Nitrocellulose Characterisation NNiittrroocceelllluulloossee CChhaarraacctteerriissaattiioonn:: –– SSuurrvveeyy ooff SSttaannddaarrddiisseedd TTeessttiinngg MMeetthhooddss –– SSttaabbiilliittyy TTeessttiinngg ooff NNCC AAAWWWEEE NNNiiitttrrroooccceeelllllluuulllooossseee SSSyyymmmpppooosssiiiuuummm AAAppprrriiilll 222000000777 Ruth Sopranetti, Markus Fahrni and Beat Vogelsanger NITROCHEMIE AG, Wimmis Switzerland / Aschau Germany 2007 AWE SympNitrocellulose _ PresentationNITROCHEMIE.ppt Vob/Sr/Fa Copyright byNitrochemie 09.05.2007 1 Nitrocellulose Characterisation Contents Part 1: International Survey of Standardised Testing Methods (cid:214) Standards for NC Testing (cid:214) Comparison of Test Methods Part 2: Stability Testing of NC (cid:214) Comparison of different Stability Test Methods (cid:214) Investigation of the Course of NO / NO Production 2 of NC at the different Test Temperatures using NO -Chemiluminescence Detection x 2007 AWE SympNitrocellulose _ PresentationNITROCHEMIE.ppt Vob/Sr/Fa Copyright byNitrochemie 09.05.2007 2 Nitrocellulose Characterisation Part 1: Survey of Standardised Testing Methods 2007 AWE SympNitrocellulose _ PresentationNITROCHEMIE.ppt Vob/Sr/Fa Copyright byNitrochemie 09.05.2007 3 Nitrocellulose Characterisation Standards on NC Testing (cid:31) The following Standards for NC Testing exist: • DEF STD 13-175 or UK M-Methods referred therein (UK Standard; used in UK and some Commonwealth nations) • MIL-DTL-244B (US Standard, used in USA and in many nations worldwide) • STANAG 4178 (NATO Standard; bases mainly on the UK Standards except for the viscosity test which is identical to the US MIL test; not well known, rarely used !) • several other National Standards (cid:31) Problem: Many of the standardized test methods are very old and do no longer fit into today's production / quality management / working safety environment: Some of the tests require handling of large amount of toxic substances (e.g. mercury), produce toxic waste, are too complicated, too costly or too time consuming (up to 4 days), or they stipulate the use of material which is only available from a single source (cid:31) MIL-DTL-244B is in revision: Tests that never fail such as "Ash" might be removed, more modern tests should be added as alternative procedures (cid:31) STANAG 4178 is also under revision (done by the CASG AC/326 SG/1 CNG; UK is Custodian Nation) (cid:214) Excellent chance to replace outdated test methods and to harmonize test procedures so that the STANAG can replace the national standards (cid:31) In order to assist this STANAG, Nitrochemie has performed a survey on NC testing 2007 AWE SympNitrocellulose _ PresentationNITROCHEMIE.ppt Vob/Sr/Fa Copyright byNitrochemie 09.05.2007 4 Nitrocellulose Characterisation Contributors to International Survey (cid:31) List of Contributors to Survey: • UK MoD: Neil Turner • QinetiQ (UK): Graham Gillies • EURENCO (France and Finland): Christian Spyckerelle • NC Mil-Spec Team (USA): Lucas Lopez, Tony Williams, Mario Paquet • Picatinny Arsenal (USA): Nathan Zink • DENEL (South Africa) Wolfgang Schimansky • SYNTHESIA (Czech Republic) Josef Tichý • ADI (Australia) John Reid, Rhonda Wheeler, • NCW (Switzerland) Beat Vogelsanger The following slides represent solely the opinions of these contributors and of the author (Beat Vogelsanger) 2007 AWE SympNitrocellulose _ PresentationNITROCHEMIE.ppt Vob/Sr/Fa Copyright byNitrochemie 09.05.2007 5 Nitrocellulose Characterisation Test Methods (1) Sample Preparation / Drying of NC (cid:31) Many different drying methods are currently used, with different methods and temperatures (e.g. in MIL-DTL-244B different drying for each subsequent test method) (cid:31) In the new Standard, one single and fast drying method should be used for all tests; or the level of moisture should be specified thereby allowing different drying methods (cid:31) This requires previous investigation of influence of drying method and remaining moisture level on results of subsequent tests Hot Air Blower Oven (40–45°C // 50°C // Steam-Operated Drying at Room- (60°C – 70°C) 60°C–70°C // 100°C–105°C) Air Bath Temperature 2007 AWE SympNitrocellulose _ PresentationNITROCHEMIE.ppt Vob/Sr/Fa Copyright byNitrochemie 09.05.2007 6 Nitrocellulose Characterisation Test Methods (2) Nitrogen Content MIL-DTL-244B (USA) DEF-STAN 13-175 (UK) Swiss Method Nitrometer Method Nitrometer Method Combustion Calorimetry Ferrous Sulphate Titration Devarda's Alloy Method Method (cid:31) The Nitrogen Content determines degree of nitrate ester substitution and thus energy content – as an intrinsic property of the NC, it can be determined in different ways (cid:31) The Nitrometer Method can no longer be used due to working safety reasons (Hg) (cid:31) The Ferrous Sulphate Titration Method is sufficiently fast and accurate but uses only small sample mass, requires cooling and produces large amounts of acid waste (cid:31) Devarda's Alloy Method is only used in the UK – automated equipment for the reduction/distillation/titration makes this method easy and quick (cid:31) Nitrochemie uses the Combustion Calorimetry Method which allows to use 10 times larger sample masses and is thus very precise; Method was calibrated using Schulze-Tiemann Method; correctness of result was confirmed by Ferrous Sulphate Titration Method (cid:31) The highly automated Nitrogen Analyzer (Combustion Elemental Analyzer) would safe working time but is only rarely used 2007 AWE SympNitrocellulose _ PresentationNITROCHEMIE.ppt Vob/Sr/Fa Copyright byNitrochemie 09.05.2007 7 Nitrocellulose Characterisation Test Methods (2) Nitrogen Content Combustion Calorimetry Method 2007 AWE SympNitrocellulose _ PresentationNITROCHEMIE.ppt Vob/Sr/Fa Copyright byNitrochemie 09.05.2007 8 Nitrocellulose Characterisation Test Methods (3) Soluble Matter (Ether-Alcohol Solubles) MIL-DTL-244B (USA) DEF-STAN 13-175 / M22 (UK) Swiss Method Preferred Meth. (all NC) Meth. A (low soluble NC; includes ashing / carbonating) Meth. 1 (low soluble NC) Alternate Meth. (high soluble NC) Meth. B (high soluble NC) Meth. 2 (high soluble NC) (cid:31) Necessary Test; measure for amount of low nitrated NC content or mixing ratio (cid:31) Outcome does not truly reveal the processability of the NC blend (cid:31) Soluble matter can be assessed in two different ways: (cid:214) Method 1) By determination of dissolved NC (direct drying of supernatant solution or precipitation of NC from supernatant solution followed by drying); this method is more accurate for low soluble NC (N ≥ 12.75%) (cid:214) Method 2) by determination of undissolved NC (filtration followed by drying); this method is more accurate for high soluble NC (N = 10.9% – 12.75%) (cid:31) The UK M-Method M22 Test A) is similar to Method 1) but additionally corrects for inorganic matter by subsequent ashing and carbonating steps → this adds a lot of work (= expenses and time) for little additional information and is regarded as not necessary by most NC specialists (also since the MIL-DTL-244B Test does without this additional step) 2007 AWE SympNitrocellulose _ PresentationNITROCHEMIE.ppt Vob/Sr/Fa Copyright byNitrochemie 09.05.2007 9 Nitrocellulose Characterisation Test Methods (4) Insoluble Impurities (Acetone Insolubles) MIL-DTL-244B (USA) DEF-STAN 13-175 (UK) Swiss Method Assesses “Total Residuals”; Standard Meth. Assesses “Insoluble Similar to MIL but with (Quantitative); Alternate Meth. (Semi-Quantitative) Organic Matter” solely Centrifuging (cid:31) Purity test, checks for unnitrated cellulose (and inorganic contaminants) (cid:31) All methods base on dissolution of the NC in acetone, followed by filtration and drying of the undissolved matter (cid:31) MIL-DTL-244B Test determines the "total residue" which consists of both organic and inorganic insoluble matter (cid:31) The UK-based tests (STANAG 4178 / UK M-Method M22) assess the insoluble organic matter solely which requires subsequent ashing and carbonating steps (ashing / carbonating determines the inorganic fraction which has to be subtracted from the "sum of organic + inorganic insolubles") UK prefers to retain distinguishing between organic and inorganic insolubles, whereas most other NC specialists prefer the easier and faster MIL Test which does without these additional steps 2007 AWE SympNitrocellulose _ PresentationNITROCHEMIE.ppt Vob/Sr/Fa Copyright byNitrochemie 09.05.2007 10