Elemental Analyzer Consumables

Our products are intimately involved with your samples

Scott Hughes, EA Consumables, Inc. Jon Davies, Elemental Microanalysis, Ltd.

Intimately Involved A lot of focus is on the laboratory instruments Things that cost a lot get a lot of attention Impressive and shiny for lab tours

The Big The Tenacious The Colorful

Intimately Involved Simple truth If you do not get complete conversion of your analyte to N2,

CO2, SO2, CO or H2, then the big expensive shiny “detectors” will not help you.

The instrumentation IS important. Has to provide: Ability to transfer sample Hot environment with a steady carrier flow Ability to add oxygen at correct time and place and …the “detector” does matter

Intimately Involved Analyzers and Consumables

Like the Chicken & Pig in making Breakfast The Analyzer participates The Consumables are intimately involved

Your sample and our products have an intimate relationship

Sample Encapsulation Combustion Aides-Reaction Blocking Oxidation Reagents Interference removal Reduction Absorption materials

Focus on the nature and applications of consumables for NC and NCS determinations

Sample Encapsulation Many Choices – Over 400 from Elemental Microanalysis Material – Tin, Silver, Nickel, Copper, Aluminum, Cellulose Form

Capsules: Pressed, Flat bottom smooth, round bottom smooth Boats, Pans, Disks/Squares, Cones

Size – 1.06mm to 32mm diameter Weight – Standard, light weight, ultra light weight Preparation – Standard, Pre-cleaned

Encapsulation Tin The “go to” encapsulation material Exothermically reacts with oxygen to help in the thermal

decomposition of the sample. Very pliable and easy to fold/work Issues

In situ carbon blank Tin oxide is corrosive to quartz at operating temperatures

Encapsulation Silver Typically used for oxygen determination, as there is no formation of an

oxide (at combustion temperatures) as is the case with tin Can tarnish in storage. Will be removed at 375oC. Also used for removal of inorganic carbon from sample by acid

fumigation or addition. No exothermic reaction. No ash, forms a silver melt in the reaction tube It is stiffer and not as easy to fold/work compared to tin Higher cost Big savings in the lightweight silver capsule options

HINT: Collect the waste. Can fund a wild lab party!

Encapsulation Aluminum Can be pre-combusted at 550oC to remove contaminants There is an art to get it to combust. Can inhibit full sample reaction.

Forms Pressed – Solids Pre-cleaned in sample well Smooth wall (flat or round bottoms) – liquids Disks/Squares/Cones – sticky, fibrous, big samples Evaporating cups – liquid reduction

Life Cycle of a Pressed Capsule Purchase of special purity foil of the

appropriate thickness and width

Life Cycle of a Pressed Capsule Purchase of special purity foil of the

appropriate thickness and width Feeds into custom made cutting/pressing

machine. Cuts round disk

Pin forms capsule in die

Ejects capsule to collection bin

Life Cycle of a Pressed Capsule Purchase of special purity foil of the

appropriate thickness and width Feeds into custom made cutting/pressing

machine. Cuts round disk

Pin forms capsule in die

Ejects capsule to collection bin

Waste is melted down and cast into ingots.

Life Cycle of a Pressed Capsule Purchase of special purity foil of the

appropriate thickness and width Feeds into custom made cutting/pressing

machine. Cuts round disk

Pin forms capsule in die

Ejects capsule to collection bin

Waste is melted down and cast into ingots.

Ingots are rolled into sheets suitable for the extruded smooth wall capsules

Life Cycle of a Pressed Capsule Purchase of special purity foil of the

appropriate thickness and width Feeds into custom made cutting/pressing

machine. Cuts round disk

Pin forms capsule in die

Ejects capsule to collection bin

Waste is melted down and cast into ingots.

Ingots are rolled into sheets suitable for the extruded smooth wall capsules

Ultra-Pure capsules get an additional solvent wash.

Weighed into final package.

Your sample and our products have an intimate relationship Sample Encapsulation Combustion Aides-Reaction Blocking Oxidation Reagents Interference removal Reduction Absorption materials

The path to N2, CO2, SO2

The combustion soup Organicish Sample + O2 + heat (~1,000oC) = Volatile combustion products CO, CO2, CH4,CO3,H2O,N2,NxOx,SO2,SO3,X-,HF

Block the formation of… Chemical Oxidation to CO2 Reduce Absorb

Combustion aides Added to sample Additional oxygen source at point of combustion Block undesired side reaction

Stable sulfides and carbonates Will fuse with alkali and alkaline earth oxides

Vanadium Pentoxide Toxic

Tungstic Oxide Powdered

Combustion aides Fine Powders

Niobium Pentoxide Added oxygen

Silver Oxide Added oxygen

Cobalt Oxide Added oxygen

Magnesium Oxide Added oxygen – bind F-

Sucrose For inorganic fertilizers

Carbon powder (high purity) as above

Tin powder Added heat

Your sample and our products have an intimate relationship Sample Encapsulation Combustion Aides-Reaction Blocking Oxidation Reagents Interference removal Reduction Absorption materials

Active Reagents, NC analysis

CE/Costech/Eurovector

Elementar Sercon/ Europa

Perkin Elmer

Chromium Oxide Copper Oxide Chromium Oxide Chromium Oxide

Cobaltous/ic Oxide, silvered

Lead Chromate Copper Oxide Silver Tungstate on Magnesium Oxide

(Silver Wool) (Silvered Copper Oxide)

Silver Vanadate

Silver wool Silver Gauze

Copper Copper Copper Copper

Silver wool Quartz chips Copper Oxide

Silver wool

Com

bust

ion

Red

uctio

n

Active Reagents, S or NCS analysis

CE/Costech/Eurovector

Elementar Sercon/ Eurpoa

Perkin Elmer

Tungstic Oxide Tungstic Oxide Tungstic Oxide on Zirconium Oxide

Tungstic Oxide on Zirconium Oxide

Copper Copper Copper

None Copper None None

Silver wool (cooler zone)

Com

bust

ion

Red

uctio

n

Not all the same Chromium Oxide

Key impurities in the Chromium Oxide can cause devitrification of quartz

Devitrification is accelerated in the presence of Na & P ions.

Most Cr2O3 is formed from sodium dichromate, so Na is always present

Elemental Microanalysis uses a different process to form Cr2O3 to results in lower sodium impurities.

After granulation, it is further heat treated to drive off other impurities

The results is much longer tube life

The tube on the left showed no signs of devitrification after 1,000 determinations.

Not all the same

Tungsten (VI) Oxide, Tungsten Trioxide, Tungstic Oxide These actually are all the same.

B1025 Tungstic Oxide, granular for Costech/Thermo/Europa Produced by reacting Scheelite (CaWO4) with HCl to form tungstic acid,

followed by decomposition to WO3

The material is tableted under very high pressure, and then ground to the appropriate size. Results is very dense material.

B1217 Tungstic Oxide, granular for Elementar Requires a less dense granular material Produced by reacting tungsten metal with oxygen at elevated

temperature. Results in a much less dense granule.

Your sample and our products have an intimate relationship Sample Encapsulation Combustion Aides-Reaction Blocking Oxidation Reagents Interference removal Reduction Absorption materials

Interference Removal Reagents Things to remove

Sulfur Cl, Br, I F H2O Oxidative help

Silver Wool/Gauze

Coboltous/ic Oxide Silvered

Copper granules silvered

Copper Oxide silvered

Silver Vanadate

Silver Tungstate/Magnesium Oxide

Magnesium Oxide

Lead Chromate

Iron Wool

Your sample and our products have an intimate relationship Sample Encapsulation Combustion Aides-Reaction Blocking Oxidation Reagents Interference removal Reduction Absorption materials

Reduction - Copper Available in many forms Copper Wires fine 0.5 x 4mm Copper Wires course 0.65 x 6mm Copper Granules fine 0.05 – 0.2mm Copper Granules standard 0.1 – 0.5mm Copper Granules course 0.3 – 0.85mm Copper wires highest purity for IRMS Electrolytic Copper Copper turning extra fine long strands Copper turnings fine long strands

Reduction – Copper Cu + O2 + NxOx + SO3 CuO + Cu2O + N2 + SO2

Cu + SO2 (lower temperature) CuS + CuO + Cu2O Surface reaction

More available surface area, more capacity

In general wrt capacity Granular > Wires

Fine > Standard > Coarse

An old penny > Electrolytic copper

“Normal Copper” has very low capacity Copper is first oxidized and then subsequently reduced

IRMS grade – longer reaction time

Your sample and our products have an intimate relationship Sample Encapsulation Combustion Aides-Reaction Blocking Oxidation Reagents Interference removal Reduction Absorption materials

Absorption Materials Water Magnesium Perchlorate

Regular and Indicating 25g can ship as a HazMat excepted quantity Gets hard when wet, can cause blockages

Sicapent (phosphorous pentoxide on inert support indicating) Very low water vapor pressure Most effective desiccant Good flow properties when wet – easy to remove Nobody likes to handle (forms phosphorous acid when wet)

Absorption Materials Carbon Dioxide Carbosorb (NaOH on support) EMAsorb (our version of Carbosorb – black to grey)

Soda Lime (mostly calcium hydroxide, some NaOH, and KOH)

All above are HazMats 25g bottles can be shipped under excepted quantity rules

Chromosorbs Polymers based on diatomaceous earth (mostly SiO2) P types have twice the density and capacity of W types Low blank for CNS so OK for liquid absorbant

Intimately Involved Conclusions For successful EA-IRMS determinations:

Complete conversion of sample into analyte gases Removal of interfering substances Reagents can be tailored for specific types of samples Preparation of the reagents has a significant effect on

effectiveness and life of the reagents. Chickens and Pigs can get along together Let just skip breakfast!