SIZING OF PAPER

By

Dr. Chhaya Sharma

INDIAN INSTITUTE OF TECHNOLOGY, ROORKEE SAHARANPUR CAMPUS, DEPARTMENT OF PAPER TECHNOLOGY SAHARANPUR 247001 (INDIA)

INTRODUCTION
Most grades of paper and board, excluding those used for tissues and hygiene applications; need to be resistant to wetting and penetration by liquids. Sizing is defined as a process wherein chemical additives are introduced to provide paper or paperboard with this resistance, viz., to make it more water-repellent. When chemicals are added to the papermaking furnish and retained on the fibers by appropriate means in the wet end of the system, the process is termed "internal sizing" , when paper is internally sized the sheet remain porous. Surface sizing is carried out by applying a size to the web surface at the dry end of the process. Surface sizing seals off the surface pores of the sheet and therefore must be used for products requiring a vapour barrier. Until the 1980s, the basic method applied in the majority of paper mills utilized rosin plus alum for internal sizing, but conversions to synthetic cellulose-reactive systems based on either alkyl ketene dimers (AKD) or alkenyl succinic acid derivatives (ASA) have more recently become increasingly typical.

Internal sizing is an important part of the wet end chemical operations on a paper or board machine.
The purpose, as stated above, is to modify the surface of the fibers to control penetration of aqueous liquids into the paper. The penetration usually correlates with the absorbency, repellency (hydrophobicity), and spreading of the aqueous liquid concerned. Control of these important properties can be required for three purposes:

1. Control of the penetration rate of the aqueous phase in a converting operation such as size press treatment or coating. 2. Control of liquid absorption or wetting in a printing process; and 3. Control of the serviceability of many grades of paper and board, e.g., milk carton, packaging papers, wallpaper, etc.

The degree of sizing of the product remains as constant as possible until ultimate consumer use or converting.
Although in most cases the purpose of internal sizing is to prevent quick penetration by water, occasionally it is needed for the control of penetration of other fluid types, e.g. acids, alkalies, oils, alcohols, chemical dispersions, etc.

It should be noted that good resistance to one fluid does not necessarily mean resistance to another.
The applicability must be ascertained by specific tests using the fluids concerned.

An efficient sizing should meet following requirements:

It should produce fibre surface having low tendency to become wet i.e. the contact angle between water and the sizing material should be large. The sizing material should be uniformly distributed on all fibre surfaces to give water repellency throughout the paper structure.

Efficient methods should be available for fixing the sizing material stably to the fibre surfaces.
The sizing material should not react with water. The sizing material should not adversely affect the production process or the properties of the paper.

BASICS OF WETTING AND PENETRATION Wetting

The terms "wetting," "repellency," and "penetration" are all relative ones. There will always be some, at least slight attraction between a liquid and a solid in contact. No surface actually exercises a repulsive force upon a liquid. The practical distinction between a surface wetted by water and another not wetted is that the former allows water to spread over it as a continuous film, while the water on a non-wetted surface rests in small, separate droplets.

At the air - water - solid interface, these droplets form a contact angle. The primary factor that influences the rate of liquid penetration is the contact angle formed between the impinging liquid and the fiber surfaces the action of a sizing agent is to provide the fiber surfaces with a low energy coating that discourages aqueous liquids from moving extensively.

A phenomenon of importance in wetting, particularly in paper sizing, is the preferential orientation of some organic molecules on solids. These so-called amfipatic substances usually have relatively long carbon - carbon chains (mostly 10-18 carbon atoms), which have polarity differences at both ends. Because of this, the molecules preferentially orient themselves during adsorption to yield the lowest free energy state. The polar portion of the molecule will orient toward the solid's surface, leaving the nonpolar (hydrocarbon) portion facing out.

A liquid placed on the solid will contact the hydrocarbon layer to display a high contact angle and poor wettability. Paper sizing chemicals are designed to function in this amphipathic way.
However, unless well anchored to the solid, the adsorbed molecules can reorient themselves when contacted with polar liquids such as water, with increased wettability and loss of sizing. Significant advances in sizing permanence are due to better methods to anchor the sizing material to cellulose fibers, and affecting the correct orientation in an irreversible way.

Penetration
The penetration or absorption of water into the structure of paper can occur in several different ways:
By filling of pores and roughness pits at the surface By penetration of liquid through capillaries, pores, and cavities in the sheet By migration along fiber surfaces (through fiber-fiber contact = interfiber penetration) By absorption into and diffusion inside fibers = interfiber penetration By gas-phase migration (viz., by evaporation-condensation) By a sorption-desorption process. Chemisorption is also possible.

Owing to the dynamic character of these alternatives, they usually cannot be distinctly separated from each other although one mechanism can be dominant.
This depends upon the properties of the liquid (water), sheet structure, ambient conditions (e.g., pressure, temperature), time available for the penetration, and the hydrophobicity of the sheet components (primarily the fibers). Moreover, it should be taken into account that the sheet structure changes during the course of the penetration. Thus water gives rise to disruption of hydrogen bonds, relaxation of fibers, swelling of the network, and dimensional changes of pores and capillaries. Quantitative treatment of penetration phenomena is therefore difficult. As in the case of contact angles, the attempts made relate to idealized conditions.

Factors affecting penetration

Paper properties affecting the manner of penetration of a liquid (e.g., water) and its absorption route are
The degree of sizing (hydrophobicity) of the fibers. The inner structure of the sheet, viz., pores and cavities. The structure of the paper surface.
The more hydrophobic, that is the more strongly sized the fibers are, the more slowly the sheet structure absorbs water or water-based phases such as dispersions because penetration then to an increasing extent will occur via fiber - fiber contacts and by sorption phenomena. As the passage of liquid through the paper not only depends upon the hydrophobicity of the paper but also upon the surface tension of the liquid and its chemical nature, even relatively small changes in water quality can affect penetration significantly. Typically, the lower the surface tension of a liquid, the easier it can penetrate the paper by a sorption-desorption mechanism. At the same time, chemicals present in the liquid will be sorbed on to the fibers, especially if the surface tension is lower than about 50 dyne/cm. With time, this results in continuous change of fiber hydrophobicity, as well as continuous change of the surface tension of the fluid as it penetrates the paper.

On the other hand, the liquid can penetrate the paper by passage through pores and voids and, in principle, can almost entirely bypass fiber- fiber routes. In this case, the penetration primarily depends upon two factors: the average pore radius and the surface tension of the liquid. The smaller the size of pores in a paper, the lower must the surface tension is to make penetration through the pores possible. Thus the surface tension of the liquid not only determines the speed at which pores are filled and absorption proceeds, but also whether penetration proceeds along fiber-to-fiber routes.

The properties of the paper surface can be modified in several ways, the most important being surface sizing, coating, and calendering.
If, for example, the pores at the surface of a base paper are small, a surface treatment that produces a film can almost fully close the pores. This exercises an influence upon the absorbency of the paper, regardless of any liquid-repellent sizing. Thus a paper surface sized by application of starch or polyvinyl alcohol can resist penetration of water over a relatively long period of time despite its hydrophilic character. The purpose of internal sizing of the base paper, in this case, would be to preclude excessive absorption of surface size in the size press.

Thus in the testing of surface sized, coated, or even calendared paper, the rate of penetration of a test liquid through the surface layer can be different from the rate (even slower than) in the inner structure of the paper. Although the slope of time-penetration plots through the middle of an untreated base paper and of the same paper after surface sizing are practically the same, the slopes of the two plots through the surface layers are significantly different with slower penetration after surface sizing as indicated in below:

Effect of surface sizing with starchy upon the penetration of HSK ink.

The way of forming and finishing the paper (e.g., refining, pressing, calendering) can affect the degree of sizing considerably. For example, pore volumes can obviously vary depending upon the way paper or board has been manufactured. In order for a liquid to penetrate through the sheet, it must pass through interconnecting capillary pores. If the pores are sufficiently small to even slightly resist free penetration and the sheet structure is such that fiber-fiber contacts are more abundant in the x-y plane than in the zdirection, the water preferentially tends to move in the x - y direction.

INTERNAL SIZING
The purpose of internal sizing is to modify the surface of paper to control water penetration, in order to either limit the pickup in a converting operation, e.g., at the size press or coater, or to impart water repellency to the end product. The three most common internal sizing agents currently being used and treated in this text are rosin systems, alkyl ketene dimers (AKD), and alkenyl succinic anhydrides (ASA).

Rosin sizing at acid pH

Internal sizing with rosin at acid pH (usually pH 4-5), assisted by aluminum sulfate the basic method upon which the performance of sizing processes are judged. Historically, rosin sizing has offered many advantages to the papermaker (e.g., versatility, reliability, predictability), and neither onmachine sizing nor repulpability are problems.

Developments during recent decades enable most commercial products today to contain chemically modified or fortified rosins.
These improvements have contributed to the fact that rosin sizing at acid pH is still a popular way to obtain resistance to aqueous penetration, although conversions from acid to neutral or alkaline pH in papermaking in many cases have necessitated the use of special sizes such as alkyl ketene dimer or alkenyl succinic anhydride.

Rosin
Rosin is a complex mixture of resinous substances occurring in the natural oleo-resin of softwood.

The composition of rosin varies according to the source and converting procedures applied.
Some 87%-90% of the rosin is a mixture of diterpene acids, termed resin acids. Other rosin components are about 10% neutral material and a small amount (3%-5%) of fatty acids.

Due to the structural difference between the acids, the pimaric type isomers are more stable than the abietic ones. The stability of the resin acids can be improved by catalytic dehydrogenation. The hydrophobic tricyclic portion of the molecule and the carboxyl group, making up an amfipatic structure, play important roles in rosin sizing. The hydrophobic part, if properly oriented, will impart resistance against aqueous penetrants.

Rosin sizes
To improve sizing efficiency, most rosin preparations today are reacted with 8%-15% maleic anhydride or fumaric acid to produce a tricarboxylic acid adduct.

The product obtained is called fortified rosin.

The two carboxyl groups added are stronger acids than the initial single abietic carboxyl. This means that a stronger electronegative character is imparted to dispersed or emulsified rosin particles, resulting in a smaller particle size thought to be favorable in the precipitation and sintering of the size. Nevertheless, the mechanisms of rosin sizing remain unaffected by fortification.

Since rosin itself is water insoluble, it is necessary to convert the rosin to modifications dispersible in the aqueous papermaking system. This is accomplished in two ways as follows: By saponification of the rosin with alkali hydroxide to produce a water-soluble soap, viz., an alkali resinates. By producing a finely divided dispersion of free resin acid, with sub-micron particle dimension. The stability of the product usually must be achieved by the aid of a protective colloid.

Mechanisms of rosin sizing

Papermaking fibers in water suspension behave like a polyanion on account of acidic groups present in their chemical structure. Rosin, whether in soluble form as an alkali resinate, or in the insoluble dispersed free acid form, is also anionic and consequently has practically no inherent affinity for cellulosic or lignous fibers. The rosin must be "precipitated," i.e., deposited and fixed, onto the surface of the solid phase by the aid of aluminum sulfate ("papermaker's alum" or simply "alum") or a cationic alumina floc. However, the development of sizing by using rosin and alum depends upon a number of chemical and physical factors which must be taken into account and controlled for successful operation. Surface-chemical conditions very often pointed out as prerequisites for successful development of sizing are included in the following four steps

An aluminum resinate size precipitate must be prepared which potentially will exhibit low free surface energy and thus a high degree of water repellency, that is, a high contact angle with a drop of water. The size precipitate must be retained or fixed as uniformly as possible upon the fiber surface. The fixed precipitate must be oriented properly on the fiber surface. The resinate on the fiber surface must be convertible into a stable low free energy film which remains intact even though fluids are brought into contact with it.

These criteria are required for both dispersed and soap sizes. In both instances, the rosin must react with aluminum species to form an Alresinate. The formation of the proper type of Al-resinate can be considered as the most critical phase in the sizing procedure.

Quantities of Rosin Size and Alum

The rosin size is an expensive chemical and should be used only as much as is necessary. Theoretically about 0.1% rosin on fibre weight is required to provide a monomolecular layer covering the fibre surface. In practice it is impossible to achieve a completely uniform distribution of the sizing material, and about 1.0 % is considered necessary to give satisfactory sizing. Further addition of rosin sizing gives only a marginally increased hydrophobicity to the paper. From a theoretical point of view, even the required amount of alum is quite small, about the same quantity as of rosin size. In practice the added amount of alum normally is about twice the amount of rosin size.

Effect of Stock Composition on Rosin Sizing

Carbonylic and phenolic hydroxide groups are beneficial to the sizing process. Kraft pulp responds more strongly than the sulphite pulps to the sizing. Within one type of pulp unbleached grades are easier to size than the bleached ones. Pulps of high cellulose content such as cotton linters are hard to rosin size. As the rosin size is to cover the fibre surfaces one might expect the required amount of size to increase proportionally to the fibre surface area produced during for instance beating. In practice, however, the increase in rosin size requirement during beating only improves the effect of a given amount of rosin sizing. Further beating reduces the sizing somewhat. Fillers harm the rosin sizing. The filler particles are hydrophillic and compete with the rosin size particles to be fixed to the fibres.

In the wire section the rosin sizing may be harmed by too rapid sheet drainage.

At this point of the process, the rosin particles are relatively weakly fixed to the fibre.
High drainage rates therefore may wash the rosin sizing particles away from the fibres. The effect is most pronounced at the wire side, producing a two sided rosin sized sheet. Increased paper machine speed or reduced headbox consistency established for improving the sheet formation, may thus harm the rosin sizing of the produced paper.

Too high water flow speed from the web in the press nip may adversely affect the sizing.
The dry solids content level at which the paper leaves the press section may influence the final sizing degree. A very high moisture content in the paper when entering into the dryer section may be very disadvantageous. Optimum dryness content is about 42%. The rosin size particles are loosely fixed to the fibres at low dryness. Fairly high drying speed here may cause the size particles to be pushed away. Because of this the temperature on the first few drying cylinders should be low.

From about 55% dryness the rosin size particles will be sufficiently fixed.
This problem is especially pronounced for MG paper where the drying is especially rapid and efficient. Normally, the degree of sizing of the glossy paper side is poorer than that of the outer MG paper side.

Increased degree of process water recirculation raises equilibrium level of dissolved material in the white water system, affecting the sizing adversely. As already mentioned, alkali earth metals precipitate the resin acids into insoluble salts. Hard process water thus harms the rosin sizing. Super calendering the paper may reduce water repellency of a given sized paper.

Effect of Rosin Sizing on Paper Properties

The rosin size material has yellowish shade. Papers from bleached pulps therefore will have their brightness somewhat reduced, normally 1-2%. Alum may also reduce brightness by precipitating other discoloured materials present in the suspension, onto the fibres. The paper strength properties are marginally affected by the rosin sizing because of slight reduction in fibre to fibre binding. The permanence of the paper is adversely affected by rosin sizing due to its acidic nature. Acidity combined with the moisture content present in paper causes acid hydrolysis of the cellulosic chains; the degree of polymerization of the cellulose gradually drops. Over a long period of time the paper become brittle and loses strength.

Rosin sizing causes the paper to be water repellent and not generally repelling to all liquids. Today writing is often made using ball and felt pens, where the ink is dissolved in organic liquids. The rosin sizing does not provide paper with any significant resistance towards penetration of these liquids.

Some factors affecting sizing efficiency

Sizing efficiency in a multi-component furnish depends not only upon alum and rosin dosages but also upon the distribution and location of the size on the surfaces of furnish components. Size distribution and consumption are affected by a number of processing conditions such as dosage points, chemical environment (e.g., pH, dissolved substances, concentrations of size and other additives) and furnish composition (components, consistencies). These vary from mill to mill and even from one paper machine to another within a mill and efficient operation depends upon empirical experience gained on each individual machine. Sizing efficiency can be poor under some adverse conditions, such as high water hardness, viz., dissolved calcium and magnesium ions, unfavorable alkalinity, or interfering ions or "trash" in the system.

Thus calcium and magnesium ions compete successfully with aluminum not only in reactions but over a wide pH range, forming with rosin cheese-like agglomerated precipitates lacking hydrophobic properties. Aluminum required to retain rosin can be consumed more rapidly by other additives or by anionic trash. It is advisable in these instances to dose a sufficient quantity of alum first, to ensure that the rosin added later reacts with the aluminum rather than with hardness or interfering substances. This is known as reversed sizing procedure. On sizing with dispersions, a reversed procedure is actually the only efficient way of introducing the chemicals since aluminum is required to create cationic locations for attachment of the dispersed resin acid particles.

Overused alum returned to the system with recycled white water can cause problems by agglomerating rosin size added to a chest where mixing is poor and furnish pH is off optimum. Part or all of the size can coagulate in an undesirable condition that cannot be corrected at a later stage of the process but might instead participate in deposit formation (e.g., plugging of wires, felts, and suction box covers).

Sizing is affected adversely by long hold times and high temperature of the stock.
Both factors give rise to hydrolytic decomposition of aluminum resinates, as well as changes in the structure of alumina in the wet end, and should be taken in account on the basis of practical laboratory tests. For example, exposing alumina for 10 minutes to 65oC temperature reduces its available cationic charge by 70%.

The stability of a rosin dispersion decreases with temperature; this can in severe cases result in contamination of the paper machine by deposited resin acid. Temperature resistant, low-viscosity liquid rosin formulations are available on the market. Sizing like most wet end operations involves adsorption/precipitation at surfaces, and participation in the interactions depends upon available free surface areas. Fines and fillers have large hydrodynamic surface areas and capture a disproportionate amount (compared to their weight-%) of alum and size. In experiments carried out with radioactively tagged free acid and soap sizes, filler separated from the sized furnish picked up 2-3 times more alum and adsorbed even 20 times more rosin than the coarse fiber fraction. The adsorption ratios, however, did not follow strictly the ratios of surface areas. It was concluded that the size probably forms thick multilayer on fines and fillers, while, on coarse fibers, it appears as a more efficient thinner film.

Soap sizes perform relatively more efficiently in a highly filled furnish and on machines operating with low fines/filler retention.
As a general rule, the more fillers or fines there are in the furnish, the worse the sizing value is in comparison with unfilled furnish.

However, the amount and type of filler affect efficiency because different fillers have different specific surface areas.
Titanium dioxide seems to be more difficult to size than clay. In principle, refining should not be carried out after the dosage of sizing agents because new fines will be created and fresh unsized fiber surfaces are exposed. More size would then be required to achieve adequate water repellency. On the other hand, moderate beating can improve sizing results on account of the effects influenced upon sheet structure - viz., increasing paper density, improving formation, and decreasing pore radii, thus retarding penetration.

By experience obtained in numerous paper mills, "pure" pulps are hard to size, while those containing residual lignin, carboxyl groups, and/or hemicelluloses interact with alum readily and size easily. Despite unbleached softwood pulp by experience being easy to size, lignin sulfonates tend to inhibit rosin sizing. The ease of soap sizing of unbleached pulps can be accounted for by the presence of small but effective amounts of chelating colloids or hydroxy acids which impart to the size precipitate special structural features needed for an optimal sizing composition.

This is backed up by the finding that high - a bleached cellulose pulp, difficult to soap-size otherwise, becomes easily sized after addition of citric acid, a tribasic hydroxy acid. Some support is obtained also from the mill experience that bleached pulps are best sized with rosin dispersions. The dispersion mechanism, starting with wet end adsorption of the resin acid and alumina without actual chemical reaction at that stage, does not require any chelating or hydroxy acid complex for the development, in the next stage, of a hydrophobic film by melting the resin acid followed by reaction with alumina and orientation under the influence of heat.

SIZING AT NEUTRAL OR ALKALINE pH

Several Factors have influenced the decisions, the primary consideration in changing from acid(pH 4--5.5) to neutral-alkaline (pH 6.5-8.5) Papermaking relates to the possibility of processing furnishes with a content of calcium carbonate. Calcium carbonate is today the filler of choice in fine paper grades. High-opacity/high-brightness pre-coat.

Some potential advantages of neutral/alkaline papermaking.

Process benefits Calcium carbonate can be used as filler and in coating Reduced energy consumption in refining and drying Higher drainage rate, easier drainage Less buildup of inorganic soluble Specific water consumption can be reduced Cheaper furnish, filler substitution for fiber Less corrosion

Product benefits Improved strength properties. The increased strength potential alternatively permits higher content of filler or weak fiber, e.g., hardwood Higher filler content affords better opacity. Good printability, e.g., good porosity, bulk, compressibility, print through, brightness. Calendering without blackening possible at higher moisture levels. Improved paper permanence Improved chemical resistance, e.g., against lactic acid, alkalies

Some potential drawbacks of neutral/ alkaline papermaking

Process drawbacks Synthetic internal sizes required. Hydrolysis of size can cause problems. Temperature limitations in the wet end Acid (pH <4) chemical pulps in integrated mills can create problems. High load of anionic trash with mechanical pulps Deposit and picking problems; wear and plugging of wires and felts High microbiological activity, slime Cumbersome optimation of retention systems Chemical incompatibility, e.g., restricted use of alum, more expensive dyes and wet-strength resins-required. Product drawbacks Size curing can be incomplete, difficulties in adjusting the degree of sizing Size reversion and fugitivity embarrassing customer complaints. Fine filler required for opacity Yellowing with mechanical pulp it pH >7.5 Insufficient toner adhesion in copying Slippery sheet surface at hard sizing (Low paper gloss)

Calcium carbonate in any system, if allowed to equilibriate, produces an alkaline pH. Recycling of coated broke therefore tends to present problems in an otherwise acid process owing to the decomposition of the CaCO3 present. The decomposition already begins gradually at pH 66.5, resulting in accumulation of sparingly soluble gypsum (calcium sulphate) and calcium hardness in the white water, and liberation of carbon dioxide. Alum, for example (being an acidic substance), will give cause to the following reactions:
3CaCO3+Al 2(SO4)3 + 3H2O 2Al (OH)3 + 3CaSO4 + 3CO2 CaCO3 + CO2 + H2O Ca (HCO3)2Ca 2+ + HCO3 CaSO4 Ca 2+ + SO 2 - 4 (a) (b) (c)

Side reactions (b) and (c) are also unacceptable, with saturation by gypsum and very high calcium hardness in the aqueous phase. Thus large quantities of calcium carbonate in broke and white water can cause severe pH swings, foam, poor retention, and pinholes in contact with alum. Conventional rosin sizing of the furnish would meet major problems and be ineffective. This of course has caused papermakers to re-evaluate their pH control and sizing procedures. The increased reuse of recovered paper with a growing content of CaCO3 leads to similar problems in the production of both paper and board. Any carbonate containing system therefore must be run preferably at a pH above 6.5.

In the field of wood-free fine paper, the neutral-alkaline papermaking technology using either natural ground calcium carbonate (GCC) or synthetic precipitated carbonate (PCC) as filler and coating pigment, seems to be relatively well mastered. There has been a continuous trend to raise the filler content. The high proportion of CaCO3 in the furnish buffers system pH to 7.8-8.5. Consequently the internal sizing of alkaline fine paper is today effected exclusively by application of synthetic agents such as alkyl ketene dimmer (AKD) or alkenyl succinic anhydride (ASA). The synthetic sizes are similar to rosin size in that they contain molecules with a hydrophobic portion that imparts the water resistance, and an end group that provides attachment to the fibers.

Contrary to rosin sizing - where electrostatic attraction is the primary mechanism of attachment, with ASA and AKD, it is thought to take place via a chemical covalent bond; therefore, the attribute "reactive" is often used for these sizing agents. However, it is well-known that sizing with synthetic sizes becomes more difficult and uneconomical as the proportion of mechanical pulp increases. With mechanical pulp in particular, the large amount of anionic "trash" and detrimental substances circulating in the system also tends to cause retention and runnability problems.

It is well -known that the concentrations of trash material increases with pH. In an acid system, alum can be used as a remedy to bind or coagulate unwanted components while, in neutral or alkaline systems containing CaCO3, pH depression to the "alum level" would not be acceptable. In many cases, however, in particular when a coating color is the only source of calcium carbonate and the percentage is small (e.g., in coated board), pH cannot be higher than 6.8-7.2. These considerations, among others, have led to the development of rosin sizing systems applicable under close to neutral conditions.

Neutral rosin sizing

Soap rosin size by necessity is limited to the acid pH range of 4-5 and cannot be considered at neutral pH.

For neutral pH conditions, the key conception is that the agents used alum and size, do not necessarily have to react in the wet end. Reaction between adsorbed hydroxyl aluminum floc and resin acid also in a neutral process takes place in the dryer section of the paper machine under the influence of heat. The logical requirements then are as follows:

To restrict any extensive depression of pH in order to preclude the reactions (a-c) with calcium carbonate. If possible, this should be accomplished by minimizing the dosage of the Al-source chemical. To create aluminum species (flocs) which are sufficiently cationic to be adsorbed by anionic surfaces in the pH region 6.5-7.5. (At a pH higher than 7.5, rosin sizing fails unconditionally.) To use or develop a modified dispersed resin acid to minimize ionization in the neutral pH region. To use a retention aid capable of retaining the anionic resin acid close to the adsorbed cationic aluminum floc.

To maintain a sufficient Al-level without decreasing the pH too much, condition 1 has been met in practice also by substituting part of the aluminum with sodium aluminates, or by dosage of an alum solution partly neutralized with sodium hydroxide.
In any case, a transient pH change will occur from neutral to slightly acid (in most cases, to about 6.5) and back to neutral. The process is therefore called pseudo-neutral.

As far as condition 2 is concerned, when alum is added to a furnish at pH 6.5-7.5, the Al-species will be ultimately converted to aluminum hydroxide Al(OH)3 which, however, does not lose its charge all at once.

It has been noted that the expected decay of cationicity fortunately takes place rather slowly so that a sufficient degree of adsorption can be achieved. However, substitution of the alum by polyaluminum chloride (PAC) has proved to be the best solution to the neutral rosin sizing problem. Like alum, PAC provides a source of alumina for the rosin sizing. PAC however is pre-hydrolyzed and therefore does not depress the pH to the extent an equivalent amount of alum would indeed. When PAC is used any pseudo-neutral pH change might even remain "unnoticed." Moreover, the alumina formed from PAC at neutral pH possesses a significantly higher cationic charge than alum-induced flocs.

Condition 3 has been met successfully by the producers of rosin dispersions by development of special although more expensive formulations. Nevertheless, the consumption of rosin at neutral pH can be considerably larger than in acid conditions, depending however much upon the local papermaking conditions. Condition 4 is not a "problem" but has meant more careful attention on application parameters such as coagulants, retention systems, filler type and usage, and chemical addition sequences.

Sizing with alkenyl succinic anhydride Emulsification

The alkenyl succinic anhydrides (ASA) are composed of an unsaturated alkenic hydrocarbon backbone coupled succinic anhydride.

The desired number of carbon atoms in the -olefins is usually (14)-16-18-(20). In general, a longer chain length and linearity produces a more efficient ASA size. If the number of carbon atoms in a linear olefin exceeds 20, the ASA will be solid at room temperature and less suitable for emulsification. Normally ASA is a yellowish oily product. This 100% active substance can be stored as such for a long time but must be well protected from water or humidity. It will not dissolve in water and, prior to application in papermaking, must be emulsified onsite at the paper mill. A small amount (3%-6%) of activator is added, plus cationic starch and a synthetic cationic polymer which serve as stabilizers.

Activators are surface-active agents that promote effective emulsification under conditions of low mechanical energy. Emulsion stability is best with synthetic polymer, and sizing efficiency is best with cationic starch improving with the amount of starch used; consequently, propriety mixed emulsification systems have been introduced.
The ratio of starch to ASA is usually in the range 2:1 to 4:1.

The emulsification process imparts a cationic charge on the oil droplets which helps to increase the stability as well as improves ASA retention on anionic fibers and sizing efficiency. The synthetic cationic polymers used enhance these properties and are often called "promoters."

Linear hydrocarbons are more hydrophobic than branched ones.

However, the greater the hydrophobicity of the ASA molecule is, the more difficult it is to prepare a stable quality ASA emulsion.

Chemistry and application of ASA

ASA undergoes the normal reactions of acid anhydrides. Particular interest in conjunction with sizing is the reaction with alcoholic hydroxyl groups to yield an ester and the hydrolysis with water. Both reactions occur in the papermaking system. ASA is highly reactive, and the reactions proceed rapidly and irreversibly. Although this would provide satisfactory development of sizing on a paper machine, the hydrolysis of ASA is undesirable. ASA chemistry and performance is related to the quality of the emulsion before it is added to the papermaking furnish. If a mediocre ASA is used, more ASA will be needed to achieve the sizing desired and more ASA will be lost by hydrolysis and, consequently, increases the probability of problems.

Formation of a covalent ester linkage between a cellulose hydroxyl group and the anhydride portion of ASA (right), and the competing hydrolysis of ASA into a dicarboxylic acid (left).

The hydrolysis of ASA accelerates with pH, time, and temperature.

In order to limit the hydrolysis of ASA emulsions, pH can be lowered immediately after the emulsification by addition of aluminum sulfate. The time lag between preparation and use should be as short as possible. There can be an incubation period at neutral pH without any appreciable hydrolysis of the product, followed by an accelerating rate. This property has been attributed to the layer of starch molecules located at the surface of the emulsified ASA particle, acting as a barrier against the transport of water to the particle. Since the barrier depends upon the outcome of emulsification, each batch should in principle be checked for the length of the protective period, if any.

The hydrolytic decomposition of ASA still continues after the dosage into the furnish and can even accelerate because usually the pH and temperature of the stock are higher than in the emulsion proper.
Addition points should be selected to minimize the residence time. A long residence time will cause size hydrolysis and lead to deposit problems. Thus the machine chest is not recommended as an addition point.

The outlet of the machine chest is a possible location provided no more than a small amount of stock is recirculated from the stuff box to the machine chest.
Addition of the emulsion here is said to provide the highest sizing with the least sizing variation. Other suitable locations for ASA dosage, with good mixing for satisfactory distribution of emulsion particles, are the inlets to the fan pump and screens.

The dicarboxylic acid formed in the hydrolysis of ASA is a liquid that does not contribute to sizing at all.
It can remain in emulsion for a while but gradually dissolves in the white water.

It then combines with cations present in the white water to form insoluble succinates.
Calcium, magnesium, and copper salts in particular form tacky deposits which can seriously impair runnability.

Positively charged polynuclear aluminum ions can neutralize the acidic groups forming cationic non-tacky precipitates that can be retained by fibers, although they do not contribute to the degree of sizing.
The aluminum ions also promote stabilization of the ASA particles. Introduction of a small amount of alum (e.g., 0.5%) is consequently recommended. The alum can be added to the thick stock, recycled white water, or ASA emulsion. The last mentioned method has proved to be most effective.

Good solids retention is extremely important in ASA sizing. As stated previously, ASA is a very effective size and, if applied in a correct way, a relative small dosage (usually 0.1-0.18% based on furnish solids) is required to produce the desired degree of sizing. As with any process of internal sizing, the fines and filler fractions with a large surface area will consume a large proportion of the amount of size introduced, and ASA adsorbed onto the unretained fines and filler surfaces will pass into the white water. Poor retention thus results in a hydrolysable ASA excess on circulating fine particles, causing poor sizing results and potentially deposit and runnability problems. The particles in circulation behave in the way anionic "trash" does.

Careful selection of retention aid is therefore an important part of planning an ASA process.

Virtually all problems with ASA size follow from poor emulsion stability or from excessive ASA hydrolysis, along with poor retention, contamination of felts, and press roll picking.
These problems are the major obstacles against acceptance of ASA products. Since the emulsification has to be carried out concurrently with paper machine operation, vulnerability in regard to break situations is a major concern. Whenever breaks on the paper machine are expected to last longer than a few minutes, a continuously operated ASA unit must be stopped, emptied, and restarted later on. ASA fed during downtime will return in the hydrolyzed state and aggravate the situation. A readymade ASA batch must many times be made batch must many times be discarded. A break in the ASA-line means that the paper machine no longer receives the size it needs to meet the grade specification, and wet broke will be generated.

The great advantage in favor of ASA is the high rate of cure in comparison with AKD size.
The reaction with cellulose hydroxyls takes place rapidly in the dryer section of the paper machine at less than 5% web humidity. More than 90% of the attainable sizing potential in most cases is achieved before the size press unit. The reaction rate is influenced by the same parameters as the hydrolysis that is primarily by pH, previous residence time, and stock temperature. The best conditions obviously depend upon the balance between the reaction rates with cellulose hydroxyls and hydrolysis of ASA, and optimum sizing can be achieved at neutral rather than at higher pH, depending upon the full set of system conditions.

Sizing with alkyl ketene dimer

Synthesis and emulsification
Structurally, alkyl ketene dimers (AKD) are unsaturated lactones. A frequently used synthesis route involves the preparation of the acid chloride of a carboxylic acid (accomplished with, e.g., phosphorus trichloride, phosphorus pentachloride or thionyl chloride), followed by intermolecular lactone ring condensation via a labile intermediate carboxylic acid obtained by dehydrohalogenation of the acid chloride with triethanolamine in an organic solvent.

Synthesis of alkyl ketene dimmers (AKD) R = C14H29 to C20H39.

As in the case of many wet end additives, for dosage into the papermaking furnish the wax must be converted into tiny particles dispersed in water. The emulsification is usually effected in a hot (75oC-90oC) solution containing the cationic starch stabilizer and a small amount of surfactant, e.g., sodium lignin sulfonate, to which are fed AKD flakes.

After melting of the AKD, microfluidizers; and cooled.

the

mixture

is

forced

through

Small amounts of a promoter (low MW cationic polymer with high charge density) and biocide can also be included. The particle size of the dispersion produced is today normally 0.5-2 microns, with a mean weight average near 1 micron. Although a low wax melting point aids in emulsification, it can be a drawback later in hot paper making systems where the temperature can rise above the melting point, and the stability of the dispersed particles can be destroyed on account of the melting of AKD inside. Recent advances in AKD synthesis and emulsification technology have made it possible to produce dispersions at considerably higher solids content than earlier.

Usually about 20%-40% of the solids content is cationic starch and/or some other more strongly cationic polymeric stabilizer. The charge of the AKD dispersion can accordingly vary from slightly to highly cationic. Recently developed "third generation" high-solids AKDs can contain as much as 150%-200% protective agent relative to the AKD wax. Their hydrolysis and migration tendency are claimed to be greatly limited in comparison with conventional AKD grades. The recommended field of application is for demanding multipurpose copy paper filled with synthetic precipitated calcium carbonate. The dispersions delivered to the customer have pH ranging from 2.5 to 3.5, owing to acidification with either sulfuric or hydrochloric acid.

This prolongs shelf life by reducing potential hydrolysis of the AKD.

At pH>6, it becomes more reactive by opening of the lactone ring in the molecule. Because of the acidity, corrosion-resistant equipment is needed for storage and pumping. The AKD producers usually store and ship the AKD below 20oC.

If the storage time at the paper mill is longer than a month, the temperature of the storage tank should be maintained below this temperature but should be protected from freezing in winter time.

AKD reactivity
The AKDs are believed to react with the hydroxyl groups of cellulose to form -keto esters (Fig.). However, alkyl ketene dimers also react with water under the formation of an unstable -keto acid which decarboxylates to the corresponding ketone, e.g., stearone or palmitone (Fig.). In comparison with ASA size, AKD is considerably less reactive. The competing hydrolysis reaction was critical with earlier AKDdispersions. However, the stability of most commercial products has been improved significantly in recent years as far as hydrolysis is concerned. Contrary to the hydrolysis product of an ASA size which is always lost in the white water, the ketone resulting from the hydrolytic decomposition of AKD is a solid (melting point 80oC-85oC) which can be retained in the sheet but does not contribute to sizing.

Thus the risk of deposit formation is less with AKD, although the labile intermediate -keto acid, if formed in the aqueous phase, can form relatively stable tacky precipitates with calcium ions.

The mechanism of AKD sizing implied that a variable amount, 50%80% of the AKD used could contribute to -keto ester formation, and that the reaction was catalyzed by polyamide epichlorohydrin resin and bicarbonate ions and followed pseudo first-order kinetics.
Effects of pH, electrolytes, and extractives were also noted. No sizing was obtained unless the AKD reacted chemically. Unreacted AKD contributed to sizing provided that there was some reacted AKD on the fiber surface, with reacted AKD being 2-3 times more efficient than unreacted AKD. The AKD may cover only a part of the cellulose surface, yielding sufficient sizing when as little as 15% of the surface is covered by AKD.

The thickness of the AKD layer was no more than approximately 3 nm.

Reaction between AKD and the hydroxyl groups of cellulose, with formation of a -keto ester linkage.

Hydrolytic decomposition of AKD via a labile -keto fatty acid into ketone (e.g. stearone. Palmitone.

Mechanism of interaction
The interaction between AKD and the cellulosic fiber proceeds in four stages

The dispersed, cationically stabilized particles are first adsorbed onto the fiber surface by electrostatic attraction. The AKD-dosage point for carrying out this step varies and lies typically within the area machine chest fan pump level box. Additional cationic starch can be added to assist the retention of AKD either before or along with the dosage of the AKD. As the web is being heated and dried in the paper machine, the adsorbed AKD wax starts to melt and after spreading covers at least part of the fiber surface as a thin layer. This intimate contact with the cellulose fibers will eventually make chemical reaction possible.

The chemical reaction with the cellulose hydroxyls, however, cannot proceed to any marked extent or at a sufficient rate until the major proportion of the water has been evaporated from the web. As for web moisture content, the start and rate of reaction will depend upon pH, alkalinity, and temperature.
As the chemical reaction gradually proceeds under the influence of heat, there occurs an energetic rearrangement of the molecules so that the hydrophobic ends of the molecules turn out from the surface, thus imparting water repellency to the web. Also this curing stage is favored by a high temperature and low web moisture content. Once initiated, curing can also proceed at a slow rate in the paper reel at the pope and in storage.

AKD must spread on the surface of fibers before any esterification could take place, there is no fundamental reason that this should be a prerequisite also for the hydrolytic interaction of AKD with water.
The extent and rate of the competing hydrolysis of AKD are also favored by pH and heat but still require the presence of water. With temperature increase, the rate of hydrolysis increases more steeply than the rate of esterification and the hydrolysis in a mill system becomes a significant factor. The ketone-forming side reaction, in addition to losing cellulosereactive groups in the expensive size, can and does cause undesirable performance problems. Care therefore should be taken to design the web-drying profile in a way that expels excess water as early and quickly as practicable.

Also the curing (viz., orientation) must be initiated appropriately because chemical reaction alone is insufficient for good sizing. If on-machine surface sizing or coating will be carried out, curing should preferably be complete prior to the treatment concerned. For these reasons, it is common to dry the web to very low moisture content before the size press, typically to 3%-5% but many times even 1%-3%, especially on fastrunning machines.
This can assist greatly but, even under these conditions, there will still be considerable off-machine development of sizing.

Considerable proportion of the AKD dosage can remain on the fibers in an unreacted state.

Although this proportion also contributes to sizing, it is less effective on account of "loose" orientation which, however, improves if a properly oriented monomolecular film of reacted AKD already exists on the fiber.
As little as 0.005%-0.008% reacted AKD is believed to yield sufficient monomolecular coverage, while dosage rates are considerably higher and typically vary from 0.05 to 0.2%, calculated as solid AKD wax based upon fiber.

Another way to speed up the curing before a converting unit is to carry out the AKD sizing in the presence of an auxiliary so-called promoter resin. The promoters are, for example, polyamide epichlorohydrin (PAE) resins or different types of cationic polyamines. The high cationic charge of some currently marketed AKD dispersions is probably due to promoter resin having already been incorporated in the size by the AKD manufacturer. Unfortunately, promoters like PAE resin not only increase the reactivity of AKD but also can speed up the hydrolysis to the useless ketone.

Thus at pH 8 the rate of hydrolysis of AKD has been estimated to be six times faster at room temperature in the presence of PAE than without it.

The accelerator effect has been still larger at 50oC, where the rate of hydrolysis was approximately 18 times higher with PAE resin. The cure-promoting roles (PDADMAC) were investigated it was noted that a threshold retention of AKD is required for sizing and that both kinds of polyelectrolytes aid chemical reaction as well as cure. These two phenomena, however, independently of each other. probably occur

The retention (viz., adsorption) of AKD seemed to be a greater factor for cure promotion than for its reaction with the fiber.
Cure rates were better with polyamines than with PDADMACs.

Some factors affecting AKD sizing

Fillers, fines, and retention
Fillers and fines increase the amount of AKD required in much the same way as is the case with size demand in rosin sizing and ASA sizing. This is primarily due to the increased surface area to be sized. AKD is very efficient at sizing pulp in the absence of both starch and PCC. Calcium carbonate filler, and its high surface area modification, in particular, greatly impairs sizing response.

When cationic starch is added, it enhances the sizing by preferentially depositing the AKD on the fiber surfaces.

It was noted in the same study that the total retention of AKD is a function of starch dose while the percentage of that AKD which is chemically bound is a function of the charge level of the starch. As far as hemicellulosic fines are concerned, the proportionally greater size demand is in part due to chemical reaction with hydroxyl groups. With filler, however, its chemical inertness with respect to AKD is a complication which means that any sizing on filler surfaces is probably brought about by adsorbed but unreacted AKD.

Two significant factors decrease sizing efficiency already in the wet end of the paper machine.
The first is that fillers and fines are not retained as efficiently as fiber, and a large proportion (more than 50% on most machines) of material carrying adsorbed AKD ends up in the white water where the AKD hydrolyzes at a rate depending upon pH, temperature, and time, and can lose part or even all of its efficiency before the next pass. The second factor is that the retention system can agglomerate the filler with adsorbed AKD so extensively that a large proportion of the size is trapped inside the agglomerates and cannot spread over fibers and react in the normal way during the drying stage.

The best way to limit the above adverse effects is to add the AKD to the thick stock before addition of filler.
AKD can be added in the thick stock flow prior to the fan pump and will adsorb to the fibers before contact with filler. The goal should always be to size the fiber, not the filler.

It follows that one of the most important factors in AKD (as well as in ASA) sizing is to have an optimized overall retention system. With proper retention and flocculation of fillers fines, the total surface area of particles recirculated is reduced; these would otherwise consume much of the AKD, cationic starch, and promoter added, and possibly cationizes the system by heterocoagulation.

A cationic system might not accept AKD easily and sizing efficiency can deteriorate.

Optimization of the overall retention system is often more critical than the choice of AKD grade for the system and should include mapping of the anionic and cationic levels of the wet end, and of inorganic and organic fines in the short circulation loop.
Currently the retention aids applied in alkaline AKDsized papermaking are to an increasing extent nanoand microparticle flocculation systems or novel site blocking enhanced bridging flocculation systems.

pH and alkalinity
Alkalinity is a measure of the buffering capacity of the aqueous system principally due to the concentration of bicarbonate ions (HCO3-), expressed as the equivalent amount of calcium carbonate in mg/L (ppm). The effects of pH and alkalinity on AKD sizing are interrelated. The pH of the papermaking system affects sizing but is not independent of alkalinity. Alkalinity effectively contributes to the reaction between AKD and cellulose. The underlying mechanism is not fully understood, but the bicarbonate ions have been found to exercise a proton-transfer catalytic effect. A moderate alkalinity level (e.g., 50-200 ppm) is generally considered favorable if not indispensable, as curing otherwise can fail.

At satisfactory alkalinity, the effect of pH upon sizeability is quite clear: Although the rate of cure increases with pH, post-cure will usually proceed satisfactorily to practically the same end point at any pH higher than 7. Soluble alkalinity is the easiest way to ensure a stable, buffered system pH, to increase the sizing efficiency of AKD, and to counteract negative effects of alum. High alkalinity (in excess of 400 ppm) should be avoided - it is most often due to a high concentration of hydroxide ions and high pH favoring the hydrolysis of AKD, and can also cause reversion of sizing (= loss of size response with time after the paper has been made).

Sources yielding high alkalinity are sodium hydroxide, calcium hydroxide, and over dosage of sodium carbonate Na2CO3.

Insufficient alkalinity is best corrected by dosage of sodium bicarbonate NaHCO3.

Systems with calcium carbonate filler usually self-adjust in respect of both pH and alkalinity, and dosage of additional bicarbonate ions is not required. This increased alkalinity can cause further hydrolysis into ketone of the unreacted AKD fraction in the sheet resulting in loss of sizing. The extent of this hydrolysis is directly related to the surface area and calcium hydroxide concentration on the PCC.

Size reversion is when paper is in specification at the reel and, upon aging, the sizing level decreases to a level where it then remains constant.
Fugitivity or loss of sizing, results when paper is in specification at the reel and, upon natural aging, all of sizing is lost. Hence size reversion and fugitivity are different issues. Today, the use of satellite-carbonate (synthetic precipitated CaCO3 (PCC), and in particular with the use of on-site produced "satellite" filler), is growing also in Europe, primarily because it provides the papermaker with a choice of a customized filler to better meet grade requirements. The synthesis permits variation of the particle size and morphology, and many optical and physical properties of paper such as tensile strength, stiffness, porosity, bulk, and brightness can be significantly altered.

Recyclability of AKD-sized paper A significant proportion of the unreacted AKD will be lost by hydrolysis into ketone because of the relatively long chest hold time in warm water. After recycling of paper containing cationic polymers, at least 60% still remained adsorbed to the fibers, and a significant surface area was thus available for interaction with fresh cationic agents.

AKD size present on the recycled fibers, however, did not affect the adsorption behavior of cationic polymers.

The explanation given is that AKD does not interact specifically with the charged groups of cellulose, and most of these groups are left for interaction with the cationic polymer used. AKD probably covers only a fraction (e.g., 15%) of the fiber surface.

Recycled fibers from AKD-sized sheets were still hydrophobic to some extent.
A minor amount of AKD (0.03%-0.06%) had to be added to achieve full sizing again even when the sheet initially was hard-sized. It was also noted that aging of the sized paper had no further effect so far as reslushing and recycling were concerned.

DIFFERENCE B/W ROSIN AND SYNTHETIC SIZES:

The primary difference between the two is the chemical nature of the anchoring mechanism that holds the size molecule the place. For rosin, it is an ionic bond between the carboxyl group of the rosin and precipitated aluminum species. This complex in turn, is held on the fiber by ionic and polar bond forces. The synthetic size have a reactive group that can form a covalent bond directly between the size and the cellulose, a bond that is less hydrophilic and much more stable to water than is an ionic bond. A second difference is that the hydrophobic portion of the synthetic size molecule consists of a long straight hydrocarbon chain, in contrast to the fused ring character of the rosin acid. Other major difference is the changed role of alum. Since alum is not necessary as an anchoring medium for synthetic size, the wet end of the paper machine can be run at a pH higher than that required for rosin sizing.

The reaction of the synthetic sizing agent with the fibre is chemical in nature and can be relatively slow, compared to the essentially instantaneous ionic and polar interactions between rosin, alum and fiber. Usually alkaline conditions in the wet end favor a more rapid development of sizing, and the presence of alum may slow the reaction. Whereas the bond may be slow to form, it is also slow to break, and synthetic sizes will stand up to aggressive liquid such as acids, alkalis, lactic acid, alcohol, and liquids at elevated temperatures.
Synthetic sizes are insoluble in water but at the same time are reactive with water because any functional group that can react with the hydroxyl group of cellulose can also react with water. They must be emulsified before use, but the emulsions are not stable indefinitely. Depending on the reactivity of the size, the emulsions may be manufactured by the chemical supplier, or they may be prepared by the paper maker shortly before use.

Synthetic sizes are extremely efficient. It is not unusual in some grades to find a synthetic size being used at levels of 0.05 to 0.07 percent based on fiber weight. These low levels of sizing agents can be an economic benefit to the user. In addition, the use of low level of size means less interface with fiber bonding and, therefore, a stronger sheet. The other primary reason for converting to alkaline paper making is to employ calcium carbonate, especially in place of titanium dioxide. In general, cost of calcium carbonate is approximately one-tenth that of titanium dioxide. For many applications two parts or less of CaCO3 can give similar optical properties when substituted for one part of titanium dioxide.

TYPES OF SYNTHETIC SIZES

Three reactive are in commercial uses which are as follows:

ALKYL KETENE DIMER (AKD) This is a widely used synthetic size with the following formulae: R CH = C CH R
OC=O It can react at a pH of 6.5 8.5 with the hydroxyl group of cellulose to form an ester. AKD is a solid that melts at about 50oC. it is available commercially as a solid for emulsification at the mill, or as a prepared emulsion. A prepared emulsion containing a cationic resin is also available AKD is flow to react which means that its emulsions retain high activity for a relatively long time upto 2 months at normal temperature. However, it is flow to develop sizing and it is less tolerant of alum and low pH than the other synthetic sizes.

The reaction of cellulose sizing is:

One of the major drawbacks of AKD size is that the rate of hydrolysis reaction can not be ruled out, which exhibits some undesirable properties, as: Loss of sizing efficiency. Increased sizing cost. Non reactive waxy Ketone by-product. Increased slipperiness. ALKENYL SUCCINIC ANHYDRIDE (ASA) This synthetic size is most reactive of the three sizes described. Its formula is:

ASA differs from other sizes in that it is a liquid mixture of isomeric compounds. Because of the high reactivity, emulsion activity is lost in a matter of haw; therefore, emulsions must be prepared in paper mill. Close tolerance pumps and other high shear devices can be used to form the emulsions. ASA can be used at low pH (S.O.) and with alum, but cave is more rapid under alkaline conditions. ASA sizing and hydrolysis reactions are as:

Unlike the other two sizes, ASA is not particularly effective against aggressive liquids such as lactic acid. It does, however, give ink and water resistant far in excess of what can be achieved with rosin size. it is particularly suitable for writing and printing grades of paper.

STEARIC ANHYDRIDE
It has the following formula: CH3 (CH2)16 C O C (CH2)16 CH3 O O

It reacts with cellulose to form an ester.

It is a solid, melting at about 60oC. it is available commercially as the solid for in-mill emulsification or as an emulsion containing an cationic resin. Because of its high rate of reaction, emulsions of stearic anhydride lose activity more rapidly than AKD emulsions, and they are generally not effective after 2 to 3 weeks. Sizing reaction is also more rapid than with AKD, and alum and low pH (as low as 5.5 to 6.0) can be used successfully with it. OTHER SIZES: Sodium Stearate Bituminous (Asphalt) Emulsions Petroleum Resins Fluoro Carbons

L2 = [( R cos ) / 2] t

Where
t = time = fluid radius R = capillary radius = contact angle = surface tension of fluid L = depth of fluid penetration in time, t