S
PECIAL FEATURE
/ Reducing styrene e x p o s u r e in the c o m p o s i t e s industry nvironmental and pollution issues, In l i n e w i t h t h e c u r r e n t ' g r e e n particularly in relation to the workawareness', the i s s u e o f p o l l u t i o n place, have become the subject of in the w o r k p l a c e , w h i c h for the increasing concern in recent years. For the c o m p o s i t e s i n d u s t r y p r i n c i p a l l y composites industry the major problem is m e a n s t h e p r o b l e m o f s t y r e n e t h a t of styrene emissions from the polyester e m i s s i o n s , is o n c e again a high resins, solvents and reinforcement materials priority topic. In the UK, industry used. The styrene monomer has been the is currently c o m i n g to terms with subject of a number of toxicological investn e w l e g i s l a t i o n on the 'control o f igations worldwide and, although a recent ruling in the USA says t h a t it is not s u b s t a n c e s h a z a r d o u s to h e a l t h ' carcinogenic, styrene is still considered to ( C O S H H ) and similar r e g u l a t i o n s create health problems. In view of this the are also e n f o r c e d in o t h e r Eur- h e a l t h a n d safety a u t h o r i t i e s in m a n y o p e a n c o u n t r i e s and the USA. In countries have set threshold limit values the f o l l o w i n g article t h e N o r w e g i a n (TLV) for styrene monomers. The short term resin manufacturer J o t u n Polymer average exposure and eight-hour average exposure limits for the Scandinavian counl o o k s at the way in w h i c h Scandi- tries and West Germany are shown in Figure navian c o m p o s i t e s p r o d u c e r s have 1. dealt with the e m i s s i o n problem. Particular a t t e n t i o n is paid to the Controlling styrene benefits of using environmental emissions p o l y e s t e r resins, such as J o t u n ' s N o r p o l LSE range.
E
FIGURE 1: Threshold limit values for styrene monomer in Norway, Sweden, Denmark, Finland and West Germany.
For the moulder faced with having to comply with r e d u c e d emission levels t h e r e are several courses of action which alone or in combination will contribute to the reduction of styrene inside a factory: (1) A clean tidy workplace. (2) A good fabrication layout. (3) Using proper and adequate ventilation. (4) If possible, evaluating another laminating process. (5) Using a low styrene emission (LSE) resin. (6) Using, if possible, water based cleaning agents.
O A tidy workplace Studies have shown t h a t in untidy working areas a styrene monomer/solvent concentra-
REINFORCED PLASTICS FEBRUARY 1990
0034-3617/90/$3.50 © 1990, Elsevier Science Publishers Ltd.
S
PECIAL FEATURE
FIGURE 2: The weight loss from Jotun's Norpol standard resin compared to Norpol LSE resin.
FIGURE 3: Styrene evaporation during the hand lay-up process.
tion of b e t w e e n 20 a n d 50 p p m is p o s s i b l e even b e f o r e t h e l a m i n a t i n g p r o c e s s begins. This is t o t a l l y u n n e c e s s a r y and, by t a k i n g a few s i m p l e m e a s u r e s , t h e e x p o s u r e c a n be r e d u c e d to a l m o s t zero. --Laminates and spilt resin should be c l e a n e d off t h e floor a f t e r t h e l a m i n a t i n g p r o c e s s is finished. - - O p e n resin b u c k e t s a n d d r u m s , a n d o p e n c l e a n i n g s o l v e n t c o n t a i n e r s , s h o u l d n o t be s t o r e d in t h e l a m i n a t i n g area. - - O p e n w a s t e c o n t a i n e r s for r e m n a n t s of l a m i n a t e , a n d resin c o n t a m i n a t e d r a g s a n d p a p e r s h o u l d be avoided.
FIGURE 4: Styrene evaporation dur/ng the spray-up process.
• Ventilation during lamination. If a high s t y r e n e level is to be a v o i d e d d u r i n g t h e a c t u a l l a m i n a t i n g p r o c e s s it e s s e n t i a l t h a t t h e w o r k i n g a r e a is c o r r e c t l y v e n t i l a t e d . The v e n t i l a t i o n of a large a r e a is p a r t i c u l a r l y costly, t h e r e f o r e t h e o p e r a t i o n s w h i c h p r o d u c e t h e h i g h e s t e m i s s i o n levels, s u c h as g e l c o a t i n g a n d l a m i n a t i n g , s h o u l d be isolat e d in s e p a r a t e v e n t i l a t e d b o o t h s to p r e v e n t t h e f u m e s f r o m e s c a p i n g into a r e a s w h e r e no resin w o r k is t a k i n g place. S p o t v e n t i l a t i o n of t h e m o u l d s c a n be used, often c o m b i n e d w i t h t h e i n s t a l l a t i o n of f r e s h air inlets a n d p o l l u t e d a i r e x t r a c t i o n systems. However, c a r e m u s t be t a k e n w h e n c o n s t r u c t i n g s u c h s y s t e m s to e n s u r e t h a t t h e a i r velocity is n o t too high. Using low velocity a i r i n j e c t i o n a s p e e d of a r o u n d 0.5 m / s c a n be o b t a i n e d , w h i c h will n o t c a u s e d r a f t s or turbulence. Further unnecessary styrene exposure can be a v o i d e d by c a r r y i n g o u t t h e p o s t - l a m i n a ting or g e l c o a t i n g c u r e in a well v e n t i l a t e d area.
• Optimizing the laminating process T h e c h o i c e of l a m i n a t i o n p r o c e s s o f t e n d e p e n d s u p o n t h e c o m p o s i t e article w h i c h
is t o b e made. Obviously, open-mould techn i q u e s result in higher styrene exposures t h a n semiopen or closed-mould
me-
thods. Opt i m i z i n g t h e l a m i n a t i n g p r o c e s s is t h e r e f o r e i m p o r t a n t in t e r m s of r e d u c i n g t h e styrene emission. W h e r e v e r possible, s e m i - o p e n or closed m o u l d s s h o u l d be c o n s i d e r e d . T h e r e are s o m e p r o b l e m s a s s o c i a t e d w i t h this, for e x a m p l e very large m o u l d s a r e difficult to close; however, a m o u l d e r could c o n s i d e r p r o c e s s i n g all s m a l l p a r t s by resin injection, b a g m o u l d i n g , etc.
Low styrene e m i s s i o n resins O n e of t h e m o s t i m p o r t a n t f a c t o r s in r e d u c i n g styrene m o n o m e r e x p o s u r e s , a p a r t f r o m p r o p e r v e n t i l a t i o n , is t h e q u a l i t y of t h e u n s a t u r a t e d p o l y e s t e r resin used. In r e c e n t years the polyester manufacturing industry h a s c o n c e n t r a t e d c o n s i d e r a b l e effort on t h e d e v e l o p m e n t of resin s y s t e m s w i t h g r e a t l y reduced styrene evaporation. J o t u n P o l y m e r i n t r o d u c e d its first enviro n m e n t a l p o l y e s t e r resin in 1971, since this d e v e l o p m e n t w o r k h a s b e e n continuing; t h e r a n g e n o w i n c l u d e s specially a d a p t e d orthophthalic, isophthalic and flame-retardant resins. The c o m p a n y ' s N o r p o l e n v i r o n m e n t a l
REINFORCED PLASTICS FEBRUARY 1990 I
S
PECIAL FEATURE
FIGURE 5: Tensile test ASTM D 297 is used to determine secondary bonding strength.
FIGURE 6: The interlaminar shear strength is measured using ASTM D 2733-1970 Method B.
polyester resins i nc o rporat e a film forming additive which has the ability to: -- be h o m o g e n e o u s l y d i s s o l v e d / d i s p e r s e d into the liquid resin -- rapidly form a styrene v a p o u r tight film on the liquid surface. Figure 2 com pa r es the weight loss from a s t a n d a r d l a m i n a t i n g resin with J o t u n ' s Norpol LSE resins. The effect of t he film forming additive during an open laminating process can be seen. Tests such as these were used in the FIGURE 7: Laminates are tested for short beam shear using BS 2782 Part 3 Method 341 A.
REINFORCED PLASTICS FEBRUARY 1990
company's development p r o g r a m m e s to find t he o p t i m u m film forming additives, with r e g a r d to film forming speed, tig h tn e ss against styrene m o n o m e r and compatibility with t he liquid resin. A f u r t h e r p a r a m e t e r to be considered during the development was the effect of the additive during the laminating process. Figure 3 compares a s t a n d a r d resin and Norpol LSE during h a n d lay-up; t he curves are obt ai ned by continuously registering the styrene concentration above the mould with photo-ionizer equipment. J o t u n also tested the perfo rm a n c e of its LSE resins during spray-up, a commonly used manufacturing technique in Scandinavia. Figure 4 shows the styrene emissions from s t a n d a r d and LSE resins. It can be seen t h a t t he Norpol LSE resin resulted in a lower styrene concent rat i on in all four stages of the spray-up process. When the styrene emission is reduced the material consu m p tio n is also decreased, with the actual loss falling by 4050%. The film forming additives used in LSE resins are usually paraffin waxes or wax-like additives, These substances are well known in the reinforced plastics industry for their good release properties; therefore a major effort in producing LSE resins has been d i r e c t e d t o w a r d s systems w h ic h give a s e c o n d a r y b o n d i n g effect w h e n n o r m a l laminating procedures are followed. J o t u n says t h a t it has m anaged to combine good secondary bonding with t h e low styrene emission rates shown in Figures 2-4. The c o m p a n y tested the secondary bonding effect of a variety of different additives using five techniques: FIGURE 8: Impact testing of laminates made from Norpol standard resin and Norpol LSE resin.
S
PECIAL FEATURE
(1) T r a n s v e r s e t e n s i l e s t r e n g t h . (2) I n t e r l a m i n a r s h e a r s t r e n g t h . (3) Shin1 b e a m s h e a r s t r e n g t h . (4) I m p a c t tests. (5) Peel tests. The o b j e c t i v e in all five t e s t s w a s to a c h i e v e at. l e a s t an e q u i v a l e n t s e c o n d a r y bonding strength to that of standard p o l y e s t e r resins. T h e r e s u l t s a r e s h o w n in Figures 5-9.
Summary Within the S c a n d i n a v i a n c o m p o s i t e s ind u s t r y t h e strict s t y r e n e e x p o s u r e limits h a v e been m e t by: I m p l e m e n t i n g r o u t i n e s to t a k e c a r e of u n n e c e s s a r y s t y r e n e e x p o s u r e in t h e facto .ry, e.g. wast(.' h a n d l i n g , k e e p i n g t h e w o r k a r e a clean a n d tidy. -Improving p r o c e s s a n d fact o r y lay-out, k e e p i n g t h e lam i n a t i n g w o r k in s e p a r a t e areas. I m p l e m e n t i n g a d e q u a t e vent i l a t i o n s y s t e m s in a r e a s where laminating and g e l c o a t i n g t a k e s place. In c a s e s w h e r e p r o d u c t design allows, u s i n g closed or semi-open moulding techniques. C h a n g i n g t h e resin quality, w h e r e v e r possible, to use a n LSE resin. -l~sing personal respiratory e q u i p m e n t in critical o p e r a tions. In a d d i t i o n to c l e a n i n g u p t h e w o r k p l a c e , t a k i n g (:are of t h e e x t e r n a l e m d r o n m e n t is b e c o m ing m c r e a s i n g l y i m p o r t a n t . By using closed m o u l d s y s t e m s a n d LSE resins the composites moulder can s u b s t a n t i a l l y r e d u c e t h e level of s t y r e n e e m i s s i o n s . Finally, t h e r e are a n u m b e r of g a s cleaning systems under developm e n t a n d it m u s t be h o p e d t h a t o n e of t h e s e will be successful in extracting styrene monomer from factories at a reasonable cost. l
FIGURE 9: Peel test to determine secondary bonding of laminates made with Norpol LSE.
ATT: G.R.P. F a b r i c a t o r s . . . A
MAGNUM IND.
M a g n u m now has e q u i p m e n t to fit all of your needs. We have over 1 0 0 y e a r s of c o m b i n e d experience in the ( ;. R. P. Industry and have established ourselves as leaders in new d e v e l o p m e n t of accurate, simple, low m a i n t e n a n c e equipment.
The following is a list of equipment currently in our product line: ' Automah{ Guns for Robotic Applications
• Low Pressure Airless Air Assist
• •
• • • • • • • • •
External Mix Spray Systems Low Pressure, Self Balancing Intemal Mix Airless Air Assist Spray Systems 3 Coml:x)nent internal Mix Airless ~r Assist Polyester Foam Systems Catai~ed Resin Roller impregnator Systems Catalyzed Resin Dispensing System Polyester Putt7 Dispensing Systems Sprayable Benzoyl Peroxide Systems Dual Color Slave Systems ~4ull~ple Color Gel Systems Custom Designed Systems Patented Airless Air Assist Spray Guns Conversion Kits
REINFORCEI)
PLASTICS
• Self Balancing internal Mix Guns • High Pressure ~', Low Pressure Catalyst Pumps • Wide Range of Resin & Gel Pump Ratios G Outputs • Catalyst Injector Systems , Catalyst Ratio Test Nozzles • BaLanced Impingement Catalyst Tip • True ,~r Containment &r Assist Nozzles • 2 Part Cleanable ?'Jr Assist Catalyst Tips • Booms up to 34 Long • Gear Dnven Drum Agitators • 5 Gallon Pail Agitators
FEBRITARY 1990