The THT Rapid Screening Device Safety Calorimeter RSD R S D RAPID SCREENING DE •6 samples / references simultaneously V •Scanning Calorimetry IC •Isothermal Calorimetry E •Dosing, Stirring, Cryogenic •Temperature & Pressure •mg to 100g sample size - all in one instrument Introduction to the THT RSD Novel • Rapid • Sensitive • Versatile • Inexpensive A unique calorimeter with OPTIONS! UNIQUELY UP TO 6 SAMPLES SIMULTANEOUSLY The RSD has a thermally controlled robust calorimeter sample chamber. This will allow up to 6 samples with 6 thermocouples and 6 pressure transducers. Sample holders may be tube holders (mg), glass or metal ARC™ bombs (1g-10g), or simply a larger vessel (10-100g) HOW IT WORKS The heated calorimeter chamber is closed with a circular pathway to allow air (or inert gas) to circulate repeatedly during the test. The gas passes through the sample chamber and over the main heater. Circulation is achieved by a high temperature fan and a control thermocouple regulates power to the heater to implement the test protocol. OPTIONS • Cryogenic operation to -100°C • Stirring • Dosing • Gas Release / Collection The THT Rapid Screening Device (RSD™) is the most versatile hazards safety calorimeter. WHAT TO TEST This brochure shows how using the RSD will help chemists and Typically a sample (in solvent) plus reference (solvent alone or engineers quantify exothermic (and endothermic) reactions from air). Maybe 3 or 4 samples (differing batches, concentration, materials of low hazard to high explosives! suppliers) against 1 or more references. Liquids, solid, mixtures, gas/liquid, pastes, any sample type! Compared to DSC, the RSD takes much larger samples and pressure measurement is standard. Compared to Dewar, oven and home built calorimeters, the RSD is quantitative, safe in use and industry recognised. Compared to other screening safety calorimeters, the RSD takes up to 6 samples simultaneously, has design features to provide comparative and differential data of highest quality and uniquely incorporates multiple safety features. Hardware & Software Using the RSD TEST PROTOCOLS: Qualitative analysis: present the sample data in tabular and SIMPLE, RAPID AND AS EASY AS 1, 2, 3... graphical form. • Temperature against time 1. (ONE) • Pressure against time Choose from the range of holders best suited to your sample. An • Temperature rate against temperature ARC bomb (Stainless Steel, Titanium, Hastelloy, Glass), a simple tube, a glass 2ml or 4ml vial – a re-useable cylindrical holder, a gas flow holder – or simply put the sample in any suitable container. Weigh the sample into the holder and connect to the ‘RSD head’. Repeat this with further samples, a reference material, an empty holder and put these into the holding tray. Connect the thermocouples and gas lines, close and screw down the calorimeter lid. Shut the outer cover. 2. (TWO) Differential analysis Select the data set for analysis and the reference. The reference may be air, an inert solvent, or a sample from a different batch. Generate graphs where the reference data is subtracted from the sample data – just as is done in DSC 2. (TWO) Using the industry standard National Instruments LabVIEW software set up protocol can be quickly completed (typically 2 minutes). Enter sample information (for each sample), then the test conditions, start and end temperatures, cut out temperature, pressure. 3. (THREE) Click Start and relax; maybe check the test is going to plan or ‘on-the-fly’ change conditions as needed. The RSD has multiple safety interlocks. One or two hours later the test may be finished automatically and the system cooled or the test can be terminated manually. Analyse the data on this PC or transfer to your memory stick. 3. (THREE) Quantitative analysis ANALYSIS: NI LABVIEW BASED FOR EASE OF USE Finally where appropriate, use the inbuilt thermodynamic and SIMPLE, RAPID AND AS EASY AS 1, 2, 3... kinetic routines to determine heat of reaction, activation energy if the data allows this (please do not over-analyse complex data). Open data on any PC with the RSD Some data is not suited to quantitative analysis. 1. (ONE) Pre-analysis: remove data not needed for analysis and Save. • Cut • Filter • Size Performance illustrated with DTBP UNRIVALLED PERFORMANCE COMPARED TO ANY OTHER Pressure data as P (DTBP-Toluene) Vs Temperature of toluene SAFETY SCREENING CALORIMETER for 5%. 10%, 15% DTBP. Di-tertiary Butyl Peroxide (DTBP) is an ideal sample to evaluate performance of a safety calorimeter. Exothermic decomposition 50 5% DTBP of DTBP leads to explosion. Dilution, normally with toluene, r) 35 10% DTBP provides a range of samples with varying Heat of Decomposition. Ba 15% DTBP Scientific literature reports show spread in thermokinetic e ( 20 parameters, values are dependent upon experimental protocol; sur however decomposition of DTBP is often taken as first order with es 5 a Heat of Reaction near 1200 J/g. Pr -10 300 140 100 135 170 205 240 Toluene 10% DTBP 5% DTBP 15% DTBP Temperature (°C) 250 105 Ramp heating tests typically cause onset of reaction to be 200 70 recorded at higher temperature than step heated (ARC-type) 150 35 tests. Closer inspection of RSD data shows this with the thermal data more so than the pressure data. 100 0 30 38 46 54 62 3.0 Toluene Reference Time (min) r) 2.5 Ba 20% DTBP in Toluene Raw data from a test with 4 samples 0%, 5%, 10% and 15% e ( 2.0 DTBP is shown above; data from 2 samples of 20% DTBP with sur toluene and air (as recorded inside the calorimeter chamber) are es 1.5 Pr shown below; this illustrates reproducibility, shows no ‘cross-talk’ 1.0 with the toluene and the chamber air temperature. In the first stage of data analysis, results can be plotted against 110 115 120 125 130 temperature and most usefully ‘differential data’; ie the DTBP Temperature (°C) data minus the toluene data; to show heat from DTBP alone. DTBP data at low concentration is equally interesting. Classic safety calorimeters are sensitive, but due to test conditions the 220 ) 20% DTBP RSD can detect a smaller heat release than the DSC, ARC or °C 195 20% DTBP similar systems. In the RSD the thermocouple is in the sample Toluene and the temperature ramp forces heat release over a short time. ture ( 170 Air pera Below RSD results for one test with 1%, 2% and 3% DTBP in 145 toluene. No heat could be detected in other calorimeters; 1% Tem 120 would equal a heat release from a sample whose Heat of Reaction 35 45 55 65 75 is 12 J/g. The RSD will detect heat release to close on 1 J/g or 5J. Such data illustrates the ability of the RSD to quantify hazards or Time (min) heat release associated with ‘waste streams’. This is uniquely possible with the RSD and RSD RAP software and 5.0 is illustrated as T (DTBP-Toluene) Vs Temperature of toluene 1% DTBP ) 2% DTBP with 5%, 10% and 15% DTBP. 3.5 3% DTBP T (°C 2.0 50 5% DTBP 0.5 ) 35 10% DTBP C(° 15% DTBP -1.0 T 20 80 120 160 200 240 5 Temperature (°C) -10 100 135 170 205 240 Temperature (°C) Applications Data Quantitative, Flexibile and Versatile - not just DTBP and simple samples! The flexible RSD can be used for varied applications. The previous page detailed not just a simple exothermic material but also low energy (waste stream) application. 250 15 ) Sample 1 °C 225 Sample 2 5 Reference ) ture ( C 200 -5 T(° pera 175 -15 Tem 150 -25 47 49 51 53 55 0 100 200 300 400 Time (min) Reference Temperature (°C) Data above shows an application to high energy Complex organic chemical; illustrates melting below explosives. Two ‘similar’ explosives run in one test; 100°C followed by multi-stage exothermic decomposition Sample 1 is a fresh sample, Sample 2 has been aged to above 180°C. simulate 6 months storage at high ambient temperature. The aged sample is less stable. 5.0 90 3.5 ) )C °C 65 2.0 T(° ture ( 40 0.5 pera 15 -1.0 Tem -100 -65 -30 5 40 -10 Reference Temperature (°C) 0 100 200 300 400 Time (min) The RSD at cryogenic temperature. The ‘Swern reaction’ mixture, shows an exothermic reaction heated from -100°C Oxidation example; illustrates heat of oxidation of a powdered coal sample in a flow of oxygen at 60ml/min THERMOKINETIC DATA ANALYSIS 1.0 RSD RAP software has full routines for thermo kinetic data analysis. Determination of Heat of Reaction, 0.0 Activation Energy, Order of Reaction. There are various ) baseline constructions and ability to make data correction C -1.0 based upon sample holder used. Nevertheless reliable T(° quantitative data will only be observed if the reaction is -2.0 singular and obeys Arrhenius kinetics. -3.0 40 75 110 145 180 Temperature (°C) Ammonium Nitrate; illustrates RSD testing of samples undergoing endothermic processes. Ammonium nitrate has two phase transitions prior to melting and decomposition. Options and Specification OPTIONS GAS COLLECTION RSD capability is enhanced with low cost options. These extend The gas collection option is the range of applications. manually operated. Allowing residual gas collection after (or LIQUID DOSING during) a test. Gas collection Liquid dosing at ambient or low pressure is from up to 6 samples is achieved by manually operated valves. The possible. The 10-25ml collection added liquid is pre-equilibrated to the same cylinders are ‘quick release’ to temperatures as the sample. Volume dosing allow transfer to a gas analyser. can be done up to 50ml. GAS FLOW SPECIFICATION Gas flow during the test may be achieved at ambient or elevated pressure. Elevated pressure flow requires Temperature Range -100 to 500°C more sophisticated control, flow cells are available from THT. Modes of Operation Isothermal, step, scanning For example they allow flow of air (or oxygen) to study Scan Rate 0 - 10°C/min oxidation or combustion reactions. Detection Sensitivity Less than 10 J/g CRYOGENIC Pressure Range Up to 160 bar (alternative ranges Extending the temperature range available) below ambient is possible and Pressure Resolution 0.2 bar temperatures below -100°C can Sample Size >20mg be achieved with control of liquid nitrogen / cold nitrogen gas Sample Quantity 1 - 6 samples flow. Such capability is unique to Stirring Up to 2000 rpm the RSD. Software Dedicated Windows based control and data analysis software through link to PC STIRRING PC Requirements Windows The RSD stirring assembly is USB Port positioned between 2 sample Monitor Resolution 1280 x 1024 holders and therefore will stir Footprint 70 (W) x 43 (H) x 40 (D) cm both. Stirring can be achieved in both glass and metal sample Power Supply Single phase, 200-240V, 13A holders. Stirring will homogenise 2 non-miscible liquid phase or disperse liquid/solid 2-phase samples. Stirring speed can be varied as required. 1 North House • Bond Avenue • Bletchley • MK1 1SW • England T: +44 1908 646800 F: +44 1908 645209 E: info@thtuk.com W: www.thtuk.com PO Box 25 • Whitestown • Indiana • 46075 • USA T: +1 317 222 1904 F: +1 317 660 2092 E: info@thtusa.com W: www.thtusa.com Suite 1416 • No 1101 Pu Dong Road (S) • Shanghai • 200 120 • China T: +86 21 5836 2582 F: +86 21 5836 2581 E: info@thtchina.com W www.thtchina.com 808, Eighth Floor Tower - I • Pearls Omaxe • NetaJi Subhash Place • PitamPura • Delhi - 110034 • India T: +91 11 4701 0775 F: T: +91 11 4701 0779 E: info@thtindia.com W www.thtindia.com