Transactions on Electronics Packaging Manufacturing

Comparison of Printed Circuit Board Property Variations in Response to Simulated Lead-free Soldering

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IEEE Transactions on Electronics Packaging Manufacturing TEPM-2009-024.R1 Regular Paper 26-Nov-2009

Tsai, Ming-Yi; Chang Gung University, Mechanical Engineering Pecht, Michael; Univ of Maryland, CALCE-Electronic Packaging Ctr Printed circuit board, FR-4, lead-free soldering, halogen-free, glass transition temperature

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Comparison of Printed Circuit Board Property Variations in Response to Simulated Lead-free Soldering
Bhanu Sood1, Ravikumar Sanapala1, Diganta Das1, Michael Pecht*1,2, C. Y. Huang3 and M. Y. Tsai3 1. Center for Advanced Life Cycle Engineering (CALCE), University of Maryland, College Park, MD 20742, *Corresponding Author (pecht@calce.umd.edu) 2. Prognostics and Health Management Center City University of Hong Kong Hong Kong, China

3. Department of Mechanical Engineering, Chang Gung University, Kwei-Shan, Tao-Yuan, Taiwan 333, R.O.C.

Use of lead-free solders such as Sn/Ag/Cu results in exposure of printed circuit boards to higher temperatures during assembly compared with eutectic tin-lead solder. If the thermo-mechanical and electrical properties of the laminate materials get affected by exposure to this higher temperature, that may impact the performance and reliability of the circuit card. Variations, if any, in laminate material properties before and after board assembly should be considered in the selection of appropriate laminates. The board and system designers need to be cognizant of such variations and account for them during laminate selection for an application. This paper presents guidelines for laminate selection along with the process used to derive the guidelines. The process includes measurement of key material properties (glass transition temperature, coefficient of thermal expansion, decomposition temperature, time-to-delamination, water absorption, flammability, dielectric constant, and dissipation factor), and their responses to lead-free soldering assembly conditions. A range of commercially available FR-4 printed circuit board laminate materials, classified on the basis of glass transition temperature (high, medium, and low), curing agents (dicyandiamide and

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ABSTRACT

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phenolic), flame retardants (halogenated and halogen-free), and the presence of fillers, are included in the measurements. The measurements are conducted in accordance with IPC-TM-650 test methods before and after exposure to multiple lead-free soldering profiles. The extent of variations in the properties due to lead-free soldering exposures are reported and analyzed as a function of classification parameters. The causes behind the variations in material properties are investigated by Fourier Transform Infrared Spectroscopy analysis and a conjunctional property analysis. This study also suggests that the preconditioning steps specified in the IPC test methods should address the initial moisture content of the laminate test samples in material property measurement tests, otherwise significant errors can be introduced.

Key Words: Printed circuit board, FR-4, lead-free soldering, halogen-free, glass transition

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INTRODUCTION

temperature

FR-4 1 laminate, the most widely used printed circuit board (PCB) material, is a composite of epoxy resin with woven fiberglass reinforcement. The typical constituents of FR-4 laminate and the fabrication steps of an FR-4 PCB are shown in Table 1 and Figure 1,

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Woven glass (typically E-grade) fiber cloth reinforces the laminate, providing mechanical strength. Glass fabric is woven with two sets of fiber bundles: warp and fill. The warp bundles are those that lie in the machine direction of the fabric, while the fill bundles lie across the warp direction. Coupling agents such as organo-silanes are coated onto the fabric to promote adhesion between the glass and resin.

FR-4 is the National Electrical Manufacturers Association (NEMA) grade (FR represents flame retardant (to UL94 V-0) and type 4 indicates woven glass reinforced epoxy resin).

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The resin system acts as a binder and load transferring agent for the laminate and primarily consists of various epoxy groups. Additives such as curing agents, flame retardants, fillers, and accelerators are added to tune the properties of the laminates. Curing agents are some of the most critical of such additives, since they control the cross-linking of the epoxy matrix, thereby thermosetting the composite structure. Dicyandiamide (DICY) and phenol novolac (phenolic) are the commonly used curing agents in epoxy laminates. Phenolic-cured epoxy systems offer better thermal resistance, chemical resistance, humidity resistance, and improved mechanical properties, but have poor processability (e.g., drilling) compared to DICY-cured systems [1]. Flame retardants are added into the epoxy matrix to reduce the flammability of the laminate material. Tetrabromobisphenol-A (TBBPA) is the most commonly used halogenated flame retardant for epoxy resin systems. Phosphorous and aluminum hydroxide are some of the commonly used halogen-free flame retardants. Inorganic fillers such as aluminum hydroxide are added to the epoxy resin to lower the coefficient of thermal expansion (CTE) of the laminate while enhancing the flame retardancy and reducing material costs. Accelerators such as Imidazole are used to increase the rate of the curing reaction and control the cross-linking density of the epoxy system.

A prepreg is first fabricated from a glass cloth impregnated with semi-cured resin. Multiple prepregs are thermally pressed to obtain a core or laminate. Copper foil is then laminated with prepregs to obtain a copper-clad laminate. Several prepregs and cores are stacked together under temperature and pressure to fabricate a multi-layered PCB. Through-holes and micro-via interconnects are drilled into the structure as per the application-specific design data and then plated with copper. A solder mask is applied on the board surface to cover the board leaving only the areas to be soldered exposed. Flux is applied at those exposed areas. The boards are assembled by reflow and/or wave soldering depending on the type of components (surface mount or through-hole) after the printing of the solder and
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the placement of the components. In addition, the rework and repair of boards may involve exposure to one or more de-soldering and soldering steps. The transition to lead-free soldering of printed circuit boards using solder alloys such as Sn/Ag/Cu has resulted in a peak reflow temperature increase of 3040 C during assembly compared with traditional eutectic Sn/Pb solder [2]. These high temperature exposures can alter the circuit board laminate material properties, thereby affecting the performance and reliability of the circuit board and the electronic assembly. The knowledge of laminate material properties and their dependence on the material constituents combined with their variations, if any, due to lead-free soldering exposures should be considered in the selection of laminates for appropriate applications. This paper addresses the effects of high temperature exposures associated with lead-free soldering conditions on the key laminate material properties of glass transition temperature (Tg), coefficient of thermal expansion (CTE), decomposition temperature (Td), time-to-delamination (T-260), water absorption, flammability, dielectric constant (Dk), and dissipation factor (Df). Previous studies [3-7] have identified these specific properties as some of the primary metrics in assessing the lead-free process compatibility of laminates. No comprehensive reports are available on the effect of increased soldering temperatures on laminate properties. This study focuses on providing guidelines for laminate selection based on material constituents by assessing key material properties and their responses to lead-free soldering assembly conditions.

Fourteen commercially available FR-4 PCB laminates from two laminate suppliers (I and II) were used in this study. The measurement results of eight laminate material properties on as-received materials and materials exposed to multiple lead-free soldering assembly cycles are reported in this paper. (a) Test Materials

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The laminate materials used for the study are classified as shown in Table 2. Laminates are broadly categorized on the basis of their glass transition temperatures as high Tg (Tg>165C), mid Tg (140C<Tg<165C), and low Tg (Tg<140C) materials. Under each Tg category, laminates are grouped based on the type of curing agent (dicyandiamide (DICY) or phenol novolac (phenolic)), the presence of fillers, and the type of flame retardant used (halogenated or halogen-free). The study also includes laminates marketed for high frequency applications (materials E and K). Laminates among the pairs C1/C2, D1/D2, and G1/G2 differed only by the presence of fillers. The difference between the C1/C2 and G1/G2 pairs was the ratio of high Tg resin. The material pair C1/C2 had a higher percentage of tetrafunctional high Tg resin than did G1/G2. The material type C2 also had a higher percentage of fillers than G2. The rest of the formulation was the same among C1/C2 and G1/G2. Laminate materials with a nominal thickness of 1.2 mm and 1 oz. (0.035 mm) copper cladding were used for evaluating all the properties except time-to-delamination. Laminates from supplier I had 6 plies of glass weave style 2 7628 with a resin content of 41%, and the laminates from supplier II had 6 plies of glass weave style 7629. Time-to-delamination was measured on bare fabricated boards only for materials A, B, C1, C2, G1, and J. The fabricated boards consist of a 12-layer stack up (nominal thickness of 2.5 mm) with alternative layers of cores (with 1 oz. copper cladding on both sides) and prepregs of glass weave styles 1080, 2116, and 7628. The inner layers consisted of a staggered circular copper etch pattern, but the outer layers of copper did not have any etch pattern.

(b) Exposure Conditions

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The parameters such as glass fiber bundle diameter, number of fiber bundles, and linear density of the fabric define the type of glass weave style.

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Laminate samples from all the material types were divided into four lots. The first lot was the control and represented the samples as received from the laminate suppliers. The second lot was exposed to three reflow cycles (3X-R), the third lot to six reflow cycles (6X-R), and the fourth lot to a combination of two reflow cycles and one wave soldering cycle (2X-R+1X-W). The lead-free reflow profile (measured using thermo-couples placed at different locations on the first test board) used to conduct the exposures is shown in Figure 2 and meets the lead-free reflow profiles recommended by IPC/JEDEC-J-STD-020D [8]. For the lead-free wave soldering exposures, samples were passed through two preheat zones maintained at 94C and 155C, respectively (belt speed: 1 m/min), followed by the lead-free solder wave (Sn-0.7Cu-0.05Ni+Ge, commonly known as SN100C) with a maximum pot temperature set at 260C. (c) Test Methods

The test methods and equipment used for measuring the properties are listed in Table 3. All the properties under consideration were measured as per the IPC-TM-650 test methods. The measurement procedures for each of the properties are discussed in the following

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Glass transition temperature (Tg): The glass transition temperature (Tg) of a resin system is the temperature at which a material transforms from a rigid and glass-like state to a rubbery and compliant state due to the reversible breakage of Van der Waals bonds between the polymer molecular chains. The Tg of the laminates was measured using a Perkin-Elmer differential scanning calorimeter (Pyris 1 DSC) as per the IPC-TM-650 2.4.25 test method [9]. Two samples weighing between 1530 mg were used for the measurement. First, the copper cladding was etched from the samples using a sodium persulphate solution. The samples were then baked for 2 hours at 105C and cooled to room temperature in a dessicator prior to the measurement.
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The specimens were subjected to a temperature scan of 25C to 220C in the DSC at a ramp rate of 20C/min. Tg was identified as the midpoint of the step transition in the DSC measurement plot. Coefficient of thermal expansion (CTE): The coefficient of thermal expansion (CTE) of a material is the fractional change of linear dimensions with temperature. Out-of-plane CTE is dominated by the resin system, whereas in-plane (in the warp and fill directions) CTE is dominated by the glass fabric. Out-of-plane CTE influences failure mechanisms such as barrel cracking and delamination, and in-plane CTE affects the shear failures of solder joints. The CTE of laminate materials in the out-of-plane direction was measured using a Perkin-Elmer thermomechanical analyzer (Pyris TMA 7) as per the IPC-TM-650 2.4.24 test method [10]. Two samples of 7 mm 7 mm size were used for the measurement. The copper cladding was etched off and the samples were baked for 2 hours at 105C and cooled to room temperature in a dessicator prior to measurement. The samples were then subjected to a temperature scan of 25C to 250C at a 10C/minute ramp rate. The glass transition temperature (Tg) was identified as the temperature at which the slope of the TMA measurement plot changes, and the CTE was measured below and above Tg. Decomposition temperature (Td): Decomposition temperature (Td) is the temperature at which a resin system undergoes irreversible physical and chemical degradation with thermal destruction of the cross-links, resulting in weight loss of the material. The weight loss in the sample is due to the release of volatile components in the epoxy structure. The Td of the laminates was measured using a Shimadzu thermogravimetric analyzer (Shimadzu TGA 50) as per the IPC-TM-650 2.4.24.6 test method [11]. One test specimen from each material type weighing between 8 and 20 mg was used for the measurement. The copper cladding was etched off and the samples were baked at 110C for 24 hours and cooled to room temperature in a dessicator prior to the measurement. The specimens were subjected to a temperature scan of 25C to 550C at a ramp rate of 10C/minute in an inert nitrogen
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atmosphere. A change in weight of the sample was obtained as a function of temperature, and the Td was recorded at 2% and 5% weight loss (compared to sample weight at 50C). Time-to-delamination (T-260): Time-to-delamination is the time taken by a laminate material to delaminate (defined as the separation between layers of prepregs and copper-clad cores in a multilayered structure) when exposed to a constant temperature. Due to the lead-free soldering process reaching peak temperatures of around 260C, the

time-to-delamination measured at 260C (T-260) was used as a metric for assessing the lead-free process compatibility of laminates. T-260 is indicative of the ability of a laminate material to withstand multiple soldering cycles without delamination. The T-260 values of the fabricated boards were measured using a Perkin-Elmer thermomechanical analyzer (Pyris TMA 7) as per the IPC-TM-650 2.4.24.1 test method [12]. Two samples of 7 mm 7 mm size were used for the measurement. The samples were baked for 2 hours at 105C and cooled to room temperature in a dessicator prior to measurement. The samples were then subjected to a temperature scan of 25C to 260C at a ramp rate of 10C/minute and then held at 260C until an irreversible change in thickness (assumed to be caused by layer to layer delamination) of the sample was observed or 60 minutes elapsed, whichever occurred first. A constant probe load of 5 mN was applied during the scan. Time-to-delamination was determined as the time between the onset of isotherm (260C) and the onset of delamination.

Water absorption: Water absorption is a measure of the amount of water absorbed by laminate materials immersed in distilled water for 24 hours at ambient temperature. Water absorption influences several PCB failure mechanisms such as corrosion and conductive filament formation. The water absorption of laminates was measured as per the IPC-TM-650 2.6.2.1 test method [13]. Three samples 5 cm 5 cm in size were used for the measurement. The copper cladding was etched off and the samples were baked at 105C for 1 hour and cooled to room
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temperature in a dessicator prior to measurement. The samples were weighed using a microbalance before and after immersion in distilled water for 24 hours. After removal of the samples from the water, they were cleaned by wiping with a clean damp cloth. The percentage of water absorption is calculated by the following expression.
% Water absorption = Wet weight Conditione d weight 100 Conditione d weight

Flammability: Flammability is the measure of a materials tendency to extinguish a flame once the specimen has been ignited and separated from the flame source. FR-4 PCB laminates, being plastics, are inherently flammable, and flame retardants are added into the resin system to enhance their self-extinguishing properties. Typical steps involved in a PCB combustion process are shown in Figure 3 [14].

Flammability was measured as per the IPC-TM-650 2.3.10 method [15]. Five specimens per material type were cut into sizes of 127 mm 12.7 mm from the 18" 24" panels (shown in Figure 4). The edges were polished and the copper cladding was etched off of the samples. The specimens were baked for two hours on a hot plate maintained at 105C and then cooled to room temperature in a dessicator. The samples were then conditioned at 25C at 50% RH for 24 hours prior to testing. The samples were then ignited using a Bunsen burner with a 19 mm high blue flame. The gas supply to the burner was adjusted to maintain the height. The samples were placed over the flame (as shown in Figure 5) for 10 seconds and then withdrawn. If active combustion ceases prior to a specimen being completely consumed, the samples are placed under the flame again for 10 seconds and withdrawn. The following parameters were recorded: (1) duration of specimen burning after the first flame application, (2) duration of specimen burning after the second flame application, and (3) whether any specimen burns up to the holding clamp on any ignition. Total specimen burning time was then calculated by calculating the sum of the individual burning times in both flame applications. The test results were compared to the UL 94 V-0 flammability criteria. The
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UL94 V-0 criteria state that the time of burning per specimen after two flame applications should not be more than 10 seconds, and the total burning time for the 10 flame applications for each set of 5 specimens should not be more than 50 seconds. Dielectric constant (Dk): Dk is the ratio of the permittivity of a medium to that of a vacuum. Propagation velocity of a signal and the characteristic impedances of transmission lines are influenced by the dielectric constant of the laminate. PCBs with lower values of dielectric constant are best suited for high frequency or high power applications to minimize electric power losses. PCBs with higher values of dielectric constant are better suited for capacitance applications.

Dissipation factor (Df): Df is the ratio of the power loss in a dielectric material to the total power transmitted through the dielectric. It should be as low as possible to keep the power losses small, and lower dissipation factor is a requirement for high-frequency applications. Dk and Df were measured using an Agilent E4991A RF Impedance/Material Analyzer in combination with the Agilent 16453A test fixture, as per the IPC-TM-650 2.5.5.9 test method [16]. The test equipment is shown in Figure 6. Three specimens per material type were cut into sizes of 50 mm 50 mm. The edges were polished and the copper cladding was etched off of the samples. The specimens were baked for two hours on a hot plate maintained at 105C and then cooled to room temperature in a dessicator. Prior to testing, all samples were conditioned at 25C and 50% RH for 24 hours. The electrodes of the test fixture formed a capacitor with the sample as the dielectric medium between them. By measuring the capacitance of this system, the dielectric constant and the dissipation factor were calculated (capacitance method). This measurement was performed for all frequencies between 1 MHz to 1 GHz using the test fixture. A typical plot for Dk measurement is shown in Figure 7. RESULTS AND DISCUSSION

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In all the properties considered, pre-exposure measurement results were used to characterize the laminate materials and are referred to as the control samples. The effects of laminate material constituents such as curing agent, fillers, and flame retardants in relation to changes in the material properties due to lead-free soldering exposures are discussed in the following subsections. The samples for measurement were chosen from two different locations on the same laminate panel, satisfying the minimum requirement for sample size as per the IPC-TM-650 test methods. Also, the test equipment used for measurements were calibrated as per manufacturer-specified standards or methods and checked for their repeatability. (a) Glass Transition Temperature (Tg) The pre- and post-exposure measurement results were grouped by material (e.g., A, B) as shown in Figure 8. The average of two measurements and the deviation of test results from the average are plotted. The first data point shown in each group corresponds to the measurements on the control samples, the second point to 3X reflowed samples, the third point to 6X reflowed samples, and the fourth point to the samples that are exposed to a combination of 2X reflow and 1X wave soldering cycles. The same pattern of data representation is followed in the plots of all other properties except for time-to-delamination. The materials that underwent a variation in Tg of greater than 5C after the exposures are

shown in Figure 8 within separate boxes.

The Tg of a laminate system primarily depends on the type of epoxy (bi-, tetra-, or multi-functional) or its percentage composition. Higher cross-linking density in the multi-functional epoxy systems compared to their bi-functional counterparts results in a higher Tg. Thus, the control sample results show laminates can have similar Tg ranges irrespective of the type of curing agent, flame retardant, and the presence of fillers. The post-exposure results show that five out of seven high Tg and four out of five mid Tg materials had relatively stable Tg values with a variation of less than 5C. All of these were phenolic-cured materials. The materials that underwent a variation of greater than 5C were
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all DICY-cured (A, B, F, J, and K). An increase in Tg was observed in low Tg DICY-cured materials, whereas high and mid Tg DICY-cured materials underwent a reduction in Tg. The highest variation in Tg (a reduction of about 20C from control) was observed in a high Tg DICY-cured halogen-free material with fillers (B). (b) Coefficient of Thermal Expansion (CTE) The out-of-plane CTE (below and above Tg) measurement results are shown in Figure 9. The average of two measurements and the deviation of test results from the average are plotted. The same pattern of data representation as that of the Tg results is followed. Materials with a variation of greater than 15% in their above Tg CTE values due to exposure are shown in separate boxes.

The analysis of control sample results was performed based on the above Tg out-of-plane CTE as the effect of material constituents was prominent in the above Tg compared to the below Tg CTE. The results showed that the high Tg material (A) had a lower CTE than the low Tg material (J) with similar constituents (DICY-cured with halogenated flame retardant) because of higher cross-linking in its epoxy system. The effect of the type of curing agent was not observed in the CTE results. Filled materials (D2, G2) had lower CTE values compared to unfilled materials (D1, G1) due to lower epoxy content. Halogen-free materials (B, I) had lower CTE values than halogenated materials (A, H) with similar characteristics such as Tg range and type of curing agent.

The post-exposure results showed a reduction in above Tg out-of-plane CTE in most of the materials. The filler content, type of flame-retardant (halogen/halogen-free), and type of curing agent (DICY/phenolic) showed similar effects on the change of the CTE due to lead-free soldering exposures. A reduction of about 25% in above Tg CTE was observed in material B, whereas a variation of more than 15% was observed in below Tg CTE of materials B, C1, and G2. (c) Decomposition Temperature (Td)
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The decomposition temperature measurement results corresponding to 2% and 5% weight loss are plotted in Figure 10. The same pattern of data representation as that for the Tg results is followed. Lead-free soldering exposures did not show noticeable variation in Td (>10C), and hence no materials are shown within separate boxes. The laminate sample weight loss was below 1% until 250C and a reduction of about 20% of the weight of sample was observed at the end of the test at 550C for all the samples. Pre-exposure measurement results showed that a low Tg material (J) had a higher Td compared to a high Tg material (A) with similar constituents. The effects of the type of curing agent on the Td of the laminates are shown in Figure 11. Among the halogenated materials, phenolic-cured materials (G1, C1) withstood higher temperatures before 2% and 5% weight loss compared to their DICY-cured counterparts (A, J). These lower decomposition temperatures in DICY-cured epoxy systems can be attributed to the presence of linear aliphatic molecular bonds with amine linkages compared to thermally stable aromatic bonds with ether linkages of phenolic-cured systems [1, 7]. The effect of the presence of fillers on the Td of the laminates is shown in Figure 12. Laminates with fillers (C2, D2, G2) have a lower Td compared to their counterparts without fillers (C1, D1, G1). Previous studies [17-19] on the effect of fillers on thermal decomposition of epoxy systems have demonstrated that inorganic fillers such as alumina or silica accelerate the thermal decomposition process due to the catalysis effect. But the effect of fillers on decomposition temperature appears to be marginal compared to the effect of the type of curing agent. The effects of different types of flame retardants on the Td values of the laminates are shown in Figure 13. Halogen-free material that was DICY-cured (B) withstood higher temperatures before 2% and 5% weight degradation compared to the halogenated DICY-cured material (A). On the contrary, phenolic-cured halogen-free material (I) has lower decomposition temperatures compared to its halogenated counterpart (H). Irrespective of the type of curing agent, halogenated resin systems (A and H) underwent degradation from 2% to 5% within a narrow temperature range,
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which was not observed in halogen-free systems (B and I). Halogen-free laminate materials filled with a high percentage of filler and lower amounts of resin are sometimes known to give erroneous decomposition temperature readings. The relationship of curing agents, fillers, and flame retardants to the decomposition temperature as observed for the control samples remained the same after lead-free soldering exposures. A maximum variation of 7C in decomposition temperature was observed due to the exposures. The exposures did not affect the material to the extent of changing its degradation behavior.

(d) Time-to-Delamination (T-260) Time-to-delamination was measured for fabricated boards on a subset of materials, i.e., A, B, C1, C2, G1, and J, and the results are shown in Figure 14. Fabricated boards for characterization were available only for these materials. The properties spanned a range of Tg, curing agents, flame retardants, and the presence or absence of fillers. An average of two measurements and the deviation of test results from the average are plotted in Figure 14. The order of data representation under each material is the same as that of Tg results. The control results show that three materialsA, B, and Jdelaminated within 20 minutes, whereas materials C1, C2, and G1 did not delaminate within the exposure period of 60 minutes. The test was stopped at 60 minutes for these materials. Material J had a higher T-260 than did A and B. Thus, DICY-cured materials have lower time-to-delamination compared to phenolic-cured ones regardless of their Tg. Low Tg DICY-cured materials have a higher T-260 compared to their high Tg counterparts. The effect of the type of flame retardant and the presence of fillers is not as prominent as that of the curing agent. Lead-free soldering exposures tend to lower the time-to-delamination of materials A, B, and J, all of which are DICY-cured. Materials C1, C2, and G1, which were phenolic-cured, did not delaminate within 60 minutes. (e) Water Absorption
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The pre- and post-exposure water absorption measurement results are shown in Figure 15. The average and the range of results from the average of three measurements are plotted. The same pattern of data representation as for Tg in the previous section was followed. Materials with a variation of greater than 25% in water absorption from control are highlighted in Figure 15. Measurements on the control sample showed that high Tg materials (A, B) have higher water absorption compared to low Tg materials (J, K) with similar constituents. This could be attributed to the availability of increased free volume due to higher cross-linking density in the high Tg materials compared to low Tg materials [21]. DICY-cured materials (A, F) were more hydrophilic compared to phenolic-cured materials (C1, I). This could be because of the presence of highly polar bonds in the DICY-cured systems compared to phenolic-cured systems [1]. The effect of the presence of fillers and type of flame retardant was not as prominent as that of the type of curing agent. The post-exposure results showed an increase in water absorption due to lead-free soldering exposures. The material type with the highest increase (55%) in water absorption value after 6X reflow exposure was a low Tg DICY-cured halogenated material (J). (f) Flammability

The measurement results are shown in Figure 16. Total burning time is plotted for the materials selected. The control results show that the UL 94 V-0 flammability criteria were satisfied by all the samples. DICY-cured materials (A, B) showed higher combustion times compared to phenolic-cured systems (C1, H, I) irrespective of Tg, type of flame retardant, or the presence of fillers. Within DICY and phenolic-cured systems, materials with halogen-free flame retardant had higher combustion times compared to halogenated flame retardant systems (B vs. A; I vs. H). Materials with similar constituents, but only differing by the presence of fillers, had higher combustion times compared to materials without fillers (B vs. A; H vs. C1). Although flame-retardants are the primary constituents that affect the
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flammability of a material, other factors such as type of curing agent (DICY/phenolic) and the presence of fillers also have an indirect effect on flammability. The post-exposure measurement results showed that the samples still met the UL 94 V-0 flammability criteria after lead-free soldering exposures. DICY-cured systems or materials that are halogen-free showed an increase in the combustion times with 6X lead-free reflow exposures. (g) Dielectric constant and dissipation factor The dielectric constant (Dk) and dissipation factor (Df) measurement results are shown in Figure 17 and in Figure 18, respectively. The average of three measurements and range are plotted. The control results showed that all of the materials, except those marketed for high frequency applications, showed similar Dk and Df values. Thus, factors such as type of curing agent, type of flame retardant, and the presence of fillers had no significant impact on the permittivity and dissipation factor of the laminate materials. Laminates designed for high frequency applications had dissimilar epoxy systems and hence showed lower Dk and Df values.

The post-exposure results showed that lead-free soldering exposures appeared to increase the dielectric constant and dissipation factor of some of the material types. Materials having a variation of greater than 5% in dielectric constant and 50% in dissipation factor from control are shown in the thick-lined boxes in Figure 17 and Figure 18, respectively. The material type with both the highest (9.7%) increase in Dk and the highest (50%) increase in Df was a mid Tg phenolic-cured halogen free material with fillers (type I). ANALYSIS OF RESULTS This study demonstrated that lead-free soldering exposures can transform a PCB material, leading to cleavage of bonds at the chain ends of the epoxy system resulting in an enhanced-cure structure; or leading in the cleavage of bonds in a polymer backbone resulting in a degraded structure. The former mechanism results in an increase in the
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cross-linking density of the epoxy matrix, whereas the latter results in a change in the material structure due to the loss of certain functional groups [20]. Both of these can potentially change the material properties of laminates. Although the current study does not include an evaluation of the effect of eutectic tin-lead soldering conditions on laminate material properties, the results showed that the high temperature exposures associated with lead-free soldering resulted in a noticeable variation in the material properties of some of the laminates. Some past studies [5] on laminate types similar to the ones studied in this paper show minimal changes in Tg, CTE, and Td after exposure to simulated eutectic tin-lead soldering excursions. Fourier transform infrared spectroscopy (FT-IR) analysis was also performed to verify whether there was any polymer degradation, and a conjunctional analysis of material properties was performed to verify the enhanced-cure structure. (a) Fourier Transform Infrared Spectroscopy (FT-IR) Analysis FT-IR analysis is performed firstly to identify the key functional groups in the laminate materials and to investigate any changes in these groups due to lead-free soldering exposures. Further, an attempt was made to correlate the compositional changes observed by FTIR to the variation in material properties observed in the various measurements. Samples from control and 6X reflowed lots of the materials (B, H) that underwent maximum variation in their properties due to lead-free soldering exposures were selected for the analysis. A small piece of the laminate material was scraped off of the sample using a stainless steel scalpel and was mounted on an IR-reflective brass plate. A Mattson FT-IR spectrometer with Galaxy Microscope attachment was used for the analysis. An IR beam was passed through the sample and then reflected off of the brass plate and passed back through the sample, where it was detected and analyzed. Each sample was scanned 32 times with 4 cm-1 resolution to obtain the spectrum.

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FT-IR did not reveal a noticeable change in the wave numbers corresponding to the functional groups in the spectra between the control and 6X reflowed samples (i.e., the shape of the spectrum was retained). This indicated that the variation in material properties could possibly be attributed to an increase in cross-linking of the resin system rather than to the degradation of the polymer network. The results of decomposition temperature measurements also complement this conclusion, as no variation in the Td of the materials was observed due to lead-free soldering exposures. The complex molecular structure of the laminates combined with the overlap of bond energies made it difficult to interpret the spectra by locating the exact wave numbers corresponding to the functional groups. The peaks corresponding to key functional groups in the control and 6X reflowed samples of material H are shown in Figure 19. Phenyl-Br: 1066 cm-1, Benzene ring: 16001450 cm-1, CH: 30002850 cm-1, OH: 35003400 cm-1 are identified and are shown by dotted lines in Figure 19. (b) Conjunctional Properties Analysis

Materials B and H were selected for a conjunctional property analysis in order to investigate the underlying causes for the variations in material properties. The analysis is focused on relating the variations in material properties to the assumed enhanced-cure structure. This analysis, along with observed variations in properties between the control and the 6X reflowed samples of materials B and H are listed in Table 4. It should be noted that material B is a high Tg DICY-cured halogen-free material with fillers, whereas H is a mid Tg phenolic-cured halogenated material with fillers. The Tg of a polymer is dependent on parameters such as molecular weight of the material, tacticity, the degree of cross-linking, and entrapped plasticizers [27]. A decrease in Tg of an epoxy system is usually associated with the entrapped plasticizers, whereas an increase in Tg is associated with the increase in cross-linking density. Water typically acts as a plasticizer in the epoxy systems, resulting in a reduction in Tg [22, 28-31]. As discussed earlier, laminates exposed to soldering conditions have higher water absorption than the unexposed laminates. A
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decrease in Tg observed in material B could be the result of the plasticizing effect of moisture that might have been retained in the sample even after the preconditioning (2 hours of baking at 105C) performed prior to Tg measurement as per the IPC test method. Material B is a DICY-cured system and hence has highly polar bonds compared to phenolic-cured material H. Additionally, B is a high Tg material having high cross-linking density to begin with, compared to mid Tg material H. The combined effect of high polarity and the presence of greater free-volume in the structure could have resulted in higher moisture absorption in material B, leading to a reduction in Tg. To further verify the hypothesis, the Tg of the 6X reflowed samples of material B were measured after baking for 24 hours at 110C. It was found that the Tg reduction between the control and the 6X reflowed samples decreased from 15C to 8C, thus reinforcing the hypothesis that the increase in the hydrophilic nature of the material would result in a degradation of Tg. Overall, the variation in properties due to lead-free soldering exposures could be related to the degree of cross-linking and the extent of water absorption in the exposed samples.

Both materials B and H experienced a reduction of CTE in the 6X reflowed samples. This reduction can be attributed to the increased cross-linking density of the epoxy resin in the enhanced-cure structure. The increase in water absorption in materials B and H can be explained by the underlying mechanism. Water absorption in the epoxy matrix occurs due partly to the availability of free-volume in the structure and the affinity of water molecules to the polar sites present in the polymer [21-23]. An increase in the cross-linking density of the resin system enhances the free-volume of the polymer structure, resulting in an increase in water absorption [19, 24-26].

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SUMMARY AND CONCLUSIONS

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PCB material selection for lead-free processing is not only based on final properties, but is also impacted by factors such as regulatory compliance, application environment, cost, reliability, sources, and availability. High temperature exposures to PCB materials resulted in variations in the material properties of certain FR-4 laminate material types. It is recommended that laminate manufacturers should conduct in-house qualification tests to measure variations in properties and take corrective actions by fine tuning the material constituents or fabrication process conditions for achieving thermally stable laminates. Data obtained from such in-house tests should also be reported to customers. Electronic product manufacturers, on the other hand, should gather this information on material constituents from the laminate manufacturers and consider the extent of variations in material properties due to lead-free soldering exposures before deciding on a PCB laminate material. In this study, we observed that lead-free soldering exposures tend to lower the Tg, out-of-plane CTE, and T-260 of certain types of laminate materials. A general trend of increase in water absorption due to exposures was observed in most of the laminates studied. The exposures did not affect the laminate materials to the extent of changing their degradation behavior (Td). The samples continued to meet UL 94 V-0 flammability criteria after lead-free soldering exposures. However, DICY-cured and halogen-free materials showed an increase in combustion times with lead-free reflow. We also observed that lead-free exposures resulted in an increase in the dielectric constants and dissipation factors of some materials. Based on the experience of testing conducted as part of this study, there were some instances where the test methods used were found to be either ambiguous or insufficient. Thus, we propose a review of these methods to make the measurements repeatable between material types and testing laboratory locations. For instance, the inadequacy of the methods was observed during the water absorption tests. As per IPC TM 650 2.6.2.1, the samples after removal from the water bath should be wiped clean of excess water and placed on the microbalance, but the type of cloth to be used to remove the excess water before weighing is
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not specified. Additionally, the fashion in which the laminates should be cleaned is not mentioned. During the course of this study, the authors found that the use of different cloth materials could remove different amounts of water from the laminate surface and could provide different weight readings on the microbalance, which could result in erroneous water absorption results. In the case of material property measurement tests where preconditioning is required, no specific steps are listed to account for or measure the initial moisture content of the laminates. It is known from past studies that epoxy laminates can hold different amounts of moisture. This moisture content is dependent on the laminate chemistry, including epoxy type, filler type, and concentration, glass reinforcement, and type of flame retardant. As an example, an etched laminate sample exposed to 24 hours of baking at 105C may lose 2% of its moisture content but yet retain a majority of its moisture. When the moisture content of the first material after preconditioning is compared with a different laminate material with a lower initial moisture content attributed to epoxy type, flame retardant, or filler concentration, studies have found varying amounts of moisture may be present in the laminate epoxy. The preconditioning steps specified in the IPC test methods do not address the initial moisture content of the laminate test samples and significant errors can be introduced. This methodology and the results of the study were reviewed by several organizations involved with various aspects of electronics manufacturing. Since it was found that the study method was scientific and the results useful, a follow-up study was initiated by the Center for Advanced Life Cycle Engineering (CALCE) at the University of Maryland, College Park, to assess the impact of halogen-free flame retardants on the thermal and electrical properties of FR4 laminate materials.

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The authors would like to acknowledge the Nan Ya Plastics Co. for their help, advice, and support and the members of the CALCE Electronic Products and Systems Consortium at the University of Maryland for their sponsorship of the project. The authors would also like to thank Mark Zimmerman of CALCE for copyediting this paper.

REFERENCES 1. Peng Y., Qi X., and Chrisafides C., The influence of curing systems on epoxide-based PCB laminate performance, Circuit World, Vol. 31, No. 4, pp. 14-20, 2005. 2. Ganesan S., and Pecht M., Lead-free electronics, IEEE Press, Wiley-Interscience, A. John Wiley and Sons, Inc., New Jersey, USA, 2006. 3. Sanapala R., Sood B., Das D., and Pecht M., Effect of Lead-Free Soldering on Key Material Properties of FR-4 Printed Circuit Board Laminates, IEEE Transactions on Electronics Packaging Manufacturing, Vol. 32, No. 4, pp. 272-280, 2009. 4. Kelley E., An assessment of the impact of lead-free assembly processes on base material and PCB reliability, Proceedings of IPC APEX Conference, pp. S16-2-1, 2004. 5. Bergum E., Thermal analysis of base materials through assembly: can current analytical techniques predict and characterize differences in laminate performance prior to exposure to thermal excursions during assembly?, Printed Circuit Design & Manufacture,

September 2003.

6. Kelley E., and Bergum E., Laminate material selection for RoHS assembly, Part 1, Printed Circuit Design & Manufacture, pp. 30-34, November 2006. 7. Christiansen W., Shirrell D., Aguirre B., and Wilkins J., Thermal stability of electrical grade laminates based on epoxy resins, Proceedings of IPC Printed Circuits EXPO, Anaheim, CA, pp. S03-1-1-S03-1-7, 2001. 8. IPC/JEDEC J-STD-020D, Moisture/reflow sensitivity classification for non-hermetic solid state surface mount devices, August 2007. 9. IPC-TM-650 2.4.25, Glass transition temperature and cure factor by DSC, The Institute for Interconnecting and Packaging Electronic Circuits, Northbrook, IL, December 1994. 10. IPC-TM-650 2.4.24, Glass transition temperature and z-axis thermal expansion by TMA, The Institute for Interconnecting and Packaging Electronic Circuits, Northbrook, IL, December 1994.

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11. IPC-TM-650 2.4.24.6, Decomposition of laminate material using TGA, The Institute for Interconnecting and Packaging Electronic Circuits, Bannockburn, IL, April 2006. 12. IPC-TM-650 2.4.24.1, Time-to-delamination (by TMA method), The Institute for Interconnecting and Packaging Electronic Circuits, Northbrook, IL, December 1994. 13. IPC-TM-650 2.6.2.1A, Water absorption, metal clad plastic laminates, The Institute for Interconnecting and Packaging Electronic Circuits, Northbrook, IL, May 1986. 14. Lambert, W.R, The impact of materials on the flammability of printed wiring board products, Proceedings of the 43rd Electronic Components and Technology Conference, pp. 134 - 142, June 1993. 15. IPC-TM-650 2.3.10, Flammability of laminate, The Institute for Interconnecting and Packaging Electronic Circuits, Northbrook, IL, December 1994. 16. IPC-TM-650 2.5.5.9, Permittivity and loss tangent, parallel plate, 1MHz to 1.5 GHz, The Institute for Interconnecting and Packaging Electronic Circuits, Northbrook, IL,

November 1998.

17. Paterson-Jones JC., Percy VA., Giles RGF., and Stephen AM., The thermal degradation of model compounds of amine-cured epoxide resins. II. The thermal degradation of 1,3-diphenoxypropan-2-ol and 1,3-diphenoxypropene, Journal of Applied Polymer Science, Vol. 17, No. 6, pp. 1877-1887, 1973. 18. Brito Z., and Sanchez G., Influence of metallic fillers on the thermal and mechanical behavior in composites of epoxy matrix, Composite Structures, Vol. 48, No. 1-3, pp.

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79-81, 2000.

19. Sanchez G., Brito Z., Mujica V., and Perdomo G., The thermal behavior of cured epoxy-resins: The influence of metallic fillers, Polymer Degradation Stability, Vol. 40, No. 1, pp. 109-114, 1993. 20. Levchik S., and Weil E., Thermal decomposition, combustion and flame-retardancy of epoxy resins-a review of the recent literature, Polymer International, Vol. 53, pp. 1901-1929, 2004. 21. Diamant Y., Marom G., and Broutman L., The effect of network structure on moisture absorption of epoxy resins, Journal of Applied Polymer Science, Vol. 26, pp. 3015-3025, 1981. 22. Marsh L., Lasky R., Seraphim D., and Springer G., Moisture solubility and diffusion in epoxy and epoxy-glass composites, IBM Journal of Research and Development, Vol. 28, No. 6, pp. 655-661, 1984.

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23. Maggana C., and Pissis P., Water sorption and diffusion studies in an epoxy resin system, Journal of Polymer Science: Part B: Polymer Physics, Vol. 37, Issue 11, pp. 1165-1182, 1999. 24. Ko M., Kim M., Effect of post-mold curing on plastic IC package reliability, Journal of Applied Polymer Science, Vol. 69, No. 11, pp. 2187-2193, 1998. 25. Gonon P., Sylvestre A., Teysseyre J., and Prior C., Combined effects of humidity and thermal stress on the dielectric properties of epoxy-silica composites, Materials Science and Engineering B , Vol. 83, No. 1-3, pp. 158-164, June 2001. 26. Aronhime M., Peng X., and Gillham J., Effect of time-temperature path of cure on the water absorption of high Tg epoxy resins, Journal of Applied Polymer Science, Vol. 32, pp. 3589-3626, 1986. 27. Wondraczek K., Adams J., and Fuhrmann J., Effect of thermal degradation on glass transition temperature of PMMA, Macromolecular Chemistry and Physics, Vol. 205, No. 14, pp. 1858-1862, 2004. 28. Sala G., Composition degradation due to fluid absorption, Composites Part B: Engineering, Vol. 31, No. 5, pp. 357-373, July 2000. 29. Smith C., Water absorption in glass fiber-epoxide resin laminates, Circuit World, Vol.

14, No. 3, pp. 22 -26, 1988.

30. Flor G., Campari-Vigano G., and Feduzi R., A thermal study on moisture absorption by epoxy composites, Journal of Thermal Analysis and Calorimetry, Vol. 35, No. 7, pp.

2255-2264, November 1989.

31. Johnson J., Resin matrices and their contributions to composite properties, Philosophical Transactions of the Royal Society of London. Series A, Vol. 294, No. 1411, pp. 487-494, 1980.

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List of Tables
Table 1 Typical Constituent of FR-4 Laminates........................................................................... Table 2 Material Classification..................................................................................................... Table 3 Measurement Methods..................................................................................................... Table 4 Summary of Variation in Properties for Materials B and H between Control and 6X Reflowed Samples. .......................................................................................................................

List of Figures
Figure 1 FR-4 Printed circuit board fabrication ........................................................................... Figure 2 Lead-free reflow profile used for the exposures ............................................................ Figure 3 Typical PCB combustion steps....................................................................................... Figure 4 Laminate panels and cut samples................................................................................... Figure 5 Test set-up for flammability measurements ................................................................... Figure 6 Agilent E4991A impedance analyzer with Agilent 16453A test fixture ........................ Figure 7 Typical plot of Dk ........................................................................................................... Figure 8 Effect of lead-free soldering exposures on Tg ................................................................ Figure 9 Effect of lead-free soldering exposures on out-of-plane CTE ....................................... Figure 10 Effect of lead-free soldering exposures on Td (2% and 5% weight loss)..................... Figure 11 Effect of type of curing agent on Td of the laminates .................................................. Figure 12 Effect of presence of fillers on Td of the laminates...................................................... Figure 13 Effect of type of flame retardant on Td of the laminates.............................................. Figure 14 Effect of lead-free soldering exposures on T-260 ........................................................ Figure 15 Effect of lead-free soldering exposures on water absorption....................................... Figure 16 Effect of lead-free soldering conditions on flammability ............................................ Figure 17 Effect of lead-free soldering conditions on dielectric constant.................................... Figure 18 Effect of lead-free soldering conditions on dissipation factor ..................................... Figure 19 FT-IR spectra of a control and 6X reflowed sample of material H..............................

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Table 1 Typical Constituent of FR-4 Laminates Major function(s) Provides mechanical strength Bonds inorganic glass with organic resin Coupling agent and transfers stresses across the matrix Acts as a binder and load transferring Resin agent Enhances linear/cross polymerization in Curing agent the resin Flame retardant Fillers Accelerators Reduces flammability of the material Reduces thermal expansion Increases reaction rate, reduces curing temperature, controls cross-link density Constituent Reinforcement Example material(s) Woven glass (E-grade) fiber Organosilanes Epoxy (DGEBA) Dicyandiamide (DICY), Phenol novolac (phenolic) Halogenated (TBBPA) or Halogen-free (Phosphorous compounds) Aluminum silicate, Aluminum hydroxide Organophosphine, Imidazole

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Table 2 Material Classification Material classification Curing agent DICY Fillers No Yes No Yes No Yes Yes Yes No Yes Yes Yes No Yes Halogen-free No Yes No No No No Yes Yes No No No Yes No No

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Material ID A B C1 C2 D1 D2 E F G1 G2 H I J

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Mid range Tg (140C<Tg<165C) Low Tg (Tg < 140C)

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Table 3 Measurement Methods

Property

Units

Test Method

Equipment

Glass transition temperature (Tg) Coefficient of thermal expansion (CTE) Decomposition temperature (Td) Time-to-delamination (T-260) Water absorption Flammability Dielectric constant (Dk) Dissipation factor (Df)

IPC-TM-650 2.4.25 IPC-TM-650 2.4.24 IPC-TM-650 2.4.24.6 IPC-TM-650 2.4.24.1 IPC-TM-650 2.6.2.1 IPC-TM-650 2.3.10 2.5.5.9 2.5.5.9

Differential scanning calorimeter (DSC) Thermomechanical analyzer (TMA) Thermogravimetric analyzer (TGA) Thermomechanical analyzer (TMA) Micro-balance Bunsen burner and gas supply RF impedance/ material analyzer RF impedance/ material analyzer

ppm/C

minutes %

Table 4 Summary of Variation in Properties for Materials B and H between Control and 6X Reflowed Samples Property Coefficient of thermal expansion (CTE, out-of-plane) Water absorption Glass transition temperature (Tg) Material ID B, H B, H B Observed Variation Decrease Increase Decrease Magnitude of Variation > 15% > 25% > 5C

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Transfer of thermal energy to the laminate Pyrolysis (Thermal degradation of solid matrix, in the absence of oxygen, to release combustible gases) Formation of flammable mixture (combustible gases + oxygen) Ignition occurs if the flammable mixture is heated above its ignition temperature (heat is transferred from the laminate to the mixture through radiation/convection) Flame propagates as new fuel becomes available and as degradation is accelerated by the added thermal energy from the flame When the energy source is removed, flame alone doesnt supply sufficient heat to maintain thermal Pyrolysis

100oC to 250oC Functional group eliminations from chain ends (e.g., water molecules); PWB discoloration 250oC to 500oC Scission of high energy bonds leading to production of flammable monomers Above 500oC Aromatic, condensed ring systems, either intrinsic to the polymer or formed as a result of recombination of fragments, will decompose

Gas-phase combustion consists of free radical chain reactions involving oxidation of hydrocarbons Non-pyrolyzed hydrocarbons: liberated as smoke, and condense as soot beyond flame front Non-volatalized hydrocarbons: These are high molecular weight polymer weight fragments and remain as char.

Flame retardants act to extinguish the flame

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Figure 3 Typical PCB combustion steps.

Figure 4 Laminate panels and cut samples.

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12.7 mm Clamp 6.4 mm

127 mm Laminate

19 mm 9.5 mm

Figure 6 Agilent E4991A impedance analyzer with Agilent 16453A test fixture.

5.5 5.0 4.5 4.0 3.5 3.0 0 100 200 300 400 500

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Bunsen burner

Figure 5 Test set up for flammability measurements.

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Figure 7 Typical plot of Dk.
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Figure 8 Effect of lead-free soldering exposures on Tg (Note: the sequence of data points shown is: Control 3X R 6X R 2X R+1X W).

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Figure 9 Effect of lead-free soldering exposures on out-of-plane CTE (Note: the sequence of data points shown is: Control 3X R 6X R 2X R+1X W).

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Figure 10 Effect of lead-free soldering exposures on Td (2% and 5% weight loss) (Note: the sequence of data points shown is: Control 3X R 6X R 2X R+1X W).

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Decomposition temperature (degrees C)

380 370 360 350 340 330 320 310 300 290
J
Low Tg Low Tg

G1

M id Tg High Tg

C1

M id Tg High Tg

G1

C1

A
High Tg

A
High Tg

Dicy cured Phenolic cured

Figure 11 Effect of type of curing agent on Td of the laminates.

Fo
C1 C2

2% weight loss

5% weight loss

rP

ee

Decomposition temperature (degrees C)

370 360 350 340 330 320 310

G1

G2

rR ev
High Tg Midrange Tg
34
J K

No fillers Fillers present

Figure 12 Effect of presence of fillers on Td of the laminates.

iew

Low Tg

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Decomposition temperature (degrees C)

380 370 360 350 340 330 320 310 300 290
2% weight loss
A Dicy B Dicy I Phenolic A Dicy H Phenolic

H Phenolic

B Dicy

I Phenolic

Halogenated Halogen-free

5% weight loss

Figure 13 Effect of type of flame retardant on Td of the laminates.

Fo

rP ee rR
35

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Figure 15 Effect of lead-free soldering exposures on water absorption (Note: the sequence of data points shown is: Control 3X R 6X R 2X R+1X W).

Fo
Figure 14 Effect of lead-free soldering exposures on T-260.

rP

ee rR
36

ev iew

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50.00 45.00

Total burning time (seconds)

40.00 35.00 30.00 25.00 20.00 15.00 10.00 5.00 0.00

Control 3X Reflow 6X Reflow 2X-R+1X-W

Figure 16 Effect of lead-free soldering conditions on flammability.

Fo
A
C1 C2 High Tg

B High Tg

C1

H Mid Tg

rP
D1

5.2 5

ee

Dielectric constant (Dk)

4.8 4.6 4.4 4.2 4 3.8 3.6

rR ev

D2

G1

G2

Figure 17 Effect of lead-free soldering conditions on dielectric constant.

iew
Mid Tg

Low Tg

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0.025

0.02

Dissipation factor (Df)

0.015

0.01

0.005

C1

C2 High Tg

D1

D2

G1

G2 Mid Tg

Figure 18 Effect of lead-free soldering conditions on dissipation factor.

Figure 19 FT-IR spectra of a control and 6X reflowed sample of material H.

Fo

Low Tg

rP ee rR
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ev iew