
APPENDIX 1 : Commissioning data Aluminium sample number EC/060/07

t_open
(ms)
t_close t_ignition
(ms) (ms)
Vacuum (barg)
dP/dt (bar/s)
Pmax (barg)
Comments
16a 16b 16c 16d 16e 16f 16g 17a 17b 17c 17d 17e 17f 17g 17h 17i 18a 18b 18c 18d 18e 18f 18g
250 500 750 1000 1250 1500 1750 250 500 750 1000 1250 1400 1500 1600 1750 250 500 750 1000 1250 1500 1750
5 kJ Sobbe 5 kJ Sobbe 5 kJ Sobbe 5 kJ Sobbe 5 kJ Sobbe 5 kJ Sobbe 5 kJ Sobbe 1 kJ Sobbe 1 kJ Sobbe 1 kJ Sobbe 1 kJ Sobbe 1 kJ Sobbe 1 kJ Sobbe 1 kJ Sobbe 1 kJ Sobbe 1 kJ Sobbe 2 kJ Sobbe 2 kJ Sobbe 2 kJ Sobbe 2 kJ Sobbe 2 kJ Sobbe 2 kJ Sobbe 2 kJ Sobbe
10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10
60 60 60 60 60 60 65 65 65 65 65 65 65 65 65 65 65 65 65 65 65 65 65
78 78 78 78 78 78 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83 83
-0.9 -0.9 -0.9 -0.9 -0.9 -0.9 -0.9 -0.9 -0.9 -0.9 -0.9 -0.9 -0.9 -0.9 -0.9 -0.9 -0.9 -0.9 -0.9 -0.9 -0.9 -0.9 -0.9
972 1800 2100 3100 2250 3700 5000 20 400 588 375 1100 1250 1400 1200 1450 212 750 833 1666 1250 1250 1950
6.7 8.6 9.4 8.9 8.9 9.0 9.5 1.7 4.7 6.7 7.7 7.7 9.6 9.6 10.5 10.8 4.2 6.4 6.5 7.9 8.0 8.25 8.6
66
APPENDIX 1 : Commissioning data Aluminium sample number EC/060/07

t_open
(ms)
t_close t_ignition
(ms) (ms)
Vacuum (barg)
dP/dt (bar/s)
Pmax (barg)
Comments
18h 18i 18j 18k 18l 19a 19b 19c 19d
2000 1625 1875 1812 1750 1750 1750 1750 1750
2 kJ Sobbe 2 kJ Sobbe 2 kJ Sobbe 2 kJ Sobbe 2 kJ Sobbe 2 kJ Sobbe 2 kJ Sobbe 2 kJ Sobbe 2 kJ Sobbe
10 10 10 10 10 10 10 10 10
65 65 65 65 65 65 65 65 65
83 83 83 83 83 100 90 120 120
-0.9 -0.9 -0.9 -0.9 -0.9 -0.9 -0.9 -0.9 -0.9
1700 1300 1500 1025 1000 1200 1425
8.4 9.4 8.6 8.9 8.6 8.9 9.8 misfire
750
9.6
Comparing tests18g and 19a-d , the optimum ignition point = 83 ms
1750 20a 20b 21a 21b 1625 1500 1500
3 kJ Sobbe 3 kJ Sobbe
10 10
65 65 65 65
83 83 83 83
-0.9 -0.9 -0.9 -0.9
1700 1800 1400 850
9.5 9.1 9.1 8.4
1 kJ Sobbe 10 + 0.1 Mg 1 kJ Sobbe 10 + 0.3 Mg
67
12
REFERENCES
BS 5958-1:1991 Code of practice for Control of undesirable static electricity Part 1: General considerations. BS EN 61241-2-2 (1996). Electrical apparatus for use in the presence of combustible dust Part 2: Test methods Section 2.2 Method for determining the electrical resistivity of dust in layers. BS EN 14034-1 (2004). Determination of explosion characteristics of dust clouds Part 1: Determination of the maximum explosion pressure max of dust clouds. BS EN 14034-2 (2006). Determination of explosion characteristics of dust clouds Part 2: Determination of the maximum rate of pressure rise (dp/dt)max of dust clouds. BS EN 13821 (2002). Potentially explosive atmospheres Explosion prevention and protection Determination of minimum ignition energy of dust/air mixtures. Barton J. (2002). Dust explosion prevention and protection a practical guide. Published by Institution of Chemical Engineers ISBN 0 85295 410 7. BIA-Report (1997). Combustion and explosion characteristics of dusts. ISBN 3-88383-469-6 CCPS (2005). Guidelines for safe handling of powders and bulk materials. Centre for Chemical Process Safety of the American Institute of Chemical Engineers. ISBN 0-8169-0951-2. Eckhoff R K (1997). Dust explosions in the process industries. ISBN 0 7506 3270 4. Nanosafe Report (2008). European Strategy for Nanosafety. Dissemination Report February 2008 DR-152-200802-2. Project ID: NMP2-CT-2005-515843 NFPA 77 (2007). Recommended Practice on Static Electricity 2007 Edition. National Fire Protection Association. Preining O (1998). The physical nature of very, very small particles and its impact on their behaviour. J. Aerosol Science., 29, 481-495. PD CLC/TR 50404 (2003). BSI published document. Electrostatics Code of practice for the avoidance of hazards due to static electricity. Seaton, A., L. Tran, et al. (2009). "Nanoparticles, human health hazard and regulation." J.R. Soc. Interface doi:10.1098/rsif.2009.0252.focus.
Published by the Health and Safety Executive
02/10

Nanotechnology is a rapidly expanding technology in which existing and novel materials are engineered at the nanoscale, typically in the range of 1 to 100 nanometres. Engineered nanomaterials include uniquely manufactured products with unique shapes and enhanced physical and chemical properties, compared with conventional materials of the same composition. There is currently little available information on the explosion risks of these materials. The Health and Safety Executive therefore commissioned this project to investigate the potential fire and explosion hazards associated with nanopowders. Test equipment and procedures were developed to assess the key properties of a selected number of nanopowders. A specialised 2 litre test vessel was developed to determine the explosion characteristics and modified standard test apparatus was used to measure the minimum ignition energy of nanopowders. Resistivity and electrostatic charging characteristics were assessed using specially designed test apparatus. Key information including KSt, Pmax and MIE values were obtained for a range of metal and carbon nanopowders. Generally, the explosibility (maximum explosion pressure, rates of pressure rise and equivalent KSt) of nanopowders were found to be broadly similar to conventional micron-scale powders. However, the minimum ignition energies of some nanopowders were found to be lower than the equivalent material at micron-scale. It was demonstrated that with increasing relative humidity the resistivity of most nanopowders decreases. There was also a tendency for nanopowders to have higher resistivity values than conventional micron-scale powders. All the powders produced electrostatic charge. Generally, the charge developed by nanopowders was comparable with the micron-scale powders. This report and the work it describes were funded by the Health and Safety Executive (HSE). Its contents, including any opinions and/or conclusions expressed, are those of the authors alone and do not necessarily reflect HSE policy.
RR782
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Fire and explosion properties of nanopowders

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Fire and explosion properties of nanopowders

Figure 1: Vessel general arrangement

Figure 2: Test vessel

Figure 3: Test vessel

Figure 4: Glovebox 3.3 CONTROL AND INSTRUMENTATION

Laboratory instrument reference PT140

Charge amplifier sensitivity 152.1 154.1

MINIMUM IGNITION ENERGY

FIRE HAZARDS IN NANOPOWDERS

Figure 9: Resistivity test cell

Table 2 (continued): Nanopowders

Intrinsiq Materials Ltd

Aluminium Carbon Black

Intrinsiq Materials Ltd Cabot

Ref: PQN301 Batch 17 Monarch 800

Table 3: Micron-scale powders

EC/112/08 EC/004/09 EC/111/08 EC/113/08 EC/026/08 EC/118/08 EC/120/08 EC/122/08

Fluka Ronald Briton Ltd Acros Organics Sigma Aldrich Fluka

100% < 75 micron 190522500 484164-50G 2-12 micron Sieved to 63 micron

COMMISSIONING TESTS EXPLOSION SEVERITY

Dp/dt, KSt value and Pmax

7.3 9.8 7.6

558 714 382

151 194 104

7.4 7.5 7.8

600 725 320

7.3 6.3 6.2

Kmax 20 litre sphere vessel (bar m/s)

20 litre vessel - Pmax (bar)

Rate of pressure rise in 2 litre vessel (bar/s)

2 litre test vessel - Pmax (bar)

Figure 10: Comparison of 20 litre and 2 litre test apparatus

Figure 11: Pressure time trace

Figure 12: Pressure-time trace

Figure 13: Lycopodium - 20 litre sphere test

Rate of pressure rise (bar/s)

Explosion pressure (barg)

5.0 200 400 600 800 1000 1200 1400

100 200 400 600 800 1000 1200 1400

Dust concentration (g/m3)

Dust concentration (g/m3)

Figure 10: Lycopodium - 2 litre sphere test

EXPLOSION SEVERITY OF NANOPOWDERS

EC/147/07 EC/152/07 EC/148/07 EC/042/08 EC/158/07 EC/116/08 EC/117/08 EC/153/07

2.9 5.6 1.2 5.2 6.0 6.9 5.6 6.4

68 377 10 62.5 112 591 137 339

Rate of pressure rise (bar/s)

Explosion pressure (bar g)

1400 1200 1000 800 600 400

200 0 1000 2000 3000 4000 5000 6000 7000

Dust concentration (g/m3)

Dust concentration (g/m3)

Figure 15: Aluminium nanopowder sample EC/011/09

Explosion pressure (bar g)

Rate of pressure rise (bar/s)

800 500 1000 1500 2000 2500 3000 3500 4000

Dust concentration (g/m3)

Dust concentration (g/m3)

Figure 12: Aluminium nanopowder sample EC/104/08