October 2007 October 2007

Paint

Coatings Industry

Globally Serving Liquid and Powder Manufacturers and Formulators

Development of Novel Toughening Technology

for Fusion-Bonded-Epoxy (FBE) Powder Coatings

usion-bonded-epoxy (FBE) powder coatings, The size and shape of the inclusions are dependent on the first developed by 3M Co., are used worldcure kinetics. Additionally, the glass transition temperawide where long-term corrosion protection is ture (Tg) of these materials most often decreases because critical such as on oil, gas and water pipelines. some of the CTBN remains dissolved in the epoxy matrix However, the performance requirements for and acts as a plasticizer. FBEs are challenging because the hard, highly crosslinked Other toughening methods involve the use of completely coatings are expected to survive demanding pipe manufacimmiscible or pre-formed modifiers, such as thermoplastics turing processes and installation1 conditions as well as field or core-shell rubbers. These can be difficult to evenly disperse performance at elevated temperatures. It may be possible to in epoxy formulations or can cause significant increases in improve the performance of FBE coatings for pipeline corrothe viscosity of a formulation. However, they typically do not sion protection by increasing the toughness of the coating.2 decrease the Tg of the cured product. Many approaches have been used to toughen epoxy sysFrom previous work by Bates et al.,18 it was established tems, often in composite applications, that using small amounts of certain where toughening agents act through block copoly mers as epoxy toughNovel block copolymer various mechanisms to dissipate an ening agents may alleviate many applied load.3 Among the toughening of these processing concerns. Using toughening technology agents used are liquid rubbers,4-7 coresmall amounts minimizes the potendramatically enhances shell particles,8-10 glass beads11-13 and tial for adversely affecting viscosity as thermoplastic modified epoxies14-16 as the flexibility and impact well as loss of properties such as Tg. well as combinations of the above.17 Additionally, in some cases, the block Complications with these products resistance of FBE coatings copolymer morphology was found to may include significantly increasing develop spontaneously upon blendwithout compromising the viscosity of formulations containing with the uncured resin (Figure ing them, a dependence of the mor1b). Surprisingly, the morphology was other key properties. phology on cure kinetics, the necesmaintained during cure, making the sity of vigorous mixing to disperse system independent of the cure conthe modifiers or the addition of further additives to prevent ditions. Recently, Leibler et al. incorporated ABC triblock particle agglomeration. For example, liquid rubber modicopolymers in a cured epoxy and studied the resulting fiers, such as carboxy-terminated butadiene acrylonitrile ordered morphologies as part of their efforts to use triblock (CTBN), are initially miscible with the uncured epoxy copolymers to improve impact resistance.17 resins. They phase separate during curing of the epoxy forThe present paper discusses the use of a block copolymer to mulation to typically form spherical inclusions (Figure 1a). enhance the performance of FBE powder coatings in terms of
By Ha Pham, Fabio Aguirre, Marv Dettloff and Nikhil Verghese | The Dow Chemical Company, Freeport, TX Reprinted with permission from the October 2007 issue of Paint & Coatings Industry magazine

Figure 1 | Comparison of traditional liquid rubber modified epoxies (a) that are initially miscible with the uncured epoxy, but phase
separate during cure, and block copolymer modified epoxies (b) where the block copolymer self-assembles in the uncured resin and curing locks in the morphology already present.

CURE

CURE

~ 0.1 - >1 m

~ 10 - 50 nm

LEGEND:

= bifunctional epoxy

= curing agent

= cured epoxy

improved flexibility and impact resistance while still maintaining the ability to provide corrosion protection. It is important to note that the block copolymers function by creating second phase morphologies and not by acting as compatibilizers for various components in the FBE.19-23

Toughening of Fusion-BondedEpoxy Powder Coatings

Epoxy resin-based powder coatings have been the standard corrosion protection system for pipelines in the oil, gas and water industry for many years because of their outstanding adhesion, chemical resistance, temperature resistance and corrosion protection. These coatings are factory applied on pipeline (a) (b) segments, then the pipeline segments are transported to the field and welded in place. The welded joints are protected with a special fieldapplied powder coating process or with other systems such as liquid coatings or shrink-wrap sleeves. These coatings are expected to last between 20 and 30 years without requiring a significant amount of monitoring or repair. To achieve this level of durability, the Table 1 | Typical formulation used for powder coatings. coatings must be perfectly applied with literally no Control Toughened bare metal exposed to the environment. Ingredients (phr) (phr) However, the coatings may be damaged dur4-Type epoxy resin 100 100 ing transportation or installation, especially when Dicyandiamide (DICY) curing agent 1.5 1.5 the pipe is installed in remote areas with difficult Imidazole accelerator 1.2 1.2 Wollastonite extender 45.8 45.8 access or rocky terrain. To overcome this problem, Flow modifier 1.5 1.5 a multi-layer coating system was developed in the Block copolymer toughening agent 8 mid-eighties, which involved adding a layer of Prediction Profiler *phr: part per hundred of resin high-density polyethylene (HDPE) or polypropylene over250 epoxy coating. the Table 2 | Performance results for the Control versus Toughened powder coatings. While 200 system is more damage resistant than this Test Control Toughened 150 the single-layer epoxy coating, it costs about 30% Tg ( C) 110 107 more per unit area applied. If a thicker and tougher Flexibility @ -38 C / 100 10 cracks/bar avg. No cracks 3 4 6 10 15 20 25 65 micron single- or dual-layer 5 epoxy7 powder coating 30 45 50 55 60~40070 75 thickness could 5 be developed that had performance 20 approaching 60Flexibility @ -45 C / 12 cracks/bar avg. No cracks ~375 FVC a lower-cost DICY SR (%)micron thickness Toughening the three-layer system it might provide (%) Flexibility @ -38 C / 17 cracks/bar avg. No cracks Agent (wt %) ~500 micron thickness option to the three-layer system.
Pill Flow (mm) 199.3333 11.44158

To demonstrate the toughening effect of a blockcopolymer in FBE powder coatings, a standard pipe coating formulation was modified as noted in Table 1. These mixtures were pre-ground in a high-intensity mixer for 45 seconds, compounded in a twin screw extruder, cooled and ground to a powder coating of approximately 50 micron average particle size. The powder was applied using a fluidized bed to give a thickness of 350 - 400 microns on 2.5 cm x 0.95 cm x 15.24 cm hot rolled steel bars that had been sand blasted to an anchoring profile of 60 to 100 microns. The steel bars were pre-heated to 250 C. The coating was post-cured for 2 minutes at 250 C then the bars were immediately quenched in water until they reached ambient temperature. The bars were tested for (c) flexibility in a four-point bend apparatus commonly used in this field. The bending process was done at subzero temperatures over a 10-second period. The number of cracks that formed in the coating was counted after the bars equilibrated at ambient temperature. No cracks indicate that the coating is tougher and, hence, it is unlikely that it fail in the field.

CURE CURE

CURE CURE

Development of Novel Toughening Technology for Fusion-Bonded-Epoxy (FBE) Powder Coatings

~ 0.1 - >1 m ~ 0.1 - >1 m ~ 10 - 50 nm ~ 10 - 50 nm ~ 10 - 50 nm

LEGEND: LEGEND: LEGEND:

= bifunctional epoxy = bifunctional epoxy

The test results are shown in Table 2. Typical pipe = bifunctional epoxy cannot be agent = curing applied atcured epoxy = thicknesses powder coatings above 400 micron because they will fail the flexibility test. The control sample presented some cracks at 375 microns. The toughened sample passed the flexibility test at the same temperature (-38 C) at 500+ microns. Similarly, the control formulation cannot pass the flexibility test at temperatures much lower than -38 C. The toughened coating was able to pass the test at -45 C with no cracks (Figure 2). The Tgs of the coatings, as measured by DSC, were almost the same. This shows that there was indeed a toughening mechanism in action and not simply flexibilization,

= curing agent = curing agent ~ 0.1 - >1 m

= cured epoxy = cured epoxy

Figure 5 | Effect of test temperature on the impact performance of Control powder-coated panel with 10% FVC.

Figure 2 | Pictures of the bent samples, (a) (b) Control powder coating at 375 micron (a) (c) thickness bent at -38 C, (b) toughened powder coating at 500 microns (c) at -38 bent (a) (b)
C and (c) toughened powder coating at 375 microns bent at -45 C.

(a)

(b)

(c)

which could be achieved in different ways. In order to further understand the effect of the block copolymer toughening agent on other critical FBE coating properties such as flowability, glass transition temperature and impact resistance, a detailed evaluation was carried out using a statistical design of experiments (DoE). The following three independent variables were selected for study. They were incorporated into a Box-Behnken DoE, which required that 15 runs or formulations be evaluated (including three replicates). Amount of toughening agent (%): 2.5; 5.0; and 7.5 weight percentage of the total formulation. Filler Volume Concentration (FVC %): 10; 20; and 30. DICY Stoichiometric Ratio (%): 45; 60; and 75.

Block Copolymer Toughening Agent Effects Coating Powder Flowability

Figure 3 | Effects of DoE variables on coating powder pill flow. Prediction Profiler Prediction Profiler 250 250 Prediction Profiler 200 200 250 150 150 200 100 3 4 5 6 7 10 15 20 25 30 45 50 55 60 65 70 100 3 4 5 6 7 10 15 20 25 30 45 50 55 60 65 70 150 20 60 5 20(%) 5 100 DICY 60 (%) SR Toughening 7 10 15FVC 25 30 45 50 55 60 65 70 3 4 5 6 20 FVC (%) DICY SR (%) Toughening Agent (wt %) 20 60 5 Agent (wt %) FVC (%) DICY SR (%) Toughening Agent (wt %) Figure 4 | Effect of DoE variables on glass transition temperature (Tg). Prediction Profiler Prediction Profiler 113 113 112 Prediction Profiler 112 111 113 111 110 112 110 109 111 3 4 5 6 7 109 3 4 5 6 7 110 5 5 109 Toughening 7 3 4 5 6 Toughening Agent (wt %) 5 Agent (wt %) Toughening Agent (wt %)

75 75 75

DMTA Tg TgTg DMTA DMTA 112.09 112.09 112.09 0.372315 0.372315 0.372315

An important attribute of any coating powder is its ability to flow before it gels. Most thermoplastics or core-shell particles used as toughening agents increase the melt viscosity of the epoxy resin and hence the flowability of the coating powder is reduced, causing adhesion problems due to the poor surface coverage. Pill flow is a laboratory test that provides information on the flowability of the coating before it gels.1 The linear distance of the pill flow was measured and recorded in mm. Samples were run in triplicate. As shown in Figure 3, the block copolymer toughening agent did not affect the pill flow of the coating powder to a significant extent in the range tested. The lines and markers within the plots show how the predicted value changes when one changes the current value of an individual X (Toughening Agent, FVC and DICY) variable. The 95% confidence interval for the predicted values is shown by a dotted curve surrounding the prediction trace.

Pill Flow (mm) (mm) Pill Flow (mm) Pill Flow 199.3333 199.3333 199.3333 11.44158 11.44158 11.44158

Glass Transition Temperature of Powder Coating

10 10 10 15 15 15 20 20 25 25 30 45 50 55 60 65 70 75 30 45 50 55 60 65 70 75 30 45 50 55 60 65 70 75

20 20 FVC20 25 (%) FVC (%) 20 FVC (%)

60 60 DICY SR (%) DICY SR (%) 60 DICY SR (%)

Improving the flexibility and impact resistance of FBE powder coating without affecting flowability and the glass transition temperature of the coating appears to be counterintuitive but it is possible by using the block copolymer toughening agent. As

Development of Novel Toughening Technology for Fusion-Bonded-Epoxy (FBE) Powder Coatings

shown in Figure 4, the Tg of the powder coating measured on free-films by Dynamic Mechanical Thermal Analysis (DMTA) was only slightly affected by the toughening agent at the concentrations tested. On the other hand, it was highly affected by the curing agent (DICY) stoichiometric ratio.

Impact Resistance of Powder Coating

The impact resistance test was performed according to the CAN/CSA-Z245.20 standard. The impact diameters on the coating from -30 C down to -55 C are shown in Figures 5, 6 and 7. The control powder coating with no toughening agent added and 10% FVC showed clear damage, mostly via delamination. A toughened powder coating at 5% by weight of the toughener with the same FVC showed good impact resistance with small impact diameter and no evidence of delamination of the coating from the substrate down to -40 C. Figure 8 shows that the block copolymer toughening agent, in combination with high extender conFigure 6 | Effect of test temperature on the impact performance of toughened powder-coated panels with 10% FVC.

tent and at an optimum DICY stoichiometric ratio, can significantly improve the impact resistance of the FBE coating (Figure 7). For comparison, the control system with high extender content and no toughening agent was highly brittle and would not be suitable for uses in pipeline corrosion protection. Other tests like gel time, cathodic disbondment and hot wet adhesion described in the CSA-Z245.20 standard were conducted and no detrimental effect of the toughening agent on these properties was detected.

Conclusions
This work clearly demonstrates the ability of the novel block copolymer toughening technology to dramatically enhance the flexibility and impact resistance of FBE coatings without compromising other key properties such as Tg, flowability and corrosion protection. In doing so, this novel technology has broken the conventional Viscosity-Tg-Toughness paradigm, in which toughenability often comes at a large penalty to viscosity and Tg of the cured product. n

References
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Figure 7 | Effect of test temperature on the impact performance of toughened powder-coated panels with 30% FVC.

Figure 8 | Effect of DoE variables on FBE coating impact resistance. Prediction Profiler Impact Diameter (mm) 4.457692 0.310836 7 6 5 4
3 4 5 6 7 10 15 20 25 30 45 50 55 60 65 70 75

5 Toughening Agent (wt %)

20 FVC (%)

60 DICY SR (%)

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