Sampling silicone contaminant

Applications of ISS to polymer analysis can provide some extremely useful and unique information that cannot be obtained by other means. This makes it extremely complementary to use ISS with other techniques, such as XPS and static SIMS. Some particularly important applications include the analysis of oxidation or degradation of polymers, adhesive failures, delaminations, silicone contamination, discolorations, and contamination by both organic or inorganic materials within the very outer layers of a sample. XPS and static SIMS are extremely comple-mentar when used in these studies, although these contaminants often are undetected by XPS and too complex because of interferences in SIMS. The concentration, and especially the thickness, of these thin surfiice layers has been found to have profound affects on adhesion. Besides problems in adhesion, ISS has proven very useful in studies related to printing operations, which are extremely sensitive to surface chemistry in the very outer layers. 

Typical XPS spectra are shownoin Figure 5. This technique samples a greater depth (about 30 A) and is able to give some detailed chemical state information about the composition ( ). Survey scans of the polymer reveal trace amounts of silicon contaminant, but represent only about 2% of the total surface area and can be subtracted from the final spectra. Silicones are... 

Silicone contamination has been implicated as a cause of failure in telephone switching systems and other devices that contain relay switch contacts (507). Analysis of airborne particulates near telephone switching stations showed the presence of silicones at these locations. Where the indoor use of silicones is intentionally minimized, outdoor levels were found to be higher than inside concentrations (508). Samples of particulates taken at two New Jersey office buildings revealed silicone levels that were considerably higher indoors than outdoors. In these cases, indoor silicone aerosols are believed to be generated primarily by photocopiers, which use silicone fuser oils. 

Note 5—CAUTION —Isolate silicones from other bituminous testing equipment and samples to avoid contamination, and wear disposable rubber gloves whenever handling silicones or apparatus coated with them. Silicone contamination can produce erroneous results... 

In SAM the electron beam can be focussed to provide a spatial resolution of < 12 nm, and areas as small as a few micrometers square can be scanned, providing compositional information on heterogeneous samples. For example, the energy resolution is sufficient to distinguish the spectrum of elemental silicon from that of silicon in the form of its oxide, so that a contaminated area on a semiconductor device could be identified by overlaying the Auger maps of the two forms of silicon obtained from such a specimen. 

If we add a known amount of a compound to our solution, we can use it to quantify the material of interest. This is great except that we may not want to contaminate our material with some other compound. A number of people have looked at using standards that are volatile so that they can be got rid of later (TMS is an example that we have seen published). The problem with this approach is that if the sample is volatile then you need to run it quickly before it disappears. TMS disappears really quickly from DMSO so it is probably not a good idea in this case. TMS also suffers from the fact that it has a long relaxation time so you have to be very careful with your experiment to ensure that you do not saturate the signal. The last major problem with TMS is that it comes at the same part of the spectrum as silicon grease which can be present in samples. Choosing a standard so that it has a short relaxation time, is volatile and comes in a part of the spectrum free of interference is really tricky. In fact, we wouldn t recommend it at all. 

Standard black O-rings made of an acrylonitrile-butadiene copolymer (such as Perbunan) have proved to be stable in HF at concentrations up to 50%. If contamination of the silicon sample is an issue, the nitrile O-rings may be replaced by vi-nylidene fluoride-hexafluoropropylene (Viton) O-rings [9],... 

A chip-based nanospray interface between an HPLC and the MS has been introduced by Advion Biosystems (Ithaca, NY). This instrument aligns a specialized pipette tip with a microfabricated nozzle, set in an arrayed pattern on a silicon wafer. The advantage of this interface is that each sample is sprayed through a new nozzle, thus virtually eliminating cross contamination. 

Sodium contamination and drift effects have traditionally been measured using static bias-temperature stress on metal-oxide-silicon (MOS) capacitors (7). This technique depends upon the perfection of the oxidized silicon interface to permit its use as a sensitive detector of charges induced in the silicon surface as a result of the density and distribution of mobile ions in the oxide above it. To measure the sodium ion barrier properties of another insulator by an analogous procedure, oxidized silicon samples would be coated with the film in question, a measured amount of sodium contamination would be placed on the surface, and a top electrode would be affixed to attempt to drift the sodium through the film with an applied dc bias voltage. Resulting inward motion of the sodium would be sensed by shifts in the MOS capacitance-voltage characteristic. 

For incorporation of crown ethers and cryptates into the RTV encapsulant system as sodium and potassium ion scavengers, the total ionic contaminants must first precisely be determined. Atomic absorption is used to measure these ions in commercial silicone RTVs and silicone fluids. Values of "10 ppm for sodium and potassium were obtained in the best samples. Chloride level was determined by potentiometric titration of the silicone with AgN03. A quantity of ion trap (either crown ethers or cryptates) was then added to the RTV silicone encapsulant, and its molar concentration was equal to the combined sodium and potassium contaminant levels. 

Reasonable care must be taken in handling salt cells and plates. Moisture-free samples should be used. Fingers should not come in contact with the optical surfaces. Care should be taken to prevent contamination with silicones, which are hard to remove and have strong absorption patterns. 

An inert gas is bubbled through the sample. The volatile hydrocarbons are transferred into the vapor phase and trapped over a sorbent bed containing 2,6-diphenylene oxide polymer (Tenax GC). A methyl silicone (3% OV-1 on Chromosorb-W, 60/80 mesh) packing protects the trapping material from contamination. Other adsorbents such as Carbopack B and Carbosieve S III may also be used. If pentane and other low boiling hydrocarbons need to be detected, the sorbent trap should be filled with activated charcoal, silica gel, and Tenax, respectively, in equal amounts. 

Besides the advantages that passive sampling may offer, it is important to recognize that in many cases these devices measure a different fraction of contaminants than that defined for the checking of EQS compliance within the WFD. This becomes especially important when monitoring very hydrophobic chemicals (log Kow > 4), where a large fraction of the total amount present in a spot water sample is bound to colloids and particles. In contrast, most passive samplers used for monitoring hydrophobic compounds (e.g., SPMD, Chemcatcher, and silicone materials) measure only the truly dissolved fraction of these chemicals. 

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