AFGM Edsa Shangri-la MANILA SEPTEMBER 21, 2006 CONTAINER GLASS FEEDERS : RECENT DEVELOPMENTS IN THE CHOICE OF REFRACTORY MATERIALS AFGM Edsa Shangri-la MANILA SEPTEMBER 21, 2006

It is clearly understood that feeders play a crucial role in the quality of glass produced by the furnace. Any defects generated in the feeder zones could well be found in the finished product, since the glass at this stage works at relatively low temperatures and has a low capacity to absorb any flaws. In addition, market demands for quality are constantly on the increase. Defects and flaws which were acceptable in the recent past are now often cause for rejecting the glass. This jeopardizes both yield and profitability of glass production. Regardless of the design used to channel the glass from the distributor to the machines,and to condition it thermally for forming,the choice of the refractories in glass contact is increasingly important.

SAINT-GOBAIN SEFPRO GLASS CONTACT PRODUCT RANGE

Product Range AZS Brand name ER 1681 RN ZA 33 Type of product Fused cast Bonded Chemical analysis % Al2O3 ZrO2 50.9 32.5 75.5 10.5 Physical characteristics Bulk density Open porosity % Expansion at 1000 °C (%) 3.5 2 0.9 3.0 16 0.7 Glass quality Bubbling index 1100 °C-1h (0-10) Stoning index 1250 °C- 36h (0-5) AZS cat scratches Corrosion resistance (MGR – 72 h – 1350 °C) 1-2 0-1 + 100 80

Product range Alumina Brand name JARGAL M SCIMOS M BPAL ARKAL 60 PR Type of product Fused cast Bonded Chemical analysis % Al2O3 ZrO2 95.0 - 93.0 68.0 Physical characteristics Bulk density Open porosity % Expansion at 1000 °C (%) 3.17 3 0.75 3.10 14 0.80 2.57 15 0.52 Glass quality Bubbling index 1100 °C-1h (0-10) Stoning index 1250 °C-36h (0-5) AZS cat scratches Corrosion resistance (MGR – 72 h – 1350 °C) 0-2 100 1-2 0-1 80 4-5 2-3 45

Out of these 5 types of products, which one is the best technico-economical candidate to be used as feeder channel blocks for containers?

Corrosion curves as a function of temperature ( PFT test ) in mm 12 ER 1681 9 6 3 JARGAL M BPAL ZA33 1200° 1300° 1350° 1400° 1500° 1600° Temperatures in ° Celsius

These curves show clearly that, for feeder applications, where temperatures commonly occur between 1200°C and 1280°C, corrosion resistance difference between BPAL/ZA33 and fused cast AZS or Alumina is very low. For campaigns 8 – 12 years, which is the usual lifetime in containers, no need to use fused cast channel blocks.

What about « CAT SCRATCHES »? One of the types of flaws most often encountered in container glass are flaws known as « cat scratches ». Market sensitivity to this flaw is constantly growing, and the flaw affects not only white and flint glass, but also colored glass.

CAT SCRATCHES : definition Vitreous defect, Band of fine parallel cords, Located at the outside surface of the article, Diameter between 5 and 30 µm. Microprobe analysis are done on the cat scratches section

CAT SCRATCHES: refractory characteristics Throat Feeder Working end Melting / Refining Decrease of the glass potential to dissolve defects 1350°C 1550°C Corrosion rate or temperature 1200°C Main characteristic Corrosion Defect formation potential

Based on several decades of experience in expert appraisals of glass inclusions, the research teams at Saint-Gobain SEFPRO have developed highly precise typology of these cat scratches. In 85% of the cases, they are characterized by the simultaneous presence of significant amounts of zirconia and alumina.

Research into the ZrO2/Al2O3 ratio, and the presence of certain elements which clearly show a fusion origin (V2O5 for example in the case of fuel-heated furnaces) have helped identify the origin, which, in 80% to 90% of the cases, is the end zone of the furnace : distributor and feeders. This understanding has led many glassmakers to reduce the use of Zircon-Mullite type materials as much as possible, and generally speaking to reduce the use of any material with significant amounts of zirconia, in their feeders.

As a consequence of these results: A good way to significantly decrease AZS cat-scratches is to remove ZrO2 from « cold-end »: - Working end = JARGAL M / SCIMOS M - Feeders = BPAL

BPAL channel blocks feasability TO-DATE : inside width : 1500 mm 60 ’’ bottom/walls thickness : 150 mm 6 ’’ lenght : 610 mm 18 ’’ inside height : 300 mm 12  ’’ Bigger sizes on request.

ABOUT 500 FEEDER LINES SINCE 1990 BPAL references ABOUT 500 FEEDER LINES SINCE 1990 WORLDWIDE

BPAL

BPAL

BPAL

Baby-food/flint glass/8.5 years campaign BPAL

Baby-food/flint glass/8.5 years campaign BPAL

HPAL LAST DEVELOPMENT (2005-2006) ON BONDED ALUMINA FEEDER CHANNEL BLOCKS HPAL Even better corrosion resistance vs BPAL + Almost no blistering in contact with extra-white soda-lime glass

New alumina product for feeder SEFPRO BPAL HPAL JARGAL M Product Sintered Fused Bulk density (gr/cm3) 3.1 3.2 3.17 Open Porosity (%) 14 17 3 Cold crushing strenght (Mpa) 190 160 200 Chemical analysis Al2O3 93 95 SiO2 6 2 0.5 Fe2O3 0.1 Corrosion resistance index @ 1300°C - 170h 100 115-120 125 Brand Name

ABOUT BLISTERING Beside « cat scratches » , market can also be sensitive to another type of flaw, particulary for white glass: Blisters. In the bonded Alumina range of products for channel blocks one can find differences on blistering, going more deeply in the laboratory testing.

Blistering test “Le Pontet” - 1100°C – 1h : immersed sample in the glass - Scale : 0-1 (very low blistering)  10 (very high blistering) 1100°C – 1h, white / flint soda lime glass (Fe2O3 = 1000 ppm) : No big differentiation HPAL 2 JARGAL M 1 BPAL

New crucible blistering test - 1250°C – 30h or more : glass inside crucible, like in the feeder. - Scale : 10 (low blistering) 100 (high blistering). - Closer to feeder running conditions (T°, air, …) - More blistering differences than in “LP” test. - Need more tests in order to have a large data base

New crucible blistering test 1250°C – 30h – white / flint soda lime glass : More differentiation JARGAL M high Alumina product BPAL HPAL 10 20 30 40 50 60 70 80 90 100

New crucible blistering test 1250°C – 30h – extra-white soda lime glass (Fe2O3 < 300 ppm) : JARGAL M high Alumina product BPAL HPAL 10 20 30 40 50 60 70 80 90 100

HPAL First two orders to be delivered end 2006 New alumina product for feeder 1100 mm HPAL First two orders to be delivered end 2006

NEW PRODUCTS IN THE FIELD OF EXPENDABLES Spouts with Zirchrom 85 inserts ZA33 LB : Low seeding after starting up ZA33HR : Higher thermal shock resistance to prevent fracturation

SPOUT with ZIRCHROM 85 insert ZA 33 (11 % ZrO2) or ZIRAL 61 (19 % ZrO2) Patented high chrome product (83,5 % Cr2O3) with better thermal shock resistance than any other More than 3 times the life of monolithic spouts

Spouts with bonded chrome insert (ZIRCHROM 85) Case story 1 - Cascade bowl ZA 33/ZIRCHROM 85 insert - soda-lime glass CHR - spout temperature : 1225° C - average pull : 80/100 T pd - average ring changes : every 8 weeks - spout change : 8 hours, glass to glass - Service life : 26 months (furnace repair) - ZA33/F.C insert life (average) : about 12 months  

Spouts with bonded chrome insert (ZIRCHROM 85) Case story 2 Pre-heating procedure 6 h 6 h 6 h Daily pull 50 tpd 40 tpd 15 tpd Gob temperature 1170 °C 1180 °C 1280 °C Glass flint flint flint Average job changes/ Months 4 2 7 Service Life 20 to 26 months ZA 33 mono service life 6 to 8 months

Reduction of Seeding after starting up and during production Expendables : ZA33LB Reduction of Seeding after starting up and during production Target : table-ware / flaconnage : - short runs - critical problem : mainly with plungers « seeding » during 1 to 10 h or more after starting, whatever the supplier production losses : 8 to 12 K EUR/hour (EUROPE)

Blistering test for expendables Test conditions : @ 1250°C, after 30h or with a record of the blistering during the test. JARGAL M Refractory sample Glass

Blistering after 30 h Test conditions : Extra White soda lime glass, @ 1250°C – 30h 333 ZA33 LB Index 4 333 : seeding during the starting hours (>30h within conditions of the present test) ZA33 LB : Lower blistering, decreasing with time Index 1 blisters

EXPENDABLES : new product ZA33 Tubes fracturation during production worldwide problem with any type of tube from any supplier : - breakage during heating-up - breakage after 1,2,3 … weeks of production - breakage frequency unpredictable difficulties to differentiate products (333, ZIRAL 61, competition) with standard thermal shock tests (USA thermal shocks test) a specific test has been developed by R & D in order to differentiate products

A new thermal shock testing method Methodology Our methodology is based on the study of the impact of the thermal shock on the mechanical properties of the materials. Samples of the material are first submitted to one or multiple severe thermal shock (rapid heat up to the test temperature followed by a thermal quenching in cold water) and then mechanically characterized (typically flexural strength MOR). The residual MOR of the material is compared to the original strength of the material, and a characteristic ratio is calculated : TR (%) = ( MOR before quenching – MOR after quenching ) x 100 MOR before quenching The lower the ratio, the better the material withstands thermal shocks. Among a family of materials having the same crystallographic properties, the best material thermal shock wise is the one with the lowest MOR loss ratio and higher residual strength after quenching. *MOR=Modulus of rupture

A new Thermal shock testing method Equipment Samples : 120 x 20 x 20 mm bars are sampled and dried in oven @ 110 °C Procedure : Samples are machined, 2 sets of 5 from same bloc 5 samples are loaded in the furnace preheated at the test temperature, and soaked for 20 mn samples are removed from the furnace and immediately quenched in water once cool, samples are dried in an oven flexural modulus of rupture are measured at room temperature on both sets of samples Cold Water box for quenching Electrical furnace

New product ZA33 Whatever the quenching temperature is, the new product presents always lower MOR losses (and so a better thermal shock resistance). *MOR=Modulus of Rupture

New product ZA33 This better thermal shock resistance remains available after 1, 2 or 3 shocks.

  Standard   THERMAL SHOCK 1250 °C- 20°C     New

Saint-Gobain SEFPRO - R & D Saint-Gobain SEFPRO is permanently looking for high perfomance refractories in partnerships with customers thank’s to it’s strong R&D, dedicated to glass industry. Saint-Gobain SEFPRO has the largest Research Center in the world specialising in refractories and their interactions with different types of glass. 140 engineers and technicians in the R&D use the most progressive, multidisciplinary technologies.

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