ASTM D5544-16(2023)
(Test Method)Standard Test Method for On-Line Measurement of Residue After Evaporation of High-Purity Water
Standard Test Method for On-Line Measurement of Residue After Evaporation of High-Purity Water
SIGNIFICANCE AND USE
5.1 Even so-called high-purity water will contain contaminants. While not always present, these contaminants may contribute one or more of the following: dissolved active ionic substances such as calcium, magnesium, sodium, potassium, manganese, ammonium, bicarbonates, sulfates, nitrates, chloride and fluoride ions, ferric and ferrous ions, and silicates; dissolved organic substances such as pesticides, herbicides, plasticizers, styrene monomers, deionization resin material; and colloidal suspensions such as silica. While this test method facilitates the monitoring of these contaminants in high-purity water, in real time, with one instrument, this test method is not capable of identifying the various sources of residue contamination or detecting dissolved gases or suspended particles.
5.2 This test method is calibrated using weighed amounts of an artificial contaminant (potassium chloride). The density of potassium chloride is reasonably typical of contaminants found in high-purity water; however, the response of this test method is clearly based on a response to potassium chloride. The response to actual contaminants found in high-purity water may differ from the test method's calibration. This test method is not different from many other analytical test methods in this respect.
5.3 Together with other monitoring methods, this test method is useful for diagnosing sources of RAE in ultra-pure water systems. In particular, this test method can be used to detect leakages such as colloidal silica breakthrough from the effluent of a primary anion or mixed-bed deionizer. In addition, this test method has been used to measure the rinse-up time for new liquid filters and has been adapted for batch-type sampling (this adaptation is not described in this test method).
5.4 Obtaining an immediate indication of contamination in high-purity water has significance to those industries using high-purity water for manufacturing components; production can be halted immediate...
SCOPE
1.1 This test method covers the determination of dissolved organic and inorganic matter and colloidal material found in high-purity water used in the semiconductor, and related industries. This material is referred to as residue after evaporation (RAE). The range of the test method is from 0.001 μg/L (ppb) to 60 μg/L (ppb).
1.2 This test method uses a continuous, real time monitoring technique to measure the concentration of RAE. A pressurized sample of high-purity water is supplied to the test method's apparatus continuously through ultra-clean fittings and tubing. Contaminants from the atmosphere are therefore prevented from entering the sample. General information on the test method and a literature review on the continuous measurement of RAE has been published.2
1.3 The values stated in SI units are to be regarded as standard. The values given in parentheses are mathematical conversions to inch-pound units that are provided for information only and are not considered standard.
1.4 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety, health, and environmental practices and determine the applicability of regulatory limitations prior to use. For specific hazards statements, see Section 8.
1.5 This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
General Information
Relations
Standards Content (Sample)
This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
Designation: D5544 − 16 (Reapproved 2023)
Standard Test Method for
On-Line Measurement of Residue After Evaporation of High-
Purity Water
This standard is issued under the fixed designation D5544; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope 2. Referenced Documents
2.1 ASTM Standards:
1.1 This test method covers the determination of dissolved
organic and inorganic matter and colloidal material found in D1129 Terminology Relating to Water
D2777 Practice for Determination of Precision and Bias of
high-purity water used in the semiconductor, and related
industries. This material is referred to as residue after evapo- Applicable Test Methods of Committee D19 on Water
D3370 Practices for Sampling Water from Flowing Process
ration (RAE). The range of the test method is from 0.001 μg/L
(ppb) to 60 μg/L (ppb). Streams
D3864 Guide for On-Line Monitoring Systems for Water
1.2 This test method uses a continuous, real time monitoring
Analysis
technique to measure the concentration of RAE. A pressurized
D3919 Practice for Measuring Trace Elements in Water by
sample of high-purity water is supplied to the test method’s
Graphite Furnace Atomic Absorption Spectrophotometry
apparatus continuously through ultra-clean fittings and tubing.
D5127 Guide for Ultra-Pure Water Used in the Electronics
Contaminants from the atmosphere are therefore prevented
and Semiconductor Industries
from entering the sample. General information on the test
E1184 Practice for Determination of Elements by Graphite
method and a literature review on the continuous measurement
2 Furnace Atomic Absorption Spectrometry
of RAE has been published.
3. Terminology
1.3 The values stated in SI units are to be regarded as
standard. The values given in parentheses are mathematical
3.1 Definitions—For definitions of terms used in this test
conversions to inch-pound units that are provided for informa-
method, refer to Terminology D1129.
tion only and are not considered standard.
3.2 Definitions of Terms Specific to This Standard:
1.4 This standard does not purport to address all of the
3.2.1 aerosol, n—any solid or liquid particles, with a nomi-
safety concerns, if any, associated with its use. It is the
nal size range from 10 nm to 100 μm, suspended in a gas
responsibility of the user of this standard to establish appro-
(usually air).
priate safety, health, and environmental practices and deter-
3.2.2 colloidal suspension, n—any material in suspension
mine the applicability of regulatory limitations prior to use.
(for example, silica) with a nominal particle size less than
For specific hazards statements, see Section 8.
100 nm.
1.5 This international standard was developed in accor-
3.2.3 water-based condensation particle counter (WCPC),
dance with internationally recognized principles on standard-
n—instrument for detecting very small aerosol particles in a
ization established in the Decision on Principles for the
size range from approximately 7 nm to 2 μm to 3 μm.
Development of International Standards, Guides and Recom-
3.2.3.1 Discussion—The WCPC cannot differentiate among
mendations issued by the World Trade Organization Technical
particles of varying size within this size range; the counter
Barriers to Trade (TBT) Committee.
reports the number of particles with a size greater than that
defined by the detection-efficiency curve. Detection is indepen-
dent of particle composition.
This test method is under the jurisdiction of ASTM Committee D19 on Water
3.2.4 detection effıciency, n—in this test method, detection
and is the direct responsibility of Subcommittee D19.03 on Sampling Water and
Water-Formed Deposits, Analysis of Water for Power Generation and Process Use, efficiency represents a curve relating particle size to a counter’s
On-Line Water Analysis, and Surveillance of Water.
ability to detect that size.
Current edition approved Nov. 1, 2023. Published December 2023. Originally
approved in 1994. Last previous edition approved in 2016 as D5544 – 16. DOI:
10.1520/D5544-16R23. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Blackford, D. B., “Use of Nonvolatile Residue Monitoring in Semiconductor contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Water Applications” Ultrapure Water Journal, Tall Oaks Publishing, November Standards volume information, refer to the standard’s Document Summary page on
2008, pp. 16–23. the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D5544 − 16 (2023)
3.2.5 polydisperse, adj—a type of size population, in this high-purity water at a constant flow rate, and a source of
case of aerosol particles, composed of many different sizes; the compressed air, or nitrogen, at a constant flow rate and
opposite of monodisperse, which is a type of size distribution pressure, to generate a stable aerosol of high-purity water
of just one size. droplets. Under these conditions, the nebulizer produces a
polydisperse size distribution of droplets with a median size of
3.2.6 realtime, n—the time that an event is occurring plus
approximately 1 μm, and a concentration of approximately
the response time.
7 12
10 droplets ⁄s, or 10 droplets ⁄mL.
3.2.6.1 Discussion—In this case, the response time is 3 min
to 5 min, therefore, contamination is recorded 3 min to 5 min
4.2 The droplets are heated at 120 °C. After the heating,
after it occurs.
additional compressed air or nitrogen is introduced from the
supply to prevent re-condensation and to quickly move the
3.2.7 residue after evaporation, n—contaminants remaining
residue particles to the Water-based Condensation Particle
after all water is evaporated; sometimes known as nonvolatile
Counter (WCPC).
residue or total dissolved and suspended solids.
4.3 The WCPC works as follows: Residue particles pass
4. Summary of Test Method
through a region called the Saturator (see Fig. 1) where the
4.1 This test method consists of continuously removing a residue particles are saturated with water vapor and tempera-
representative sample of high-purity water from a pressurized ture equilibrated. The residue particles and water vapor then
supply line (refer to Practices D3370, Practice C on Continual pass into a region called the Growth Tube, where the wetted
Sampling, and Practice D3864). The temperature of the incom- walls of the porous media are heated to raise vapor pressure.
ing high-purity water should ideally be at room temperature, The high diffusivity of the vapor allows it to reach the center
but not more than 50 °C. A nebulizer is supplied with the of the sample stream at a faster rate than the thermal diffusivity
FIG. 1 Schematic Diagram of Apparatus Required for This Test Method
D5544 − 16 (2023)
of the vapor can equilibrate to the higher temperatures near the 6. Apparatus
walls, resulting in a supersaturated condition along the radius
6.1 The schematic arrangement of the system is shown in
of the flow stream. Residue particles in the flow stream act as
Fig. 1. The apparatus is available as a complete instrument.
nuclei for condensation. Water condenses on the residue
6.2 60 μm Filter, high purity water flows into the apparatus
particles to form large droplets with only one residue particle at
at approximately 120 mL/min and immediately passes through
the center of each droplet. Droplets can then be counted with a
a 60 μm sintered stainless filter that removes any large debris
relatively simple optical particle counter. A more elaborate
and then flows to flow controller.
description of the WCPC’s method for distinguishing between
6.3 Flow Controller, made of a non-contaminating material
clean and dirty water is described in Appendix X1.
such as perfluoroalkoxy (PFA), necessary to supply the nebu-
4.4 A calibration technique (described in detail in Section
lizer with high-purity water at the desired flow rate. The flow
10) uses concentration standards of high-purity potassium
controller must contain an air actuated pressure regulator to
chloride (KCl) to convert the WCPC count concentration in
ensure that water is delivered to the nebulizer at a stable flow
particles per cubic centimetre into RAE concentration in
rate, despite external fluctuations. High-purity water must be
micrograms per litre or milligrams per litre. A graphite furnace
delivered to the flow controller and nebulizer through ultra-
atomic absorption spectrometer (GFAAS), or equivalent
clean tubes and fittings made from PFA. Nebulizers usually
method, can be used to check the concentration of KCl in this
require a very low flow rate, approximately 1 mL/min, for
test method standard (see Practices D3919 and E1184).
efficient operation. However, such a low flow rate is inadequate
for routine monitoring because it results in a long response
5. Significance and Use
time. This test method is designed to overcome the problem of
long response times by using a flow controller to deliver
5.1 Even so-called high-purity water will contain contami-
approximately 120 mL/min of high-purity water to the moni-
nants. While not always present, these contaminants may
toring site and then to divert approximately 1 mL/min of the
contribute one or more of the following: dissolved active ionic
flow to the nebulizer through a short tube. This short tube
substances such as calcium, magnesium, sodium, potassium,
facilitates a short response time. From the pressure regulator,
manganese, ammonium, bicarbonates, sulfates, nitrates, chlo-
the water flows to the nebulizer through a tee fitting and a
ride and fluoride ions, ferric and ferrous ions, and silicates;
section of PFA 500 μm capillary tubing. The PFA tubing
dissolved organic substances such as pesticides, herbicides,
gradually lowers the water pressure and prevents any out-
plasticizers, styrene monomers, deionization resin material;
gassing of dissolved gases in the incoming water.
and colloidal suspensions such as silica. While this test method
6.4 Measuring the Flow Rate, the flow rate of water flowing
facilitates the monitoring of these contaminants in high-purity
through the nebulizer is used as an indicator that the NRM
water, in real time, with one instrument, this test method is not
8000 is set up and operating correctly. Instead of using a
capable of identifying the various sources of residue contami-
conventional flow meter, the NRM 8000 incorporates a new,
nation or detecting dissolved gases or suspended particles.
patented method of measuring the flow rate. Of the water
5.2 This test method is calibrated using weighed amounts of flowing through the nebulizer, 95 % leaves it as part of a waste
stream. The waste water is collected by a weir and stand-pipe
an artificial contaminant (potassium chloride). The density of
system and then delivered as a steady stream of water droplets
potassium chloride is reasonably typical of contaminants found
of identical size. These droplets fall through a simple light
in high-purity water; however, the response of this test method
beam. As each droplet breaks the beam, a detector senses a
is clearly based on a response to potassium chloride. The
scattered light signal, or pulse, and a counter keeps track of the
response to actual contaminants found in high-purity water
pulses. An algorithm converts the pulse count to a flowrate (in
may differ from the test method’s calibration. This test method
mL/min.) which is shown on the front panel display.
is not different from many other analytical test methods in this
respect.
6.5 Nebulizer, required to produce a polydisperse size dis-
tribution of droplets with a median size of approximately 1 μm
5.3 Together with other monitoring methods, this test
and a concentration of approximately 10 droplets/s. Within the
method is useful for diagnosing sources of RAE in ultra-pure
customed designed nebulizer, the water and compressed air/
water systems. In particular, this test method can be used to
nitrogen (supplied at a constant flow rate and pressure)
detect leakages such as colloidal silica breakthrough from the
combine to form the required stable, poly-dispersed aerosol of
effluent of a primary anion or mixed-bed deionizer. In addition,
ultrapure water droplets. The nebulizer must be supplied with
this test method has been used to measure the rinse-up time for
clean, dried filtered compressed air or nitrogen and must be
new liquid filters and has been adapted for batch-type sampling
machined from a material that will not contaminate the
(this adaptation is not described in this test method).
high-purity water. Passivated 316L stainless steel has been
5.4 Obtaining an immediate indication of contamination in
high-purity water has significance to those industries using
The sole source of supply of the apparatus known to the committee at this time
high-purity water for manufacturing components; production
is Fluid Measurement Technologies, 4106 Hoffman Road, White Bear Lake, MN
can be halted immediately to correct a contamination problem.
55110. If you are aware of alternative suppliers, please provide this information to
The emerging nano-particle technology industry will also
ASTM International Headquarters. Your comments will receive careful consider-
benefit from this information. ation at a meeting of the responsible technical committee , which you may attend.
D5544 − 16 (2023)
used successfully in this test method. Details of how to 7.2 Potassium Chloride (KCl) as a Dry Powder—KCl
4,6
passivate stainless steel can be found in the Metal Finishing purity should be >99.98 %. Weighed amounts of KCl, in dry
Guidebook. form, are dissolved in water to generate calibration solutions of
known concentration. See 10.2 and 10.2.1 for preparing these
6.6 Heater and Dilution air/nitrogen, the ultrapure water
calibration solutions. The solutions must be prepared carefully
droplets produced by the nebulizer are rapidly heated at
under clean laboratory conditions. Use clean 250 mL PFA
120 °C. Each water droplet is evaporated to dryness, leaving
beakers and a microbalance capable of measuring to 0.01 mg.
behind a particle of residue consisting of dissolved inorganic
material. Every nebulizer droplet results in a residue particle:
8. Hazards
the cleaner the ultrapure water, the smaller
...
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