RETENTION CHEMISTRY

Retention is defined as the relative ability to hold the various components of the furnish in the sheet as it consolidates. The retention is of two types.

Over all retention:

It is the ratio of the total amount of the material that is going into the paper machine wet end compared to the total amount coming off the reel at the dry end. The values are in the neighbourhood of 90-95%.

First Pass Retention:

It compares how efficiently a given component in the head box stock is retained on one pass through the forming fabric. It is measured by comparing the ratio of the quantity of the component in the head box to the quantity being reeled up on the dry end.

One pass retention

One Pass Solid Retention:
It measures the retention of all solids in the head box system as the sheet forms on the moving fabric.

One Pass Fiber Retention:

It is the retention of the fiber fraction of the stock suspension in the head box.

One Pass Fine Retention:

It is the retention of the fine fraction of the head box stock system. The retention in the paper machine is controlled by closing the system completely. No material would escape and after equilibrium was established, the over all retention would be 100%. Then what is the importance of one pass retention.

Importance of one pass retention

Better drainage: Increasing one pass retention reduces
the fines responsible for slow drainage and increases water drainability. Less felt filling: High load of fines is the main cause of felt filling and plugging. This reduces water expulsion at the press. Decreased two sidedness: When mechanical filtration is the main cause of retention, two sidedness of the sheet is inevitable. Increased first pass retention with retention aid reduces the two sidedness and leads to greater sheet homogeneity. This is due to adsorption of fines on the fibers, evening out Z directional distribution of fines. More efficient use of additives: Because of high surface area of fines, these adsorb more than its share of additives in the system, resulting in efficient use of the additives. Cleaner System: Excessive loading of fines leads to a dirty system that is prone to slime and pitch build up. This causes numerous runnability problems and a poor quality product. Better retention removes the deposit problems

Fines
The fines are the portion of the furnish or head box stock that passes through a 76 m/200 mesh screen when fractionated on a single screen classifier like Britt Jar. Pulp fines are derived from the stock from the wood. These are liberated during pulping and bleaching process. These include parenchyma and ray cells, vessel elements from hard woods and epithetical cells from linings of resin ducts These can be fragments of tracheids, fibers and vessels broken during pulping process and harsh bleaching conditions exposes and strips the fiber wall Primary fines are thin, veil like lamellar structure. This type of fine is developed as fiber is refined. It is thin and veil like lamellar particle produced by the abrasion of the fiber surface as the fibers pass through the refiner elements. Most of the fines come from S1 or S2 layers of the fiber secondary wall.

Primary Fines:

Secondary Fines:

Fiber and fines wet end chemistry

Interactions between fiber and fines can be directly related to their surface and colloidal chemistry Important characteristics are sorption capacity, swelling behaviour and ion exchange properties. These are controlled by surface area, surface charge and surface chemical composition of fiber & fines. Specific surface area of fines is 5-8 times more than fibers and most of the interactions are surface interactions, thus fines play a predominant role Fine retention is very important as it contributes towards paper strength and other properties. Fines may represent 40-60% of the head box stock, fine retention is crucial to the efficient material utilization

Surface Charge
The main source of charge on fibers is from carboxyl , phenolic hydroxyl and hydroxyl groups which ionize when dispersed in water. Carboxyl groups are ionized above pH 2.5, phenolic groups at pH 8-9 giving a net negative charge on the fiber between pH 4 and 8.5. The number and distribution of the charged groups on the surface of the fibers & fines dictates the ion exchange capacity of the system. The order of the affinity is
N(CH3 )+4 < Li+ < Na + < k+ < Ag + < Ca2+ = Mg 2+ < Ba 2+ <Al3+

During normal paper making, carboxyl groups are contributing majority of charged sites in fibers/ fines Dissociation of the filler or anionic dispersant used to keep individual particles separated may also be a source of charge

Fines
Finally powdered white mineral fillers are used extensively by paper makers to impart numerous properties to paper. Important characteristics of filler are summarized in Tables
Uses of mineral fillers in papermaking 1 2 3 4 5 6 7 8 Brightness improvement Opacity achievement Whiteness improvement Gloss development Improved smoothness Improved printability Fiber substitution Titanium dioxide extension

Types of filler pigments

Titanium dioxide

Calcium Carbonate

Anatase

Ground

Rutile

Precipitated

Kaolin clay

Aluminium trihydrate

Talc

Silicas

Plastic pigments

Ca sulphoaluminates

Important physical properties of filler pigments

Refractive Index

2
3 4 5 6 7 8 9

Particle size distribution

Particle shape Specific surface area Specific gravity Ink absorptivity Brightness Whiteness Surface charge

Filler properties that are important to wet end chemistry

Particle size

Degree of aggregation

Particle shape

Specific surface area

Surface charge

Chemical composition

Average particle sizes for common fillers Pigment Avg. particle size m 0.37 0.37 0.60 0.80 0.82 % between 0.2-0.8 m 85 85 33 43 29

Plastic pigments Titanium dioxide Filter clay Precipitated Calcium carbonate Sodium silico aluminate

Ground Calcium carbonate Aluminium hydrate

Calcined clay Talc Calcium alumino sulphate

0.95 1.0
1.1 1.2 2.1

33 26
34 27 6

Summary of results of study between filler particle size and retention

Increased particle size or aggregated size lead to increased filler retention by filtration action and a net over all increase in retention Coagulation-retention by colloidal adsorption interactions decreased with increasing particle size Flocculating pigment particles with retention aid give dramatic improvement in overall retention Difficulty of retaining fine filler particle lead to build up in the circulatory white

Influence of particle size on filter retention

 Paper maker would strive to aggregate filler as much as possible in order to maximize first pass retention Aggregation of filler decreases its light scattering power and opacifying power Paper maker has to make a compromise between high retention and high opacity Particle shape also influence light scattering performance of pigments as well as their response to gloss during calendaring or prevention of gloss Particle shape affect the extent to which fillers decrease air resistance and drying rate of paper

Wet end chemistry

There is an inverse relationship that exists for most filler between particle size and surface area which suggest that higher surface area materials will be more difficult to retain Second is the absorptive capacity which is higher for high surface area fillers The impact would be high filler loadings that are detrimental to sizing because sizing material adsorbs on to the filler and is rendered in effective

 Dye adsorption is greater for fillers which increases two sidedness if the filler is not evenly distributed in the Z direction High surface area pigments require more retention aid to affect a particular retention level because polymer is diluted by large surface area over which it becomes distributed. The pigment filler particles when dispersed in water usually carry a negative surface charge from the dissociation of functional groups The surface charge is related with Zeta potential a parameter used for surface charge

 The surface charge on the particle play a key role in the retention of the fines If the surface charge is of the same sign and magnitude is sufficient, the particles are repelled and remain in dispersed state but if the charge is small or no charge, attractive vander wall forces overcome repulsive forces and cause particles to aggregate By manipulating surface charge one can manipulate the dispersing/aggregating behaviour of filler system

 Surface charge can be altered by adjusting the pH of suspending medium or addition of soluble inorganic salts like alum, calcium chloride or by addition of polymeric dispersing agents like polyacrylates, polyphosphates or by incorporation of charge groups on surface of particle when the pigment is manufactured The Figure shows effect of pH on the surface charge

The influence of pH on the surface charge of filler particles

The influence of pH on surface charge of filler particle Filler charge consideration affects the wet end chemistry in several ways A stable, well dispersed slurry provides good light scattering performance & requires use of dispersant These dispersants inhibit the first pass retention of filler particles on the paper machine

 Paper maker overcomes this situation by changing charge on filler with alum or by using a polymeric retention aid to produce filler aggregates by bridging between individual pigment particles Other approach is through interaction of pigment dispersing agents with other chemicals in system Anionic polyacrylate dispersant reacts cationic polyacrylamide retention aids and render them ineffective Dispersants will also interfere with other cationic chemicals in the system

Mechanism of Retention
Particles in the head box systems can be retained as sheet is formed by one or combination of following mechanism: filtration, mechanical entrapment and co-flocculation Filtration is separation of pigment particles from water leaving the web only as pigment particles are bigger than interstices between fibers in the mat forming on the paper making wire Mechanical entrapment takes place when a pigment particle becomes wedged in the imperfection in fiber wall or trapped in the cell lumen Both of these mechanisms are purely mechanical The third way is through co-flocculation of pigment and pulp fines with the fiber or with themselves Particle materials are retained in paper stock or not retained as a function of efficiency of mechanical colloidal retention mechanisms

Colloidal Retention
During sheet formation process, the mixture of fibers, fines and other materials is caused to flow into the moving wire or fabric As the liquid drains all most (av.96%) of the fibers is retained on the fabric The small portion of the fiber that does pass through the moving fabric when stock jet first impinges on to the moving fabric before any web has formed At this stage, there is a good chance that some fibers may be oriented such that they pass vertically through the interstices in the fabric with the initial flow of water

Hard Flocs Vs Soft Flocs

A soft floc, after it has been exposed to shear during a dispersion cycle reflocculates to the same level of retention that is exhibited on initial flocculation This type of floc has limited resistance to shear, giving only modest improvement in retention at high levels of shear It is produced by salts and low molecular weight polyelectrolytes. A hard floc shows greater tenacity when exposed to shear and will give excellent retention with strong turbulence when this type of floc is exposed to redispersion, the floc that forms will exhibit lower levels of retention Hard floc is produced by high molecular weight polyelectrolytes and a dual polymer system.

Reaction of soft flocs formed by salts to redispersion

 The data shown in Table indicate that after the stock is flocculated with salts, the retention is independent of original flocculated stock or reflocculated dispersed stock This is characteristics of soft flocculation mechanism. The addition of salts neutralizes the surface charge by adsorbing on to the surface There is no possibility of any rearrangement taking place on the surface When the floc is redispersed, these ions are desorbed and readsorb on to the surface, providing surface as it was during initial coagulation This suggests that retention should be equal before and after redispersion as shown in Table Ions of increasing valence will produce stronger coagulation as indicated by higher retention for the same dosage levels

 Lower molecular weight polymers (< 10,000) will tend to act in the same way as metal ions In most of the cases the molecules will be small enough to form discrete patches of polymers on the surface of the particles These patches are centers of concentrated cationic charge on the surface of particles. The polymer in the patch does not extend far into liquid to form a bridge. It however form strong bond through columbic interaction between the cationic patch and anionic surface on the other particle When exposed to turbulence, the surfaces are separated but the polyelectrolyte remains attached with the surface and remain unaffected by shear In this case retention will be the same before and after exposure to dispersion. (PEI-B curve of 6000 molecular weight).

 The data shown in Table indicate that after the stock is flocculated with salts, the retention is independent of original flocculated stock or reflocculated dispersed stock. This is characteristics of soft flocculation mechanism. The addition of salts neutralizes the surface charge by adsorbing on to the surface. There is no possibility of any rearrangement taking place on the surface. When the floc is redispersed, these ions are desorbed and readsorb on to the surface, providing surface as it was during initial coagulation. This suggests that retention should be equal before and after redispersion as shown in Table. Ions of increasing valence will produce stronger coagulation as indicated by higher retention for the same dosage levels

 If molecule is of some what higher molecular weight, there may be some effect on exposure to shear The molecule may be flattered out, bonding with adjacent areas on the surface. This may reduce the length of the loop extending into liquid phase Secondly the functional groups will bond with surface site reducing the charge density of patch After exposure to redispersion conditions, patch which was initially quite efficient flocculant will respond like a lower molecular weight material. (PEI-A curve of 50,000 molecular weight).

Soft floc curves with polyetyleneimine

 With hard floc conditions, floc seems to decay after repeated exposure to redispersive shear (with high molecular weight cationic polyacrylamide copolymer) The retention decreases with number of redispersion cycles and stock start acting like soft floc after three dispersions returning to the same level of retention after exposure to further shear

Effects of dispersion on hard flocs

Diagrams of adsoption, flocculation, reconformation and reflocculation on a particle surface

A: The particle has collided with another particle resulting in initial flocculation B: The particle has collided with another particle resulting in initial flocculation This is typical of the strong and tenacious bridging floc that is produced by high molecular weight polyelectrolyte The bridges physically tie the surfaces together. This linkage is much stronger than the electrostatic attractive forces produced by charge neutralization. C: When the system is exposed to shear, the surfaces may be separated

 One option is that polymeric molecule may remain intact with one surface, the other option is that the polymeric molecule may rupture, part of the molecule going with each surface Regardless of the two options, the high molecular weight molecule will be susceptible to reconfirmation on the surface due to the action of shear forces from the turbulence imposed on the system. D: Here the polyelectrolyte molecule has flattered out, the loops no longer extending into the liquid. Its structure is more like a patch adsorption and flocculation model. When surfaces collide and reflocculate the resulting floc now acts in a patch or soft floc mode.

When a system is exposed to shear, portions of the system that have been directly exposed to the turbulence will have undergone polymer rupture linkage and reconfirmation Other parts that have not been strongly treated will remain intact The result is the drop in the over all level of retention. The longer the system is exposed to the shear, the greater the number of separations and reconfirmations that take place Eventually system reaches equilibrium level such that further exposure does little to affect the level of retention This is the point where the system begins to respond as a soft floc

 A retention aid is any material that is added to the head box system that will help to increase retention of the solid fractions in furnish Usually this refers to particulate and colloidal fractions as they are more difficult to retain than fiber fraction.

Retention Aid

Inorganic Salts:
Salts are shown to produce weak but reformable flocs The fiber and particles are usually negatively charged The cations, enters the double layer, reducing surface potential The increased quantity of salt may move the system is an electric point where the Zeta potential is Zero

 At this point inter particle repulsions will be minimum, the system will flocculate and improvement in retention will be observed The higher is the cationic charge, the more it is effective as retention aid. Trivalent aluminium is more effective than divalent magnesium and monovalent sodium Aluminum ion gives best performance in the pH range 4.5 5.5 where it forms multi atomic structure by olation mechanism the most common structure is tetravalent [Al8 (OH) 20] +4. The pH affects the degree of dissociation of functional groups contributing to the surface charge. pH has a minor role in the retention of pulp fines

Retention curves showing the effect of increasing valence of cations

Organic polyelectrolytes
Organic polyelectrolytes are second category of retention aids There can be natural or synthetic products

Natural Materials:
Starch and modified starches have been used by paper industry to improve inter fiber bonding, drainage and retention aid Chemically starch is similar to cellulose It is a polymer of glucopyranose Coupled by alpha ether linkage at carbon 1 and 4. In cellulose the orientation is beta either linkage at carbon 1 and 4. Starch consists of both linear fraction called amylase and branched fraction called amylopection

Amylose

Amylopectin structure

 Branching most commonly occurs through carbon 6 and occasionally through carbon 3 For every 18-27 glucose units, on an average there is one branch point. Modified starches are available which differ in properties such as amylopectin to amylase ratio, granule dimensions, gelatinized temperature and average molecular weight of the component fractions Physical, chemical and genetic modifications have increased the number of useful properties of starches.

 Thermochemical conversions, acid hydrolysis and enzyme conversions all lead to decrease in the molecular weight of the starch and corresponding decrease in the solution viscosity of the starch solutions A large number of starch derivatives cationic, anionic and nonionic are used to improve the dry strength, fine retention, drainage, formation, stiffness and dimensional stability of the paper product

Cationic Starches
Cationic starches have good solubility and well retained by wood fibers The higher retention as compared to unmodified starch, yields economic gains in spite of their premium cost. Cationic starches greatly minimize water pollution effects The economic need to reduce the quantity of fines & fillers in effluents from paper machine provides a good incentive for the usage of such products

 Degree of substitution is 0.02 i.e. average two cationic groups attached to starch for each 100 glucose units This imparts a high dispersibility and solubility to starch Cationic starches are adsorbed irreversibly on the surface of fibers, the adsorption increases with increase in surface area and increasing carboxyl content of the fiber The sorption is rapid and approaches 100% retention with time. Excessive adsorption of cationic starches can lead to charge reversal on the fines causing them to be less retained during sheet formation Same consideration applies to retention of filler particles In general cationic starches are not as good retention aids as synthetic polymers when higher machine speeds and shear rates are encountered

 In practice about 1% concentration that does not subject the material to high shear rates before it reaches the forming section of the paper machine Cationic starches are more shear sensitive than synthetic polymers These should not be brought in contact with high concentration of anionic material if high chemical efficiency is required Presence of excess alum decreases the attractive forces between fibers and cationic starch

Anionic and Amphoterics starches

These contain phosphate functional groups. These function in the presence of at least 1% alum and at a pH range 4.3 to 6.0. High level of retention is obtained if sufficient quantity of alum is present Adsorption is reversible and >80% adsorbed starch is readily removed by heating Amphoteric starches contain both cationic and anionic groups These agents retain their charge under widely differing levels of pH, water hardness and alum concentration

Gums
Guar is a galactomannan, a carbohydrate Back-bone of the polymer is of mannose units that are connected by 1-4 beta-D mannopyranose linkage Galactase unit joined irregularly through alpha linkage at C-6 position Guar is a high mol. wt. molecule which has an affinity for cellulose and bonds via hydrogen bond Derivatised guar gum is oxidized, carboxy methylated , hydroxyl alkylated and quaternized ethers of guar Substitution takes place at the three hydroxyl groups Guar gums have low charge density and molecular weight compared to conventional synthetic materials and form soft flocs not resistant to shear as produced by other retention aids These do not have detrimental affect on formation and optical properties as other high molecular weight synthetic polyelectrolyte have

Structures of cellulose and guar

Quaternized guar molecule

Synthetic Poly electrolytes

It is a polymer which has charged functional groups which impart water solubility and allow it to behave like electrolyte? It can be blended with other uncharged monomers so that charge density can be moderated Poly electrolytes can be classified as cationic anionic or amphoteric

Nonionic Poly electrolytes

These do not have any formal charge but develop transient charge in water through protonation, making them water soluble and act as polyelectrolyte Examples are Polyethylene oxide (PEO), poly vinyl alcohol (PVA), poly acryl amide (PAM) Among these PAM is the most commonly used nonionic polymer Used as dry strength additive and flocculant Flocs formed by nonionic polymers are generally small & weak because flocculation is based on weaker hydrogen bond type bridging These are classified as soft flocs

Examples of non-ionic polyelectrolytes

Anionic Polyelectrolytes
These are sulphonic, phosphonic or carboxylic acid functional based groups These are marketed as neutralized salts which enhance its solubility The most common commercial anionic polymer is the anionic polyacrylamide copolymer produced by the copolymerization of acryeamide or acrylic acid monomer or by the acid hydrolyses of acrylamide Percentage carboxylic groups range from 5% to 50% depending upon hydrolysis condition Molecular weight should be million or greater so that the molecule

 can effectively bridge between two adjacent surfaces These require the presence of some kind of intermediary like alum so that the anionic polymer can bind with the anionic surface of the cellulose fibers, fines and filler particles through a bridging mechanism Where rosin and alum are used anionic poly electrolytes can be used with a fair degree of success Because of the high molecular weight of the polymer it will form hard flocs via bridging mechanism, but these flocs break easily due to tenacious anchoring of the particle surface through alum.

Cationic Polyelectrolytes These polymers are produced by incorporating tri substituted sulphur groups (sulphonium ions) tetra substituted phophourous groups (phosphonium ions) or tetra substituted nitrogen group (quaternary ammonium ions) through copolymerization or post polymerization grafting The most important group is ammonium group may be mono, di and tri substituted which retain their charge in an acidic conditions where as tetra substituted quatriammonium salts retain their positive charge in acid, neutral or alkaline medium

Cationic monomers used in polyelectrolyte synthesis

 These are blended with acrylamide to form copolymers with very high molecular weight and have excellent water solubility due to excellent hydrogen bonding Many copolymers have a cationic polymer content of 10 mole % with a molecular weight between 1-4 million Cationic poly electrolyte wills floc these systems through bridging between the negative sites Molecular weight will determine the length of the loop and tale into the liquid surrounding the particle Lower molecular weight molecules adsorb on the surface like a patch at one or more centers of cationic charge

Diagram of a patch floc

Because there is no physical linking between two surfaces through polymer molecule, it is not as strong as bridge produced by high molecular weight polyelectrolyte but is stronger than the floc produced by charge neutralization mechanism achieved with salts

 High molecular weight material with long chain length extends out into the solution to interact/adsorb on to the other surface forming stronger hard flocs A poly electrolyte with very high charge density assumes a rod like confirmation either lays flat on the surface or extends out into the liquid with only one chain by which to bridge These three situations low, medium and high charge density are represented in the figure

Cationic acrylamide copolymers

Schematic of a bridging floc

Effect of charge density on polymer confirmation and flocculation efficiency

Amphoteric Polymers
Amphoteric poly electrolytes have both positive and negative functional groups in same polymer chain Effective in wide pH range from acidic to alkaline pH

Dual Polymer Systems:

This involves the addition of low molecular weight cationic polyelectrolytes like polyethylene mine (PEI) followed by high molecular weight anionic poly acrylamide copolymer Dual addition or two step addition developed an extremely tenacious floc that could with stand very high degree of turbulence and deliver high levels of fines retention Order of addition of the polymers is very critical to the formation of very strong hard flocs

Example of an amphoteric polyelectrolyte

Diagram of the flocculation mechanism for the dual polymer system

 The addition of lower molecular weight polymer (60,000) is added to form a cationic patch on the surface of fiber or particle This patch forms a very firm anchoring point for the anionic polymer added in the second step The high molecular weight anionic polymer is adsorbed on the surface via cationic patch The majority of the surface will be still anionic so that anionic polymer is attracted to the cationic site Some times the anionic polymer is very strongly attracted to the whole surface, flattering out the surface and decreasing their effectiveness. If dual additive floc is disrupted and allowed to reflocculate it will not form as strong a floc or exhibit good retention as it did in its original state.

Micro Particle Flocculant Systems PAM/bentonite:

When lower molecular weight cationic poly acrylamide copolymer is introduced into wet end followed by the addition of bentonite (micro particle floc formed is resistant to redispersion, improve drainability and do not develop formation problems found in other dual polymer systems When exposed to shear, floc breaks down and re-flocculates in the same manner as in original state That means retention and drainage responses are the same as those in the initial condition

 Cationic starch followed by divided anionic silica particles acts in a similar manner as PAM/bentonite syste These systems work very well in the presence of high levels of anionic interference agents Because of high surface area, these rigid micro particles serve as adsorption sites for anionic trash These systems hold a great deal of promise for flexibility in the use of retention and drainage aids in paper making wet end systems.

Role of Zeta Potential Zeta potential can provide al sensitive indication of the absorptive capacity of the stock system to a given additive. By indicating charge on the stock, zeta potential can be used to predict whether cationic or anionic additives should be more strongly adsorbed. After a particular system is operating well, the zeta potential can be used to indicate up sets by flagging deviations from a set point

Effects of turbulence and retention aids on sheet structure on formation Micro flocculation:
The flocculation of the particulate matter in the sheet, pulp fines and fillers Scattering power of the filler and porosity of the sheet will be affected Macro Flocculation: This will be visible to naked eye This is caused by clumping of fibers and results in basis weight fluctuation These fluctuations appear as wild formation

 Flocculation:
Retention aid is added near the screens which may give good retention and acceptable formation Addition in the head box increases the retention but destroys the sheet formation Addition neat the fan pump experiences high sheet, breaking flocs and reducing. Micro Formation: The addition of retention aid alters the distribution of fines in the system When mechanical capture is the main mechanism of retention the fines will be distributed in the sheet as shown in figure.

Z directional distribution of filler for the mechanical entrapment mechanism

The filler content changes in the Z direction passes through a maxima and decreases The filler content increases upto thickness of the sheet from top and then decreases to the bottom (wire) side

 For a hand sheet the filler distribution increases from top side to bottom side More filler particles are removed during drainage from the wire side. When retention aid is added,Z direction fine distribution tends to smooth out because filler and fiber fines are retained by colloidal interactions rather than mechanical interactions Similar results are obtained with fourdrinier or twin wire formers.

Change in Z directional distribution with polyelectrolyte addition

Change in Z directional distribution with polyelectrolyte addition

The aggregation of filler particles reduces the opacifying power More filler (1-2% extra) may be added to maintain the opacity of the sheet

Colloidal retention index using the Britt Jar