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Feature Article
Stretch Tio2
By Lilli Manolis Sherman, Senior Editor
With prices going up and up, and supplies getting snugger, it's time to re-examine the available extender
pigments that can make TiO2 go further.
The 10-year run of cheap and plentiful titanium dioxide is over. While prices are still some distance below the
levels of 1989, and no actual shortages are in sight, there is every indication that TiO2 prices will climb farther
and delivery lead times will continue to grow longer. All this adds up to a revival of interest in white mineral
fillers that can be used as partial TiO2 replacements to extend supplies and minimize costs.
While nothing can match the opacity of prime rutile TiO2, some white, bright mineral fillers and alternative
grades of TiO2 can offer some relief from rising prices. Other ways to get more value out of white pigments
include new TiO2 grades that offer improved dispersion and durability.
Although today's TiO2 prices are 9-14% below those of 1989 (and 20-24% lower than '89 in constant dollars),
producers say that is still below the level required to support new investment in future capacity.
Though worldwide supply is still ample, there are signs of reviving market demand in Asia, and supply in North
America is becoming a bit more snug. Market demand has been particularly strong in the last few years. For
example, while TiO2 consumption in 1998 was down by about 3-5% globally over the previous year, it was up
about 1% in North America following growth of 7-9% in 1997. Domestic consumption this year will grow by 2-
3%, according to IBMA's Fisher. Producers' plant utilization rates are in the 90% range.
TiO2 suppliers expect their industry to become less cyclical and less subject to price volatility as a result of the
consolidation and globalization that has been taking place among both pigment suppliers and buyers. Still, with
global demand projected to keep rising over the next couple of years and no major capacity additions planned,
other than debottlenecking, supply is expected to get tighter.
One area of disagreement among plastics-color experts is how to describe the mechanism of TiO2 extension.
Bill Kearns, technical specialist at M.A. Hanna C olor, expresses one school of thought when he says TiO2 can be
extended by separating the typical 0.2-micron particles of the pigment with larger particles of a less expensive
material. This "spacer" approach reportedly has been effective in coatings, but is a topic of debate in plastics.
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material. This "spacer" approach reportedly has been effective in coatings, but is a topic of debate in plastics.
The critical difference apparently is that in thin coatings, the volume fraction of TiO2 pigment can be above
50%, but it is much lower in plastics.
Victor Mimeault, technical v.p. of Ampacet C orp., notes that a white concentrate containing 50% by weight TiO2
has a pigment volume fraction of only 12-14%. "At such low volume fractions, the TiO2 particles are already
apart, so the spacers cannot and do not contribute to opacity."
Seconding that view is Bill Lashway, plastics services manager at Millennium. "Due to the low final loading--2-
4% by weight--in most film applications, adding sufficient extender to physically space out the already widely
scattered TiO2 would compromise the film's physical properties and add cost." He adds that extenders may be
more beneficial in heavier films and molded parts, where product thickness adds to opacity.
Engelhard C orp. has done extensive work in evaluating two of its specialty clays as TiO2 extenders in color
concentrates. ASP 170 is a fine-particle (0.4-micron) hydrous kaolin said to offer effective spacing of TiO2
particles for excellent color and opacity retention. Ultrex 96 is a special calcined kaolin with 0.9-micron median
particle size. It reportedly has the highest brightness (96 GE brightness) of any kaolin-based extender. These
two pigments cost about 20% and 40% as much as TiO2, respectively.
Interesting results were observed when these pigments were evaluated as partial replacements in a typical
50%-TiO2 white LLDPE concentrate. In injection molded parts, replacement of 10% TiO2 with Ultrex 96 retains
both good color and opacity (Table 2). Even at a 20% replacement, very good color is achieved, with only a
light drop in opacity. ASP 170 provides good color at lower levels of substitution (5%), but does not provide as
much opacity as Ultrex 96.
In blown film (Table 3), 5% and 10% replacements of TiO2 with ASP 170 retain color and opacity equal to those
of the all-TiO2 control. At 20% replacement, the resulting film shows excellent color with only a slight drop in
opacity.
Engelhard also reports that Ultrex 96 can replace up to 20% of the 7 phr TiO2 used in white PVC siding. Initial
whiteness is reportedly equal or slightly better than with all TiO2. Initial yellowness is equal to the TiO2 control
at a 10% replacement level, while both accelerated and actual outdoor weathering tests show that Ultrex 96 at
10% replacement performs even better than the TiO2 control.
One caution is offered by David Skelhorn, technical director of mineral supplier EC C International. He says
formulators must remember that "kaolin clays and calcium carbonate do not provide TiO2's inherent uv
stability."
Blending rutile and anatase TiO2 grades to reduce cost is not widely recommended. Besides lower opacity,
anatase can result in color problems, according to John Prichard, manager of plastics at DuPont. On the other
hand, anatase TiO2 is actually necessary in some formulations, he notes. For instance, anatase grades do not
quench fluorescent whitening agents as much as rutile grades. Another example of where anatase pigments are
used is in polyolefin masterbatches for extrusion coating of photographic film.
Use of lower-priced, "wide-spec" rutile TiO2 grades that are not pure white are also an option for partial TiO2
replacement. Such a product is being imported from Ukraine by K&T Export/Import. C alled Titan 2, this
0.3-micron grade is being evaluated by some color masterbatch suppliers and compounders. It sells for 78-
82�/lb. K&T says it can provide good whiteness and acceptable opacity when substituted for 15% (or more
for non-critical applications) of the standard TiO2 in a formulation.
Another "alternative" TiO2 is a synthetic rutile TiO2 from Hitox C orp. Buff-colored Hitox pigment has slightly
larger and more irregularly shaped particles than typical rutile TiO2. It sells for 68�/lb, and can substitute for
up to 45% of standard TiO2 in products that require opacity but do not have to be pure white.
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More white candidates
Barium sulfate is used to some degree as a TiO2 extender, but its price differential is not as advantageous as
those of kaolin and calcium carbonate. J.M. Huber has introduced a new surface-treated barium sulfate that is
said to perform well at up to 50% replacement of TiO2. C alled Huberbrite Interlok, it has been used by one
extruder of flexible PVC to replace all the TiO2 in his formulation. The product has an average particle size of
1.0 micron and appears to be promising for polyolefin uses as well.
Other alternative white pigments include lithopone (a co-precipitate of barium sulfate and zinc oxide) and
technical-grade zinc oxide. Lithopone is not much used in the U.S. because it tends to react with some grades of
TiO2, resulting in a noxious odor. Zinc oxide has been used during past TiO2 shortages, but degradation of
plastics such as polypropylene has severely limited its use.
While cautious in sharing information on TiO2 extenders they may use, major color-concentrate manufacturers,
such as Ampacet, C lariant's Masterbatches Div., M.A. Hanna C olor, Teknor C olor, and WedTech indicate they
are always on the lookout for better alternatives, particularly if they offer moderate opacity.
Kearns of M.A. Hanna C olor says a specialty fine-ground calcined kaolin with a particle size of 0.9 micron can
typically replace TiO2 at levels of up to 15% while retaining acceptable brightness (96% GE Brightness) and
only a slight loss of opacity. Fine-ground barium sulfate with a particle size of 8.5 microns can also be used at
about the same TiO2 replacement level, but it will have lower brightness (93%) and will cost more, he notes.
Ampacet C orp., says Mimeault, approaches extenders as a way to cut cost by minimizing resin use rather than
TiO2. For example, as an alternative to the usual 50% TiO2/50% PE white masterbatch, Ampacet offers one
containing 50% TiO2, 25% calcium carbonate, and 25% PE. Another formulation contains 40% TiO2, 30%
lithopone, and 30% resin. Mimeault says it offers almost the same opacity as a 50% TiO2 masterbatch and is a
"gentler, softer white" because it is less abrasive. These two masterbatches sell for around 7-12% less than the
standard 50% TiO2 product. (A different way to get more for your money and save resin cost is to use a more
highly loaded concentrate--e.g., 80% TiO2, advises Ampacet's director of marketing Frank Iannotti.)
WedTech business manager Rick Tizzard says, "The extended white most commonly seen in the film industry
contains 50% TiO2, 20% calcium carbonate, and 30% carrier resin." WedTech's version, grade 1022, is aimed
at grocery sacks and typically costs 1-2�/lb less than standard 50%-TiO2 masterbatch. Although calcium
carbonate does little to improve opacity, it can add bubble stability in blown film, he notes. The trade-off, he
says, is that TiO2 extenders add density to the finished product, which can offset some of the savings.
Wedtech has also developed a new white masterbatch that uses a proprietary extender. WT-164 masterbatch is
geared for white t-shirt bags and is said to give good opacity. The company recommends it as an alternative to
a 50%-TiO2 masterbatch for a saving of about 2�/lb.
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