° Fabricating Tips DERAKANE epoxy vinyl ester resinsContents Foreword 1 Section 1 — Selecting reinforcements, catalysts, and cure-conurol additives 2 reinforcement types 2 ‘evaluating glass 3 lass storage 4 catalysts 4 non-foaming MEKP substitutes 5 promoters, accelerators, gel time retardant 56 acetone replacements . oa trade names and material suppliers . 8-9 Section 2— Other additives 10 surfactants, antifoam agents 10 thixotropic additives 10 ‘mold release agents u ‘LY protection materials 12 wax top coats 3 styrene suppressanvisecondary adhesion promoter 13 Section 3— Food contact, ‘ 44 resins able to comply . 14 fabricating for FDA/USDA compliance 14 Section 4 — Formulating guide 15 preparing a masterbatch of resin 15 conversion factors 15 ‘measuring small quantities of chemicals 15 Section 5 — Typical gel time formulations 16-25 Section 6 — Working life of resins 26 factors affecting working life 26 effect of antimony compounds 26 Section 7 Troubleshooting guide a gels too slow a resin does not get hard after gelling 27 gels too fast 27 resin gel time drifts 28 ‘too much exotherm 28 Ts rl von of Faby Ts tas an and wine rew erator hse wt he veaton ef AP nn The sew see sips FORUSDR ‘capes, ana tealestooig oui. ay coins eps somaton ang ‘sve ocetn, oman a plestn of Dao abe st Meaton fe Indi rd soap cess Fabs Ties. poies pac igeaton Yip aban chase the most fst ash sem an etree crise fr many Papen Section 8 — Making a laminate and applying ERP linings making a test laminate ‘guide to making a laminate postcuring secondary bonding applying a test batch making a laminate lining lining metal lining FRP lining concrete epoxy Vingl ester resin anchors for concrete Section 9 — Inspecting a laminate checking for complete cure recognizing FRP defects Section 10 — Other processing techniques spray-up applications filament winding pulsrusion, resin transfer molding Section 11 — Industrial health information MSD sheets ‘base resins and styrene dilutions physical properties fire and explosion hazard data in case of fire reactivity data firstaid . personnel protection spills ‘environmental and disposal information health and hazard data Resin storage storage temperature resin shel ife inventory rotation aerating the resin bulkstorage. storage of promoted resin product stewardship Subject Index Section 12@ DERAKANE epoxy vinyl ester resins— © fabricating tips FOREWORD ‘Welcome to the newest edition of Fabricating Tips. In addition to updating the previous bulletin, we have expanded the Contents table, the Subject Index and several sections with more information: * fabricating an abrasion resistant lining, + fabticating a conductive lining, + new entifoam and thixotropic. agents, ‘+ improved secondary adhesion, + the use ofa styrene suppressant/secondary adhesion promoter instead of a wax coat, + anew non-foaming MEKP substicute, + acetone replacement solvents, + another accelerator for BPO catalyzations Excellent chemical and corrosion resistance coupled with outstanding heat performance and toughness have made DeraKani* epoxy vinyl ester resins materials of choice for a wide range of FRP Fiberglass-Reinforced Plastics) applications. All convention- al fabricating technigues are used with DERAKANE resins to produce FRP structures having an advanta- ‘g:0us combination of strength, toughness, and corrosion resistance DERAKANE vinyl ester resins provide finished structures that require ltdle ‘maintenance over a long service life. TolemakofThe Dow Ceicl Conpany ‘This bulletin is intended to provide practical information that will help fabricators choose the most effective combination of DERAKANE epoxy vinyl ester resin and reinforce ment for many end-use applications. However, because the FRP industry has such a wide range of needs, our comments and suggestions are general Fabricators should deter- mine suitability as to any product, additive, process, formula, ratio, or end-use through their own expertise or tests, and no warran- ty; express or implied, is made ‘with respect to the fabricating tips contained in this bulletin. Ifyou need further information, please phone 1-800-441-4DOW If you ‘would like in-plant technical assistance, just ask your Dow sales representative. Note: Potential hazards exist in the handling, storage, and use of DERAKANE resins and the various materials used in preparing resin formulations. Before working with, ‘any material, be sure to ask the supplicr for appropriate safety and storage recommendations and observe all precautions and safe handling recommendations General ‘guidelines on the safe handling and storage of DERAKANE resins are offered in Sections 7 and 8 of this bulletin, and Material Safety Data Sheets will be provided by your ‘Dow sales representative, or may be ‘obtained by phoning 1-800-441- 4DOW Information on the safe use of these products is also found in Denaxane Resins Industrial Health, Form Number 125-00098. All this, information is based on extensive experience and is offered in good faith, but The Dow Chemical Company cannot accept responsibil- ity fot processes or actions not under its direct control, Itis the fabricator’s responsiblity to use safe operating and disposal practices that are in compliance with all applicable laws and governmental regulationsSection 1—Selecting reinforcements, catalysts, and cure-control additives’ DERAKANE epoxy vinyl ester resins have proven to be the FRP industry's best choice for quality and reliability in the fabrication of corrosion-tesistant structures and equipment. However, for consis- tently high-quality end products, the other materials used in fabrica~ tion must be selected with care, precisely formulated, and used by well-trained workers who are familiar with the special techniques of FRP. “This section is a basic guide to the selection of reinforcements, catalysts, promoters, accelerators, and gel-time retarders NOTE: The names and telephone numbers of national suppliers of prod uct types discussed below» are provided a the end of this section. (Page 8) TYPES OF REINFORCEMENT MOST FREQUENTLY USED IN FRP CONSTRUCTION! Seven types of reinforcement are frequentiy used with DERAKANE resins: surfacing veil, chopped strand, chopped strand mat, woven roving, biaxial mat, continuous strand, and unidirectional mat + Tre connin dp suis, Bano SERRE SE SESE atl oe ey ane, proces el, moor care Sens Se te Fabrication of an FRP laminate ‘usually begins with the interior layers (the surface to be in contact with corrosive materials). The first laminate layers are commonly known as the corrosion liner. The corrosion liner’s main function is to provide corrosion protection. A surfacing veil saturated with catalyzed resin forms the base for successive layers. The corrosion liner generally consists of the surfacing veil and two layers of chopped strand mat, which are also saturated with catalyzed resin ‘The chemical resistance of a fber- glass composite is provided by the resin; surfacing veils are used to help control the thickness of the resin-tich layer and give strength to the most critical part of the corrosion barziez ‘The interior surface, which is normally 10 to 20 mils thick, contains about 90% resin and 10% veil material ‘Nexus* Veil (Dacron' homopolyme:) ‘Monofilament glass or polyester fibers ere commonly used as surf ‘ng veil materials. Several surfacing veil types are available The ones most frequently used are made from “C” glass or from Dacront 106 homopolymer. Veil materials made from “A” glass and other polyester fibers are less commonly used, Dut are gaining acceptance in the industry. @ "tran of Dupont de Nemours & CoChopped Strand Mat ‘Chopped strand mat reinforcement consists of a felted matrix of chopped strand “E” or “ECR” glass fibers, 0.5” to 2 0” long and loosely held together by a styrene~ soluble resin binder. “ECR” mat is made with more corrosion resistant “E” type glass fibers. ‘When these mats have been wetted with resin, they are easily shaped ‘Two mats are generally used with the surfacing veil to form the carro- sion liner, providing about 80 mils of additional corrosion protection: Chopped strand mats are also used in the structural layer between layers ‘of woven roving or as the sole rein- forcement for the structural wall ‘The chopped mat layers in the fin- ished laminate consist of about 70% resin and 30% glass The short fiber bundles and high resin content help to produce laminates with good strength and excellent chemical resistance. CertainTeed® M113 and OCF* 723 and PPG* MPM HTX mats have given consistently good results ‘with DERAKANE resins Other chopped strand mats may work as well, but should be thorough- ly evaluated for laminate quatity Woven roving is a coarse, heavy fabric made of Jong, continuous lass fiber strands. It is commonly used in alternate layers with chopped strand mats in the struc- tural layer of laminates, and forms the primary structure of many large hand-layup vessels. In hand layup, the resulting laminates are general- Iy about 40-50% glass. In hand layup with DERAKANE resins, Certain'Teed* 324 roving has given the most consistent results. Other rovings may work as well, but should be thoroughly evaluated for Jaminate quality. Continuous Roving Continuous strand roving comes in vatious densities and sizing finishes for applications in filament winding and pultrusion. Gun roving is used as a substitute for chopped strand ‘at in the corrosion barrier and the structural wall. The resulting laminates are generally about 30-40% glass. CertainTeed? 258, Certain Teed*292, OCF*357, OCF*881, and Hybon® 600 gun rovings have given consistently ‘good results with DERAKANE resins. EVALUATING GLASS FOR USE IN FRP ‘When glass shipments are received, they should be checked ot audited by a designated “key” operator, who makes and evaluates a five- ot six-ply laminate. The resin should wet the glass rapidly The cured laminate should have few jack- straws or glintsSTORAGE OF GLASS FIBERS Glass fiber products should be stored carefully so that they will remain clean and will not absorb water, Glass that is dirty or has absorbed water should not be used, because the presence of dirt or moisture could inhibic resin/fiber- lass compatibility, resulting in poor laminate quality CATALYSIS (INITIATORS), PROMOTERS, ACCELERATORS, RETARDERS Catalysts are materials which initiate the chemical reaction that causes the resin to cure. Promoters and accelerators are used to speed up and enhance the cure. Retarders are used to extend gel time ‘Two types of catalysts are used ‘with DERAKANE resins: one which requires cobalt naphthenate and one which does not, Methyl ethyl Ketone petoxide (MEKP) and cumene hydroperoxide (CHP) are normally used with promoters, typically cobalt naphthenate (CoNap), and accelerators, typically dimethylaniline (DMA). CHP promoted with CoNap, can be used with rapid- cre resins (specifically DERAKANE 470-36) to reduce the exotherm heat buildup) Benzoyl peroxide (BPO) requires only DMA and is used in the production of FRP where heavy metals must be avoided A broad range of working times can be achieved by varying the amounts of catalysts, promoters, and accelerators within recommended Timits. To assure complete resin cure, it is esential to use the recommended amounts of these components. USING ‘TOO LITTLE COULD RESULT IN INCOMPLETE RESIN CURE —USINGTOO MUCH COULD RESULT IN REDUCED LAMINATE PROPERTIES Smaller amounts of catalysts and accelerators are required for curing DERAKANE resins than for curing polyesters because of the efficient ‘molecular structure of DERAKANE sesins Typical amounts of the most ‘common catalysts, accelerators and ‘promoters used with DERAKANE resins are listed in Tables 7-10. As already stated, its essential to use the correct ratios of the activa~ tors. Also, thorough mixing is neces- sary for optimum results, and itis important to mix the activators into the resin in the proper sequence. NOTE: The promoter should never be rixed directly with a peroride catalyst (such as MEKP). Mising eoould cause 4 violent reaction and a fire or explosion could result. For example, standard procedure is to mix CoNap and DMA thor- ‘oughly into the resin before MEKP isadded, CATALYSTS ‘MEKP — Methyl Ethyl Ketone Peroxide MEKP js sold as a 9% active~ ‘oxygen solution of MEKP and a plasticizer. Different brands behave very differently when used with, DERAKANE resins. This varying reactivity results from subtle differ- ences in the monomer and dimer content of the various peroxides ‘The following brands have shown consistent reactivity and have pro~ vided rapid resin cure development when used with DERaxANE resins: Hi Point® 90 Lupersol* DHD 9 Notac® MEKP 925 1 Other brands may work as well, bbut should be thoroughly evaluated before actual use MERP should be stored in a well- sealed container to prevent water contamination. Water in the catalyst will adversely affect resin cure MEP can be checked for excessive ‘water content by mixing small amounts with equal parts of styrene. A haze in the mixture indicates excessive water For optimum results, it s impor- tant to maintain the recommended ratio of MEKP to CoNep in the cure system. A minimum ratio of 3:1 (MEKP: CoNap) is required. A ‘maximum ratio of 10:1 has also proven satisfactory. NOTE. A minimum of 0.2% CoNap (6% cobalt) is suggested for all the DERAKANE resins, except 470. (See Tables 7-11.) Using proportions outside of a 3:1 to 10:1 range may produce a poorly cured Jaminate with low Barcol hardness and inadequate corrosion protection. ‘The ratios can be made less critical by use of dimethylaniline or dimethy- ecetoacetamide as an acceleratorBPO — Benzoyl Peroxide ‘The catalyst BPO is available in powder, emulsion, and paste forms for curing all DERAXANE resins. ‘The pastes and emulsions are easi- ce to use than the powders, Cadox 408 has proven satisfactory in our laboratory evaluations. Other brands of BPO are also available ‘The specific brand listed above contains 40% active BPO. Formu- Iation work has been done with 98% active BPO; thus, 2-1/2 times as much of a 40% paste would be required to achieve similar results. ‘Typical amounts of BPO used with DeRAKANE resins sre found in ‘Tables 7-11 BPO solutions tend to settie on standing and should be thoroughly mixed immediately before use to ensure uniformity For room temperature applica- tions, BPO is accelerated with, dimethylenitine. Standard procedure is to mix the dimethylaniline thoroughly into the resin before adding the BPO solution. Since BPO powders and pastes tend to settle to the bottom of resin solutions, ensure that the stirrer used evenly disperses BPO throughout the resin. For ‘optimum tesults, the ratio should be from 10 to 15 parts active BPO to 1 art dimethylaniline. Ratios outside that range may cause resin not to gel ‘The resin may gel and not cure, or 2 high degree of resin cure may never develop, even with post-curing, Diethylaniline can be used instead of dimethylanitine to extend resins? ee] times, Optimum ratios are from 4 to 12 parts active BPO to 1 part dicthylaniline CHP —Cumene Hydroperoxide ‘The use of CHP with DERaKANE 470-36 resin results in lower exotherms, less shrinkage, and less warpage In cool weather, in fact, small amount of dimethylaniline may be used to accelerate cure CHP is 80% active peroxide and 20% cumene, and material of this ratio has been used in formulation work, ‘Mixing procedures are similar to those used with systems of MEKP and CoNap. The following brands of CHP have shown consistent reactivity when used to catalyze DERAKANE 470 xesin: Lucidol® and Superox® 727. Other brands may work as well, ‘but should be thoroughly evaluated before use NONEOAMING MEKP SUBSTITUTES Trigonox 239A (239A) and CHP-5 are available for use with DERAKANE epoxy vinyl ester resins ‘These systems can eliminate the foaming experienced with epoxy vinyl ester resins catalyzed with’ MEKP/cobalt naphthenate cat- alyzed systems. Another advantage of 239A and CHP-5 is that, when used to catalyze DERAKANE 41 1- type resins, peak exotherms are lowered 40° to 50°F (based on 50 g. mass), as compared to equivalent ‘MEKP/cobalt naphthenate catalyst systems, NOTE. The peak exocherms for Dzxaxane 470 and other resins are Toewered by only about 20°R ‘Trigonox 239A and CHP-5 pro- vide as complete and as rapid a cure as MEKP with DERAKANE resins at ambient temperatures and function with normal accelerator! promoter systems. The typical gel time formu- lations for 239A and CHP-5 are similar to those shown for MEKP with the different DeRaxaNE resins and should be used as guidetines for formulation development When 239A or CHP-5 are used, the addi- tion of 0.1 wt CoNap (6% cobalt) above the CoNap levels recommend- ed in the formulation tables should provide gel times comparable to those fot MEKP. PROMOTER ‘CoNap — Cobalt Naphthenate CoNap promoter is a dark, pur- plish liquid sold in solutions of 6%, 12%, and 21% active cobalt in a solvent. ‘The 6% solution has been used in formulation work with DERAxANE cpoxy vinyl ester resins Different ‘brands have shown litle difference in reactivity with DERAKANE resins Acc sTORS NIN-Dimethylaniline OMA), ‘NIN-Diethylaniline (DEA) and N:N-Dimethylacetoncetamide (DMAA) N.N-Dimetiylaniline and N.N- Diethylaniline are amines used in small quantities to accelerate ‘MEKP, BPO, and CHP type cures. NN-Dimethylacetoacetamide is also an amine which can be used to accelerate MEKP, CHP, 239A, and CHP-5 cures. Formulation work has been done with 100% active DMA and DEA, and 80% active DMAAGELTIME RETARDER 2,4-Pentanedione ‘(Acetylacetone) ‘The retarder 2,4-Pentanedione (2,4-P) can be incorporated into systems of MEKP, CHP, 239A, ot CHP-5 and CoNap at a level of 0.05 to 0.30 to retard the gelling of DDERAKANE resins. The gel time can be extended as much as tenfold without adverse effects on the final cure or the corrosion resistance of the laminate This material can be formulated into high-build coat- ings to give an extended pot life or can be used for fabrication when very long gel times are required. ‘Table | and Table 2 show how gel time can be extended by adding 2B Similar effects are observed with all DERAKANE resins, Table 1 shows that the amount of time is very dependent on temperature and the levels of peroxide/promoter used Caution: Gel time will not be delayed by addition of 2,4-P when a vinyl ester cure is catalyzed with BPO using DMA as an accelerator Also, in many polyester systems, 2,4-Pentanedione may act as an accelerator “Type eters ware rps ypc eat errr) wn) 2 2B 0 @ 2 6 % 2 1m 25 8 Brrr inc) 2 6 8 im 2 ‘TABLE t ‘Delayed Gel Times for DERAKANE 411-45 Resin* Mee Clap Du 24 wr wr We WM 400 0% 000 000 10) 025 600 005 100 02 00 010 400 035 00 020 10 0% 00 0% 100 20 oro co 100 om oto 008 100 om O10 O10 100 02 O10 02 100 oz oo 030 200 om o10 ow 200 oz o%0 010 100 om oto 00 100 om oro 010 400 om 020 ow 190 02 oz 010 i Delayed Gel Times for Dzraxane 470-36 Resin* cH cota MA BAP wr wm we wT 150 on o10 000 10 020 ow 00s 19 on 010 010 150 020 010 05 200 oa 010 co 20 020 010 on 10 0 02 oo 19 020 020 010 19 om 010 ooo 19 cr) O10 010 ae aR TYP PEAK TNE ounres) a 3 74 19 20 » 8 118 a si7 ‘TPIGAL PEK TRE outs) 40 3 0 a “4 ww 2 w a oACETONE REPLACEMENT SOLVENTS Acetone replacement solvent prod- ucts have been made available through various manufacturers to help fabricators meet government regulations that have set limits on the yearly maximum allowable VOC's. Since these acetone replacement solvents ate relatively non-volatile, every effort should be made to prevent contamination of resin laminates with more than I wt% of an acetone replacement ‘During fabrication, working tools cleaned in an acetone replacement solvent should be as dry as possible before coming in contact with a resin laminate. DERAKANE resins containing less than 1 wt% of an acetone replacement solvent should contimue to provide satisfactory corrosion resistance and structural strength. Listed below are some of the acetone replacement solvents on the market today that are known to have been used and/or tested with DERAKANE resins successfully, Diacetone Alcohol (DAA) Dibasic Ester (DBE)’ ‘Ship Shape (SS)* Re-entry FGL Solvent-2000° Replacetone* (This is a water based system and extra care must be taken to prevent resin laminate contamination.) BBA Solvent® F302 “DaPone “GAP Cheol Copeition “Enron Siva Conprton SQuatTess Emery, oe Bunk Boake lee SAFETY NOTE ‘The Dow Chemical Company does not manufacture or market the catalysts, promoters, accelera- tors, and retarders used with ‘Deraxane resins. Technical data and safe handling and storage information should be obtained from the manufacturers of MEKP, BPO, CHP, 239A, CHP-5, CoNap, DMA, DEA, DMAA, and 24-P. ‘The catalyst MEKP is especially dangerous to the eyes. Workers should wear goggles at all times when handling, measuring, and mixing the catalyst. MEKP is a contact poison, and may cause skin burns. Proper protective clothing should be used 10 ‘minimize contact, To avoid a violent reaction, promoters should never be ‘mixed directly with a peroxide such, as MEKP. ‘The accelerator DMA is also a contact poison ‘To prevent absorp tion through the skin, workers should, ‘wear protective clothing as well as eve protection when handling, ‘measuring, ot mixing this material‘TRADE NAMES AND MATERIAL SUPPLIERS, Trade Name Tyre ‘Manufacturer Phone No, SURFACING VEILS Nexus* Polyester PEG (919) 279-8063 ABFAB® Polyester ABCO Industries, Ine. (803) 576-6821 Avelle 1213AP Polyester Sterling Paper Corp. (203) 888-7200 Reemay 2410 Polyester Sterling Paper Corp, (203) 888-7200 Regina® F2/30 C Glass Regina Fiberglass Led (O11) 44-276-874461 Surmat* 100-SE “AP Glass Nico-Fibers, Ine (614) 394-2491 Superior Glass type SSM “A” Glass Superior Glass Fibers (614) 569-4175 Freudenberg T-1777 “C” Glass Freudenberg (508) 454-0461 x 240 MATS MU3 “B” Glass Certain Teed Corporation (817) 691-0020 OCE* 123 “EY Glass (Owens-Corning Fiberglas (419) 248-8000 OCF’ M723 “ECR” Glass Owens-Comning Fiberglas (419) 248-8000 ‘MPM 2000 “E” Glass PPG Industries (800) 245-1542 WOVEN ROVING 324 CertainTeed Corporation (S17) 691-0020 HYBON? Woven Roving HTX PPG Industries (800) 245-1542 302 Baymills Inc (705) 526-7867 CONTINUOUS ROVING HYBON? 2001 PPG Industries (800) 245-1542 ‘Type 30 P366C X6 ‘Straight Shot RO99*/660 & 67B GUN ROVING (Owens-Corning Fiberglas Certain‘Teed Corporation (419) 248-8000 (B17) 691-0020 HYBON? 700 HTX PPG Industries (800) 245-1542 OGF 357 & 881 Owens-Corning Fiberglas (419) 248-8000 Certain Teed* 255 & 292 CertainTeed Corporation (B17) 691-0020 ‘CATALYSTS HiPoint® 90 ‘MEKP ‘Witco Chemical Company (003) 938-5141 Lupersol® DHD 9 MEKP ATOCHEM Notth Amecica (800) 558-5575 ‘Norac® MEKP 9251 MEKP “The Norac Company (818) 334-2908 Cadox® 40E BPO ‘Akzo Chemicals Ine (800) 666-1200 Cadox® 40ES BPO ‘Akzo Chemicals Inc (800) 666-1200 Cadox* BTW 50 BPO ‘Akzo Chemicals Inc. (800) 666-1200 Cadox® BIW 55 BRO Alvo Chemicals Ine. (800) 666-1200 Luperco® AFR 400 BPO ATOCHEM North Ametica (800) 558-5575 Benox® L40LV BPO Norac Company (818) 334-2908 Lucidot* cHP ATOCHEM North America (800) 558-5575 Superox* CHP Reichhold Chemical Co” (019) 990-7500D> ‘Trade Name ‘Type Manufacturer Phone No CATALYSTS — NON-FOAMING MEKP SUBSTITUTES ‘Trigonox* 239A Akzo Chemicals Inc (800) 666-1200 CHP-5 Witco Chemical Company (903) 938-5141 PROMOTERS 6% Cobalt Naphthenate Hiuls America (908) 981-5000 ‘Mooney Chemical (800) 321-9696 6% Cobalt Octoate Hiuls America (908) 981-5000 ‘Mooney Chemical (800) 321-9696 ACCELERATORS N, N-Dimethylaniline DMA E.1 DuPont de Nemours (800) 441-9442 Aldrich Chemical Co, (800) 558-9160 Buffalo Color Corporation (800) 631-0171 Fisher Scientific (800) 766-7000 Pfalz Bauer (800) 225-5172 N-Dimethylaceto- acetamide DMAA Fisher Scientific (800) 766-7000 N,N-Diethylaniline DEA Aldrich Chemical Co (800) 558-9160 Fisher Scientific (800) 766-7000 Paltz Bauer (800) 225-5172 GELTIME RETARDER 2, 4-Pentanedione 24 Union Carbide (800) 336-7384 Aldrich Chemical Co. (800) 558-9160 Fisher Scientific (800) 766-7000 Pfaltz Bauer (800) 225-5172 ‘ACETONE REPLACEMENTS Diacetone Aleohol No water ‘Hoechst Celanese Chemical Group (800) 235-2637 ‘Shell Chemical Company (800) 872-7435 Union Carbide Corporation (203) 794-2000 Dibasic Ester No water EI DuPont de Nemours (800) 231-0998 Ship Shape No water GAF Corporation (800) 438-1859 Re-Entry FGI, Solvent 2000 No water Envirosolv (904) 724-1990 Replacetone Water base Qual Tech Enterprises, Ine (415) 467-7887 BBA Solvent F302 No water Bush Boake Allen (904) 783-2180Section 2—Other additives" SURFACTANTS AND ANTIFOAM AGENTS: Air bubbles in a laminate reduce its strength and may seriously affect its corrosion resistance properties Air bubbles in the corrosion liner! can be more damaging than those in the structural layer, The follow- ing practices should always be followed to minimize air bubbles: 1. Avoid violent mixing, which mixes air into resin, However, ‘be sure the catalyst is mixed thoroughly into the resin. 2. Apply resin to the mandrels {fist—then apply glass and roll it {nto the resin. Air bubble prot lems are inevitable when resin is applied to “dry” glass 3. Roll the laminate from the center to the edges. Roll firmly, but not too hard. Excessive pressure might fracture existing bubbles and make them more difficult to remove 4. Eliminate all the bubbles from one ply before starting on the next 5. Thoroughly clean rollers Detween uses. "Como nee Vel- Mat Mat = 100 mie ASEM, ‘Sesurd Carroson Testing Coupon per ASTM C (3121-5129) VebMar Mace This batt contains Sp and mgzetions but 90 ‘Rhtny-stpcs opis pen ee Ernie doce nay ate sy pee ‘Stag tel Som expertise oe tess i 10 ‘The addition of certain surfactants and antifoam agents can improve the glass wet-out and air bubble release of DERAKANE resins, One of the most effective surfactants evaluated is BYK? A515, When added toa DERAKANE resin at a level of 0.1%, this product significantly reduces the resins’ surface tension, thus ‘improving glass wet-out and air ‘bubble roll-out. BYK’ A510 and A555 antifoam agents ata level of 0.1% cause entrapped air bubbles to readily ‘burst by themselves These antifoar agents and surfactant at 0.1% do not reduce the corrosion resistance of properly cured laminates. Another widely used antifoarn agent is SAG 47° silicone-based antifoam compound. The suggested ‘maximum amount of SAG 47 for DERAKANE resins is 0.05 wt% NOTE: BYK A515, AS10,A555, and ‘SAG 47 are not on the lit of additives complying with FDA requivements for ERP applications. ‘The compatdility between DERAKANE resins and glass fibers can be improved by adding 2.4- Pentanedione to the resin at levels up 10 0.05% At such low levels, 2,4-P is unlikely to significantly affect the gel time of resin systems with a mini- mum of 0.3% CoNap (6% cobalt) SYK Chemie USA, (205) 265.2086 "Don Cate Chee & Paes Company, (goo) 333-5862 ‘THIXOTROPIC ADDITIVES In fabricating certain structures with DERAKANE resins, it may be desizable to control resin flow ot runoff by adding a thixotropic material—usually a thickener-filler ‘The most efficient and effective of these additives for use with DERAKANF resins are Cab-O-Sitt- TS-720 and Aerosil* 202. (See Table 3.) In structural applications, the level of thixotropic additives should bbe as low as possible to maximize the strength of the laminate. Also, because thixotropic additives reduce corrosion resistance to some chemi- cals, they should never be used in corrosion-resistant liners, When thixoropic materials are used, ‘uniform wetting is necessary for optimum results, and high speed, high sheer mixer, such as a Cowles Dissolver’ ot its equivalent, should bbe used for blending FRP fabricators should contact additive manufacturers for recom- mendations on safe handling and storage of thixotropic additives scaber Carperaon, (800) 51-3676 “Digens Coen, (201) 64-6100 Cores Dron Motchooe Insc ee, ‘gin 135000‘TABLE 3 Effect of Cab-O-Sil TS-720 Thixouropic Additive (Comparable Results Are Obtained With Aerosil 202.)* Peneexr aopuct DOTTVE SRP Dene 41145 0 580 1 200 2 5800 3 t200 Dewan 41-250 a 180 1 70 2 200 3 00 Devan 470-38 0 10 1 co 2 50 3 ‘e000 Dewan 7045 a % 1 Co 2 500 3 700 Dawe 5104 ° 20 1 ean 2 11500 3 800 anne S100 80 ° a0 1 180 2 ‘noo 3 28500 Dew 8 ° oo 1 120 2 so a 13200 “yes be crac ware eats sone 80 100 2x20 7e0 10 70 510 0 20 390 0 400 a 280 760 1640 en 150 500 70 0 1750 m0 5500 0 00 970 810 TexoTROPIC ices 08s in 2a 208 oss 208 a7 688 oa 373 an 088 285 363 435 093 258 32 os 231 328 46 ow 178 278 355 MOLD RELEASE AGENTS ‘Wax, or films of PVA, Mylar’, or cellophane may be used as mold release agents to facilitate the removal of fabricated parts from metal, wooden, cardboard, or plastic molds and mandrels. It is impottant to check the release characteristics of any mold release agent before using it in production Wax Hard-based paraffin waxes and carnauba waxes are used success- fully as mold release agents in part fabrication with DeRaKANE resins Several brands provide excellent results, including: ‘Meguiars! Mirror Glaze ‘Trewax’ Johnsons* Traffic Wax TR’ Mold Release ‘These products are generally avail- able from local fiberglass supply distributors ‘Waxes based on acrylics have not been accepted for use as mold release agents because they tend to inhibit ‘The use of some silicone-based ‘mold release agents has been shown to inhibit iaminate cures of DERAKANE resin, Optimum results are obtained by applying the wax to the mold or mandrel with a clean cloth, then ‘buffing the surface vigorously to a hard, glossy, ultrathin film. Several ‘coats of wax should be applied before ‘a mold is used, then a single coating of wax after each release ‘Excess wax left on the mold sur- face may inhibit resin cure, resulting ina hazy corrosion liner. Even 181 Jono ant Sos Ine VP Indes un‘though the surface beneath the wax ray be fully cured, the hazy surface may give a low Barcol reading (see Section 9, “Inspecting a Laminate”) If this occurs, remove approximately 2 to 3 mils of the wax coating by sanding, then check the surface again using the Barcol hardness check described on page 35. If a high-gloss surface is desired, overcoat the buffed wax surface of the mold with a PVA film Films of PVA Polyvinyl Alcohol) Films of polyvinyl alcohol, when properly applied, can provide excellent mold release for parts made with DERAKANE resins PVA films may be sprayed or painted over waxed ot polished metal molds. After application, the film must be dried thoroughly, because any residual moisture could inhibit the cure of DERAKANE resins cured with MEKP or CHP catalyst systems. Because PVA films are ‘hydrophilic, it may be necessary Gn high humidity atmospheres) to force-dry them with heat lamps, Films of Mylar® and Cellophane ‘Tapes of Mylar and cellophane 1-6" wide and 1-2 mils thick have bbeen used successfully over mandrels as a mold release, Films of Mylar 5-10 mils thick have excellent release characteristics and are used on benchtops for the pro- duction of parts and flat sheets 2 TABLE 4 Polyamide Epoxy Paints Typically Used in Topcoating ‘uiuracTURE? NUMBER costing ‘sorae7e8 Cook seotst/ 0-082 Pont 23 S757 VE Pes cso uesseta TABLE 5 Typical Wax Topcoat* FORMULATION Parts tea Paraie Syrene ccouoR ‘ETL THORNE ery mis Msi Gry mis Met Gry ‘omis ise Gry emis GALLONS, 16a 205 88) seo (180) 7209 (00) 144 9(160e0) ‘Syren edo 0° (6) abe meas tin wh ong ofa sO ean anaer ‘ih vgrusgtaen oem astsparsen. Bae nrg wit he maa, ort sal bse 0 er stand te posible nazar associated wit handing styrene, and to take appropiate precautions before working? ‘wen taal Puta Dene Resin Gallons 16ion ‘Asi Parthto Prt wit onus aaon ac catahee wth apropictat, prac, ané costo for 5 1020+ pa te, -sttrg ptt rman a nate pl stray 20°F) nea rear ULTRAVIOLET PROTECTION ERP parts fabricated with either polyester or vinyl ester resins may display surface chalking and discol- oration after long exposure to ultraviolet radiation These effects may be reduced or eliminated by: * incorporating UV absorbers into the resins + pigmenting outer resin layers; ‘+ painting the surface with epoxy- polyamide paints; incorporating fillers. UV absorbers do not always pro- vide effective protection for long- term service and they also inhibit resin cure. ‘Two that can be used without inhibiting the resin are ‘Cyasorb! UV-24 Timuvin' 326 ‘These products are incorporated into the external coat ata level of 01-03%. + ramen Cyanami 0 652-6013 + Gl Chea O10) 37-860“Manufacturers who wish to for- ‘ulate a pigmented gel coat should contact a pigment manufacturer A REMINDER: Many inspectors requite that the equipment be inspected visually before pigmented topcoats are applied. Don’t paint or pigment unless the specifier has requested it ‘equipment is finished several days or weeks before the inspection, arinding the exterior before topcoat ing can be avoided by using a polyamide epoxy coating The only surface preparation required is the removal of dirt, dust, oil, grease, and wax with a degreaser-type solvent and clean rags. ‘The polyamide epoxy paint is mixed and applied according to the ‘manufacturer's instructions, making sure that the air and surface temper atures ate above 50°F (10°C) throughout application and cure. The coating should not be applied when ‘the weather is humid or when rain is expected ‘The polyamide epoxy paints listed in‘Table 4 have been used successful- ly on equipment fabricated with ‘DaraxaNé resins For non-pigmented equipment, a surfacing veil made with polyester ‘bers has been shown to prevent ber bloom Nexus vel, ype 100-10, has provided consistent results, AIR INHIBITION AND WAX TOPCOATS (Oxygen in the air may inhibit the complete cure of an exposed FRP surface. If surface inhibition occurs, it may result in reduced chemical resistance, and/or prema- tute faiture, Several techniques are ‘used to overcome this problem, alll of which involve preventing or reducing air contact at the curing surface ‘A waxitesin topcoat acts as a film to protect the surface from air con- tact, A layer (2-3 mils) of resin con- taining a small amount (0.4%) of pataffin wax with a melting point of 120°F (49°C) is applied. During polymerization, the wax rises to the surface and forms a thin wax film. ‘Wax topcoats should be used as. the final coating of all secondary Jayups, and on all repairs of arcas exposed t0 a corrosive environment Caution Wee: ropeoats should not be used beteeen laminate layers because they may interfere soit adhesion of one layer to the next ‘The small amount of parafiin is readily incorporated into the system by preparing 2 masterbatch of 10% wax in hot (140°F) styrene (refer to ‘Table 5), Wax-styrene mixtures can also be purchased ftom FRP distrib- tutors. Add sufficient wax-styrene mixture to the resin to provide a wax topcoat system containing about 0.4% paraffin (between 3-5% of wwax-styrene mixture) The resin should then be catalyzed to give a 5- to 20-minute working life, as needed A fast gelling system is suggested ‘A styrene suppressant/secondary adhesion promoter (SS/SAP) may be used in place of a wax topcoat. A styrene suppressant is added to the entire amount of resin used in a Jaminate. This alleviates the need for wax topcoat application A secondary laminate containing an SS/SAP applied 20 to 24 hours after the lay-up ofa primary laminate having the SS/SAP can achieve satis- factory adhesion with DERAKANE epoxy vinyl ester resin types 411, 441-400, 510A and 5100-350 XUS-71998.00, a developmental epoxy vinyl ester resin additive (SSISAP), has provided satisfactory adhesion and wax topcoats. Fabricators should determine if their shop's secondary lay-up techniques provide satisfactory adhesion when an SS/SAP is used. Since DERAKANE 470 type epoxy vinyl ester resins produce such hot exotherms when curing, a wax top- ‘coat may not be necessary to prevent air inhibition of resin cure,’To deter~ mine if the laminate is sufficiently cuted at the surface an “acetone wipe test” should be performed. Ifthe cured resin surface passes the “acc- tone wipe test,” a wax topcoat is not necessary NOTE: The uses cited above are sub- ject to good manufacturing practices ‘and any limitations that may be ‘imposed by governmental regulations All applicable regutations should be ‘consulted for complete details. 13Section 3—Food Contact and FDA/USDA Compliance” FOOD CONTACT DERaKANE 411, 411C and 441- 400 epoxy vinyl ester resins, when properly formulated and cured, will comply with the US Food, Drug, and Cosmetic Act, 2s amended, and applicable FDA regulations (@1 CFR 17 .2420).These resins may be used as articles or compo- nents of articies intended for repeated use in contact with food, subject to certain limitations described in that regulation NOTE: Its the responsibility of the customeriuser to vest the finished lami- ‘nate or coating to determine compli- ‘ance with 21 CFR 177.2420 and all other appropriate regulations DeRaKANe 411, 4116, and 441-400 epoxy vinyl ester resins are chemically acceptable in processing fr storage areas for contact with ‘meat or poultry food products pre~ pared under federal inspection and used at temperatures below 250°F (021°C). This acceptance has been aiven by the United States Depart- ment of Agriculture Catalyst levels should not exceed levels set out in the FDA regulations in 21 CFR 177.2420 NOTE: Deraxane 411 resin is available with different styrene levels Achievement of appropriate complete cure (using recommended catalyst leo= lt, etc.) together with careful attention 10 the special five-step post-fabrication techniques listed above wall enhance the fabricators’ abiley to comply with regulations. + ae oi to Soa are ‘through their own expertise of teste “u FABRICATING FOR FDA/USDA COMPLIANCE Attention to the following proce- dure can help you achieve FDA compliance: 1, Use a catalyst for mulation that will yield a resin laminate with Low residual styrene after a room temperature cure. FDA regula- tion 21CFR 17 2420 lists the following approved catalysts, promoters and accelerators: MEKP, CHP, BPO, CoNep, DMA and DEA. 2. Thoroughly clean the part to remove any dust or ditt prior to postcuring, 3. Postcure with dey heat for 2 hours at 200°F (93°C) or 4 hours at 180°F, The purpose is to reduce residual styrene to the range of 0.01-0.2%. 4. After postcuring, steam-treat the part or steep it in hot water for 8-16 hours at 160°F (71°C) ot higher. Iris recommended that only hot water be used in FRP lined metal vessels. This should remove all residual styrene from the laminate surface 5. Wash the part thoroughly with detergent and rinse it thoroughly before placing it in service. fSection 4—Formulating guide’ PREPARING A MASTER- BATCH OF RESIN A successful technique for obtain- ing consistent curing characteris- tics is to prepare a masterbatch containing the resin, CoNap, and dimethylanitine (if required) in a quantity appropriate for your ‘operation, (Masterbatches of 5 to 55 gallons are common ) The masterbatch contains promoters and accelerators. It does not contain ‘catalysts: A properly prepared ‘masterbatch will have a shelf life of several weeks ‘Masterbatches should be carefully prepared by a designated, reliable technician, and should be checked frequently for curing characteristics and uniformity The masterbatch approach assures that the proper ratio of promoters and accelerators will be used each time. Master- batches also give operators latitude in determining the amount of cata- lyst needed and the time required for a specific job. Ic helps them compen sate for changes in temperature and other ambient conditions. A masterbatch is prepared by thoroughly mixing CoNap and the See Pris Reseech La Tae (212) 6728300, 46© ©) Die Temperature Settings—In TABLE 18 the production of high-quality : os atts, die temperature settings Gel Times at 20°F ate ctitical. The choice of Dente carauyst aL Twe ea PeCTINE ‘catalyst, catalyst level, reinforce-_PESI Svs aan) TEMPERATURE CC) Fe priate une toa 6 we 9 ect the proper die temper 4145 toni “a 8 38 ature setting, When trying a aes 20118 o a 38 new system for the first time, it a5, ‘on a0 Pr 7 ‘od is best to begin with a relatively 418, 15% BPO, a3 228 100 low die temperature setting and 411-5 20% 8F0 88 a a6 gradually raise the temperature jig ost 32 26 6 to find the optimum operating So 0 conditions. oe . 02535100 9 a 0 For producing thick parts, it aaa : may become necessary to use a radio frequency (RE) preheater, “16 sph ie e bd a ‘The RF preheater is used to hheat the inside of a part before 41148 ss et 7 19 we the part enters the die Sas Preheating increases line speed 41148 oss 56 m 78 and helps prevent internal 15% CHP cracking of the part * Tysons; tobe comsued a wranes er spoctcatons TABLE 19 GelTimes at 150°F* Dene caTAYST aL TINE Peak Peake es SYSTEM ‘aan TEWPERATURE("C) gu) 46 1 6 160 2 165 8 ants 15160 " 1m 4 aris 20% 168 8 178 2 40% 1086 tt © 179 18 41036 15% t6 1 14 8 ie 20% 168 105 a8 2 Typ gl times; not to beans as warts or speictions. 47‘TABLE 20 2) Reinforcements — Many types pa —— of reinforcements may be used Coaepe site ae in the RTM process; the most Dane cars cane Pea reikTive common is continuous strand FISH syste (ui TEMPERATURE) (il) mat, such as OCF M8608" Continuous strand mat is ae fae - i a available in several different weights. Directional stitched — prea 6s 202 us mat is often used to provide at 10% Bro 186 mo a specific mechanical properties 47096 025% 168 16 as 87 in a given direction. vo%cHP Preformable mats are also a Hee ff I a available A thermoplastic eae binder in these mats allows the reinforcement to be heated and __ 05% 160 68 28 8 then formed into the desired 10% oP shape in a separate operation roa 0% 180 6a 2 81 reforms allow the reinforce- 18H ‘ment to fit into the mold quickly. This results in faster cycle times because it eliminates the need for time- consuming placement of the fibers at the production press. 3) Catalyst Formulations Both elevated-temperature and room-temperature catalyst formulations can be used in the RTM process. To be suitable for this process, the catalyst smust be a pumpable liquid, Elevated-temperature catalysts RESINTRANSFER MOLDING _pressiires, and good wet-out of and resins are placed in sepa- : : F the reinforcement. Resins with _rate tanks and mixed before Resin transfer molding (RTM) is a viscosities of less than 250 cps being pumped into a heated process Lesions os s are generally best. The follow- mold. (Table 15 lists 10-hour pumping app: ranster cata- ing DERAKANE epoxy vinyl half-life temperatures of four lyst and zesin from holding tanks ester resins have been used elevated-temperature catalysts through a mixing device into a closed ‘successfully in RTM: ‘that may be useful for RTM.) mold containing reinforcement ‘DERAKANE 411-45 ‘Room-temperature catalyst smatetial DERAKANE 411-350 formulations are similar in 1) Resin — DERAKANE epoxy DprakaNe 411C-50 composition to formulations vinyl ester resins are available ‘Dunaxane 5100-350 used in hand layup except that at appropriate viscosities for Denaxane 470-36 the resin is usually divided into resin transfer molding, RTM Denaxant 470-45 ‘two streams to be mixed in requires a low viscosity resin to DenaKane 8084 equal amounts. Half the resin allow for a rapid filling of the tool (mold), low pumping "ower Coming Ferlat 48,© is mixed with a peroxide catalyst and the other half is mixed with the promoter and accelerator The two streams are pumped through the mixer into either a heated mold or a room-temperature mold Catalyst formulations similar to those used at room temperature can also be used at intermediate temperatures (between 100°F and 180°F) to improve the cycle time. (Table 20 shows reactivity data based on platen gel testing of some of these systems.) These systems can be very useful for obtaining rapid cycle times at relatively low temperatures The catalyst formulation and mold temper- ature must be adjusted to assure a full cure 4) Mold Releases — Internal or external mold releases may be used in RTM. A common tech- nique is to maintain easy part removal by use of an internal mold release and occasionally apply a coat of external mold release as needed, The follow- ing mold releases have worked well with DERAKANE resins: Kantsik! FX9 INT: EQ-6 Zele® UN The use of some silicone- based mold release agents has ‘been shown to inhibit the cure of DERAKANE resins NOTE: Use an external mold release with room temperature casalyst systems. Gel times of 00m temperature catalyst systems Speci Product Co. (201-134-4700) Al Pave Reser Yah, Ie (21672-8300) TET Davoot de Nemours € Coy Ine TABLE 21 Platen Gel Times (Minutes)* ‘Moderate Temperature Catalyst Systems DERAKANE 411C-50 TBIPERATURE*E 109 05 10 175 1%8PO0 1% OMA ne 48 24 1% BPO 1% DMT 5 ar 12 08 2% BPOD TS. OMA 87 2 15 ag 23 800.1% OMT 27 24 7 05 1 S%CHPD2% DNAS CoMap 90 23 13 " 80 — Baan porte oma = Dinetazaine over — Dima okie cP = Camere roperoside Cola prometar — Cob apts “Type gel ees; not ob conse as warts ospedcters care greatly increased by the 6) Tooling — Tools for RTM presence of internal mold releases, may be made from several including those mentioned above. different types of materials, 5) Equipment — RTM equip- which vary greatly in cost and ‘ment includes a metering and durability pumping device for the resin Composite tooling or epoxy formulation. This usually con- ‘tooling is inexpensive and easy sists of twvo positive displace- to obtain. Epoxy tools are an ‘ment piston pumps which excellent choice for making deliver the same ratio of each prototype parts or for low: component for every shot volume production. However, RIM also requires molds they have a limited life and designed to assure complete air may only be heated to moder- release and complete wet-out ate temperatures, of the reinforcement. Aluminum or steel tools A clamping mechanism for should be used for processes holding the mold closed during requiring high pressures, high injection and curing of the temperatures, and high volume resin is also required. Clamping production. Metal tools can can be accomplished by the use be designed for heating with of bag molds, mechanical hot waters, steam, of oil presses, or hydraulic presses, Aluminum tools are less For high production volume expensive than steel tools, applications an automated but are also less durable press may be used to achieve shorter cycle times 49Section 11—Industrial health information MATERIAL SAFETY DATA SHEETS ‘Material Safety Data sheets for DFRAKANE epoxy vinyl ester resins are available from Dow to help users of DERAKANE resins meet their own handling needs and the requirements of OSHA and other governmental agencies. The follow ing comments pertain to all DERAKANE resin products, and are general guidelines for handling these resins safely. The Material Safety Data sheet for the specific ‘DERAKANE product should be consulted for more detailed health hazard and handling information before using the product. NOTE: The information provided in Material Safety Data sheets applies only to DERAKANE resins and not 10 other products used in formulating, including iniiacors, promoters, acceler ‘ators, solvents, and other additives. Specific safety and handling proce- dures for these additives should be requested from the product manufac~ turer. When various materials are used in combination, forraulators should fallow the most sringent safety and handling procedures applicable to the products being used. CAUTION: Do not blend pro- muoters directly with peroxide since rapid decomposition or explosion could occur. 50 BASE RESINS AND ‘STYRENE DILUTIONS DDERAKANE epoxy vinyl ester resins are made from epoxy resin methacrylates, The base resins themselves do not pose any signifi- cant health or handling difficulties ‘These base resins, however, are diluted with styrene monomer. Because of theit styrene monomer content and the recent focus on health issues concerning styrene monomer, it may be advisable to review exposure levels and the rec- ommended procedures for han- dling DERAKANE resins in your facility. Recommended procedures for storing DeRAKANE resins are provided in Section 12 of this bulletin ) PHYSICAL PROPERTIES ‘The notation, “based on styrene,” appears beside several of the physi- cal properties listed in Table 22 ‘This means that the value reported applies to styrene itself, not to the resin, and therefore represents a “worst case” scenario ‘TABLE 22 Liquid Property Data for ‘Typical Epoxy Vinyl Ester Resin* ring pie 2st 460 bast on sen) Yipor Presa Tami o20e (Gast entre) aor ent 36 (ted on tae) Sovilyinvetr nib Speatoarrty 100-122 eae Yotow to anter vies tad ue unger stene aoc * oti b eonstrundas spedeatons ‘The boiling point of styrene is Jower than the exotherm temperature often reached during resin polymer- ization For this reason, secondary Taminating sequences should be scheduled so that exotherm occurs at nearly the same time in all the resin or after exotherm in the primary Jeminate is finished Pure styrene vapor is heavier than airs thus, if ventilation is poor, the ‘vapor evolved may not completely ‘ix with ais. This may cause a condi- tion where styrene fumes may be more concentrated at floor level than at the ceiling. This point is important to keep in mind in designing general or local exhaust ventilation systems for FRP shops. ‘The odor threshold for styrene has been reported to be les than I ppm. ‘That is way even cured pieces of FRP ‘may still have a faint styrene odor qFIRE AND EXPLOSION HAZARD DATA. Liquid resin material should be treated as a flammable material Keep it away from heat, flames, and spark-producing equipment. ‘The burning characteristics of the liguid resin are comparable to those of styrene. The red FLAMMABLE label is required on drums since the resins have a flash point under 100°F The resins are flammable and must be kept away from all sources of ignition. There should be absokute- ly no smoking in the work or storage areas. Caution should be exercised with respect to the location of flame- fired equipment such as hot water heaters, space heaters, etc ‘TABLE 23 Flash Point and Flammable Limits in Air Fash pit Taser, 29090 ammabeints na Lover tit 1.9% based on seco) pert 81% (tased on syne) The flash point is the minimum temperature at which the material aves off a vapor in sufficient quantity 10 ignite in ait, as tested by one of the approved methods. Since the flash point is less than 80°F, flammable ‘concentrations of vapors may be pre- sent when liquid DERAKANE resins ate being used in the FRP shop ‘The lower flammable limit is the ‘minimum concentration of a vapor in air which will burn when exposed to an ignition source. Conversely, the upper flammable limit is the maxi- mum concentration of a vapor that ‘will burn when exposed to an ignition source These limits are specific for a given temperature and axe usually given for 25°C (77°F) It is important to prevent the formation of explosive or combustible mixtures and to take precautions to avoid igni- tion of any such mixtures formed Resin handling areas should be well ventilated and motors must be explo- sion-proof or totally enclosed. All equipment, drums, tank trucks, and hhose connections must be grounded for the safe discharge of static electricity. JIN CASE OF FIRE Fires involving DRAKANE resins ccan be extinguished safely with foam, dry powder, ox carbon dioxide. Water is not normally an effective extinguishing agent for use With these water-insoluble resins ‘The use of foam requires caution if motors, hot plates, fans, or other kinds of cleczrical equipment are involved in the fire. When these resins burn, they may give off toxie ‘by-products, such as carbon monoxide. For this reason, breath- ing of fumes, smoke, and vapors berated by a resin fre should be carefully avoided. If there is a possibility of gross exposure to these toxic by-products, a positive- pressure, self contained breathing apparatus, or equivalent, may be required Extra care should be taken in fire situations ia which other resin drums are stored in the area. When the drums are exposed to heat ot flame, an exothermic reaction can develop, possibly accompanied by hszerdous decomposition of the product. The gases generated by decomposition ‘may include carbon monoxide Decomposition of brominated resins ‘may release hydrogen bromide. REACTIVITY DATA, ‘DERAKANE resins are reactive and can polymerize even without the addition of peroxides, Polymesi- zation initiated without peroxides is usually the result of inhibitor depletion, and the reaction pro- ceeds slowly. However, exposure to high temperature, sunlight, or cez- tain other chemicals can result in rapid polymerization with signifi- cant genetation of heat. When this, happens, decomposition gases, such as carbon monoxide, may be formed. Icis best to store drums of DERaxANE resins indoors or away fiom direct sunlight. However, when the material is being used on a field job, this is not always possi- ble. For that reason, the drums are painted white to limit the amount of heat they will absorb. 51FIRST AID Eye Contact, Styrene vapors, if present at a high ‘enough concentration in the air, may cause tears and eye irritation. If the eyes become irritated, venti~ lation needs to be improved. Workers should protect their eyes from splashes by using chemical goggles. If resin is accidentally sprayed into the eyes, itis impor- tant for the person to irrigate them continuously with low-pressure for at least 15 minutes. Medical per- sonnel should be notified immedi- ately Include in the description of the accident other components of the mixture (peroxides, promoters, and fillers), because this informa- tion may affect the treatment the physician recommends. ‘Skin Contact Tfresin comes in contact with the skin, it should be washed off with soap (if available) and water, not solvents, Prolonged or repeated contact with the skin may cause localized irritation, even a burn Also, the sticky nature of the resins makes them very difficult to wash off exposed skin. Wearing protec- tive body-covering clothing and impervious gloves can help mini- ‘nize direct skin contact with the resin. Inhalation Inhalation of styrene vapors is the principal respiratory health con- cern associated with the use of ‘DERAKANE resins. Exposute to high ‘concentrations of vapors may lead to central nervous system effects (anesthesia or narcosis) and cause “upper respiratory irritation Effective March 1989, the OSHA. Permissible Exposure Limit (PEL) for styrene became 50 ppm as an 8 ‘hour Time Weighted Average (TWA) In addition, there is a Short Term Exposure Limit (STEL) of 100 ppm asa.15 minute TWA A person adversely affected by styrene vapors should be removed to fiesh ait, made to rest, and kept warm Ifthe individual is not breath- ing, mouth-to-mouth resuscitation should be given. Medical attention should be obtained immediately Ingestion IfDrraxane resins are accidentally swallowed, medical attention should be sought immediately. The physician should treat the condi- tion symptomatically and should not induce vomiting PERSONNEL PROTECTION ‘Human contact with resins, initia- tors, and other modifiers should be minimized, Use of chemical gog- gles, clean, body-covering clothing and impervious gloves will reduce ‘the potential for skin and eye con- tact Proper ventilation and any appropriate engineering procedures should be used in the work area to ‘maintain styrene monomer vapor concentrations below OSHA’S Petmissible Exposure Limit (PEL) of 50 ppm and OSHA’s 15-minute Short-Term Exposure Limit (STEL) of 100 ppm. Good general ventilation should be satisfactory for most conditions, However, local ‘exhaust may be required where ‘emissions of vapor are high and where there is litle air circulation, ‘particularly in confined areas. IFrespiratory protection is required, air-purifying respitators with organic vapor cartridges may be used for styrene concentrations up to a recommended maximum of 500 ppm. The service life of these car- ttidges depends on vapor concentra- tion, the user’s breathing rate, and relative humidity, among other fac- tors, and should be determined for cach work environment The car tridges should be replaced if styrene ‘odor becomes noticeable to the res- pirator wearer If there is a possibility of gross styrene exposure, @ positive pressure, self-contained breathing apparatus, o1 equivalent, may be required, ‘Cured DERAKANE resins—those ‘that are completely polymerized—are considered to be toxicologically inert and to present no handling hazards The finished resins, however, may represent a health hazard from ‘inhalation of dusts generated during grinding or machining, especially if they contain glass, silica powder, asbestos, or metal powdersSPILLS Small spills of DERAKANE resin can be handled by applying sand or other absorbent material to the spill and shoveling it into a con- tainer. The residue should be removed from the floor with hot, soapy water. Larger spills should be contained with a dike and the ‘excess resin should be collected in containers Again, the residue should be removed with hot, soapy water CAUTION: Solvents should not be used in the final deanup, because thein use could create unnecessary hazards of vapor inhalation and possible ignizion Only trained personnel should participate in the cleanup, and they ‘must be properly protected from skin and eye contact and breathing vapors, See “Personnel Protection” Before any cleanup is begun, the spill atea should be checked carefully and any possible sources of ignition should be removed, ENVIRONMENTAL AND DISPOSAL INFORMATION Spills should be soaked up with a non-reactive absorbent such as sand, Residual resin should be cleaned up with hot soapy water or steam. Solvents are not zecom- ‘mended for clean up unless the recommended exposure guidelines are followed: DERAKANE resins can be disposed through burning in an adequate incinerator. Brominated resins (DERAKANE 510A, 510N, and 510C-350) must be burned in an incinerator equipped with a halogen scrubber Current regulations allow for ‘cured resins to be disposed in an approved landfill in accordance with federal, state and local regulations This is another area of emerging reg- ulations The regulations which may have an impact on disposal of cured ‘waste resin include RCRA, California Proposition 65 and Rule 1162 As these rules become defined further, Dow will be working with fabricators and distributors to keep ‘them informed. NOTE. In disposal of any wastes, all Jederal, state, and lacal regulations ‘must be met HEALTH AND HAZARD DATA. Tn March of 1987 The Inter- national Agency for Research on Cancer (ARC), decided to reclas- sify styrene from its 1982 status, “not classifiable as to carcino- genicity to humans,” to Group 2B as a “possible carcinogen to humans” This decision was based on new criteria for evaluation and did not reflect the generation of any new carcinogenicity data since the previous classification five years earlier. In fact, no animal exposure studies have been identified which demonstrate conclusively that styrene is carcinogenic ‘Asa result of the reclassification of styrene, all DERAKANE epoxy vinyl ester resins are now classified as a “potential carcinogen to humans” on their Material Safety Data sheets because the resins contain more then 0.1% styrene monomer. 53Section 12—Resin storage STORAGETEMPERATURES TABLE 24 Stotage temperatures for Resin Shelf Life DERARANE eposy vinyl ester resins should be maintained below 75°F #MONTHSMELFUFE ours SHELF UFE eT SHELELFE for maximum shelf life. DERAKANE resins should be kept away from all PAWMESTT GHD oo aoe sources of heat, which might create RMsNEA7DSE ee ee ened irene Decne 70485 | Dew 100350 Dee 417-50 Deo ee Dias 475-2000 Deve 5100-800 Dene 4-350 ambient conditions but itbaneled 4A 4T-7OPAT Dime s108 Dua 125A improperly, may polymerize slowiy. #4117007 eens cee In fact, exposure to sunlight or other “ae sources of high temperature can lead DRWMEAT- GAD" to rapid polymerization with danger-___ Powe 5106200 ‘ous exotherm. Fifty-five gallon perineal Pods drums should be stored in a cool, dry “natin cuts place out of direct sunlight. ‘The deums are painted white to minimize INVENTORY ROTATION AERATINGTHE RESIN heat absorption from sunlight i et oeae = : fo minimize potential shelf life cause inhibitors in DERAKANE RESIN Soe E EE problems, you should maintain _resins work by reacting with oxygen DERAKANE resins provide superior YOUr inverstory of DERAKANE resin to prevent premature cross- link~ performance in reinforced plastic 008 frst, first-out basis. Always ing, petiodic replenishing of the applications This is due, in part, we your oldest resin first dissolved oxygen will extend the 10 their high degree of reactivity. Aside effect of high reactivity, however, is somewhat limited shelf life. The shel life warranty for each resin is stated on the drum, DERAKANE resins should be used within the stated shelf life Dow can- not honor any claims for credit on DERAKANE resin that has been stored beyond the maximum storage time. 54 ‘The following publications provide excellent resin storage information: NEPA No. 30—Flammable and Combustible Liquids Code, as adopted by the National Fire Protection Association. ‘NEPA No. 70—National Electrical Code, as adopted by the National Fire Protection Association ‘NEPA No 77—Recommended Practice of Static Electricity, as aclopted by the National Fire Protection Association, resin’s shelf life. This operation should be done only in well venti- lated areas free from ignition sources because flammable vapor ‘mixtures may be formed in the Process ‘The recommended way to replen- ish dissolved oxygen is by stirring the resin in the drums with both the ‘bung and vent caps removed, using an air-powered drum mixer. Another possible way is to bubble small amounts of clean, dry air into the drums through a dip pipe NOTE: The dip pipe should not contain any sine o copper allo, since these material could change the reactivity of the resinFor increased safety, a 2:1 mixture by volume of nitrogen and air may be used to keep gas exiting the drum during sparging below the styrene/ gas flammability limits. Both the drum and the sparging line should be grounded Oxygen can also be replenished by ‘opening the bung and the vent in the “head space above the resin, After this is completed, the drum should be closed tight, then rolled on its side to mix the air into the resin ‘Any steps to extend the shelf life of DERAKANE resins must be taken before the resin starts to gel. Ifthe resin has begun to gel, it should be discarded in accordance with approved disposal procedures, since the gelled particles would not cure properly and finished products made with the resin might have unsatisfac- tory chemical resistance. BULK STORAG! DERAKANE resins are frequently stored in bulk storage tanks A propetly designed bulk storage sys- 5 tem should do the following: * Eliminate flammability hazards * Protect resin against temperature extremes + Prevent contaminatior + Retard polymerization in infrequently used lines, ‘The following procedures must be followed carefully to ensure proper bulk storage of DERAKANE resins: 1. Maintain resin temperature below 75°F (24°C) in an electrically grounded vessel (Continuous monitoring of the bulk resin temperature is recommended ) Periodically circulate the resin in the storage tank and process Fines to prevent polymer buildup in stagnant sections Keep resin properly acrated by circulating the contents of the storage tank to ensure com- plete turnover of the resin. This can be controlled with Step 2 Use proper materials for con- taining, transferring, and stor ing the resin. Suitable materials, could be, for example, mild steel, black iron, or 304 stain Jess steel, Alloys containing, copper ot zinc should not be uuseds they can adversely affect the reactivity of the resin, Rubber parts should also be avoided, because styrene monomer is an excellent solvent for most mubbers except Viton fluoroelastomer ‘Check resin gel time periodi- cally to ensure continued high resin quality, 6. Use the resin within the suggested storage life Use an air pad over the resin in the tank to ensure maintenance of adequately dissolved oxygen in the resin. STORAGE OF PROMOTED RESIN DERAKANE resin that has been pro- moted by the customer with cobalt naphthenate and/or dimethyl line or modified with other addi- tives may have a substantially shorter shelf life than unmodified DERAKANS resins, Because of the possibility of reduced shelf life, any formulating of resin required for fabrication should be delayed until shortly before use to ensure consis- tent properties. Formulated resin should be used as quickly as possi- ble to prevent problems fiom oceurring Because additives can have a destabilizing effect on DERAKANE resins, the stated storage times do not apply to resins that have been modified from theit “as received” condition. PRODUCT STEWARDSHIP Dow encourages its customers and potential users of Dow products to review theit applications of such products fiom the standpoint of ‘human health and environmental quality. To help ensure that Dow products are not used in ways for Which they are not intended or tested, Dow personnel will assist customers in dealing with ecological and product safety considerations Your Dow sales representative can arrange the proper contacts. Dow product literature, including Material Safety Data Sheets, should be consulted prior to use of Dow products “These may be obtained from your Dow sales representative or by calling the Customer Information Center at: 1-800-441-4D0W. 55Subject index Abrasion resistance 37 Laminate construction. 29 Acetone teplacements 7 Masterbatch preparation : 15, Accelerators 5 Material Safety Data Sheets 50 Aerating resin 54 Material suppliers a! Air inhibition 13 Mold release agents uy Anchors for concrete 37 Non-foaming catalysts (initiators) 5 Antimony compounds 26 Paints 12 | Antifoam agents 10 Personnel protection 52 Applying FRP lining, 29 Physical properties 50, ~to metal 35 Polyamide epoxy paints. 12 ~to BRP 36 Product stewardship 55 | ~ to conexete 36 Promoted resin storage 55 Bulk storage 55 Promoters 5 Catalysts (initiators) 4 Poltrusion 4 Checking for complete cure 38 Reactivity of resins 51 Conductive linings 33 Reinforcement for pultrusion 46 Defects 38 Reinforcements used in FRP 42 | Disposal 53 Resin shelf lif 54 Environmental information 53 Resin transfer molding 48 © Equipment for resin Retarders (gel time) 6 transfer molding 48 Safety (industrial health information) ... ..7, 15, 37,50 | Exposure limits (personal protection) 52 Spills 53 Estending resin shelf life 54 Spray-up a2 | FDAUSDA compliance 14 Storage temperatures 54 Filament winding 43 Styrene, carcinogenicity i First aid 52 classification (health and hazard information)... 53. | Food contact 14 Styrene suppressant! | Formulating guide 45 secondary adhesion promoter (air inhibition) . ....13 Formulating for spray-up 42 Surfactants 10 Gel times (opical) 16 Thixotropic additives 10 Gass evaluation, 3 Tooling for RTM 49 Glass fibers storage 4 Trade names. 8 Glass types 2 Troubleshooting 27 | Inspecting laminates 38 Ultaviolet protection 12 Internal mold releases 44 Wax topcoats B | Inventory rotation 54 Working life of resins 26 56am For additional information in U.S. and Canada, call 1-800-441-4DOW (4369) In Mexico, call 525-227-1900 NOTICE: Dow heaves the infomation snc rcmsmendaton erin 9 Be secure an bl tof Orbe, {008 However, nc any sarc oth by Dwr ‘eth efscace he proper sc and doc oits prodaci proved who chags sd ince we conden en pial re not witha ons Dew res ‘De obaton rab auch aust a ote ct pute eo ne fac eades oe ther iterate hereon any coe Sap, fins nor is esd frm acy puter owned by Dow or then sobe fret torsnsn hsm concring ae and ego ibe on US fe nea eg Ukans except where pei seterences made to thos of eas fracas See we cdo and goreamcaal ean ay ile fe econ fs and ony change ws ne de Buyers spoon wo deen he Dow» prod ar Pope or Buyer ie, ado mute Buyer orgs tad ‘Supa practices sen coeptance nis ns eguans,ornance snd ochergvoraenal nace span the ogaeson) ang hen Oe Dow Plastics We don't succeed unless you do. © ‘The Dow Chemical Company, 2040 Dow Center, Midland, MI 48674 Dow Chemical Canada Inc., P 0. Box 1012, 1086 Modeland Rd., Satnia, Ont N7T TK Dow Quimica Mexicana, SA. de GV, Av. Paseo de las Pelmas 555-3, Lomas de Chapultepec, Mexico 11000 D-F Mexico