See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/237297781

White Residue Formation on Printed Circuit Board Assemblies

Article

CITATION READS
1 563

1 author:

Mulugeta D Abtew
Sanmina Corporation
8 PUBLICATIONS   1,380 CITATIONS   

SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Research in soldering View project

All content following this page was uploaded by Mulugeta D Abtew on 16 October 2018.

The user has requested enhancement of the downloaded file.

 WHITE RESIDUE FORMATION ON PRINTED CIRCUIT BOARD ASSEMBLIES

TM Chan, Engineering Manager

KS Moo, Senior Process Engineer
KH Teoh, Process Engineer
Sanmina-SCI PENANG, MALAYSIA

Mulugeta Abtew, Global Technology Solutions

Sanmina-SCI Corporation

ABSTRACT
Experimental and analytical approach was undertaken to
investigate and correct white residue and corrosion failures
found on multiple PCBAs. SEM and EDX evaluation of the
failure sites reveled the presence of Chloride, Sodium and
Carbon. Ion Chromatography test of residue found on the
failure sites also revealed the presence of 0.01-0.75 µg/in2
Chloride and 0.35 µg/in2 Bromide. The result of Fourier
Transform Infrared Spectroscopy (FTIR) analysis identified the
contaminant as flux residue coming from both aqueous and No-
Clean Flux used in the assembly process. The field failure was
successfully duplicated at the factory. Further more, response of
both aqueous and no-clean flux to white residue formation was
evaluated. Experimental results revealed that solder joints of
active devices tend to produce white residue independent of
ionic contamination level when both moisture and bias are
applied to the site. The combination of experimental results and
duplication of the failure at the manufacturing site, indicated
that device power up during PCB testing combined with
inadequate moisture control were found to be the primary cause
of the failure. New testing and device power up schemes were
developed and implemented
The soldering and cleaning of electronic products involve a
significant number of materials with varying chemical and
physical properties. A typical PCA soldering process may
involve many chemical species including Acids (Abietic,
Neoabietic, Dehydroabietic, Palustic, Pimaric and Isopimaric),
Esters (Resin acid, Fatty acid), Diterpene, Alcohol,
Hydrocarbons, Wax, Halides, Epoxy, Lead, Tin, and many
others. The byproducts of the reactions of these various
chemicals subjected to soldering temperature are also as varied
and complex. White residue is commonly associated with the
presence of metallic salts of Pb, Sn and Cu forming a
tenaciously adherent film, which is virtually insoluble in water,
alcohol or in any known cleaning solvent used for PCA
cleaning. The various metal salts, which may appear after
soldering and their solubility in aqueous solution (3) is listed in
Table 1. Considering the chemical complexity of PCA soldering
in general and white residue formation in particular, it is very
difficult to isolate specific cause or causes for white residue
formation. However, based on experience and experimental
studies a number of possible causes for white residue formation
reported in the literature (3) are summarized in Table 2.

INTRODUCTION Table 1. Solubility of post soldering metal salts in aqueous

solution
The phenomenon of white residue formation on Printed Circuit
Assemblies (PCA) after soldering is one of the most complex Compound Solubility (g/100 Color
problems in electronic assembly (1). As shown in Figure 1, white CC)
residue is usually observed on PCA surfaces and on or around CuCl2 70.6 Green
solder joints and is encountered with a wide range of materials CuCl 0.006 Green
used in PCB assembly including rosin fluxes, cleaning solvents, CuBr2 Soluble Black
water-soluble fluxes, circuit board resins and epoxies, solder SnCl2 Slightly Soluble White
mask and component materials. The formation mechanism and SnBr2 83.9 Pale Yellow
the chemistry of white residue are very complex (2) with PbCl2 85.2 White
unpredictable outcomes. Consequently, a complete PbBr2 1.0 White
understanding of the reaction process is very difficult. The PbCO3 0.8 White
residue is known to occur suddenly with no known change of Copper Resinate Insoluble Green
process parameters or material. Though the residue is Tin Resinate Insoluble Tan
commonly white, it also exhibits pale-yellow, blue or gray
appearances.
Generally, white residue formation both in rosin-based no-clean
fluxes and water soluble fluxes is often encountered in
relatively high temperature (>215oC) soldering conditions of
PCAs with large thermal mass where excess heat is likely to be
generated. White residue formation is also known to occur after
PCAs are cleaned in an aqueous cleaning system where the
water temperature is relatively high (>60oC). However, the
presence or formation of white residue during PCA functional
test and device power up is not a common occurrence. In this
report the results of experimental evaluations performed to
investigate and characterize the formation of white residue
observed with both no-clean and water soluble fluxes during
functional test and device power up of PCAs is discussed.
PCA FAILURE SUMMARY
A series of functional failures were encountered on multiple
PCAs under service conditions. Preliminary investigation and
inspection of the PCAs revealed white residue deposition
around the failure sites. As shown in Figures 1 and 2, the white
residue was found on the surface of the PCA and on and around
solder joints. Further more, it was noted that the white residue
was found around devices that get relatively hot during
operation. The failed PCAs were soldered with a no-clean
solder paste and flux. Scanning Electron Microscopy (SEM)
images and Energy Dispersive X-ray (EDX) elemental spectrum
of the white residue found at the failure sites are shown in
Figure 3 and 4 respectively. In addition, Ion Chromatography
(IC) results of the white residue found at the failure sites are
also presented in Table 3
Figure 1. White residue on failed PCA surface
Table 2. Summary of possible causes for white residue
formation.
Possible Mechanisms
Cause
Oxidized Formation insoluble white residue of
Rosin Peroxides and Ketocompounds as a result
Residue of reaction with Abietic acid (unsaturated
double bond) in the presence of high heat.
Polymerized Polymerization of rosin due to exposure to
Rosin high temperature and tin oxide serving as a
Residue catalyst forming a tenaciously adherent
white film insoluble in common solvents.
Hydrolyzed Hydrolization of the rosin acids due to
Rosin absorbed moisture creating an insoluble
Residues white reside after soldiering.
Laminate, Flux polymerization initiated possibly by
Flux and the presence of excess epichlorohydrin in
Solder the laminate and tin oxide serving as a
Residue catalyst.
Solder and Formation of insoluble metal salts (tin and
Rosin Flux lead abietates and pimarates) as a result of
Residue the reaction between solder or component
terminations with carboxylic acid in the
flux.
Solder and Formations of white reside of metal halide
Halide salts of tin and lead chloride as a result of
Activators reaction between molten solder and halide
activators in the flux.
Laminate and When a laminate is under-cured,
Flux Residue brominated phenol in the curing reaction
readily decomposes at soldering
temperature (>135oC) generating free
bromide ions, which in turn reacts with Pb
forming a white residue of lead bromide.
Aqueous White film residue tin oxide can be
Cleaning generated in aqueous cleaning systems
Residue where the alkaline saponifier concentration
is too high (pH>11).
When compared to a known good PCA, both the SEM and IC
results of the failed PCAs indicated the presence of high level
of Chlorine in the white residue with clear evidence of
corrosion. Based on the EDX spectrum, it is highly likely that
the composition of the white residue may be PbCl2 or PbCO3.
Based on information from the suppliers, both the flux and
solder paste used on the failed PCAs were halide free.
Therefore, the source of the Chlorine is not clear. However, it is
highly likely that the Chlorine might have come either from the
Hot Air Solder Leveling (HASL) finish of the PCB substrate or
from component terminations or both. Comparative EDX
results between a known good assembly and a failed assembly
is listed in Table 4.

Figure 2. White residue on device leads

Figure 4. EDX Spectrum of white residue

BACKGROUND

During PCA soldering process, the metals Sn, Pb and Cu

experience oxidation and their oxides react with the various
acids from both the rosin and organic acid of the water soluble
flux forming metallic salts. Lead Carbonate and Lead Chloride
are metallic salts commonly formed during PCBA soldering (4).
These compounds are typically white in color.

Lead Carbonate, 2PbCO3Pb(OH)2 is a result of the reaction

between PbO and Carbonate. The carbonate is formed by the
dissolution of CO2 from the atmosphere in moisture (H2O).
Lead Chloride is a result of the reaction between Pb and
Figure 3. SEM image of white residue Chlorine. Generally, both Lead and Tin carbonate and Chloride
can form. However, Lead Carbonate or Chloride are more likely
Table 3. EDX elemental results between failed and known good to be formed during soldering than Tin Carbonate or Tin
PCAs. Chloride because the solder surface is generally lead reach and
the reaction process is thermodynamically (5) more favorable for
Failed PCA Known Good Lead reaction than Tin. In the presence of moisture or relatively
Element PCA high humidity (>75% RH) conditions, a corrosion loop can be
Spot 1 Spot 2 Spot 3 Spot 1 Spot 2 formed as a result of the reaction between PbCl2 and CO2 in the
C 16.12 42.40 21.65 46.73 71.09 presence of moisture. The byproduct of the reactions between
O 5.44 25.22 17.90 13.68 18.09 PbCl2, CO2 and H2O (Moisture) are Lead Carbonate and
Na 35.48 3.72 21.22 - - Hydrochloric. The acid, then continuous to react with metallic
Cl 33.62 0.78 11.03 - - Pb in the solder to form more Lead Chloride (5).
Al - 1.74 - 0.36 0.24
It has been shown that Temperature and Humidity are two
Pb 9.34 8.28 8.50 11.89 - critical parameters that control the reaction kinetics of corrosion
Pb - - - - - failures in general and white residue formation in particular (6).
Sn - 13.75 16.74 10.14 0.94 The effect of temperature and humidity on failure mechanisms
as a result of physio-chemical reactions follows the Arrhenius B ≈ 7000K, equivalent to 0.6 eV
Equation (5). C ≈ 4.4X10-4

Using Eq.4, one can predict the service life of a PCA under
−B defined temperature and humidity conditions in relation to
k r = k o exp  [Equation 1] corrosion and white residue formation.
 T 

where, EXPERIMENTAL APPROACH

kr = reaction rate Based on evaluation of the failed assemblies, experimental

ko = constant approach was used to simulate the field conditions and to
B = the activation energy, Ea, of the reaction, divided duplicate the failure. The objective of the experiment was to
by the Gas Constant, K identify the parameters that caused or influenced the formation
T = absolute temperature in oK of the white residue on the failed assemblies.

Four PCAs were assembled and soldered following the normal

The effect of relative humidity, RH, on the reaction can be PCB assembly process, namely Solder Paste application,
expressed by an exponential equation [Sinnadurai]: Component Placement, Reflow Soldering, Cleaning1, Hand
Load, Wave Soldering, Cleaning and In Circuit Test ICT). Two
of the PCAs were built with a No-Clean chemistry while the
(
k H = k o1 exp C.RH 2 ) [Equation 2] other two were built using aqueous based chemistry. Once the
PCAs passed ICT, the assemblies were thoroughly inspected
where, under a 30X microscope for any trace of white residue. Then,
two assemblies, one from the no clean and one from the
aqueous batch, were randomly selected for further investigation
k o1 and C are constants after it was verified that the assemblies are free of any trace of
white residue. The two assemblies were then functionally tested
The relationships expressed in Eq.1 and Eq.2 show that reaction under normal environmental conditions where the humidity
rates scales up with higher temperature and higher humidity level was maintained at 55% RH. Power was applied on the
conditions. The activation energy for white residue formation PCA during functional test and the locations on the boards
can also be determined experimentally from Eq.1. Assuming where white residue had formed on the previously failed PCAs
that the effects of temperature and humidity on the reaction rate were closely monitored for white residue formation.
are independent, the acceleration factor, AF, for temperature
and humidity can be computed by combining Eq.1 and Eq.2. The remaining two PCAs were also functionally tested with full
power on. However, in this case the humidity level was
uncontrolled and drops of de-ionized water were intentionally
  1   added around the vicinity of the powered on device leads.
AF = exp  B −
1
(
 + C RH test
2
− RH life
2
) [Eq.3] Progress was monitored on predefined locations (where white
  Tlife Ttest 
  reside had been observed on previously failed PCAs) via visual
inspection under a 20X microscope.

The subscripts ‘test’ refers to the laboratory test conditions, and To measure the level of contamination on both incoming PCBs
‘life’ the actual service conditions. Expected service life is and components, a random sample of PCBs and components
estimated or predicted by multiplying the laboratory test time to were selected from stock and Ion Chromatography evaluation
fail by the acceleration factor as shown in Equation 4. was performed following IPC-TM-650 Test Methods.

Expected Life Time = AF X Test time to fail [Equat. 4]

RESULTS AND ANALYSIS
The value of the constants B and C are experimentally
determined and are case specific. However, for general Ion Chromatography results for incoming PCB and components
estimations the following values can be used as suggested by are shown in Tables 4 and 5 respectively. The level of ionic
Sinnadurai (5):
1
Applicable only to PCAs built with water soluble chemistry
 contamination found on both incoming PCBs and components
appear to be significantly below the maximum allowable ionic
contamination levels for PCAs as shown in Table 4. The IC
results generally show only the average level of contamination
without any indication about the distribution of the
contamination on the PCA. This means, it is possible for a
much higher level, > 4 µg/In2, of ionic contamination to be
present on the PCAs concentrated on a specific location than
what are shown in Table 5 and 6. High level of ionic
contamination concentrated in a few locations may have caused
failure in combination with applicable temperature and
humidity conditions. It is not known what level of ionic
contamination can actually induce corrosion failures or initiate
white residue formation. However, one study has shown that as
low as 4 µg/In2 of Chloride ion concentration will cause
corrosion failure at 60oC Temperature and 80% RH (6).

Table 4. Allowable Ionic contamination level for PCAs.2

Figure 5. White residue formed 3 minutes after power on.
Flux Type Low Risk Marginal Risk High Risk
RMA <8.0 µg/in2 8.0-10.0 µg/in2 >10 µg/in2
Aqueous <6.0 µg/in2 6.0-8.0 µg/in2 >8 µg/in2
No-clean <3.0 µg/in2 3.0-4.5 µg/in2 >4.5 µg/in2

Table 5: Ion Chromatography result for bare PCB samples

Ionic Contamination
Ref
Chloride Bromide Sulphate
Sample Area
(Cl) (Br) (SO4)
No
Concentration (ug/sq inch)
1 0.3673 <0.0253 0.1888
1 2 0.1348 <0.0122 0.0920
3 0.1087 <0.0122 0.1207
1 0.0992 <0.0051 0.0154
2 2 0.1123 <0.0051 0.0297 Figure 6. White residue formed 5 minutes after power on.
3 0.0590 <0.0051 0.0088
1 0.1025 <0.0170 0.0614
3 2 0.0451 <0.0122 0.0166 No white residue formation was observed on the first batch
3 0.0167 <0.0051 <0.0051 PCAs functionally tested under controlled humidity
environment. However, formation of white residue was
observed on the batch of PCAs functionally tested under
Table 6: Ion Chromatography result for component samples uncontrolled humidity environment. The white residue on the
failed PCAs started to form at two locations on affected devices
Ionic Contamination two minutes after power on. Then more residue started to form
Chloride Bromide Sulphate and spread over the PCA surfaces. Figure 5 and 6 show the
Sample
(Cl) (Br) (SO4) extent of white residue formed after 3 and 5 minutes of power
Concentration (ug/sq inch) on respectively.
4 0.7346 <0.0263 6.6983
5 0.1105 <0.0430 0.0301 The white residue initially occurred only on powered on active
6 0.0167 <0.3584 <0.3584 devices later spreading to passive components. But, it was also
noted that white residue did not form on all powered on
devices. Those powered on devices that did not have white
2 residue forming on or around their leads appear to be devices
The ionic contamination levels are determined by IC test.
that had low power input (<1.5W). It was not known what
temperature the components or component leads have to reach
after power on for the white residue to start forming. However,
it was clear that white residue formed only on devices that were
powered on and have relatively higher input power (>3.0 W).
This implies that the extent of input power to a device and the
resulting rise in temperature during operation not only affect
device performance but may also crate favorable conditions for
corrosion and white residue formation. It should also be noted
that with increasing interconnect density, this may be a critical
problem that warrants design considerations in the area of
power management and device temperature control.
CONCLUSION
Experimental investigation was performed to identify the cause
of field failure on multiple PCAs. White residue and corrosion
spots were identified at failure sites. Ion Chromatography and
SEM/EDX analysis of the residue on the failure site indicated
the presence of high level of Chloride. The failure was
successfully duplicated at the factory. White residue formation
REFERENCES
1. Zou, Y. Z., “White Residue on Soldered Printed
4.
Circuit Assemblies,” National Physical
Laboratory, 1988.
2. Tautscher, C.J., “The Contamination of Printed
5.
Wiring Boards and Assemblies,” Omega
Scientific Services, Bothell, WA (1976).
3. Bernier, F.D., “The Nature of White Residue on
6.
Printed Circuit Assemblies, Technical Report,
Kester Solder, 1988.
View publication stats
was encountered during device power on under high humidity
(>75% RH) conditions. Experimental results also indicated a
correlation between input power to a device and white residue
formation provided high humidity environment. Specifically,
white residue formation was observed on device locations that
had an input power greater than 3.0 W. No actual temperature
measurements of devices or device leads were conducted while
the devices were in operating conditions. But, it is suggested
that the rise in temperature of the device body during operation
as a result of relatively high input power may be contributing to
corrosion and white residue formation given a humid
environment. New testing and device power up schemes were
developed and implemented to alleviate the problem. It was
also noted that in addition to moisture and contamination
control during assembly, white residue formation is also related
to the design and testing of PCAs in the area of power
management and device operating temperature. Further studies
are suggested to correlate input power and device temperature
rise and to identify the device body temperature regions that
trigger corrosion and white residue formation in high humidity
environment.
Ellis, B.N., Cleaning and Contamination of
Electronic Components and Assemblies,
Electrochemical Publications Limited, (1986).
Lea, C., After CFCs? Options for Cleaning
Electronics Assemblies, Electrochemical
Publications Limited, (1992).
“ Corrosion of Indium Based Solders”, Amdhal
Technical Bulletin, 1990.