Determining the Accuracy of Dyne Solutions

Question: We have some dynes that are aging, but still appear to be fine. How can we assure that their performance will still be like new?

Answer: First, it is important to realize that there are three primary reasons why dyne solutions lose accuracy: contamination, evaporation, and aging, during which chemical reactions take place among the constituents. Recommended shelf life is discussed here.

Second, if there is any noticeable change in either the hue or the color density of the test fluids and they are near or past their expiration date, it is probably best to simply replace them.

As to qualification of test solutions, their most critical attribute by far is surface tension, and the most reliable measurement method is with a tensiometer. Please keep in mind that, especially for the lower dyne levels, the nominal surface tension value stated on the bottle is not exactly the same as its true surface tension. The discrepancies derive from the empirical nature of the test, which is based on wetting vs. de-wetting after two seconds of exposure to air. During that brief time frame, evaporation comes into play, altering the balance of test fluid constituents, especially at the periphery, where the liquid/solid interface is evaluated. The chart below shows the relationship of nominal vs. measured surface tension, based on actual production lot testing in our quality lab.

Be certain that the tensiometer is properly calibrated, and make any required adjustments to raw data to derive the correct adjusted surface tensions. Be sure to follow all instructions in your instrument’s owner’s manual. More detailed information on tensiometer calibration, use, and data adjustment is available here. It is critical that all test vessels and apparatus are entirely free of contamination.

As long as your results are all within about +/- 0.5 dynes/cm of the measured surface tensions shown below, the test fluids can be considered accurate with regard to wettability.

Nominal Dyne Level Measured Surface Tension(b) Specific Density(a) Volumetric %2-ethoxyethanol(c) Volumetric %Formamide(c)
30 28.6 0.929 100.0 0.0
32  30.1  0.950 89.5 10.5
34 32.6 0.982 73.5 26.5
36  35.5  1.014 57.5 42.5
38 37.8 1.037 46.0 54.0
40 39.9  1.056 36.5 63.5
42 42.1 1.072 28.5 71.5
44  44.2  1.085 22.0 78.0
46 46.0 1.095 17.2 82.8
48  48.0  1.103 13.0 87.0
50 49.9 1.110 9.3 90.7
52  51.9  1.116 6.3 93.7
54  54.1  1.122 3.5 96.5
56 56.9 1.127 1.0 99.0

Nominal dyne level and measured surface tension are shown in dynes/cm (equivalent to mJ/m2).

(a) Measured in g/ml at 25°C; derived from data at
(b) Measured at 72°F (22°C); adjusted and corrected tensiometer results from Diversified Enterprises production lots.
(c) ASTM Std. D2578-09: Standard test method for wetting tension of polyethylene and polypropylene films.

An alternate qualification technique would be to make contact angle measurements of the dyne solutions, when first purchased, on a known low surface energy material such as untreated virgin polyethylene, paraffin, or PTFE. If there is a doubt about the wettability of a given bottle of test fluid at a later date, a comparison of measured vs. expected results will identify any change in wettability. Either static (also known as Young’s) contact angles or retreating contact angles should be measured – not advancing contact angles. Be sure to record which method was used for future comparison. Also be sure that retains of the substrate used for these measurements are kept well sealed, free from contamination, and stored under laboratory conditions.

Even with these precautions, the polymer’s surface energy may change slightly over time, so this would be a more appropriate qualification method if only one or two dyne levels is suspect, rather than a whole batch. The key is to identify whether or not the suspect dyne levels appear as outliers in the curve describing dyne level vs. contact angle. For example, if your initial contact angles for 34, 38, and 42 dynes/cm test fluids, measured on HDPE, had been 20°, 32°, and 42°, and your retest showed contact angles of 22°, 26°, and 44°, that would be a clear signal that the 38 dyne/cm test fluid had changed meaningfully – its contact angle decreased by 6°, whereas the other two increased by 2° each.

A third method of qualification would be to compare the results of the questionable dyne solutions vs. those obtained with a fresh, unused set. This is probably the ideal verification: Whereas surface tension per se is the dominant determinant of accuracy, other factors can affect results to some degree. These include changes in pH or solubility, and the chance that a balance of evaporation and adsorption of contaminants has changed the test fluid’s chemical constituency without affecting its surface tension. At the liquid/solid interface where the dyne test takes place, these subtle changes can sometimes have a significant effect.

Under no circumstances should reagent grade surface tension test fluids be “validated” via a comparison to results from dyne pens of any kind, least of all go/no go permanent markers. Even ACCU DYNE TESTTM Marker Pens, which are designed to minimize the effect of surface contaminants on test results, are not appropriate for qualifying bottled solutions. On the other hand, keeping a master set of bottled test fluids in the Quality Lab – as a standard to which test markers can be compared if questions arise – is good practice, as the master batches will have been better protected during storage, and will be far less likely to have suffered from contamination or evaporation.

Neither do we recommend qualifying dyne solutions by comparing your dyne test results to contact angles produced with water as a probe fluid unless you maintain quality records from both tests on a continuing basis. In that case, a divergence from the expected correlation would certainly alert the tester that both methods need to be verified! If, however, you do not routinely do contact angle measurements, relying on tables or graphs that show a”conversion” from contact angle to dyne level is not a sound policy: The actual relationship between the data sets will often vary by up to a few dynes/cm, and sometimes even more, depending on the material you are testing.

Finally, in some cases, test fluid labels may become illegible or be removed. In that case, identification of correct dyne level would be the objective. Consider a case in which bottles of 34, 40, and 44 dyne/cm test fluids were in doubt. If you do not have access to a tensiometer, but do have a way to measure specific density, the three dyne levels can be readily discerned due to the significant change in specific density vs. dyne level, as shown in the chart above. I would not recommend this method for dyne levels with specific densities that are too similar; trying to sort an entire set of all levels in this fashion would be quite a puzzle indeed!

Shelf Life of Surface Tension Test Fluids

Question: How do you establish the shelf life of your products, and what influences how quickly they degrade?

Answer: This is one of the most difficult questions that we hear – and a frequent one, to boot.

I do not believe there is anyone on earth who truly understands the myriad of variables – let alone their inter-relationships – that affect the degradation of surface tension test fluids. So, the answer to the first half of the question is that, based on feedback from endusers and standard industry practice over time, we have de facto established shelf lives of five and six months, respectively, for ACCU DYNE TESTTM surface tension test fluids and Marker Pens.

These shelf lives reflect our best estimate of a reasonable time frame through which we can guarantee that our product will not lose accuracy without some specific identifiable external cause that explains a change in performance. The extra month on the test markers is due to their sealed environment, compared to bottled test fluids, which must be opened for use(1). It’s helpful to look at shelf life as a risk/reward decision, with the time frame set at the point where risk starts to appreciably increase.

In general, without use and kept sealed and protected from intense light, heat, etc., there is little degradation in accuracy for as long as 18 months or more. The problem is that the onset point and rate of degradation are not predictable, so the assurance level regarding accuracy drops progressively, even for shelved sets of test fluids (or test markers).

The second half of the question, which is the key to the most realistic predictable shelf life in real world use, is of greater practical interest. The change in properties is based on age; frequency of use; environmental conditions (elevated temperature and, less notably, humidity levels tend to accelerate aging); and exposure to evaporation or contamination, including airborne dust and aerosols, as well as what exists on the surface of samples to be tested. Evaporation is an issue because 2-ethoxyethanol evaporates at a faster rate than formamide, meaning that an unsealed container of dyne solution will increase in surface tension due to the change in the ratio of constituents. Contaminants not only tend to reduce the surface tension of the test fluids, they can also accelerate the aging process.

For ACCU DYNE TESTTM Marker Pens, which use the same applicator tip from use to use and are sealed units, contamination is the primary concern, as long as care is taken to keep the caps tightly secured at all times when not in use. High slip films are especially likely to cause contamination problems, as the low surface energy slip agents bloom to the surface and will be more than happy to take residence in the tips of your test markers. To a lesser degree, the same is true for residual mold release on molded and formed parts. Flushing these compounds from the tip is the primary reason for flooding the tip before testing, and only reading results from the final test swath. Procedural details are available here.

As discussed extensively here, machine oils and other processing aids used in the metals industries are simply too aggressive for test markers; for these applications, the test should be performed only with bottled solutions, applied with swabs.

For bottled test fluids, evaporation, introduction of airborne contaminants, and water adsorption – a form of contamination – are the greatest threats. Obviously, the more often the bottles are used, the greater the chance that these processes will reach a level that has an impact on test results. Never re-use an applicator swab, even at the same dyne level, as doing so is a perfect way to introduce surface contaminants into the bottles of dyne solution.

It is more common for dyne solutions to wet more readily (produce a higher dyne level reading) as they age, but this effect is not universal, especially if evaporation has occurred.

Finally, for any enterprise that is ISO or similarly certified, to remain in compliance, test supplies must not be used after their approved shelf life. Ensuring regular deliveries of fresh product is probably the main advantage of our AutofillTM replenishment system, which ensures automatic and timely re-supply. Even for customers that are not certified, I strongly recommend replacing dyne testing supplies at least every eight months. We have a number of testers who purchase on an annual basis, but I feel that is pushing things too far, even under the best of conditions. And, for plants that test frequently on an ongoing basis, a replenishment schedule of three months or even less is a reasonable precaution.

I trust these comments have been helpful – I’d like to offer more precise guidelines, but uncertainty is the nature of the beast, and there doesn’t seem to be much we can do to change that.

(1) Dropper (dispenser) bottles are essentially exempt from the environmental exposure consideration, as the tips needn’t be removed for use. However, since they are made from LDPE, rather than the more stable HDPE narrow and wide mouth bottles, we are still more comfortable with a conservative shelf life assignment.