1. January 29, 1999ITEC 0411 Health and Safety Professor Joe Greene CSU, CHICO

2. January 29, 1999ITEC 0412 Topic Physical Hazards Biomechanical Hazards Chemical Hazards Sources of Chemical Hazards MSDS

3. January 29, 1999ITEC 0413 Physical Hazards Machine Motions Clamping Devices Heavy Items Electrical Systems Hydraulic/Pneumatic Pressure Systems Noise Thermal Radiation

4. January 29, 1999ITEC 0414 Biomechanical Hazards Repetitive Motions Injury not immediate but occurs over days, weeks, or months. Causes –Poor ergonomics in workplace –Incorrect computer position for hand, eyes, and legs –Poor design of machine causing reaching or twisting Proper Ergonomics can lead to healthier workplace Proper lighting, protective equipment, safe operating procedures

5. January 29, 1999ITEC 0415 Chemical Hazards Materials –Resins (See MSDS) Thermoplastic resins- low toxicity and low health hazard Thermoset resins- moderate toxicity and moderate health hazard –Reinforcements- low toxicity and moderate health hazards (dust) –Fillers- low toxicity and moderate health hazards (dust) –Solvents- moderate to high toxicity with moderate to high health hazards –Catalyst- moderate to high toxicity with moderate to high health hazards –Plasticizers- low toxicity and moderate health hazards

6. January 29, 1999ITEC 0416 Chemical Hazards Processing (example of molding machine) –Closed Mold (2 mold halves that have resin injected) Thermoplastic- low health hazard with most materialsfor –Injection Molding –Blow Molding –Extrusion –Compression Molding Thermoset- some health hazards when filling tanks –Polyurethanes- Isocyanate –Polyesters- Catalyst –Catalyst- MEK –Promoters –Inhibitors

7. January 29, 1999ITEC 0417 Chemical Hazards Processing –Open Mold (1 mold half that has resin poured or rolled) Thermoplastic- none Thermoset- some health hazards when mixing and applying resin –Polyurethanes- Isocyanate –Polyesters –Phenolics –Catalyst- MEK –Promoters –Inhibitors –Additives Metal pigments Inorganic dyes

8. January 29, 1999ITEC 0418 Chemical Hazards Processing –Reinforcements: low toxicity and moderate health hazards (dust) Glass fiber Glass bubbles or microspheres Mica Mineral fiber –Fillers Calcium Carbonate Talc Gypsum –Solvents- Variety of alcohol based products –Plasticizers- low toxicity and moderate health hazards

9. January 29, 1999ITEC 0419 Chemical Hazards Post molding operations –Sanding- dust –Grinding- dust –Polishing- dust –Surface Prep- chemical wipe –Bonding- 2 component adhesives –Tool cleaning- solvents –Tool prep- mold releases –Waste products –Scrap products –Painted plastics

10. January 29, 1999ITEC 04110 Material Safety Data Sheet (MSDS) Hazardous materials are common in the plastics industry MSDS are required to accompany any purchased hazardous industrial raw material. Plastics are defined as potentially hazardous because in the course of normal use, plastics may produce dusts, mists, gases, fumes, vapors, or smokes which are dangerous.

11. January 29, 1999ITEC 04111 Material Safety Data Sheet (MSDS) Section I: General Information Section II: Composition Section III: Physical Properties Section IV: Fire and Explosion Hazard Data Section V: Health Hazard Data Section VI: Reactivity Data Section VII: Spill or Leak Procedure Section VIII: Occupational Protective Measures Section IX: Special Precautions Section X: Transportation

12. January 29, 1999ITEC 04112 Section I: General Information Product name Manufacturer’s Identity Emergency telephone numbers Trade name of chemical Chemical family name of the material Example –Lexan –General Electric –1-800-gecares –Lexan PC Resin –Poly(Bisphenol-A carbonate) –Chemical Abstracts Services (CAS) Number- Unambigous identification of materials. Lexan= 25971-65-5 (same as Merlon)

13. January 29, 1999ITEC 04113 Section II: Composition Hazardous Ingredients –Major constituents –hazardous additives, fillers, or colorants –Example for ABS 3 % Carbon black (solid- trapped in polymer) 0.2% residual styrene monomer (gas- released during processing)

14. January 29, 1999ITEC 04114 Section II: Definitions Definitions OSHA- Occupational Safety and Health Administration ACGIH- American Conference of Governmental Industrial Hygienists PEL- Personal Exposure Limits (TWA) TWA- Time weighted average. Exposure level considered acceptable in an 8 hour day as part of a 40 hour week. REL- Recommended exposure TLV- Threshold Limit Value. Recommended by the American congress of Governmental industrial Hygienist. (TWA for 8 hours) STEL- Short term exposure limit. Acceptable exposure for 15 minutes and should not be exceeded any time during the 8 hour work day.

15. January 29, 1999ITEC 04115 Section II: Styrene Styrene as a health hazard Building block for thermoplastic styrenics, e.g., polystyrene, ABS, SAN, and others. Cross-linking building block for thermoset styrenics, e.g., polyesters, vinyl esters. ABS has 0.2 % residual styrene plus other sources (styrenic plastics) One study found a range of 1 to 7 ppm styrene in an injection molding plant Thermosets –Manufacturing of large boat hulls, boats, large tanks, tubs, shower stalls, body panels for cars and trucks. –Polyester is 35% styrene by weight. –Processing methods include fiber spray with resin in stream, handlayup by roller, closed mold RTM operations, compression molding of polyester sheet. Ventilation is essential to keep exposure within limits.

16. January 29, 1999ITEC 04116 Section III: Physical Properties Properties of material as one substance –Evaporation Rate –Melting point –Boiling point –Specific gravity –Solubility in water –Physical form

17. January 29, 1999ITEC 04117 Section IV: Fire and Explosion Hazard Data Section for fire fighting Most plastics are not explosive Upon burning most plastics will yield water and CO 2 Many plastics are self-extinguishing All thermosets are self-extinguishing Water is recommended as the best medium for extinguishing fires Toxic fumes from plastics include –black smoke, CO, hydrogen cyanide, and ammonia Flash point is very high for many plastics

18. January 29, 1999ITEC 04118 Section V: Health Hazard Data Routes of entry of toxic substances –Ingestion Oral LD-50 in rats. Lethal Dose 50 percentile of fatalities in rats Many pelletized plastics are rather inert. Extremely toxic: LD-50 less than 1 mg/kg or 10 ppm Highly toxic: LD-50 less than 50 mg/kg or 100 ppm Moderately toxic: LD-50 less than 500 mg/kg or 1000 ppm Slightly toxic: LD-50 greater than 500 mg/kg or 1000 ppm Example –LD-50 for guinea pig is 264mg/kg (264mg x mass of pig) –Assuming equal response from human: 264mg x 70kg for mass of human = 18480mg or 18.48g to be ingested.

19. January 29, 1999ITEC 04119 Section V: Routes of Entry Routes of entry of toxic substances –Inhalation Thermosets reactants can be inhaled since they are in liquid form and have a vapor pressure that indicates relative volatility. Example: Isocyanates used in polyurethane production –TDI (toluene diisocyanate) used in foams for seats or paints. –MDI (methylene diisocynate) used in RIM body panels or in paints. –Construction projects use foamed polyurethane for interior walls and roofs. –TLV is 0.005 ppm –STEL for TDI is 0.02 ppm. Local and general ventilation are extremely important when working with urethanes Effects are asthma symptoms

20. January 29, 1999ITEC 04120 Section V: Routes of Entry Routes of entry of toxic substances –Inhalation LC for lethal concentration (normally for a vapor or gas) Unlikely for peletized plastics Heated plastics yield hydrocarbons Example –Overheated PET releases acetaldehyde –STEL of 25 ppm –Odor threshold is 0.050 ppm. Example –PVD polymerization uses Vinyl chlorine gas –TLV of 5 ppm –Odor threshold of 3000 ppm (no odor warning) –Known human carcinogen

21. January 29, 1999ITEC 04121 Section V: Routes of Entry Routes of entry of toxic substances –Dermal (Skin) Most pelletized plastics do not affect dermal Isocyanates can cause rashes and blistering of skin Isocyantes can cause discoloring of skin. Hot plastic materials can cause skin burns Catalyst materials can cause skin abrasions Example –Diethylene Triamine (catalyst) CAS# 111-40-0 –ACGIH »TLVSTEL »1 ppm (skin)NE –OSHA »PELSTEL »1 ppmNE

22. January 29, 1999ITEC 04122 Section V: Routes of Entry Routes of entry of toxic substances –Eyes Injured by objects landing in the eye –glass fibers, fillers, additives, colorants, particles of plastic –liquids and gases can cause severe damage –Example »methylene- hardener for epoxy »Causes irreversible blindness in cats and visual impairment in cattle. –Carcinogenicity Pelletized plastics are often not regulated as carcinogenic Residual monomers have links to cancer (vinyl acetate, a residual monomer from PVA and EVA is present at 0.3%) at levels of 600 ppm caused some cancer in some animals (bears A3 notation) Some liquid polymers and catalysts can cause cancer in some animals

23. January 29, 1999ITEC 04123 Section VI: Reactivity Data Pelletized plastics are very stable and non-reactive Thermo-oxidative degradation can yield hazardous gases –PVC: at 100 ºC releases HCl –PMMA: at 100 ºC releases MMA –POM: at 230 ºC releases formaldehyde –Teflon (other fluoroplastics): at 250 ºC release HF –PET: at 300 ºC releases acetaldehyde –Nylons: at 300 ºC nylons release CO and ammonia –Nylon 6: at 340 ºC releases e-caprolactam –Thermoset resin degrade to toxic fumes of CO, formaldehyde, isocynates (for urethanes)

24. January 29, 1999ITEC 04124 Section VI: Reactivity Data _PVC and POM Thermal degradation of PVC –PVC degradation is a serious problem Can decompose catastrophically if overheated in barrel. Remaining materials is tightly packed carbon Fumes contain high concentrations of HCl Response team must wear air respirator, turn off machine, tear down after cooling, remove nozzle and end cap. Thermal degradation of POM (poly actetal or polyoxymethylene) Thermally degrades (>230 ºC )and releases formaldehyde Exposure can occur at purging of machine Local exhaust is essential to minimize exposure Thermal degradation of Phenolics Major uses in adhesive applications (plywood & particleboard) Compression and transfer molding operations Can release small amounts of ammonia, formaldehyde, and phenol

25. January 29, 1999ITEC 04125 Section VI: _Phenolics, Nylon 6, & PMMS Thermal degradation of Phenolics Major uses in adhesive applications (plywood & particleboard) Compression and transfer molding operations Can release small amounts of ammonia, formaldehyde, and phenol –Phenol: TLV of 5 ppm, LD-50 of 414mg/kg, and LC-50 of 821 ppm. –Formaldehyde: ceiling of 0.3 ppm Thermal degradation of Nylon 6 Degrades into monomer_ e-caprolactam, and residual caprolactam –Caprolactam vapor: TLV is 5 ppm, LD-50 (rat) is 2.14 mg/kg –Molding operation release some caprolactam vapor, with more produced during purging and extrusions Thermal degradation of PMMA (acrylic)_ Plexiglass PMMA degrades into MMA (methyl methacrylate) TLV for MMA is 100 ppm (410 mg/m 3 )

26. January 29, 1999ITEC 04126 Section VII: Spill or Leak Procedure Pelletized materials are swept up. Liquid chemicals use absorbent materials For isocyanates the absorbent materials need to allow reaction of the isocyanate with the water in the air. The reacted materials is then disposed of according to specified government regulations.

27. January 29, 1999ITEC 04127 Section VIII: Occupational Protective Measures Workplace protection –Adequate ventilation –Personal protective devices include safety glasses or goggles for eye and face protection gloves, long sleeves, face shields, ear plugs respirators

28. January 29, 1999ITEC 04128 Section IX: Special Precautions Handling Storage

29. January 29, 1999ITEC 04129 Section X: Transportation Special instructions for transporting liquid chemicals Most pelletized plastics have no special restrictions