Author Topic: Standards for EPMA-Halides  (Read 2481 times)

crystalgrower

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Standards for EPMA-Halides
« on: January 11, 2018, 03:34:44 PM »
Here is what I know about making “insoluble” halide salts to be used as  standards for microanalysis  (SfM hereafter).

First of all these are not perfectly insoluble in water.  Good crystals are possible in many cases because there  is a slight solubility. 
These salts are all truly  insoluble in 100% lab (not pharmacy) isopropanol from a glass bottle.  Not too toxic, compatible with epoxy and plastics, and was found to be safe for metal mounts. 

Second critical point is the matter of mounting perfect crystals.  Most crystal growing yields excellent octahedral or cubic crystals and then some residue of hoppered garbage.  The hoppers are worse than powder because they can retain microlayers of solvent that outgas for far too long.   

Buyer Beware  Inspect loose grains that you buy as “SfM” and return any with hoppers for a full refund.  Inspect any natural “SfM” for inclusions by using a few drops of isopropanol on a  slide, and rotate  to see any second phase under magnification.

Fluorine Commercial LiF and other synthetics including NaMgF3, K2SiF6, Cs2SiF6. My A2SiF6 never developed colour centres in full scan XRF.

I have been told (never checked) that colourless natural topaz is free from OH.  If you need an O bearing F standard then use SiO2 and Al2O3 and LiF to calibrate, because both O and F should be resolved in a good EDS.   Pieces at my local rock shop would cost less than SEM time…

DO NOT use fluoroapatite as an F standard because the crystal structure guarantees F  migration under the electron beam, that has been shown to be permanent.  Please read  Pyle et al, Reviews in Mineralogy and Geochemistry (2002) vol 48 pp 337-362  for the details.  The F migration occurs in all F-Ap regardless of origin. 

Chlorine I made Rb2PtCl6 from  both Pt-aqua regia and Alfa H2PtCl6, adding RbCl.   Nice raft of octahedral crystals grew at the top of a 1 litre Erlenmeyer flask over the space of 2 months using water with 5mL HCl and 1mL HNO3.  Cover with watch glass.  Lowest setting on hotplate, airflow at  front corner of fume hood made an excellent thermal gradient.  No hoppers formed.  You want a good supply of yellow solid at the bottom of the flask to feed the crystals at the top.  Green solid means you need more HNO3.

Rb2SnCl6 can be made by mixing saturated solution of  2RbCl into solution of  SnCl4-5H2O and a trace of HCl.  Slow evaporation while excluding air gives the white hexoctahedral  product.   It is more soluble but OK in isopropanol.  Success depends on the quality of SnCl4-5H2O which degrades with age.

Thallium chloride TlCl is extremely soft and difficult to polish.  Ugly mess.

End-member chlorapatite Ca5(PO4)3Cl2 can be made under hydrothermal conditions.   Difficult to prepare in open crucible because there is a transition on cooling below 1300°C. 
Spodiosite Ca2PO4F is easier to prepare from commercial calcium orthophosphate and CaCl2 flux in a crucible at 800-900°C.  Good project to start learning about high temperature synthesis.

Bromine Thallium bromide is insoluble.  It is commercially available in good single crystal form.  Add this after polishing all other materials in a mount to minimize exposure to ground particles. 

KPbBr3 might be useful, I have not tried.  See KPbI3 below.

Iodine  Several insoluble options 

There is one caveat to using thallium bromide-iodide—make sure of exact details of manufacture.  Certified KRS-5 is a dark orange-red single crystal optical material.  KRS-5 has 58% Br ions and 42% I ions.  KRS-5 should be seller certified as the eutectic (lowest melting point mixture of thallium bromide and thallium iodide).  It should be zone refined to ensure absence of other phases.  Check the loose piece by IR rather than in polarized light because all phases are cubic.
NB Some Taylor material was the 60Br-40I mix prepared by simple mixing and melting. To my eyes it was slightly lighter orange.

In theory it should be possible to melt thallium iodide that has been vacuum sealed in quartz without significant decomposition. 

I found it was easier to grow good-sized crystals of KPbI3 than PbI2.  Simple slow cooling of a saturated solution (beaker in large water bath) gave flakes.  Prebonding in epoxy allowed the flakes to be mounted sideways.  NB you get a hydrated form by evaporative growth. 
« Last Edit: January 26, 2018, 10:48:08 AM by crystalgrower »

jon_wade

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Re: Standards for EPMA-Halides
« Reply #1 on: April 13, 2018, 04:45:47 AM »
we are looking to purchase some halogen standards - preferably ones that aren't majorly hygroscopic.  We have  a good range of F standards, but are wondering what is out there for Br, I?  ThBrI seems the best bet but are there any others?

all the best
Jon

Probeman

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Re: Standards for EPMA-Halides
« Reply #2 on: April 13, 2018, 12:09:09 PM »
we are looking to purchase some halogen standards - preferably ones that aren't majorly hygroscopic.  We have  a good range of F standards, but are wondering what is out there for Br, I?  ThBrI seems the best bet but are there any others?

all the best
Jon

Hi Jon,
I have some candidate iodate standards sent to me by Marc Schrier a while back.  If you are willing to mount them and test them for beam stability I could send them to you.
john
The only stupid question is the one not asked!

jon_wade

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Re: Standards for EPMA-Halides
« Reply #3 on: April 15, 2018, 05:41:19 AM »
John

That would be great and worthy of many beer-vouchers!
all the best and thank you
Jon

Probeman

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Re: Standards for EPMA-Halides
« Reply #4 on: April 15, 2018, 09:22:49 AM »
John

That would be great and worthy of many beer-vouchers!
all the best and thank you
Jon

Hi Jon,
OK, now I just need to find where I stashed them!

Please send me your shipping address by email when you get a chance.
john
The only stupid question is the one not asked!

crystalgrower

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Re: Standards for EPMA-Halides
« Reply #5 on: May 10, 2018, 05:16:56 PM »
In addition to Tl(Br,I) both TlBr and TlI are stable to humidity. You get 2 calibration points with 3 substances.

In contrast  TlCl is very soft and makes a wicked mess in polishing.  Much like AgBr and AgI. 

But how high do you need the Br or I to go?

Iodates are quite soluble.  Sorry. 

BenjaminWade

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Re: Standards for EPMA-Halides
« Reply #6 on: August 18, 2020, 06:24:55 PM »
Hi Jon and all
I am in the process of looking at Br and I standards (again...), and was wondering currently what people are using, and Jon if you ever found a good one that you are currently using?

cheers

Probeman

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Re: Standards for EPMA-Halides
« Reply #7 on: August 19, 2020, 09:09:24 AM »
Hi Ben,
I got a Tl(Br,I) material from U of Toronto many years ago (see below). We also tried CsBr but it is hard to polish. It acts like rubber according to my technician at the time.

St  829 Tl(Br,I)
TakeOff = 40.0  KiloVolt = 15.0  Density =  7.371

From Claudio Cermignani (U of Toronto)
TlI-Tl-Br mixture
XRF analysis by M. Gordon
(75% total, recalculated to 100%)
Approx. half of Fe is machine blank
Elemental Composition

Average Total Oxygen:         .000     Average Total Weight%:   99.957
Average Calculated Oxygen:    .000     Average Atomic Number:   67.606
Average Excess Oxygen:        .000     Average Atomic Weight:  142.523
Oxygen Equiv. from Halogen:  2.749

ELEM:       Tl       I      Br      Na      Mg      Si       P       S
XRAY:      ma      la      la      ka      ka      ka      ka      ka
ELWT:   61.441  25.828  11.197    .966    .060    .083    .008    .075
KFAC:    .5521   .2260   .0777   .0040   .0003   .0006   .0001   .0007
ZCOR:   1.1129  1.1430  1.4405  2.3910  1.7801  1.3232  1.1830  1.0290
AT% :   42.866  29.019  19.980   5.991    .352    .421    .037    .334

ELEM:        K      Ca      Fe      Zn      Ga
XRAY:      ka      ka      ka      ka      ka
ELWT:     .110    .130    .025    .017    .017
KFAC:    .0010   .0013   .0003   .0002   .0002
ZCOR:   1.1027  1.0013   .8503   .7800   .8129
AT% :     .401    .462    .064    .037    .035
The only stupid question is the one not asked!

BenjaminWade

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Re: Standards for EPMA-Halides
« Reply #8 on: August 19, 2020, 11:22:09 PM »
Thanks John
Yes I have an Astimex synthetic TlBrI but havent probed it in anger yet. The only numbers I have from it are the general Astimex numbers, and that it was made in Atomergic Chemetals Corp, USA. I have put a couple of laser holes in it though for traces and is surprisingly very clean. Will see how I go.

Cheers

crystalgrower

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Re: Standards for EPMA-Halides
« Reply #9 on: September 04, 2020, 06:57:50 AM »
The Astimex and U of T (both one source) TlBrI is the eutectic composition.  The thinking was that this would be stable  for EPMA as repeated melting during zone refining does not appear to disturb the  composition as measured by IR spectrometry.  The literature on this is in ACS archives.

Brian Joy

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Re: Standards for EPMA-Halides
« Reply #10 on: February 16, 2021, 12:54:52 PM »
Following on the discussion of potential bromine standards, recently I had the opportunity to investigate some CsPbBr3 (22.92 wt% Cs, 35.74 wt% Pb, 41.34 wt% Br) grown by a graduate student in the Chemistry department here; I believe she used the Czochralski method to grow it.

Water should be avoided during polishing, as the compound is at least somewhat soluble in it.

Considering the composition, I was surprised at how well it held up under the beam.  At beam energy = 15 keV, beam current = 10 nA, and the beam finely focused (minimal astigmatism), the Br La count rate and absorbed current tend to be a little unstable.  In contrast, at 20 nA (focused), very bad things happen.  Working with a 10-micron beam diameter at 20 nA gives much better results.

It appears that the compound can handle beam currents below 20 nA (at 15 keV) as long as the beam is defocused to 10 microns.  I'm calling it a winner!

10 nA, focused beam:


20 nA, focused beam


20 nA, 10 micron beam diameter

Brian Joy
Queen's University
Kingston, Ontario
JEOL JXA-8230

Probeman

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Re: Standards for EPMA-Halides
« Reply #11 on: February 20, 2021, 12:39:34 PM »
Following on the discussion of potential bromine standards, recently I had the opportunity to investigate some CsPbBr3 (22.92 wt% Cs, 35.74 wt% Pb, 41.34 wt% Br) grown by a graduate student in the Chemistry department here; I believe she used the Czochralski method to grow it.

Water should be avoided during polishing, as the compound is at least somewhat soluble in it.

Considering the composition, I was surprised at how well it held up under the beam.  At beam energy = 15 keV, beam current = 10 nA, and the beam finely focused (minimal astigmatism), the Br La count rate and absorbed current tend to be a little unstable.  In contrast, at 20 nA (focused), very bad things happen.  Working with a 10-micron beam diameter at 20 nA gives much better results.

It appears that the compound can handle beam currents below 20 nA (at 15 keV) as long as the beam is defocused to 10 microns.  I'm calling it a winner!

Hi Brian,
This sounds interesting.

When I was at UC Berkeley we needed a Cs standard and so I ordered a CsBr single crystal from an electronics materials supplier.  I gave it to my technician to mount up and he reported to me that it was like trying to polish rubber! Under the beam we found it was also quite unstable but usable with a TDI correction for the standards. 

Your compound seems pretty stable with a defocussed beam, but I bet it would also work if you turn on the TDI correction for standards in PFE (in the Special Options dialog in the Acquire! window).
« Last Edit: February 21, 2021, 08:55:37 AM by Probeman »
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