Product Design
Other Possible Ingredients in Tobacco Substitute Cigarettes
Abstract
Describes the compositions of a variety of fillers, humectants, combustion modifiers, nicotine and other additives as possible ingredients in tobacco substitute cigarettes. Says the preferred fillers contain two or more inorganic salts which provide an acceptable puff number and have a smolder rate comparable to tobacco. Indicates humectants enhance both the packing and burning characteristics of tobacco substitute cigarettes while combustion modifiers often utilize ammonia salts and woodpulp cellulose. States these additives may require aroma / taste modifiers with coloring and ash cohesion agents added to further improve the burn characteristics. Notes that tobacco substitutes may be enhanced by regulating the pH of the material, applying cellulose binders and adding nicotine. Says reconstituted tobacco sheet is problematic in that a nicotine deficit occurs and synthetic or substitute materials which produce reduced particulate matter also show reduced nicotine delivery.
User-Contributed Notes
Fields
- Rank
- 1
- Author
- Sittig, M.
- Hypothesis
- Design changes over timeChanges in cigarette design over the past half century.
- Introduction of new/unconventional productsResearch and development of novel nicotine delivery devices and experimental tobacco designs.
- Mainstream constituent yieldsModification of selected mainstream smoke constituents in response to health concerns.
- Nicotine transport, transfer, and uptakeDesign changes which alter nicotine delivery or effect how the product causes and maintains dependence, including transfer of nicotine from tobacco to smoke, and uptake into the body.
- Smoke constituent testingDevelopment of methods for measurement of gas and particulate yields in mainstream and sidestream smoke.
- Toxicity and consumer intakeDevelopment of scientifically valid procedures for measuring biological activity and neurological effects of nicotine and smoke constituents.
- Use of additivesModification of tobacco products through use of additives and measuring effects on dependence, behavior, and toxicity.
- Use of tobacco processing/ blendsModification of tobacco products through changes in tobacco processing and use of blends, and measuring effects on dependence, behavior, and toxicity.
- Keyword
- Acidity (Low pH)
- Aerosol
- Alkalinity (High pH, Basic)
- Burn rate controlBurn rate is controlled through use of burn additives, density, paper, etc.
- Delivery modification
- Flavor/ Taste (Attribute measure)
- Generally_Recognized_As_Safe
- Heat flux
- Impact (Throat grab)
- Irritation (Attribute measure)
- Metabolite
- Mildness (Attribute measure)
- Nicotine delivery (Smoke nicotine or nicotine yield)
- Nicotine manipulation
- Puff count
- Pyrolysis
- Reaction products
- Sensory response
- Smoke particles
- Smoke pHAcidity/ baseness, scale from 0-14, 7 neutral
- Tobacco taste (Attribute measure)
- Total particulate matter (TPM or Tar)
- Additive
- 1,1,-diethoxy-4-(methylthio)-butane
- 3 ,7-dimethyl-2,6-octadienol
- 4-(methylthiol)-butyraldehyde
- 4-(methylthiol)butanol
- 4-(methylthiol)butyric acid
- 5-methyl furfuraldehyde
- Alginate
- Alkyl valerolactones
- Alpha carotene
- Ammonia citrate
- Ammonia dihydrogen phosphate
- Ammonia orthophosphate
- Ammonia polyphosphate
- Ammonia tartarate
- Ammonium-iron citrate
- Amyris (Amyris Oil or Sandalwood Oil)
- Anise (Anise Extract and Anise Oil)
- Apocarotenoic acid
- Barium oxalate
- Benzopyrans
- Beta carotene
- Beta-hydroxyproprionic acid
- Bixin
- Butanediol1,3-Butanediol
- Butyric acid
- Calcium carbonate
- Calcium orthophosphate
- Calcium sulfate
- Calcium tartarate
- Canthanxanthin
- Caraja gum
- Casein
- Cellulose (Cellulose Fiber)
- Citrates
- Clove (Clove Leaf Oil and Clove Bud Oil)
- Cocoa (Chocolate) (Cocoa Shells, Extract, Distillate and Powder)Composed of nearly 400 identified chemical substances as of 1967
- Cyclohexanones
- Cyclohexenones
- Dextrin
- Diammonium phosphate
- Ethanol
- Ethyl glyoxalate
- Ethylene glycol
- Ferric hydroxide
- Ferric oxide
- Formates
- Galacturonic acid
- Gamma carotene
- Gelatin
- Glyceric acid
- glycerin
- Glycolic acid
- Guar (Guar Gum)
- Gum arabic
- Inositol
- Isovaleric acid
- Lactic acid (Lactic Acid and dl-Lactic Acid)
- Locust gum (Carob bean gum)
- Lycopene
- Magnesite
- Magnesium carbonate
- Magnesium chloride
- Magnesium citrate
- Magnesium sulfate
- Magnesium-iron citrate
- Methyl heptene carbonate
- Nicotine
- Nitrates
- Nitrocellulose
- Oxalates
- Oxalic acid
- Pectin
- Pectinic acid
- Phosphoric acid
- Pivalic acid
- Polyacrylamide
- Polyalkalene glycol
- Polymannuronic acid
- Polyvinyl alcohol
- Polyvinyl methyl ether
- Polyvinylene carbonate
- Potassium chloride
- Potassium nitrate
- Potassium sulfate
- Propyl alcohol
- Propylene glycol
- Sandalwood (Sandalwood Oil, Yellow)
- Sodium alginate
- Sodium cellulose xanthogenate
- Solanesol
- Starch
- Tannic acid
- Tartarates
- Traganth gum
- Urea
- Vanilla (Vanilla Extract, Oleoresin)
- Vinyl carbonate
- Smoke Constituent
- Aldehydes
- Ketones
- Methanol
- Nicotine
- Nicotine salts
- Design Component
- Ammoniated reconstituted sheet (Ammoniated recon)
- Ash appearance
- Ash formation
- Ash temperature
- Blend ammonia
- Blend density (Rod density)
- Bubble coating
- Burn accelerator
- Burn additive
- Burn rate
- Coal temperature
- Combustion temperature
- Flavorant
- Humectant
- Inks/Dyes
- Nicotine content (Tobacco nicotine content)Total nicotine in the unburnt tobacco rod
- Nicotine transfer efficiency (NTE)
- Reconstituted tobacco
- Smolder rate
- Tobacco substitute
- Woodpulp fiber
- Burley tobacco
- Named Organization
- Journal of the American Chemical Society
- Journal of Organic Chemistry
- Tobacco Science
- United States Department of Agriculture (Agency responsible for tobacco price support program)
- Celanese Corporation (Sold materials for cigarette filters)sold materials for cigarette filters
- United States Food and Drug Administration
- I.C.I.
- Brookfield
- Subject
- acids (additives)
- additives
- Ammonia (Additives)
- Blends (Design)
- Burn Rate (Design)
- Cocoa (Additives)
- Experimental Technology (Technology)
- Formulas (Design)
- Humectants (Additives to maintain moisture)
- Irritation (Effects)
- Moisture (Design)
- nicotine technology
- nicotine analogues (Technology)
- Novel Cigarette Devices (Products)
- Particle Size (Technology)
- Product Aging (Design)
- Puff Count (Measures)
- Reaction Processes (Technology)
- Reconstituted Tobacco (Design)
- Sensory Effects—Taste (Effects)
- Smoke Constituents
- Smoke Nicotine (Measures)
- Smoke pH (Measures)
- Smoothness/Harshness (Effects)
- Test/Smoke Constituents (Testing)
- Test/Toxicity (Testing)
- Transfer to Smoke (Measures)
Document Images
~ro5-r~5
i at this temperature for
lose.
)led at 45°C and dropped
the carboxymethylcellu-
urry and dropped through
ne was removed from the
y column 16. In the ace-
from the aqueous acetone
red dryness for entry into
process was taken from
it and water in the dryer.
ioted to be visually free
entration by weight.
: second step reactor 9,
e degree of substitution
of 76%.
~ets or films may be ob-
3).
Tbbacw
Noup Locl-n C6Ypa-0.-tC6-~v
CcO 1q-+u
OTHER POSSIBLE INGREDIENTS
IN TOBACCO SUBSTITUTE CIGARETTES
FILLERS
A composition developed by J. Borthwick and J.F. Morman (91) is a tobacco
substitute based smoking mixture containing a minimum amount of organic
combustible material-and a maximum amount of harmless inorganic filler, the
composition of the filler having been selected so as to impart a commercially
acceptable burning rate to the mixture.
The term "harmless inorganic filler" is intended to include inorganic salts of
some relatively simple organic acids. For example, formates, oxalates, tartrates
and citrates can be used as "harmless inorganic fillers" but these are less satis-
factory than the preferred completely inorganic materials on account of some
undesirable pyrolytic decomposition. This decomposition becomes potentially
more harmful as the size of the organic molecule increases.
The inorganic filler preferably comprises a mixture of two or more such "inor-
ganic" salts admixed in quantities such as to obtain the balance of anions and
cations most appropriate for imparting the desirable rate of combustion to the
preselected amount of the specific organic combustible material incorporated in
the smoking mixture.
By way of example, an acceptable rate of combustion for the smoking mixture
of the process can be correlated to the puff number of 10 to 12 of a machine-
made standard Class B British cigarette containing 1.1 grams tobacco, where
each puff is of 25 ml volume in two seconds, followed by a 58 second rest or
smouldering period and where the 70 mm cigarette is smoked to a butt length
of 20 mm.
The smoking mixture containing such a filler material is intended to be used as
a comparatively safe neutral substrate which burns at a correct rate and has a
low content of relatively harmless organic fuel and a high content of harmless
inorganic filler. Flavorants, drugs, medicaments, materials to improve ash
coherence and color and other additives, including tobacco, can be incorporated
105
as desired to produce the final product sold to the smoker. The choice of the
inert inorganic fillers to be incorporated in the smoking mixture determines the
rate of combustion or how many normal puffs can be had from a given weight
of the mixture.
The art of making an acceptable burning composition involves choosing the cor-
rect proportions of fillers which relatively promote or retard the combustion.
Earlier publications in the tobacco substitute field have suggested that burning
control of tobacco substitutes is exerted through "hydrated metal salts." The
use of such materials as alkali nitrates to improve the "fireholding" of tobacco
blends is well known. It has also been suggested that potassium is an essential
constituent for the proper burning of tobacco.
It has been shown by I.C.I. experience that the water content of tobacco sub-
stitutes has only a relatively small effect on the number of puffs given by a
particular weight of cigarette but may determine whether a composition is glow-
proofed or burns satisfactorily. Hydrated and nonhydrated versions of the same
salt can be used. On the other hand, burning control is strongly influenced by
the nature of the combination of cations and anions present. This does not
imply that the combustion rate is uninfluenced by other considerations such as
fuel particle size or texture of the smoking material.
The art of retarding combustion without making a composition glowproof yet
obtaining the correct puff count from a given weight of smoking mixture by
the use of these inert fillers is another key to the success of the technique. Com-
bustion accelerators are combined with combustion retardants in proportions
which give a desirable rate of combustion for a specific organic fuel and a
particular amount thereof in the mixtures.
It is impossible to specify that more ionic species retard while others accelerate
glow combustion since some fuels do not sustain combustion in isolation. It
suffices to say that with a number of fuels a number of commonly available
acidic anions influence combustion rate and that the order of the retarding
ability of a selection of them is:
formate <oxalate <silicate <carbonate =chloride'<sulfate <phosphate <borate
Isolated exceptions to these orders indicated can, however, be found. Amongst
the cations the order is
sodium = potassium <calcium<magnesium
With the cations it would appear their effect on the burning rate depends on
their basicity, the most signficant change being from calcium to magnesium.
This implies, for example, that in smoking mixtures which are identical except
that A contains sodium sulfate and B contains the same proportion by weight
of magnesium sulfate. A will burn away more quickly. Similarly, in two com-
positions identical except that A contains calcium carbonate and B contains
calcium borate. Composition A will burn away more quickly than Composition
B.
The fillers chosen should not have the power to retain excessive quantities of
water, otherwise glowproofing will result. It is preferable, but not essential, that
I
ker. The choice of the
j mixture determines the
iad from a given weight
,wolves choosing the cor-
etard the combustion.
suggested that burning
ated metal salts." The
fireholding" of tobacco
otassium is an essential
ontent of tobacco sub-
of puffs given by a
er a composition is glow-.
3ted versions of the same
; strongly influenced by
~sent. This does not
r considerations such as
oosition glowproof yet
smoking mixture by
af the technique. Com-
rdants in proportions
organic fuel and a
while others accelerate
istion in isolation. It
commonly available
ier of the retarding
:phosphate <borate
er, be found. Amongst
I
ning rate depends on
:ium to magnesium.
:h are identical except
proportion by weight
Similarly, in two com-
iate and B contains
ickly than Composition
xcessive -quantities of
e, but not essential, that
I
Other Possible Ingredients in Tobacco Substitute Cigarettes 107
the fillers should be insoluble in water. Calcium carbonate has been used as a com-
bustion accelerator balanced against combustion retarding agents such as calcium
orthophosphate (CaHPO42H2O), magnesite (MgC03), light basic magnesium car-
bonate (3MgCO3 Mg(OH)2 3HZO), and calcium sulfate (CaSO4'hH2O). Using
these and other inorganic materials, films can be made which give shred with
filling powers comparable to tobacco shred. Although the above description
illustrates the required balance of ions being obtained by varying the respective
amounts of two inorganic salts, it is possible that a suitable rate of combustion
for a smoking mixture could be attained using an optimum amount of a single
inorganic salt as inert filler.
The main advantages of the smoking mixtures containing such fillers compared
with earlier synthetic products and, of course, tobacco, are as follows:
(a) The lower amounts of organic materials present mean that propor-
tionately lower amounts of the harmful smoke products are formed
__ while maintaining a desirable rate of combustion for the mixture. In
this connection, tests carried out on smoking mixtures of the process
show a reduction in the benzpyrene content of the smoke and a re-
duction in other chemical species known or suspected to be harm-
ful because of the reduced organic fuel content. Furthermore, the .
mixtures advantageously have the same burning characteristics as
tobacco based smoking mixtures. They keep lit and continue td
burn and they have the same rate of combustion as tobacco.
(b) The lower amounts of organic materials present gave rise to lower
amounts of any "odor off notes" which may arise from smoking
these materials (e.g., the burnt paper note of cellulose). Lower
amounts of added masking agents are required in these instances.
(c) The process permits the use of fuels which were previously impos-
sible to use on account of their physical properties, e.g., the high
solubility and nonfibrous nature of sucrose, glucose and glucuronic
acid. The high inorganic content gives body to the films of these
materials which were previously unusable in smoking mixtures.
The filler material employed in Cytrel-type compositions (50) are nontoxic par-
ticulate materials, preferably having an average minimum dimension of from
about 0.2 microns to about 1.0 millimeter. Even more preferably, the particules
will have an average minimum dimension of from about 0.2 microns to about
0.05 millimeter. It is also preferred that the particulate materials have a max-
imum dimension of about 0.25 millimeter, and more particularly, about 0.10
millimeter.
Suitable materials can be selected from organic compounds, inorganic compounds
and the els,no long as the material selected is nontoxic, i.e., pharmaco-
ic Ily inactive ' the sense of significant adverse effects in a causative relation-
log'
ship upon oral ingestion of the substance itself or its combustion products. How-
ever, a reduced delivery of undesirable components is more readily observed when
the particulate material comprises an inorganic compound, an element or a mix-
ture thereof.
While not wishing to be held to any particular theory, it is believed that the rate
of combustion of the compositions is related to the thermal conductivity coef-
ficient of the filler material employed. That is, a material having a relatively
high thermal conductivity coefficient will tend to transfer heat to adjacent par-
ticles, thus maintaining smouldering of the combustible material. Of course,
the density of particles will determine to a degree the preferred thermal conduc-
tivity.coefficient of the final smoking product. An increased particle density
will tend to promote combustion until there is no longer sufficient combustible
material to support smouldering.
Generally, however, filler materials having an equivalent thermal conductivity
coefficient of the dense, particulate filler at 800°C cm2 are preferred in the
process. It should be mentioned, however, that this factor may not be entirely
applicable to decomposable salts, although those salts may have independently
desirable characteristics, as noted below. Thermal conductivity coefficients
are readily obtainable by passing heat through a thin bed of the material to be
tested and measuring the rise in the temperature of the bed.
Also, specific thermal conductivity coefficients are readily available from the
literature. Exemplary coefficients are: 8.2 x 10-3 calories cm/sec °C cm2 for
titanium dioxide, 22.1 x 10-3 calories cm/sec °C cm2 for magnesium oxide,
7.5 x 10-3 calories cm/sec °C cm2 for fused silica, and 5.1 x 10-3 calories cm/sec
°C cm2 for zirconium dioxide. Inorganic compounds suitable as fillers prefer-
ably consist of a cation and an anion.
................... Cations------------...-..-. Anions
Lithium Manganese Silicon Oxides
Sodium Aluminum Palladium Hydrated oxides
Potassium Cerium Tin Hydroxides
Cesium Cobalt Zinc Carbonates
Magnesium Iron Titanium Phosphates
Calcium Molybdenum Zirconium Aluminates
Strontium Nickel Copper Stannates
Barium Rubidium Zincates
Silicates
Carbides
The most preferred inorganic compounds have been found to be the alkali met-
als and alkaline earth metal carbonates, oxides, silicates, alumino-silicates, alumi-
nates, and aluminum hydroxide. Inorganic compounds in their naturally occuring
state, such as dolomite, perlite, magnesite, diatomaceous earth, vermiculite, etc.,
are also suitable in the process.
As previously noted, elements may also be used as filler materials. Preferred
elements include carbon, zinc, magnesium, titanium, aluminum, and iron. While
the filler materials are generally granular in nature, they may also be in fibrous
form. Materials readily useable in fibrous form are fiberglass, mica, asbestos,
metal, metal oxide, and metal carbide whiskers. For the purposes of the process,
thin metal strips such as aluminum shaving are considered to be fibrous. Pref-
erably the fibrous materials will have an average length of from about 0.1 mm
to about 5 mm, and an average minimum dimension of the magnitude previously
noted.
In order to obtain a smouldering rate comparable to tobacco, the aforementioned
ingredients are generally combined in a ratio of from about 85:15 to about
8
0
-ial having a relatively
Per heat to adjacent par-
material. Of course,
)referred thermal conduc-
,-eased particle density
:r sufficient combustible
: thermal conductivity
are preferred in the
:tor may not be entirely
-tay have independently
iduativity coefficients
3d of the material to be
bed.
Iily available from the
ries cm/sec °C cmZ for
r magnesium oxide,
0 x 10"3 calories cm/sec
suitable as fillers prefer-
Anions
Oxides
Hydrated oxides
Hydroxides
Carbonates
Phosphates
Aluminates
Stannates
Zincates
Silicates
Carbides
und to be the alkali met-
~, alumino-silicates, alumi-
in their naturally occuring
is earth, vermiculite, etc.,
,r materials. Preferred
aminum, and iron. While
y may also be in fibrous
erglass, mica, asbestos,
-ie purposes of the process,
red to be fibrous. Pref-
of from about 0.1 mm
f the magnitude previously
)bacco, the aforementioned
~bout 85:15 to about
Other Possible Ingredients in Tobacco Substitute Cigarettes 109
15:85. Preferably, the materials are combined in a ratio of from about 25:75
to about 75:25. Combination of these materials and these ratios will generally
yield a material having a smouldering rate comparable to tobacco when smoked
under analogous conditions; that is, about 3 to 10 mm/min in conventional cig-
arette form. A smouldering rate of this magnitude will correspond to a puff
count of about 12 to 5 in a cigarette smoked on a 60 second cycle, as described
in later examples. It is to be expected, however, that specific compositions will
have different combustion rates, particularly when filler materials having different
thermal conductivity coefficients are used.
It is also within the scope of the process to employ combinations of particulate
fillers in order to obtain the ultimate smoulderi-ng rate desired. Fillers found to
be particularly suitable in controlling smouldering rates include titanium dioxide,
carbon, magnesium oxide, zeolite, silica gel, magnesium silicate, and diatomaceous
earth.
HUMECTANTS
Addition can be made of a humectant to keep the smoking material moist and
pliable and to enhance the packing characteristics as well as the burning charac-
teristics of the product. For this purpose, use can be made of a polyhydric al-
cohol, such as glycerol or a glycol, represented by ethylene glycol, propylene
glycol and the like, inositol, butane diol and the like hygroscopic materials and
mixtures thereof. These materials can be applied by spraying from water solu-
tion onto the sheet or particulates, or by admixture with the treated cellulosic
or carbohydrate material. Addition is made in amounts up to 10% by weight
and preferably within the range of 1 to 4% by weight, when added.
According to H.J. Davis (94) it is desirable to have a humectant present in order
to prevent the tobacco substitute from drying out unduly. Any of the usual
humectants used in cigarette manufacture may be employed; for example, sorbitol,
which is preferred, or other humectant polyhydric alcohol, e.g., glycerol, may be
used. The moisture content of the tobacco substitute may be within the range
of about 5 to 25%, preferably about 10 to 15%, exclusive of the moisture present
as water of hydration.
COMBUSTION MODIFIERS (GLOW CONTROL CATALYSTS)
Among the materials employed heretofore to change the burn characteristics of
tobacco substitute products are ammonium orthophosphate, diammonium acid
phosphate and ammonium dihydrogen phosphate, that is, the mono-, di- and
tribasic phosphates. Although these materials generally act as burn retardants
and therefore impart some improvement in burning characteristics to composi-
tions of tobacco, reconstituted tobacco and tobacco substitutes containing them,
they produce a black ash of very poor cohesive properties, especially in recon-
stituted tobacco and tobacco substitute products. Consequently, there exists a
need for even greater improvement in the burning characteristics, as well as the
other characteristics, such as improved ash appearance and cohesiveness, of these
- combustible materials as they are consumed.
In the formulation of tobacco substitute cigarettes from woodpulp cellulose, ac-
- A
r
cording to H.J. Davis (94), best results are obtained when there are also present
substances which modify the burning characteristics of cigarettes comprising cel-
lulose and hydrated magnesium sulfate used as a combustion modifier. It is es-
pecially desirable to add inorganic compounds, e.g., salts, which help sustain the
burning of the cigarette, particularly during the resting period of the usual smok-
ing cycle, when oxygen is not being forcibly drawn into the burning zone. Exam-
ples of such burning sustainers are potassium chloride, magnesium chloride, potas-
sium sulfate, potassium nitrate, and ferric oxide and hydroxide.
Certain burning sustainers have a particularly desirable additional effect, in that
they increase the rate of burning; examples of such materials are the carbonates
and bicarbonates, e.g., potassium, sodium, magnesium and ammonium carbonate
or bicarbonate. It is believed that the potassium, sodium and ammonium carbon-
ates react with part of the magnesium sulfate to form magnesium carbonate during
the application of these compounds.
The presence of the carbonate during burning is believed to cause an expansion
of the burning zone and is believed to permit more air to penetrate to all parts
of the burning particles, thus promoting more complete combustion. The pres-
ence of the carbonate also causes an expansion of the ash so that the ash is more
porous. In addition, the use of carbonates materially decreases the acid content
of the smoke. Potassium carbonate is particularly suitable since it not only is
a carbonate, but also supplies potassium which is very effective to maintain the
burn. Other burning sustainers which increase the rate of burning, when used in
suitable concentrations, are sodium sulfate, potassium nitrate and similar salts.
The reader should note in a preceding section shown on page 105 on "Fillers" that
the filler materials such as those used in the commercial "Cytrel" tobacco substi-
tute material by Celanese Corp. also exert a strong combustion modifier and glow
control effect.
Inorganic Salts
The glow and ashing characteristics of the smoking material can be improved by
the addition of water soluble alkali metal salts, such as sodium or potassium salts
of low molecular weight hydroxy acids, such as oxalic, citric, maleic, pivalic and
the like organic acids, or carbonates, bicarbonates or phosphates, such as potassium
citrate, sodium citrate, potassium bicarbonate, potassium maleate and dihydrogen
sodium phosphate, and mixtures thereof. In addition, the hydroxy acids, such
as oxalic, citric, maleic and pivalic and the like organic acids may be used. Such
mineralizing agents or ashing ingredients, when employed, may be incorporated
in amounts up to 30% by weight of the smokable material and preferably in an
amount within the range of 1 to 10% by weight.
Modification of thermally degraded cellulosic material by the incorporation of
an alkaline earth metal (calcium, magnesium, barium, strontium, etc.) salt of a
chloride or sulfate enhances the burning characteristics of the resulting smokable
material by control and uniformity of burning rate. Such alkaline earth metal
sulfates or chlorides can be incorporated from solution or dispersion, as by spray-
ing to wet the cellulosic material or by admixture of the salts with the cellulosic
material in solution, dispersion or dry powder form. Improved burning charac-
teristics and control is experienced when the alkaline earth metal sulfate and/or
chloride is present in an amount up to 10% by weight but it is preferred, when
n there are also present
igarettes comprising cel-
.tion modifier. It is es-
, which help sustain the
eriod of the usual smok-
the burning zone. Exam-
agnesium chloride, potas-
roxide.
Iditional effect, in that
rials are the carbonates
I ammonium carbonate
: and ammonium carbon-
gnesium carbonate during
to cause an expansion
penetrate to all parts
ombustion.. The pres-
so that the ash is more
reases the acid content
a since it not only is
ective to maintain the
burning, when used in
ate and similar salts,
je 105 on "Fillers" that
/trel" tobacco substi-
tion modifier and glow
31 can be improved by
lium or potassium salts
-ic, maleic, pivalic and
)hates, such as potassium
ialeate and dihydrogen
hydroxy acids, such
js may be used. Such
may be incorporated
ind preferably in an
-ie incorporation of
tium, etc.) salt of a
he resulting smokable
iIkaline earth metal
fispersion, as by spray-
Its with the cellulosic
wed burning charac-
metal sulfate and/or
.t is preferred, when
,
I
Other Possible Ingredients in Tobacco Substitute Cigarettes 111
present, to make use of an amount within the range of 0.5 to 5% by weight of
the cellulosic material (2).
Alkali Salts of Organic Dibasic Acids
Compositions developed by T.S. Briskin and G.R. Ward (149) are smoking prod-
ucts wherein organic salts of potassium, lithium and copper, and titanium dioxide
are incorporated into oxidized cellulosic materials for the purpose of controlling
burning and for supporting glow between puffs. The potassium, lithium and
copper organic acid salts employed are those of oxalic, lactic, glycolic, diglycolic,
pivalic and tannic acid and in amounts less than 2% by weight.
Alkaline Earth Oxalates
Compositions developed by T.S. Briskin and G. R. Ward (150) are those in which
incorporation of ash forming components is effected in the form of mineralizing
agents preferably developed in situ internally of the oxidized cellulosic fibers by
treatment first with a calcium compound in aqueous medium and then with
oxalic acid to form insoluble calcium oxalate in situ or by treatment of the cel-
lulosic materials with the freshly mixed components which remain soluble in ad-
mixture for a length of time sufficient for internal absorption into the oxidized
cellulosic system.
Compositions developed by T.S. Briskin and G.R. Ward (151) are formulated to
contain a mineralizing agent in the form of a strontium or barium oxalate, lactate,
glycolate, diglycolate or pivalate in an amount within the range of 5 to 40% by
weight of the smoking product and which may have further added thereto a
minor amount of oxalic acid.
Ammonium Polyphosphates
According to M.S. Monte (152), high-molecular weight ammonium polyphos-
phate not only provides better burn characteristics but also results in the produc-
tion of a light colored, cohesive ash when the products are consumed by com-
bustion.
The high molecular weight ammonium polyphosphates employed are white, free-
flowing powders containing about 32% phosphorus. They have relatively low
solubility in water which ranges from about 10 to 15% at 25°C. On the other
hand, boiling can destroy the unique crystal structure of these products which
results in essentially 100% solubility. The ammonium polyphosphates employed
in the practice of the process have a pH of about 5.8 in a 10% aqueous slurry.
The molecular weight (MW) of suitable ammonium polyphosphate is in a range
of from about 20,000 or less to as high as about 1,500,000 or more as determined
by light scattering techniques. A particularly useful ammonium polyphosphate
has an average molecular weight of about 200,000. In general, the ammonium
polyphosphates used in the practice of this technique lose ammonia gradually at
about 215°C and decompose to form phosphoric acid at temperatures in a range
of from 325° to 400°C.
Upon decomposition of yield of about 86 to 87% of the decomposition product
is phosphoric acid. In addition, ammonium polyphosphates suitable for use have
112 Tobacco Substitutes
a specific gravity of about 1.79 and a refractive index of 1.484. The ammonium
polyphosphates are available commercially and a particularly useful material is
P/30.
Whereas the above-cited patent refers to tobacco substitute compositions, another
disclosure by M.S. Monte (153) is for a new smoking composition having improved
burning characteristics which comprises tobacco, an ammonium polyphosphate
of high molecular weight and a natural or synthetic gum binder. The average
molecular weight of the polyphosphate is between about 20,000 and 1,500,000
and the tobacco constitutes about 60 to 95% of the composition.
ASH COHESION AGENTS
Ammonium Polyphosphates
As noted above, M.S. Monte (152) has discovered that high-molecular weight am-
monium polyphosphate not only provides better burn characteristics but also
results in the production of a light-colored, cohesive ash when the products are
consumed by combustion.
Alkaline Earth Metal Salts
Compositions developed by T.S. Briskin and G.R. Ward (154) are smoking prod-
ucts processed to incorporate ash-forming ingredients by treatment of the cel-
lulosic material with a salt forming composition in which the cation is a heavy
metal, preferably calcium, magnesium, barium or strontium, and the anion is an
organic acid group, preferably oxalic, pivalic, tannic, glycolic, diglycolic or lactic,
preferably with subsequent oxidation of the treated cellulose.
Other compositions developed by T.S. Briskin and G.R. Ward (155) contain a
mineralizing agent in the form of a calcium and%or magnesium oxalate in an
amount within the range of 5 to 40% by weight of the smoking product and
which may further have added thereto a minor amount of oxalic acid sufficient
to take up residual metal ions.
COLORING AGENTS
From an aesthetic standpoint, addition of various coloring agents to the smoking
material may be desirable. For example, one may obtain a material having a
color similar to natural tobacco by the addition of materials such as carbon, iron
oxide, food dyes, tobacco extracts, organic colorants, and inorganic pigments,
or mixtures thereof to the basic smoking materials. Of course, contrary to
natural tobacco, one may make the material any color desired. Generally, up
to about 5.0% of coloring agent based on the total composition can be employed.
Preferably, about 0.1 to about 2.0% of coloring agent is utilized.
From the standpoint of appearance, it is desirable for the smoking material to
having a dark brownish color, corresponding to that of rich cured tobacco. The
dark gray material resulting from the thermal treatment of cellulose is not readily
colored by conventional dyestuffs unless employed in undesirable enormous
amounts. It has been found that novel use, as a coloring material, can be made
f 1.484. The ammonium
larly useful material is
ute compositions, another
mposition having improved
nonium polyphosphate
i binder. The average
t 20,000 and 1,500,000
nposition.
iigh-molecular weight am-
iaracteristics but also
when the products are
(154) are smoking prod-
treatment of the cel-
h the cation is a heavy
um, and the anion is an
colic, diglycolic or lactic,
ulose.
Ward (155) contain a
iesium oxalate in an
smoking product and
of oxalic acid sufficient
ng agents to the smoking
n a material having a
:rials such as carbon, iron
id inorganic pigments,
course, contrary to
lesired. Generally, up
position can be employed.
; utilized.
) smoking material to
rich cured tobacco. The
of cellulose is not readily
ndesirable enormous
ig material, can be made
Other Possible Ingredients in Tobacco Substitute Cigarettes 113
of the material triquinonyl which produces a strong orange to brown color with
calcium or magnesium present in the cellulosic or carbohydrate product thereby
to provide a nonleachable color that is effective to convert the thermally treated
product to a rich brown color according to T.S. Briskin (2).
Although the color is preferably a tobaccolike brown or yellow-brown, colors
such as purple and pink may be used. Among the colors are those certified by
the Food and Drug Administration such as FD&C (Food, Drug & Cosmetics
Act) Yellow No. 5; FD&C Chocolate Brown, New Shade B; C.I. 17590; Brown
PG; 20170 Brown Y; 30045 Yellow-Brown K according to H.J. Davis (94).
AROMA AND TASTE IMPROVING AGENTS
The nontobacco smokable products produced by previously known processes do
not have satisfactory organoleptic properties but on the contrary organoleptic
properties which are unpleasant to a greater or lesser degree, e.g., sharpness and
poor aroma in the main and side streams. For example, even tobacco substitute
products with only a low sulfur content, e.g., in the form of sulfates, are found
to produce a smoke with an unpleasant sulfidic flavor. Tobacco substitute prod-
ucts with a high cellulose content which contain the alkali metal, alkaline earth
metal and iron salts normally present in smokable products give rise, when al-
lowed to glow, to a sharp and biting smoke with a cellulosic flavor and leave
behind a persisting astringent effect in the mouth. Moreover, the known non-
tobacco smoking products generally manifest an organoleptic incompatibility with
numerous sorts of tobacco when blended with them.
For example, the addition of substances such as magnesium citrate or calcium
tartrate which according to the prior art, may be added to a smoking material
to improve its glowing properties, results in smoking products which are com-
pletely unsatisfactory in their organoleptic properties. The sharpness of the
smoking products is not sufficiently reduced. A particularly disturbing feature
of such a product is that the burning of the cellulosic material in it gives rise to
an unpleasant flavor (cellulosic flavor) and to a smell of burnt paper, which are
practically the same as the smell and flavor of burning pure cellulose. These
products are therefore not economically utilizable as smokable products or as
additions to smokable products according to T. Eicher et al (156).
As pointed out by T.S. Briskin and G.R. Ward (157), an undesirable taste and
aroma is observed upon burning a smoking product containing heavy metal ions,
especially in the presence of oxidized cellulosic material. Even trace amounts
of calcium, magnesium, aluminum, iron, cobalt and copper ions, especially in
the presence of the oxidized cellulosic material, give a sharp acidic odor when the
smoking product is used in a cigarette, cigar or pipe.
These metallic ions form corresponding metal salts with polyuronic acids, such
as are formed upon oxidation of the cellulosic material. These polyuronic acid
salts of the residual heavy metal ions are thermally unstable and break down
during burning of the smoking products to give various odorous aldehydes, ke-
tones, acids and the like.
. t
114 Tobacco Substitutes
Heavy Metal Fixatives
A composition developed by T.S. Briskin and G.R. Ward (1,57) is designed to fix
the ions of the heavy metals present in the smoking product in a manner to in-
activate the heavy metal ions as factors contributing to any bad taste, odor or
aroma of the smoked product.
The important concept resides in a method and means for fixing the ions of
heavy metals by reaction with a suitable acid to form a thermally stable salt; in
which the reaction to form the salt with the acid takes preference over salt for-
mation with polyuronic acids; in which the salt that is formed is more thermally
stable than the corresponding salt of polyuronic acid so that the metal ions will
remain tied up while the oxidized cellulosic material burns out of the smoking
product; and in which a small amount of fixing acid is intentionally introduced
into the smoking product as insurance for typing up residual metallic ions which
might remain or which might subsequently be released.
While the concepts of this process have application primarily to oxidized cellulosic
material, it will be understood that this concept of fixing objectionable heavy
metal ions with acceptable acids to form thermally stable salts that resist deteriora-
tion during burning will have beneficial use in any cellulosic material used or
adapted to be processed into a smoking product.
As the fixing acid, it is preferred to make use of oxalic acid, but use can be
made of other acids such as pivalic acid, tannic acid, lactic acid, glycolic acid,
diglycolic acid and the like. The acids are employed in aqueous solution contain-
ing from 0.1 to 10% by weight of the acid and preferably in an amount within
the range of 0.1 to 1% by weight. When the treating solution contains more
than 10% by weight acid, the oxidized cellulose tends to be taken into the solu-
tion. This undesirable feature can be obviated by incorporating an amount of
alcohol, such as methyl, ethyl, propyl alcohol, in the aqueous medium in amounts
up to 25%. In fact, use of an alcoholic solution is desirable when use is made
of treating solution containing more than 4% by weight acid.
The acid solution is introduced into the cellulosic material in an amount to
provide sufficient acid to satisfy the heavy metal ions present in the cellulosic
material or the oxidized cellulosic material. The amount introduced is determined
by odor tests with the pyrolyzing cellulosic material according to the impurities
present in each batch. Application can be made by spraying onto the cellulosic
material or the cellulosic material, especially when in the form of a paper web,
can be passed through the solution for pickup by absorption of the desired
amount of acid.
Treatment with the acid solution to fix the metallic ions is preferably made at
a temperature within the range of 0° to 30°C. There is no need to heat beyond
30°C since the oxalic or other fixing acids are readily soluble in the aqueous me- ~
dium in the desired proportions. Salt formation by the metallic ions and acid tos
takes place quite rapidly under the conditions described without the need for
heat or long reaction time. It is important to avoid excesses of free fixing acid ~
in the treated product since such excesses tend to impart an acrid taste to the ~
smokin
roduct
.
g p
