Simple oxidation of aluminum-containing sample materials for efficient

processing by a Borate

Expertise in the fusion process - quality makes the difference

HRT fusion GmbH

Dirk Töwe

Annual Meeting of the GDMB chemist Committee

Kassel, November 11, 2015
Borate for sample preparation - known procedure

completely oxidized

sample material homogeneous glass sample for

+ XRF analysis

melting salt

Part-oxidized or metallic samples do not dissolve in the molten salt.

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The case study of a service laboratories shows the challenges in the digestion of
aluminum-containing samples.

• unlock more than 10,000 samples / month by Borate

• Most of the samples taken from the iron ore industry or materials in-house research projects

• extreme range of aufzuschließenden samples for base material and matrix, including aluminum , Rare earth
and organic samples

• For unknown, partially oxidized samples a muffle furnace was used for sample preparation.

challenges

• high rejection rate at outcrops unknown materials

• Improper treatment of aluminum-containing samples; this makes it impossible to catch up

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Approach the chemist to develop optimal digestion methods

• From extensive database selection of samples with a significant "Gain on Ignition" and a significant concentration of
partially oxidized aluminum

• Developing a generally applicable procedure for aluminum-containing sample with a focus on the pre-oxidation

• Using a melt digestion unit, which enables a very precise control of the pre-oxidation steps

objective

• Oxidation of the sample material on the fluxer without a prior high temperature treatment
in a muffle furnace

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nieka ® Gas-fluxer G4

• new series of gas fluxers with an extremely precise

control of all parameters melting

• Fluxer allows development of custom methods

• flexible design of all program

steps
• Real-time tracking of the digestion = simple,
final adjustment of the digestion method

patented nieka ®
heating chambers

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nieka ® Gas-fluxer - quality and innovative melt processing
facilities

productivity
• very high throughput by significantly reduced digestion times
• low operating costs (no compressed air, no oxygen)
• Self-monitoring and self-diagnosis of the system

accuracy
• patented, reliable temperature measurement of each crucible
• automatic Eigenkalibration each pressure sensor
• optimum reproducibility of results

efficiency
• patented, individual heating chambers to increase efficiency and significantly reduce energy consumption. Specimen Related
suitable for both high and low decomposition temperatures.

user friendliness
• large built-in touch screen, TCP / IP Ethernet port, USB, network

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Aluminum containing samples particularly illustrate the problem when
using the usual method.

Previous procedure The new method

• Pre-oxidation step in a muffle furnace: A whole night at 1050 ° C • Metallic aluminum is not soluble in a borate melt.

• The total digestion time on the digestion device exceeds 20 min. and • Therefore, the chemist of nieka developed to convert the aluminum to
also the use of the muffle furnace significantly reduces throughput. a method using hydroxide.

• The digestion device previously used does not allow for precise • The digestion technique was developed in compliance with the changes
temperature settings and regulation to allow direct processing. of the required aluminum speciation and the properties of the hydroxide
salt.

The new method

• Conversion of aluminum
• Using a multi-step oxidation process before the main digestion step
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Conversion / decomposition of aluminum

• objective:

Conversion of the aluminum in the sample materials in a more soluble form - lithium aluminate LiAlO 2

• Using lithium hydroxide LiOH due to its oxidation properties both in aqueous and molten state

• Solubility in water (at 20 ° C): 12.8 g / 100 ml

• Melting point: 462 ° C

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A simple method with two phases allows quick and accurate insight.

Phase 1 - first chemical reaction Phase 2 - processing on the fluxer

• Pt / Au crucible with 0.5 g of sample material
• Adding 1.5 g of LiOH
• Addition of 1 ml water, demineralized
• Human Interest, wet sample material: hydroxide of the first
step
• Addition of 6.7 g of molten salt lit / LiM /
LiBr 66.67 / 32.83 / 0.5%

The crucible is at least 10 minutes at room temperature; on the

Direct processing on the Fluxer possible without previous
first oxidation step
drying step.
takes place.

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 Stop-and-go in Phase 2: a flexible approach for simpler method development

Usual procedure Multi-step oxidation process Main digestion: melting

borate, sample dissolves

Main insight program

Before oxidation 2: melting
d. LiOH

Low temp. for 45

Before oxidation sec.
temperature

Total duration of the

Outcrop less than
eight
no heat
minutes

• Use of only A: the exothermic reaction generated during the first

In the usual procedure directly the main digestion program with its step B: existing in a platinum crucible energy
individual process steps begins after the pre-oxidation ..
• The sample material dries in less than a minute without causing
splashes.
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The new method allows a rapid digestion of aluminum-containing samples and
provides perfect homogeneous discs.

homogeneous glass sample for XRF analysis lit / LiM

67/33 + 0.5% LiBr

Advantages of the method

• Time required for the digestion - without the first manual oxidation step - less than 12 minutes (drying, 2. oxidation,
digestion or four minutes cooling)
• WITHOUT preheating the muffle furnace
• Result: perfectly homogeneous glass samples (RSD Al 2 O 3 0.14%)

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Overview of the matrix of the investigated sample materials

• Based on the study: five specimens of similar basic matrix (see table)

• Depending material 12 glass samples were melted.

LOI (%) al 2 O 3 (%) SiO 2 (%) F (%)

sample 1 - 12.8 93.3 2.7 1.9

sample 2 - 15.1 99.7 3.3 1.3

sample 3 - 17.5 98.1 3.6 1.8

sample 4 - 15.8 95.3 3.3 1.7

sample 5 - 14.6 96.5 2.4 1.9

• There were only materials selected where there were big problems.
• Samples that were not to work on the fluxer.
• Samples had to be preheated in any case for hours in a muffle furnace.

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The multi-step oxidation is an efficient and time-saving method.

• Pre-oxidation steps crucial ingredients may be your digestion method. Selecting the right oxidant and melting salt is
crucial.

• Fused cast devices from different manufacturers have individually differing heating characteristics.

• Knowledge of the plant specifics allows the development of more efficient methods.

• The Borate is not a black box system:

An important part of method development is the observation and understanding of the individual, inherent steps
of the process as a key to success.

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Summary: Easy oxidation of aluminum-containing sample materials for efficient
processing by a Borate

• LiOH enables direct oxidation of aluminum-containing materials and manufacturing good suitable for XRF
analysis glass samples.

• The method developed can (in other difficult sample materials such as
eg FeSi) are applied.

• The stop-and-go approach on the fluxer ensures fewer manipulations and allows precise and rapid sample
processing.

• The use of more than one oxidation (Aqueous and molten salt) allows a controlled reaction, and full oxidation even
of difficult sample materials.

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Thank you for your attention!

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